Sample records for la1-xsrxmno3 perovskite nanoparticles

  1. Size-induced changes of structural and ferromagnetic properties in La1-xSrxMnO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Hintze, Cornelia E.; Fuchs, Dirk; Merz, Michael; Amari, Houari; Kübel, Christian; Huang, Meng-Jie; Powell, Annie; v. Löhneysen, Hilbert

    2017-06-01

    La1-xSrxMnO3 nanocrystals were grown using a microemulsion approach with different water-to-surfactant ratios Rw resulting in diameters between 20 and 40 nm. The variation of Rw entails a variation in the Sr concentrations between x = 0.35 and 0.50. This technique allows the controlled growth of structurally well-defined nanoparticles using the same calcination conditions. With decreasing particle size, the unit-cell volume increases together with the Mn-O bond length, while the Mn-O-Mn bond angle was found to decrease. The size-dependent change of structural properties is possibly related to surface effects or disorder. With the decrease in particle size, the ferromagnetic ordering temperature TC decreases significantly by up to 20%. The reduction of TC can be well understood with respect to the structural changes: the increase of Mn-O bond length and the decrease of Mn-O-Mn bond angle weaken the double-exchange coupling and hence reduce T C . In addition the intrinsic finite-size effect reduces T C . The observed size-induced change of magnetic properties may allow for a controlled manipulation of magnetism in La1-xSrxMnO3 nanoparticles by varying the particle size.

  2. Atomistic Modeling of Cation Diffusion in Transition Metal Perovskites La1-xSrxMnO3+/-δfor Solid Oxide Fuel Cell Cathodes Applications

    NASA Astrophysics Data System (ADS)

    Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; Sorescu, Dan; Abernathy, Harry

    Cation diffusion in La1-xSrxMnO3+/-δ (LSM) and in related perovskite materials play an important role in controlling long term performance and stability of solid oxide fuel cell (SOFCs) cathodes. Due to sluggish rates of cation diffusion and complex coupling between defect chemistry and cation diffusion pathways, currently there is still lack of quantitative theoretical model predictions on cation diffusivity vs. T and P(O2) to describe experimental cation tracer diffusivities. In this work, based on ab initio modeling of LSM defect chemistry and migration barriers of the possible cation diffusion pathways, we assess the rates of A-site and B-site cation diffusion in a wide range of T and P(O2) at x =0.0 and 0.2 for SOFC applications. We demonstrate the active cation diffusion pathways in LSM involve cation defect clusters as cation transport carriers, where reduction in the cation migration barriers, which are governed by the steric effect associated with the metal-oxygen cage in the perovskite lattice, is much greater than the penalty of repulsive interaction in the A-site and B-site cation vacancy clusters, leading to higher cation diffusion rates as compared to those of single cation vacancy hopping mechanisms. The predicted Mn and La/Sr cation self-diffusion coefficients of LSM at at x =0.0 and 0.2 along with their 1/T and P(O2) dependences, are in good agreement with the experimental tracer diffusion coefficients.

  3. Noteworthy performance of La(1-x)Ca(x)MnO3 perovskites in generating H2 and CO by the thermochemical splitting of H2O and CO2.

    PubMed

    Dey, Sunita; Naidu, B S; Govindaraj, A; Rao, C N R

    2015-01-07

    Perovskite oxides of the composition La1-xCaxMnO3 (LCM) have been investigated for the thermochemical splitting of H2O and CO2 to produce H2 and CO, respectively. The study was carried out in comparison with La1-xSrxMnO3, CeO2 and other oxides. The LCM system exhibits superior characteristics in high-temperature evolution of oxygen, and in reducing CO2 to CO and H2O to H2. The best results were obtained with La0.5Ca0.5MnO3 whose performance is noteworthy compared to that of other oxides including ceria. The orthorhombic structure of LCM seems to be a crucial factor.

  4. Decreasing the Hydroxylation Affinity of La 1–x Sr x MnO 3 Perovskites To Promote Oxygen Reduction Electrocatalysis

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Stoerzinger, Kelsey A.; Hong, Wesley T.; Wang, Xiao Renshaw

    Understanding the interaction between oxides and water is critical to design many of their functionalities, including the electrocatalysis of molecular oxygen reduction. In this study, we probed the hydroxylation of model (001)-oriented La(1-x)SrxMnO3 (LSMO) perovskite surfaces, where the electronic structure and manganese valence was controlled by five substitution levels of lanthanum with strontium, using ambient pressure X-ray photoelectron spectroscopy in a humid environment. The degree of hydroxyl formation on the oxide surface correlated with the proximity of the valence band center relative to the Fermi level. LSMO perovskites with a valence band center closer to the Fermi level were moremore » reactive toward water, forming more hydroxyl species at a given relative humidity. More hydroxyl species correlate with greater electron-donating character to the surface free energy in wetting, and reduce the activity to catalyze oxygen reduction reaction (ORR) kinetics in basic solution. New strategies to design more active catalysts should include design of electronically conducting oxides with lower valence band centers relative to the Fermi level at ORR-relevant potentials.« less

  5. Nanostructured Perovskite LaCo1-xMnxO3 as Bifunctional Catalysts for Rechargeable Metal-Air Batteries

    NASA Astrophysics Data System (ADS)

    Ge, Xiaoming; Li, Bing; Wuu, Delvin; Sumboja, Afriyanti; An, Tao; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

    2015-09-01

    Bifunctional catalyst that is active for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most important components of rechargeable metal-air batteries. Nanostructured perovskite bifunctional catalysts comprising La, Co and Mn(LaCo1-xMnxO3, LCMO) are synthesized by hydrothermal methods. The morphology, structure and electrochemical activity of the perovskite bifunctional catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and rotating disk electrode (RDE) techniques. Nanorod, nanodisc and nanoparticle are typical morphologies of LCMO. The electrocatalytic activity of LCMO is significantly improved by the addition of conductive materials such as carbon nanotube. To demonstrate the practical utilization, LCMO in the composition of LaCo0.8Mn0.2O3(LCMO82) is used as air cathode catalysts for rechargeable zinc-air batteries. The battery prototype can sustain 470 h or 40 discharge-charge cycles equivalent.

  6. LaFe 0.9Ni 0.1O 3 perovskite catalyst with enhanced activity and coke-resistance for dry reforming of ethane

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zhao, Baohuai; Yan, Binhang; Yao, Siyu

    In this work, a LaFe 0.9Ni 0.1O 3 perovskite catalyst was evaluated for dry reforming of ethane (DRE), with two conventional oxide supported Ni catalysts (Ni/La 2O 3 and NiFe/La 2O 3) being used as references. LaFe 0.9Ni 0.1O 3 showed the best activity and high coke-/sintering-resistance. TEM, TGA, and Raman characterizations confirmed that the deactivation of Ni/La 2O 3 was owing to the growth of Ni particles and the accumulation of coke, although the formation of La 2O 2CO 3 was able to remove part of the coke during the reaction. The introduction of Fe-related species inhibited the cokemore » formation while decreased the activity due to the loss of active sites. A portion of Ni ions in the perovskite lattice could be reduced to form highly dispersed and stable Ni nanoparticles on the surface during the reaction and oxygen vacancies were left in the perovskite lattice. Pulse reactor studies revealed that the oxygen vacancies in the perovskite could facilitate the activation and dissociation of CO 2 to form CO and reactive oxygen species. Additionally, C 2H 6 was activated with the assistance of oxygen from the surface or subsurface of LaFe 0.9Ni 0.1O 3 to form CO, rather than directly dissociated to surface carbon species as observed over Ni/La 2O 3.« less

  7. LaFe 0.9Ni 0.1O 3 perovskite catalyst with enhanced activity and coke-resistance for dry reforming of ethane

    DOE PAGES

    Zhao, Baohuai; Yan, Binhang; Yao, Siyu; ...

    2017-12-29

    In this work, a LaFe 0.9Ni 0.1O 3 perovskite catalyst was evaluated for dry reforming of ethane (DRE), with two conventional oxide supported Ni catalysts (Ni/La 2O 3 and NiFe/La 2O 3) being used as references. LaFe 0.9Ni 0.1O 3 showed the best activity and high coke-/sintering-resistance. TEM, TGA, and Raman characterizations confirmed that the deactivation of Ni/La 2O 3 was owing to the growth of Ni particles and the accumulation of coke, although the formation of La 2O 2CO 3 was able to remove part of the coke during the reaction. The introduction of Fe-related species inhibited the cokemore » formation while decreased the activity due to the loss of active sites. A portion of Ni ions in the perovskite lattice could be reduced to form highly dispersed and stable Ni nanoparticles on the surface during the reaction and oxygen vacancies were left in the perovskite lattice. Pulse reactor studies revealed that the oxygen vacancies in the perovskite could facilitate the activation and dissociation of CO 2 to form CO and reactive oxygen species. Additionally, C 2H 6 was activated with the assistance of oxygen from the surface or subsurface of LaFe 0.9Ni 0.1O 3 to form CO, rather than directly dissociated to surface carbon species as observed over Ni/La 2O 3.« less

  8. Ferroelectric and electrical characterization of multiferroic BiFeO3 at the single nanoparticle level

    NASA Astrophysics Data System (ADS)

    Vasudevan, R. K.; Bogle, K. A.; Kumar, A.; Jesse, S.; Magaraggia, R.; Stamps, R.; Ogale, S. B.; Potdar, H. S.; Nagarajan, V.

    2011-12-01

    Ferroelectric BiFeO3 (BFO) nanoparticles deposited on epitaxial substrates of SrRuO3 (SRO) and La1-xSrxMnO3 (LSMO) were studied using band excitation piezoresponse spectroscopy (BEPS), piezoresponse force microscopy (PFM), and ferromagnetic resonance (FMR). BEPS confirms that the nanoparticles are ferroelectric in nature. Switching behavior of nanoparticle clusters were studied and showed evidence for inhomogeneous switching. The dimensionality of domains within nanoparticles was found to be fractal in nature, with a dimensionality constant of ˜1.4, on par with ferroelectric BFO thin-films under 100 nm in thickness. Ferromagnetic resonance studies indicate BFO nanoparticles only weakly affect the magnetic response of LSMO.

  9. Perovskite-based heterostructures integrating ferromagnetic-insulating La0.1Bi0.9MnO3

    NASA Astrophysics Data System (ADS)

    Gajek, M.; Bibes, M.; Barthélémy, A.; Varela, M.; Fontcuberta, J.

    2005-05-01

    We report on the growth of thin films and heterostructures of the ferromagnetic-insulating perovskite La0.1Bi0.9MnO3. We show that the La0.1Bi0.9MnO3 perovskite grows single phased, epitaxially, and with a single out-of-plane orientation either on SrTiO3 substrates or onto strained La2/3Sr1/3MnO3 and SrRuO3 ferromagnetic-metallic buffer layers. We discuss the magnetic properties of the La0.1Bi0.9MnO3 films and heterostructures in view of their possible potential as magnetoelectric or spin-dependent tunneling devices.

  10. 2:1 Charge disproportionation in perovskite-structure oxide La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Guo, Haichuan; Hosaka, Yoshiteru; Seki, Hayato

    La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+} was synthesized at a high pressure and high temperature. The compound crystallizes in a √2a×2a×√2a perovskite cell in which the La and Ca ions at the A site are disordered. At 217 K the Fe{sup 3.67+} shows charge disproportionation to Fe{sup 3+} and Fe{sup 5+} in a ratio of 2:1, and this disproportionation is accompanied by transitions in magnetic and transport properties. The charge-disproportionated Fe{sup 3+} and Fe{sup 5+} are arranged along the <111> direction of the cubic perovskite cell. The local electronic and magnetic environments of Fe in La{sub 1/3}Ca{sub 2/3}FeO{submore » 3} are quite similar to those of Fe in La{sub 1/3}Sr{sub 2/3}FeO{sub 3}, and the 2:1 charge disproportionation pattern of Fe{sup 3+} and Fe{sup 5+} in La{sub 1/3}Ca{sub 2/3}FeO{sub 3} is also the same as that in La{sub 1/3}Sr{sub 2/3}FeO{sub 3}. - Graphical abstract: The perovskite-structure oxide La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+} shows charge disproportionation to Fe{sup 3+} and Fe{sup 5+} in a ratio of 2:1, and the charge-disproportionated Fe{sup 3+} and Fe{sup 5+} are arranged along the <111> direction of the cubic perovskite cell. - Highlights: • La{sub 1/3}Ca{sub 2/3}FeO{sub 3} with unusually-high-valence Fe{sup 3.67+} was synthesized at a high pressure and high temperature. • At 217 K the Fe{sup 3.67+} shows charge disproportionation (CD) to Fe{sup 3+} and Fe{sup 5+} in a ratio of 2:1. • The charge-disproportionated Fe{sup 3+} and Fe{sup 5+} are arranged along the <111> direction of the cubic perovskite cell. • The disproportionation is accompanied by transitions in magnetic and transport properties.« less

  11. Synthesis, characterization and study of magnetic, electrical and dielectric properties of La1-xDyxCo1-yFeyO3 nanoparticles prepared by wet chemical route

    NASA Astrophysics Data System (ADS)

    Choudhry, Qurshia; Azhar Khan, Muhammad; Nasar, Gulfam; Mahmood, Azhar; Shahid, Muhammad; Shakir, Imran; Farooq Warsi, Muhammad

    2015-11-01

    Dy3+ and Fe3+ co-doped LaCoO3 perovskite nanoparticles were prepared by chemical co-precipitation route. Structural elucidation was carried out by thermo gravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectroscopy. The data of all these characterization techniques confirmed the orthorhombic phase with particles size in the range of 20-60 nm. The magnetic parameters, DC-resistivity and dielectric properties were measured for La1-xDyxCo1-yFeyO3 nanoparticles. The purpose of all these application studies was to evaluate the prepared materials for practical applications. The substitution of Dy3+ and Fe3+ with La3+ and Co3+ respectively greatly influenced the magnetic, DC-resistivity and dielectric parameters.

  12. Perovskite LaFeO3/montmorillonite nanocomposites: synthesis, interface characteristics and enhanced photocatalytic activity

    PubMed Central

    Peng, Kang; Fu, Liangjie; Yang, Huaming; Ouyang, Jing

    2016-01-01

    Perovskite LaFeO3/montmorillonite nanocomposites (LaFeO3/MMT) have been successfully prepared via assembling LaFeO3 nanoparticles on the surface of montmorillonite with citric acid assisted sol-gel method. The results indicated that the uniform LaFeO3 nanoparticles were densely deposited onto the surface of montmorillonite, mainly ranging in diameter from 10 nm to 15 nm. The photocatalytic activity of LaFeO3/MMT was evaluated by the degradation of Rhodamine B (RhB) under visible light irradiation, indicating that LaFeO3/MMT exhibited remarkable adsorption efficiency and excellent photocatalytic activity with the overall removal rate of RhB up to 99.34% after visible light irradiation lasting for 90 min. The interface characteristic and possible degradation mechanism were explored. The interface characterization of LaFeO3/MMT suggested that LaFeO3 nanoparticles could be immobilized on the surface of montmorillonite with the Si-O-Fe bonds. The abundant hydroxyl groups of montmorillonite, semiconductor photocatalysis of LaFeO3 and Fenton-like reaction could enhance the photocatalytic degradation through a synergistic effect. Therefore, the LaFeO3/MMT is a very promising photocatalyst in future industrial application to treat effectively wastewater of dyes. PMID:26778180

  13. Polycrystalline La1-xSrxMnO3 films on silicon: Influence of post-Deposition annealing on structural, (Magneto-)Optical, and (Magneto-)Electrical properties

    NASA Astrophysics Data System (ADS)

    Thoma, Patrick; Monecke, Manuel; Buja, Oana-Maria; Solonenko, Dmytro; Dudric, Roxana; Ciubotariu, Oana-Tereza; Albrecht, Manfred; Deac, Iosif G.; Tetean, Romulus; Zahn, Dietrich R. T.; Salvan, Georgeta

    2018-01-01

    The integration of La1-xSrxMnO3 (LSMO) thin film technology into established industrial silicon processes is regarded as challenging due to lattice mismatch, thermal expansion, and chemical reactions at the interface of LSMO and silicon. In this work, we investigated the physical properties of thin La0.73Sr0.27MnO3 films deposited by magnetron sputtering on silicon without a lattice matching buffer layer. The influence of a post-deposition annealing treatment on the structural, (magneto-)optical, and (magneto-)electrical properties was investigated by a variety of techniques. Using Rutherford backscattering spectroscopy, atomic force microscopy, Raman spectroscopy, and X-ray diffraction we could show that the thin films exhibit a polycrystalline, rhombohedral structure after a post-deposition annealing of at least 700 °C. The dielectric tensor in the spectral range from 1.7 eV to 5 eV determined from spectroscopic ellipsometry in combination with magneto-optical Kerr effect spectroscopy was found to be comparable to that of lattice matched films on single crystal substrates reported in literature [1]. The values of the metal-isolator transition temperature and temperature-dependent resistivities also reflect a high degree of crystalline quality of the thermally treated films.

  14. Resonant halide perovskite nanoparticles

    NASA Astrophysics Data System (ADS)

    Tiguntseva, Ekaterina Y.; Ishteev, Arthur R.; Komissarenko, Filipp E.; Zuev, Dmitry A.; Ushakova, Elena V.; Milichko, Valentin A.; Nesterov-Mueller, Alexander; Makarov, Sergey V.; Zakhidov, Anvar A.

    2017-09-01

    The hybrid halide perovskites is a prospective material for fabrication of cost-effective optical devices. Unique perovskites properties are used for solar cells and different photonic applications. Recently, perovskite-based nanophotonics has emerged. Here, we consider perovskite like a high-refractive index dielectric material, which can be considered to be a basis for nanoparticles fabrication with Mie resonances. As a result, we fabricate and study resonant perovskite nanoparticles with different sizes. We reveal, that spherical nanoparticles show enhanced photoluminescence signal. The achieved results lay a cornerstone in the field of novel types of organic-inorganic nanophotonics devices with optical properties improved by Mie resonances.

  15. Electrocatalytic performances of LaNi1-xMgxO3 perovskite oxides as bi-functional catalysts for lithium air batteries

    NASA Astrophysics Data System (ADS)

    Du, Zhenzhen; Yang, Peng; Wang, Long; Lu, Yuhao; Goodenough, J. B.; Zhang, Jian; Zhang, Dawei

    2014-11-01

    Mg-doped perovskite oxides LaNi1-xMgxO3 (x = 0, 0.08, 0.15) electrocatalysts are synthesized by a sol-gel method using citric acid as complex agent and ethylene glycol as thickening agent. The intrinsic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity of as-prepared perovskite oxides in aqueous electrolyte are examined on a rotating disk electrode (RDE) set up. Li-air primary batteries on the basis of Mg-doped perovskite oxides LaNi1-xMgxO3 (x = 0, 0.08, 0.15) and nonaqueous electrolyte are also fabricated and tested. In terms of the ORR current densities and OER current densities, the performance is enhanced in the order of LaNiO3, LaNi0.92Mg0.08O3 and LaNi0.85Mg0.15O3. Most notably, partially substituting nickel with magnesium suppresses formation of Ni2+ and ensures high concentration of both OER and ORR reaction energy favorable Ni3+ (eg = 1) on the surface of perovskite catalysts. Nonaqueous Li-air primary battery using LaNi0.92Mg0.08O3 and LaNi0.85Mg0.15O3 as the cathode catalysts exhibit improved performances compared with LaNiO3 catalyst, which are consistent with the ORR current densities.

  16. The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site

    PubMed Central

    Evans, Christopher D.; Smith, Paul J.; Manning, Troy D.; Miedziak, Peter J.; Brett, Gemma L.; Armstrong, Robert D.; Bartley, Jonathan K.; Taylor, Stuart H.; Rosseinsky, Matthew J.; Hutchings, Graham J.

    2016-01-01

    Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology. PMID:27074316

  17. The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site.

    PubMed

    Evans, Christopher D; Kondrat, Simon A; Smith, Paul J; Manning, Troy D; Miedziak, Peter J; Brett, Gemma L; Armstrong, Robert D; Bartley, Jonathan K; Taylor, Stuart H; Rosseinsky, Matthew J; Hutchings, Graham J

    2016-07-04

    Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology.

  18. Material properties of perovskites in the quasi-ternary system LaFeO3-LaCoO3-LaNiO3

    NASA Astrophysics Data System (ADS)

    Tietz, F.; Arul Raj, I.; Ma, Q.; Baumann, S.; Mahmoud, A.; Hermann, R. P.

    2016-05-01

    An overview is presented on the variation of electrical conductivity, oxygen permeation, and thermal expansion coefficient as a function of the composition of perovskites in the quasi-ternary system LaFeO3-LaCoO3-LaNiO3. Powders of thirteen nominal perovskite compositions were synthesized under identical conditions by the Pechini method. The powder X-ray diffraction data of two series, namely La(Ni0.5Fe0.5)1-xCoxO3 and LaNi0.5-xFexCo0.5O3, are presented after the powders had been sintered at 1100 °C for 6 h in air. The measurements revealed a rhombohedral structure for all compositions except LaNi0.5Fe0.5O3 for which 60% rhombohedral and 40% orthorhombic phase was found. The maximum DC electrical conductivity value of the perovskites at 800 °C was 1229 S cm-1 for the composition LaCoO3 and the minimum was 91 S cm-1 for the composition LaCo0.5Fe0.5O3. The oxygen permeation of samples with promising conductivities at 800 °C was one order of magnitude lower than that of La0.6Sr0.4Co0.8Fe0.2O3 (LSCF). The highest value of 0.017 ml cm-2 min-1 at 950 °C was obtained with LaNi0.5Co0.5O3. The coefficients of thermal expansion varied in the range of 13.2×10-6 K-1 and 21.9×10-6 K-1 for LaNi0.5Fe0.5O3 and LaCoO3, respectively. 57Fe Mössbauer spectroscopy was used as probe for the oxidation states, local environment and magnetic properties of iron ions as a function of chemical composition. The substitution had a great influence on the chemical properties of the materials.

  19. Water electrolysis on La 1-xSr xCoO 3perovskite electrocatalysts

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.

    2016-03-23

    Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr 2+ substitution into La 1-xSr xCoO 3-δ. We attempt tomore » rationalize the high activities of La 1-xSr xCoO 3-δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO 2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.« less

  20. Water electrolysis on La 1-xSr xCoO 3perovskite electrocatalysts

    DOE PAGES

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; ...

    2016-03-23

    Here, perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr 2+ substitution into La 1–xSr xCoO 3–δ. We attemptmore » to rationalize the high activities of La 1–xSr xCoO 3–δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO 2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.« less

  1. Perovskite-related LaTiO3.41.

    PubMed

    Daniels, Peter; Lichtenberg, Frank; van Smaalen, Sander

    2003-02-01

    Crystals of pentalanthanum pentatitanium heptadecaoxide (La(5)Ti(5)O(17) with 0.3% oxygen excess, or LaTiO(3.41)) have been synthesized by floating-zone melting, and the structure has been solved using single-crystal X-ray diffraction intensities. The monoclinic (P2(1)/c) structure consists of perovskite-like slabs of vertex-sharing TiO(6) octahedra, which are separated by additional oxygen layers. The slabs are five octahedra wide. Due to the adjustment of the TiO(6) octahedra to meet the coordination requirements of the La(3+) cations, a superstructure develops along the a axis.

  2. Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts

    PubMed Central

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; Hardin, William G.; Dai, Sheng; Kolpak, Alexie M.; Johnston, Keith P.; Stevenson, Keith J.

    2016-01-01

    Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr2+ substitution into La1−xSrxCoO3−δ. We attempt to rationalize the high activities of La1−xSrxCoO3−δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis. PMID:27006166

  3. Material properties of perovskites in the quasi-ternary system LaFeO 3LaCoO 3LaNiO 3

    DOE PAGES

    Tietz, F.; Arul Raj, I.; Ma, Q.; ...

    2016-02-02

    We present an overview on the variation of electrical conductivity, oxygen permeation, oxygen surface exchange and thermal expansion coefficient as a function of the composition of perovskites in the quasi-ternary system LaFeO 3LaCoO 3LaNiO 3. Powders of thirteen nominal perovskite compositions were synthesized under identical conditions by the Pechini method. The powder X-ray diffraction data of two series, namely La(Ni 0.5Fe 0.5) 1-xCo xO 3 and LaNi 0.5- xFe xCo 0.5O 3, are presented after the powders had been sintered at 1100 C for 6 h in air. The measurements revealed a rhombohedral structure for all compositions except LaNi 0.5Femore » 0.5O 3 for which 60% rhombohedral and 40% orthorhombic phase was found. Moreover, the maximum DC electrical conductivity value of the perovskites at 800 C was 1229 S cm-1 for the composition LaCoO 3 and the minimum was 91 S cm-1 for the composition LaCo 0.5Fe 0.5O 3. The oxygen permeation of samples with promising conductivities at 800 C was one order of magnitude lower than that of La 0.6Sr 0.4Co 0.8Fe 0.2O 3 (LSCF). The highest value of 0.017 ml cm -2 min-1 at 950 C was obtained with LaNi 0.5Co 0.5O 3. The coefficients of thermal expansion varied in the range of 13.2 x 10 -6 K -1 and 21.9 x 10 -6 K -1 for LaNi 0.5Fe 0.5O 3 and LaCoO 3, respectively. 57Fe M ssbauer spectroscopy was used as probe for the oxidation states, local environment and magnetic properties of iron ions as a function of chemical composition. Ultimately, the substitution had a great influence on the chemical properties of the materials.« less

  4. Tuning Perpendicular Magnetic Anisotropy by Oxygen Octahedral Rotations in ( La 1 - x Sr x MnO 3 ) / ( SrIrO 3 ) Superlattices

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yi, Di; Flint, Charles L.; Balakrishnan, Purnima P.

    Perpendicular magnetic anisotropy (PMA) plays a critical role in the development of spintronics, thereby demanding new strategies to control PMA. Here we demonstrate a conceptually new type of interface induced PMA that is controlled by oxygen octahedral rotation. In superlattices comprised of La1-xSrxMnO3 and SrIrO3, we find that all superlattices (0<=x<=1) exhibit ferromagnetism despite the fact that La1-xSrxMnO3 is antiferromagnetic for x>0.5. PMA as high as 4×10^6 erg/cm^3 is observed by increasing x and attributed to a decrease of oxygen octahedral rotation at interfaces. We also demonstrate that oxygen octahedral deformation cannot explain the trend in PMA. These results revealmore » a new degree of freedom to control PMA, enabling discovery of emergent magnetic textures and topological phenomena.« less

  5. Superparamagnetic LaSrMnO3 nanoparticles for magnetic nanohyperthermia and their biocompatibility

    NASA Astrophysics Data System (ADS)

    Aneja, Mohit; Tovstolytkin, Alexandr; Singh Lotey, Gurmeet

    2017-11-01

    The nanohyperthermia investigation of superparamagnetic La0.77Sr0.23MnO3 nanoparticles synthesized by hydrothermal method has been carried out. The synthesized nanoparticles are found to be highly uniform in size and shape with average particle size 18 nm. Structural analysis confirms the pseudo-cubic perovskite crystal structure with space group of (R3c). The magnetization versus applied magnetic field (M-H) hysteresis loops measurements revealed the superparmagnetic nature of the synthesized nanoparticles. The induction heating of synthesized nanoparticles for their applications in nanohyperthermia has been studied. The in vitro cytotoxicity test of the synthesized superparamagnetic nanoparticles has been probed by evaluating the viability of HeLa (Human Negroid Cervix Epitheloid Carcinoma) cell lines. The mechanism responsible for nanohyperthermia heating of the synthesized nanoparticles has been discussed.

  6. Characterization of ordering in A-site deficient perovskite Ca 1–xLa 2x/3TiO 3 using STEM/EELS

    DOE PAGES

    Danaie, Mohsen; Kepaptsoglou, Demie; Ramasse, Quentin M.; ...

    2016-09-15

    The vacancy ordering behavior of an A-site deficient perovskite system, Ca 1–xLa 2x/3TiO 3, was studied using atomic resolution scanning transmission electron microscopy (STEM) in conjunction with electron energy-loss spectroscopy (EELS), with the aim of determining the role of A-site composition changes. At low La content (x = 0.2), adopting Pbnm symmetry, there was no indication of long-range ordering. Domains, with clear boundaries, were observed in bright-field (BF) imaging, but were not immediately visible in the corresponding high-angle annular dark-field (HAADF) image. These boundaries, with the aid of displacement maps from A-site cations in the HAADF signal, are shown tomore » be tilt boundaries. At the La-rich end of the composition (x = 0.9), adopting Cmmm symmetry, long-range ordering of vacancies and La 3+ ions was observed, with alternating La-rich and La-poor layers on (001)p planes, creating a double perovskite lattice along the c axis. These highly ordered domains can be found isolated within a random distribution of vacancies/La 3+, or within a large population, encompassing a large volume. In regions with a high number density of double perovskite domains, these highly ordered domains were separated by twin boundaries, with 90° or 180° lattice rotations across boundaries. In conclusion, the occurrence and characteristics of these ordered structures are discussed and compared with similar perovskite systems.« less

  7. Microstructural, Magnetic, and Optical Properties of Pr-Doped Perovskite Manganite La0.67Ca0.33MnO3 Nanoparticles Synthesized via Sol-Gel Process

    NASA Astrophysics Data System (ADS)

    Xia, Weiren; Wu, Heng; Xue, Piaojie; Zhu, Xinhua

    2018-05-01

    We report on microstructural, magnetic, and optical properties of Pr-doped perovskite manganite (La1 - xPrx)0.67Ca0.33MnO3 (LPCMO, x = 0.0-0.5) nanoparticles synthesized via sol-gel process. Structural characterizations (X-ray and electron diffraction patterns, (high resolution) TEM images) provide information regarding the phase formation and the single-crystalline nature of the LPCMO systems. X-ray and electron diffraction patterns reveal that all the LPCMO samples crystallize in perovskite crystallography with an orthorhombic structure ( Pnma space group), where the MnO6 octahedron is elongated along the b axis due to the Jahn-Teller effect. That is confirmed by Raman spectra. Crystallite sizes and grain sizes were calculated from XRD and TEM respectively, and the lattice fringes resolved in the high-resolution TEM images of individual LPCMO nanoparticle confirmed its single-crystalline nature. FTIR spectra identify the characteristic Mn-O bond stretching vibration mode near 600 cm- 1, which shifts towards high wavenumbers with increasing post-annealing temperature or Pr-doping concentration, resulting in further distortion of the MnO6 octahedron. XPS revealed dual oxidation states of Mn3+ and Mn4+ in the LPCMO nanoparticles. UV-vis absorption spectra confirm the semiconducting nature of the LPCMO nanoparticles with optical bandgaps of 2.55-2.71 eV. Magnetic measurements as a function of temperature and magnetic field at field cooling and zero-field cooling modes, provided a Curie temperature around 230 K, saturation magnetization of about 81 emu/g, and coercive field of 390 Oe at 10 K. Such magnetic properties and the semiconducting nature of the LPCMO nanoparticles will make them as suitable candidate for magnetic semiconductor spintronics.

  8. Microstructural, Magnetic, and Optical Properties of Pr-Doped Perovskite Manganite La0.67Ca0.33MnO3 Nanoparticles Synthesized via Sol-Gel Process.

    PubMed

    Xia, Weiren; Wu, Heng; Xue, Piaojie; Zhu, Xinhua

    2018-05-04

    We report on microstructural, magnetic, and optical properties of Pr-doped perovskite manganite (La 1 - x Pr x ) 0.67 Ca 0.33 MnO 3 (LPCMO, x = 0.0-0.5) nanoparticles synthesized via sol-gel process. Structural characterizations (X-ray and electron diffraction patterns, (high resolution) TEM images) provide information regarding the phase formation and the single-crystalline nature of the LPCMO systems. X-ray and electron diffraction patterns reveal that all the LPCMO samples crystallize in perovskite crystallography with an orthorhombic structure (Pnma space group), where the MnO 6 octahedron is elongated along the b axis due to the Jahn-Teller effect. That is confirmed by Raman spectra. Crystallite sizes and grain sizes were calculated from XRD and TEM respectively, and the lattice fringes resolved in the high-resolution TEM images of individual LPCMO nanoparticle confirmed its single-crystalline nature. FTIR spectra identify the characteristic Mn-O bond stretching vibration mode near 600 cm - 1 , which shifts towards high wavenumbers with increasing post-annealing temperature or Pr-doping concentration, resulting in further distortion of the MnO 6 octahedron. XPS revealed dual oxidation states of Mn 3+ and Mn 4+ in the LPCMO nanoparticles. UV-vis absorption spectra confirm the semiconducting nature of the LPCMO nanoparticles with optical bandgaps of 2.55-2.71 eV. Magnetic measurements as a function of temperature and magnetic field at field cooling and zero-field cooling modes, provided a Curie temperature around 230 K, saturation magnetization of about 81 emu/g, and coercive field of 390 Oe at 10 K. Such magnetic properties and the semiconducting nature of the LPCMO nanoparticles will make them as suitable candidate for magnetic semiconductor spintronics.

  9. Investigation on the structural, magnetic and magnetocaloric properties of nanocrystalline Pr-deficient Pr1-xSrxMnO3-δ manganites

    NASA Astrophysics Data System (ADS)

    Arun, B.; Athira, M.; Akshay, V. R.; Sudakshina, B.; Mutta, Geeta R.; Vasundhara, M.

    2018-02-01

    We have investigated the structural, magnetic and magnetocaloric properties of nanocrystalline Pr-deficient Pr1-xSrxMnO3Perovskite manganites. Rietveld refinement of the X-ray powder diffraction patterns confirms that all the studied compounds have crystallized into an orthorhombic structure with Pbnm space group. Transmission electron microscopy analysis reveals nanocrystalline compounds with crystallite size less than 50 nm. The selected area electron diffraction patterns reveal the highly crystalline nature of the compounds and energy dispersive X-ray spectroscopic analysis shows that the obtained compositions are nearly identical with the nominal one. The oxygen stoichiometry is estimated by iodometric titration method and stoichiometric compositions are confirmed by X-ray Fluorescence Spectrometry analysis. A large bifurcation is observed in the ZFC/FC curves and Arrott plots not show a linear relation but have a convex curvature nature. The temperature dependence of inverse magnetic susceptibility at higher temperature confirms the existence of ferromagnetic clusters. The experimental results reveal that the reduction of crystallite size to nano metric scale in Pr-deficient manganites adversely influences structural, magnetic and magnetocaloric properties as compared to its bulk counterparts reported earlier.

  10. Perovskite nanoparticle-sensitized Ga 2O 3 nanorod arrays for CO detection at high temperature

    DOE PAGES

    Lin, Hui -Jan; Baltrus, John P.; Gao, Haiyong; ...

    2016-04-04

    Here, noble metal nanoparticles are extensively used for sensitizing metal oxide chemical sensors through the catalytic spillover mechanism. However, due to earth-scarcity and high cost of noble metals, finding replacements presents a great economic benefit. Besides, high temperature and harsh environment sensor applications demand material stability under conditions approaching thermal and chemical stability limits of noble metals. In this study, we employed thermally stable perovskite-type La 0.8Sr 0.2FeO 3 (LSFO) nanoparticle surface decoration on Ga 2O 3 nanorod array gas sensors and discovered an order of magnitude enhanced sensitivity to carbon monoxide at 500 °C. The LSFO nanoparticle catalysts wasmore » of comparable performance to that achieved by Pt nanoparticles, with a much lower weight loading than Pt. Detailed electron microscopy and X-ray photoelectron spectroscopy studies suggested the LSFO nanoparticle sensitization effect is attributed to a spillover-like effect associated with the gas-LSFO-Ga 2O 3 triple-interfaces that spread the negatively charged surface oxygen ions from LSFO nanoparticles surfaces over to β-Ga 2O 3 nanorod surfaces with faster surface CO oxidation reactions.« less

  11. Perovskite Nanoparticle-Sensitized Ga2O3 Nanorod Arrays for CO Detection at High Temperature.

    PubMed

    Lin, Hui-Jan; Baltrus, John P; Gao, Haiyong; Ding, Yong; Nam, Chang-Yong; Ohodnicki, Paul; Gao, Pu-Xian

    2016-04-13

    Noble metal nanoparticles are extensively used for sensitizing metal oxide chemical sensors through the catalytic spillover mechanism. However, due to earth-scarcity and high cost of noble metals, finding replacements presents a great economic benefit. Besides, high temperature and harsh environment sensor applications demand material stability under conditions approaching thermal and chemical stability limits of noble metals. In this study, we employed thermally stable perovskite-type La(0.8)Sr(0.2)FeO3 (LSFO) nanoparticle surface decoration on Ga2O3 nanorod array gas sensors and discovered an order of magnitude enhanced sensitivity to carbon monoxide at 500 °C. The LSFO nanoparticle catalysts was of comparable performance to that achieved by Pt nanoparticles, with a much lower weight loading than Pt. Detailed electron microscopy and X-ray photoelectron spectroscopy studies suggested the LSFO nanoparticle sensitization effect is attributed to a spillover-like effect associated with the gas-LSFO-Ga2O3 triple-interfaces that spread the negatively charged surface oxygen ions from LSFO nanoparticles surfaces over to β-Ga2O3 nanorod surfaces with faster surface CO oxidation reactions.

  12. Boosting the Peroxidase-Like Activity of Nanostructured Nickel by Inducing Its 3+ Oxidation State in LaNiO3 Perovskite and Its Application for Biomedical Assays.

    PubMed

    Wang, Xiaoyu; Cao, Wen; Qin, Li; Lin, Tingsheng; Chen, Wei; Lin, Shichao; Yao, Jia; Zhao, Xiaozhi; Zhou, Min; Hang, Cheng; Wei, Hui

    2017-01-01

    Catalytic nanomaterials with intrinsic enzyme-like activities, called nanozymes, have recently attracted significant research interest due to their unique advantages relative to natural enzymes and conventional artificial enzymes. Among the nanozymes developed, particular interests have been devoted to nanozymes with peroxidase mimicking activities because of their promising applications in biosensing, bioimaging, biomedicine, etc. Till now, lots of functional nanomaterials have been used to mimic peroxidase. However, few studies have focused on the Ni-based nanomaterials for peroxidase mimics. In this work, we obtained the porous LaNiO 3 nanocubes with high peroxidase-like activity by inducing its 3+ oxidation state in LaNiO 3 perovskite and optimizing the morphology of LaNiO 3 perovskite. The peroxidase mimicking activity of the porous LaNiO 3 nanocubes with Ni 3+ was about 58~fold and 22~fold higher than that of NiO with Ni 2+ and Ni nanoparticles with Ni 0 . More, the porous LaNiO 3 nanocubes exhibited about 2-fold higher activity when compared with LaNiO 3 nanoparticles. Based on the superior peroxidase-like activity of porous LaNiO 3 nanocubes, facile colorimetric assays for H 2 O 2 , glucose, and sarcosine detection were developed. Our present work not only demonstrates a useful strategy for modulating nanozymes' activities but also provides promising bioassays for clinical diagnostics.

  13. Boosting the Peroxidase-Like Activity of Nanostructured Nickel by Inducing Its 3+ Oxidation State in LaNiO3 Perovskite and Its Application for Biomedical Assays

    PubMed Central

    Wang, Xiaoyu; Cao, Wen; Qin, Li; Lin, Tingsheng; Chen, Wei; Lin, Shichao; Yao, Jia; Zhao, Xiaozhi; Zhou, Min; Hang, Cheng; Wei, Hui

    2017-01-01

    Catalytic nanomaterials with intrinsic enzyme-like activities, called nanozymes, have recently attracted significant research interest due to their unique advantages relative to natural enzymes and conventional artificial enzymes. Among the nanozymes developed, particular interests have been devoted to nanozymes with peroxidase mimicking activities because of their promising applications in biosensing, bioimaging, biomedicine, etc. Till now, lots of functional nanomaterials have been used to mimic peroxidase. However, few studies have focused on the Ni-based nanomaterials for peroxidase mimics. In this work, we obtained the porous LaNiO3 nanocubes with high peroxidase-like activity by inducing its 3+ oxidation state in LaNiO3 perovskite and optimizing the morphology of LaNiO3 perovskite. The peroxidase mimicking activity of the porous LaNiO3 nanocubes with Ni3+ was about 58~fold and 22~fold higher than that of NiO with Ni2+ and Ni nanoparticles with Ni0. More, the porous LaNiO3 nanocubes exhibited about 2-fold higher activity when compared with LaNiO3 nanoparticles. Based on the superior peroxidase-like activity of porous LaNiO3 nanocubes, facile colorimetric assays for H2O2, glucose, and sarcosine detection were developed. Our present work not only demonstrates a useful strategy for modulating nanozymes' activities but also provides promising bioassays for clinical diagnostics. PMID:28740550

  14. Transparent and flexible photodetectors based on CH3NH3PbI3 perovskite nanoparticles

    NASA Astrophysics Data System (ADS)

    Jeon, Young Pyo; Woo, Sung Jun; Kim, Tae Whan

    2018-03-01

    Transparent and flexible photodetectors (PDs) based on CH3NH3PbI3 perovskite nanoparticles (NPs) were fabricated by using co-evaporation of methyl ammonium iodide and lead iodide. X-ray diffraction patterns and high-resolution transmission electron microscopy images demonstrated the formation of perovskite NPs. The optical transmittance of the perovskite NPs/glass was above 80% over the entire range of visible wavelengths, indicative of high transparency. The PDs based on CH3NH3PbI3 perovskite NPs were sensitive to a broad range of visible light from 450 to 650 nm. The currents in the PDs under exposure to red, green, and blue light-emitting diodes were enhanced to 5, 10, and 20 times that of the PD in the dark, respectively. The rise and the decay times of the PDs were 50 and 120 μs. The current in the perovskite NP PD on a polyethylene terephthalate substrate was enhanced by approximately 69% when the NP PD was exposed to a blue LED emitting at a wavelength of 459 nm. Despite multiple bending, the transparent and flexible PDs based on methyl ammonium iodide and lead iodide NPs showed reproducibility and high stability in performance.

  15. Anisotropic spin-density distribution and magnetic anisotropy of strained La1-xSrxMnO3 thin films: angle-dependent x-ray magnetic circular dichroism

    NASA Astrophysics Data System (ADS)

    Shibata, Goro; Kitamura, Miho; Minohara, Makoto; Yoshimatsu, Kohei; Kadono, Toshiharu; Ishigami, Keisuke; Harano, Takayuki; Takahashi, Yukio; Sakamoto, Shoya; Nonaka, Yosuke; Ikeda, Keisuke; Chi, Zhendong; Furuse, Mitsuho; Fuchino, Shuichiro; Okano, Makoto; Fujihira, Jun-ichi; Uchida, Akira; Watanabe, Kazunori; Fujihira, Hideyuki; Fujihira, Seiichi; Tanaka, Arata; Kumigashira, Hiroshi; Koide, Tsuneharu; Fujimori, Atsushi

    2018-01-01

    Magnetic anisotropies of ferromagnetic thin films are induced by epitaxial strain from the substrate via strain-induced anisotropy in the orbital magnetic moment and that in the spatial distribution of spin-polarized electrons. However, the preferential orbital occupation in ferromagnetic metallic La1-xSrxMnO3 (LSMO) thin films studied by x-ray linear dichroism (XLD) has always been found out-of-plane for both tensile and compressive epitaxial strain and hence irrespective of the magnetic anisotropy. In order to resolve this mystery, we directly probed the preferential orbital occupation of spin-polarized electrons in LSMO thin films under strain by angle-dependent x-ray magnetic circular dichroism (XMCD). Anisotropy of the spin-density distribution was found to be in-plane for the tensile strain and out-of-plane for the compressive strain, consistent with the observed magnetic anisotropy. The ubiquitous out-of-plane preferential orbital occupation seen by XLD is attributed to the occupation of both spin-up and spin-down out-of-plane orbitals in the surface magnetic dead layer.

  16. Perovskite-Type Oxides. I. Structural, Magnetic, and Morphological Properties of LaMn 1- xCu xO 3 and LaCo 1- xCu xO 3 Solid Solutions with Large Surface Area

    NASA Astrophysics Data System (ADS)

    Porta, Piero; De Rossi, Sergio; Faticanti, Marco; Minelli, Giuliano; Pettiti, Ida; Lisi, Luciana; Turco, Maria

    1999-09-01

    Perovskite-type compounds of general formula LaMn1-xCuxO3 and LaCo1-xCuxO3 (x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0) were prepared by calcining the citrate gel precursors at 823, 923, and 1073 K. The decomposition of the precursors was followed by thermal analysis and the oxides were investigated by means of elemental analysis (atomic absorption and redox titration), X-ray powder diffraction, BET surface area, X-ray absorption (EXAFS and XANES), electron microscopy (SEM and TEM), and magnetic susceptibility. LaMn1-xCuxO3 samples are perovskite-like single phases up to x=0.6. At x=0.8 CuO and La2CuO4 phases are present in addition to perovskite. For x=1.0 the material is formed by CuO and La2CuO4. Mn(IV) was found by redox titration in all Mn-based perovskite samples, its fraction increasing with the increase in copper content. EXAFS and XANES analyses confirmed the presence of Mn(IV). Cation vacancies in equal amounts in the 12-coordinated A and octahedral B sites are suggested in the samples with x=0.0 and x=0.2, while for x=0.6 anionic vacancies are present. Materials with sufficiently high surface area (22-36 m2 g-1 for samples fired at 923 K and 14-22 m2 g-1 for those fired at 1073 K) were obtained. Crystallite sizes in the ranges 390-500 and 590-940 Å for samples calcined at 923 and 1073 K, respectively, were determined from the FWHM of the (102) X-ray diffraction peak. TEM patterns of LaMnO3 showed almost regular hexagonal prismatic crystals with sizes of the same order of magnitude (800 Å) of those drawn from X-ray diffraction, while no evidence of defect clustering was drawn out from TEM and electron diffraction images. For the sample with x=0.6, TEM and electron diffraction patterns revealed perturbation of the structure. Magnetic susceptibility studies show a ferromagnetic behavior that decreases with increase in x. LaCo1-xCuxO3 samples are perovskite-like single phases up to x=0.2. For x=0.4 a small amount of La2CuO4, in addition to perovskite, is detected. For

  17. Magneto-optical studies of SrGa{sub 0.7} Co{sub 0.3} O{sub 3−δ} perovskite thin films with embedded cobalt nanoparticles

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Veis, M., E-mail: veis@karlov.mff.cuni.cz; Zahradnik, M.; Ohnoutek, L.

    2015-05-07

    Sr(Ga{sub 0.7} Co{sub 0.3})O{sub 3−δ}/Co perovskite/metal thin films have been systematically studied by means of Faraday and Kerr magneto-optical spectroscopies. The samples were prepared by pulsed laser deposition on (001) (LaAlO{sub 3}) {sub 0.3}(Sr{sub 2}AlTaO{sub 6}) {sub 0.7} (LSAT) and Si substrates, and grew as a perovskite matrix containing approximately 6% by volume of embedded metallic Co nanoparticles with diameter less than 20 nm, which were distributed throughout the film and at the film-substrate interface. The film thickness ranged from 130 to 310 nm. The perovskite matrix was single crystal on LSAT and polycrystalline on Si. The magneto-optical spectroscopy was carried out in bothmore » Faraday and Kerr configurations in the photon energy range from 0.5 to 5 eV in magnetic fields sufficient for sample saturation, showing a strong thickness dependence of the magneto-optical effect. This dependence was attributed to the different metallic Co content, nanoparticle size, and accumulation at the film-substrate interface.« less

  18. Au–CsPbBr 3 Hybrid Architecture: Anchoring Gold Nanoparticles on Cubic Perovskite Nanocrystals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Balakrishnan, Subila K.; Kamat, Prashant V.

    A selective growth of gold (Au) nanoparticles on the corners of CsPbBr 3 nanocrystals (NCs) is made possible with the treatment of Au(III) salts such as Au(III) bromide and Au(III) chloride in solution. The surface bound oleylamine ligands not only stabilize NCs but also facilitate reduction of the Au(III) salts followed by nucleation of the Au nanoparticles on the corners of the perovskite NCs. The luminescence quantum yield of NCs is decreased when Au nanoparticles are formed on the corners of CsPbBr 3 NCs, suggesting interaction between the two systems. Formation of Au nanoparticles as well as an anion exchangemore » is seen when Au(III) bromide was replaced with Au(III) chloride as a precursor. This simple strategy of designing perovskite-gold hybrid nanostructures with good colloidal stability offers new opportunities to explore their photocatalytic properties.« less

  19. Au–CsPbBr 3 Hybrid Architecture: Anchoring Gold Nanoparticles on Cubic Perovskite Nanocrystals

    DOE PAGES

    Balakrishnan, Subila K.; Kamat, Prashant V.

    2016-11-29

    A selective growth of gold (Au) nanoparticles on the corners of CsPbBr 3 nanocrystals (NCs) is made possible with the treatment of Au(III) salts such as Au(III) bromide and Au(III) chloride in solution. The surface bound oleylamine ligands not only stabilize NCs but also facilitate reduction of the Au(III) salts followed by nucleation of the Au nanoparticles on the corners of the perovskite NCs. The luminescence quantum yield of NCs is decreased when Au nanoparticles are formed on the corners of CsPbBr 3 NCs, suggesting interaction between the two systems. Formation of Au nanoparticles as well as an anion exchangemore » is seen when Au(III) bromide was replaced with Au(III) chloride as a precursor. This simple strategy of designing perovskite-gold hybrid nanostructures with good colloidal stability offers new opportunities to explore their photocatalytic properties.« less

  20. Synthesis and structural properties of Ba(1-x)LaxTiO3 perovskite nanoparticles fabricated by solvothermal synthesis route

    NASA Astrophysics Data System (ADS)

    Puli, Venkata Sreenivas; Adireddy, Shiva; Elupula, Ravinder; Molugu, Sudheer; Shipman, Josh; Chrisey, Douglas B.

    2017-05-01

    We report the successful synthesis and structural characterization of barium lanthanum titanate Ba(1-x)LaxTiO3 (x=0.003,0.006,0.010) nanoparticles. The colloidal nanoparticles were prepared with high yield by a solvothermal method at temperatures as low as 150°C for 24h. The as-prepared nanopowders were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), and Raman spectroscopy. The XRD studies revealed pseudo-cubic crystalline structure, with no impurity phases at room temperature. However ferroelectric tetragonal modes were clearly observed using Raman spectroscopy measurements. From TEM measurements, uniformly sized BLT nanoparticles were observed. Selected area diffraction TEM images revealed polycrystalline perovskite ring patterns, identified as corresponding to the tetragonal phase.

  1. Efficient Bulk Heterojunction CH3NH3PbI3-TiO2 Solar Cells with TiO2 Nanoparticles at Grain Boundaries of Perovskite by Multi-Cycle-Coating Strategy.

    PubMed

    Shao, Jun; Yang, Songwang; Liu, Yan

    2017-05-17

    A novel bulk heterojunction (BHJ) perovskite solar cell (PSC), where the perovskite grains act as donor and the TiO 2 nanoparticles act as acceptor, is reported. This efficient BHJ PSC was simply solution processed from a mixed precursor of CH 3 NH 3 PbI 3 (MAPbI 3 ) and TiO 2 nanoparticles. With dissolution and recrystallization by multi-cycle-coating, a unique composite structure ranging from a MAPbI 3 -TiO 2 -dominated layer on the substrate side to a pure perovskite layer on the top side is formed, which is beneficial for the blocking of possible contact between TiO 2 and the hole transport material at the interface. Scanning electron microscopy clearly shows that TiO 2 nanoparticles accumulate along the grain boundaries (GBs) of perovskite. The TiO 2 nanoparticles at the GBs quickly extract and reserve photogenerated electrons before they transport into the perovskite phase, as described in the multitrapping model, retarding the electron-hole recombination and reducing the energy loss, resulting in increased V OC and fill factor. Moreover, the pinning effect of the TiO 2 nanoparticles at the GBs from the strong bindings between TiO 2 and MAPbI 3 suppresses massive ion migration along the GBs, leading to improved operational stability and diminished hysteresis. Photoluminescence (PL) quenching and PL decay confirm the efficient exciton dissociation on the heterointerface. Electrochemical impedance spectroscopy and open-circuit photovoltage decay measurements show the reduced recombination loss and improved carrier lifetime of the BHJ PSCs. This novel strategy of device design effectively combines the benefits of both planar and mesostructured architectures whilst avoiding their shortcomings, eventually leading to a high PCE of 17.42% under 1 Sun illumination. The newly proposed approach also provides a new way to fabricate a TiO 2 -containing perovskite active layer at a low temperature.

  2. Size-driven magnetic transitions in La1/3Ca2/3MnO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Markovich, V.; Fita, I.; Wisniewski, A.; Mogilyansky, D.; Puzniak, R.; Titelman, L.; Gorodetsky, G.

    2010-09-01

    Magnetic properties of electron-doped La1/3Ca2/3MnO3 manganite nanoparticles with average particle size ranging from 12 to 42 nm, prepared by the glycine-nitrate method, have been investigated in temperature range 5-300 K and in magnetic fields up to 90 kOe. Reduction in the particle size suppresses antiferromagnetism and decreases the Néel temperature. In contrast to bulk crystals, the charge ordering does not occur in all studied nanoparticles, while a weak ferromagnetism appears above 200 K. Low temperature magnetic hysteresis loops indicate upon exchange bias effect displayed by horizontal and vertical shifts in field cooled processes. The spontaneous and remanent magnetization at low temperature shows a relatively complex variation with particle size. The size-induced structural/magnetic disorder drives the La1/3Ca2/3MnO3 nanoparticles to a pronounced glassy behavior for the smallest 12 nm particles, as evidenced by large difference between zero field cooled and field cooled magnetization, frequency dependent ac-susceptibility, as well as characteristic slowing down in the spin dynamics. Time evolution of magnetization recorded in magnetic fields after field cooling to low temperatures exhibits pronounced relaxation and a very noisy behavior that may be caused by formation of some collective states. Magnetic properties of the nanoparticle samples are compared with those of La0.2Ca0.8MnO3 nanoparticles. These results shed some light on the coupling between charges and spin degrees of freedom in antiferromagnetic manganite nanoparticles.

  3. Influence of oxygen vacancies on the magnetic and electrical properties of La1-xSrxMnO3-x/2 manganites

    NASA Astrophysics Data System (ADS)

    Trukhanov, S. V.; Lobanovski, L. S.; Bushinsky, M. V.; Khomchenko, V. A.; Pushkarev, N. V.; Troyanchuk, I. O.; Maignan, A.; Flahaut, D.; Szymczak, H.; Szymczak, R.

    2004-11-01

    The crystal structure, magnetization and electrical transport depending on the temperature and magnetic field for the doped stoichiometric La_{1-x}^{3 + } Sr_x^{2 + } Mn_{1-x}^{3 + } Mn_x^{4 + } O_3^{2-} as well as anion-deficient La_{1-x}^{3 + } Sr_x^{2 + } Mn^{3 + }O_{3-x/2}^{2-} (0le x le 0.30) ortomanganite systems have been experimentally studied. It is established that the stochiometric samples in the region of the 0 le x le 0.125 are an O'-orthorhombic perovskites whereas in the 0.175 le x le 0.30 - a rhombohedric. For the anion-deficient system the symmetry type of the unit cell is similar to the stoichiometric one. As a doping level increases the samples in the ground state undergo a number of the magnetic transitions. It is assumed that the samples with the large amount of oxygen vacancies are a cluster spin glasses (0.175 < x le 0.30) and temperature of the magnetic moment freezing is 40 K. All the anion-deficient samples are semiconductors and show considerable magnetoresistance over a wide temperature range with a peak for the x = 0.175 only. Concentration dependences of the spontaneous magnetization and magnetic ordering temperature for the anion-deficient La_{1-x}^{3 + } Sr_x^{2 + } Mn^{3 + }O_{3-x/2}^{2-} system have been established by the magnetic measurements and compared with those for the stoichiometric La_{1-x}^{3 + } Sr_x^{2 + } Mn_{1-x}^{3 + } Mn_x^{4 + } O_3^{2-} one. The magnetic propeprties of the anion-deficient samples may be interpreted on the base of the superexchange interaction and phase separation (chemical disorder) models.

  4. Ag modified LaCoO3 perovskite oxide for photocatalytic application

    NASA Astrophysics Data System (ADS)

    Jayapandi, S.; Prakasini, V. Anitha; Anitha, K.

    2018-04-01

    The present investigation has been carried out to develop a novel photocatalytic material based on lanthanum cobaltite (LaCoO3) and silver (Ag) doped LaCoO3 perovskite oxide. Pure LaCoO3 and 5 Mol% Ag doped LaCoO3 (Ag-LaCoO3) have been synthesized by simple co-precipitation method and characterized by X-ray diffraction (XRD), ultraviolet-visible (UV-Vis) and photoluminescence (PL) techniques and its photocatalytic activity was evaluated by photodegradation of methylene blue under sunlight irradiation. The observed XRD, UV and PL results indicate that Ag influences on the crystallite size and absorption coefficient of LaCoO3 perovskite oxide. The percentage of dye degradations was calculated as 60% and 99 % for LaCoO3 and 5 Mol% Ag-LaCoO3 pervoskite oxides respectively for 10 minutes (10 min) exposure to sunlight, which indicates that 5 mol% of Ag-LaCoO3, has better photodegradation activity. Hence, the present investigation confirms that Ag influences the photocatalytic activity of a material and the observations will be helpful for further developing new photocatalytic materials.

  5. Cobalt-Doped Perovskite-Type Oxide LaMnO3 as Bifunctional Oxygen Catalysts for Hybrid Lithium-Oxygen Batteries.

    PubMed

    Liu, Xiao; Gong, Hao; Wang, Tao; Guo, Hu; Song, Li; Xia, Wei; Gao, Bin; Jiang, Zhongyi; Feng, Linfei; He, Jianping

    2018-03-02

    Perovskite-type oxides based on rare-earth metals containing lanthanum manganate are promising catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolyte. Perovskite-type LaMnO 3 shows excellent ORR performance, but poor OER activity. To improve the OER performance of LaMnO 3 , the element cobalt is doped into perovskite-type LaMnO 3 through a sol-gel method followed by a calcination process. To assess electrocatalytic activities for the ORR and OER, a series of LaMn 1-x Co x O 3 (x=0, 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5) perovskite oxides were synthesized. The results indicate that the amount of doped cobalt has a significant effect on the catalytic performance of LaMn 1-x Co x O 3 . If x=0.3, LaMn 0.7 Co 0.3 O 3 not only shows a tolerable electrocatalytic activity for the ORR, but also exhibits a great improvement (>200 mV) on the catalytic activity for the OER; this indicates that the doping of cobalt is an effective approach to improve the OER performance of LaMnO 3 . Furthermore, the results demonstrate that LaMn 0.7 Co 0.3 O 3 is a promising cost-effective bifunctional catalyst with high performance in the ORR and OER for application in hybrid Li-O 2 batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Effect of A-site deficiency in LaMn{sub 0.9}Co{sub 0.1}O{sub 3} perovskites on their catalytic performance for soot combustion

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dinamarca, Robinson; Garcia, Ximena; Jimenez, Romel

    Highlights: • A-site defective perovskites increases the oxidation state of the B-cation. • Not always non-stoichiometric perovskites exhibit higher catalytic activity in soot combustion. • The highly symmetric cubic crystalline structure diminishes the redox properties of perovskites. - Abstract: The influence of lanthanum stoichiometry in Ag-doped (La{sub 1-x}Ag{sub x}Mn{sub 0.9}Co{sub 0.1}O{sub 3}) and A-site deficient (La{sub 1-x}Mn{sub 0.9}Co{sub 0.1}O{sub 3-δ}) perovskites with x equal to 10, 20 and 30 at.% has been investigated in catalysts for soot combustion. The catalysts were prepared by the amorphous citrate method and characterized by XRD, nitrogen adsorption, XPS, O{sub 2}-TPD and TPR. The formationmore » of a rhombohedral excess-oxygen perovskite for Ag-doped and a cubic perovskite structure for an A-site deficient series is confirmed. The efficient catalytic performance of the larger Ag-doped perovskite structure is attributed to the rhombohedral crystalline structure, Ag{sub 2}O segregated phases and the redox pair Mn{sup 4+}/Mn{sup 3+}. A poor catalytic activity for soot combustion was observed with A-site deficient perovskites, despite the increase in the redox pair Mn{sup 4+}/Mn{sup 3+}, which is attributed to the cubic crystalline structure.« less

  7. Nanoparticles of spinel and perovskite ferromagnets and prospects for their application in medicine

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Belous, A. G., E-mail: belous@ionc.kar.net, E-mail: solopan@ukr.net, E-mail: yelenicho@ukr.net; Solopan, S. O., E-mail: belous@ionc.kar.net, E-mail: solopan@ukr.net, E-mail: yelenicho@ukr.net; Yelenich, O. V., E-mail: belous@ionc.kar.net, E-mail: solopan@ukr.net, E-mail: yelenicho@ukr.net

    In this work, nanoparticles of La{sub 0.75}Sr{sub 0.25}MnO{sub 3} compounds with perovskite structure and AFe{sub 2}O{sub 4} (A = Mn, Fe, Co, Ni, Zn) with spinel structure have been synthesized by precipitation from diethylene glycol and microemulsion using Triton X-100 surfactant. Comparative X-ray diffraction and magnetic studies of the synthesized nanoparticles have been carried out. Magnetic fluids prepared from synthesized nanopowders have been characterized by calorimetric measurements of specific loss power (SLP)

  8. Curie-Weiss behavior of Y1-xSrxMnO3 (x = 0 and 0.03)

    NASA Astrophysics Data System (ADS)

    Thakur, Rajesh K.; Thakur, Rasna; Gaur, N. K.; Bharathi, A.; Kaurav, N.; Okram, G. S.

    2015-06-01

    The effect of bivalent cation Sr-doping on magnetic properties in multiferroic YMnO3 manganites was systemically studied by DC magnetic measurements. Both of the reported samples were prepared by solid-state reaction method with composition Y1-xSrxMnO3 (x = 0.00 and 0.03). The X-ray diffraction (XRD) results show that the compounds are synthesized in hexagonal crystal structure with space group P63cm (JCPDS: 25-1079) and slight increase in the lattice parameter is observed with strontium doping. The magnetisation versus temperature curve shows no clear anomaly near the antiferromagnetic transition temperature (TN), however from the magnetic measurements at 1000Oe a slight increase in the magnetisation is clearly witnessed with increasing Stront ium content to the Y-site.

  9. Modulating Excitonic Recombination Effects through One-Step Synthesis of Perovskite Nanoparticles for Light-Emitting Diodes.

    PubMed

    Kulkarni, Sneha A; Muduli, Subas; Xing, Guichuan; Yantara, Natalia; Li, Mingjie; Chen, Shi; Sum, Tze Chien; Mathews, Nripan; White, Tim J; Mhaisalkar, Subodh G

    2017-10-09

    The primary advantages of halide perovskites for light-emitting diodes (LEDs) are solution processability, direct band gap, good charge-carrier diffusion lengths, low trap density, and reasonable carrier mobility. The luminescence in 3 D halide perovskite thin films originates from free electron-hole bimolecular recombination. However, the slow bimolecular recombination rate is a fundamental performance limitation. Perovskite nanoparticles could result in improved performance but processability and cumbersome synthetic procedures remain challenges. Herein, these constraints are overcome by tailoring the 3 D perovskite as a near monodisperse nanoparticle film prepared through a one-step in situ deposition method. Replacing methyl ammonium bromide (CH 3 NH 3 Br, MABr) partially by octyl ammonium bromide [CH 3 (CH 2 ) 7 NH 3 Br, OABr] in defined mole ratios in the perovskite precursor proved crucial for the nanoparticle formation. Films consisting of the in situ formed nanoparticles displayed signatures associated with excitonic recombination, rather than that of bimolecular recombination associated with 3 D perovskites. This transition was accompanied by enhanced photoluminescence quantum yield (PLQY≈20.5 % vs. 3.40 %). Perovskite LEDs fabricated from the nanoparticle films exhibit a one order of magnitude improvement in current efficiency and doubling in luminance efficiency. The material processing systematics derived from this study provides the means to control perovskite morphologies through the selection and mixing of appropriate additives. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Hierarchically porous LaFeO3 perovskite prepared from the pomelo peel bio-template for catalytic oxidation of NO

    NASA Astrophysics Data System (ADS)

    Zhao, Shaojun; Wang, Li; Wang, Ying; Li, Xing

    2018-05-01

    In this paper, pomelo peel was used as biological template to obtain hierarchically porous LaFeO3 perovskite for the catalytic oxidation of NO to NO2. In addition, X-ray diffraction (XRD), scanning electron microscopy (SEM), N2 adsorption-desorption analyses, X-ray photoelectron spectra (XPS), NO temperature-programmed desorption (NO-TPD), oxygen temperature-programmed desorption (O2-TPD) and hydrogen temperature-programmed reduction (H2-TPR) were used to investigate the micro-structure and the redox properties of the hierarchically porous LaFeO3 perovskite prepared from pomelo peel biological template and the LaFeO3 perovskite without the biological template. The results indicated that the hierarchically porous LaFeO3 perovskite successfully replicated the porous structure of pomelo peel with high specific surface area. Compared to the LaFeO3 perovskite prepared without the pomelo peel template, the hierarchically porous LaFeO3 perovskite showed better catalytic oxidization of NO to NO2 under the same conditions. The maximum NO conversions for LaFeO3 prepared with and without template were 90% at 305 °C and 76% at 313 °C, respectively. This is mainly attributed to the higher ratio of Fe4+/Fe3+, the hierarchically porous structure with more adsorbed oxygen species and higher surface area for the hierarchically porous LaFeO3 perovskite compared with the sample prepared without the pomelo peel template.

  11. Composition-dependent emission linewidth broadening in lead bromide perovskite (APbBr3, A = Cs and CH3NH3) nanoparticles.

    PubMed

    Ham, Sujin; Chung, Heejae; Kim, Tae-Woo; Kim, Jiwon; Kim, Dongho

    2018-02-01

    Lead halide perovskite nanoparticles (NPs) are attractive as they exhibit excellent color purity and have a tunable band gap, and can thus be applied in highly efficient photovoltaic and light-emitting diodes. Fundamental studies of emission linewidth broadening due to spectral shifts in perovskite NPs may suggest a way to improve their color purity. However, the carrier-induced Stark shift that causes spectral diffusion still requires investigation. In this study, we explore composition-related emission linewidth broadening by comparing CsPbBr3 and CH 3 NH 3 PbBr 3 (MAPbBr3) perovskite NPs. We find that the MAPbBr3 NPs are more sensitive to fluctuations in the local electric fields than the CsPbBr3 NPs due to an intrinsic difference in the dipole moment between the two A cations (Cs and MA), which shows a carrier-induced Stark shift. The results indicate that the compositions of perovskite NPs are closely associated with emission linewidth broadening and they also provide insights into the development of NP-based devices with high color purity.

  12. Laser deposition of resonant silicon nanoparticles on perovskite for photoluminescence enhancement

    NASA Astrophysics Data System (ADS)

    Tiguntseva, E. Y.; Zalogina, A. S.; Milichko, V. A.; Zuev, D. A.; Omelyanovich, M. M.; Ishteev, A.; Cerdan Pasaran, A.; Haroldson, R.; Makarov, S. V.; Zakhidov, A. A.

    2017-11-01

    Hybrid lead halide perovskite based optoelectronics is a promising area of modern technologies yielding excellent characteristics of light emitting diodes and lasers as well as high efficiencies of photovoltaic devices. However, the efficiency of perovskite based devices hold a potential of further improvement. Here we demonstrate high photoluminescence efficiency of perovskites thin films via deposition of resonant silicon nanoparticles on their surface. The deposited nanoparticles have a number of advances over their plasmonic counterparts, which were applied in previous studies. We show experimentally the increase of photoluminescence of perovskite film with the silicon nanoparticles by 150 % as compared to the film without the nanoparticles. The results are supported by numerical calculations. Our results pave the way to high throughput implementation of low loss resonant nanoparticles in order to create highly effective perovskite based optoelectronic devices.

  13. Thermoelectric properties of a doped LaNiO3 perovskite system prepared using a spark-plasma sintering process

    NASA Astrophysics Data System (ADS)

    Tak, Jang-Yeul; Choi, Soon-Mok; Seo, Won-Seon; Cho, Hyung Koun

    2013-07-01

    Both perovskites LaNiO3 and LaCuO3 have a limitation associated with phase transitions for high-temperature thermoelectric applications. The optimized conditions were investigated to obtain the LaNi1- x Cu x O3- δ perovskite single phase showing a Cu-doping effect into Ni sites against unintended deoxidized phases. Three advantages of synergetic effects due to the simultaneous presence of nickel and copper were investigated: a low melting temperature of CuO as compared to that of NiO, the absence of intermediated deoxidized phases in the LaCuO3 system, and the Cu doping effect, which suppresses the formation of intermediate secondary phases. A solid solution was also fabricated using a spark-plasma sintering (SPS) process for the purpose of sintering LaNi1- x Cu x O3- δ compositions at a low sintering temperature.

  14. Tunable thermodynamic activity of La x Sr1-x Mn y Al1-y O3-δ (0 ≤ x ≤ 1, 0 ≤ y ≤ 1) perovskites for solar thermochemical fuel synthesis.

    PubMed

    Ezbiri, M; Takacs, M; Theiler, D; Michalsky, R; Steinfeld, A

    2017-02-28

    Nonstoichiometric metal oxides with variable valence are attractive redox materials for thermochemical and electrochemical fuel processing. To guide the design of advanced redox materials for solar-driven splitting of CO 2 and/or H 2 O to produce CO and/or H 2 (syngas), we investigate the equilibrium thermodynamics of the La x Sr 1- x Mn y Al 1- y O 3- δ perovskite family (0 ≤ x ≤ 1, 0 ≤ y ≤ 1) and La 0.6 Ca 0.4 Mn 0.8 Al 0.2 O 3- δ , and compare them to those of CeO 2 as the baseline. Oxygen nonstoichiometry measurements from 1573 to 1773 K and from 0.206 to 180 mbar O 2 show a tunable reduction extent, increasing with increasing Sr content. Maximal nonstoichiometry of 0.32 is established with La 0.2 Sr 0.8 Mn 0.8 Al 0.2 O 3- δ at 1773 K and 2.37 mbar O 2 . As a trend, we find that oxygen capacities are most sensitive to the A-cation composition. Partial molar enthalpy, entropy and Gibbs free energy changes for oxide reduction are extracted from the experimental data using defect models for Mn 4+ /Mn 3+ and Mn 3+ /Mn 2+ redox couples. We find that perovskites exhibit typically decreasing enthalpy changes with increasing nonstoichiometries. This desirable characteristic is most pronounced by La 0.6 Sr 0.4 Mn 0.4 Al 0.6 O 3- δ , rendering it attractive for CO 2 and H 2 O splitting. Generally, perovskites show lower enthalpy and entropy changes than ceria, resulting in more favorable reduction but less favorable oxidation equilibria. The energy penalties due to larger temperature swings and excess oxidants are discussed in particular. Using electronic structure theory, we conclude with a practical methodology estimating thermodynamic activity to rationally design perovskites with variable stoichiometry and valence.

  15. Effect of Synthesis Temperature on Structure and Magnetic Properties of (La,Nd)0.7Sr0.3MnO3 Nanoparticles.

    PubMed

    Shlapa, Yulia; Solopan, Sergii; Bodnaruk, Andrii; Kulyk, Mykola; Kalita, Viktor; Tykhonenko-Polishchuk, Yulia; Tovstolytkin, Alexandr; Belous, Anatolii

    2017-12-01

    Two sets of Nd-doped La 0.7 Sr 0.3 MnO 3 nanoparticles were synthesized via sol-gel method with further heat treatment at 1073 and 1573 K, respectively. Crystallographic and magnetic properties of obtained nanoparticles were studied, and the effect of synthesis conditions on these properties was investigated. According to X-ray data, all particles crystallized in the distorted perovskite structure. Magnetic parameters, such as saturation magnetization, coercivity, Curie temperature, and specific loss power, which is released on the exposure of an ensemble of nanoparticles to AC magnetic field, were determined for both sets of samples. The correlation between the values of Curie temperature and maximal heating temperature under AC magnetic field was found. It was revealed that for the samples synthesized at 1573 K, the dependences of crystallographic and magnetic parameters on Nd content were monotonous, while for the samples synthesized at 1073 K, they were non-monotonous. It was concluded that Nd-doped La 0.7 Sr 0.3 MnO 3 nanoparticles are promising materials for self-controlled magnetic hyperthermia applications, but the researchers should be aware of the unusual behavior of the particles synthesized at relatively low temperatures.

  16. The Luminescence of CH3 NH3 PbBr3 Perovskite Nanoparticles Crests the Summit and Their Photostability under Wet Conditions is Enhanced.

    PubMed

    Gonzalez-Carrero, Soranyel; Francés-Soriano, Laura; González-Béjar, María; Agouram, Saïd; Galian, Raquel E; Pérez-Prieto, Julia

    2016-10-01

    CH 3 NH 3 PbBr 3 perovskite nanoparticles (P AD ) are prepared with a photoluminescence quantum yield of ≈100% in air atmosphere by using the quasi-spherical shaped 2-adamantylammonium bromide (ADBr) as the only capping ligand. The photostability under wet conditions of this kind of nanoparticles is enhanced by using cucurbit[7]uril-adamantylammonium (AD@CB) host-guest complexes as the capping ligand. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Random lasing actions in self-assembled perovskite nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Shuai; Sun, Wenzhao; Li, Jiankai; Gu, Zhiyuan; Wang, Kaiyang; Xiao, Shumin; Song, Qinghai

    2016-05-01

    Solution-based perovskite nanoparticles have been intensively studied in the past few years due to their applications in both photovoltaic and optoelectronic devices. Here, based on the common ground between solution-based perovskite and random lasers, we have studied the mirrorless lasing actions in self-assembled perovskite nanoparticles. After synthesis from a solution, discrete lasing peaks have been observed from optically pumped perovskites without any well-defined cavity boundaries. We have demonstrated that the origin of the random lasing emissions is the scattering between the nanostructures in the perovskite microplates. The obtained quality (Q) factors and thresholds of random lasers are around 500 and 60 μJ/cm2, respectively. Both values are comparable to the conventional perovskite microdisk lasers with polygon-shaped cavity boundaries. From the corresponding studies on laser spectra and fluorescence microscope images, the lasing actions are considered random lasers that are generated by strong multiple scattering in random gain media. In additional to conventional single-photon excitation, due to the strong nonlinear effects of perovskites, two-photon pumped random lasers have also been demonstrated for the first time. We believe this research will find its potential applications in low-cost coherent light sources and biomedical detection.

  18. High mobility La-doped BaSnO3 on non-perovskite MgO substrate

    NASA Astrophysics Data System (ADS)

    Kim, Youjung; Shin, Juyeon; Kim, Young Mo; Char, Kookrin

    (Ba,La)SnO3 is a transparent perovskite oxide with high electron mobility and excellent oxygen stability. Field effect device with (Ba,La)SnO3 channel was reported to show good output characteristics on STO substrate. Here, we fabricated (Ba,La)SnO3\\ films and field effect devices with (Ba,La)SnO3 channel on non-perovskite MgO substrates, which are available in large size wafers. X-ray diffraction and transmission electron microscope (TEM) images of (Ba,La)SnO3\\ films on MgO substrates show that the films are epitaxial with many threading dislocations. (Ba,La)SnO3 exhibits the high mobility with 97.2 cm2/Vs at 2 % La doping on top of 150 nm thick BaSnO3 buffer layer. Excellent carrier modulation was observed in field effect devices. FET performances on MgO substrates are slightly better than those on SrTiO3 substrates in spite of the higher dislocation density on MgO than on SrTiO3 substrates. These high mobility BaSnO3 thin films and transistors on MgO substrates will accelerate development for applications in high temperature and high power electronics. Samsung Science and Technology Foundation.

  19. Hollow Fibers Networked with Perovskite Nanoparticles for H2 Production from Heavy Oil

    PubMed Central

    Jeon, Yukwon; Park, Dae-Hwan; Park, Joo-Il; Yoon, Seong-Ho; Mochida, Isao; Choy, Jin-Ho; Shul, Yong-Gun

    2013-01-01

    Design of catalytic materials has been highlighted to build ultraclean use of heavy oil including liquid-to-gas technology to directly convert heavy hydrocarbons into H2–rich gas fuels. If the H2 is produced from such heavy oil through high-active and durable catalysts in reforming process that is being constructed in hydrogen infrastructure, it will be addressed into renewable energy systems. Herein, the three different hollow fiber catalysts networked with perovskite nanoparticles, LaCr0.8Ru0.2O3, LaCr0.8Ru0.1Ni0.1O3, and LaCr0.8Ni0.2O3 were prepared by using activated carbon fiber as a sacrificial template for H2 production from heavy gas oil reforming. The most important findings were arrived at: (i) catalysts had hollow fibrous architectures with well-crystallized structures, (ii) hollow fibers had a high specific surface area with a particle size of ≈50 nm, and (iii) the Ru substituted ones showed high efficiency for H2 production with substantial durability under high concentrations of S, N, and aromatic compounds. PMID:24104596

  20. Hollow Fibers Networked with Perovskite Nanoparticles for H2 Production from Heavy Oil

    NASA Astrophysics Data System (ADS)

    Jeon, Yukwon; Park, Dae-Hwan; Park, Joo-Il; Yoon, Seong-Ho; Mochida, Isao; Choy, Jin-Ho; Shul, Yong-Gun

    2013-10-01

    Design of catalytic materials has been highlighted to build ultraclean use of heavy oil including liquid-to-gas technology to directly convert heavy hydrocarbons into H2-rich gas fuels. If the H2 is produced from such heavy oil through high-active and durable catalysts in reforming process that is being constructed in hydrogen infrastructure, it will be addressed into renewable energy systems. Herein, the three different hollow fiber catalysts networked with perovskite nanoparticles, LaCr0.8Ru0.2O3, LaCr0.8Ru0.1Ni0.1O3, and LaCr0.8Ni0.2O3 were prepared by using activated carbon fiber as a sacrificial template for H2 production from heavy gas oil reforming. The most important findings were arrived at: (i) catalysts had hollow fibrous architectures with well-crystallized structures, (ii) hollow fibers had a high specific surface area with a particle size of ~50 nm, and (iii) the Ru substituted ones showed high efficiency for H2 production with substantial durability under high concentrations of S, N, and aromatic compounds.

  1. Hollow fibers networked with perovskite nanoparticles for H2 production from heavy oil.

    PubMed

    Jeon, Yukwon; Park, Dae-Hwan; Park, Joo-Il; Yoon, Seong-Ho; Mochida, Isao; Choy, Jin-Ho; Shul, Yong-Gun

    2013-10-09

    Design of catalytic materials has been highlighted to build ultraclean use of heavy oil including liquid-to-gas technology to directly convert heavy hydrocarbons into H2-rich gas fuels. If the H2 is produced from such heavy oil through high-active and durable catalysts in reforming process that is being constructed in hydrogen infrastructure, it will be addressed into renewable energy systems. Herein, the three different hollow fiber catalysts networked with perovskite nanoparticles, LaCr(0.8)Ru(0.2)O3, LaCr(0.8)Ru(0.1)Ni(0.1)O3, and LaCr(0.8)Ni(0.2)O3 were prepared by using activated carbon fiber as a sacrificial template for H2 production from heavy gas oil reforming. The most important findings were arrived at: (i) catalysts had hollow fibrous architectures with well-crystallized structures, (ii) hollow fibers had a high specific surface area with a particle size of ≈50 nm, and (iii) the Ru substituted ones showed high efficiency for H2 production with substantial durability under high concentrations of S, N, and aromatic compounds.

  2. p-i-n heterojunctions with BiFeO3 perovskite nanoparticles and p- and n-type oxides: photovoltaic properties.

    PubMed

    Chatterjee, Soumyo; Bera, Abhijit; Pal, Amlan J

    2014-11-26

    We formed p-i-n heterojunctions based on a thin film of BiFeO3 nanoparticles. The perovskite acting as an intrinsic semiconductor was sandwiched between a p-type and an n-type oxide semiconductor as hole- and electron-collecting layer, respectively, making the heterojunction act as an all-inorganic oxide p-i-n device. We have characterized the perovskite and carrier collecting materials, such as NiO and MoO3 nanoparticles as p-type materials and ZnO nanoparticles as the n-type material, with scanning tunneling spectroscopy; from the spectrum of the density of states, we could locate the band edges to infer the nature of the active semiconductor materials. The energy level diagram of p-i-n heterojunctions showed that type-II band alignment formed at the p-i and i-n interfaces, favoring carrier separation at both of them. We have compared the photovoltaic properties of the perovskite in p-i-n heterojunctions and also in p-i and i-n junctions. From current-voltage characteristics and impedance spectroscopy, we have observed that two depletion regions were formed at the p-i and i-n interfaces of a p-i-n heterojunction. The two depletion regions operative at p-i-n heterojunctions have yielded better photovoltaic properties as compared to devices having one depletion region in the p-i or the i-n junction. The results evidenced photovoltaic devices based on all-inorganic oxide, nontoxic, and perovskite materials.

  3. Multimodal Superparamagnetic Nanoparticles with Unusually Enhanced Specific Absorption Rate for Synergetic Cancer Therapeutics and Magnetic Resonance Imaging.

    PubMed

    Thorat, Nanasaheb D; Bohara, Raghvendra A; Malgras, Victor; Tofail, Syed A M; Ahamad, Tansir; Alshehri, Saad M; Wu, Kevin C-W; Yamauchi, Yusuke

    2016-06-15

    Superparamagnetic nanoparticles (SPMNPs) used for magnetic resonance imaging (MRI) and magnetic fluid hyperthermia (MFH) cancer therapy frequently face trade off between a high magnetization saturation and their good colloidal stability, high specific absorption rate (SAR), and most importantly biological compatibility. This necessitates the development of new nanomaterials, as MFH and MRI are considered to be one of the most promising combined noninvasive treatments. In the present study, we investigated polyethylene glycol (PEG) functionalized La1-xSrxMnO3 (LSMO) SPMNPs for efficient cancer hyperthermia therapy and MRI application. The superparamagnetic nanomaterial revealed excellent colloidal stability and biocompatibility. A high SAR of 390 W/g was observed due to higher colloidal stability leading to an increased Brownian and Neel's spin relaxation. Cell viability of PEG capped nanoparticles is up to 80% on different cell lines tested rigorously using different methods. PEG coating provided excellent hemocompatibility to human red blood cells as PEG functionalized SPMNPs reduced hemolysis efficiently compared to its uncoated counterpart. Magnetic fluid hyperthermia of SPMNPs resulted in cancer cell death up to 80%. Additionally, improved MRI characteristics were also observed for the PEG capped La1-xSrxMnO3 formulation in aqueous medium compared to the bare LSMO. Taken together, PEG capped SPMNPs can be useful for diagnosis, efficient magnetic fluid hyperthermia, and multimodal cancer treatment as the amphiphilicity of PEG can easily be utilized to encapsulate hydrophobic drugs.

  4. Resonant silicon nanoparticles for enhancement of light absorption and photoluminescence from hybrid perovskite films and metasurfaces.

    PubMed

    Tiguntseva, E; Chebykin, A; Ishteev, A; Haroldson, R; Balachandran, B; Ushakova, E; Komissarenko, F; Wang, H; Milichko, V; Tsypkin, A; Zuev, D; Hu, W; Makarov, S; Zakhidov, A

    2017-08-31

    Recently, hybrid halide perovskites have emerged as one of the most promising types of materials for thin-film photovoltaic and light-emitting devices because of their low-cost and potential for high efficiency. Further boosting their performance without detrimentally increasing the complexity of the architecture is critically important for commercialization. Despite a number of plasmonic nanoparticle based designs having been proposed for solar cell improvement, inherent optical losses of the nanoparticles reduce photoluminescence from perovskites. Here we use low-loss high-refractive-index dielectric (silicon) nanoparticles for improving the optical properties of organo-metallic perovskite (MAPbI 3 ) films and metasurfaces to achieve strong enhancement of photoluminescence as well as useful light absorption. As a result, we observed experimentally a 50% enhancement of photoluminescence intensity from a perovskite layer with silicon nanoparticles and 200% enhancement for a nanoimprinted metasurface with silicon nanoparticles on top. Strong increase in light absorption is also demonstrated and described by theoretical calculations. Since both silicon nanoparticle fabrication/deposition and metasurface nanoimprinting techniques are low-cost, we believe that the developed all-dielectric approach paves the way to novel scalable and highly effective designs of perovskite based metadevices.

  5. Electronic structure and chemical bonding in La1-x Sr x MnO3 perovskite ceramics

    NASA Astrophysics Data System (ADS)

    Thenmozhi, N.; Sasikumar, S.; Sonai, S.; Saravanan, R.

    2017-04-01

    This study reports on the synthesis of La1-x Sr x MnO3 (x  =  0.3, 0.4 and 0.5) manganites by high temperature solid state reaction method using lanthanum oxide, strontium carbonate and manganese oxide as starting materials. The synthesized samples were characterized by XRD, UV-vis, SEM/EDS and VSM. Structural characterization shows that all the prepared samples have the perovskite rhombohedral structure. Influence of Sr doping on electron density distributions in the lattice structure of LaMnO3 were analyzed through maximum entropy method (MEM). Cell parameters are found to be decreasing with the addition of Sr content. The qualitative and quantitative analysis by MEM reveals that, incorporation of Sr into LaMnO3 lattice enhances the ionic nature between La and O ions and decreases the covalent nature between Mn and O ions. Optical band gap values are determined from the UV-visible absorption spectra. Particles with polygonal form are observed from the SEM micrographs. The elemental compositions of the synthesized samples are confirmed by EDS. The magnetic properties studied from the M-H plot taken at room temperature indicated that, the prepared samples are exhibited ferromagnetic behavior.

  6. Ferromagnetism in LaCoO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Zhou, Shiming; Shi, Lei; Zhao, Jiyin; He, Laifa; Yang, Haipeng; Zhang, Shangming

    2007-11-01

    We have investigated the structural and magnetic properties of LaCoO3 nanoparticles prepared by a sol-gel method. A ferromagnetic order with TC˜85K has been observed in the nanoparticles. The infrared spectra give evidence for a stabilizing of higher spin state and a reduced Jahn-Teller distortion in the nanoparticles with respect to the bulk LaCoO3 , which is consistent with the recent reports in the strained films [Phys. Rev. B 75, 144402 (2007)] and proposed to be the possible origin of the observed ferromagnetic order in LaCoO3 .

  7. High-temperature properties of (La,Ca)(Fe,Mg,Mo)O3perovskites as prospective electrode materials for symmetrical SOFC

    NASA Astrophysics Data System (ADS)

    Istomin, S. Ya.; Morozov, A. V.; Abdullayev, M. M.; Batuk, M.; Hadermann, J.; Kazakov, S. M.; Sobolev, A. V.; Presniakov, I. A.; Antipov, E. V.

    2018-02-01

    La1-yCayFe0.5+x(Mg,Mo)0.5-xO3-δ oxides with the orthorhombic GdFeO3-type perovskite structure have been synthesized at 1573 K. Transmission electron microscopy study for selected samples shows the coexistence of domains of perovskite phases with ordered and disordered B-cations. Mössbauer spectroscopy studies performed at 300 K and 573 K show that while compositions with low Ca-content (La0.55Ca0.45Fe0.5Mg0.2625Mo0.2375O3-δ and La0.5Ca0.5Fe0.6Mg0.175Mo0.225O3-δ) are nearly oxygen stoichiometric, La0.2Ca0.8Fe0.5Mg0.2625Mo0.2375O3-δ is oxygen deficient with δ ≈ 0.15. Oxides are stable in reducing atmosphere (Ar/H2, 8%) at 1173 K for 12 h. No additional phases have been observed at XRPD patterns of all studied perovskites and Ce1-xGdxO2-x/2 electrolyte mixtures treated at 1173-1373K, while Fe-rich compositions (x≥0.1) react with Zr1-xYxO2-x/2 electrolyte above 1273 K. Dilatometry studies reveal that all samples show rather low thermal expansion coefficients (TECs) in air of 11.4-12.7 ppm K-1. In reducing atmosphere their TECs were found to increase up to 12.1-15.4 ppm K-1 due to chemical expansion effect. High-temperature electrical conductivity measurements in air and Ar/H2 atmosphere show that the highest conductivity is observed for Fe- and Ca-rich compositions. Moderate values of electrical conductivity and TEC together with stability towards chemical interaction with typical SOFC electrolytes make novel Fe-containing perovskites promising electrode materials for symmetrical solid oxide fuel cell.

  8. Dual-Function Au@Y2O3:Eu3+ Smart Film for Enhanced Power Conversion Efficiency and Long-Term Stability of Perovskite Solar Cells.

    PubMed

    Kim, Chang Woo; Eom, Tae Young; Yang, In Seok; Kim, Byung Su; Lee, Wan In; Kang, Yong Soo; Kang, Young Soo

    2017-07-28

    In the present study, a dual-functional smart film combining the effects of wavelength conversion and amplification of the converted wave by the localized surface plasmon resonance has been investigated for a perovskite solar cell. This dual-functional film, composed of Au nanoparticles coated on the surface of Y 2 O 3 :Eu 3+ phosphor (Au@Y 2 O 3 :Eu 3+ ) nanoparticle monolayer, enhances the solar energy conversion efficiency to electrical energy and long-term stability of photovoltaic cells. Coupling between the Y 2 O 3 :Eu 3+ phosphor monolayer and ultraviolet solar light induces the latter to be converted into visible light with a quantum yield above 80%. Concurrently, the Au nanoparticle monolayer on the phosphor nanoparticle monolayer amplifies the converted visible light by up to 170%. This synergy leads to an increased solar light energy conversion efficiency of perovskite solar cells. Simultaneously, the dual-function film suppresses the photodegradation of perovskite by UV light, resulting in long-term stability. Introducing the hybrid smart Au@Y 2 O 3 :Eu 3+ film in perovskite solar cells increases their overall solar-to-electrical energy conversion efficiency to 16.1% and enhances long-term stability, as compared to the value of 15.2% for standard perovskite solar cells. The synergism between the wavelength conversion effect of the phosphor nanoparticle monolayer and the wave amplification by the localized surface plasmon resonance of the Au nanoparticle monolayer in a perovskite solar cell is comparatively investigated, providing a viable strategy of broadening the solar spectrum utilization.

  9. (La1-xSrx)0.98MnO3 perovskite with A-site deficiencies toward oxygen reduction reaction in aluminum-air batteries

    NASA Astrophysics Data System (ADS)

    Xue, Yejian; Miao, He; Sun, Shanshan; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2017-02-01

    The strontium doped Mn-based perovskites have been proposed as one of the best oxygen reduction reaction catalysts (ORRCs) to substitute the noble metal. However, few studies have investigated the catalytic activities of LSM with the A-site deficiencies. Here, the (La1-xSrx)0.98MnO3 (LSM) perovskites with A-site deficiencies are prepared by a modified solid-liquid method. The structure, morphology, valence state and oxygen adsorption behaviors of these LSM samples are characterized, and their catalytic activities toward ORR are studied by the rotating ring-disk electrode (RRDE) and aluminum-air battery technologies. The results show that the appropriate doping with Sr and introducing A-site stoichiometry can effectively tailor the Mn valence and increase the oxygen adsorption capacity of LSM. Among all the LSM samples in this work, the (La0.7Sr0.3)0.98MnO3 perovskite composited with 50% carbon (50%LSM30) exhibits the best ORR catalytic activity due to the excellent oxygen adsorption capacity. Also, this catalyst has much higher durability than that of commercial 20%Pt/C. Moreover, the maximum power density of the aluminum-air battery using 50%LSM30 as the ORRC can reach 191.3 mW cm-2. Our work indicates that the LSM/C composite catalysts with A-site deficiencies can be used as a promising ORRC in the metal-air batteries.

  10. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO 3 Perovskites

    DOE PAGES

    Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W.; ...

    2016-02-11

    Strain is known to greatly influence low-temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. Still, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO 3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals such as Pt. We attribute the improved bifunctionality to strain-induced splitting ofmore » the e g orbitals, which can customize orbital asymmetry at the surface. Lastly, analogous to strain-induced shifts in the d-band center of noble metals relative to the Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides.« less

  11. ZnO/perovskite core–shell nanorod array based monolithic catalysts with enhanced propane oxidation and material utilization efficiency at low temperature

    DOE PAGES

    Wang, Sibo; Ren, Zheng; Song, Wenqiao; ...

    2015-04-24

    Here, a hydrothermal strategy combined with colloidal deposition synthesis was successfully used to grow ZnO/perovskite (LaBO 3, B=Mn, Co, Ni) core-shell nanorod arrays within three dimensional (3-D) honeycomb cordierite substrates. A facile sonication assisted colloidal wash coating process is able to coat a uniformly dispersed perovskite nanoparticles onto the large scale ZnO nanorod arrays rooted on the channel surfaces of the 3D cordierite substrate achieved by hydrothermal synthesis. Compared to traditional wash-coated perovskite catalysts, an enhanced catalytic performance was observed for propane oxidation with 25°C lower light-off temperature than wash-coated perovskite catalyst of similar LaMnO 3 loading (4.3mg). Temperature programmedmore » reduction and desorption under H 2 and O 2 atmosphere, respectively, were used to study the reducibility and oxygen activity of these core-shell nanorod arrays based monolithic catalysts, revealing a catalytic activity sequence of LaCoO 3>LaMnO 3>La 2NiO 4 at the initial stage of catalytic reaction. The good dispersion and size control in La-based perovskite nanoparticles and their interfaces to ZnO nanorod arrays support may contribute to the enhancement of catalytic performance. Lastly, this work may provide a new type of Pt-group metals (PGM) free catalysts with improved catalytic performance for hydrocarbon oxidations at low temperatures.« less

  12. Direct and indirect measurement of the magnetocaloric effect in La0.67Ca0.33-xSrxMnO3 ± δ (x \\in [0;0.33] )

    NASA Astrophysics Data System (ADS)

    Dinesen, A. R.; Linderoth, S.; Mørup, S.

    2005-10-01

    The magnetocaloric properties of a series of manganites with the composition La0.67Ca0.33-xSrxMnO3 ± δ, x \\in [ 0;0.33] (LCSM), have been investigated by direct and indirect measuring techniques. The compounds showed a magnetocaloric effect near the Curie temperature, which increased from 267 K for x = 0 to 369 K for x = 0.33. Both the adiabatic temperature change and the isothermal magnetic entropy change were found to decrease upon increased replacement of Ca with Sr, in good agreement with previous reports. However, all samples showed almost the same relative cooling power, RCP, because the decrease in maximum magnetocaloric effect was accompanied by a widening of the magnetocaloric peaks. The compounds showed RCP values of about 300 mJ cm-3 upon a field change of 1.2 T, which is about three times less than the RCP of gadolinium, the prototype material for magnetic cooling at ambient conditions. However, the LCSM materials show a magnetocaloric effect in temperature ranges where the magnetocaloric effect in pure Gd is vanishing. LCSM might therefore have potential as a working substance in multi-component refrigerant units, where the possibility of tailoring compounds with a specific magnetic transition temperature is essential.

  13. Relaxor ferroelectricity, ferromagnetic and optical second harmonic properties in lanthanum lithium niobate (La0.05Li0.85NbO3) nanoparticles

    NASA Astrophysics Data System (ADS)

    Díaz-Moreno, Carlos A.; Ding, Yu; Li, Chunqiang; Portelles, Jorge; Heiras, J.; Hurtado-Macias, A.; Farias, J. R.; González-Hernández, J.; Yacamán, M. J.; López, Jorge

    2017-07-01

    Relaxor ferroelectricity, ferromagnetism and Second Harmonic Generation properties were founded and studied as a function of a reduction heat treatment at 650 °C in a Ar-5%H2 atmosphere in stoichiometric La0.05Li0.85NbO3 nanoparticles of 40 nm. A diffuse dielectric anomaly related with relaxor behavior from 25 °C to 800 °C in a frequency range from 100 Hz to 1 MHz was founded. It also shows ferromagnetic anhysterestic type and ferroelectric hysteresis loops at room temperature with a magnetic spin remnant of 2.5 × 10-3 emu/g and polarization saturation of 0.235 μC/cm2, remnant polarization of 0.141 μC/cm2, coercive field of 1.35 kV/cm, respectively. It shows very good second harmonic generation signal at 450 nm and 500 nm. High Resolution Transmission Electron Microscopy, X-ray Photoelectron Spectroscopy and Raman spectroscopy, indicate an ABO3 perovskite structure, new electronic binding energy structure for La (5s, 4d), Li (1s), Nb (4s, 3d, 4p) and oxygen (1s, 2s) and new vibrations modes on octahedron NbO6 related to multiferroic single phase nanoparticles, respectively.

  14. Electron paramagnetic resonance analysis of La(1-x)M(x)MnO(3+δ) (M = Ce, Sr) perovskite-like nanostructured catalysts.

    PubMed

    Oliva, Cesare; Allieta, Mattia; Scavini, Marco; Biffi, Cesare; Rossetti, Ilenia; Forni, Lucio

    2012-08-06

    The physical-chemical properties of some nanostructured perovskite-like catalysts of general formula La(1-x)M(x)MnO(3+δ) (M = Ce, Sr) have been investigated, in particular by using the electron paramagnetic resonance (EPR) technique. We show that the interplay between the -O-Mn(3+)-O-Mn(4+)-O- electron double-exchange and the electron mobility is strictly dependent on the dopant nature and the annealing conditions in air. A relationship between the observed properties of these samples and their activity in the methane flameless catalytic combustion is proposed.

  15. Annealing Effect on (FAPbI3)1−x(MAPbBr3)x Perovskite Films in Inverted-Type Perovskite Solar Cells

    PubMed Central

    Chen, Lung-Chien; Wu, Jia-Ren; Tseng, Zhong-Liang; Chen, Cheng-Chiang; Chang, Sheng Hsiung; Huang, Jun-Kai; Lee, King-Lien; Cheng, Hsin-Ming

    2016-01-01

    This study determines the effects of annealing treatment on the structure and the optical and electronic behaviors of the mixed (FAPbI3)1−x(MAPbBr3)x perovskite system. The experimental results reveal that (FAPbI3)1−x(MAPbBr3)x (x ~ 0.2) is an effective light-absorbing material for use in inverted planar perovskite solar cells owing to its large absorbance and tunable band gap. Therefore, good band-matching between the (FAPbI3)1−x(MAPbBr3)x and C60 in photovoltaic devices can be controlled by annealing at various temperatures. Accordingly, an inverted mixed perovskite solar cell with a record efficiency of 12.0% under AM1.5G irradiation is realized. PMID:28773874

  16. TC-tuned biocompatible suspension of La0.73Sr0.27MnO3 for magnetic hyperthermia.

    PubMed

    Prasad, N K; Rathinasamy, K; Panda, D; Bahadur, D

    2008-05-01

    La(1-x)Sr(x)MnO(3), a ferromagnet with high magnetization and Curie temperature T(C) below 70 degrees C, enables its use for magnetic hyperthermia treatment of cancer with a possibility of in vivo temperature control. We found that La(0.73)Sr(0.27)MnO(3) particles of size range 20-100 nm showed saturation magnetization around 38 emu/g at 20 kOe and a T(C) value of 45 degrees C. Aqueous suspension of these nanoparticles was prepared using a polymer, acrypol 934, and the biocompatibility of the suspension was examined using HeLa cells. A good heating ability of the magnetic suspension was obtained in the presence of AC magnetic field, and it was found to increase with the amplitude of field. The suspension having concentration of 0.66 mg/mL (e.g., 0.66 mg of nanoparticles with acropyl per milliliter of culture media) was observed to be biocompatible even after 96 h of treatment, as estimated by sulforhodamine B and trypan blue dye exclusion assays. Further, the treatment with the aforementioned concentration did not alter the microtubule cytoskeleton or the nucleus of the cells. However, the bare particles (concentration of 0.66 mg of nanoparticles per milliliter of culture media, but without acropyl) decreased the viability of cell significantly. Our in vitro studies suggest that the suspension (concentration of 0.66 mg/mL) may further be analyzed for in vivo studies. Copyright 2007 Wiley Periodicals, Inc.

  17. Band gap and mobility of epitaxial perovskite BaSn1 -xHfxO3 thin films

    NASA Astrophysics Data System (ADS)

    Shin, Juyeon; Lim, Jinyoung; Ha, Taewoo; Kim, Young Mo; Park, Chulkwon; Yu, Jaejun; Kim, Jae Hoon; Char, Kookrin

    2018-02-01

    A wide band-gap perovskite oxide BaSn O3 is attracting much attention due to its high electron mobility and oxygen stability. On the other hand, BaHf O3 was recently reported to be an effective high-k gate oxide. Here, we investigate the band gap and mobility of solid solutions of BaS n1 -xH fxO3 (x =0 -1 ) (BSHO) as a basis to build advanced perovskite oxide heterostructures. All the films were epitaxially grown on MgO substrates using pulsed laser deposition. Density functional theory calculations confirmed that Hf substitution does not create midgap states while increasing the band gap. From x-ray diffraction and optical transmittance measurements, the lattice constants and the band-gap values are significantly modified by Hf substitution. We also measured the transport properties of n -type La-doped BSHO films [(Ba ,La ) (Sn ,Hf ) O3 ] , investigating the feasibility of modulation doping in the BaSn O3/BSHO heterostructures. The Hall measurement data revealed that, as the Hf content increases, the activation rate of the La dopant decreases and the scattering rate of the electrons sharply increases. These properties of BSHO films may be useful for applications in various heterostructures based on the BaSn O3 system.

  18. High-pressure Irreversible Amorphization of La1/3NbO3

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    I Halevy; A Hen; A Broide

    2011-12-31

    The crystallographic structure of La{sub 1/3}NbO{sub 3} perovskite was studied at high pressures using a diamond-anvil cell and synchrotron radiation. High-pressure energy dispersive (EDS) x-ray diffraction and high-pressure angle dispersive (ADS) x-ray diffraction revealed an irreversible amorphization at {approx}10 GPa. A large change in the bulk modulus accompanied the high-pressure amorphization.

  19. Perovskites Bi0.8La0.2FeO3 and Bi0.8La0.2Fe0.95Cr0.05O3: Crystal structure and magnetic and charge states of iron ions

    NASA Astrophysics Data System (ADS)

    Sigov, A. S.; Pokatilov, V. S.; Makarova, A. O.; Pokatilov, V. V.

    2014-06-01

    Perovskites of the Bi0.8La0.2Fe1 - x Cr x O3 system ( x = 0, 0.05) were investigated by Mössbauer spectroscopy in the temperature range of 298-800 K. The samples were fabricated by solid-state synthesis and had a rhombic structure. Iron ions in Bi0.8La0.2FeO3 and Bi0.8La0.2Fe0.95Cr0.05O3 are situated in trivalent states. The magnetic transition temperatures (the Néel temperatures T N ) T N = 677.5 ± 2.5 K for Bi0.8La0.2FeO3 and T N = 647.6 ± 2.5 K for Bi0.8La0.2Fe0.95Cr0.05O3 are measured. The substitution of trivalent iron ions from trivalent chromium ions in the amount x = 0.05 in Bi0.8La0.2Fe0.95Cr0.05O3 perovskite decreases the hyperfine magnetic field at nuclei 57Fe in Fe+3-O-Cr+3 chains by 30 kOe.

  20. Tuning nanoparticle size for enhanced functionality in perovskite thin films deposited by metal organic deposition

    DOE PAGES

    Miura, Masashi; Maiorov, Boris Alfredo; Sato, Michio; ...

    2017-11-17

    Because of pressing global environmental challenges, focus has been placed on materials for efficient energy use, and this has triggered the search for nanostructural modification methods to improve performance. Achieving a high density of tunable-sized second-phase nanoparticles while ensuring the matrix remains intact is a long-sought goal. In this paper, we present an effective, scalable method to achieve this goal using metal organic deposition in a perovskite system REBa 2Cu 3O 7 (rare earth (RE)) that enhances the superconducting properties to surpass that of previous achievements. We present two industrially compatible routes to tune the nanoparticle size by controlling diffusionmore » during the nanoparticle formation stage by selecting the second-phase material and modulating the precursor composition spatially. Combining these routes leads to an extremely high density (8 × 10 22 m -3) of small nanoparticles (7 nm) that increase critical currents and reduce detrimental effects of thermal fluctuations at all magnetic field strengths and temperatures. This method can be directly applied to other perovskite materials where nanoparticle addition is beneficial.« less

  1. Tuning nanoparticle size for enhanced functionality in perovskite thin films deposited by metal organic deposition

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Miura, Masashi; Maiorov, Boris Alfredo; Sato, Michio

    Because of pressing global environmental challenges, focus has been placed on materials for efficient energy use, and this has triggered the search for nanostructural modification methods to improve performance. Achieving a high density of tunable-sized second-phase nanoparticles while ensuring the matrix remains intact is a long-sought goal. In this paper, we present an effective, scalable method to achieve this goal using metal organic deposition in a perovskite system REBa 2Cu 3O 7 (rare earth (RE)) that enhances the superconducting properties to surpass that of previous achievements. We present two industrially compatible routes to tune the nanoparticle size by controlling diffusionmore » during the nanoparticle formation stage by selecting the second-phase material and modulating the precursor composition spatially. Combining these routes leads to an extremely high density (8 × 10 22 m -3) of small nanoparticles (7 nm) that increase critical currents and reduce detrimental effects of thermal fluctuations at all magnetic field strengths and temperatures. This method can be directly applied to other perovskite materials where nanoparticle addition is beneficial.« less

  2. Monodisperse Dual-Functional Upconversion Nanoparticles Enabled Near-Infrared Organolead Halide Perovskite Solar Cells.

    PubMed

    He, Ming; Pang, Xinchang; Liu, Xueqin; Jiang, Beibei; He, Yanjie; Snaith, Henry; Lin, Zhiqun

    2016-03-18

    Extending the spectral absorption of organolead halide perovskite solar cells from visible into near-infrared (NIR) range renders the minimization of non-absorption loss of solar photons with improved energy alignment. Herein, we report on, for the first time, a viable strategy of capitalizing on judiciously synthesized monodisperse NaYF4 :Yb/Er upconversion nanoparticles (UCNPs) as the mesoporous electrode for CH3 NH3 PbI3 perovskite solar cells and more importantly confer perovskite solar cells to be operative under NIR light. Uniform NaYF4 :Yb/Er UCNPs are first crafted by employing rationally designed double hydrophilic star-like poly(acrylic acid)-block-poly(ethylene oxide) (PAA-b-PEO) diblock copolymer as nanoreactor, imparting the solubility of UCNPs and the tunability of film porosity during the manufacturing process. The subsequent incorporation of NaYF4 :Yb/Er UCNPs as the mesoporous electrode led to a high efficiency of 17.8 %, which was further increased to 18.1 % upon NIR irradiation. The in situ integration of upconversion materials as functional components of perovskite solar cells offers the expanded flexibility for engineering the device architecture and broadening the solar spectral use. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3.

    PubMed

    Marini, C; Noked, O; Kantor, I; Joseph, B; Mathon, O; Shuker, R; Kennedy, B J; Pascarelli, S; Sterer, E

    2016-02-03

    Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb(5+) towards Nb(4+) above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ∼14.5 GPa.

  4. Electronic conduction in La-based perovskite-type oxides

    PubMed Central

    Ohbayashi, Kazushige; Koumoto, Kunihito

    2015-01-01

    A systematic study of La-based perovskite-type oxides from the viewpoint of their electronic conduction properties was performed. LaCo0.5Ni0.5O3±δ was found to be a promising candidate as a replacement for standard metals used in oxide electrodes and wiring that are operated at temperatures up to 1173 K in air because of its high electrical conductivity and stability at high temperatures. LaCo0.5Ni0.5O3±δ exhibits a high conductivity of 1.9 × 103 S cm−1 at room temperature (R.T.) because of a high carrier concentration n of 2.2 × 1022 cm−3 and a small effective mass m∗ of 0.10 me. Notably, LaCo0.5Ni0.5O3±δ exhibits this high electrical conductivity from R.T. to 1173 K, and little change in the oxygen content occurs under these conditions. LaCo0.5Ni0.5O3±δ is the most suitable for the fabrication of oxide electrodes and wiring, though La1−xSrxCoO3±δ and La1−xSrxMnO3±δ also exhibit high electronic conductivity at R.T., with maximum electrical conductivities of 4.4 × 103 S cm−1 for La0.5Sr0.5CoO3±δ and 1.5 × 103 S cm−1 for La0.6Sr0.4MnO3±δ because oxygen release occurs in La1−xSrxCoO3±δ as elevating temperature and the electrical conductivity of La0.6Sr0.4MnO3±δ slightly decreases at temperatures above 400 K. PMID:27877778

  5. Effect of anode firing on the performance of lanthanum and nickel co-doped SrTiO3 (La0.2Sr0.8Ti0.9Ni0.1O3-δ) anode of solid oxide fuel cell

    NASA Astrophysics Data System (ADS)

    Park, Byung Hyun; Choi, Gyeong Man

    2015-10-01

    Perovskite oxides have potential for use as alternative anode materials in solid oxide fuel cells (SOFCs) due to stability in anode atmosphere; donor-doped SrTiO3 (e.g., La0.2Sr0.8TiO3-δ) is a good candidate for this purpose. Electro-catalytic nanoparticles can be produced in oxide anodes by the ex-solution method, e.g., by incorporating Ni into a perovskite oxide in air, then reducing the oxide in H2 atmosphere. In this study, we varied the temperature (1100, 1250 °C) and atmosphere (air, H2) of La0.2Sr0.8Ti0.9Ni0.1O3-δ (LSTN) anode firing to control the degree of Ni ex-solution and microstructure. LSTN fired at 1250 °C in H2 showed the best anodic performance for scandia-stabilized zirconia (ScSZ) electrolyte-supported cells in H2 and CH4 fuels due to the favorable microstructure and Ni ex-solution.

  6. Characterization of LaRhO3 perovskites for dry (CO2) reforming of methane (DRM)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Johansson, Ted; Pakhare, Devendra; Haynes, Daniel

    2014-01-01

    Abstract This work reports on the characterization of LaRhO3 perovskite as a catalyst for dry reforming of methane. The catalyst was studied using CH4-temperature programmed reduction (TPR), H2-TPR, and temperature programmed surface reaction (TPSR), and the changes in the crystal structure of the catalyst due to these treatments were studied by X-ray diffraction (XRD). XRD pattern of the freshly calcined perovskites showed the formation of highly crystalline LaRhO3 and La2O3 phases. H2-TPR of the fresh calcined catalyst showed a shoulder at 342°C and a broad peak at 448°C, suggesting that the reduction of Rh in perovskite occurs in multiple steps.more » XRD pattern of the reduced catalyst suggests complete reduction of the LaRhO3 phase and the formation of metallic Rh and minor amounts of La(OH)3. The CH4-TPR data show qualitatively similar results as H2-TPR, with a shoulder and a broad peak in the same temperature range. Following the H2-TPR up to 950°C, the same batch of catalyst was oxidized by flowing 5 vol. % O2/He up to 500°C and a second H2-TPR (also up to 950°C) was conducted. This second H2-TPR differed significantly from that of the fresh calcined catalyst. The single sharp peak at 163°C in the second H2-TPR suggests a significant change in the catalyst, probably causedby the transformation of about 90 % of the perovskite into Rh/La2O3. This was confirmed by the XRD studies of the catalyst reduced after the oxidation at 500°C. TPSR of the dry reforming reaction on the fresh calcined catalyst showed CO and H2 formation starting at 400°C, with complete consumption of the reactants at 650°C. The uneven consumption of reactants between 400°C and 650°C suggests that reactions other than DRM occur, including reverse water gas shift (RWGS) and the Boudouard reaction (BR), probably as a result of in-situ changes in the catalyst, consistent with the H2-TPR results. TPSR, after a H2-TPR up to 950°C, showed that the dry reforming reaction did not

  7. Electrode quenching control for highly efficient CsPbBr3 perovskite light-emitting diodes via surface plasmon resonance and enhanced hole injection by Au nanoparticles

    NASA Astrophysics Data System (ADS)

    Meng, Yan; Wu, Xiaoyan; Xiong, Ziyang; Lin, Chunyan; Xiong, Zuhong; Blount, Ethan; Chen, Ping

    2018-04-01

    Compared to organic-inorganic hybrid metal halide perovskites, all-inorganic cesium lead halides (e.g, CsPbBr3) hold greater promise in being emissive materials for light-emitting diodes owing to their superior optoelectronic properties as well as their higher stabilities. However, there is still considerable potential for breakthroughs in the current efficiency of CsPbBr3 perovskite light-emitting diodes (PeLEDs). Electrode quenching is one of the main problems limiting the current efficiency of PeLEDs when poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) is used as the hole injection layer. In this work, electrode quenching control was realized via incorporating Au NPs into PEDOT:PSS. As a result, the CsPbBr3 PeLEDs realized an improvement in maximum luminescence ranging from ˜2348 to ˜7660 cd m-2 (˜226% enhancement) and current efficiency from 1.65 to 3.08 cd A-1 (˜86% enhancement). Such substantial enhancement of the electroluminescent performance can be attributed to effective electrode quenching control at the PEDOT:PSS/CsPbBr3 perovskite interface via the combined effects of local surface plasma resonance coupling and enhanced hole transportation in the PEDOT:PSS layer by Au nanoparticles.

  8. Electrode quenching control for highly efficient CsPbBr3 perovskite light-emitting diodes via surface plasmon resonance and enhanced hole injection by Au nanoparticles.

    PubMed

    Meng, Yan; Wu, Xiaoyan; Xiong, Ziyang; Lin, Chunyan; Xiong, Zuhong; Blount, Ethan; Chen, Ping

    2018-04-27

    Compared to organic-inorganic hybrid metal halide perovskites, all-inorganic cesium lead halides (e.g, CsPbBr 3 ) hold greater promise in being emissive materials for light-emitting diodes owing to their superior optoelectronic properties as well as their higher stabilities. However, there is still considerable potential for breakthroughs in the current efficiency of CsPbBr 3 perovskite light-emitting diodes (PeLEDs). Electrode quenching is one of the main problems limiting the current efficiency of PeLEDs when poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) is used as the hole injection layer. In this work, electrode quenching control was realized via incorporating Au NPs into PEDOT:PSS. As a result, the CsPbBr 3 PeLEDs realized an improvement in maximum luminescence ranging from ∼2348 to ∼7660 cd m -2 (∼226% enhancement) and current efficiency from 1.65 to 3.08 cd A -1 (∼86% enhancement). Such substantial enhancement of the electroluminescent performance can be attributed to effective electrode quenching control at the PEDOT:PSS/CsPbBr 3 perovskite interface via the combined effects of local surface plasma resonance coupling and enhanced hole transportation in the PEDOT:PSS layer by Au nanoparticles.

  9. Density functional study on redox energetics of LaMO{sub 3−δ} (M=Sc–Cu) perovskite-type oxides

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pishahang, Mehdi, E-mail: Mehdi.Pishahang@sintef.no; Erik Mohn, Chris; Stølen, Svein

    2016-01-15

    This study evaluates the redox energetics of LaMO{sub 3−δ} (M=Sc–Cu) perovskite-type oxides via generalized gradient approximation (GGA) to DFT. Two different approaches to redox energetics of oxygen deficient perovskites of strongly non-stoichiometric (δ=0.5) and dilute defect limits (δ→0) are studied. In the first approach the enthalpies of oxidation are calculated using the stoichiometric end-compounds of LaMO{sub 3} and LaMO{sub 2.5}. The most common structures for the reduced lanthanides and strontides similar to the ones experimentally reported for SrMnO{sub 2.5}, SrFeO{sub 2.5}, and LaNiO{sub 2.5} are considered. The second approach to the oxidation enthalpies termed (δ→0) follow the trend observed experimentally.more » This approach represents the experimental conditions of the measured oxygen enthalpies, and is hampered less by the artificial features due to spurious self-interaction errors in GGA.« less

  10. Preparation and catalytic activities of LaFeO3 and Fe2O3 for HMX thermal decomposition.

    PubMed

    Wei, Zhi-Xian; Xu, Yan-Qing; Liu, Hai-Yan; Hu, Chang-Wen

    2009-06-15

    Perovskite-type LaFeO(3) and alpha-Fe(2)O(3) with high specific surface areas were directly prepared with appropriate stearic acid-nitrates ratios by a novel stearic acid solution combustion method. The obtained powders were characterized by XRD, FT-IR and XPS techniques. The catalytic activities of perovskite-type LaFeO(3) and alpha-Fe(2)O(3) for the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) were investigated by TG and TG-EGA techniques. The experimental results show that the catalytic activity of perovskite-type LaFeO(3) was much higher than that of alpha-Fe(2)O(3) because of higher concentration of surface-adsorbed oxygen (O(ad)) and hydroxyl of LaFeO(3). The study points out a potential way to develop new and more active perovskite-type catalysts for the HMX thermal decomposition.

  11. La{sup 3+} doping of the Sr{sub 2}CoWO{sub 6} double perovskite: A structural and magnetic study

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lopez, C.A.; Viola, M.C.; Pedregosa, J.C.

    2008-11-15

    La-doped Sr{sub 2}CoWO{sub 6} double perovskites have been prepared in air in polycrystalline form by solid-state reaction. These materials have been studied by X-ray powder diffraction (XRPD), neutron powder diffraction (NPD) and magnetic susceptibility. The structural refinement was performed from combined XRPD and NPD data (D2B instrument, {lambda}=1.594 A). At room temperature, the replacement of Sr{sup 2+} by La{sup 3+} induces a change of the tetragonal structure, space group I4/m of the undoped Sr{sub 2}CoWO{sub 6} into the distorted monoclinic crystal structure, space group P2{sub 1}/n, Z=2. The structure of La-doped phases contains alternating CoO{sub 6} and (Co/W)O{sub 6} octahedra,more » almost fully ordered. On the other hand, the replacement of Sr{sup 2+} by La{sup 3+} induces a partial replacement of W{sup 6+} by Co{sup 2+} into the B sites, i.e. Sr{sub 2-x}La{sub x}CoW{sub 1-y}Co{sub y}O{sub 6} (y=x/4) with segregation of SrWO{sub 4}. Magnetic and neutron diffraction measurements indicate an antiferromagnetic ordering below T{sub N}=24 K independently of the La-substitution. - Graphical abstract: La-doped Sr{sub 2}CoWO{sub 6} double perovskites have been prepared in polycrystalline form by solid-state reaction. The general formula of these compounds is Sr{sub 2-x}La{sub x}CoW{sub 1-y}Co{sub y}O{sub 6} (y=x/4). XRPD, NPD and magnetic susceptibility studies were performed. The structure of monoclinic La-doped phases contains alternating CoO{sub 6} and (Co/W)O{sub 6} octahedra, almost fully ordered. NPD and magnetic measurements indicate an antiferromagnetic ordering at low temperature.« less

  12. Electrochemical sensing of modified ABO3 perovskite: LaFe0.8 R0.2O3(R= Cr, Co, Al)

    NASA Astrophysics Data System (ADS)

    Vidya Rajan, N.; Alexander, L. K.

    2017-06-01

    Perovskite LaFeO3 with orthorhombic structure has been synthesized by citric acid mediated solution method. The effectiveness of ionic radii and Oxidation state of the doping material on ionic conductivity of the host matrix was evaluated by B-site (Fe) doping on LaFeO3 with Cr, Co and Al, resulting LaFe0.8 R0.2O3 (R = Cr, Co, Al). XRD with Rietveld refinement and Raman spectroscopic analysis demonstrate successful synthesis. The effect of the 20% B site doping on electrochemical activity is reported. The doped materials exhibit a decrease in sensing activity towards the non enzymatic detection of H2O2.

  13. The influence of Ca substitution on LaFeO3 nanoparticles in terms of structural and magnetic properties.

    PubMed

    Lin, Qing; Xu, Jianmei; Yang, Fang; Yang, Xingxing; He, Yun

    2018-01-01

    The nanocrystalline structure of La 1 -x Ca x FeO 3 was prepared by a sol-gel method involving an auto-combustion process. The incorporation of rare-earths in LaFeO 3 induces strain in magnetic properties, especially in terms of the following parameters: replacement amount, oxygen partial pressure, and calcination temperature. To determine the effects of the amount of Ca 2+ ion doping agent and the calcination temperature on the microstructure, particle morphology, and magnetic properties of LaFeO 3 crystal, we performed the following respective analytical methods: X-ray powder diffraction, Fourier-transform infrared (FT-IR) spectroscopy, scanning electron microscopy, and vibrating sample magnetometer tests. The orthorhombic structure of LaFeO 3 perovskite did not change even when it was doped with Ca 2+ ions, and its space group continued to be Pnma (No.62). FT-IR spectra confirmed that the main band appearing at 568 cm -1 is due to the antisymmetric stretching vibration of Fe-O-Fe bonds in FeO 6 . The introduction of Ca inhibits the growth of grains but the morphology of particles is improved. With an increasing concentration of Ca 2+ ions, magnetic behavior of the samples also witnessed an increasing trend in a proportionate manner. With an increase in calcination temperature, the enclosed area of the magnetic hysteresis curve of the sample reduced remarkably. The growth of nanoparticles can be restrained with an increase of Ca content that is used as doping agent. The magnetic behavior of La 1 -x Ca x FeO 3 tilts towards G-type antiferromagnetism; the magnetic orientation is achieved from the super exchange interaction of Fe 3+ ions with oxygen ions.

  14. La 3+ doping of the Sr 2CoWO 6 double perovskite: A structural and magnetic study

    NASA Astrophysics Data System (ADS)

    López, C. A.; Viola, M. C.; Pedregosa, J. C.; Carbonio, R. E.; Sánchez, R. D.; Fernández-Díaz, M. T.

    2008-11-01

    La-doped Sr 2CoWO 6 double perovskites have been prepared in air in polycrystalline form by solid-state reaction. These materials have been studied by X-ray powder diffraction (XRPD), neutron powder diffraction (NPD) and magnetic susceptibility. The structural refinement was performed from combined XRPD and NPD data (D2B instrument, λ=1.594 Å). At room temperature, the replacement of Sr 2+ by La 3+ induces a change of the tetragonal structure, space group I4/ m of the undoped Sr 2CoWO 6 into the distorted monoclinic crystal structure, space group P2 1/ n, Z=2. The structure of La-doped phases contains alternating CoO 6 and (Co/W)O 6 octahedra, almost fully ordered. On the other hand, the replacement of Sr 2+ by La 3+ induces a partial replacement of W 6+ by Co 2+ into the B sites, i.e. Sr 2-xLa xCoW 1-yCo yO 6 ( y= x/4) with segregation of SrWO 4. Magnetic and neutron diffraction measurements indicate an antiferromagnetic ordering below TN=24 K independently of the La-substitution.

  15. Influence of nanogold additives on phase formation, microstructure and dielectric properties of perovskite BaTiO3 ceramics

    NASA Astrophysics Data System (ADS)

    Nonkumwong, Jeeranan; Ananta, Supon; Srisombat, Laongnuan

    2015-06-01

    The formation of perovskite phase, microstructure and dielectric properties of nanogold-modified barium titanate (BaTiO3) ceramics was examined as a function of gold nanoparticle contents by employing a combination of X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray, Archimedes principle and dielectric measurement techniques. These ceramics were fabricated from a simple mixed-oxide method. The amount of gold nanoparticles was found to be one of the key factors controlling densification, grain growth and dielectric response in BaTiO3 ceramics. It was found that under suitable amount of nanogold addition (4 mol%), highly dense perovskite BaTiO3 ceramics with homogeneous microstructures of refined grains (~0.5-3.1 μm) and excellence dielectric properties can be produced.

  16. Pressure-induced amorphization of La{sub 1/3}TaO{sub 3}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Noked, O., E-mail: noked@bgu.ac.il; Physics Department, Ben-Gurion University, Beer Sheva 84105; Melchior, A.

    2013-06-15

    La{sub 1/3}TaO{sub 3}, an A-site cation deficient perovskite, has been studied under pressure by synchrotron X-ray powder diffraction and Raman spectroscopy. It undergoes irreversible pressure induced amorphization at P=18.5 GPa. An almost linear unit cell volume decrease vs. pressure is observed from ambient pressure up to the phase transition. The Raman spectroscopy also shows amorphization at the same pressure, with positive shifts of all modes as a function of pressure. The pressure dependence of the E{sub g} and A{sub 1g} Raman modes arising from the octahedral oxygen network is discussed. - Graphical abstract: La{sub 1/3}Tao{sub 3} exhibits linear pressure–volume relationmore » until irreversible pressure induced amorphization at 18.5 Gpa. - Highlights: • La{sub 1/3}TaO{sub 3} has been studied under pressure by synchrotron XRD and Raman spectroscopy. • La{sub 1/3}TaO{sub 3} undergoes irreversible pressure induced amorphization around 18.5 GPa. • The transition is manifested in both XRD and Raman measurements. • A linear P–V relation is observed from ambient pressure up to the phase transition.« less

  17. Strain-sensitive spin-state ordering in thin films of perovskite LaCoO3

    NASA Astrophysics Data System (ADS)

    Fujioka, J.; Yamasaki, Y.; Doi, A.; Nakao, H.; Kumai, R.; Murakami, Y.; Nakamura, M.; Kawasaki, M.; Arima, T.; Tokura, Y.

    2015-11-01

    We have investigated the lattice distortion coupled to the Co 3 d -spin-state ordering in thin films of perovskite LaCoO3 with various epitaxial strains by measurements of the magnetization, x-ray diffraction, and optical spectra. In the system with tensile strain about 0.5%, a lattice distortion characterized by the modulation vector q =(1 /6 ,1 /6 ,1 /6 ) emerges at 40 K, followed by a ferromagnetic ordering at 24 K. Alternatively, in systems with tensile strain exceeding 1%, the lattice distortion characterized by q =(1 /4 ,1 /4 ,1 /4 ) emerges at 120 K or higher, and subsequently the ferromagnetic or ferrimagnetic ordering occurs around 90 K. The evolution of infrared phonon spectra and resonant x-ray scattering at the Co K edge suggests that the population change in the Co 3 d spin state causes the strain-induced switching of spin-state ordering as well as of magnetic ordering in this canonical spin-state crossover system.

  18. Behavior of lanthanum containing barium stannate nanoparticles synthesized by cetyltriammonium bromide assisted wet chemistry route

    NASA Astrophysics Data System (ADS)

    Kumar, Astakala Anil; Kumar, Ashok; Quamara, J. K.

    2018-02-01

    In present study, we report dielectric, ferroelectric and pyroelectric behavior of pristine and La3+ containing barium stannate nanoparticles synthesized via wet chemical route involving cetyltriammonium bromide assisted thermal decomposition of binary precursors. The X-ray diffraction patterns of pristine and La3+ (2, 4 and 6 at%) doped BaSnO3 nanoparticles showed the formation of cubic perovskite phase. On substitution of Ba2+ lattice sites by La3+ at the La content of 6 at%, the sample exhibited fourfold increase in conductivity in comparison to pristine BaSnO3. Polarization hysteresis (P-E) curves of La containing barium stannate nanoparticles showed anti-ferroelectric behavior. The pyroelectric coefficient of pristine and La (2, 4 and 6 at%) containing BaSnO3 nanoparticles at 473 K were found to be 7.8, 11.6, 14.1 and 17.2 μCm-2K-1, respectively. Further, the responsivity and detectivity values were higher in comparison to the materials, such as AlN, GaN, CdS and ZnO.

  19. High-pressure floating-zone growth of perovskite nickelate LaNiO 3 single crystals

    DOE PAGES

    Zhang, Junjie; Zheng, Hong; Ren, Yang; ...

    2017-04-07

    We report the first single crystal growth of the correlated metal LaNiO 3 using a high-pressure optical-image floating zone furnace. The crystals were studied using single crystal/powder X-ray diffraction, resistivity, specific heat, and magnetic susceptibility. The availability of bulk LaNiO 3 crystals will (i) promote deep understanding in this correlated material, including the mechanism of enhanced paramagnetic susceptibility, and (ii) provide rich opportunities as a substrate for thin film growth such as important ferroelectric and/or multiferroic materials. As a result, this study demonstrates the power of high pO 2 single crystal growth of nickelate perovskites and correlated electron oxides moremore » generally.« less

  20. Thermodynamic properties of Ba{sub 1-x}La{sub x}CoO{sub 3}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gaur, N. K., E-mail: srl-nkgaur@yahoo.co.in; Thakur, Rasna, E-mail: rasnathakur@yahoo.com; Thakur, Rajesh K., E-mail: thakur.rajesh2009@gmail.com

    2016-05-06

    We have predicted the thermodynamic behavior of Ba{sub 1-x}La{sub x}CoO{sub 3} family at temperature 1K≤T≤300K using the Modified Rigid Ion Model (MRIM). The specific heat of BaCoO{sub 3} with La doping in the perovskite structure at A-site has been reported. Also, the cohesive energy (ϕ), molecular force constant (f), Reststrahlen frequency (υ), Debye temperature (θ{sub D}), specific heat (C) and Gruneisen parameter (γ) of Ba{sub 1-x}La{sub x}CoO{sub 3} compounds are discussed.

  1. Structural and magnetic analysis of La0.67Ca0.33MnO3 nanoparticles thermally treated: Acoustic detection of the magnetocaloric effect

    NASA Astrophysics Data System (ADS)

    Pena, C. F.; Soffner, M. E.; Mansanares, A. M.; Sampaio, J. A.; Gandra, F. C. G.; da Silva, E. C.; Vargas, H.

    2017-10-01

    Nanoparticles of La0.67Ca0.33MnO3 were synthesized via the sol-gel method, thermally treated and characterized using X-ray diffraction, magnetization, electron spin resonance and magnetoacoustic experiments. The formation of the desired perovskite structure was verified and the average size of the nanoparticles was also determined. An increase of the particle size by rising the treatment temperature was observed. The Curie temperature and the isothermal entropy variation of the samples were obtained from the magnetization data. The isothermal entropy change, produced under the application of an external magnetic field, which expresses the magnetocaloric effect, became significantly larger for the samples treated at higher temperatures. These results are in good agreement with those obtained by magnetoacoustics, based on the direct and contactless measurement of the temperature change, validating the ability of the technique to study the magnetocaloric effect in reduced mass and nanoparticles samples.

  2. Fabrication of aligned porous LaNi0.6Fe0.4O3 perovskite by water based freeze casting

    NASA Astrophysics Data System (ADS)

    Soltani, Niloofar; Martínez-Bautista, Rubén; Bahrami, Amin; Huerta Arcos, Lázaro; Cassir, Michel; Chávez Carvayar, José

    2018-05-01

    A novel porous cathode of LaNi0.6Fe0.4O3 perovskite with aligned porosities was engineered for solid oxide fuel cells. LaNi0.6Fe0.4O3 was produced through metal nitrate and acid citric combustion method and calcined at different temperatures. The synthesized LNF at 600 °C shows specific surface area (SBET) of 24.4 m2 g-1 and an average pore size of 12.2 nm. The chemical composition and structure of LaNi0.6Fe0.4O3 synthesized at temperature 600-1400 °C, were analyzed by XRD, XPS and HRTEM. SEM observations of freeze cast nano-sized LNF showed the vertically aligned hexagonal walls. These walls contain a great value of fine pores which accelerate the gas transportation.

  3. Thermoelectric properties of LaRh(1-x)Ni(x)O(3).

    PubMed

    Shibasaki, S; Takahashi, Y; Terasaki, I

    2009-03-18

    We report measurements and analyses of resistivity, thermopower and thermal conductivity of polycrystalline samples of perovskite LaRh(1-x)Ni(x)O(3). The thermopower is found to be large at 800 K (185 µV K(-1) for x = 0.3), which is ascribed to the high-temperature stability of the low-spin state of Rh(3+)/Rh(4+) ions. This clearly contrasts with the thermopower of the isostructural oxide LaCoO(3), which rapidly decreases above 500 K owing to the spin-state transition. The spin state of the transition-metal ions is one of the most important parameters in oxide thermoelectrics.

  4. High-Temperature Thermoelectric Properties of (1 - x) SrTiO3 - ( x) La1/3NbO3 Ceramic Solid Solution

    NASA Astrophysics Data System (ADS)

    Srivastava, Deepanshu; Azough, F.; Molinari, M.; Parker, S. C.; Freer, R.

    2015-06-01

    Ceramics based on SrTiO3 are of growing interest as thermoelectric materials because of their high-temperature stability and non-toxicity. Substitution of La and Nb into the perovskite structure provides opportunities to control both the microstructure and properties. Ceramic solid solutions of (1 - x) SrTiO3 - ( x) La1/3NbO3 were prepared by the mixed oxide route, using compositional steps of x = 0.1. Pressed pellets were sintered at temperatures of 1573 K to 1723 K in air. Addition of aliovalent ions (La3+, Nb5+) on the A/B sites (Sr2+, Ti4+) led to A-Site cation deficiency in the stoichiometric compositions and other defect structures which increased carrier concentration. A maximum ZT of 0.004 was obtained for the x = 0.2 stoichiometric sample, although much higher ZT values are possible by sample reduction.

  5. Investigation of luminescent properties of LaF3:Nd3+ nanoparticles

    NASA Astrophysics Data System (ADS)

    Wyrwas, Marek; Miluski, Piotr; Zmojda, Jacek; Kochanowicz, Marcin; Jelen, Piotr; Sitarz, Maciej; Dorosz, Dominik

    2015-09-01

    Lanthanum fluoride nanoparticles doped with Nd3+ ions obtained via solvothermal method have been presented. Doped nanoparticles were prepared in two-step method. Firstly rare-earth chlorides were synthesized from oxides and then they were used to prepare LaF3 particles. The luminescence spectra shows typical for crystalline materials Stark splitting at 880 nm corresponding 4F3/2 to 4I9/2 level transition and 1060 nm matching 4F3/2 to 4I11/2 level transition. The highest luminescence intensity was achieved for sample doped with 0.75% wt. of Nd3+, and the longest decay time for sample doped with 0.5% wt. which reached 328 μs. The XRD pattern analysis confirmed that obtained material consists of crystalline LaF3, the grain size was estimated from Sherrer's formula and equaled about 25nm.

  6. La and Al co-doped CaMnO 3 perovskite oxides: From interplay of surface properties to anion exchange membrane fuel cell performance

    DOE PAGES

    Dzara, Michael J.; Christ, Jason M.; Joghee, Prabhuram; ...

    2017-09-01

    This work reports the first account of perovskite oxide and carbon composite oxygen reduction reaction (ORR) catalysts integrated into anion exchange membrane fuel cells (AEMFCs). Perovskite oxides with a theoretical stoichiometry of Ca 0.9La 0.1Al 0.1Mn 0.9O 3-δ are synthesized by an aerogel method and calcined at various temperatures, resulting in a set of materials with varied surface chemistry and surface area. Material composition is evaluated by X-ray diffraction, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The perovskite oxide calcined at 800 degrees C shows the importance of balance between surface area, purity of the perovskite phase, and surfacemore » composition, resulting in the highest ORR mass activity when evaluated in rotating disk electrodes. Integration of this catalyst into AEMFCs reveals that the best AEMFC performance is obtained when using composites with 30:70 perovskite oxide:carbon composition. Doubling the loading leads to an increase in the power density from 30 to 76 mW cm -2. The AEMFC prepared with a composite based on perovskite oxide and N-carbon achieves a power density of 44 mW cm -2, demonstrating an ~50% increase when compared to the highest performing composite with undoped carbon at the same loading.« less

  7. La and Al co-doped CaMnO3 perovskite oxides: From interplay of surface properties to anion exchange membrane fuel cell performance

    NASA Astrophysics Data System (ADS)

    Dzara, Michael J.; Christ, Jason M.; Joghee, Prabhuram; Ngo, Chilan; Cadigan, Christopher A.; Bender, Guido; Richards, Ryan M.; O'Hayre, Ryan; Pylypenko, Svitlana

    2018-01-01

    This work reports the first account of perovskite oxide and carbon composite oxygen reduction reaction (ORR) catalysts integrated into anion exchange membrane fuel cells (AEMFCs). Perovskite oxides with a theoretical stoichiometry of Ca0.9La0.1Al0.1Mn0.9O3-δ are synthesized by an aerogel method and calcined at various temperatures, resulting in a set of materials with varied surface chemistry and surface area. Material composition is evaluated by X-ray diffraction, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The perovskite oxide calcined at 800 °C shows the importance of balance between surface area, purity of the perovskite phase, and surface composition, resulting in the highest ORR mass activity when evaluated in rotating disk electrodes. Integration of this catalyst into AEMFCs reveals that the best AEMFC performance is obtained when using composites with 30:70 perovskite oxide:carbon composition. Doubling the loading leads to an increase in the power density from 30 to 76 mW cm-2. The AEMFC prepared with a composite based on perovskite oxide and N-carbon achieves a power density of 44 mW cm-2, demonstrating an ∼50% increase when compared to the highest performing composite with undoped carbon at the same loading.

  8. Crystallite size strain analysis of nanocrystalline La0.7Sr0.3MnO3 perovskite by Williamson-Hall plot method

    NASA Astrophysics Data System (ADS)

    Kumar, Dinesh; Verma, Narendra Kumar; Singh, Chandra Bhal; Singh, Akhilesh Kumar

    2018-04-01

    The nanocrystalline Sr-doped LaMnO3 (La0.7Sr0.3MnO3 = LSMO) perovskite manganites having different crystallite size were synthesized using the nitrate-glycine auto-combustion method. The phase purity of the manganites was checked by X-ray diffraction (XRD) measurement. The XRD patterns of the sample reveal that La0.7S0.3MnO3 crystallizes into rhombohedral crystal structure with space group R-3c. The size-dependence of structural lattice parameters have been investigated with the help of Rietveld refinement. The structural parameters increase as a function of crystallite size. The crystallite-size and internal strain as a function of crystallite-size have been calculated using Williamson-Hall plot.

  9. Growth of CH3NH3PbI3 Perovskite on Stainless Steel Substrate Layered by ZnO Nanoparticles Using One-Step Spin Coating Route

    NASA Astrophysics Data System (ADS)

    Fuad, A.; Fibriyanti, A. A.; Mufti, N.; Taufiq, A.; Maryam, S.; Hidayat, N.

    2018-04-01

    In this work, we report the preparation of CH3NH3PbI3 perovskite using one-step spin coating route for solar cell application. CH3NH3I• PbI2•DMF•DMSO complexes were coated on stainless steel as a subtrate layered by ZnO nanoparticles as an electron transport layer. To obtain samples with a special performance, we annealed the samples at a temperature of 100, 120, and 140°C for 10 minutes. The samples were then characterized by means of XRD, SEM/EDX, and Spectroscopic Ellipsometry. The analysis of XRD data presented that the CH3NH3PbI3 perovskites were successfully prepared and crystallized in tetragonal structure confirming from crystalline planes (110) and (220). Meanwhile, the particle size of the samples prepared at a temperature of 100, 120, and 140°C presented 42.96, 54.73, and 55.19 nm, respectively with coincide with the SEM images. The results indicated that the increase in temperature during synthesis influenced the particle growth. Furthermore, the characterization using Spectroscopic Ellipsometry exhibited that the CH3NH3PbI3 successfully layered on the substrate sizing nano metric scale that open high opportunity to be applied to solar cells with high performance.

  10. Toxicological Assessment of CoO and La2O3 Metal Oxide Nanoparticles in Human Small Airway Epithelial Cells

    PubMed Central

    Pirela, Sandra V.; Shaffer, Justine; Mihalchik, Amy L.; Chisholm, William P.; Andrew, Michael E.; Schwegler-Berry, Diane; Castranova, Vincent; Demokritou, Philip; Qian, Yong

    2016-01-01

    Cobalt monoxide (CoO) and lanthanum oxide (La2O3) nanoparticles are 2 metal oxide nanoparticles with different redox potentials according to their semiconductor properties. By utilizing these two nanoparticles, this study sought to determine how metal oxide nanoparticle’s mode of toxicological action is related to their physio-chemical properties in human small airway epithelial cells (SAEC). We investigated cellular toxicity, production of superoxide radicals and alterations in gene expression related to oxidative stress, and cellular death at 6 and 24 h following exposure to CoO and La2O3 (administered doses: 0, 5, 25, and 50 µg/ml) nanoparticles. CoO nanoparticles induced gene expression related to oxidative stress at 6 h. After characterizing the nanoparticles, transmission electron microscope analysis showed SAEC engulfed CoO and La2O3 nanoparticles. CoO nanoparticles were toxic after 6 and 24 h of exposure to 25.0 and 50.0 µg/ml administered doses, whereas, La2O3 nanoparticles were toxic only after 24 h using the same administered doses. Based upon the Volumetric Centrifugation Method in vivo Sedimentation, Diffusion, and Dosimetry, the dose of CoO and La2O3 nanoparticles delivered at 6 and 24 h were determined to be: CoO: 1.25, 6.25, and 12.5 µg/ml; La2O3: 5, 25, and 50 µg/ml and CoO: 4, 20, and 40 µg/ml; and La2O3: 5, 25, 50 µg/ml, respectively. CoO nanoparticles produced more superoxide radicals and caused greater stimulation of total tyrosine and threonine phosphorylation at both 6 and 24 h when compared with La2O3 nanoparticles. Taken together, these data provide evidence that different toxicological modes of action were involved in CoO and La2O3 metal oxide nanoparticle-induced cellular toxicity. PMID:26769336

  11. Solution-Processible Crystalline NiO Nanoparticles for High-Performance Planar Perovskite Photovoltaic Cells.

    PubMed

    Kwon, Uisik; Kim, Bong-Gi; Nguyen, Duc Cuong; Park, Jong-Hyeon; Ha, Na Young; Kim, Seung-Joo; Ko, Seung Hwan; Lee, Soonil; Lee, Daeho; Park, Hui Joon

    2016-07-28

    In this work, we report on solution-based p-i-n-type planar-structured CH3NH3PbI3 perovskite photovoltaic (PV) cells, in which precrystallized NiO nanoparticles (NPs) without post-treatment are used to form a hole transport layer (HTL). X-ray diffraction and high-resolution transmission electron microscopy showed the crystallinity of the NPs, and atomic force microscopy and scanning electron microscopy confirmed the uniform surfaces of the resultant NiO thin film and the subsequent perovskite photoactive layer. Compared to the conventional poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) ( PSS) HTL, the NiO HTL had excellent energy-level alignment with that of CH3NH3PbI3 and improved electron-blocking capability, as analyzed by photoelectron spectroscopy and diode modeling, resulting in Voc ~0.13 V higher than conventional PSS-based devices. Consequently, a power conversion efficiency (PCE) of 15.4% with a high fill factor (FF, 0.74), short-circuit current density (Jsc, 20.2 mA·cm(-2)), and open circuit voltage (Voc, 1.04 V) having negligible hysteresis and superior air stability has been achieved.

  12. Solution-Processible Crystalline NiO Nanoparticles for High-Performance Planar Perovskite Photovoltaic Cells

    PubMed Central

    Kwon, Uisik; Kim, Bong-Gi; Nguyen, Duc Cuong; Park, Jong-Hyeon; Ha, Na Young; Kim, Seung-Joo; Ko, Seung Hwan; Lee, Soonil; Lee, Daeho; Park, Hui Joon

    2016-01-01

    In this work, we report on solution-based p-i-n-type planar-structured CH3NH3PbI3 perovskite photovoltaic (PV) cells, in which precrystallized NiO nanoparticles (NPs) without post-treatment are used to form a hole transport layer (HTL). X-ray diffraction and high-resolution transmission electron microscopy showed the crystallinity of the NPs, and atomic force microscopy and scanning electron microscopy confirmed the uniform surfaces of the resultant NiO thin film and the subsequent perovskite photoactive layer. Compared to the conventional poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) HTL, the NiO HTL had excellent energy-level alignment with that of CH3NH3PbI3 and improved electron-blocking capability, as analyzed by photoelectron spectroscopy and diode modeling, resulting in Voc ~0.13 V higher than conventional PEDOT:PSS-based devices. Consequently, a power conversion efficiency (PCE) of 15.4% with a high fill factor (FF, 0.74), short-circuit current density (Jsc, 20.2 mA·cm−2), and open circuit voltage (Voc, 1.04 V) having negligible hysteresis and superior air stability has been achieved. PMID:27465263

  13. Controlling the Electronic Properties in La1/3Sr 2/3FeO3-delta Complex Perovskite Oxides

    NASA Astrophysics Data System (ADS)

    Krick, Alex L.

    the temperature-dependent resistivity. Carrier behavior within the superlattices was also explored by fitting the temperature dependent resistivity to common conduction models. The conduction mechanism fits show that the transport at high temperatures is dominated by weakly insulating behavior due to small polaron conduction and at low temperatures the resistivity can be fit to both a novel power law and 3-dimensional variable range hopping. Additionally, reversible changes of the structural and electronic transport properties of La1/3Sr2/3FeO3-delta/Gd-doped CeO2 (GDC) heterostructures arising from the manipulation of delta are presented. Thermally induced oxygen loss leads to a c-axis lattice expansion and an increase in resistivity in an LSFO film capped with GDC. In a three-terminal device where a gate bias is applied across the GDC layer to alter the LSFO oxygen stoichiometry, the ferrite channel is shown to undergo an order of magnitude change in resistance using gate voltages of less than 1 V applied at 500 K. The changes in resistance remain upon cooling to room temperature, in the absence of a gate bias, suggesting solid state ionic gating of perovskite oxides as a promising platform for applications in non-volatile, multistate devices. Along with the experiments of controlling delta in a device format, the kinetics of oxygen loss as a function of biaxial strain was investigated.

  14. Investigation of La xSr 1-xCo yM 1-yO 3-δ (M = Mn Fe) perovskite materials as thermochemical energy storage media

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Babiniec, Sean Michael; Coker, Eric Nicholas; Miller, James E.

    2015-06-23

    Materials in the La xSr 1–xCo yMn 1–yO 3–δ (LSCM) and La xSr 1–xCo yFe 1–yO 3–δ (LSCF) families are candidates for high-temperature thermochemical energy storage due to their facility for cyclic endothermic reduction and exothermic oxidation. A set of 16 LSCM and 21 LSCF compositions were synthesized by a modified Pechini method and characterized by powder X-ray diffraction and thermogravimetric analysis. All materials were found to be various symmetries of the perovskite phase. LSCM was indexed as tetragonal, cubic, rhombohedral, or orthorhombic as a function of increased lanthanum content. For LSCF, compositions containing low lanthanum content were indexed asmore » cubic while materials with high lanthanum content were indexed as rhombohedral. An initial screening of redox activity was completed by thermogravimetric analysis for each composition. The top three compositions with the greatest recoverable redox capacity for each family were further characterized in equilibrium thermogravimetric experiments over a range of temperatures and oxygen partial pressures. As a result, these equilibrium experiments allowed the extraction of thermodynamic parameters for LSCM and LSCF compositions operated in thermochemical energy storage conditions.« less

  15. Thermal expansion and specific heat of La1-xTexCoO3

    NASA Astrophysics Data System (ADS)

    Thakur, Rasna; Thakur, Rajesh K.; Gaur, N. K.

    2018-05-01

    We present the specific heat and thermal expansion of La1-xTexCoO3 family using Modified Rigid Ion Model (MRIM). The effect of Te doping on the thermal and cohesive properties have been studied by an atomistic approach. The Debye temperature of these perovskite materials is also predicted. The effect of Tellurium doping on lattice specific heat (C), thermal expansion (α) of La1-xTexCoO3 (x= 0.05-0.25) as a function of temperature (1K≤T≤1000K) is reported probably for the first time.

  16. High-pressure synthesis, crystal structure and magnetic properties of TlCrO3 perovskite.

    PubMed

    Yi, Wei; Matsushita, Yoshitaka; Katsuya, Yoshio; Yamaura, Kazunari; Tsujimoto, Yoshihiro; Presniakov, Igor A; Sobolev, Alexey V; Glazkova, Yana S; Lekina, Yuliya O; Tsujii, Naohito; Nimori, Shigeki; Takehana, Kanji; Imanaka, Yasutaka; Belik, Alexei A

    2015-06-21

    TlMO(3) perovskites (M(3+) = transition metals) are exceptional members of trivalent perovskite families because of the strong covalency of Tl(3+)-O bonds. Here we report on the synthesis, crystal structure and properties of TlCrO(3) investigated by Mössbauer spectroscopy, specific heat, dc/ac magnetization and dielectric measurements. TlCrO(3) perovskite is prepared under high pressure (6 GPa) and high temperature (1500 K) conditions. The crystal structure of TlCrO(3) is refined using synchrotron X-ray powder diffraction data: space group Pnma (no. 62), Z = 4 and lattice parameters a = 5.40318(1) Å, b = 7.64699(1) Å and c = 5.30196(1) Å at 293 K. No structural phase transitions are found between 5 and 300 K. TlCrO(3) crystallizes in the GdFeO(3)-type structure similar to other members of the perovskite chromite family, ACrO(3) (A(3+) = Sc, In, Y and La-Lu). The unit cell volume and Cr-O-Cr bond angles of TlCrO(3) are close to those of DyCrO(3); however, the Néel temperature of TlCrO(3) (TN≈ 89 K) is much smaller than that of DyCrO(3) and close to that of InCrO(3). Isothermal magnetization studies show that TlCrO(3) is a fully compensated antiferromagnet similar to ScCrO(3) and InCrO(3), but different from RCrO(3) (R(3+) = Y and La-Lu). Ac and dc magnetization measurements with a fine step of 0.2 K reveal the existence of two Néel temperatures with very close values at T(N2) = 87.0 K and T(N1) = 89.3 K. Magnetic anomalies near T(N2 )are suppressed by static magnetic fields and by 5% iron doping.

  17. Porous LaCo1-xNixO3-δ Nanostructures as an Efficient Electrocatalyst for Water Oxidation and for a Zinc-Air Battery.

    PubMed

    Vignesh, Ahilan; Prabu, Moni; Shanmugam, Sangaraju

    2016-03-09

    Perovskites have emerged as promising earth-abundant alternatives to precious metals for catalyzing the oxygen evolution reaction (OER). Herein, we report the synthesis of a series of porous perovskite nanostructures, LaCo0.97O3-δ, with systematic Ni substitution in Co octahedral sites. Their electrocatalytic activity during the water oxidation reaction was studied in alkaline electrolytes. The electrocatalytic OER activity and stability of the perovskite nanostructure was evaluated using the rotating disk electrode technique. We show that the progressive replacement of Co by Ni in the LaCo0.97O3perovskite structure greatly altered the electrocatalytic activity and that the La(Co0.71Ni0.25)0.96O3-δ composition exhibited the lowest OER overpotential of 324 and 265 mV at 10 mA cm(-2) in 0.1 M KOH and 1 M KOH, respectively. This value was much lower than that of the noble metal catalysts, IrO2, Ru/C, and Pt/C. Furthermore, the La(Co0.71Ni0.25)0.96O3-δ nanostructure showed outstanding electrode stability, with no observable decrease in performance up to 114th cycle in the auxiliary linear sweep voltammetry that lasted for 10 h in chronoamperometry studies. The excellent oxygen evolution activity of the La(Co0.71Ni0.25)0.96O3perovskite nanostructure can be attributed to its intrinsic structure, interconnected particle arrangement, and unique redox characteristics. The enhanced intrinsic electrocatalytic activity of the La(Co0.71Ni0.25)0.96O3-δ catalyst was correlated with several parameters, such as the electrochemical surface area, the roughness factor, and the turnover frequency, with respect to variation in the transition metals of the perovskite structure. Subsequently, La(Co0.71Ni0.25)0.96O3-δ was utilized as the air cathode in a zinc-air battery application.

  18. Layered-structural monoclinic–orthorhombic perovskite La{sub 2}Ti{sub 2}O{sub 7} to orthorhombic LaTiO{sub 3} phase transition and their microstructure characterization

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Herrera, G., E-mail: manuel.herrera@enp.unam.mx; Departamento de Química Inorgánica, Universidad de Valencia, 46100 Burjasot, Valencia; Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, 04510 México D. F.

    2014-03-01

    The layered-structural ceramics, such as lanthanum titanate (La{sub 2}Ti{sub 2}O{sub 7}), have been known for their good temperature and low dielectric loss at microwave frequencies that make them good candidate materials for high frequency applications. However, few studies have been conducted on the synthesis optimization by sol gel reaction, in particular by acrylamide polymerization route. The interest in La{sub 2}Ti{sub 2}O{sub 7} ceramic has been greatly increased recently due to the effect of oriented grains. This anisotropy of the microstructure leads to anisotropy in dielectric, electrical and mechanical properties. In this study, grain oriented lanthanum titanate was produced by themore » sol–gel acrylamide polymerization route. The characterizations of the samples were achieved by thermal analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and transmission electron microscopy (TEM). X-ray diffraction indicates that the formation of monoclinic perovskite La{sub 2}Ti{sub 2}O{sub 7} nanocrystals is a necessary first step to obtain orthorhombic LaTiO{sub 3} nanocomposites (with space group Pbnm). In this work we identified that the monoclinic perovskite La{sub 2}Ti{sub 2}O{sub 7} with space group P2{sub 1} transforms its structure into one with the orthorhombic space group Cmc2{sub 1} at approximately 1073 K. The microstructure associated consisted of flaky monoclinic La{sub 2}Ti{sub 2}O{sub 7} nanocomposites in comparison with round-shaped LaTiO{sub 3} nanocomposites. - Highlights: • The flaky-like La{sub 2}Ti{sub 2}O{sub 7} compound was synthesized by sol–gel acrylamide route. • Simultaneous monitoring of the DTA and XRD with temperature was performed. • Phase transformation characterization of La{sub 2}Ti{sub 2}O{sub 7} has been carried out. • The variation of the La{sub 2}Ti{sub 2}O{sub 7} and LaTiO{sub 3} grain morphology has been compared.« less

  19. Structural and dielectric characteristics of double perovskite La2(NiFe)1/2MnO6

    NASA Astrophysics Data System (ADS)

    Nasir, Mohd.; Kandasami, Asokan; Sen, Somaditya

    2018-05-01

    Recently, La2NiMnO6 has drawn significant interest because large magnetic field induced changes in dielectric properties makes this compound a promising material for potential spintronic device applications. In the present study, the structural and dielectric characteristics of sol-gel prepared La2(Ni1/2Fe1/2)MnO6 double perovskite ceramics were evaluated. La2(Ni1/2Fe1/2)MnO6 was crystallized in the monoclinic P21/n structure with ordered Ni2+/Fe2+ and Mn4+ cations. A giant dielectric constant with relaxor-like behavior was observed, which was attributed to the dipolar effects arising from hopping between Ni2+/Fe2+ and Mn4+ ions.

  20. Colloidally prepared La-doped BaSnO3 electrodes for efficient, photostable perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Shin, Seong Sik; Yeom, Eun Joo; Yang, Woon Seok; Hur, Seyoon; Kim, Min Gyu; Im, Jino; Seo, Jangwon; Noh, Jun Hong; Seok, Sang Il

    2017-04-01

    Perovskite solar cells (PSCs) exceeding a power conversion efficiency (PCE) of 20% have mainly been demonstrated by using mesoporous titanium dioxide (mp-TiO2) as an electron-transporting layer. However, TiO2 can reduce the stability of PSCs under illumination (including ultraviolet light). Lanthanum (La)-doped BaSnO3 (LBSO) perovskite would be an ideal replacement given its electron mobility and electronic structure, but LBSO cannot be synthesized as well-dispersible fine particles or crystallized below 500°C. We report a superoxide colloidal solution route for preparing a LBSO electrode under very mild conditions (below 300°C). The PSCs fabricated with LBSO and methylammonium lead iodide (MAPbI3) show a steady-state power conversion efficiency of 21.2%, versus 19.7% for a mp-TiO2 device. The LBSO-based PSCs could retain 93% of their initial performance after 1000 hours of full-Sun illumination.

  1. Comprehensive investigation of core-shell dimer nanoparticles size, distance and thicknesses on performance of a hybrid organic-inorganic halide perovskite solar cell

    NASA Astrophysics Data System (ADS)

    Heidarzadeh, Hamid

    2018-03-01

    Significant performance enhancement in an ultrathin perovskite (CH3NH3PbI3) solar cell is done using plasmonic embedded core–shell dimer nanoparticles. Three-dimensional finite difference time-domain (FDTD) method is used. A perovskite absorber with a volume of 400 × 400 × 200 nm3 is considered. At first, a cell with one embedded nanoparticle is simulated. Absorptance of CH3NH3PbI3 absorber and gold nanoparticle are obtained. An optimization is done. Then a cell with embedded dimer nanoparticles is evaluated. The results show higher photocurrent enhancement for that in compared to a cell with one embedded nanoparticle. To further photocurrent enhancement, gold-SiO2 core–shell nanoparticles are used. Photocurrents of 23.37 mA cm‑2, 23.3 mA cm‑2, 22.5 mA cm‑2 and 21.47 mA cm‑2 are obtained for a cell with two embedded core–shell nanoparticles with core radius of 60 nm and shell thickness of 2 nm, 5 nm, 10 nm and 20 nm, respectively. It is important to mention that the photocurrent is 17.9 mA cm‑2 for reference cell and 19.8 mA cm‑2 for a cell with one embedded nanoparticle. Higher photocurrent is due to the near-field plasmonic effect.

  2. Nature of potential barrier in (Ca 1/4,Cu 3/4)TiO 3 polycrystalline perovskite

    NASA Astrophysics Data System (ADS)

    Marques, V. P. B.; Bueno, P. R.; Simões, A. Z.; Cilense, M.; Varela, J. A.; Longo, E.; Leite, E. R.

    2006-04-01

    The nonohmic electrical features of (Ca 1/4,Cu 3/4)TiO 3 perovskite ceramics, which have very strong gigantic dielectric is believed originate from potential barriers at the grain boundaries. In the present study, we used the admittance and impedance spectroscopy technique to investigate (Ca 1/4,Cu 3/4)TiO 3 perovskite ceramics with low nonohmic electrical properties. The study was conducted under two different conditions: on as-sintered ceramics and on ceramics thermally treated in an oxygen-rich atmosphere. The results confirm that thermal treatment in oxygen-rich atmospheres influence the nonohmic properties. Annealing at oxygen-rich atmospheres improve the nonohmic behavior and annealing at oxygen-poor atmospheres decrease the nonohmic properties, a behavior already reported for common metal oxide nonohmic devices and here firstly evidenced for the (Ca 1/4,Cu 3/4)TiO 3 perovskite related materials. The results show that oxygen also influences the capacitance values at low frequencies, a behavior that is indicative of the Schottky-type nature of the potential barrier.

  3. Toward the Design of a Hierarchical Perovskite Support: Ultra-Sintering-Resistant Gold Nanocatalysts for CO Oxidation

    DOE PAGES

    Tian, Chengcheng; Zhu, Xiang; Abney, Carter W.; ...

    2017-04-12

    An ultrastable Au nanocatalyst based on a heterostructured perovskite support with high surface area and uniform LaFeO3 nanocoatings was successfully synthesized and tested for CO oxidation. Strikingly, small Au nanoparticles (4-6 nm) are obtained after calcination in air at 700 °C and under reaction conditions. The designed Au catalyst not only possessed extreme sintering resistance but also showed high catalytic activity and stability because of the strong interfacial interaction between Au and the heterostructured perovskite support.

  4. Magnetic properties of La0.95Sr0.05CoO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Prakash, Ravi; Shukla, Rishabh; Priyanka, Dhaka, R. S.

    2017-05-01

    We report the magnetic and structural properties of La(1-x)SrxCoO3 (x = 0 & 0.05) nanoparticles. The analysis of room temperature powder x-ray diffraction confirms the crystalline nature and single phase of the prepared samples. The magnetic measurements show ferromagnetic transition at TC˜85 K, the spontaneous magnetic moment MS ˜172 emu/mol, and the coercive field HC ˜7 kOe in parent compound, which are in agreement with the literature. Interestingly, with hole doping by Sr2+ substitution at La3+ site the magnetization data show drastic changes, as the TC increases to ˜270 K, the value of MS (˜557 emu/mole) increases about three times, whereas, the HC (˜0.6 kOe) decreases. Below TC, the nanoparticles show a much larger FC moment and a significant difference in FC and ZFC (zero field cooled) behaviors. For x = 0.05, we determined the values of effective magnetic moment (µeff = 3.62 µB/Co), the Curie temperature (θCW = -28 K) and the spin state (Savg = 1.38), which are significantly different than LaCoO3. Our study suggests an important role of charge carriers in controlling of intermediate spin state by hole doping in nanoparticles.

  5. Exploring the Room-Temperature Ferromagnetism and Temperature-Dependent Dielectric Properties of Sr/Ni-Doped LaFeO3 Nanoparticles Synthesized by Reverse Micelle Method

    NASA Astrophysics Data System (ADS)

    Naseem, Swaleha; Khan, Shakeel; Husain, Shahid; Khan, Wasi

    2018-03-01

    This paper reports the thermal, microstructural, dielectric and magnetic properties of La0.75Sr0.25Fe0.65Ni0.35O3 nanoparticles (NPs) synthesized via reverse micelle technique. The thermogravimetric analysis of as-prepared NPs confirmed a good thermal stability of the sample. Powder x-ray diffraction data analyzed with a Rietveld refinement technique revealed single-phase and orthorhombic distorted perovskite crystal structure of the NPs having Pbnm space group. The transmission electron microscopy images show the crystalline nature and formation of nanostructures with a fairly uniform distribution of particles throughout the sample. Temperature-dependent dielectric properties of the NPs in accordance with the Kramers-Kronig transformation (KKT) model, universal dielectric response model and jump relaxation model have been discussed. Electrode or interface polarization is likely the cause of the observed dielectric behavior. Due to grain boundaries and Schottky barriers of the metallic electrodes of semiconductors, the depletion region is observed, which gives rise to Maxwell-Wagner relaxation and hence high dielectric constants. Magnetic studies revealed the ferromagnetic nature of the prepared NPs upon Sr and Ni doping in LaFeO3 perovskite at room temperature. Therefore, these NPs could be a potential candidate as electrode material in solid oxide fuel cells.

  6. Study of the glassy magnetic behaviour and charge-ordering phase transitions in La0.75Ca0.25FeO3perovskite

    NASA Astrophysics Data System (ADS)

    Abdel-Khalek, E. K.; Mohamed, E. A.; Salem, A. F.

    2017-06-01

    In this work, La0.75Ca0.25FeO3perovskite sample was prepared by the coprecipitation method. The nanoparticle was found to crystallize in the orthorhombic (Pbnm) phase as confirmed by X-ray diffraction (XRD) and transmission electron microscopic (TEM). The oxygen non-stoichiometry (δ) and magnetic states of iron ions (three magnetic sextets and non-magnetic doublet) were investigated by Mössbauer spectroscopy at room temperature (RT). The shape of the magnetic hysteresis loop of the sample reveals the existence of a weak ferromagnetism at RT. The magnetization vs. temperature curves, measured in the 9 to 200 K range, showed that the sample exhibits two magnetic-phase transition temperatures at 29 K (Tg) and 120 K (TCO). The magnetization isotherms, M (H), around these magnetic-phase transition temperatures for the sample are analyzed.

  7. High surface area LaMnO3 nanoparticles enhancing electrochemical catalytic activity for rechargeable lithium-air batteries

    NASA Astrophysics Data System (ADS)

    Li, Chuanhua; Yu, Zhiyong; Liu, Hanxing; Chen, Kang

    2018-02-01

    To improve sluggish kinetics of ORR and OER (oxygen reduction and evolution reaction) on the air electrode, the high surface area LaMnO3 nanoparticle catalysts were synthesized by sol-gel method. The specific surface area of as-synthesized pure phase LaMnO3 nanoparticles is 21.21 m2 g-1. The onset potential of high surface area LaMnO3 in alkaline solution is -0.0202 V which is comparable to commercial Pt/C. When the assembled high surface area LaMnO3-based lithium-air batteries were measured at 100 mA g-1, the initial discharge specific capacity could reach 6851.9 mA h g-1(carbon). In addition, lithium-oxygen batteries including high surface area LaMnO3 catalysts could be cycled for 52 cycles at 200 mA g-1 under a limited discharge-charge depth of 500 mA h gcarbon-1.

  8. Effect of Silver Nanoparticles on the Sorption Characteristics of La1 - x Ag x MnO3 ± y

    NASA Astrophysics Data System (ADS)

    Ostroushko, A. A.; Adamova, L. V.; Koveza, E. V.; Russkikh, O. V.; Kuznetsov, M. V.

    2018-03-01

    The effect silver nanoparticles have on the sorption characteristics of perovskite lanthanum manganite relative to methanol, benzene, and hexane vapors is studied by means of gravimetric equilibrium interval sorption. The state of silver particles is investigated using spectroscopic tools. Sorption data are compared to the catalytic activity in deep oxidation reactions of organic compounds over lanthanum manganite-based catalysts.

  9. Symmetry mismatch-driven perpendicular magnetic anisotropy for perovskite/brownmillerite heterostructures.

    PubMed

    Zhang, Jing; Zhong, Zhicheng; Guan, Xiangxiang; Shen, Xi; Zhang, Jine; Han, Furong; Zhang, Hui; Zhang, Hongrui; Yan, Xi; Zhang, Qinghua; Gu, Lin; Hu, Fengxia; Yu, Richeng; Shen, Baogen; Sun, Jirong

    2018-05-15

    Grouping different transition metal oxides together by interface engineering is an important route toward emergent phenomenon. While most of the previous works focused on the interface effects in perovskite/perovskite heterostructures, here we reported on a symmetry mismatch-driven spin reorientation toward perpendicular magnetic anisotropy in perovskite/brownmillerite heterostructures, which is scarcely seen in tensile perovskite/perovskite heterostructures. We show that alternately stacking perovskite La 2/3 Sr 1/3 MnO 3 and brownmillerite LaCoO 2.5 causes a strong interface reconstruction due to symmetry discontinuity at interface: neighboring MnO 6 octahedra and CoO 4 tetrahedra at the perovskite/brownmillerite interface cooperatively relax in a manner that is unavailable for perovskite/perovskite interface, leading to distinct orbital reconstructions and thus the perpendicular magnetic anisotropy. Moreover, the perpendicular magnetic anisotropy is robust, with an anisotropy constant two orders of magnitude greater than the in-plane anisotropy of the perovskite/perovskite interface. The present work demonstrates the great potential of symmetry engineering in designing artificial materials on demand.

  10. Tunneling barrier in nanoparticle junctions of La2/3(Ca,Sr)1/3MnO3: Nonlinear current-voltage characteristics

    NASA Astrophysics Data System (ADS)

    Niebieskikwiat, D.; Sánchez, R. D.; Lamas, D. G.; Caneiro, A.; Hueso, L. E.; Rivas, J.

    2003-05-01

    We study the nonlinear current-voltage (I-V) characteristics and analyze the voltage-dependent tunneling conductance in nanoparticles of La2/3A1/3MnO3 (A=Ca, Sr). The powders were prepared by different wet-chemical routes and low calcination temperatures were used to obtain an average particle size D≈30 nm. The data are comprehensively explained in terms of the tunneling picture, which allows one to estimate the height of the grain boundary insulating barrier (φ) for each sample. For constant D, our results show that the sample preparation route is mainly responsible for the value of φ in nanoparticles, while the Coulomb gap in the Coulomb blockade regime is ˜3 times higher for Sr- than for Ca-doping. We also show that a small fraction of the barriers contribute to the nonlinear transport, and the current is mainly carried through low-resistive percolated paths. In addition, despite the different barrier strengths, the low-field magnetoresistance (LFMR) is similar for all samples, implying that φ is not the fundamental parameter determining the LFMR.

  11. In-situ neutron diffraction of LaCoO3 perovskite under uniaxial compression. I. Crystal structure analysis and texture development

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Aman, Amjad; Chen, Yan; Lugovy, Mykola

    2014-01-01

    The dynamics of texture formation, changes in crystal structure and stress accommodation mechanisms are studied in R3c rhombohedral LaCoO3 perovskite during in-situ uniaxial compression experiment by neutron diffraction. The neutron diffraction revealed the complex crystallographic changes causing the texture formation and significant straining along certain crystallographic directions during in-situ compression, which are responsible for the appearance of hysteresis and non-linear ferroelastic deformation in LaCoO3 perovskite. The irreversible strain after the first loading was connected with the appearance of non-recoverable changes in the intensity ratio of certain crystallographic peaks, causing non-reversible texture formation. However in the second loading/unloading cycle the hysteresismore » loop was closed and no irreversible strain appears after deformation. The significant texture formation is responsible for increase in the Young s modulus of LaCoO3 at high compressive loads, where the reported values of Young s modulus increase from 76 GPa measured at the very beginning of the loading to 194 GPa at 900 MPa applied compressive stress measured at the beginning of the unloading curve.« less

  12. Structural and mechanical properties of lanthanide doped La1/3Nb0.8Ta0.2O3 thin films prepared by sol-gel method

    NASA Astrophysics Data System (ADS)

    Brunckova, Helena; Medvecky, Lubomir; Kovalcikova, Alexandra; Fides, Martin; Mudra, Erika; Durisin, Juraj; Skvarla, Jiri; Kanuchova, Maria

    2017-04-01

    Transparent Eu and Nd doped lanthanum niobate tantalate La1/3Nb0.8Ta0.2O3 (LNT) thin films (˜150 nm) were prepared by sol-gel/spin-coating process on Pt/SiO2/Si substrates and annealing at 1100 °C. The x-ray diffraction analysis of films confirmed formation of the perovskite La1/3NbO3 and La1/3TaO3 phases with traces of pyrochlore LaNbO4. Eu and Nd doped LNT films were smoother with roughness 17.1 and 25.4 nm in comparison with LNT (43.3 nm). In all films was observed heterogeneous microstructure with the perovskite spherical and pyrochlore needle-like particles. The mechanical properties of films were characterized for the first time by conventional and continuous stiffness (CSM) nanoindentation. The Eu and Nd doped LNT film modulus (E) and hardness (H) were higher than LNT (˜99.8 and 4.4 GPa) determined by conventional nanoindentation. It was measured the significant effect of substrate on properties of Eu or Nd films (H ˜ 5.9 or 4.9 GPa and E ˜ 107.3 or 104.1 GPa) by CSM nanoindentation.

  13. Spatial distribution of transferred charges across the heterointerface between perovskite transition metal oxides LaNiO{sub 3} and LaMnO{sub 3}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kitamura, Miho; Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization; Horiba, Koji

    2016-03-14

    To investigate the interfacial charge-transfer phenomena between perovskite transition metal oxides LaNiO{sub 3} (LNO) and LaMnO{sub 3} (LMO), we have performed in situ x-ray absorption spectroscopy (XAS) measurements on LNO/LMO multilayers. The Ni-L{sub 2,3} and Mn-L{sub 2,3} XAS spectra clearly show the occurrence of electron transfer from Mn to Ni ions in the interface region. Detailed analysis of the thickness dependence of these XAS spectra has revealed that the spatial distribution of the transferred charges across the interface is significantly different between the two constituent layers. The observed spatial distribution is presumably described by the charge spreading model that treatsmore » the transfer integral between neighboring transition metal ions and the Coulomb interaction, rather than the Thomas–Fermi screening model.« less

  14. Size- and pressure-controlled ferromagnetism in LaCoO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Fita, I.; Markovich, V.; Mogilyansky, D.; Puzniak, R.; Wisniewski, A.; Titelman, L.; Vradman, L.; Herskowitz, M.; Varyukhin, V. N.; Gorodetsky, G.

    2008-06-01

    Magnetic properties of nanocrystalline LaCoO3 with particle size of 25, 30, 32, and 38 nm, prepared by the citrate method, were investigated in temperature range 2-320 K, magnetic field up to 50 kOe, and under hydrostatic pressure up to 11 kbar. All nanoparticles exhibit weak ferromagnetism below TC≈85K , in agreement with recent observation on LaCoO3 particles and tensile thin films. It was found that with decreasing particle size, i.e., with increasing the surface to volume ratio, the unit-cell volume increases monotonically due to the surface effect. The ferromagnetic moment increases as well, simultaneously with lattice expansion, whereas TC remains nearly unchanged. On the other hand, an applied hydrostatic pressure suppresses strongly the ferromagnetic phase leading to its full disappearance at 10 kbar, while the TC does not change visibly under pressure. It appears that the ferromagnetism in LaCoO3 nanoparticles is controlled by the unit-cell volume. This clear correlation suggests that the nature of ferromagnetic ground state of LaCoO3 is likely related to orbitally ordered Jahn-Teller active Co3+ ions with intermediate-spin (IS) state, which may persist in the expanded lattice at low temperatures. A robust orbital order presumed among the IS Co3+ species can explain the very stable TC observed for LaCoO3 samples prepared under different conditions: single crystal powders, nanoparticles, and thin films.

  15. Mechanical behavior and electrical conductivity of La1-xCaxCoO3 (x = 0, 0.2, 0.4, 0.55) perovskites

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pathak, Siddhartha; Steinmetz, David; Kuebler, Jakob

    2010-01-01

    This paper compares the important mechanical properties and the electrical conductivities from room temperature to 800oC of four LaCoO3 based cobaltite compositions with 0, 20, 40 and 55% Ca2+ ions substituted on the A site of the perovskite structure respectively. Ca2+ doped lanthanum cobaltite materials are strong candidates for use as cathodes in lower temperature solid oxide fuel cells operating at or below 800oC. Among these four cobaltite compositions, two (LaCoO3 and La0.8Ca0.2CoO3) were found to be phase pure materials, whereas the remaining two compositions (La0.6Ca0.4CoO3 and La0.45Ca0.55CoO3) contained precipitation of secondary phases such as CaO and Co3O4. The mechanicalmore » properties of the four compositions, in terms of Young s modulus, four-point bending strength and fracture toughness measurements, were measured at both room temperature and 800oC. At room temperature, doping with Ca2+ was found to substantially increase the mechanical properties of the cobaltites, whereas at 800oC the pure LaCoO3 composition exhibited higher modulus and strength values than La0.8Ca0.2CoO3. All of the four compositions exhibited ferroelastic behavior, as shown by the hysteresis loops generated during uniaxial load-unload compression tests. Electrical conductivity measurements showed the La0.8Ca0.2CoO3 composition to have the highest conductivity among the four compositions.« less

  16. Epitaxial strain effect in perovskite RENiO3 films (RE = La-Eu) prepared by metal organic decomposition

    NASA Astrophysics Data System (ADS)

    Ikeda, Ai; Manabe, Takaaki; Naito, Michio

    2014-10-01

    We report the synthesis of perovskite RENiO3 films (RE = La, Pr, Nd, Sm, and Eu) by metal organic decomposition (MOD). The RENiO3 family is an ideal system for studying the metal-insulator transition due to the simplicity of the materials. One of the drawbacks is that the bulk synthesis of the RENiO3 requires processing at high oxygen pressures to stabilize Ni3+. Fundamentally, MOD is similar to solid-state reaction, but it turned out that the MOD synthesis tends to stabilize RENiO3 without the need for high oxygen pressure. The films prepared by MOD show high crystallinity and low resistivity. Furthermore, we have investigated the epitaxial strain effect and observed a dramatic effect in PrNiO3 and NdNiO3 films on LaAlO3 substrates. The metal-insulator transition in the PrNiO3 films on LaAlO3 is fully suppressed, whereas the metal-insulator transition temperature is considerably lowered in the NdNiO3 films on LaAlO3.

  17. Structure of 18R shifted hexagonal perovskite La{sub 6}MgTi{sub 4}O{sub 18} revisited by neutron diffraction

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lu, Fengqi; Kuang, Xiaojun, E-mail: kuangxj@glut.edu.cn

    The structure of 18-layer shifted B-site deficient hexagonal perovskite La{sub 6}MgTi{sub 4}O{sub 18} compound has been re-examined by neutron powder diffraction. Structural analysis reveals that La{sub 6}MgTi{sub 4}O{sub 18} compound adopts a 18R octahedral-tilted structure with LaO{sub 3} layer stacking sequence of (hhcccc){sub 3} in space group R{sup {sup -}}3, in contrast with the previously proposed R3m. La{sub 6}MgTi{sub 4}O{sub 18} demonstrates partially ordered Mg cation distribution with a preference on the central octahedral sites over the outer octahedral sites in the cubic perovskite blocks isolated by the single vacant octahedral layers between the two consecutive hexagonal layers. The instabilitymore » of the La{sub 6}MgTi{sub 4}O{sub 18} on alumina ceramic substrate at high temperature and its dependencies of cell parameters and permittivity were characterized as well. - Graphical abstract: 18-layer shifted hexagonal perovskite La{sub 6}MgTi{sub 4}O{sub 18} adopts octahedral-tilted structure in R{sup {sup -}}3 and demonstrates partially ordered Mg distribution in the cubic perovskite blocks isolated by the vacant octahedral layers. - Highlights: • Neutron diffraction reveals an octahedra-tilted structure in R{sup {sup -}}3 for La{sub 6}MgTi{sub 4}O{sub 18}. • Mg/Ti distribution in La{sub 6}MgTi{sub 4}O{sub 18} is partially ordered in the perovskite blocks. • Instability of La{sub 6}MgTi{sub 4}O{sub 18} on alumina ceramic at high temperature is demonstrated.« less

  18. The unusual magnetism of nanoparticle LaCoO3.

    PubMed

    Durand, A M; Belanger, D P; Hamil, T J; Ye, F; Chi, S; Fernandez-Baca, J A; Booth, C H; Abdollahian, Y; Bhat, M

    2015-05-08

    Bulk and nanoparticle powders of LaCoO3 (LCO) were synthesized and their magnetic and structural properties were studied using SQUID magnetometry and neutron diffraction. The bulk and large nanoparticles exhibit weak ferromagnetism (FM) below T ≈ 85 K and a crossover from strong to weak antiferromagnetic (AFM) correlations near a transition expressed in the lattice parameters, To≈40 K. This crossover does not occur in the smallest nanoparticles; instead, the magnetic behavior is predominantly ferromagnetic. The amount of FM in the nanoparticles depends on the amount of Co3O4 impurity phase, which induces tensile strain on the LCO lattice. A core-interface model is introduced, with the core region exhibiting the AFM crossover and with FM in the interface region near surfaces and impurity phases.

  19. The unusual magnetism of nanoparticle LaCoO 3

    DOE PAGES

    Durand, A. M.; Belanger, D. P.; Hamil, T. J.; ...

    2015-04-15

    Bulk and nanoparticle powders of LaCoO 3 (LCO) were synthesized and their magnetic and structural properties were studied using SQUID magnetometry and neutron diffraction. The bulk and large nanoparticles exhibit weak ferromagnetism (FM) below T≈85K and a crossover from strong to weak antiferromagnetic (AFM) correlations near a transition expressed in the lattice parameters, To ≈ 40 K. This crossover does not occur in the smallest nanoparticles; instead, the magnetic behavior is predominantly ferromagnetic. The amount of FM in the nanoparticles depends on the amount of Co 3O 4 impurity phase, which induces tensile strain on the LCO lattice. A core-interfacemore » model is introduced, with the core region exhibiting the AFM crossover and with FM in the interface region near surfaces and impurity phases.« less

  20. The unusual magnetism of nanoparticle LaCoO3

    NASA Astrophysics Data System (ADS)

    Durand, A. M.; Belanger, D. P.; Hamil, T. J.; Ye, F.; Chi, S.; Fernandez-Baca, J. A.; Booth, C. H.; Abdollahian, Y.; Bhat, M.

    2015-05-01

    Bulk and nanoparticle powders of LaCoO3 (LCO) were synthesized and their magnetic and structural properties were studied using SQUID magnetometry and neutron diffraction. The bulk and large nanoparticles exhibit weak ferromagnetism (FM) below T ≈ 85 K and a crossover from strong to weak antiferromagnetic (AFM) correlations near a transition expressed in the lattice parameters, To≈40 K. This crossover does not occur in the smallest nanoparticles; instead, the magnetic behavior is predominantly ferromagnetic. The amount of FM in the nanoparticles depends on the amount of Co3O4 impurity phase, which induces tensile strain on the LCO lattice. A core-interface model is introduced, with the core region exhibiting the AFM crossover and with FM in the interface region near surfaces and impurity phases.

  1. Partial nitrogen loss in SrTaO2N and LaTiO2N oxynitride perovskites

    NASA Astrophysics Data System (ADS)

    Chen, Daixi; Habu, Daiki; Masubuchi, Yuji; Torii, Shuki; Kamiyama, Takashi; Kikkawa, Shinichi

    2016-04-01

    SrTaO2N heated in a helium atmosphere began to release nitrogen of approximately 30 at% at 950 °C while maintaining the perovskite structure and its color changed from orange to dark green. Then it decomposed above 1200 °C to a black mixture of Sr1.4Ta0.6O2.73, Ta2N, and Sr5Ta4O15. The second decomposition was not clearly observed when SrTaO2N was heated in a nitrogen atmosphere below 1550 °C. After heating at 1500 °C for 3 h under a 0.2 MPa nitrogen atmosphere, the perovskite product became dark green and conductive. Structure refinement results suggested that the product was a mixture of tetragonal and cubic perovskites with a decreased ordering of N3-/O2-. The sintered body was changed to an n-type semiconductor after a partial loss of nitrogen to be reduced from the originally insulating SrTaO2N perovskite lattice. LaTiO2N was confirmed to have a similar cis-configuration of the TiO4N2 octahedron as that of TaO4N2 in SrTaO2N. It also released some of its nitrogen at 800 °C changing its color from brown to black and then decomposed to a mixture of LaTiO3, La2O3, and TiN at 1100 °C. These temperatures are lower than those in SrTaO2N.

  2. Spin-state responses to light impurity substitution in low-spin perovskite LaCoO3

    NASA Astrophysics Data System (ADS)

    Tomiyasu, Keisuke; Kubota, Yuuki; Shimomura, Saya; Onodera, Mitsugi; Koyama, Syun-Ichi; Nojima, Tsutomu; Ishihara, Sumio; Nakao, Hironori; Murakami, Youichi

    2013-06-01

    We studied the spin-state responses to light impurity substitution in low-spin perovskite LaCoO3 (Co3+: d6) through magnetization, x-ray fluorescence, and electrical resistivity measurements of single-crystal LaCo0.99M0.01O3 (M = Cr, Mn, Fe, Ni). In the magnetization curves measured at 1.8 K, a change in the spin-state was not observed for Cr, Mn, or Fe substitution but was observed for Ni substitution. Strong magnetic anisotropy was also found in the Ni-substituted sample. The fluorescence measurements revealed that the valences were roughly estimated to be Cr3+, Mn(4-δ)+, Fe(3+δ')+, and Ni3+. From the observed chemical trends, we propose that the chemical potential is a key factor in inducing the change of the low-spin state. By expanding a model of the ferromagnetic spin-state heptamer generated by hole doping [Podlesnyak , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.101.247603 101, 247603 (2008)], the emergence of highly anisotropic spin-state molecular ferromagnets induced by low-spin Ni3+ with Jahn-Teller activity is suggested. We also discuss applicability of the present results to other materials with Fe (d6).

  3. Transport of NaYF4:Er3+, Yb3+ up-converting nanoparticles into HeLa cells

    NASA Astrophysics Data System (ADS)

    Sikora, Bożena; Fronc, Krzysztof; Kamińska, Izabela; Koper, Kamil; Szewczyk, Sebastian; Paterczyk, Bohdan; Wojciechowski, Tomasz; Sobczak, Kamil; Minikayev, Roman; Paszkowicz, Wojciech; Stępień, Piotr; Elbaum, Danek

    2013-06-01

    An effective, simple and practically useful method to incorporate fluorescent nanoparticles inside live biological cells was developed. The internalization time and concentration dependence of a frequently used liposomal transfection factor (Lipofectamine 2000) was studied. A user friendly, one-step technique to obtain water and organic solvent soluble Er3+ and Yb3+ doped NaYF4 nanoparticles coated with polyvinylpyrrolidone was obtained. Structural analysis of the nanoparticles confirmed the formation of nanocrystals of the desired sizes and spectral properties. The internalization of NaYF4 nanoparticles in HeLa cervical cancer cells was determined at different nanoparticle concentrations and for incubation periods from 3 to 24 h. The images revealed a redistribution of nanoparticles inside the cell, which increases with incubation time and concentration levels, and depends on the presence of the transfection factor. The study identifies, for the first time, factors responsible for an effective endocytosis of the up-converting nanoparticles to HeLa cells. Thus, the method could be applied to investigate a wide range of future ‘smart’ theranostic agents. Nanoparticles incorporated into the liposomes appear to be very promising fluorescent probes for imaging real-time cellular dynamics.

  4. Transport Properties and Magnetoresistance of La0.8Ca0.13Ag0.07MnO3 Perovskite Manganite Synthesized by Sol-Gel Method

    NASA Astrophysics Data System (ADS)

    Kurniawan, B.; Ruli, F.; Imaduddin, A.; Kamila, R.

    2018-05-01

    In this paper, we investigate the transport properties and magnetoresistance effect of La0.8Ca0.13Ag0.07MnO3 perovskite manganite synthesized by sol-gel method. The XRD pattern of the sample shows a rhombohedral perovskite structure with space group R3¯c. The EDX analysis confirms that the sample contains all expected chemical elements without any additional impurity. The temperature dependence of electrical resistivity was measured using a cryogenic magnetometer. The results show a metal-insulator transition temperature (TM-I ) at 280 K. The resistivity of the sample increases with an increase of temperature below TM-I . Theoretical analyses of the temperature dependence of resistivity suggest that the resistivity due to electron-electron scattering is predominant below TI-M. The resistivity of the sample decreases when applied magnetic field 1 T at a temperature range of 10 K to 300 K. The magnetoresistance of La0.8Ca0.13Ag0.07MnO3 emanates from spin-polarized tunneling process at the grain boundary.

  5. One-pot electrospinning and gas-sensing properties of LaMnO3 perovskite/SnO2 heterojunction nanofibers

    NASA Astrophysics Data System (ADS)

    Chen, Dongdong; Yi, Jianxin

    2018-03-01

    Using nanostructured composite materials is an effective way to obtain high-performance gas sensors. This work used p-type LaMnO3 perovskite-structured semiconductor as a novel promoter for SnO2 nanofibers and studied the gas-sensing characteristics. Nanofibers of 0-2.5-mol% LaMnO3/SnO2 were synthesized via one-pot electrospinning. Compared with pristine SnO2, LaMnO3/SnO2 composite nanofibers exhibited smaller particle size (10-30 nm) and higher BET surface area. XPS revealed that oxygen surface absorption decreased with increasing LaMnO3 content. 0.3-mol% LaMnO3/SnO2 exhibited significantly enhanced ethanol sensitivity relative to pristine SnO2. A response of 20 was obtained at the optimum temperature of 260 °C for 100-ppm ethanol. Higher LaMnO3 loading led to decrease of the ethanol response. The impact of LaMnO3 loading on the sensing behavior of SnO2 nanofibers was discussed in terms of p-n heterojunction formation and changes in the microstructure and catalytic properties.

  6. Dielectric properties of layered perovskite Sr1-xAxBi2Nb2O9 ferroelectrics (A=La, Ca and x=0,0.1)

    NASA Astrophysics Data System (ADS)

    Forbess, M. J.; Seraji, S.; Wu, Y.; Nguyen, C. P.; Cao, G. Z.

    2000-05-01

    In this letter, we report an experimental study on the influences of 10 at. % Ca2+ and La3+ doping on dielectric properties and dc conductivity of SrBi2Nb2O9 ferroelectric ceramics. All the samples were made by two-step solid-state reaction sintering at temperatures up to 1150 °C for 0.5-1 h in air. X-ray diffraction analysis indicated that single-phase layered perovskite ferroelectrics were obtained and no appreciable secondary phase was found. The Curie point was found to increase from 418 °C without doping to 475 °C with Ca2+ doping and to 480 °C with La3+ doping. Dielectric constants, loss tangent, and dc conductivity of SrBi2Nb2O9 ferroelectrics doped with Ca2+ and La3+ were studied and the relationships among doping, crystal structure, and dielectric properties were discussed.

  7. Sono-photo-Fenton oxidation of bisphenol-A over a LaFeO3 perovskite catalyst.

    PubMed

    Dükkancı, Meral

    2018-01-01

    In this study, oxidation of bisphenol-A (IUPAC name - 2,2-(4,4-dihydroxyphenyl, BPA), which is an endocrine disrupting phenolic compound used in the polycarbonate plastic and epoxy resin industry, was investigated using sono-photo-Fenton process under visible light irradiation in the presence of an iron containing perovskite catalyst, LaFeO 3 . The catalyst prepared by sol-gel method, calcined at 500°C showed a catalytic activity in BPA oxidation using sono-photo-Fenton process with a degradation degree and a chemical oxygen demand (COD) reduction of 21.8% and 11.2%, respectively. Degradation of BPA was studied by using individual and combined advanced oxidation techniques including sonication, heterogeneous Fenton reaction and photo oxidation over this catalyst to understand the effect of each process on degradation of BPA. It was seen, the role of sonication was very important in hybrid sono-photo-Fenton process due to the pyrolysis and sonoluminescence effects caused by ultrasonic irradiation. The prepared LaFeO 3 perovskite catalyst was a good sonocatalyst rather than a photocatalyst. Sonication was not only the effective process to degrade BPA but also it was the cost effective process in terms of energy consumption. The studies show that the energy consumption is lower in the sono-Fenton process than those in the photo-Fenton and sono-photo- Fenton processes. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Effect of Sr substitution on the room temperature electrical properties of La1-xSrxFeO3 nano-crystalline materials

    NASA Astrophysics Data System (ADS)

    Kafa, C. A.; Triyono, D.; Laysandra, H.

    2017-07-01

    LaFeO3 is a material with Perovskite structure which electrical properties got investigated a lot, because as a p-type semiconductor it showed good gas sensing behavior through resistivity comparison. Sr doping on LaFeO3 is able to improve the electrical conductivity through structural modification. Using the Sr atoms doping concentration (x) from 0.1 to 0.4, La1-xSrxFeO3 nanocrystal pellets were synthesized using sol-gel method, followed by gradual heat treatment and uniaxial compaction. Structural analysis from XRD characterization shows that the structure of the materials is Orthorhombic Perovskite. The topography of the sample by SEM reveals grain and grain boundary existence with emerging agglomeration. The electrical properties of the material, as functions of frequency, were measured by Impedance Spectroscopy method using RLC meter. Through the Nyquist plot and Bode plot, the electrical conductivity of La1-xSrxFeO3 is contributed by grain and grain boundaries. It is reported that La0.6Sr0.4FeO3 sample has the most superior electrical conductivity of all samples, and the electrical permittivity of both La0.8Sr0.2FeO3 and La0.7Sr0.3FeO3 are the most stable.

  9. New Rhenium-Doped SrCo1−xRexO3−δ Perovskites Performing as Cathodes in Solid Oxide Fuel Cells

    PubMed Central

    Troncoso, Loreto; Gardey, María Celeste; Fernández-Díaz, María Teresa; Alonso, José Antonio

    2016-01-01

    In the aim to stabilize novel three-dimensional perovskite oxides based upon SrCoO3−δ, we have designed and prepared SrCo1−xRexO3−δ phases (x = 0.05 and 0.10), successfully avoiding the competitive hexagonal 2H polytypes. Their performance as cathode materials in intermediate-temperature solid oxide fuel cells (IT-SOFC) has been investigated. The characterization of these oxides included X-ray (XRD) and in situ temperature-dependent neutron powder diffraction (NPD) experiments for x = 0.10. At room temperature, SrCo1−xRexO3−δ perovskites are defined in the P4/mmm space group, which corresponds to a subtle tetragonal perovskite superstructure with unit-cell parameters a = b ≈ ao, c = 2ao (ao = 3.861 and 3.868 Å, for x = 0.05 and 0.10, respectively). The crystal structure evolves above 380 °C to a simple cubic perovskite unit cell, as observed from in-situ NPD data. The electrical conductivity gave maximum values of 43.5 S·cm−1 and 51.6 S·cm−1 for x = 0.05 and x = 0.10, respectively, at 850 °C. The area specific resistance (ASR) polarization resistance determined in symmetrical cells is as low as 0.087 Ω·cm2 and 0.065 Ω·cm2 for x = 0.05 and x = 0.10, respectively, at 850 °C. In single test cells these materials generated a maximum power of around 0.6 W/cm2 at 850 °C with pure H2 as a fuel, in an electrolyte-supported configuration with La0.8Sr0.2Ga0.83Mg0.17O3−δ (LSGM) as the electrolyte. Therefore, we propose the SrCo1−xRexO3−δ (x = 0.10 and 0.05) perovskite oxides as promising candidates for cathodes in IT-SOFC. PMID:28773844

  10. Theory and Application of Photoelectron Diffraction for Complex Oxide Systems

    NASA Astrophysics Data System (ADS)

    Chassé, Angelika; Chassé, Thomas

    2018-06-01

    X-ray photoelectron diffraction (XPD) has been used to investigate film structures and local sites of surface and dopant atoms in complex oxide materials. We have performed angular-resolved measurements of intensity distribution curves (ADCs) and patterns (ADPs) of elemental core level intensities from binary to quaternary mixed oxide samples and compared them to multiple-scattering cluster (MSC) calculations in order to derive information on structural models and related parameters. MSC calculations permitted to describe both bulk diffraction features of binary oxide MnO(001) and the thickness-dependence of the tetragonal distortion of epitaxial MnO films on Ag(001). XPD was further used to investigate the surface termination of perovskite SrTiO3 and BaTiO3 substrates in order to evaluate influence of different ex situ and in situ preparation procedures on the surface layers, which are crucial for quality of following film growth. Despite the similarity of local environments of Sr (Ba) and Ti atoms in the perovskite film structure an angular region in the ADCs was identified as a fingerprint with the help of MSC simulations which provided clear conclusions on the perovskite oxide surfaces. Dopant sites in quaternary perovskite manganites La1-xCaxMnO3, La1-xSrxMnO3, and La1-xCexMnO3 were studied with polar angle scans of the photoemission intensities of host and dopant atoms. Both direct comparison of experimental ADCs and to the simulations within MSC models confirm the occupation of A sites by the dopants and the structural quality of the complex oxide films.

  11. Crystallographic site swapping of La3+ ion in BaA'LaTeO6 (A' = Na, K, Rb) double perovskite type compounds: diffraction and photoluminescence evidence for the site swapping.

    PubMed

    Phatak, R; Gupta, S K; Krishnan, K; Sali, S K; Godbole, S V; Das, A

    2014-02-28

    Double perovskite type compounds of the formula BaA'LaTeO6 (A' = Na, K, Rb) were synthesized by solid state route and their crystal structures were determined by Rietveld analysis using powder X-ray diffraction and neutron diffraction data. Na compound crystallizes in the monoclinic system with P2₁/n space group whereas, K and Rb compounds crystallize in Fm3m space group. All the three compounds show rock salt type ordering at B site. Crystal structure analysis shows that La ion occupies A site in Na compound whereas, it occupies B site in K and Rb compounds according to the general formula of AA'BB'O6 for a double perovskite type compound. Effect of this crystallographic site swapping of the La ion was also observed in the photoluminescence study by doping Eu(3+) in La(3+) site. The large decrease in the intensity of the electric dipole ((5)D0-(7)F2) transition in the Rb compound compared to the Na compound indicates that Eu(3+) ion resides in the centrosymmetric octahedral environment in the Rb compound.

  12. Low temperature nucleation of Griffiths Phase in Co doped LaMnO3 nanostructures

    NASA Astrophysics Data System (ADS)

    Adeela, N.; Khan, U.; Naz, S.; Iqbal, M.; Irfan, M.; Cheng, Y.

    2017-11-01

    We have reported magnetic properties of La1-xCoxMnO3 nanostructures synthesized by hydrothermal route. The crystal structure has been characterized by X-ray diffraction (XRD) technique, which shows rhombohedral perovskite structure at room temperature. Scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS) have been used to analyse morphology and chemical composition of prepared nanoparticles. Magnetic hysteresis loops of all the samples exhibit ferromagnetic behaviour at 10 K. Inverse susceptibility graphs as a function of temperature represent deviation from Curie Weiss law. The indication for short range ferromagnetic clusters well above Curie temperature is observed due to the Griffiths Phase (GP). It is proposed that the presence of GP arises from induced size effects of La and Co ions.

  13. Conducting tin halides with a layered organic-based perovskite structure

    NASA Astrophysics Data System (ADS)

    Mitzi, D. B.; Feild, C. A.; Harrison, W. T. A.; Guloy, A. M.

    1994-06-01

    THE discovery1 of high-temperature superconductivity in layered copper oxide perovskites has generated considerable fundamental and technological interest in this class of materials. Only a few other examples of conducting layered perovskites are known; these are also oxides such as (La1-xSrx)n+1 MnnO3n+1 (ref. 2), Lan+1NinO3n+1 (ref. 3) and Ban+1PbnO3n+1 (ref. 4), all of which exhibit a trend from semiconducting to metallic behaviour with increasing number of perovskite layers (n). We report here the synthesis of a family of organic-based layered halide perovskites, (C4H9NH3)2(CH3NH3)n-1Snnl3n+1 which show a similar transition from semiconducting to metallic behaviour with increasing n. The incorporation of an organic modulation layer between the conducting tin iodide sheets potentially provides greater flexibility for tuning the electrical properties of the perovskite sheets, and we suggest that such an approach will prove valuable for exploring the range of transport properties possible with layered perovskites.

  14. Trapping charges at grain boundaries and degradation of CH3NH3Pb(I1-x Br x )3 perovskite solar cells.

    PubMed

    Nguyen, Bich Phuong; Kim, Gee Yeong; Jo, William; Kim, Byeong Jo; Jung, Hyun Suk

    2017-08-04

    The electrical properties of CH 3 NH 3 Pb(I 1-x Br x ) 3 (x = 0.13) perovskite materials were investigated under ambient conditions. The local work function and the local current were measured using Kelvin probe force microscopy and conductive atomic force microscopy, respectively. The degradation of the perovskite layers depends on their grain size. As the material degrades, an additional peak in the surface potential appears simultaneously with a sudden increase and subsequent relaxation of the local current. The potential bending at the grain boundaries and the intragrains is the most likely reason for the change of the local current surface of the perovskite layers. The improved understanding of the degradation mechanism garnered from this study helps pave the way toward an improved photo-conversion efficiency in perovskite solar cells.

  15. Trapping charges at grain boundaries and degradation of CH3NH3Pb(I1-x Br x )3 perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Phuong Nguyen, Bich; Kim, Gee Yeong; Jo, William; Kim, Byeong Jo; Jung, Hyun Suk

    2017-08-01

    The electrical properties of CH3NH3Pb(I1-x Br x )3 (x = 0.13) perovskite materials were investigated under ambient conditions. The local work function and the local current were measured using Kelvin probe force microscopy and conductive atomic force microscopy, respectively. The degradation of the perovskite layers depends on their grain size. As the material degrades, an additional peak in the surface potential appears simultaneously with a sudden increase and subsequent relaxation of the local current. The potential bending at the grain boundaries and the intragrains is the most likely reason for the change of the local current surface of the perovskite layers. The improved understanding of the degradation mechanism garnered from this study helps pave the way toward an improved photo-conversion efficiency in perovskite solar cells.

  16. New Type of 2D Perovskites with Alternating Cations in the Interlayer Space, (C(NH 2 ) 3 )(CH 3 NH 3 ) n Pb n I 3n+1 : Structure, Properties, and Photovoltaic Performance

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Soe, Chan Myae Myae; Stoumpos, Constantinos C.; Kepenekian, Mikaël

    We present the new homologous series (C(NH2)3)(CH3NH3)nPbnI3n+1 (n = 1, 2, 3) of layered 2D perovskites. Structural characterization by single-crystal X-ray diffraction reveals that these compounds adopt an unprecedented structure type, which is stabilized by the alternating ordering of the guanidinium and methylammonium cations in the interlayer space (ACI). Compared to the more common Ruddlesden–Popper (RP) 2D perovskites, the ACI perovskites have a different stacking motif and adopt a higher crystal symmetry. The higher symmetry of the ACI perovskites is expressed in their physical properties, which show a characteristic decrease of the bandgap with respect to their RP perovskite counterpartsmore » with the same perovskite layer thickness (n). The compounds show a monotonic decrease in the optical gap as n increases: Eg = 2.27 eV for n = 1 to Eg = 1.99 eV for n = 2 and Eg = 1.73 eV for n = 3, which show slightly narrower gaps compared to the corresponding RP perovskites. First-principles theoretical electronic structure calculations confirm the experimental optical gap trends suggesting that the ACI perovskites are direct bandgap semiconductors with wide valence and conduction bandwidths. To assess the potential of the ACI perovskites toward solar cell applications, we studied the (C(NH2)3)(CH3NH3)3Pb3I10 (n = 3) compound. Compact thin films from the (C(NH2)3)(CH3NH3)3Pb3I10 compound with excellent surface coverage can be obtained from the antisolvent dripping method. Planar photovoltaic devices from optimized ACI perovskite films yield a power-conversion-efficiency of 7.26% with a high open-circuit voltage of ~1 V and a striking fill factor of ~80%.« less

  17. Magnetic properties of rare-earth-doped La0.7Sr0.3MnO3.

    PubMed

    Veverka, Pavel; Kaman, Ondřej; Knížek, Karel; Novák, Pavel; Maryško, Miroslav; Jirák, Zdeněk

    2017-01-25

    Rare-earth-doped ferromagnetic manganites La 0.63 RE 0.07 Sr 0.30 MnO 3 (RE  =  Gd, Tb, Dy, and Ho) are synthesized in the form of sintered ceramics and nanocrystalline phases with the mean size of crystallites  ≈30 nm. The electronic states of the dopants are investigated by SQUID magnetometry and theoretically interpreted based on the calculations of the crystal field splitting of rare-earth energy levels. The samples show the orthorhombic perovskite structure of Ibmm symmetry, with a complete FM order of Mn spins in bulk and reduced order in nanoparticles. Non-zero moments are also detected at the perovskite A sites, which can be attributed to magnetic polarization of the rare-earth dopants. The measurements in external field up to 70 kOe show a standard Curie-type contribution of the spin-only moments of Gd 3+ ions, whereas Kramers ions Dy 3+ and non-Kramers ions Ho 3+ contribute by Ising moments due to their doublet ground states. The behaviour of non-Kramers ions Tb 3+ is anomalous, pointing to singlet ground state with giant Van Vleck paramagnetism. The Tb 3+ doping leads also to a notably increased coercivity compared to other La 0.63 RE 0.07 Sr 0.30 MnO 3 systems.

  18. Engineering electrocatalytic activity in nanosized perovskite cobaltite through surface spin-state transition

    PubMed Central

    Zhou, Shiming; Miao, Xianbing; Zhao, Xu; Ma, Chao; Qiu, Yuhao; Hu, Zhenpeng; Zhao, Jiyin; Shi, Lei; Zeng, Jie

    2016-01-01

    The activity of electrocatalysts exhibits a strongly dependence on their electronic structures. Specifically, for perovskite oxides, Shao-Horn and co-workers have reported a correlation between the oxygen evolution reaction activity and the eg orbital occupation of transition-metal ions, which provides guidelines for the design of highly active catalysts. Here we demonstrate a facile method to engineer the eg filling of perovskite cobaltite LaCoO3 for improving the oxygen evolution reaction activity. By reducing the particle size to ∼80 nm, the eg filling of cobalt ions is successfully increased from unity to near the optimal configuration of 1.2 expected by Shao-Horn's principle. Consequently, the activity is significantly enhanced, comparable to those of recently reported cobalt oxides with eg∼1.2 configurations. This enhancement is ascribed to the emergence of spin-state transition from low-spin to high-spin states for cobalt ions at the surface of the nanoparticles, leading to more active sites with increased reactivity. PMID:27187067

  19. Ag-doped manganite nanoparticles: new materials for temperature-controlled medical hyperthermia.

    PubMed

    Melnikov, O V; Gorbenko, O Yu; Markelova, M N; Kaul, A R; Atsarkin, V A; Demidov, V V; Soto, C; Roy, E J; Odintsov, B M

    2009-12-15

    The purpose of this study was to introduce newly synthesized nanomaterials as an alternative to superparamagnetic ironoxide based particles (SPIO) and thus to launch a new platform for highly controllable hyperthermia cancer therapy and imaging. The new material that forms the basis for this article is lanthanum manganite particles with silver ions inserted into the perovskite lattice: La(1-x)Ag(x)MnO(3+delta). Adjusting the silver doping level, it is possible to control the Curie temperature (T(c)) in the hyperthermia range of interest (41-44 degrees C). A new class of nanoparticles based on silver-doped manganites La(1-x)Ag(x)MnO(3+delta) is suggested. New nanoparticles are stable, and their properties were not affected by the typical ambient conditions in the living tissue. It is possible to monitor the particle uptake and retention by MRI. When these particles are placed into an alternating magnetic field, their temperature increases to the definite value near T(c) and then remains constant if the magnetic field is maintained. During the hyperthermia procedure, the temperature can be restricted, thereby preventing the necrosis of normal tissue. A new class of nanoparticles based on silver-doped manganites La(1-x)Ag(x)MnO(3+delta) was suggested. Ag-doped perovskite manganites particles clearly demonstrated the effect of adjustable Curie temperature necessary for highly controllable cellular hyperthermia. The magnetic relaxation properties of the particles are comparable with that of SPIO, and so we were able to monitor the particle movement and retention by MRI. Thus, the new material combines the MRI contrast enhancement capability with targeted hyperthermia treatment.

  20. nomalous Interface and Surface Strontium Segregation in (La 1-ySr y) 2CoO 4 /La 1-xSr xCoO 3- Heterostructured Thin Films

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Feng, Zhenxing; Yacoby, Yuzhak; Gadre, Milind

    2014-01-01

    Heterostructured materials have shown unusual physiochemical properties at the interfaces such as two dimensional electron gas systems, high-temperature superconductivity, and enhanced catalysis. Here we report the first atomic-scale evidence of the microscopic structure of a perovskite/Ruddlesden-Popper heterostructure (having La1-xSrxCoO3- /(La1-ySry)2CoO4 ), and anomalous strontium segregation at the interface and in the Ruddlesden-Popper structure using direct X-ray methods combined with ab initio calculations. The remarkably enhanced activity of such heterostructured surfaces relative to bulk perovskite and Ruddlesden-Popper oxides previously shown for oxygen electrocatalysis at elevated temperatures can be attributed to reduced thermodynamic penalty of oxygen vacancies in the oxide structure associatedmore » with Sr segregation observed in the heterostructure. Our findings provide insights for the design of highly active catalysts for energy conversion and storage applications.« less

  1. “Ba{sub 6}Nb{sub 4}RuO{sub 18}” and “LaBa{sub 4}Nb{sub 3}RuO{sub 15}” – The structural consequences of substituting paramagnetic cations into A{sub n}B{sub n−1}O{sub 3n} cation-deficient perovskite oxides

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kamil, Elynor L.; Morgan, Harry W.T.; Hayward, Michael A., E-mail: michael.hayward@chem.ox.ac.uk

    The B-cation deficient perovskite phases Ba{sub 6}Nb{sub 4}RuO{sub 18} and LaBa{sub 4}Nb{sub 3}RuO{sub 15} were prepared by ceramic synthesis. Neutron powder diffraction analysis indicates that rather than the 6-layer and 5-layer cation-deficient perovskite structures expected for these phases (by analogy to the known structures of Ba{sub 6}Nb{sub 4}TiO{sub 18} and LaBa{sub 4}Nb{sub 3}TiO{sub 15}) they adopt 5-layer and 4-layer B-cation deficient perovskite structures respectively, and are better described as Ba{sub 5}Nb{sub 3.33}Ru{sub 0.81}O{sub 15} and Ba{sub 3.16}La{sub 0.84}Nb{sub 2.36}Ru{sub 0.72}O{sub 12}. The factors that lead to the compositionally analogous Nb/Ru and Nb/Ti phases adopting different structures are discussed on themore » basis of the difference between d{sup 0} and non-d{sup 0} transition metal cations. - Graphical abstract: The ruthenium-containing B-cation deficient perovskite phases, Ba{sub 5}Nb{sub 3.33}Ru{sub 0.81}O{sub 15} and Ba{sub 3.16}La{sub 0.84}Nb{sub 2.36}Ru{sub 0.72}O{sub 12}, adopt 5-layer and 4-layer structures respectively, rather than the 6-layer and 5-layer cation-deficient structures adopted by the analogous titanium-containing phases Ba{sub 6}Nb{sub 4}TiO{sub 18} and LaBa{sub 4}Nb{sub 3}TiO{sub 15}. Display Omitted - Highlights: • B-cation deficient perovskite containing paramagnetic cations. • B-cation deficient structure determined by neutron powder diffraction. • Low ‘solubility’ of BaRuO{sub 3} in Ba{sub 5}Nb{sub 4}O{sub 15} leads to novel structure.« less

  2. SYNTHESIS AND Zn2+ ION CONDUCTION OF A PEROVSKITE (La, Zn)TiO3

    NASA Astrophysics Data System (ADS)

    Mashiko, W.; Katsumata, T.; Inaguma, Y.

    (La,Zn)TiO3 was synthesized by an ion exchange method using ZnCl2 molten salt. By a powder X-ray diffraction, it was confirmed that perovskite structure was retained after ion exchange. The composition of ion exchanged sample was determined to be La0.55(6)Li0.064(4)Zn0.13(1)Ti1.0(1)O2.97 by ICP analysis, and the homogeneous distribution of Zn in this sample was confirmed by the scanning electron microscope (SEM). The bulk and total conductivity of the sample at the room temperature was measured to be 6.9 × 10-7 S·cm-1, 1.7 × 10-7 S·cm-1, respectively. The mobile species was confirmed to be Zn2+ by the electrolysis at 500°C.

  3. Magnetic field tunable ac electrical transport of LaFeO3-wax nanocomposites

    NASA Astrophysics Data System (ADS)

    Roy, Supratim; Mandal, S. K.; Debnath, Rajesh; Nath, Debajyoti; Dey, P.

    2018-04-01

    Single phase perovskite LaFeO3 nanoparticles have been prepared through chemical pyrophoric reaction process. It is further grinded with paraffin wax of quantity 0.5 wt% of total composition to obtain an organic composite 99.5%LaFeO3-0.5%Wax. Studies of ac electrical properties viz. complex impedance, dielectric response, loss coefficient have been done in presence of external dc magnetic field, which reveals a good magnetoimpedance (˜221%) and a negative magnetodielectric (˜ 64%). The value of impedance, its real and imaginary part is observed to increase with dc field. The composite exhibits high dielectric constant (˜4760). The ac conductivity is found to decrease with applied field and increase with ac frequency.

  4. Unanticipated spin gap measured in the frustrated quasi-FCC d3 double perovskites La2 LiXO6 (X = Ru, Os)

    NASA Astrophysics Data System (ADS)

    Maharaj, Dalini D.; Sala, Gabriele; Marjerrison, Casey A.; Greedan, John; Gaulin, Bruce; Stone, Matthew

    There is much current interest in the influence of strong spin-orbit (SO) interactions on exotic ground state selection in new 4d and 5d magnets, particularly involving 4d5 Ir. Here we consider double perovskites of the form A2 BB'O6 which are based on heavy 4d or 5d magnetic ions, where the SO interaction is expected to be significant as it increases as ~Z4 . The double perovskite structure can accommodate a variety of magnetic ions on the B' site, providing a playground for systematic studies of the exotic ground states stabilized by strong SO coupling. Here, we report inelastic neutron scattering (INS) measurements conducted on the frustrated monoclinic magnets, La2LiXO6 (X = Ru, Os), wherein the magnetic moments decorate a quasi face-centered-cubic lattice. Our results show the development of a spin gap in the spin excitation spectrum of size ΔOs = 8 meV and ΔRu = 2.5meV concomitant with TN, which is unexpected for orbitally quenched d3 systems. We liken these results to INS results obtained for Ba2YXO6 and La2NaXO6, which were also shown to exhibit spin gaps that correlate with TN. We shall discuss trends observed in these three d3 double perovskite families which correlate strong SO coupling, spin gap and TN.

  5. Interplay of 3 d - and 5 d -sublattice magnetism in the double perovskite substitution series La2Zn1 -xCoxIrO6

    NASA Astrophysics Data System (ADS)

    Vogl, M.; Corredor, L. T.; Dey, T.; Morrow, R.; Scaravaggi, F.; Wolter, A. U. B.; Aswartham, S.; Wurmehl, S.; Büchner, B.

    2018-01-01

    We report on the interplay of 3 d - and 5 d -sublattice magnetism in polycrystalline samples of the double perovskite substitution series La2Zn1 -xCoxIrO6 . Powder x-ray diffraction reveals no major structural changes within the series. In magnetization measurements, a gradual shift of the transition temperature from TN ≈91 K for the Co parent compound to TN ≈8.7 K for the Zn parent compound is observed. The data on the Zn-rich members of the substitution series indicate that this is accompanied by changing roles of the 3 d sublattice of Co2 + and the strongly spin-orbit coupled 5 d -sublattice of Ir4 + with its jeff=1 /2 ground state, as a function of the Co/Zn ratio. Temperature-dependent specific-heat studies revealed a reduced magnetic entropy, pointing towards a large spin-orbit coupling and orbital contribution in the system.

  6. Dynamic properties of cluster glass in La0.25Ca0.75MnO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Huang, X. H.; Ding, J. F.; Jiang, Z. L.; Yin, Y. W.; Yu, Q. X.; Li, X. G.

    2009-10-01

    The dynamic magnetic properties of cluster glass in La0.25Ca0.75MnO3 nanoparticles with average particle size range from 40 to 1000 nm have been investigated by measuring the frequency and dc magnetic field (H) dependencies of the ac susceptibility. The frequency-dependent Tf, the freezing temperature of the ferromagnetic clusters determined by the peak in the real part of the ac susceptibility χ' versus T curve with H =0, is fit to a power law. The relaxation time constant τ0 decreases as the particle size increases from 40 to 350 nm, which indicates the decrease in the size of the clusters at the surface of the nanoparticle. The relationship between H and Tf(H) deviates from the De Almeida-Thouless-type phase boundary at relatively high fields for the samples with size range from 40 to 350 nm. Moreover, for the samples with particle sizes of 40 and 100 nm, τ0 increases with increasing H, which indicates the increasing cluster size and may be ascribed to the competition between the influence of H and the local anisotropy field in the shell spins. All these results may give rise to a new insight into the behaviors of the cluster glass state in the nanosized antiferromagnetic charge-ordered perovskite manganites.

  7. Structural and magnetic characterization of La{sub 0.8}Sr{sub 0.2}MnO{sub 3} nanoparticles prepared via a facile microwave-assisted method

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Moradi, J., E-mail: j_moradi@yahoo.com; Ghazi, M.E.; Ehsani, M.H., E-mail: mhe_ehsani@yahoo.com

    2014-07-01

    Nanoparticles of La{sub 0.8}Sr{sub 0.2}MnO{sub 3} (LSMO) with different particle sizes are synthesized by a very fast, inexpensive, reproducible, and environmentally friendly method: the microwave irradiation of the corresponding mixture of nitrates. The structural and magnetic properties of the samples are investigated by the X-Ray diffraction (XRD), Fourier transform infra-red (FT-IR) spectroscopy, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and magnetic (DC magnetization and AC susceptibility) measurements. The XRD study coupled with the Rietveld refinement show that all samples crystallize in a rhombohedral structure with the space group of R−3C. The FT-IR spectroscopy and FE-SEM images indicate formationmore » of the perovskite structure of LSMO. The DC magnetization measurements confirm the decrease in the particle size effects on the magnetic properties, e.g. reduction in the ferromagnetic (FM) moment and increase in the surface spin disorder. Magnetic dynamics of the samples studied by AC magnetic susceptibility shows that the magnetic behavior of the nanometer-sized samples is well-described by the Vogel-Fulcher and critical slowing down laws. Strong interaction between magnetic nanoparticles of LSMO was detected by fitting the experimental data with the mentioned models. - Graphical abstract: Temperature dependence of the magnetization M(T) was measured in the zero-field-cooling (ZFC) and field-cooling (FC) modes at the applied magnetic field of 100 Oe for the La{sub 0.8}Sr{sub 0.2}MnO{sub 3} with different size prepared via a facile microwave-assisted method. - Highlights: • Nanoparticles of La{sub 0.8}Sr{sub 0.2}MnO{sub 3} were synthesized by the microwave irradiation process. • The structural studies show that all samples crystallize in a rhombohedral structure with space group of R−3C. • The DC magnetic studies confirm tuning of the magnetic properties due to the particle size effects.

  8. Unraveling the Chemical Nature of the 3D "Hollow" Hybrid Halide Perovskites.

    PubMed

    Spanopoulos, Ioannis; Ke, Weijun; Stoumpos, Constantinos C; Schueller, Emily C; Kontsevoi, Oleg Y; Seshadri, Ram; Kanatzidis, Mercouri G

    2018-05-02

    The newly introduced class of 3D halide perovskites, termed "hollow" perovskites, has been recently demonstrated as light absorbing semiconductor materials for fabricating lead-free perovskite solar cells with enhanced efficiency and superior stability. Hollow perovskites derive from three-dimensional (3D) AMX 3 perovskites ( A = methylammonium (MA), formamidinium (FA); M = Sn, Pb; X = Cl, Br, I), where small molecules such as ethylenediammonium cations ( en) can be incorporated as the dication without altering the structure dimensionality. We present in this work the inherent structural properties of the hollow perovskites and expand this class of materials to the Pb-based analogues. Through a combination of physical and spectroscopic methods (XRD, gas pycnometry, 1 H NMR, TGA, SEM/EDX), we have assigned the general formula (A) 1- x ( en) x (M) 1-0.7 x (X) 3-0.4 x to the hollow perovskites. The incorporation of en in the 3D perovskite structure leads to massive M and X vacancies in the 3D [ MX 3 ] framework, thus the term hollow. The resulting materials are semiconductors with significantly blue-shifted direct band gaps from 1.25 to 1.51 eV for Sn-based perovskites and from 1.53 to 2.1 eV for the Pb-based analogues. The increased structural disorder and hollow nature were validated by single crystal X-ray diffraction analysis as well as pair distribution function (PDF) analysis. Density functional theory (DFT) calculations support the experimental trends and suggest that the observed widening of the band gap is attributed to the massive M and X vacancies, which create a less connected 3D hollow structure. The resulting materials have superior air stability, where in the case of Sn-based hollow perovskites it exceeds two orders of temporal magnitude compared to the conventional full perovskites of MASnI 3 and FASnI 3 . The hollow perovskite compounds pose as a new platform of promising light absorbers that can be utilized in single junction or tandem solar cells.

  9. Effect of Fe3O4 addition on dielectric properties of LaFeO3 nano-crystalline materials synthesized by sol-gel method

    NASA Astrophysics Data System (ADS)

    Laysandra, H.; Triyono, D.

    2017-04-01

    Dielectric properties of nano-crystalline material LaFeO3.xFe3O4 with x = 0, 0.1, 0.2, 0.3, and 0.4 at.% have been studied by impedance spectroscopy method. LaFeO3 was synthesized by sol-gel method resulting nano-particle. Then, it was mixed with Fe3O4 powder. The mixture powder was pressed to form pellet and then sintered at 1300°C for 1 h to form nano-crystalline of LaFeO3.xFe3O4. X-ray diffraction characterization at room temperature for all samples show two phases i.e. perovskite LaFeO3 (orthorhombic) as a main phase and Fe3O4 (cubic) as second phase. It is found that the crystallite size of main phase increases with addition of Fe3O4 until 0.3 at.%. The electrical properties as a function of temperature (300-500 K) and frequency (100 Hz - 1 MHz) are presented in Nyquist and Bode plots. It is observed that from equivalent circuit and their parameters, dielectrical properties are contributed by grain and grain boundary. The dielectric constant, ε‧ were calculated by parallel plate method and their values reach up to 107 exhibiting typical colossal dielectric constant (CDC) material like behavior.

  10. Size effects on the magnetic properties of LaCoO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Wei, Q.; Zhang, T.; Wang, X. P.; Fang, Q. F.

    2012-02-01

    Magnetic properties of LaCoO3 nanoparticles prepared by a sol-gel method with average particle size (D) ranging from 20 to 500 nm are investigated. All samples exhibit obvious ferromagnetic transition. With decreasing particle size from 500 to 120 nm, the transition temperature Tc decreases slightly from 85 K, however Tc decreases dramatically when D ≤ 85 nm. Low-field magnetic moment at 10 K decreases with reduction of particle size, while the high-field magnetization exhibits a converse behavior, which is different with previous reports. The coercivity Hc decreases as the particle size is reduced. It is different with other nanosystems that no exchange bias effect is observed in nanosized LaCoO3 particles. These interesting results arise from the surface effect induced by sized effect and the structure change in LaCoO3 nanoparticles.

  11. High performance of mixed halide perovskite solar cells: Role of halogen atom and plasmonic nanoparticles on the ideal current density of cell

    NASA Astrophysics Data System (ADS)

    Mohebpour, Mohammad Ali; Saffari, Mohaddeseh; Soleimani, Hamid Rahimpour; Tagani, Meysam Bagheri

    2018-03-01

    To be able to increase the efficiency of perovskite solar cells which is one of the most substantial challenges ahead in photovoltaic industry, the structural and optical properties of perovskite CH3NH3PbI3-xBrx for values x = 1-3 have been studied employing density functional theory (DFT). Using the optical constants extracted from DFT calculations, the amount of light reflectance and ideal current density of a simulated single-junction perovskite solar cell have been investigated. The results of DFT calculations indicate that adding halogen bromide to CH3NH3PbI3 compound causes the relocation of energy bands in band structure which its consequence is increasing the bandgap. In addition, the effect of increasing Br in this structure can be seen as a reduction in lattice constant, refractive index, extinction and absorption coefficient. As well, results of the simulation suggest a significant current density enhancement as much as 22% can be achieved by an optimized array of Platinum nanoparticles that is remarkable. This plan is able to be a prelude for accomplishment of solar cells with higher energy conversion efficiency.

  12. Low-Frequency Dielectric Responses of Barium Strontium Titanate Thin Films with Conducting Perovskite LaNiO3 Electrode

    NASA Astrophysics Data System (ADS)

    Lee, Su-Jae; Moon, Seung-Eon; Ryu, Han-Cheol; Kwak, Min-Hwan; Kim, Young-Tae

    2002-07-01

    Highly (h00)-oriented (Ba,Sr)TiO3 [BST] thin films were deposited by pulsed laser depositi on on the perovskite LaNiO3 metallic oxide layer as a bottom electrode. The LaNiO3 films were deposited on SiO2/Si substrates by the rf-magnetron sputtering method. The crystal line phases of the BST film were characterized by X-ray θ-2θ, ω-rocking curve and Φ-scan diffraction measurements. The surface microstructure observed by scanning electron mi croscopy was very dense and smooth. The low-frequency dielectric responses of the BST films grown at various substrate temperatures were measured as a function of frequency in the frequency range from 0.1 Hz to 10 MHz. The BST films have the dielectric constant of 265 at 1 kHz and showed multiple dielectric relaxations in the measured frequency region. The origins of these low-frequency dielectric relaxations are attributed to ionized space charge carriers such as the oxygen vacancies and defects in the BST film, the interfacial polarization in the grain boundary region and the electrode polarization. We also studied the capacitance-voltage characteristics of BST films.

  13. Pressure Induced Iron Spin Crossover in MgGeO3 Perovskite and Post-perovskite

    NASA Astrophysics Data System (ADS)

    Wentzcovitch, R. M.; Shukla, G.; Topsakal, M.

    2014-12-01

    MgGeO3-perovskite is known to be a low-pressure analog of MgSiO3-perovskite in many respects, but especially in regard to the post-perovskite transition. As such, investigation of spin state changes in Fe-bearing MgGeO3 might help to clarify some aspects of this type of state change in Fe-bearing MgSiO3. Using DFT+U calculations, we have investigated pressure induced state changes in Fe-bearing MgGeO3 perovskite and post-perovskite. Owing to the relatively larger atomic size of germanium compared to silicon, germanate phases have larger unit cell volume and interatomic distances than equivalent silicate phases at same pressures. As a result, all pressure induced state changes in iron occur at higher pressures in germanate phases than in the silicate ones, be it a spin state change or position change of (ferrous) iron in the perovskite cage. The effect of iron in the post-perovskite transition is also investigated.

  14. Influence of crystallite size on the magnetic and heat generation properties of La0.77Sr0.23MnO3 nanoparticles for hyperthermia applications

    NASA Astrophysics Data System (ADS)

    Das, Harinarayan; Inukai, Akihiro; Debnath, Nipa; Kawaguchi, Takahiko; Sakamoto, Naonori; Hoque, Sheikh Manjura; Aono, Hiromichi; Shinozaki, Kazuo; Suzuki, Hisao; Wakiya, Naoki

    2018-01-01

    In this paper, we report a detailed study of magnetic properties and AC magnetic heat generation characteristics of La0.77Sr0.23MnO3 (LSMO) nanoparticles to investigate appropriate crystallite size with a view to the proper application of self-controlled magnetic hyperthermia treatments of cancer. A series of nanocrystalline LSMO manganite was synthesized through the chemical route called as "polymerized complex method" and then subsequently annealed at the different temperature from 600 to 1400 °C to obtain various crystallite size. Phase formation and crystal structure of the prepared powder were determined by the powder X-ray diffraction (XRD) using Rietveld analysis. The XRD patterns reveal that all powder samples are a single phase rhombohedral perovskite-like structure with R 3 bar c space group. The mean crystallite size of prepared particles varied from 19 to 243.8 nm with the increase of the annealing temperature starting from 600 to 1400 °C. The field emission scanning electron microscopy (FE-SEM) analysis shows the surface morphology with a strong agglomeration of fine nanoparticles. The Magnetic study reveals that these nanoparticles exhibit ferromagnetic nature with different value of magnetization, coercivity, Curie temperature which is strongly dependent on their crystallite size. The maximum saturation temperature (TS = 66 °C) under AC magnetic field (H = 1.77 kA/m, f = 370 kHz) was found for the crystallite size of 39.5 nm due to its pure single domain phase. Such LSMO nanoparticles, having the higher heating rate, can be used in magnetically induced hyperthermia cancer treatment.

  15. Oxide perovskite crystals for HTSC film substrates microwave applications

    NASA Technical Reports Server (NTRS)

    Bhalla, A. S.; Guo, Ruyan

    1995-01-01

    The research focused upon generating new substrate materials for the deposition of superconducting yttrium barium cuprate (YBCO) has yielded several new hosts in complex perovskites, modified perovskites, and other structure families. New substrate candidates such as Sr(Al(1/2)Ta(1/2))O3 and Sr(Al(1/2)Nb(1/2))O3, Ba(Mg(1/3)Ta(2/3))O3 in complex oxide perovskite structure family and their solid solutions with ternary perovskite LaAlO3 and NdGaO3 are reported. Conventional ceramic processing techniques were used to fabricate dense ceramic samples. A laser heated molten zone growth system was utilized for the test-growth of these candidate materials in single crystal fiber form to determine crystallographic structure, melting point, thermal, and dielectric properties as well as to make positive identification of twin free systems. Some of those candidate materials present an excellent combination of properties suitable for microwave HTSC substrate applications.

  16. μ+SR Study on Layered Chromium Perovskites: Srn+1CrnO3n+1 (n = 1-3)

    NASA Astrophysics Data System (ADS)

    Nozaki, Hiroshi; Sakurai, Hiroya; Umegaki, Izumi; Ansaldo, Eduardo J.; Morris, Gerald D.; Hitti, Bassam; Arseneau, Donald J.; Andreica, Daniel; Amato, Alex; Månsson, Martin; Sugiyama, Jun

    The magnetic nature of layered chromium perovskites, Srn+1CrnO3n+1 (n = 1-3) was studied by μ+SR using powder samples prepared by a high pressure synthesis technique. According to the weak transverse field measurements, each sample entered a magnetically ordered state below 110, 200, and 90 K for the n = 1, 2, and 3 samples, respectively. Zero field (ZF) spectra below the transition temperature exhibited a clear oscillation due to the formation of quasi-static magnetic order. The Fourier transform frequency-spectrum for the ZF time-spectrum indicated the existence of the multiple oscillation components. The frequencies for the multiple oscillatory signals showed a complex temperature dependence, implying the occurrence of structural change/transitions below TN.

  17. Synthesis and Thermodynamic Stability of Ba2B‧B″O6 and Ba3B*B″2O9 Perovskites Using the Molten Salt Method

    NASA Astrophysics Data System (ADS)

    Meng, Wei; Virkar, Anil V.

    1999-12-01

    A number of mixed perovskites of the types Ba2B‧B″O6 (BaB‧1/2B″1/2O3) and Ba3B*B″2O9 (BaB*1/3B″2/3O3) where B‧=Gd, La, Nd, Sm, or Y; B″=Nb and B*=Ca were synthesized by a conventional calcination process, as well as by the molten salt method. The former consists of calcining appropriate mixtures of oxide or carbonate precursors in air at elevated temperatures (∼1250°C). The latter method consists of adding appropriate mixtures of oxide or carbonate precursors to a molten salt bath at relatively low temperatures (on the order of 300 to 500°C) so that the requisite compound is formed by dissolution-reprecipitation. X-ray diffraction confirmed the formation of a single-phase perovskite in each case with calcination at 1250°C. In a molten salt bath, however, all except Ba2LaNbO6 and Ba2NdNbO6 formed the perovskite structure. On the contrary, powders of Ba2LaNbO6 and Ba2NdNbO6 formed by a high-temperature calcination process readily decomposed when introduced into the molten salt bath. The formation of the requisite perovskite at a temperature as low as 350°C in a molten salt suggests that: (a) The perovskite is stable at 350°C. (b) The molten salt exhibits sufficient precursor solubility for the dissolution-reprecipitation process to occur in a reasonable time. Similarly, the decomposition of Ba2LaNbO6 and Ba2NdNbO6 in a molten salt bath shows that these materials are thermodynamically unstable at the temperature of the molten salt bath.

  18. Full coverage of perovskite layer onto ZnO nanorods via a modified sequential two-step deposition method for efficiency enhancement in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Ruankham, Pipat; Wongratanaphisan, Duangmanee; Gardchareon, Atcharawon; Phadungdhitidhada, Surachet; Choopun, Supab; Sagawa, Takashi

    2017-07-01

    Full coverage of perovskite layer onto ZnO nanorod substrates with less pinholes is crucial for achieving high-efficiency perovskite solar cells. In this work, a two-step sequential deposition method is modified to achieve an appropriate property of perovskite (MAPbI3) film. Surface treatment of perovskite layer and its precursor have been systematically performed and their morphologies have been investigated. By pre-wetting of lead iodide (PbI2) and letting it dry before reacting with methylammonium iodide (MAI) provide better coverage of perovskite film onto ZnO nanorod substrate than one without any treatment. An additional MAI deposition followed with toluene drop-casting technique on the perovskite film is also found to increase the coverage and enhance the transformation of PbI2 to MAPbI3. These lead to longer charge carrier lifetime, resulting in an enhanced power conversion efficiency (PCE) from 1.21% to 3.05%. The modified method could been applied to a complex ZnO nanorods/TiO2 nanoparticles substrate. The enhancement in PCE to 3.41% is observed. These imply that our introduced method provides a simple way to obtain the full coverage and better transformation to MAPbI3 phase for enhancement in performances of perovskite solar cells.

  19. Pressure-induced metallization of the halide perovskite (CH 3NH 3)PbI 3

    DOE PAGES

    Jaffe, Adam; Lin, Yu; Mao, Wendy L.; ...

    2017-03-14

    We report the metallization of the hybrid perovskite semiconductor (MA)PbI 3 (MA = CH 3NH 3 +) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI 3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study ofmore » metallic properties in oxide perovskites has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Lastly, pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.« less

  20. Pressure-induced metallization of the halide perovskite (CH 3NH 3)PbI 3

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jaffe, Adam; Lin, Yu; Mao, Wendy L.

    We report the metallization of the hybrid perovskite semiconductor (MA)PbI 3 (MA = CH 3NH 3 +) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI 3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study ofmore » metallic properties in oxide perovskites has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Lastly, pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.« less

  1. Promotion of Oxygen Reduction by Exsolved Silver Nanoparticles on a Perovskite Scaffold for Low-Temperature Solid Oxide Fuel Cells.

    PubMed

    Zhu, Yinlong; Zhou, Wei; Ran, Ran; Chen, Yubo; Shao, Zongping; Liu, Meilin

    2016-01-13

    Solid oxide fuel cells (SOFCs) have potential to be the cleanest and most efficient electrochemical energy conversion devices with excellent fuel flexibility. To make SOFC systems more durable and economically competitive, however, the operation temperature must be significantly reduced, which depends sensitively on the development of highly active electrocatalysts for oxygen reduction reaction (ORR) at low temperatures. Here we report a novel silver nanoparticle-decorated perovskite oxide, prepared via a facile exsolution process from a Sr0.95Ag0.05Nb0.1Co0.9O3-δ (SANC) perovskite precursor, as a highly active and robust ORR electrocatalyst for low-temperature SOFCs. The exsolved Sr0.95Ag0.05Nb0.1Co0.9O3-δ (denoted as e-SANC) electrode is very active for ORR, achieving a very low area specific resistance (∼0.214 Ω cm(2) at 500 °C). An anode-supported cell with the new heterostructured cathode demonstrates very high peak power density (1116 mW cm(-2) at 500 °C) and stable operation for 140 h at a current density of 625 mA cm(-2). The superior ORR activity and stability are attributed to the fast oxygen surface exchange kinetics and the firm adhesion of the Ag nanoparticles to the Sr0.95Nb0.1Co0.9O3-δ (SNC0.95) support. Moreover, the e-SANC cathode displays improved tolerance to CO2. These unique features make the new heterostructured material a highly promising cathode for low-temperature SOFCs.

  2. In situ dynamic observations of perovskite crystallisation and microstructure evolution intermediated from [PbI6]4- cage nanoparticles

    NASA Astrophysics Data System (ADS)

    Hu, Qin; Zhao, Lichen; Wu, Jiang; Gao, Ke; Luo, Deying; Jiang, Yufeng; Zhang, Ziyi; Zhu, Chenhui; Schaible, Eric; Hexemer, Alexander; Wang, Cheng; Liu, Yi; Zhang, Wei; Grätzel, Michael; Liu, Feng; Russell, Thomas P.; Zhu, Rui; Gong, Qihuang

    2017-06-01

    Hybrid lead halide perovskites have emerged as high-performance photovoltaic materials with their extraordinary optoelectronic properties. In particular, the remarkable device efficiency is strongly influenced by the perovskite crystallinity and the film morphology. Here, we investigate the perovskites crystallisation kinetics and growth mechanism in real time from liquid precursor continually to the final uniform film. We utilize some advanced in situ characterisation techniques including synchrotron-based grazing incident X-ray diffraction to observe crystal structure and chemical transition of perovskites. The nano-assemble model from perovskite intermediated [PbI6]4- cage nanoparticles to bulk polycrystals is proposed to understand perovskites formation at a molecular- or nano-level. A crystallisation-depletion mechanism is developed to elucidate the periodic crystallisation and the kinetically trapped morphology at a mesoscopic level. Based on these in situ dynamics studies, the whole process of the perovskites formation and transformation from the molecular to the microstructure over relevant temperature and time scales is successfully demonstrated.

  3. Tunable thermodynamic activity of LaxSr1–xMnyAl1–yO3–δ (0 ≤ x ≤ 1, 0 ≤ y ≤ 1) perovskites for solar thermochemical fuel synthesis† †Electronic supplementary information (ESI) available: Computational details, comprehensive XRD analyses, oxygen nonstoichiometry measurements and thermodynamic characterization of the perovskites. See DOI: 10.1039/c6ta06644e Click here for additional data file.

    PubMed Central

    Ezbiri, M.; Takacs, M.; Theiler, D.; Steinfeld, A.

    2017-01-01

    Nonstoichiometric metal oxides with variable valence are attractive redox materials for thermochemical and electrochemical fuel processing. To guide the design of advanced redox materials for solar-driven splitting of CO2 and/or H2O to produce CO and/or H2 (syngas), we investigate the equilibrium thermodynamics of the LaxSr1–xMnyAl1–yO3–δ perovskite family (0 ≤ x ≤ 1, 0 ≤ y ≤ 1) and La0.6Ca0.4Mn0.8Al0.2O3–δ, and compare them to those of CeO2 as the baseline. Oxygen nonstoichiometry measurements from 1573 to 1773 K and from 0.206 to 180 mbar O2 show a tunable reduction extent, increasing with increasing Sr content. Maximal nonstoichiometry of 0.32 is established with La0.2Sr0.8Mn0.8Al0.2O3–δ at 1773 K and 2.37 mbar O2. As a trend, we find that oxygen capacities are most sensitive to the A-cation composition. Partial molar enthalpy, entropy and Gibbs free energy changes for oxide reduction are extracted from the experimental data using defect models for Mn4+/Mn3+ and Mn3+/Mn2+ redox couples. We find that perovskites exhibit typically decreasing enthalpy changes with increasing nonstoichiometries. This desirable characteristic is most pronounced by La0.6Sr0.4Mn0.4Al0.6O3–δ, rendering it attractive for CO2 and H2O splitting. Generally, perovskites show lower enthalpy and entropy changes than ceria, resulting in more favorable reduction but less favorable oxidation equilibria. The energy penalties due to larger temperature swings and excess oxidants are discussed in particular. Using electronic structure theory, we conclude with a practical methodology estimating thermodynamic activity to rationally design perovskites with variable stoichiometry and valence. PMID:28580143

  4. Micromagnetic simulation study of a disordered model for one-dimensional granular perovskite manganite oxide nanostructures

    NASA Astrophysics Data System (ADS)

    Longone, P.; Romá, F.

    2018-06-01

    Chemical techniques are an efficient method to synthesize one-dimensional perovskite manganite oxide nanostructures with a granular morphology, that is, formed by arrays of monodomain magnetic nanoparticles. Integrating the stochastic Landau-Lifshitz-Gilbert equation, we simulate the dynamics of a simple disordered model for such materials that only takes into account the morphological characteristics of their nanograins. We show that it is possible to describe reasonably well experimental hysteresis loops reported in the literature for single La0.67Ca0.33MnO3 nanotubes and powders of these nanostructures, simulating small systems consisting of only 100 nanoparticles.

  5. Frustration by competing interactions in the highly-distorted double perovskites La2NaRuO6 and La2NaOsO6

    NASA Astrophysics Data System (ADS)

    Aczel, A. A.; Bugaris, D. E.; Li, L.; Yan, J.-Q.; de La Cruz, C.; Zur Loye, H.-C.; Nagler, S. E.

    2013-03-01

    The usual classical behavior of S = 3/2, B-site ordered double perovskites results in simple, commensurate magnetic ground states. In contrast, heat capacity and neutron powder diffraction measurements for the S = 3/2 systems La2NaB'O6 (B' = Ru, Os) reveal an incommensurate magnetic ground state for La2NaRuO6 and a drastically suppressed ordered moment for La2NaOsO6. This behavior is attributed to the large monoclinic structural distortions of these double perovskites. The distortions have the effect of weakening the nearest neighbor superexchange interactions, presumably to an energy scale that is comparable to the next nearest neighbor superexchange. The exotic ground states in these materials can then arise from a competition between these two types of antiferromagnetic interactions, providing a novel mechanism for achieving frustration in the double perovskite family. Work at ORNL is supported by the Division of Scientific User Facilities and the Materials Science and Engineering Division, DOE Basic Energy Sciences. Work at the University of South Carolina is supported by the Heterogeneous Functional Materials Research Center, funded by DOE under award number de-sc0001061.

  6. Observation of relaxor ferroelectricity and multiferroic behaviour in nanoparticles of the ferromagnetic semiconductor La2NiMnO6

    NASA Astrophysics Data System (ADS)

    Masud, Md G.; Ghosh, Arijit; Sannigrahi, J.; Chaudhuri, B. K.

    2012-07-01

    We report a diffuse phase transition (extending over a finite temperature range of ˜50 K) in sol-gel derived nanoparticles (˜25 nm) of the ferromagnetic double perovskite La2NiMnO6. The macroscopic polarization (P-E hysteresis loop), validity of the Vogel-Fulcher relation and high dielectric permittivity (˜9 × 102) confirm relaxor ferroelectric phenomena in these magnetic nanoparticles. Compared to the corresponding bulk sample, appreciably large enhancement of the magnetocapacitive effect (MC ˜ 30%) is observed even under low magnetic field (0.5 T) around the broad relaxor dielectric peak temperature (˜220 K), which is close to the ferromagnetic transition temperature (θf ˜ 196 K). All of these features establish the multiferroic character of the La2NiMnO6 nanoparticles. The inhomogeneities arising from chemical and valence mixing in the present La2NiMnO6 nanoparticles and the inter-site, Ni/Mn-site disorder along with surface disorder of the individual nanoparticles resulting in local polar regions are attributed to the observed dielectric behaviour of the nanoparticles. The wave vector dependent spin-pair correlation is considered to be the plausible cause of the colossal magnetocapacitive response near the transition temperature. High permittivity and large magnetocapacitive properties make these ferromagnetic La2NiMnO6 nanoparticles technologically important.

  7. Single-Crystal Thin Films of Cesium Lead Bromide Perovskite Epitaxially Grown on Metal Oxide Perovskite (SrTiO 3)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chen, Jie; Morrow, Darien J.; Fu, Yongping

    High-quality metal halide perovskite single crystals have low defect densities and excellent photophysical properties, yet thin films are the most sought after material geometry for optoelectronic devices. Perovskite single-crystal thin films (SCTFs) would be highly desirable for high-performance devices, but their growth remains challenging, particularly for inorganic metal halide perovskites. Herein, we report the facile vapor-phase epitaxial growth of cesium lead bromide perovskite (CsPbBr 3) continuous SCTFs with controllable micrometer thickness, as well as nanoplate arrays, on traditional oxide perovskite SrTiO 3(100) substrates. Heteroepitaxial single-crystal growth is enabled by the serendipitous incommensurate lattice match between these two perovskites, and overcomingmore » the limitation of island-forming Volmer–Weber crystal growth is critical for growing large-area continuous thin films. Time-resolved photoluminescence, transient reflection spectroscopy, and electrical transport measurements show that the CsPbBr 3 epitaxial thin film has a slow charge carrier recombination rate, low surface recombination velocity (10 4 cm s –1), and low defect density of 10 12 cm –3, which are comparable to those of CsPbBr 3 single crystals. This work suggests a general approach using oxide perovskites as substrates for heteroepitaxial growth of halide perovskites. Furthermore, the high-quality halide perovskite SCTFs epitaxially integrated with multifunctional oxide perovskites could open up opportunities for a variety of high-performance optoelectronics devices.« less

  8. Single-Crystal Thin Films of Cesium Lead Bromide Perovskite Epitaxially Grown on Metal Oxide Perovskite (SrTiO 3)

    DOE PAGES

    Chen, Jie; Morrow, Darien J.; Fu, Yongping; ...

    2017-09-05

    High-quality metal halide perovskite single crystals have low defect densities and excellent photophysical properties, yet thin films are the most sought after material geometry for optoelectronic devices. Perovskite single-crystal thin films (SCTFs) would be highly desirable for high-performance devices, but their growth remains challenging, particularly for inorganic metal halide perovskites. Herein, we report the facile vapor-phase epitaxial growth of cesium lead bromide perovskite (CsPbBr 3) continuous SCTFs with controllable micrometer thickness, as well as nanoplate arrays, on traditional oxide perovskite SrTiO 3(100) substrates. Heteroepitaxial single-crystal growth is enabled by the serendipitous incommensurate lattice match between these two perovskites, and overcomingmore » the limitation of island-forming Volmer–Weber crystal growth is critical for growing large-area continuous thin films. Time-resolved photoluminescence, transient reflection spectroscopy, and electrical transport measurements show that the CsPbBr 3 epitaxial thin film has a slow charge carrier recombination rate, low surface recombination velocity (10 4 cm s –1), and low defect density of 10 12 cm –3, which are comparable to those of CsPbBr 3 single crystals. This work suggests a general approach using oxide perovskites as substrates for heteroepitaxial growth of halide perovskites. Furthermore, the high-quality halide perovskite SCTFs epitaxially integrated with multifunctional oxide perovskites could open up opportunities for a variety of high-performance optoelectronics devices.« less

  9. Synthesis of LaMnO3 in molten chlorides: effect of preparation conditions.

    PubMed

    Vradman, Leonid; Zana, Jonatan; Kirschner, Alon; Herskowitz, Moti

    2013-07-14

    LaMnO3 perovskite was successfully synthesized in molten chlorides. In order to explore the effect of the molten salt type, NaCl-KCl and LiCl-KCl eutectic mixtures were employed as a liquid medium for the perovskite formation process. The synthesis included heating the La-nitrate, Mn-nitrate and chlorides mixture to above the melting point of the corresponding chlorides. This procedure yielded a LaMnO3 phase integrated in the fused chloride matrix. Washing with water removed the salts completely, yielding pure LaMnO3 perovskite crystals. The synthesis without molten salt at 800 °C yielded several by-products in addition to the LaMnO3 phase, while with LiCl-KCl the pure perovskite phase was obtained at temperatures as low as 600 °C. Variation of temperature in the range 600-800 °C for LiCl-KCl and 700-800 °C for NaCl-KCl had no significant effect either on the morphology or on the particle size of the product. On the other hand, the effect of the molten salt type on the morphology and size of perovskite particles was remarkable. The synthesis in NaCl-KCl resulted in sub-micron LaMnO3 particles with shapes that range from truncated hexahedrons to spheres, while in LiCl-KCl mostly cubic particles of up to 2-microns were obtained. The effect of the molten salt type on LaMnO3 perovskite formation is explained based on the nucleation and crystal growth model and difference in the melting point of eutectic mixtures.

  10. First-principles study on the electronic, optical and thermodynamic properties of ABO 3 (A = La,Sr, B = Fe,Co) perovskites

    DOE PAGES

    Jia, Ting; Zeng, Zhi; Lin, H. Q.; ...

    2017-08-08

    The electronic, optical and thermodynamic properties of ABO 3 (A = La,Sr, B = Fe,Co) perovskites are investigated using first-principles calculations. The obtained results indicate that SrCoO 3 and SrFeO 3 are metals, while LaCoO 3 and LaFeO 3 are insulators and all of them exhibit strong hybridization of the Fe/Co-3d and O-2p orbitals. By correlating the energy band structures with the peaks of the imaginary part of the dielectric function, we obtained the origin of each electron excitation to provide information about the active bands for the corresponding optical transitions observed in the experiment. Moreover, the Debye temperatures θmore » D obtained from the phonon frequencies are comparable to the available data. In conclusion, the thermodynamic properties of the Helmholtz free energy F, entropy S, and constant-volume heat capacity C v are investigated based on the phonon spectra.« less

  11. Moessbauer spectroscopy of Mg(0.9)Fe(0.1)SiO3 perovskite

    NASA Technical Reports Server (NTRS)

    Jeanloz, Raymond; O'Neill, Bridget; Pasternak, Moshe P.; Taylor, R. D.; Bohlen, Steven R.

    1992-01-01

    Ambient pressure Moessbauer spectra of Mg(0.9)Fe-57(0.1)SiO3 perovskite synthesized at pressure-temperature conditions of about 50 GPa and 1700 K show that the iron is entirely high-spin Fe(2+) and appears to be primarily located in the octahedral site within the crystal structure. We observe broad Moessbauer lines, suggesting a distribution of electric-field gradients caused by disorder associated with the Fe ions. Also, the perovskite exhibits magnetic ordering at temperatures lower than 5 K, implying that there is a magnetic contribution to the absolute ('third-law') entropy of this phase.

  12. Effect of La3+ substitution with Gd3+ on the resistive switching properties of La0.7Sr0.3MnO3 thin films

    NASA Astrophysics Data System (ADS)

    Lee, Hong-Sub; Park, Chang-Sun; Park, Hyung-Ho

    2014-05-01

    This study demonstrated that the resistive switching voltage of perovskite manganite material could be controlled by A-site cation substitution in "A" MnO3 perovskite manganite structure. A partial substitution of La3+ in La0.7Sr0.3MnO3 with smaller cation Gd3+ induced A-site vacancy of the largest Sr2+ cation with surface segregation of SrOy due to ionic size mismatch, and the induced vacancies reduced migration energy barrier. The operating voltage decreased from 3.5 V to 2.5 V due to a favorable condition for electrochemical migration and redox of oxygen ions. Moreover, surface-segregated SrOy was enhanced with Gd-substitution and the SrOy reduced Schottky-like barrier height and resistive switching ratio from the potential drop and screening effect. The relationship between A-site vacancy generation resulting in surface segregation of SrOy and resistive switching behavior was also investigated by energy resolved x-ray photoelectron spectroscopy, O 1s near edge x-ray absorption spectroscopy, and current voltage measurement.

  13. Ultrasonic vibration imposed on nanoparticle-based ZnO film improves the performance of the ensuing perovskite solar cell

    NASA Astrophysics Data System (ADS)

    Miao, Yihe; Du, Peng; Wang, Zhiyu; Chen, Qianli; Eslamian, Morteza

    2018-02-01

    This work focuses on the development of nearly annealing-free ZnO-based perovskite solar cells (PSCs), suitable for low-cost manufacturing of PSCs on flexible substrates. To this end, thin film of ZnO nanoparticles is employed as the electron transporting layer (ETL), because of its low-temperature solution-processability and high electron mobility. In order to remove the structural and surface defects, ultrasonic vibration is imposed on the substrate of the as-spun wet ZnO films for a short duration of 3 min. It is shown that the ultrasonic excitation bridges the ZnO nanoparticles (cold sintering), and brings about significant improvement in the ZnO film nanostructure and functionality. In addition, ethyl acetate (EA), as an emerging volatile anti-solvent, is employed to deposit the methylammonium (MA) lead halide perovskite thin film atop the ZnO ETL, in order to prepare perovskite layers that only need an annealing time of 30 s. The ZnO-based PSCs, with a simple structure and free of additional treatments, except for the ultrasonic vibration, exhibit a promising performance with a power conversion efficiency (PCE) of over 11%, 40% higher than that of the control device. The ultrasonic vibration treatment is facile, low-cost, environmentally friendly, and compatible with the scalable coating and printing techniques, such as spray and blade coating.

  14. General working principles of CH3NH3PbX3 perovskite solar cells.

    PubMed

    Gonzalez-Pedro, Victoria; Juarez-Perez, Emilio J; Arsyad, Waode-Sukmawati; Barea, Eva M; Fabregat-Santiago, Francisco; Mora-Sero, Ivan; Bisquert, Juan

    2014-02-12

    Organometal halide perovskite-based solar cells have recently realized large conversion efficiency over 15% showing great promise for a new large scale cost-competitive photovoltaic technology. Using impedance spectroscopy measurements we are able to separate the physical parameters of carrier transport and recombination in working devices of the two principal morphologies and compositions of perovskite solar cells, viz. compact thin films of CH3NH3PbI(3-x)Clx and CH3NH3PbI3 infiltrated on nanostructured TiO2. The results show nearly identical spectral characteristics indicating a unique photovoltaic operating mechanism that provides long diffusion lengths (1 μm). Carrier conductivity in both devices is closely matched, so that the most significant differences in performance are attributed to recombination rates. These results highlight the central role of the CH3NH3PbX3 semiconductor absorber in carrier collection and provide a new tool for improved optimization of perovskite solar cells. We report for the first time a measurement of the diffusion length in a nanostructured perovskite solar cell.

  15. In situ dynamic observations of perovskite crystallisation and microstructure evolution intermediated from [PbI6]4− cage nanoparticles

    PubMed Central

    Hu, Qin; Zhao, Lichen; Wu, Jiang; Gao, Ke; Luo, Deying; Jiang, Yufeng; Zhang, Ziyi; Zhu, Chenhui; Schaible, Eric; Hexemer, Alexander; Wang, Cheng; Liu, Yi; Zhang, Wei; Grätzel, Michael; Liu, Feng; Russell, Thomas P.; Zhu, Rui; Gong, Qihuang

    2017-01-01

    Hybrid lead halide perovskites have emerged as high-performance photovoltaic materials with their extraordinary optoelectronic properties. In particular, the remarkable device efficiency is strongly influenced by the perovskite crystallinity and the film morphology. Here, we investigate the perovskites crystallisation kinetics and growth mechanism in real time from liquid precursor continually to the final uniform film. We utilize some advanced in situ characterisation techniques including synchrotron-based grazing incident X-ray diffraction to observe crystal structure and chemical transition of perovskites. The nano-assemble model from perovskite intermediated [PbI6]4− cage nanoparticles to bulk polycrystals is proposed to understand perovskites formation at a molecular- or nano-level. A crystallisation-depletion mechanism is developed to elucidate the periodic crystallisation and the kinetically trapped morphology at a mesoscopic level. Based on these in situ dynamics studies, the whole process of the perovskites formation and transformation from the molecular to the microstructure over relevant temperature and time scales is successfully demonstrated. PMID:28635947

  16. In situ dynamic observations of perovskite crystallisation and microstructure evolution intermediated from [PbI 6] 4– cage nanoparticles

    DOE PAGES

    Hu, Qin; Zhao, Lichen; Wu, Jiang; ...

    2017-06-21

    Hybrid lead halide perovskites have emerged as high-performance photovoltaic materials with their extraordinary optoelectronic properties. In particular, the remarkable device efficiency is strongly influenced by the perovskite crystallinity and the film morphology. Here, we investigate the perovskites crystallisation kinetics and growth mechanism in real time from liquid precursor continually to the final uniform film. We utilize some advanced in situ characterisation techniques including synchrotron-based grazing incident X-ray diffraction to observe crystal structure and chemical transition of perovskites. The nano-assemble model from perovskite intermediated [PbI 6] 4– cage nanoparticles to bulk polycrystals is proposed to understand perovskites formation at a molecular-more » or nano-level. A crystallisation-depletion mechanism is developed to elucidate the periodic crystallisation and the kinetically trapped morphology at a mesoscopic level. Based on these in situ dynamics studies, the whole process of the perovskites formation and transformation from the molecular to the microstructure over relevant temperature and time scales is successfully demonstrated.« less

  17. Ba3Fe1.56Ir1.44O9: A Polar Semiconducting Triple Perovskite with Near Room Temperature Magnetic Ordering.

    PubMed

    Ferreira, Timothy; Carone, Darren; Huon, Amanda; Herklotz, Andreas; Stoian, Sebastian A; Heald, Steve M; Morrison, Gregory; Smith, Mark D; Loye, Hans-Conrad Zur

    2018-05-29

    The crystal chemistry and magnetic properties for two triple perovskites, Ba 3 Fe 1.56 Ir 1.44 O 9 and Ba 3 NiIr 2 O 9 , grown as large, highly faceted single crystals from a molten strontium carbonate flux, are reported. Unlike the idealized A 3 MM 2 'O 9 hexagonal symmetry characteristic of most triple perovskites, including Ba 3 NiIr 2 O 9, Ba 3 Fe 1.56 Ir 1.44 O 9 possesses significant site-disorder, resulting in a noncentrosymmetric polar structure with trigonal symmetry. The valence of iron and iridium in the heavily distorted Fe/Ir sites was determined to be Fe(III) and Ir(V) by X-ray absorption near edge spectroscopy (XANES). Density functional theory calculations were conducted to understand the effect of the trigonal distortion on the local Fe(III)O 6 electronic structure, and the spin state of iron was determined to be S = 5/2 by Mössbauer spectroscopy. Conductivity measurements indicate thermally activated semiconducting behavior in the trigonal perovskite. Magnetic properties were measured and near room temperature magnetic ordering (T N = 270 K) was observed for Ba 3 Fe 1.56 Ir 1.44 O 9 .

  18. Direct synthesis of ultrafine tetragonal BaTiO3 nanoparticles at room temperature

    PubMed Central

    2011-01-01

    A large quantity of ultrafine tetragonal barium titanate (BaTiO3) nanoparticles is directly synthesized at room temperature. The crystalline form and grain size are checked by both X-ray diffraction and transmission electron microscopy. The results revealed that the perovskite nanoparticles as fine as 7 nm have been synthesized. The phase transition of the as-prepared nanoparticles is investigated by the temperature-dependent Raman spectrum and shows the similar tendency to that of bulk BaTiO3 materials. It is confirmed that the nanoparticles have tetragonal phase at room temperature. PMID:21781339

  19. Perovskite LaTiO₃-Ag0.2 nanomaterials for nonenzymatic glucose sensor with high performance.

    PubMed

    Wang, Yin-zhu; Zhong, Hui; Li, Xiao-mo; Jia, Fei-fei; Shi, Yi-xiang; Zhang, Wei-guang; Cheng, Zhi-peng; Zhang, Li-li; Wang, Ji-kui

    2013-10-15

    In this paper, a nonenzymatic glucose biosensor based on perovskite LaTiO3-Ag0.2(LTA) modified electrode was presented. The morphology and the composition of the perovskite LaTiO₃-Ag0.2 nanomaterials were characterized by using scanning electron microscopy (SEM) and X-ray diffraction (XRD) respectively. The LaTiO₃-Ag0.2(LTA) composite was investigated by electrochemical characterization using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Under optimal conditions, CV and chronoamperometry (I-t) study revealed that, compared with the bare glassy carbon electrode (GCE), the modified electrode showed a remarkable increase in the efficiency of the electrocatalytic oxidation of glucose, starting at around +0.70 V (vs. Ag/AgCl). The prepared sensor exhibited a high sensitivity of 784.14 µAmM⁻¹ cm⁻², a low detection limit of 2.1×10⁻⁷ M and a wide linear range from 2.5 µM to 4 mM (R=0.9997). More importantly, the LTA modified electrode was also relatively insensitive to commonly interfering species such as ascorbic acid (AA), uric acid (UA), dopamine (DA) in high potential. Moreover, the nonenzymatic sensor was applied to the determination of glucose in human serum samples and the results were in good agreement with clinical data. Electrodes modified with perovskite nanomaterials are highly promising for nonenzymatic electrochemical detection of glucose because of their high sensitivity, fast response, excellent stability and good reproducibility. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. Topological magnetic phase in LaMnO3 (111) bilayer

    NASA Astrophysics Data System (ADS)

    Weng, Yakui; Huang, Xin; Yao, Yugui; Dong, Shuai

    2015-11-01

    Candidates for correlated topological insulators, originated from the spin-orbit coupling as well as the Hubbard-type correlation, are expected in the (111) bilayer of perovskite-structural transition-metal oxides. Based on the first-principles calculation and tight-binding model, the electronic structure of a LaMnO3 (111) bilayer sandwiched in LaScO3 barriers has been investigated. For the ideal undistorted perovskite structure, the Fermi energy of LaMnO3 (111) bilayer just stays at the Dirac point, rendering a semimetal (graphenelike) which is also a half metal [different from graphene or the previously studied LaNiO3 (111) bilayer]. The Dirac cone can be opened by the spin-orbit coupling, giving rise to nontrivial topological bands corresponding to the (quantized) anomalous Hall effect. For the realistic orthorhombic distorted lattice, the Dirac point moves with increasing Hubbard repulsion (or equivalent Jahn-Teller distortion). Finally, a Mott gap opens, establishing a phase boundary between the Mott insulator and topological magnetic insulator. Our calculation finds that the gap opened by spin-orbit coupling is much smaller in the orthorhombic distorted lattice (˜1.7 meV) than the undistorted one (˜11 meV). Therefore, to suppress the lattice distortion can be helpful to enhance the robustness of the topological phase in perovskite (111) bilayers.

  1. Creating Two-Dimensional Electron Gas in Polar/Polar Perovskite Oxide Heterostructures: First-Principles Characterization of LaAlO3/A(+)B(5+)O3.

    PubMed

    Wang, Yaqin; Tang, Wu; Cheng, Jianli; Behtash, Maziar; Yang, Kesong

    2016-06-01

    By using first-principles electronic structure calculations, we explored the possibility of producing two-dimensional electron gas (2DEG) at the polar/polar (LaO)(+)/(BO2)(+) interface in the LaAlO3/A(+)B(5+)O3 (A = Na and K, B = Nb and Ta) heterostructures (HS). Unlike the prototype polar/nonpolar LaAlO3/SrTiO3 HS system where there exists a least film thickness of four LaAlO3 unit cells to have an insulator-to-metal transition, we found that the polar/polar LaAlO3/A(+)B(5+)O3 HS systems are intrinsically conducting at their interfaces without an insulator-to-metal transition. The interfacial charge carrier densities of these polar/polar HS systems are on the order of 10(14) cm(-2), much larger than that of the LaAlO3/SrTiO3 system. This is mainly attributed to two donor layers, i.e., (LaO)(+) and (BO2)(+) (B = Nb and Ta), in the polar/polar LaAlO3/A(+)B(5+)O3 systems, while only one (LaO)(+) donor layer in the polar/nonpolar LaAlO3/SrTiO3 system. In addition, it is expected that, due to less localized Nb 4d and Ta 5d orbitals with respect to Ti 3d orbitals, these LaAlO3/A(+)B(5+)O3 HS systems can exhibit potentially higher electron mobility because of their smaller electron effective mass than that in the LaAlO3/SrTiO3 system. Our results demonstrate that the electronic reconstruction at the polar/polar interface could be an alternative way to produce superior 2DEG in the perovskite-oxide-based HS systems.

  2. Antiferroelectric Nature of CH3NH3PbI3-xClx Perovskite and Its Implication for Charge Separation in Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Sewvandi, Galhenage A.; Kodera, Kei; Ma, Hao; Nakanishi, Shunsuke; Feng, Qi

    2016-07-01

    Perovskite solar cells (PSCs) have been attracted scientific interest due to high performance. Some researchers have suggested anomalous behavior of PSCs to the polarizations due to the ion migration or ferroelectric behavior. Experimental results and theoretical calculations have suggested the possibility of ferroelectricity in organic-inorganic perovskite. However, still no studies have been concretely discarded the ferroelectric nature of perovskite absorbers in PSCs. Hysteresis of P-E (polarization-electric field) loops is an important evidence to confirm the ferroelectricity. In this study, P-E loop measurements, in-depth structural study, analyses of dielectric behavior and the phase transitions of CH3NH3PbI3-xClx perovskite were carried out and investigated. The results suggest that CH3NH3PbI3-xClx perovskite is in an antiferroelectric phase at room temperature. The antiferroelectric phase can be switched to ferroelectric phase by the poling treatment and exhibits ferroelectric-like hysteresis P-E loops and dielectric behavior around room temperature; namely, the perovskite can generate a ferroelectric polarization under PSCs operating conditions. Furthermore, we also discuss the implications of ferroelectric polarization on PSCs charge separation.

  3. Antiferroelectric Nature of CH3NH3PbI3-xClx Perovskite and Its Implication for Charge Separation in Perovskite Solar Cells.

    PubMed

    Sewvandi, Galhenage A; Kodera, Kei; Ma, Hao; Nakanishi, Shunsuke; Feng, Qi

    2016-07-29

    Perovskite solar cells (PSCs) have been attracted scientific interest due to high performance. Some researchers have suggested anomalous behavior of PSCs to the polarizations due to the ion migration or ferroelectric behavior. Experimental results and theoretical calculations have suggested the possibility of ferroelectricity in organic-inorganic perovskite. However, still no studies have been concretely discarded the ferroelectric nature of perovskite absorbers in PSCs. Hysteresis of P-E (polarization-electric field) loops is an important evidence to confirm the ferroelectricity. In this study, P-E loop measurements, in-depth structural study, analyses of dielectric behavior and the phase transitions of CH3NH3PbI3-xClx perovskite were carried out and investigated. The results suggest that CH3NH3PbI3-xClx perovskite is in an antiferroelectric phase at room temperature. The antiferroelectric phase can be switched to ferroelectric phase by the poling treatment and exhibits ferroelectric-like hysteresis P-E loops and dielectric behavior around room temperature; namely, the perovskite can generate a ferroelectric polarization under PSCs operating conditions. Furthermore, we also discuss the implications of ferroelectric polarization on PSCs charge separation.

  4. Detailed study of the magnetic behaviour at low scale in La2/3Sr1/3MnO3

    NASA Astrophysics Data System (ADS)

    Arango, I. C.; E Ordoñez, J.; Dominguez, C.; Arango, C.; E Gomez, M.

    2017-12-01

    The La2/3Sr1/3MnO3 (LSMO) with Curie temperature above room temperature is the leading compound of the manganite perovskite family. Therefore, the physical properties are desirable for practical applications as magnetic sensors. However, when the dimensions are reduced the ferromagnetic properties of material are weakened. In this research, we have grown La2/3Sr1/3MnO3/SrTiO3 thin films by sputtering DC at high oxygen pressure at 830°C. X-Ray Diffraction (XRD) analysis reveals that only (0 0 2) LSMO peak are present, indicating a textured growth. The samples morphology was characterized by Atomic Force Microscopy (AFM). Additionally, LSMO microwires were patterned by UV lithography; the devices are a well-defined channel with current and voltage leads enabling four points resistance measurements. Resistivity versus temperature curves displays typical manganite behaviour with metal-insulator transition ∼350K. We study the electric and magnetotransport properties in LSMO film and in wire channel and their dependence with size (width and length) for potential applications like magnetic sensors.

  5. Molecular Self-Assembly Fabrication and Carrier Dynamics of Stable and Efficient CH3 NH3 Pb(1-x) Snx I3 Perovskite Solar Cells.

    PubMed

    Fan, Jiandong; Liu, Chong; Li, Hongliang; Zhang, Cuiling; Li, Wenzhe; Mai, Yaohua

    2017-10-09

    The Sn-based perovskite solar cells (PSCs) provide the possibility of swapping the Pb element toward developing toxic-free PSCs. Here, we innovatively employed a molecular self-assembly approach to obtain a series CH 3 NH 3 Pb (1-x) Sn x I 3 (0≤x≤1) perovskite thin films with full coverage. The optimized planar CH 3 NH 3 Pb 0.75 Sn 0.25 I 3 PSC with inverted structure was consequently realized with a maximum power conversion efficiency (PCE) over 14 %, which displayed a stabilized power output (SPO) over 12 % within 200 s at 0.6 V forward bias. Afterward, we investigated the factors that limited the efficiency improvement of hybrid Sn-Pb PSCs, and analyzed the possible reason of the hysteresis effect occurred even in the inverted structure cell. Particularly, the oxidation of hybrid Sn-Pb perovskite thin film was demonstrated to be the main reason that limited its further efficiency improvement. The imbalance of charge transport was intensified, which was associated with the increased hole defect-state density and decreased electron defect-state density after Sn was introduced. This study helps tackle the intractable issue regarding the toxic Pb in perovskite devices and is a step forward toward realizing lead-free PSCs with high stability and efficiency. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Observation of relaxor ferroelectricity and multiferroic behaviour in nanoparticles of the ferromagnetic semiconductor La(2)NiMnO(6).

    PubMed

    Masud, Md G; Ghosh, Arijit; Sannigrahi, J; Chaudhuri, B K

    2012-07-25

    We report a diffuse phase transition (extending over a finite temperature range of ∼50 K) in sol-gel derived nanoparticles (∼25 nm) of the ferromagnetic double perovskite La(2)NiMnO(6). The macroscopic polarization (P-E hysteresis loop), validity of the Vogel-Fulcher relation and high dielectric permittivity (∼9 × 10(2)) confirm relaxor ferroelectric phenomena in these magnetic nanoparticles. Compared to the corresponding bulk sample, appreciably large enhancement of the magnetocapacitive effect (MC  ∼ 30%) is observed even under low magnetic field (0.5 T) around the broad relaxor dielectric peak temperature (∼220 K), which is close to the ferromagnetic transition temperature (θ(f) ∼ 196 K). All of these features establish the multiferroic character of the La(2)NiMnO(6) nanoparticles. The inhomogeneities arising from chemical and valence mixing in the present La(2)NiMnO(6) nanoparticles and the inter-site, Ni/Mn-site disorder along with surface disorder of the individual nanoparticles resulting in local polar regions are attributed to the observed dielectric behaviour of the nanoparticles. The wave vector dependent spin-pair correlation is considered to be the plausible cause of the colossal magnetocapacitive response near the transition temperature. High permittivity and large magnetocapacitive properties make these ferromagnetic La(2)NiMnO(6) nanoparticles technologically important.

  7. Pressure-Induced Metallization of the Halide Perovskite (CH 3 NH 3 )PbI 3

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jaffe, Adam; Lin, Yu; Mao, Wendy L.

    We report the metallization of the hybrid perovskite semiconductor (MA)PbI3 (MA = CH3NH3+) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study of metallic properties in oxide perovskitesmore » has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.« less

  8. Transition from the diamagnetic insulator to ferromagnetic metal in La1-xSrxCoO3

    NASA Astrophysics Data System (ADS)

    Knížek, Karel; Jirák, Zdeněk; Hejtmánek, Jiří; Novák, Pavel

    2010-05-01

    We have analyzed, using the theoretical GGA+U calculations, different configurations of spin states (low-spin, LS; intermediate-spin, IS and high-spin, HS Co) and proposed a model that accounts for magnetic and electric transport properties of perovskite cobaltites upon doping by charge carriers. In particular, it appears that the compositional transition from the diamagnetic LS phase of LaCoO3 to the ferromagnetic metallic IS phase in La1-xSrxCoO3 ( x>0.2) involves the same mechanisms as the high-temperature transition in pure LaCoO3. The process occurs gradually via a phase-separated state, where metallic IS domains stabilized through a charge transfer between Co and Co neighbors coexist with the Co poor regions in the LS ground state (or at higher temperatures, in mixed LS/HS state). This phase separation vanishes when doping in La1-xSrxCoO3 reaches x˜0.2, and a uniform IS phase, analogous to that in pure LaCoO3 in the high-temperature limit, is established.

  9. Ce3+-doped LaF3 nanoparticles: Wet-chemical synthesis and photo-physical characteristics "optical properties of LaF3:Ce nanomaterials"

    NASA Astrophysics Data System (ADS)

    Tabatabaee, F.; Sabbagh Alvani, A. A.; Sameie, H.; Moosakhani, S.; Salimi, R.; Taherian, M.

    2014-01-01

    The most effective process parameters were determined to synthesize spherical LaF3 nanoparticles with controllable size based on ethylenediaminetetraacetic acid (EDTA) via co-precipitation technique. Thermogravimetricdifferential thermal analysis, X-ray diffraction, scanning electron microscopy, dynamic light scattering and FT-IR spectroscopy were used to characterize the resulting powders. Detailed investigations revealed that the optimal LaF3 host nano-material was obtained when NH4F was used as a fluoride source in the presence of EDTA at pH = 5. Furthermore, photoluminescence spectra showed an intense double emission peak at 289 and 302 nm for cerium-doped LaF3 nanocrystals excited at 253 nm, which was assigned to the well-known 5d→4f (2F5/2 and 2F7/2) transitions of Ce3+ levels due to luminescence center mechanism. The experimental results indicate that the synthesized LaF3:0.05Ce powders with a band gap of 5.3 eV are promising phosphors for high density scintillators.

  10. Electrical properties of the LaLi y Co1 - y O3 - δ (0 ≤ y ≤ 0.10) oxides

    NASA Astrophysics Data System (ADS)

    Vecherskii, S. I.; Konopel'ko, M. A.; Batalov, N. N.; Antonov, B. D.; Reznitskikh, O. G.; Yaroslavtseva, T. V.

    2017-08-01

    The effect of the Li ion concentration on the phase composition, the electrical conductivity, and the thermoelectric power of the LaLi y Co1- y O3-δ (0 ≤ y ≤ 0.1) oxides synthesized by cocrystallization has been studied. It is found that the region of the perovskite-like solid solution LaLi y Co1- y O3-δ is no higher than y = 0.037. In the temperature range 300-1020 K, lithium alloying leads to an increase in the electrical conductivity and a decrease in the positive thermoelectric power of the single-phase samples compared to LaCoO3-δ. The results are discussed using the density of states model proposed by Senarus Rodriguez and Goodenough for LaCoO3-δ and La1- x Sr x CoO3-δ and using the Mott theory of noncrystalline substances.

  11. Organometal Halide Perovskite Solar Absorbers and Ferroelectric Nanocomposites for Harvesting Solar Energy

    NASA Astrophysics Data System (ADS)

    Hettiarachchi, Chaminda Lakmal

    Organometal halide perovskite absorbers such as methylammonium lead iodide chloride (CH3NH3PbI3-xClx), have emerged as an exciting new material family for photovoltaics due to its appealing features that include suitable direct bandgap with intense light absorbance, band gap tunability, ultra-fast charge carrier generation, slow electron-hole recombination rates, long electron and hole diffusion lengths, microsecond-long balanced carrier mobilities, and ambipolarity. The standard method of preparing CH3NH3PbI3-xClx perovskite precursors is a tedious process involving multiple synthesis steps and, the chemicals being used (hydroiodic acid and methylamine) are quite expensive. This work describes a novel, single-step, simple, and cost-effective solution approach to prepare CH3NH3PbI3-xClx thin films by the direct reaction of the commercially available CH3NH 3Cl (or MACl) and PbI2. A detailed analysis of the structural and optical properties of CH3NH3PbI3-xCl x thin films deposited by aerosol assisted chemical vapor deposition is presented. Optimum growth conditions have been identified. It is shown that the deposited thin films are highly crystalline with intense optical absorbance. Charge carrier separation of these thin films can be enhanced by establishing a local internal electric field that can reduce electron-hole recombination resulting in increased photo current. The intrinsic ferroelectricity in nanoparticles of Barium Titanate (BaTiO3 -BTO) embedded in the solar absorber can generate such an internal field. A hybrid structure of CH3NH 3PbI3-xClx perovskite and ferroelectric BTO nanocomposite FTO/TiO2/CH3NH3PbI3-xClx : BTO/P3HT/Cu as a new type of photovoltaic device is investigated. Aerosol assisted chemical vapor deposition process that is scalable to large-scale manufacturing was used for the growth of the multilayer structure. TiO 2 and P3HT with additives were used as ETL and HTL respectively. The growth process of the solar absorber layer includes the

  12. Labeling of HeLa cells using ZrO2:Yb3+-Er3+ nanoparticles with upconversion emission

    NASA Astrophysics Data System (ADS)

    Ceja-Fdez, Andrea; López-Luke, Tzarara; Oliva, Jorge; Vivero-Escoto, Juan; Gonzalez-Yebra, Ana Lilia; Rojas, Ruben A. Rodriguez; Martínez-Pérez, Andrea; de la Rosa, Elder

    2015-04-01

    This work reports the synthesis, structural characterization, and optical properties of ZrO2:Yb3+-Er3+ (2-1 mol%) nanocrystals. The nanoparticles were coated with 3-aminopropyl triethoxysilane (APTES) and further modified with biomolecules, such as Biotin-Anti-rabbit (mouse IgG) and rabbit antibody-AntiKi-67, through a conjugation method. The conjugation was successfully confirmed by Fourier transform infrared, zeta potential, and dynamic light scattering. The internalization of the conjugated nanoparticles in human cervical cancer (HeLa) cells was followed by two-photon confocal microscopy. The ZrO2:Yb3+-Er3+ nanocrystals exhibited strong red emission under 970-nm excitation. Moreover, the luminescence change due to the addition of APTES molecules and biomolecules on the nanocrystals was also studied. These results demonstrate that ZrO2:Yb3+-Er3+ nanocrystals can be successfully functionalized with biomolecules to develop platforms for biolabeling and bioimaging.

  13. Colossal Negative Thermal Expansion in Electron-Doped PbVO3 Perovskites.

    PubMed

    Yamamoto, Hajime; Imai, Takashi; Sakai, Yuki; Azuma, Masaki

    2018-07-02

    Colossal negative thermal expansion (NTE) with a volume contraction of about 8 %, the largest value reported so far for NTE materials, was observed in an electron-doped giant tetragonal perovskite compound Pb 1-x Bi x VO 3 (x=0.2 and 0.3). A polar tetragonal (P4mm) to non-polar cubic structural transition took place upon heating. The coefficient of thermal expansion (CTE) and the working temperature could be tuned by changing the Bi content, and La substitution decreased the transition temperature to room temperature. Pb 0.76 La 0.04 Bi 0.20 VO 3 exhibited a unit cell volume contraction of 6.7 % from 200 K to 420 K. Interestingly, further gigantic NTE of about 8.5 % was observed in a dilametric measurement of a Pb 0.76 La 0.04 Bi 0.20 VO 3 polycrystalline sample. The pronounced NTE in the sintered body should be attributed to an anisotropic lattice parameter change. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Electronically conductive perovskite-based oxide nanoparticles and films for optical sensing applications

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ohodnicki, Jr., Paul R; Schultz, Andrew M

    2015-04-28

    The disclosure relates to a method of detecting a change in a chemical composition by contacting a electronically conducting perovskite-based metal oxide material with a monitored stream, illuminating the electronically conducting perovskite-based metal oxide with incident light, collecting exiting light, monitoring an optical signal based on a comparison of the incident light and the exiting light, and detecting a shift in the optical signal. The electronically conducting perovskite-based metal oxide has a perovskite-based crystal structure and an electronic conductivity of at least 10.sup.-1 S/cm, where parameters are specified at the gas stream temperature. The electronically conducting perovskite-based metal oxide hasmore » an empirical formula A.sub.xB.sub.yO.sub.3-.delta., where A is at least a first element at the A-site, B is at least a second element at the B-site, and where 0.8« less

  15. Enhancing Perovskite Solar Cell Performance by Interface Engineering Using CH3NH3PbBr0.9I2.1 Quantum Dots.

    PubMed

    Cha, Mingyang; Da, Peimei; Wang, Jun; Wang, Weiyi; Chen, Zhanghai; Xiu, Faxian; Zheng, Gengfeng; Wang, Zhong-Sheng

    2016-07-13

    To improve the interfacial charge transfer that is crucial to the performance of perovskite solar cells, the interface engineering in a device should be rationally designed. Here we have developed an interface engineering method to tune the photovoltaic performance of planar-heterojunction perovskite solar cells by incorporating MAPbBr3-xIx (MA = CH3NH3) quantum dots (QDs) between the MAPbI3 perovskite film and the hole-transporting material (HTM) layer. By adjustment of the Br:I ratio, the as-synthesized MAPbBr3-xIx QDs show tunable fluorescence and band edge positions. When the valence band (VB) edge of MAPbBr3-xIx QDs is located below that of the MAPbI3 perovskite, the hole transfer from the MAPbI3 perovskite film to the HTM layer is hindered, and hence, the power conversion efficiency decreases. In contrast, when the VB edge of MAPbBr3-xIx QDs is located between the VB edge of the MAPbI3 perovskite film and the highest occupied molecular orbital of the HTM layer, the hole transfer from the MAPbI3 perovskite film to the HTM layer is well-facilitated, resulting in significant improvements in the fill factor, short-circuit photocurrent, and power conversion efficiency.

  16. First principles study on mixed orthorhombic perovskite CH3NH3 Pb(I1-xBrx) 3

    NASA Astrophysics Data System (ADS)

    Fang, Zhou; Yi, Zhijun

    2017-11-01

    Chemically tuned inorganic-organic hybrid halide perovskites based on iodine and bromine halide anions have been studied using first-principles calculations. Firstly, our results show that the volume of CH3NH3 Pb(I1-xBrx) 3 decreases linearly with the concentration of Br ions, and the band gap can be tuned from 1.9 eV to 2.3 eV by substituting I with Br, resulting in the shift of absorption onset from 650 nm (1.9 eV) to 540 nm (2.3 eV). Secondly, our calculations show that the color of crystal can be tuned from wine to yellow by substituting I with Br.

  17. Plasmonic Structure Enhanced Exciton Generation at the Interface between the Perovskite Absorber and Copper Nanoparticles

    PubMed Central

    Lin, Kuen-Feng; Chiang, Chien-Hung; Wu, Chun-Guey

    2014-01-01

    The refractive index and extinction coefficient of a triiodide perovskite absorber (TPA) were obtained by fitting the transmittance spectra of TPA/PEDOT:PSS/ITO/glass using the transfer matrix method. Cu nanoplasmonic structures were designed to enhance the exciton generation in the TPA and to simultaneously reduce the film thickness of the TPA. Excitons were effectively generated at the interface between TPA and Cu nanoparticles, as observed through the 3D finite-difference time-domain method. The exciton distribution is advantageous for the exciton dissociation and carrier transport. PMID:25295290

  18. Positive magnetoresistance of La0.7Sr0.3MnO3/C composites

    NASA Astrophysics Data System (ADS)

    Kabirov, Yu. V.; Gavrilyachenko, V. G.; Bogatin, A. S.

    2016-07-01

    The perovskite manganite La0.7Sr0.3MnO3 compound is used as a component in ceramic (1-x)(La0.7Sr0.3MnO3)-xC composites at x = 0.15-0.85. It is found that every studied specimen is characterized by the linear dependence of the positive magnetoresistance (PMR) on the magnetic field strength at room temperature. The 0.6(La0.7Sr0.3MnO3)-0.4C composite has the largest magnetoresistance value (15%) at room temperature and intensity of magnetic field H=15kOe. A possible mechanism for the PMR of (1-x)(La0.7Sr0.3MnO3)-xC composites is discussed.

  19. Antiferroelectric Nature of CH3NH3PbI3−xClx Perovskite and Its Implication for Charge Separation in Perovskite Solar Cells

    PubMed Central

    Sewvandi, Galhenage A.; Kodera, Kei; Ma, Hao; Nakanishi, Shunsuke; Feng, Qi

    2016-01-01

    Perovskite solar cells (PSCs) have been attracted scientific interest due to high performance. Some researchers have suggested anomalous behavior of PSCs to the polarizations due to the ion migration or ferroelectric behavior. Experimental results and theoretical calculations have suggested the possibility of ferroelectricity in organic-inorganic perovskite. However, still no studies have been concretely discarded the ferroelectric nature of perovskite absorbers in PSCs. Hysteresis of P-E (polarization-electric field) loops is an important evidence to confirm the ferroelectricity. In this study, P-E loop measurements, in-depth structural study, analyses of dielectric behavior and the phase transitions of CH3NH3PbI3−xClx perovskite were carried out and investigated. The results suggest that CH3NH3PbI3−xClx perovskite is in an antiferroelectric phase at room temperature. The antiferroelectric phase can be switched to ferroelectric phase by the poling treatment and exhibits ferroelectric-like hysteresis P-E loops and dielectric behavior around room temperature; namely, the perovskite can generate a ferroelectric polarization under PSCs operating conditions. Furthermore, we also discuss the implications of ferroelectric polarization on PSCs charge separation. PMID:27468802

  20. Laser post-processing of halide perovskites for enhanced photoluminescence and absorbance

    NASA Astrophysics Data System (ADS)

    Tiguntseva, E. Y.; Saraeva, I. N.; Kudryashov, S. I.; Ushakova, E. V.; Komissarenko, F. E.; Ishteev, A. R.; Tsypkin, A. N.; Haroldson, R.; Milichko, V. A.; Zuev, D. A.; Makarov, S. V.; Zakhidov, A. A.

    2017-11-01

    Hybrid halide perovskites have emerged as one of the most promising type of materials for thin-film photovoltaic and light-emitting devices. Further boosting their performance is critically important for commercialization. Here we use femtosecond laser for post-processing of organo-metalic perovskite (MAPbI3) films. The high throughput laser approaches include both ablative silicon nanoparticles integration and laser-induced annealing. By using these techniques, we achieve strong enhancement of photoluminescence as well as useful light absorption. As a result, we observed experimentally 10-fold enhancement of absorbance in a perovskite layer with the silicon nanoparticles. Direct laser annealing allows for increasing of photoluminescence over 130%, and increase absorbance over 300% in near-IR range. We believe that the developed approaches pave the way to novel scalable and highly effective designs of perovskite based devices.

  1. Glory of piezoelectric perovskites.

    PubMed

    Uchino, Kenji

    2015-08-01

    This article reviews the history of piezoelectric perovskites and forecasts future development trends, including Uchino's discoveries such as the Pb(Mg 1/3 Nb 2/3 )O 3 -PbTiO 3 electrostrictor, Pb(Zn 1/3 Nb 2/3 )O 3 -PbTiO 3 single crystal, (Pb, La)(Zr, Ti)O 3 photostriction, and Pb(Zr, Ti)O 3 -Terfenol magnetoelectric composites. We discuss five key trends in the development of piezomaterials: performance to reliability, hard to soft, macro to nano, homo to hetero, and single to multi-functional.

  2. Structural and magnetic properties of SrMn1-xRuxO3 perovskites

    NASA Astrophysics Data System (ADS)

    Dabrowski, B.; Kolesnik, S.; Chmaissem, O.; Maxwell, T.

    2007-03-01

    Ferromagnetism of SrRuO3 is unique among 4d transition metal based perovskite oxides. On substitution of Mn its TC decreases from 163 K to 0 for x˜0.5-0.6 followed by a formation of an antiferromagnetic insulating state at a quantum critical point. The other end member of the SrMn1-xRuxO3 family, a cubic perovskite SrMnO3 is a G-type antiferromagnet with TN=233 K. We have synthesized the complete SrMn1-xRuxO3 solid solution. The polycrystalline samples were characterized by neutron difraction, magnetic, and transport experiments. The incorporation of Ru in the SrMnO3 matrix (0.1<=x<=0.4) results in a phase transition to a C-type antiferromagnetic state accompanied by a cubic-tetragonal transition. The intermediate substitution level induces a spin-glass behavior, due to competing ferro- and antiferromagnetic interactions. Mixed valence Mn^3+/Mn^4+ and Ru^4+/Ru^5+ pairs introduce additional frustration to the magnetic states. The glassy behavior can be observed for x up to 0.7 in the tetragonal structure. Supported by NSF (DMR-0302617) and the U.S. Department of Education

  3. Magnetic properties of GdMnO3 nanoparticles embedded in mesoporous silica

    NASA Astrophysics Data System (ADS)

    Tajiri, Takayuki; Mito, Masaki; Deguchi, Hiroyuki; Kohno, Atsushi

    2018-05-01

    Perovskite manganite GdMnO3 nanoparticles were synthesized using mesoporous silica as a template, and their magnetic properties and crystal structure were investigated. Powder X-ray diffraction data indicated successful synthesis of the GdMnO3 nanoparticles, with mean particle sizes of 13.9 and 20.9 nm. The lattice constants for the nanoparticles were slightly different from those for the bulk material and varied with the particle size. The magnetic transition temperatures for the nanoparticles were higher than those of the bulk crystal. The synthesized GdMnO3 nanoparticles exhibited superparamagnetic behaviors: The blocking temperature, coercive field, and transition temperature depended on the particle size. Magnetic measurements and crystal structure analysis suggest that the changes in the magnetic properties for GdMnO3 nanoparticles can be attributed to the modulation of the crystallographic structure.

  4. Structural properties of perovskite films on zinc oxide nanoparticles-reduced graphene oxide (ZnO-NPs/rGO) prepared by electrophoretic deposition technique

    NASA Astrophysics Data System (ADS)

    Bahtiar, Ayi; Nurazizah, Euis Siti; Latiffah, Efa; Risdiana, Furukawa, Yukio

    2018-02-01

    Perovskite solar cells highly believed as next generation solar cells to replace currently available inorganic silicon solar cells due to their high power conversion efficiency and easy processing to thin films using solution processing techniques. Performance and stability, however still need to be improved for mass production and widely used for public electricity generation. Perovskite solar cells are commonly deposited on Titanium Dioxide (TiO2) film as an effective electron transport layer (ETL). We used Zinc Oxide nanoparticles (ZnO-NPs) as ETL in perovskite solar cells due to the low temperature required for crystallization and can be formed into different shapes of nanostructures. However, perovskite film can easily degrade into insulating lead iodide due to deprotonation of the methylammoniumcation at the surface of ZnO-NPs, in particular when it stored in ambient air with high relative humidity. The degradation of perovskite layer is therefore needed to be overcome. Here, we capped ZnO-NPs with reduced graphene oxide (rGO) to overcome the degradation of perovskite film where ZnO-NPs is synthesized by sol-gel method. The average nanoparticle size of ZnO is 15 nm. ZnO-NPs and ZnO-NPs-rGO films are prepared using electrophoretic deposition technique, which can produce large area with good homogeneity and high reproducibility. The stability of perovskite layer can significantly be improved by capping ZnO with rGO, which is indicated by absence of color change of perovskite after storage for 5 (five) days in ambient air with relative humidity above 95%. Moreover, the X-Ray Diffaction peaks of perovskite film are more preserved when deposited on ZnO/rGO film than using only ZnO film. We strongly believe, by capping ZnO film with rGO, both the performance and stability of perovskite solar cells can be improved significantly.

  5. Chemical Substitution-Induced and Competitive Formation of 6H and 3C Perovskite Structures in Ba3-xSrxZnSb2O9: The Coexistence of Two Perovskites in 0.3 ≤ x ≤ 1.0.

    PubMed

    Li, Jing; Jiang, Pengfei; Gao, Wenliang; Cong, Rihong; Yang, Tao

    2017-11-20

    6H and 3C perovskites are important prototype structures in materials science. We systemically studied the structural evolution induced by the Sr 2+ -to-Ba 2+ substitution to the parent 6H perovskite Ba 3 ZnSb 2 O 9 . The 6H perovskite is only stable in the narrow range of x ≤ 0.2, which attributes to the impressibility of [Sb 2 O 9 ]. The preference of 90° Sb-O-Sb connection and the strong Sb 5+ -Sb 5+ electrostatic repulsion in [Sb 2 O 9 ] are competitive factors to stabilize or destabilize the 6H structure when chemical pressure was introduced by Sr 2+ incorporation. Therefore, in the following, a wide two-phase region containing 1:2 ordered 6H-Ba 2.8 Sr 0.2 ZnSb 2 O 9 and rock-salt ordered 3C-Ba 2 SrZnSb 2 O 9 was observed (0.3 ≤ x ≤ 1.0). In the final, the successive symmetry descending was established from cubic (Fm3̅m, 1.3 ≤ x ≤ 1.8) to tetragonal (I4/m, 2.0 ≤ x ≤ 2.4), and finally to monoclinic (I2/m, 2.6 ≤ x ≤ 3.0). Here we proved that the electronic configurations of B-site cations, with either empty, partially, or fully filled d-shell, would also affect the structure stabilization, through the orientation preference of the B-O covalent bonding. Our investigation gives a deeper understanding of the factors to the competitive formation of perovskite structures, facilitating the fine manipulation on their physical properties.

  6. Crystal structure and electrical conductivity of lanthanum-calcium chromites-titanates La 1-xCa xCr 1-yTi yO 3-δ ( x=0-1, y=0-1)

    NASA Astrophysics Data System (ADS)

    Vashook, V.; Vasylechko, L.; Zosel, J.; Gruner, W.; Ullmann, H.; Guth, U.

    2004-10-01

    Five series of perovskite-type compounds in the system La1-xCaxCr1-yTiyO3 with the nominal compositions y = 0 , x = 0 - 0.5 ; y = 0.2 , x = 0.2 - 0.8 ; y = 0.5 , x = 0.5 - 1.0 ; y = 0.8 , x = 0.6 - 1.0 and y = 1 , x = 0.8 - 1 were synthesized by a ceramic technique in air (final heating 1350 °C). On the basis of the X-ray analysis of the samples with (Ca/Ti)⩾1, the phase diagram of the CaTiO3-LaCrIIIO3-CaCrIVO3 quasi-ternary system was constructed. Extended solid solution with a wide homogeneity range is formed in the quasi-ternary system CaCrIVO3-CaTiO3-LaCrIIIO3. The solid solution La(1-x‧-y)Ca(x‧+y)CrIVx‧CrIII(1-x‧-y)TiyO3 exists by up to 0.6-0.7 mol fractions of CaCrIVO3 (x‧ < 0.6 - 0.7) at the experimental conditions. The crystal structure of the compounds is orthorhombic in the space group Pbnm at room temperature. The lattice parameters and the average interatomic distances of the samples within the solid solution ranges decrease uniformly with increasing Ca content. Outside the quasi-ternary system, the nominal compositions La0.1Ca0.9TiO3, La0.2Ca0.8TiO3, La0.4Ca0.6Cr0.2Ti0.8O3 and La0.3Ca0.7Cr0.2Ti0.8O3 in the system La1-xCaxCr1-yTiyO3 were found as single phases with an orthorhombic structure. In the temperature range between 850 and 1000 °C, the synthesized single-phase compositions are stable at pO2=6×10-16-0.21×105 Pa. Oxygen stoichiometry and electrical conductivity of the separate compounds were investigated as functions of temperature and oxygen partial pressure. The chemical stability of these oxides with respect to oxygen release during thermal dissociation decreases with increasing Ca-content. At 900 °C and oxygen partial pressure 1×10-15-0.21×105 Pa, the compounds with x > y (acceptor doped) are p-type semiconductors and those with x < y (donor doped) and x = y are n-type semiconductors. The type and level of electrical conductivity are functions of the concentration ratios of cations occupying the B-sites of the perovskite

  7. The Light-Induced Field-Effect Solar Cell Concept - Perovskite Nanoparticle Coating Introduces Polarization Enhancing Silicon Cell Efficiency.

    PubMed

    Wang, Yusheng; Xia, Zhouhui; Liu, Lijia; Xu, Weidong; Yuan, Zhongcheng; Zhang, Yupeng; Sirringhaus, Henning; Lifshitz, Yeshayahu; Lee, Shui-Tong; Bao, Qiaoliang; Sun, Baoquan

    2017-05-01

    Solar cell generates electrical energy from light one via pulling excited carrier away under built-in asymmetry. Doped semiconductor with antireflection layer is general strategy to achieve this including crystalline silicon (c-Si) solar cell. However, loss of extra energy beyond band gap and light reflection in particular wavelength range is known to hinder the efficiency of c-Si cell. Here, it is found that part of short wavelength sunlight can be converted into polarization electrical field, which strengthens asymmetry in organic-c-Si heterojunction solar cell through molecule alignment process. The light harvested by organometal trihalide perovskite nanoparticles (NPs) induces molecular alignment on a conducting polymer, which generates positive electrical surface field. Furthermore, a "field-effect solar cell" is successfully developed and implemented by combining perovskite NPs with organic/c-Si heterojunction associating with light-induced molecule alignment, which achieves an efficiency of 14.3%. In comparison, the device with the analogous structure without perovskite NPs only exhibits an efficiency of 12.7%. This finding provides a novel concept to design solar cell by sacrificing part of sunlight to provide "extra" asymmetrical field continuously as to drive photogenerated carrier toward respective contacts under direct sunlight. Moreover, it also points out a method to combine promising perovskite material with c-Si solar cell. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Spin State Control of the Perovskite Rh/Co Oxides

    PubMed Central

    Terasaki, Ichiro; Shibasaki, Soichiro; Yoshida, Shin; Kobayashi, Wataru

    2010-01-01

    We show why and how the spin state of transition-metal ions affects the thermoelectric properties of transition-metal oxides by investigating two perovskite-related oxides. In the A-site ordered cobalt oxide Sr3YCo4O10.5, partial substitution of Ca for Sr acts as chemical pressure, which compresses the unit cell volume to drive the spin state crossover, and concomitantly changes the magnetization and thermopower. In the perovskite rhodium oxide LaRhO3, partial substitution of Sr for La acts as hole-doping, and the resistivity and thermopower decrease systematically with the Sr concentration. The thermopower remains large values at high temperatures (>150 μV/K at 800 K), which makes a remarkable contrast to La1−xSrxCoO3. We associate this with the stability of the low spin state of the Rh3+ ions.

  9. Electrical conductivity and thermoelectric power of La1- x Li x CoO3-δ (0 ≤ x ≤ 0.1) oxides

    NASA Astrophysics Data System (ADS)

    Vecherskii, S. I.; Konopel'ko, M. A.; Batalov, N. N.; Antonov, B. D.; Reznitskikh, O. G.; Yaroslavtseva, T. V.

    2016-12-01

    The influence of the concentration of lithium ions on the phase composition, the electrical conductivity, and the thermoelectric power of La1- x Li x CoO3-δ (0 ≤ x ≤ 0.1) oxides synthesized by the ceramic method has been investigated. It has been found that the region of the existence of perovskite-type La1- x Li x CoO3-δ solid solutions does not exceed x = 0.05. The doping with lithium leads to an increase in the electrical conductivity of single-phase samples in comparison with that of the LaCoO3 compound. As the temperature increases from 300 to 400 K, the thermoelectric power of the LaCoO3 compound increases from the negative to positive values and then decreases, but remains positive in the temperature range from 400 to 1020 K. The thermoelectric power of the other samples has a positive sign. The results obtained have been discussed based on the models of the electron density of states in LaCoO3 and La1- x Sr x CoO3-δ, proposed in the studies of Señarís-Rodríguez and Goodenough, as well as in the framework of the theory of non-crystalline materials, developed by Mott.

  10. 0D-2D and 1D-2D Semiconductor Hybrids Composed of All Inorganic Perovskite Nanocrystals and Single-Layer Graphene with Improved Light Harvesting

    DOE PAGES

    Chen, Jia-Shiang; Doane, Tennyson L.; Li, Mingxing; ...

    2017-12-27

    In this study, inorganic cesium lead iodide (CsPbI 3) perovskite nanoparticles (PNPs) and perovskite nanowires (PNWs) with single-layer graphene (SLG) are combined to obtain 0D–2D PNP–SLG and 1D–2D PNW–SLG hybrids with improved light harvesting. Time-resolved single-nanostructure photoluminescence studies of PNPs, PNWs, and related hybrids reveal (i) quasi-two-state photoluminescence blinking in PNPs, (ii) highly polarized photoluminescence emitted by PNWs and (iii) efficient interfacial electron transfer between perovskite nanostructures and SLG in both PNP–SLG and PNW–SLG hybrids. Thus, doping of poorly absorbing, highly conductive SLG with perovskite nanocrystals and nanowires provides a simple, yet efficient path to obtain hybrids with increased light-harvestingmore » properties for potential utilization in the next-generation photodetectors and photovoltaic devices, including polarization sensitive photodetectors.« less

  11. 0D-2D and 1D-2D Semiconductor Hybrids Composed of All Inorganic Perovskite Nanocrystals and Single-Layer Graphene with Improved Light Harvesting

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Chen, Jia-Shiang; Doane, Tennyson L.; Li, Mingxing

    In this study, inorganic cesium lead iodide (CsPbI 3) perovskite nanoparticles (PNPs) and perovskite nanowires (PNWs) with single-layer graphene (SLG) are combined to obtain 0D–2D PNP–SLG and 1D–2D PNW–SLG hybrids with improved light harvesting. Time-resolved single-nanostructure photoluminescence studies of PNPs, PNWs, and related hybrids reveal (i) quasi-two-state photoluminescence blinking in PNPs, (ii) highly polarized photoluminescence emitted by PNWs and (iii) efficient interfacial electron transfer between perovskite nanostructures and SLG in both PNP–SLG and PNW–SLG hybrids. Thus, doping of poorly absorbing, highly conductive SLG with perovskite nanocrystals and nanowires provides a simple, yet efficient path to obtain hybrids with increased light-harvestingmore » properties for potential utilization in the next-generation photodetectors and photovoltaic devices, including polarization sensitive photodetectors.« less

  12. Electrical and structural behaviour of the perovskite LaCr0.4Co0.4Fe0.2O3

    NASA Astrophysics Data System (ADS)

    Rativa-Parada, W.; Gómez-Cuaspud, J. A.; Vera-López, E.; Carda-Castelló, J. B.

    2017-12-01

    The electrical and structural properties of the LaCr0.4Co0.4Fe0.2O3 perovskite are investigated. The oxide is synthetized by polymerization-combustion method, using citric acid as a chelating agent and low calcination temperature. The X-ray diffraction, Raman spectroscopy and transmission electron microscopy analysis show conformation of a pure phase with rhombohedral (R-3c) structure and confirmed high structural crystallinity facilitated by synthesis method. The characterization by means of impedance spectroscopy is performed at room temperature. It is observed that the oxides behave as materials of the semiconductor type and that the conductivity increase in accordance to a thermal excitation phenomenon.

  13. Tunable anomalous orbital structure in a spinel-perovskite interface γ-Al2O3/SrTiO3

    NASA Astrophysics Data System (ADS)

    Cao, Yanwei; Liu, Xiaoran; Shafer, Padraic; Middey, Srimanta; Meyers, Derek; Kareev, Mikhail; Zhong, Zhicheng; Kim, Jong-Woo; Ryan, Philip; Arenholz, Elke; Chakhalian, Jak

    In all archetypical reported (001)-oriented perovskite heterostructures, for example LaTiO3/SrTiO3, LaAlO3/SrTiO3,YTiO3/SrTiO3 and so on, it has been deduced that the preferential occupation of two-dimensional electron gases is in-plane dxy state. In sharp contrast to this, the investigated electronic structure of a spinel-perovskite heterostructure γ-Al2O3/SrTiO3 by resonant soft X-ray linear dichroism, demonstrates that the preferential occupation is in out-of-plane dxz/dyz states for interfacial electrons. Moreover, the impact of strain further corroborates that this anomalous orbital structure can be linked to the altered crystal field at the interface and symmetry breaking of the interfacial structural units. Our findings provide another interesting route to engineer emergent quantum states with deterministic orbital symmetry. J.C. and Y.C. was supported by the Gordon and Betty Moore Foundation EPiQS Initiative through Grant No. GBMF4534. S.M. and M.K. were supported by the DOD-ARO under Grant No. 0402-172.

  14. Sound velocity of MgSiO 3 perovskite to Mbar pressure

    NASA Astrophysics Data System (ADS)

    Murakami, Motohiko; Sinogeikin, Stanislav V.; Hellwig, Holger; Bass, Jay D.; Li, Jie

    2007-04-01

    Brillouin scattering measurements of the aggregate shear wave velocities in MgSiO 3 perovskite were conducted at high pressure conditions relevant to the Earth's lowermost mantle, approaching 1 Mbar. Infrared laser annealing of samples in a diamond anvil cell allowed us to obtain high quality Brillouin spectra and to drastically extend the upper limit of pressure for Brillouin measurements. We found that the pressure derivative of the shear modulus (d G / d P = G') of MgSiO 3 perovskite is 1.56 ± 0.04, which is distinctly lower than that of previous lower-pressure experiments below 9 GPa. Extrapolation of the high-pressure shear velocities of perovskite to ambient pressure, are in excellent agreement with earlier room pressure Brillouin measurements. The shear modulus, shear velocity and longitudinal velocity at ambient pressure were determined to be G0 = 172.9(15) GPa, VS = 6.49(3) and VP = 10.85(3) km/sec. The mineralogical model that provides a best fit to global seismological 1-D velocity profiles is one that contains 85-90 vol% perovskite in the lower mantle. The results of this study are the first to demonstrate that the elastic wave velocities for a near-adiabatic lower mantle with a bulk composition dominated by magnesium silicate perovskite are consistent with the average lower mantle seismic velocity structure. The large pressure range over which acoustic measurements of MgSiO 3 perovskite performed in this study has thus allowed us to put tighter constraints on compositional models of the Earth's lower mantle.

  15. Magnetic phase diagram and critical behavior of electron-doped LaxCa1-xMnO3(0⩽x⩽0.25) nanoparticles

    NASA Astrophysics Data System (ADS)

    Wang, Yang; Fan, Hong Jin

    2011-06-01

    A comparative study of electron-doped perovskite manganites LaxCa1-xMnO3 (0 ⩽ x ⩽ 0.25) in nanoparticle and bulk form is reported. The bulks and nanoparticles exhibit different magnetic evolutions. Overall with increasing x, the bulks have a phase-separated ground state with ferromagnetic (FM) clusters and antiferromagnetic (AFM) matrix coexisting. The FM clusters gradually grow, and the magnetization M peaks at x= 0.1. Subsequently, charge-ordering (CO) or local CO occurs, which suppresses the increase in FM clusters but favors the development of antiferromagnetism so M starts to decrease. Finally the system becomes a homogeneous AFM state at x > 0.18. For the nanoparticles in the range of 0 ⩽ x ⩽ 0.1, the ground state is similar to that of the bulks, but M is slightly increased because of a surface ferromagnetism. Nevertheless because of the structure distortion induced by surface pressure and the size effect, CO does not occur in the nanoparticles. Consequently, the ferromagnetism still gradually develops at x > 0.1 and thus M monotonously rises. M reaches a maximum at x= 0.18, after which the competition between ferromagnetism and antiferromagnetism induces a cluster-glass (CG) state. On the basis of these observations the phase diagrams for both bulks and nanoparticles are established. For the nanoparticles that display enhanced ferromagnetism the critical behavior analysis indicates that they fall into a three-dimensional (3D) Heisenberg ferromagnet class.

  16. A Facile Methodology for Engineering the Morphology of CsPbX3 Perovskite Nanocrystals under Ambient Condition

    NASA Astrophysics Data System (ADS)

    Seth, Sudipta; Samanta, Anunay

    2016-11-01

    A facile and highly reproducible room temperature, open atmosphere synthesis of cesium lead halide perovskite nanocrystals of six different morphologies is reported just by varying the solvent, ligand and reaction time. Sequential evolution of the quantum dots, nanoplates and nanobars in one medium and nanocubes, nanorods and nanowires in another medium is demonstrated. These perovskite nanoparticles are shown to be of excellent crystalline quality with high fluorescence quantum yield. A mechanism of the formation of nanoparticles of different shapes and sizes is proposed. Considering the key role of morphology in nanotechnology, this simple method of fabrication of a wide range of high quality nanocrystals of different shapes and sizes of all-inorganic lead halide perovskites, whose potential is already demonstrated in light emitting and photovoltaic applications, is likely to help widening the scope and utility of these materials in optoelectronic devices.

  17. Glory of piezoelectric perovskites

    PubMed Central

    Uchino, Kenji

    2015-01-01

    This article reviews the history of piezoelectric perovskites and forecasts future development trends, including Uchino’s discoveries such as the Pb(Mg1/3Nb2/3)O3–PbTiO3 electrostrictor, Pb(Zn1/3Nb2/3)O3–PbTiO3 single crystal, (Pb, La)(Zr, Ti)O3 photostriction, and Pb(Zr, Ti)O3–Terfenol magnetoelectric composites. We discuss five key trends in the development of piezomaterials: performance to reliability, hard to soft, macro to nano, homo to hetero, and single to multi-functional. PMID:27877827

  18. (CH3 NH3 )2 PdCl4 : A Compound with Two-Dimensional Organic-Inorganic Layered Perovskite Structure.

    PubMed

    Huang, Tang Jiao; Thiang, Zhang Xian; Yin, Xuesong; Tang, Chunhua; Qi, Guojun; Gong, Hao

    2016-02-01

    The synthesis of previously unknown perovskite (CH 3 NH 3 ) 2 PdCl 4 is reported. Despite using an organic cation with the smallest possible alkyl group, a 2D organic-inorganic layered Pd-based perovskites was still formed. This demonstrates that Pd-based 2D perovskites can be obtained even if the size of the organic cation is below the size limit predicted by the Goldschmidt tolerance-factor formula. The (CH 3 NH 3 ) 2 PdCl 4 phase has a bulk resistivity of 1.4 Ω cm, a direct optical gap of 2.22 eV, and an absorption coefficient on the order of 10 4  cm -1 . XRD measurements suggest that the compound is moderately stable in air, an important advantage over several existing organic-inorganic perovskites that are prone to phase degradation problems when exposed to the atmosphere. Given the recent interest in organic-inorganic perovskites, the synthesis of this new Pd-based organic-inorganic perovskite may be helpful in the preparation and understanding of other organic-inorganic perovskites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Topological magnetic phase in LaMnO3 (111) bilayer

    NASA Astrophysics Data System (ADS)

    Weng, Yakui; Huang, Xin; Yao, Yugui; Dong, Shuai

    Candidates for correlated topological insulators, originated from the spin-orbit coupling as well as Hubbard type correlation, are expected in the (111) bilayer of perovskite-structural transition-metal oxides. Based on the first-principles calculation and tight-binding model, the electronic structure of a LaMnO3 (111) bilayer sandwiched in LaScO3 barriers has been investigated. For the ideal undistorted perovskite structure, the Fermi energy of LaMnO3 (111) bilayer just stays at the Dirac point, rendering a semi-metal (graphene-like) which is also a half-metal (different from graphene nor previous studied LaNiO3 (111) bilayer). The Dirac cone can be opened by the spin-orbit coupling, giving rise to nontrivial topological bands corresponding to the (quantized) anomalous Hall effect. For the realistic orthorhombic distorted lattice, the Dirac point moves with increasing Hubbard repulsion (or equivalent Jahn-Teller distortion). Finally, a Mott gap opens, establishing a phase boundary between the Mott insulator and topological magnetic insulator. Our calculation finds that the gap opened by spin-orbit coupling is much smaller in the orthorhombic distorted lattice (~ 1 . 7 meV) than the undistorted one (~11 meV).

  20. Effects of Fe-Enrichment on the Equation of State and Stability of (Mg,Fe)SiO3 Perovskite and Post-Perovskite

    NASA Astrophysics Data System (ADS)

    Dorfman, S. M.; Holl, C. M.; Meng, Y.; Prakapenka, V.; Duffy, T. S.

    2010-12-01

    Fe-enrichment in the deep lower mantle has been proposed as an explanation for seismic anomalies such as large low shear velocity provinces (LLSVPs) and ultralow velocity zones (ULVZs). In order to resolve the effect of Fe on the stability and equation of state of the lower mantle’s dominant constituent, (Mg,Fe)SiO3 perovskite, we have studied Fe-rich natural orthopyroxenes, (Mg0.61Fe0.37Ca0.02)SiO3 and (Mg0.25Fe0.70Ca0.05)SiO3 (compositions determined by microprobe analysis), at lower mantle P-T conditions. Pyroxene starting materials were mixed with Au (pressure calibrant and laser absorber) and loaded with NaCl or Ne (pressure medium and thermal insulator) in a symmetric diamond anvil cell. X-ray diffraction experiments at pressures up to 122 GPa with in-situ laser heating were performed at the GSECARS (13-ID-D) and HPCAT (16-ID-B) sectors of the Advanced Photon Source. Heating samples to 2000 K produced single-phase orthorhombic GdFeO3-type perovskite at 63 GPa for the Mg# 61 composition and at 72 GPa for the Mg# 25 composition. At lower pressures (56 GPa for Mg# 61, 67 GPa for Mg# 25), heating both compositions resulted in a mixture of perovskite, SiO2 and (Mg,Fe)O. These measurements provide new constraints on the dependence of (Mg,Fe)SiO3 perovskite stability on pressure and composition. Upon further compression to 93 GPa and higher pressures with laser heating, Mg# 25 perovskite transformed to a two-phase mixture of perovskite and post-perovskite. This is consistent with previous findings that Fe substitution destabilizes (Mg,Fe)SiO3 perovskite relative to (Mg,Fe)SiO3 post-perovskite (Mao et al. 2004, Caracas and Cohen 2005). The bulk modulus at 80 GPa (K80) is ~550 GPa for both Fe-rich perovskites, comparable to values measured for MgSiO3 perovskite (Lundin et al. 2008). However, the volume of Fe-rich perovskites increases linearly with Fe-content. The (Mg0.25Fe0.70Ca0.05)SiO3 perovskite is 3% greater at 80 GPa than V80 for the Mg end

  1. Microstructural, optical and electrical properties of LaFe0.5Cr0.5O3 perovskite nanostructures

    NASA Astrophysics Data System (ADS)

    Ali, S. Asad; Naseem, Swaleha; Khan, Wasi; Sharma, A.; Naqvi, A. H.

    2016-05-01

    Perovskite nanocrystalline powder of LaFe0.5Cr0.5O3 was synthesized by sol-gel combustion route and characterized by x-ray diffractometer (XRD), scanning electron microscopy (SEM) equipped with EDS, UV-visible and LCR meter at room temperature Rietveld refinement of the XRD data confirms that the sample is in single phase-rhombohedral structure with space group R-3C. SEM micrograph shows clear nanostructure of the sample and EDS ensures the presence of all elements in good stoichiometric. The optical absorption indicates the maximum absorption at 315 nm and optical band gap of 2.94 eV was estimated using Tauc's relation. Dielectric constant (ɛ') and loss were found to decrease with increase in frequencies. The dielectric behavior was explained on the basis of Maxwell-Wagner's two layer model.

  2. Determination of stoichiometry and concentration of trace elements in thin BaxSr1-xTiO3 perovskite layers.

    PubMed

    Becker, J S; Boulyga, S F

    2001-07-01

    This paper describes an analytical procedure for determining the stoichiometry of BaxSr1-xTiO3 perovskite layers using inductively coupled plasma mass spectrometry (ICP-MS). The analytical results of mass spectrometry measurements are compared to those of X-ray fluorescence analysis (XRF). The performance and the limits of solid-state mass spectrometry analytical methods for the surface analysis of thin BaxSr1-xTiO3 perovskite layers sputtered neutral mass spectrometry (SNMS)--are investigated and discussed.

  3. Crystal Chemistry and Conductivity Studies in the System La 0.5+ x+ yLi 0.5-3 xTi 1-3 yCr 3 yO 3

    NASA Astrophysics Data System (ADS)

    Martínez-Sarrión, M. L.; Mestres, L.; Morales, M.; Herraiz, M.

    2000-12-01

    The stoichiometry polymorphism and electrical behavior of solid solutions La0.5+x+yLi0.5-3xTi1-3yCr3yO3 with perovskite-type structure were studied. Data are given in the form of a solid solutions triangle, phase diagrams, XRD patterns for the three polymorphs, A, β, and C, composition dependence of their lattice parameters, and ionic and electronic conductivity plots. Microstructure and composition were studied by SEM/EDS and electron probe microanalysis. These compounds are mixed conductors. Ionic conductivity decreased when the amount of lithium diminished and electronic conductivity increased with chromium content.

  4. Hierarchical Mesoporous/Macroporous Perovskite La0.5Sr0.5CoO3-x Nanotubes: A Bifunctional Catalyst with Enhanced Activity and Cycle Stability for Rechargeable Lithium Oxygen Batteries.

    PubMed

    Liu, Guoxue; Chen, Hongbin; Xia, Lu; Wang, Suqing; Ding, Liang-Xin; Li, Dongdong; Xiao, Kang; Dai, Sheng; Wang, Haihui

    2015-10-14

    Perovskites show excellent specific catalytic activity toward both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline solutions; however, small surface areas of the perovskites synthesized by traditional sol-gel methods lead to low utilization of catalytic sites, which gives rise to poor Li-O2 batteries performance and restricts their application. Herein, a hierarchical mesporous/macroporous perovskite La0.5Sr0.5CoO3-x (HPN-LSC) nanotube is developed to promote its application in Li-O2 batteries. The HPN-LSC nanotubes were synthesized via electrospinning technique followed by postannealing. The as-prepared HPN-LSC catalyst exhibits outstanding intrinsic ORR and OER catalytic activity. The HPN-LSC/KB electrode displays excellent performance toward both discharge and charge processes for Li-O2 batteries, which enhances the reversibility, the round-trip efficiency, and the capacity of resultant batteries. The synergy of high catalytic activity and hierarchical mesoporous/macroporous nanotubular structure results in the Li-O2 batteries with good rate capability and excellent cycle stability of sustaining 50 cycles at a current density of 0.1 mA cm(-2) with an upper-limit capacity of 500 mAh g(-1). The results will benefit for the future development of high-performance Li-O2 batteries using hierarchical mesoporous/macroporous nanostructured perovskite-type catalysts.

  5. High pressure luminescence of Nd3+ in YAlO3 perovskite nanocrystals: A crystal-field analysis

    NASA Astrophysics Data System (ADS)

    Hernández-Rodríguez, Miguel A.; Muñoz-Santiuste, Juan E.; Lavín, Víctor; Lozano-Gorrín, Antonio D.; Rodríguez-Hernández, Plácida; Muñoz, Alfonso; Venkatramu, Vemula; Martín, Inocencio R.; Rodríguez-Mendoza, Ulises R.

    2018-01-01

    Pressure-induced energy blue- and red-shifts of the 4F3/2 → 4I9/2,11/2 near-infrared emission lines of Nd3+ ions in YAlO3 perovskite nano-particles have been measured from ambient conditions up to 29 GPa. Different positive and negative linear pressure coefficients have been calibrated for the emission lines and related to pressure-induced changes in the interactions between those Nd3+ ions and their twelve oxygen ligands at the yttrium site. Potentiality of the simple overlap model, combined with ab initio structural calculations, in the description of the effects of these interactions on the energy levels and luminescence properties of the optically active Nd3+ ion is emphasized. Simulations show how the energies of the 4f3 ground configuration and the barycenters of the multiplets increase with pressure, whereas the Coulomb interaction between f-electrons decreases and the crystal-field strength increases. All these effects combined explain the wavelength blue-shifts of some near-infrared emission lines of Nd3+ ions. Large pressure rates of various emission lines suggest that a YAlO3 perovskite nano-crystal can be a potential candidate for near-infrared optical pressure sensors.

  6. Ferromagnetic and multiferroic interfaces in granular perovskite composite xLa{sub 0.5}Sr{sub 0.5}CoO{sub 3}-(1−x)BiFeO{sub 3}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lohr, Javier H.; Saleta, Martín E.; Sánchez, Rodolfo D., E-mail: rodo@cab.cnea.gov.ar

    Nanopowder of ferromagnetic La{sub 0.5}Sr{sub 0.5}CoO{sub 3} (LSCO) and multiferroic BiFeO{sub 3} (BFO) were synthesized by spray pyrolysis method. Different compositions of multiferroic xLSCO-(1−x)BFO composites were synthesized at 800 °C for 2 h. Scanning electron microscopy and energy dispersive spectroscopy elemental mapping were performed to study the morphology of composites. Ferri/ferromagnetic responses above T{sub C} (LSCO) are observed, which are associated with the interfaces LSCO/BFO. This interface presents a different behavior compared to the original perovskites, and the magnitude of the magnetization depends on x. Electrical DC conductivity as a function of temperature for LSCO nanopowder (x = 1) presents a different behaviormore » than that reported in bulk material. For x = 1 and 0.9, the model by Glazman and Matveev [Zh. Eksp. Teor. Fiz. 94, 332 (1988)] is proposed to describe the electrical conductivity. On the other hand, x = 0, 0.1, and 0.5 present a variable range hopping behavior. Complex impedance spectroscopy as a function of frequency indicates a pure resistive behavior for x ≥ 0.5 compositions, while a complex resistive-capacitive behavior is observed for low x values (0, 0.1). In these samples, low values of magnetoelectric coupling were measured with an AC lock-in technique.« less

  7. Device simulation of lead-free CH3NH3SnI3 perovskite solar cells with high efficiency

    NASA Astrophysics Data System (ADS)

    Du, Hui-Jing; Wang, Wei-Chao; Zhu, Jian-Zhuo

    2016-10-01

    The lead-free perovskite solar cells (PSCs) have drawn a great deal of research interest due to the Pb toxicity of the lead halide perovskite. CH3NH3SnI3 is a viable alternative to CH3NH3PbX3, because it has a narrower band gap of 1.3 eV and a wider visible absorption spectrum than the lead halide perovskite. The progress of fabricating tin iodide PSCs with good stability has stimulated the studies of these CH3NH3SnI3 based cells greatly. In the paper, we study the influences of various parameters on the solar cell performance through theoretical analysis and device simulation. It is found in the simulation that the solar cell performance can be improved to some extent by adjusting the doping concentration of the perovskite absorption layer and the electron affinity of the buffer and HTM, while the reduction of the defect density of the perovskite absorption layer significantly improves the cell performance. By further optimizing the parameters of the doping concentration (1.3× 1016 cm-3) and the defect density (1× 1015 cm-3) of perovskite absorption layer, and the electron affinity of buffer (4.0 eV) and HTM (2.6 eV), we finally obtain some encouraging results of the J sc of 31.59 mA/cm2, V oc of 0.92 V, FF of 79.99%, and PCE of 23.36%. The results show that the lead-free CH3NH3SnI3 PSC is a potential environmentally friendly solar cell with high efficiency. Improving the Sn2 + stability and reducing the defect density of CH3NH3SnI3 are key issues for the future research, which can be solved by improving the fabrication and encapsulation process of the cell. Project supported by the Graduate Student Education Teaching Reform Project, China (Grant No. JG201512) and the Young Teachers Research Project of Yanshan University, China (Grant No. 13LGB028).

  8. Single Crystal Elasticity of Iron Bearing Perovskite and Post Perovskite Analog

    NASA Astrophysics Data System (ADS)

    Yoneda, A.; Fukui, H.; Baron, A. Q. R.

    2014-12-01

    We measured single crystal elasticity of (1) pure and iron bearing MgSiO3 perovskite, and (2) Pbnm-CaIrO3 and Cmcm-CaIrO3, a representative analog of MgSiO3 perovskite and post perovskite, respectively, by means of inelastic X ray scattering at BL35XU, SPring-8. The present results for MgSiO3 perovskite demonstrate that elastic anisotropy of magnesium perovskite is highly enhanced by iron incorporation. Furthermore anti-correlation between bulk sound velocity and shear wave velocity was confirmed with iron content, which is against the theoretical prediction. The anti-correlation found in this study is important, because it enables us to interpret the recent seismological observation of the anti-correlation in the deep lower mantle by means of iron content difference in perovskite. On the other hand, we can learn difference of elasticity between perovskite and post perovskite thorough measurement on CaIrO3, as analog of MgSiO3 perovskite and post perovskite. From a characteristics of the single crystal elasticity of CaIrO3 compounds, we interpreted the texture pattern in the D" layer consistent with recent seismic observation.

  9. A-site ordered quadruple perovskite oxides

    NASA Astrophysics Data System (ADS)

    Youwen, Long

    2016-07-01

    The A-site ordered perovskite oxides with chemical formula display many intriguing physical properties due to the introduction of transition metals at both A‧ and B sites. Here, research on the recently discovered intermetallic charge transfer occurring between A‧-site Cu and B-site Fe ions in LaCu3Fe4O12 and its analogues is reviewed, along with work on the magnetoelectric multiferroicity observed in LaMn3Cr4O12 with cubic perovskite structure. The Cu-Fe intermetallic charge transfer leads to a first-order isostructural phase transition accompanied by drastic variations in magnetism and electrical transport properties. The LaMn3Cr4O12 is a novel spin-driven multiferroic system with strong magnetoelectric coupling effects. The compound is the first example of cubic perovskite multiferroics to be found. It opens up a new arena for studying unexpected multiferroic mechanisms. Project supported by the National Basic Research Program of China (Grant No. 2014CB921500), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB07030300), and the National Natural Science Foundation of China (Grant No. 11574378).

  10. Field emission properties and strong localization effect in conduction mechanism of nanostructured perovskite LaNiO{sub 3}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Kamble, Ramesh B., E-mail: rbk.physics@coep.ac.in; Department of Physics, College of Engineering, Pune 411005, Maharashtra; Tanty, Narendra

    2016-08-22

    We report the potential field emission of highly conducting metallic perovskite lanthanum nickelate (LaNiO{sub 3}) from the nanostructured pyramidal and whisker shaped tips as electron emitters. Nano particles of lanthanum nickelate (LNO) were prepared by sol-gel route. Structural and morphological studies have been carried out. Field emission of LNO exhibited high emission current density, J = 3.37 mA/cm{sup 2} at a low threshold electric field, E{sub th} = 16.91 V/μm, obeying Fowler–Nordheim tunneling. The DC electrical resistivity exhibited upturn at 11.6 K indicating localization of electron at low temperature. Magnetoresistance measurement at different temperatures confirmed strong localization in nanostructured LNO obeying Anderson localization effect at low temperature.

  11. Low Surface Recombination Velocity in Solution-Grown CH 3NH 3PbBr 3 Perovskite Single Crystal

    DOE PAGES

    Yang, Ye; Yan, Yong; Yang, Mengjin; ...

    2015-08-06

    Organic-inorganic hybrid perovskites are attracting intense research effort due to their impressive performance in solar cells. While the carrier transport parameters such as mobility and bulk carrier lifetime shows sufficient characteristics, the surface recombination, which can have major impact on the solar cell performance, has not been studied. Here we measure surface recombination dynamics in CH 3NH 3PbBr 3 perovskite single crystals using broadband transient reflectance spectroscopy. The surface recombination velocity is found to be 3.4±0.1 10 3 cm s -1, B2–3 orders of magnitude lower than that in many important unpassivated semiconductors employed in solar cells. Our result suggestsmore » that the planar grain size for the perovskite thin films should be larger thanB30 mm to avoid the influence of surface recombination on the effective carrier lifetime.« less

  12. Variation of the conductance enhancement at BaSnO3/LaInxGa1-xO3 polar Interface

    NASA Astrophysics Data System (ADS)

    Kim, Young Mo; Shin, Juyeon; Kim, Youjung; Char, Kookrin

    We have recently reported that La-doped BaSnO3 (BLSO) displayed conductance enhancement by more than 104 times when LaInO3 (LIO) layer was grown on top of the BLSO layer. The conductance enhancement implies the two-dimensional electron gas (2DEG) formation at the interface. To identify the origin of the conductance enhancement, we developed other heterostructures based on different overlayers. Since LaGaO3 is also a polar perovskite like the LIO with its band gap of 4.4 eV and its lattice constant of 3.9, we investigated the variation of the conductance enhancement at LaIn1-xGaxO3 (LIGO)/BLSO interface while varying the Ga ratio. We first checked the interfacial epitaxial growth of LIGO on BSO by x-ray diffraction measurement and transmission electron microscopy. The sheet conductances of BLSO layer before and after the deposition of LIGO layer were measured. Putting together the structural and electrical properties of the LIGO/BLSO interfaces with various Ga compositions, we will discuss the origin of the conductance enhancement in terms of the strain-induced polarization in the LIGO layer. Samsung Science and Technology Foundation.

  13. Iron-based perovskite cathodes for solid oxide fuel cells

    DOEpatents

    Ralph, James M.; Rossignol, Cecile C.R.; Vaughey, John T.

    2007-01-02

    An A and/or A' site deficient perovskite of general formula of (A.sub.1-xA'.sub.x).sub.1-yFeO.sub.3-.delta. or of general formula A.sub.1-x-yA'.sub.xFeO.sub.3-67, wherein A is La alone or with one or more of the rare earth metals or a rare earth metal other than Ce alone or a combination of rare earth metals and X is in the range of from 0 to about 1; A' is Sr or Ca or mixtures thereof and Y is in the range of from about 0.01 to about 0.3; .delta. represents the amount of compensating oxygen loss. If either A or A' is zero the remaining A or A' is deficient. A fuel cell incorporating the inventive perovskite as a cathode is disclosed as well as an oxygen separation membrane. The inventive perovskite is preferably single phase.

  14. Pt nanoparticles residing in the pores of porous LaNiO₃ nanocubes as high-efficiency electrocatalyst for direct methanol fuel cells.

    PubMed

    Yu, Nan; Kuai, Long; Wang, Qing; Geng, Baoyou

    2012-09-07

    Pt-filled porous LaNiO₃ cubes are prepared through a facile route. The characterizations reveal that large numbers of pores (9-10 nm) are distributed homogeneously in porous LaNiO₃ cubes. The Pt nanoparticles residing in the pores of porous LaNiO₃ cubes are about 5 nm in size. The investigation on the electrocatalytic activity reveals that electrocatalytic activity of the obtained Pt loaded porous LaNiO₃ nanocubes exhibit a significantly improved electrochemical active surface area (EASA) and a remarkably enhanced electrocatalytic performance toward methanol oxidation. The results are significant for improving the efficiency of Pt-based catalysts for DMFCs as well as the applications of perovskite compounds.

  15. Efficient CH3NH3PbI3 perovskite/fullerene planar heterojunction hybrid solar cells with oxidized Ni/Au/Cu transparent electrode

    NASA Astrophysics Data System (ADS)

    Lai, Wei-Chih; Lin, Kun-Wei; Guo, Tzung-Fang; Chen, Peter; Liao, Yuan-Yu

    2018-02-01

    We demonstrated the performance of inverted CH3NH3PbI3 perovskite-based solar cells (SCs) with a thermally oxidized nickel/gold/copper (Ni/Au/Cu) trilayer transparent electrode. Oxidized Ni/Au/Cu is a high transparent layer and has less resistance than the oxidized Ni/Au layer. Like the oxidized Ni/Au layer, oxidized Ni and Cu in oxidized Ni/Au/Cu could perform as a hole transport layer of the perovskite-based SCs. It leads to improved perovskite SC performance on an open circuit voltage of 1.01 V, a short circuit current density of 14.36 mA/cm2, a fill factor of 76.7%, and a power conversion efficiency (η%) of 11.1%. The η% of perovskite SCs with oxidized Ni (10 nm)/Au (6 nm)/Cu (1 nm) improved by approximately 10% compared with that of perovskite SCs with oxidized Ni/Au.

  16. Study of defects in an electroresistive Au/La2/3Sr1/3MnO3/SrTiO3(001) heterostructure by positron annihilation

    NASA Astrophysics Data System (ADS)

    Ferragut, R.; Dupaquier, A.; Brivio, S.; Bertacco, R.; Egger, W.

    2011-09-01

    Defects in an ultrathin Au/La2/3Sr1/3MnO3/SrTiO3 (Au/LSMO/STO) heterostructure displaying electroresistive behavior were studied using variable energy positron annihilation spectroscopy. Vacancy-like defects were found to be the dominant positron traps in the LSMO and STO thin perovskite oxides with a number density >1017 cm-3 and 2 × 1017 cm-3 in the STO substrate. High defect density was revealed by strong positron trapping at the Au/LSMO interface. Oxygen deficiency in LSMO would be the main source of these traps. Besides, a low density of sub-nano voids of ˜6 Å was found in the substrate and in the thin LSMO/STO films.

  17. Oxygen vacancy formation characteristics in the bulk and across different surface terminations of La (1₋x)Sr xFe (1₋y)Co yO (3₋δ) perovskite oxides for CO 2 conversion

    DOE PAGES

    Maiti, Debtanu; Daza, Yolanda A.; Yung, Matthew M.; ...

    2016-03-07

    Density functional theory (DFT) based investigation of two parameters of prime interest -- oxygen vacancy and surface terminations along (100) and (110) planes -- has been conducted for La (1-x)Sr xFe(1-y)Co yO (3-more » $$\\delta$$) perovskite oxides in view of their application towards thermochemical carbon dioxide conversion reactions. The bulk oxygen vacancy formation energies for these mixed perovskite oxides are found to increase with increasing lanthanum and iron contents in the 'A' site and 'B' site, respectively. Surface terminations along (100) and (110) crystal planes are studied to probe their stability and their capabilities to accommodate surface oxygen vacancies. Amongst the various terminations, the oxygen-rich (110) surface and strontium-rich (100) surface are the most stable, while transition metal-rich terminations along (100) revealed preference towards the production of oxygen vacancies. The carbon dioxide adsorption strength, a key descriptor for CO 2 conversion reactions, is found to increase on oxygen vacant surfaces thus establishing the importance of oxygen vacancies in CO 2 conversion reactions. Amongst all the surface terminations, the lanthanum-oxygen terminated surface exhibited the strongest CO 2 adsorption strength. Finally, the theoretical prediction of the oxygen vacancy trends and the stability of the samples were corroborated by the temperature-programmed reduction and oxidation reactions and in situ XRD crystallography.« less

  18. Research progress on electronic phase separation in low-dimensional perovskite manganite nanostructures

    PubMed Central

    2014-01-01

    Perovskite oxide manganites with a general formula of R1-x AxMnO3 (where R is a trivalent rare-earth element such as La, Pr, Sm, and A is a divalent alkaline-earth element such as Ca, Sr, and Ba) have received much attention due to their unusual electron-transport and magnetic properties, which are indispensable for applications in microelectronic, magnetic, and spintronic devices. Recent advances in the science and technology have resulted in the feature sizes of microelectronic devices based on perovskite manganite oxides down-scaling into nanoscale dimensions. At the nanoscale, low-dimensional perovskite manganite oxide nanostructures display novel physical properties that are different from their bulk and film counterparts. Recently, there is strong experimental evidence to indicate that the low-dimensional perovskite manganite oxide nanostructures are electronically inhomogeneous, consisting of different spatial regions with different electronic orders, a phenomenon that is named as electronic phase separation (EPS). As the geometry sizes of the low-dimensional manganite nanostructures are reduced to the characteristic EPS length scale (typically several tens of nanometers in manganites), the EPS is expected to be strongly modulated, leading to quite dramatic changes in functionality and more emergent phenomena. Therefore, reduced dimensionality opens a door to the new functionalities in perovskite manganite oxides and offers a way to gain new insight into the nature of EPS. During the past few years, much progress has been made in understanding the physical nature of the EPS in low-dimensional perovskite manganite nanostructures both from experimentalists and theorists, which have a profound impact on the oxide nanoelectronics. This nanoreview covers the research progresses of the EPS in low-dimensional perovskite manganite nanostructures such as nanoparticles, nanowires/nanotubes, and nanostructured films and/or patterns. The possible physical origins of the

  19. Perovskite-perovskite tandem photovoltaics with optimized band gaps

    NASA Astrophysics Data System (ADS)

    Eperon, Giles E.; Leijtens, Tomas; Bush, Kevin A.; Prasanna, Rohit; Green, Thomas; Wang, Jacob Tse-Wei; McMeekin, David P.; Volonakis, George; Milot, Rebecca L.; May, Richard; Palmstrom, Axel; Slotcavage, Daniel J.; Belisle, Rebecca A.; Patel, Jay B.; Parrott, Elizabeth S.; Sutton, Rebecca J.; Ma, Wen; Moghadam, Farhad; Conings, Bert; Babayigit, Aslihan; Boyen, Hans-Gerd; Bent, Stacey; Giustino, Feliciano; Herz, Laura M.; Johnston, Michael B.; McGehee, Michael D.; Snaith, Henry J.

    2016-11-01

    We demonstrate four- and two-terminal perovskite-perovskite tandem solar cells with ideally matched band gaps. We develop an infrared-absorbing 1.2-electron volt band-gap perovskite, FA0.75Cs0.25Sn0.5Pb0.5I3, that can deliver 14.8% efficiency. By combining this material with a wider-band gap FA0.83Cs0.17Pb(I0.5Br0.5)3 material, we achieve monolithic two-terminal tandem efficiencies of 17.0% with >1.65-volt open-circuit voltage. We also make mechanically stacked four-terminal tandem cells and obtain 20.3% efficiency. Notably, we find that our infrared-absorbing perovskite cells exhibit excellent thermal and atmospheric stability, not previously achieved for Sn-based perovskites. This device architecture and materials set will enable “all-perovskite” thin-film solar cells to reach the highest efficiencies in the long term at the lowest costs.

  20. Transition from orbital liquid to Jahn-Teller insulator in orthorhombic perovskites RTiO3.

    PubMed

    Cheng, J-G; Sui, Y; Zhou, J-S; Goodenough, J B; Su, W H

    2008-08-22

    Following the same strategy used for RVO3, thermal conductivity measurements have been made on a series of single-crystal perovskites RTiO3 (R=La,Nd,...,Yb). Results reveal explicitly a transition from an orbital liquid to an orbitally ordered phase at a magnetic transition temperature, which is common for both the antiferromagnetic and ferromagnetic phases in the phase diagram of RTiO3. This spin/orbital transition is consistent with the mode softening at T_{N} in antiferromagnetic LaTiO3 and is supported by an anomalous critical behavior at T_{c} in ferromagnetic YTiO3.

  1. The electronic and optical properties of CH3NH3MoI3 perovskite

    NASA Astrophysics Data System (ADS)

    Kansara, Shivam; Sonvane, Yogesh; Gupta, Sanjeev K.

    2018-05-01

    In this work, a first-principles theoretical study of hybrid perovskite CH3NH3MoI3 is performed using PBE exchange-correlation approximations in density functional theory. The results of electronic band structure are 0.90 eV (M-point: Direct) and 0.60 eV (R-X point: Indirect), respectively. We have also calculated the dielectric properties such as real, imaginary, extension coefficient (K) and reflectivity (R) properties of hybrid perovskite CH3NH3MoI3. The low-bandgap molecules are used to absorb near-IR range and typically having a bandgap smaller than 1.6 eV. This is particularly attractive in organic photovoltaics (OPV), photodetectors (PDs), and ambipolar field-effect transistors (FETs).

  2. Disorder induced magnetism and electrical conduction in La doped Ca2FeMoO6 double perovskite

    NASA Astrophysics Data System (ADS)

    Poddar, Asok; Bhowmik, R. N.; Muthuselvam, I. Panneer

    2010-11-01

    We report the magnetism and electrical transport properties of La doped Ca2FeMoO6 double perovskite. Reduction in magnetic moment, nonmonotonic variation in magnetic ordering temperature (TC), increasing magnetic hardness, low temperature resistivity upturn, and loss of metallic conductivity are some of the major changes that we observed due to La doping induced disorder in double perovskite structure. The increase in magnetic disorder in La doped samples and its effect on TC is more consistent with the mean field theory. The modification in electronic band structure due to La doping is understood by establishing a correlation between the temperature dependence of electrical conductivity and thermoelectric power.

  3. Control of oleylamine to perovskite ratio in synthesis of MAPbBr3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Huang, Jing; Wu, Yi-Hua; Zhu, Zhi-Gang; Shih, Wan Y.; Shih, Wei-Heng

    2018-06-01

    Methylammonium lead bromide (CH3NH3PbBr3) nanocrystals have great potentials for lighting and display applications. Previously we synthesized CH3NH3PbBr3 nanocrystals using oleylamine as capping molecule and found that by increasing the oleylamine to CH3NH3PbBr3 perovskite ratio (OPR), the photoluminescence wavelengths and morphology of CH3NH3PbBr3 nanocrystals could be varied from 530 nm (green) platelets to 460 nm (blue) particles. Here we modified the synthesis to direct injection of precursors into toluene and found that increasing OPR not only changes the wavelength and morphology of nanocrystals but also the size of the unit cells.

  4. Interplay of structural chemistry and magnetism in perovskites; A study of CaLn2Ni2WO9; Ln=La, Pr, Nd

    NASA Astrophysics Data System (ADS)

    Chin, Chun-Mann; Paria Sena, Robert; Hunter, Emily C.; Hadermann, Joke; Battle, Peter D.

    2017-07-01

    Polycrystalline samples of CaLn2Ni2WO9 (Ln=La, Pr, Nd) have been synthesized and characterised by a combination of X-ray and neutron diffraction, electron microscopy and magnetometry. Each composition adopts a perovskite-like structure with a 5.50, b 5.56, c 7.78 Å, β 90.1° in space group P21/n. Of the two crystallographically distinct six-coordinate sites, one is occupied entirely (Ln=Pr) or predominantly (Ln=La, Nd) by Ni2+ and the other by Ni2+ and W6+ in a ratio of approximately 1:2. None of the compounds shows long-range magnetic order at 5 K. The magnetometry data show that the magnetic moments of the Ni2+ cations form a spin glass below 30 K in each case. The Pr3+ moments in CaPr2Ni2WO9 also freeze but the Nd3+ moments in CaNd2Ni2WO9 do not. This behaviour is contrasted with that observed in other (A,A')B2B'O9 perovskites.

  5. Polarized emission from CsPbX3 perovskite quantum dots

    NASA Astrophysics Data System (ADS)

    Wang, Dan; Wu, Dan; Dong, Di; Chen, Wei; Hao, Junjie; Qin, Jing; Xu, Bing; Wang, Kai; Sun, Xiaowei

    2016-06-01

    Compared to organic/inorganic hybrid perovskites, full inorganic perovskite quantum dots (QDs) exhibit higher stability. In this study, full inorganic CsPbX3 (X = Br, I and mixed halide systems Br/I) perovskite QDs have been synthesized and interestingly, these QDs showed highly polarized photoluminescence which is systematically studied for the first time. Furthermore, the polarization of CsPbI3 was as high as 0.36 in hexane and 0.40 as a film. The CsPbX3 perovskite QDs with high polarization properties indicate that they possess great potential for application in new generation displays with wide colour gamut and low power consumption.Compared to organic/inorganic hybrid perovskites, full inorganic perovskite quantum dots (QDs) exhibit higher stability. In this study, full inorganic CsPbX3 (X = Br, I and mixed halide systems Br/I) perovskite QDs have been synthesized and interestingly, these QDs showed highly polarized photoluminescence which is systematically studied for the first time. Furthermore, the polarization of CsPbI3 was as high as 0.36 in hexane and 0.40 as a film. The CsPbX3 perovskite QDs with high polarization properties indicate that they possess great potential for application in new generation displays with wide colour gamut and low power consumption. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01915c

  6. Synthesis of layered perovskite oxides, ACa[sub 2-x]La[sub x]Nb[sub 3-x]Ti[sub x]O[sub 10] (A = K, Rb, Cs), and characterization of new solid acids, HCa[sub 2-x]La[sub x]Nb[sub 3-x]Ti[sub x]O[sub 10] (O < x [le] 2), exhibiting variable Bronsted acidity

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gopalakrishnan, J.; Uma, S.; Bhat, V.

    1993-01-01

    Layered perovskite oxides of the formula ACa[sub 2-x]La[sub x]Nb[sub 3-x]Ti[sub x]O[sub 10] (A = K, Rb, Cs and 0 , x [le] 2) have been prepared. The members adopt the structures of the parent ACa[sub 2]Nb[sub 3]O[sub 10]. Interlayer alkali cations in the niobium-titanium oxide series can be ion-exchanged with Li[sup +], Na[sup +], NG[sub 4][sup +], of H[sup +] to give new derivatives. Intercalation of the protonated derivatives with organic bases reveals that the Bronsted acidity of the solid solution series, HCa[sub 2-x]La[sub x]Nb[sub 3-x]Ti[sub x]O[sub 10], depends on the titanium content. While the x = 1 member (HCaLaNb[submore » 2]TiO[sub 10]) is nearly as acidic as the parent HCa[sub 2]Nb[sub 3]O[sub 10], the x = 2 member (HLA[sub 2]NbTi[sub 2]O[sub 10]) is a weak acid hardly intercalating organic bases with pK[sub a] [approximately] 11.3. The variation of acidity is probably due to an ordering of Nb/Ti atoms in the triple octahedral perovskite slabs, [Ca[sub 2-x]La[sub x]Nb[sub 3-x]Ti[sub x]O[sub 10

  7. A density functional theory study of self-regenerating catalysts LaFe(1-x)M(x)O(3-y) (M = Pd, Rh, Pt).

    PubMed

    Hamada, Ikutaro; Uozumi, Akifumi; Morikawa, Yoshitada; Yanase, Akira; Katayama-Yoshida, Hiroshi

    2011-11-23

    Periodic density functional theory was used to investigate the stability and electronic structures of precious-metal atoms in the vicinity of LaFe(1-x)M(x)O(3) (M = Pd, Rh, Pt) perovskite catalyst surfaces. It was found that the surface segregation of Pd and Pt is significantly stabilized by the introduction of O vacancies, whereas the solid-solution phase is favorable for Rh, suggesting an important role of O vacancies in the self-regeneration of Pd and Pt. On the basis of the results, we propose a possible scenario for the self-regeneration of the precious metal in the perovskite catalyst.

  8. Local structure in LaMnO3 and CaMnO3 perovskites: A quantitative structural refinement of Mn K -edge XANES data

    NASA Astrophysics Data System (ADS)

    Monesi, C.; Meneghini, C.; Bardelli, F.; Benfatto, M.; Mobilio, S.; Manju, U.; Sarma, D. D.

    2005-11-01

    Hole-doped perovskites such as La1-xCaxMnO3 present special magnetic and magnetotransport properties, and it is commonly accepted that the local atomic structure around Mn ions plays a crucial role in determining these peculiar features. Therefore experimental techniques directly probing the local atomic structure, like x-ray absorption spectroscopy (XAS), have been widely exploited to deeply understand the physics of these compounds. Quantitative XAS analysis usually concerns the extended region [extended x-ray absorption fine structure (EXAFS)] of the absorption spectra. The near-edge region [x-ray absorption near-edge spectroscopy (XANES)] of XAS spectra can provide detailed complementary information on the electronic structure and local atomic topology around the absorber. However, the complexity of the XANES analysis usually prevents a quantitative understanding of the data. This work exploits the recently developed MXAN code to achieve a quantitative structural refinement of the Mn K -edge XANES of LaMnO3 and CaMnO3 compounds; they are the end compounds of the doped manganite series LaxCa1-xMnO3 . The results derived from the EXAFS and XANES analyses are in good agreement, demonstrating that a quantitative picture of the local structure can be obtained from XANES in these crystalline compounds. Moreover, the quantitative XANES analysis provides topological information not directly achievable from EXAFS data analysis. This work demonstrates that combining the analysis of extended and near-edge regions of Mn K -edge XAS spectra could provide a complete and accurate description of Mn local atomic environment in these compounds.

  9. Properties of highly (100) oriented Pb(Mg1/3,Nb2/3)O3-PbTiO3 films on LaNiO3 bottom electrodes

    NASA Astrophysics Data System (ADS)

    Li, Y. W.; Hu, Z. G.; Yue, F. Y.; Yang, G. Y.; Shi, W. Z.; Meng, X. J.; Sun, J. L.; Chu, J. H.

    2007-12-01

    The 70%Pb(Mg1/3,Nb2/3)O3-30%PbTiO3 (PMNT) films have been fabricated on LaNiO3 (LNO) coated silicon substrate. The conductive LNO films act as a seed layer for the growth of PMNT films, which depresses the formation of pyrochlore phase and induces the high (100) preferred orientation of perovskite PMNT films. Compared with the PMNT films grown on platinum bottom electrode, the ferroelectric properties of PMNT films grown on LNO are enhanced. The frequency dependence of complex permittivity from PMNT films on LNO is the conjunct result of polarization relaxation and movement of oxygen vacancy, which can be fitted by the function containing Debye and universal dielectric response models, respectively.

  10. Nano sized La2Co2O6 double perovskite synthesized by sol gel method

    NASA Astrophysics Data System (ADS)

    Solanki, Neha; Lodhi, Pavitra Devi; Choudhary, K. K.; Kaurav, Netram

    2018-05-01

    We report here the synthesis of double perovskite La2Co2O6 (LCO) compound by a sol gel route method. The double perovskite structure of LCO system was confirmed via X-ray diffraction (XRD) analysis. Further, the lattice parameter, unit cell volume and bond length were refined by means of rietveld analysis using the full proof software. Debye Scherer formula was used to determine the particle size. The compound crystallized in triclinic structure with space group P-1 in ambient condition. We also obtained Raman modes from XRD spectra of poly-crystalline LCO sample. These results were interpreted for the observation of phonon excitations in this compound.

  11. Simplified Perovskite Solar Cell with 4.1% Efficiency Employing Inorganic CsPbBr3 as Light Absorber.

    PubMed

    Duan, Jialong; Zhao, Yuanyuan; He, Benlin; Tang, Qunwei

    2018-05-01

    Perovskite solar cells with cost-effectiveness, high power conversion efficiency, and improved stability are promising solutions to the energy crisis and environmental pollution. However, a wide-bandgap inorganic-semiconductor electron-transporting layer such as TiO 2 can harvest ultraviolet light to photodegrade perovskite halides, and the high cost of a state-of-the-art hole-transporting layer is an economic burden for commercialization. Here, the building of a simplified cesium lead bromide (CsPbBr 3 ) perovskite solar cell with fluorine-doped tin oxide (FTO)/CsPbBr 3 /carbon architecture by a multistep solution-processed deposition technology is demonstrated, achieving an efficiency as high as 4.1% and improved stability upon interfacial modification by graphene quantum dots and CsPbBrI 2 quantum dots. This work provides new opportunities of building next-generation solar cells with significantly simplified processes and reduced production costs. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Delivery of the autofluorescent protein R-phycoerythrin by calcium phosphate nanoparticles into four different eukaryotic cell lines (HeLa, HEK293T, MG-63, MC3T3): Highly efficient, but leading to endolysosomal proteolysis in HeLa and MC3T3 cells.

    PubMed

    Kopp, Mathis; Rotan, Olga; Papadopoulos, Chrisovalantis; Schulze, Nina; Meyer, Hemmo; Epple, Matthias

    2017-01-01

    Nanoparticles can be used as carriers to transport biomolecules like proteins and synthetic molecules across the cell membrane because many molecules are not able to cross the cell membrane on their own. The uptake of nanoparticles together with their cargo typically occurs via endocytosis, raising concerns about the possible degradation of the cargo in the endolysosomal system. As the tracking of a dye-labelled protein during cellular uptake and processing is not indicative of the presence of the protein itself but only for the fluorescent label, a label-free tracking was performed with the red-fluorescing model protein R-phycoerythrin (R-PE). Four different eukaryotic cell lines were investigated: HeLa, HEK293T, MG-63, and MC3T3. Alone, the protein was not taken up by any cell line; only with the help of calcium phosphate nanoparticles, an efficient uptake occurred. After the uptake into HeLa cells, the protein was found in early endosomes (shown by the marker EEA1) and lysosomes (shown by the marker Lamp1). There, it was still intact and functional (i.e. properly folded) as its red fluorescence was detected. However, a few hours after the uptake, proteolysis started as indicated by the decreasing red fluorescence intensity in the case of HeLa and MC3T3 cells. 12 h after the uptake, the protein was almost completely degraded in HeLa cells and MC3T3 cells. In HEK293T cells and MG-63 cells, no degradation of the protein was observed. In the presence of Bafilomycin A1, an inhibitor of acidification and protein degradation in lysosomes, the fluorescence of R-PE remained intact over the whole observation period in the four cell lines. These results indicate that despite an efficient nanoparticle-mediated uptake of proteins by cells, a rapid endolysosomal degradation may prevent the desired (e.g. therapeutic) effect of a protein inside a cell.

  13. Room temperature three-photon pumped CH3NH3PbBr3 perovskite microlasers.

    PubMed

    Gao, Yisheng; Wang, Shuai; Huang, Can; Yi, Ningbo; Wang, Kaiyang; Xiao, Shumin; Song, Qinghai

    2017-03-28

    Hybrid lead halide perovskites have made great strides in next-generation light-harvesting and light emitting devices. Recently, they have also shown great potentials in nonlinear optical materials. Two-photon absorption and two-photon light emission have been thoroughly studied in past two years. However, the three-photon processes are rarely explored, especially for the laser emissions. Here we synthesized high quality CH 3 NH 3 PbBr 3 perovskite microstructures with solution processed precipitation method and studied their optical properties. When the microstructures are pumped with intense 1240 nm lasers, we have observed clear optical limit effect and the band-to-band photoluminescence at 540 nm. By increasing the pumping density, whispering-gallery-mode based microlasers have been achieved from CH 3 NH 3 PbBr 3 perovskite microplate and microrod for the first time. This work demonstrates the potentials of hybrid lead halide perovskites in nonlinear photonic devices.

  14. Room temperature three-photon pumped CH3NH3PbBr3 perovskite microlasers

    NASA Astrophysics Data System (ADS)

    Gao, Yisheng; Wang, Shuai; Huang, Can; Yi, Ningbo; Wang, Kaiyang; Xiao, Shumin; Song, Qinghai

    2017-03-01

    Hybrid lead halide perovskites have made great strides in next-generation light-harvesting and light emitting devices. Recently, they have also shown great potentials in nonlinear optical materials. Two-photon absorption and two-photon light emission have been thoroughly studied in past two years. However, the three-photon processes are rarely explored, especially for the laser emissions. Here we synthesized high quality CH3NH3PbBr3 perovskite microstructures with solution processed precipitation method and studied their optical properties. When the microstructures are pumped with intense 1240 nm lasers, we have observed clear optical limit effect and the band-to-band photoluminescence at 540 nm. By increasing the pumping density, whispering-gallery-mode based microlasers have been achieved from CH3NH3PbBr3 perovskite microplate and microrod for the first time. This work demonstrates the potentials of hybrid lead halide perovskites in nonlinear photonic devices.

  15. Efficient ambient-air-stable solar cells with 2D-3D heterostructured butylammonium-caesium-formamidinium lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Wang, Zhiping; Lin, Qianqian; Chmiel, Francis P.; Sakai, Nobuya; Herz, Laura M.; Snaith, Henry J.

    2017-09-01

    Perovskite solar cells are remarkably efficient; however, they are prone to degradation in water, oxygen and ultraviolet light. Cation engineering in 3D perovskite absorbers has led to reduced degradation. Alternatively, 2D Ruddlesden-Popper layered perovskites exhibit improved stability, but have not delivered efficient solar cells so far. Here, we introduce n-butylammonium cations into a mixed-cation lead mixed-halide FA0.83Cs0.17Pb(IyBr1-y)3 3D perovskite. We observe the formation of 2D perovskite platelets, interspersed between highly orientated 3D perovskite grains, which suppress non-radiative charge recombination. We investigate the relationship between thin-film composition, crystal alignment and device performance. Solar cells with an optimal butylammonium content exhibit average stabilized power conversion efficiency of 17.5 ± 1.3% with a 1.61-eV-bandgap perovskite and 15.8 ± 0.8% with a 1.72-eV-bandgap perovskite. The stability under simulated sunlight is also enhanced. Cells sustain 80% of their 'post burn-in' efficiency after 1,000 h in air, and close to 4,000 h when encapsulated.

  16. Phase Constitution in Sr and Mg doped LaGaO3 System

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zheng, F; Bordia, Rajendra K.; Pederson, Larry R.

    Sr and Mg doped lanthanum gallate perovskites (La1-xSrxGa1-yMgyO3-delta, shortened as LSGM-XY where X and Y are the doping levels in mole percentage (mol%) at the La- or A-site and the Ga- or B-site, respectively) are promising electrolyte materials for intermediate temperature solid oxide fuel cells (SOFCs). In this study, we have investigated the primary perovskites as well as the secondary phases formed in terms of doping content changes and A/B ratio variations in these materials. Fifteen powder compositions (three doping levels, X = Y = 0, 0.1, and 0.2 mol; and five A/B ratios 0.95, 0.98, 1.00, 1.02, and 1.05)more » were synthesized by the glycine-nitrate combustion process (GNP). These powders were equilibrated by calcining at 1500 degreesC for 9 h prior to crystalline phase characterization by X-ray powder diffraction (XRD). From the results of this study and the available phase diagrams in the literature on constituent binary oxide systems, we propose a crystalline phase diagram of the La2O3-SrO-Ga2O3-MgO quaternary system at elevated temperature (1500 degreesC). (C) 2003 Elsevier Ltd. All rights reserved« less

  17. Realization of single terminated surface of perovskite oxide single crystals and their band profile: (LaAlO3)0.3(Sr2AlTaO6)0.7, SrTiO3 and KTaO3 case study

    NASA Astrophysics Data System (ADS)

    Tomar, Ruchi; Wadehra, Neha; Budhiraja, Vaishali; Prakash, Bhanu; Chakraverty, S.

    2018-01-01

    To characterize the physical properties of thin films without ambiguity and design interface with new functionalities, it is essential to have detailed knowledge of physical properties and appropriate estimation of the band profile of perovskite oxide substrates. We have developed and demonstrated a chemical free unified framework to realize single terminated surface of KTaO3, (LaAlO3)0.3 (Sr2AlTaO6)0.7 and SrTiO3 (001) oriented single crystals. The electronic band line-up of these single crystal substrates, using a combination of optical spectroscopy and Kelvin Probe Force Microscopy, has been constructed. A polar-polar interface of KTaO3 and LaBO3 (B-Transition metal ion) before and after the possible surface/electronic reconstruction has also been schematically presented.

  18. Nb5+-Doped SrCoO3Perovskites as Potential Cathodes for Solid-Oxide Fuel Cells.

    PubMed

    Cascos, Vanessa; Alonso, José Antonio; Fernández-Díaz, María Teresa

    2016-07-15

    SrCoO 3- δ outperforms as cathode material in solid-oxide fuel cells (SOFC) when the three-dimensional (3C-type) perovskite structure is stabilized by the inclusion of highly-charged transition-metal ions at the octahedral positions. In a previous work we studied the Nb incorporation at the Co positions in the SrCo 1- x Nb x O 3- δ system, in which the stabilization of a tetragonal P4 / mmm perovskite superstructure was described for the x = 0.05 composition. In the present study we extend this investigation to the x = 0.10-0.15 range, also observing the formation of the tetragonal P4 / mmm structure instead of the unwanted hexagonal phase corresponding to the 2H polytype. We also investigated the effect of Nb 5+ doping on the thermal, electrical, and electrochemical properties of SrCo 1- x Nb x O 3- δ ( x = 0.1 and 0.15) perovskite oxides performing as cathodes in SOFC. In comparison with the undoped hexagonal SrCoO 3- δ phase, the resulting compounds present high thermal stability and an increase of the electrical conductivity. The single-cell tests for these compositions ( x = 0.10 and 0.15) with La 0.8 Sr 0.2 Ga 0.83 Mg 0.17 O 3- δ (LSGM) as electrolyte and SrMo 0.8 Fe 0.2 CoO 3- δ as anode gave maximum power densities of 693 and 550 mW∙cm -2 at 850 °C respectively, using pure H₂ as fuel and air as oxidant.

  19. Prospects for Engineering Thermoelectric Properties in La1/3NbO3 Ceramics Revealed via Atomic-Level Characterization and Modeling.

    PubMed

    Kepaptsoglou, Demie; Baran, Jakub D; Azough, Feridoon; Ekren, Dursun; Srivastava, Deepanshu; Molinari, Marco; Parker, Stephen C; Ramasse, Quentin M; Freer, Robert

    2018-01-02

    A combination of experimental and computational techniques has been employed to explore the crystal structure and thermoelectric properties of A-site-deficient perovskite La 1/3 NbO 3 ceramics. Crystallographic data from X-ray and electron diffraction confirmed that the room temperature structure is orthorhombic with Cmmm as a space group. Atomically resolved imaging and analysis showed that there are two distinct A sites: one is occupied with La and vacancies, and the second site is fully unoccupied. The diffuse superstructure reflections observed through diffraction techniques are shown to originate from La vacancy ordering. La 1/3 NbO 3 ceramics sintered in air showed promising high-temperature thermoelectric properties with a high Seebeck coefficient of S 1 = -650 to -700 μV/K and a low and temperature-stable thermal conductivity of k = 2-2.2 W/m·K in the temperature range of 300-1000 K. First-principles electronic structure calculations are used to link the temperature dependence of the Seebeck coefficient measured experimentally to the evolution of the density of states with temperature and indicate possible avenues for further optimization through electron doping and control of the A-site occupancies. Moreover, lattice thermal conductivity calculations give insights into the dependence of the thermal conductivity on specific crystallographic directions of the material, which could be exploited via nanostructuring to create high-efficiency compound thermoelectrics.

  20. Highly Stable, New, Organic-Inorganic Perovskite (CH3 NH3 )2 PdBr4 : Synthesis, Structure, and Physical Properties.

    PubMed

    Liu, Xixia; Huang, Tang Jiao; Zhang, Liuyang; Tang, Baoshan; Zhang, Nengduo; Shi, Diwen; Gong, Hao

    2018-04-03

    Lead halide perovskites have attracted striking attention recently, due to their appealing properties. However, toxicity and stability are two main factors restricting their application. In this work, a less toxic and highly stable Pd-based hybrid perovskite was experimentally synthesized, after exploring different experimental conditions. This new hybrid organic-inorganic perovskite (CH 3 NH 3 ) 2 PdBr 4 was found to be an orthorhombic crystal (Cmce, Z=4) with lattice parameters a=8.00, b=7.99, c=18.89 Å. The Cmce symmetry and lattice parameters were confirmed using Pawley refinement and the atoms positions were confirmed based on DFT calculation. This perovskite compound was determined to be a p-type semiconductor, with a resistivity of 102.9 kΩ cm, a carrier concentration of 3.4 ×10 12  cm -3 , and a mobility of 23.4 cm 2  (V s) -1 . Interestingly, XRD and UV/Vis measurements indicated that the phase of this new perovskite was maintained with an optical gap of 1.91 eV after leaving in air with a high humidity of 60 % for 4 days, and unchanged for months in N 2 atmosphere; much more stable than most existing organic-inorganic perovskites. The synthesis and various characterizations of this work further the understanding of this (CH 3 NH 3 ) 2 PdBr 4 organic-inorganic hybrid perovskite material. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Magnetic, Electrical and Dielectric Properties of LaMnO3Perovskite Manganite.

    NASA Astrophysics Data System (ADS)

    v, Punith Kumar; Dayal, Vijaylakshmi

    The high pure polycrystalline LaMnO3perovskite manganite has been synthesized using conventional solid state reaction method. The studied sample crystallizes into orthorhombic O', phase indexed with Pbnm space group. The magnetization measurement exhibits that the studied sample shows paramagnetic (PM) to ferromagnetic (FM) phase transition at TC = 191.6K followed with a frustration due to antiferromagnetic (AFM) kind of spin ordering at low temperature, Tf = 85.8K. The electrical resistivity measurements carried out at 0 tesla and 8 tesla magnetic field exhibits insulating kind of behavior throughout the measured temperature range. The resistivity at 0 tesla exhibits low temperature FM insulator to high temperature PM insulator type phase transition at TC = 191.6K similarly as observed from magnetization measurement. The application of the magnetic field (8 tesla) shifts TC to higher temperature side and the charge transport follows Shklovskii Efros variable range hopping (SE VRH) mechanism. The temperature and frequency dependent dielectric permittivity studied for the sample exhibits relaxation process explained based on Debye +Maxwell-Wagner relaxation mechanism. Department of Atomic Energy-Board of Research in Nuclear Sciences, Government of INDIA.

  2. Moss-Burstein shift in La-doped BaSnO3; A novel electron transport layer material for hybrid halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Taya, Ankur; Rani, Priti; Kashyap, Manish K.

    2018-04-01

    Highly efficient hybrid (organic-inorganic) halide perovskite solar cells (PSCs) employ TiO2 as electron transport layer (ETL) but it impedes the device stability under solar illumination. Therefore, there is an imperative need to study the materials that can be the ideal replacement for TiO2 as ETL. With its growth at mild conditions recently by Shin et al. [Science, 356, 167 (2017)], La-doped BaSnO3 (LBSO) emerges out as an efficient candidate for ETL in PSCs. In this direction, we represent first-principles electronic properties and optical response of pristine and La-doped BaSnO3 using full potential linear augmented plane wave (FPLAPW) method within time efficient orbital independent modified Becke Johnson (mBJ) approach. Post La-doping, Moss-Burtsein shift is observed in BaSnO3 that establishes it as an excellent n-type transparent conducting oxide. The optical absorption spectra of LBSO has been analyzed to prove almost full transmittivity for energy ≤ 4eV which affirms LBSO as an ideal material for ETL in various PSCs.

  3. CsI Pre-Intercalation in the Inorganic Framework for Efficient and Stable FA1-x Csx PbI3 (Cl) Perovskite Solar Cells.

    PubMed

    Zhou, Ning; Shen, Yiheng; Zhang, Yu; Xu, Ziqi; Zheng, Guanhaojie; Li, Liang; Chen, Qi; Zhou, Huanping

    2017-06-01

    Engineering the chemical composition of organic and inorganic hybrid perovskite materials is one of the most feasible methods to boost the efficiency of perovskite solar cells with improved device stability. Among the diverse hybrid perovskite family of ABX 3 , formamidinium (FA)-based mixed perovskite (e.g., FA 1- x Cs x PbI 3 ) possesses optimum bandgaps, superior optoelectronic property, as well as thermal- and photostability, which is proven to be the most promising candidate for advanced solar cell. Here, FA 0.9 Cs 0.1 PbI 3 (Cl) is implemented as the light-harvesting layer in planar devices, whereas a low temperature, two-step solution deposition method is employed for the first time in this materials system. This paper comprehensively exploits the role of Cs + in the FA 0.9 Cs 0.1 PbI 3 (Cl) perovskite that affects the precursor chemistry, film nucleation and grain growth, and defect property via pre-intercalation of CsI in the inorganic framework. In addition, the resultant FA 0.9 Cs 0.1 PbI 3 (Cl) films are demonstrated to exhibit an improved optoelectronic property with an elevated device power conversion efficiency (PCE) of 18.6%, as well as a stable phase with substantial enhancement in humidity and thermal stability, as compared to that of FAPbI 3 (Cl). The present method is able to be further extended to a more complicated (FA,MA,Cs)PbX 3 material system by delivering a PCE of 19.8%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Spinel Co3O4 nanomaterials for efficient and stable large area carbon-based printed perovskite solar cells.

    PubMed

    Bashir, Amna; Shukla, Sudhanshu; Lew, Jia Haur; Shukla, Shashwat; Bruno, Annalisa; Gupta, Disha; Baikie, Tom; Patidar, Rahul; Akhter, Zareen; Priyadarshi, Anish; Mathews, Nripan; Mhaisalkar, Subodh G

    2018-02-01

    Carbon based perovskite solar cells (PSCs) are fabricated through easily scalable screen printing techniques, using abundant and cheap carbon to replace the hole transport material (HTM) and the gold electrode further reduces costs, and carbon acts as a moisture repellent that helps in maintaining the stability of the underlying perovskite active layer. An inorganic interlayer of spinel cobaltite oxides (Co 3 O 4 ) can greatly enhance the carbon based PSC performance by suppressing charge recombination and extracting holes efficiently. The main focus of this research work is to investigate the effectiveness of Co 3 O 4 spinel oxide as the hole transporting interlayer for carbon based perovskite solar cells (PSCs). In these types of PSCs, the power conversion efficiency (PCE) is restricted by the charge carrier transport and recombination processes at the carbon-perovskite interface. The spinel Co 3 O 4 nanoparticles are synthesized using the chemical precipitation method, and characterized by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and UV-Vis spectroscopy. A screen printed thin layer of p-type inorganic spinel Co 3 O 4 in carbon PSCs provides a better-energy level matching, superior efficiency, and stability. Compared to standard carbon PSCs (PCE of 11.25%) an improved PCE of 13.27% with long-term stability, up to 2500 hours under ambient conditions, is achieved. Finally, the fabrication of a monolithic perovskite module is demonstrated, having an active area of 70 cm 2 and showing a power conversion efficiency of >11% with virtually no hysteresis. This indicates that Co 3 O 4 is a promising interlayer for efficient and stable large area carbon PSCs.

  5. First principles investigation of half-metallicity and spin gapless semiconductor in CH3NH3Cr x Pb1- x I3 mixed perovskites

    NASA Astrophysics Data System (ADS)

    Huang, H. M.; Zhu, Z. W.; Zhang, C. K.; He, Z. D.; Luo, S. J.

    2018-04-01

    The structural, electronic and magnetic properties of organic-inorganic hybrid mixed perovskites CH3NH3Cr x Pb1- x I3 ( x = 0.25, 0.50, 0.75, 1.00) in cubic, tetragonal and orthorhombic phases have been investigated by first-principles calculation. The results indicate that the tetragonal CH3NH3Cr0.75Pb0.25I3 is a spin gapless semiconductor with Curie temperature of 663 K estimated using mean field approximation. All other CH3NH3Cr x Pb1- x I3 mixed perovskites are half-metallic ferromagnets together with 100% spin polarization, and their total magnetic moment are 4.00, 8.00, 12.00 and 16.00 µB per unit cell for x = 0.25, 0.50, 0.75 and 1.00, respectively. The effect of <100>, <110> and <111> orientation of organic cation CH3NH3 + on the electronic properties of CH3NH3Cr0.50Pb0.50I3 was investigated. The results show that the CH3NH3 + in different orientations have a slight effect on the lattice constants, the energy gap in minority-spin states, half-metallic gap, local magnetic moment, and Curie temperature.

  6. Thermodynamic stability of stoichiometric LaFeO3 and BiFeO3: a hybrid DFT study.

    PubMed

    Heifets, Eugene; Kotomin, Eugene A; Bagaturyants, Alexander A; Maier, Joachim

    2017-02-01

    BiFeO 3 perovskite attracts great attention due to its multiferroic properties and potential use as a parent material for Bi 1-x Sr x FeO 3-δ and Bi 1-x Sr x Fe 1-y Co y O 3-δ solid solutions in intermediate temperature cathodes of oxide fuel cells. Another iron-based LaFeO 3 perovskite is the end member for well-known solid solutions (La 1-x Sr x Fe 1-y Co y O 3-δ ) used for oxide fuel cells and other electrochemical devices. In this study an ab initio hybrid functional approach was used for the study of the thermodynamic stability of both LaFeO 3 and BiFeO 3 with respect to decompositions to binary oxides and to elements, as a function of temperature and oxygen pressure. The localized (LCAO) basis sets describing the crystalline electron wave functions were carefully re-optimized within the CRYSTAL09 computer code. The results obtained by considering Fe as an all-electron atom and within the effective core potential technique are compared in detail. Based on our calculations, the phase diagrams were constructed allowing us to predict the stability region of stoichiometric materials in terms of atomic chemical potentials. This permits determining the environmental conditions for the existence of stable BiFeO 3 and LaFeO 3 . These conditions were presented as contour maps of oxygen atoms' chemical potential as a function of temperature and partial pressure of oxygen gas. A similar analysis was also performed using the experimental Gibbs energies of formation. The obtained phase diagrams and contour maps are compared with the calculated ones.

  7. Modulated CH3NH3PbI3−xBrx film for efficient perovskite solar cells exceeding 18%

    PubMed Central

    Tu, Yongguang; Wu, Jihuai; Lan, Zhang; He, Xin; Dong, Jia; Jia, Jinbiao; Guo, Panfeng; Lin, Jianming; Huang, Miaoliang; Huang, Yunfang

    2017-01-01

    The organic-inorganic lead halide perovskite layer is a crucial factor for the high performance perovskite solar cell (PSC). We introduce CH3NH3Br in the precursor solution to prepare CH3NH3PbI3−xBrx hybrid perovskite, and an uniform perovskite layer with improved crystallinity and apparent grain contour is obtained, resulting in the significant improvement of photovoltaic performance of PSCs. The effects of CH3NH3Br on the perovskite morphology, crystallinity, absorption property, charge carrier dynamics and device characteristics are discussed, and the improvement of open circuit voltage of the device depended on Br doping is confirmed. Based on above, the device based on CH3NH3PbI2.86Br0.14 exhibits a champion power conversion efficiency (PCE) of 18.02%. This study represents an efficient method for high-performance perovskite solar cell by modulating CH3NH3PbI3−xBrx film. PMID:28303938

  8. Effect of A-Site Cation Ordering on Chemical Stability, Oxygen Stoichiometry and Electrical Conductivity in Layered LaBaCo2O5+δ Double Perovskite

    PubMed Central

    Bernuy-Lopez, Carlos; Høydalsvik, Kristin; Einarsrud, Mari-Ann; Grande, Tor

    2016-01-01

    The effect of the A-site cation ordering on the chemical stability, oxygen stoichiometry and electrical conductivity in layered LaBaCo2O5+δ double perovskite was studied as a function of temperature and partial pressure of oxygen. Tetragonal A-site cation ordered layered LaBaCo2O5+δ double perovskite was obtained by annealing cubic A-site cation disordered La0.5Ba0.5CoO3perovskite at 1100 °C in N2. High temperature X-ray diffraction between room temperature (RT) and 800 °C revealed that LaBaCo2O5+δ remains tetragonal during heating in oxidizing atmosphere, but goes through two phase transitions in N2 and between 450 °C and 675 °C from tetragonal P4/mmm to orthorhombic Pmmm and back to P4/mmm due to oxygen vacancy ordering followed by disordering of the oxygen vacancies. An anisotropic chemical and thermal expansion of LaBaCo2O5+δ was demonstrated. La0.5Ba0.5CoO3-δ remained cubic at the studied temperature irrespective of partial pressure of oxygen. LaBaCo2O5+δ is metastable with respect to La0.5Ba0.5CoO3-δ at oxidizing conditions inferred from the thermal evolution of the oxygen deficiency and oxidation state of Co in the two materials. The oxidation state of Co is higher in La0.5Ba0.5CoO3-δ resulting in a higher electrical conductivity relative to LaBaCo2O5+δ. The conductivity in both materials was reduced with decreasing partial pressure of oxygen pointing to a p-type semiconducting behavior. PMID:28773279

  9. Isotropic Kink and Quasiparticle Excitations in the Three-Dimensional Perovskite Manganite La_{0.6}Sr_{0.4}MnO_{3}.

    PubMed

    Horiba, Koji; Kitamura, Miho; Yoshimatsu, Kohei; Minohara, Makoto; Sakai, Enju; Kobayashi, Masaki; Fujimori, Atsushi; Kumigashira, Hiroshi

    2016-02-19

    In order to reveal the many-body interactions in three-dimensional perovskite manganites that show colossal magnetoresistance, we performed an in situ angle-resolved photoemission spectroscopy on La_{0.6}Sr_{0.4}MnO_{3} and investigated the behavior of quasiparticles. We observed quasiparticle peaks near the Fermi momentum in both the electron and the hole bands, and clear kinks throughout the entire hole Fermi surface in the band dispersion. This isotropic behavior of quasiparticles and kinks suggests that polaronic quasiparticles produced by the coupling of electrons with Jahn-Teller phonons play an important role in the colossal magnetoresistance properties of the ferromagnetic metallic phase of three-dimensional manganites.

  10. Phase formation and UV luminescence of Gd3+ doped perovskite-type YScO3

    NASA Astrophysics Data System (ADS)

    Shimizu, Yuhei; Ueda, Kazushige

    2016-10-01

    Synthesis of pure and Gd3+doped perovskite-type YScO3 was attempted by a polymerized complex (PC) method and solid state reaction (SSR) method. Crystalline phases and UV luminescence of samples were examined with varying heating temperatures. The perovskite-type single phase was not simply formed in the SSR method, as reported in some literatures, and two cubic C-type phases of starting oxide materials remained forming slightly mixed solid solutions. UV luminescence of Gd3+ doped samples increased with an increase in heating temperatures and volume of the perovskite-type phase. In contrast, a non-crystalline precursor was crystallized to a single C-type phase at 800 °C in the PC method forming a completely mixed solid solution. Then, the phase of perovskite-type YScO3 formed at 1200 °C and its single phase was obtained at 1400 °C. It was revealed that high homogeneousness of cations was essential to generate the single perovskite-phase of YScO3. Because Gd3+ ions were also dissolved into the single C-type phase in Gd3+ doped samples, intense UV luminescence was observed above 800 °C in both C-type phase and perovskite-type phase.

  11. Hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 nanowires with ultrahigh capacity for Li-air batteries

    PubMed Central

    Zhao, Yunlong; Xu, Lin; Mai, Liqiang; Han, Chunhua; An, Qinyou; Xu, Xu; Liu, Xue; Zhang, Qingjie

    2012-01-01

    Lithium-air batteries have captured worldwide attention due to their highest energy density among the chemical batteries. To provide continuous oxygen channels, here, we synthesized hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 (LSCO) nanowires. We tested the intrinsic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity in both aqueous electrolytes and nonaqueous electrolytes via rotating disk electrode (RDE) measurements and demonstrated that the hierarchical mesoporous LSCO nanowires are high-performance catalysts for the ORR with low peak-up potential and high limiting diffusion current. Furthermore, we fabricated Li-air batteries on the basis of hierarchical mesoporous LSCO nanowires and nonaqueous electrolytes, which exhibited ultrahigh capacity, ca. over 11,000 mAh⋅g –1, one order of magnitude higher than that of LSCO nanoparticles. Besides, the possible reaction mechanism is proposed to explain the catalytic activity of the LSCO mesoporous nanowire. PMID:23150570

  12. Spectral engineering of LaF3:Ce3+ nanoparticles: The role of Ce3+ in surface sites

    NASA Astrophysics Data System (ADS)

    Jacobsohn, L. G.; Toncelli, A.; Sprinkle, K. B.; Kucera, C. J.; Ballato, J.

    2012-04-01

    Due to the high surface-to-volume ratio, luminescence centers on the surface have relative dominance in the overall spectral response of nanoparticles. The luminescence of LaF3:Ce3+ nanoparticles was investigated in the spectral and temporal domains with a particular focus on the role of Ce3+ on the surface. These nanoparticles present two luminescence bands at 4.10 eV and 4.37 eV attributed to Ce3+ transitions from the 5d level to the spin-orbit split 4f ground levels 2F5/2 and 2F7/2, in addition to a low-energy band at 3.62 eV that has been attributed to Ce3+ ions residing in perturbed sites. The growth of up to three undoped shells, ca. 0.9 nm thick each, around the core promoted a progressive enhancement of luminescence output, concomitant with an increase in the fluorescence lifetime due to the weakening of energy transfer through multipolar interaction between Ce3+ in the core and quenching defects on the surface. Also, the growth of the first shell led to a decrease in the relative intensity of the low-energy band and a 0.23 eV shift to higher energies. These results were interpreted as being due to the existence of two types of perturbed sites, one on the surface that is eliminated by the growth of the first shell, and another within the volume of the nanoparticle, similar to observations in bulk single crystals. This work demonstrates how surface engineering can affect and control the luminescence behavior of this nanomaterial.

  13. Effect of Different CH3NH3PbI3 Morphologies on Photovoltaic Properties of Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Chen, Lung-Chien; Lee, Kuan-Lin; Wu, Wen-Ti; Hsu, Chien-Feng; Tseng, Zong-Liang; Sun, Xiao Hong; Kao, Yu-Ting

    2018-05-01

    In this study, the perovskite layers were prepared by two-step wet process with different CH3NH3I (MAI) concentrations. The cell structure was glass/FTO/TiO2-mesoporous/CH3NH3PbI3 (MAPbI3)/spiro-OMeTAD/Ag. The MAPbI3 perovskite films were prepared using high and low MAI concentrations in a two-step process. The perovskite films were optimized at different spin coating speed and different annealing temperatures to enhance the power conversion efficiency (PCE) of perovskite solar cells. The PCE of the resulting device based on the different perovskite morphologies was discussed. The PCE of the best cell was up to 17.42%, open circuit voltage of 0.97 V, short current density of 24.06 mA/cm2, and fill factor of 0.747.

  14. Effect of Different CH3NH3PbI3 Morphologies on Photovoltaic Properties of Perovskite Solar Cells.

    PubMed

    Chen, Lung-Chien; Lee, Kuan-Lin; Wu, Wen-Ti; Hsu, Chien-Feng; Tseng, Zong-Liang; Sun, Xiao Hong; Kao, Yu-Ting

    2018-05-08

    In this study, the perovskite layers were prepared by two-step wet process with different CH 3 NH 3 I (MAI) concentrations. The cell structure was glass/FTO/TiO 2 -mesoporous/CH 3 NH 3 PbI 3 (MAPbI 3 )/spiro-OMeTAD/Ag. The MAPbI 3 perovskite films were prepared using high and low MAI concentrations in a two-step process. The perovskite films were optimized at different spin coating speed and different annealing temperatures to enhance the power conversion efficiency (PCE) of perovskite solar cells. The PCE of the resulting device based on the different perovskite morphologies was discussed. The PCE of the best cell was up to 17.42%, open circuit voltage of 0.97 V, short current density of 24.06 mA/cm 2 , and fill factor of 0.747.

  15. Phase formation and UV luminescence of Gd{sup 3+} doped perovskite-type YScO{sub 3}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shimizu, Yuhei; Ueda, Kazushige, E-mail: kueda@che.kyutech.ac.jp

    Synthesis of pure and Gd{sup 3+}doped perovskite-type YScO{sub 3} was attempted by a polymerized complex (PC) method and solid state reaction (SSR) method. Crystalline phases and UV luminescence of samples were examined with varying heating temperatures. The perovskite-type single phase was not simply formed in the SSR method, as reported in some literatures, and two cubic C-type phases of starting oxide materials remained forming slightly mixed solid solutions. UV luminescence of Gd{sup 3+} doped samples increased with an increase in heating temperatures and volume of the perovskite-type phase. In contrast, a non-crystalline precursor was crystallized to a single C-type phasemore » at 800 °C in the PC method forming a completely mixed solid solution. Then, the phase of perovskite-type YScO{sub 3} formed at 1200 °C and its single phase was obtained at 1400 °C. It was revealed that high homogeneousness of cations was essential to generate the single perovskite-phase of YScO{sub 3}. Because Gd{sup 3+} ions were also dissolved into the single C-type phase in Gd{sup 3+} doped samples, intense UV luminescence was observed above 800 °C in both C-type phase and perovskite-type phase. - Graphical abstract: A pure perovskite-type YScO{sub 3} phase was successfully synthesized by a polymerized complex (PC) method. The perovskite-type YScO{sub 3} was generated through a solid solution of C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} with drastic change of morphology. The PC method enabled a preparation of the single phase of the perovskite-type YScO{sub 3} at lower temperature and in shorter heating time. Gd{sup 3+} doped perovskite-type YScO{sub 3} was found to show a strong sharp UV emission at 314 nm. - Highlights: • Pure YScO{sub 3} phase was successfully synthesized by polymerized complex (PC) method. • Pure perovskite-type YScO{sub 3} phase was generated from pure C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} one. • YScO{sub 3} was obtained at lower

  16. Structural and thermodynamic aspects of organic-inorganic mixed halide (CH3NH3PbI3-xBrx) perovskite

    NASA Astrophysics Data System (ADS)

    Singh, Rajan Kumar; Kumar, Ranveer; Jain, Neha; Singh, Jai; Mishra, S. K.

    2018-05-01

    Mixed Bromine and iodine lead halide perovskite CH3NH3PbI3-xBrx have been synthesized by solution phase method using CH3NH3I and PbBr2 precursors in ambient conditions. X-ray diffraction indicates the formation of cubic perovskite at room temperature with space group of Pm3m. The mixed perovskite improved crystallanity and grain contour which may significant improve photovoltaic performance of perovskite devices. Thermodynamic behavior of such type of material also indicates energy absorption nature of materials.

  17. Influence of halide composition on the structural, electronic, and optical properties of mixed CH3NH3Pb (I1-xBrx) 3 perovskites calculated using the virtual crystal approximation method

    NASA Astrophysics Data System (ADS)

    Jong, Un-Gi; Yu, Chol-Jun; Ri, Jin-Song; Kim, Nam-Hyok; Ri, Guk-Chol

    2016-09-01

    Extensive studies have demonstrated the promising capability of the organic-inorganic hybrid halide perovskite CH3NH3PbI3 in solar cells with a high power conversion efficiency exceeding 20%. However, the intrinsic as well as extrinsic instabilities of this material remain the major challenge to the commercialization of perovskite-based solar cells. Mixing halides is expected to resolve this problem. Here, we investigate the effect of chemical substitution in the position of the halogen atom on the structural, electronic, and optical properties of mixed halide perovskites CH3NH3Pb (I1-xBrx) 3 with a pseudocubic phase using the virtual crystal approximation method within density functional theory. With an increase of Br content x from 0.0 to 1.0, the lattice constant decreases in proportion to x with the function of a (x )=6.420 -0.333 x (Å), while the band gap and the exciton binding energy increase with the quadratic function of Eg(x ) =1.542 +0.374 x +0.185 x2 (eV) and the linear function of Eb(x ) =0.045 +0.057 x (eV), respectively. The photoabsorption coefficients are also calculated, showing a blueshift of the absorption onsets for higher Br contents. We calculate the phase decomposition energy of these materials and analyze the electronic charge density difference to estimate the material stability. Based on the calculated results, we suggest that the best match between efficiency and stability can be achieved at x ≈0.2 in CH3NH3Pb (I1-xBrx) 3 perovskites.

  18. Growth of MAPbBr3 perovskite crystals and its interfacial properties with Al and Ag contacts for perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Najeeb, Mansoor Ani; Ahmad, Zubair; Shakoor, R. A.; Alashraf, Abdulla; Bhadra, Jolly; Al-Thani, N. J.; Al-Muhtaseb, Shaheen A.; Mohamed, A. M. A.

    2017-11-01

    In this work, the MAPbBr3 perovskite crystals were grown and the interfacial properties of the poly-crystalline MAPbBr3 with Aluminum (Al) and Silver (Ag) contacts has been investigated. MAPbBr3 crystals are turned into the poly-crystalline pellets (PCP) using compaction technique and the Al/PCP, Al/interface layer/PCP, Ag/PCP, and Ag/interface layer/PCP contacts were investigated. Scanning Electron Microscopic (SEM), Energy-dispersive X-ray spectroscopy (EDX) and current-voltage (I-V) characteristic technique were used to have an insight of the degradation mechanism happening at the Metal/perovskite interface. The Ag/PCP contact appears to be stable, whereas Al is found to be highly reactive with the MAPbBr3 perovskite crystals due to the infiltration setback of Al in to the perovskite crystals. The interface layer showed a slight effect on the penetration of Al in to the perovskite crystals however it does not seem to be an appropriate solution. It is noteworthy that the stability of the underlying metal/perovskite contact is very crucial towards the perovskite solar cells with extended device lifetime.

  19. Scalable Direct Writing of Lanthanide-Doped KMnF3 Perovskite Nanowires into Aligned Arrays with Polarized Up-Conversion Emission.

    PubMed

    Shi, Shuo; Sun, Ling-Dong; Xue, Ying-Xian; Dong, Hao; Wu, Ke; Guo, Shi-Chen; Wu, Bo-Tao; Yan, Chun-Hua

    2018-05-09

    The use of one-dimensional nano- and microstructured semiconductor and lanthanide materials is attractive for polarized-light-emission studies. Up-conversion emission from single-nanorod or anisotropic nanoparticles with a degree of polarization has also been discussed. However, microscale arrays of nanoparticles, especially well-aligned one-dimensional nanostructures as well as their up-conversion polarization characterization, have not been investigated yet. Herein, we present a novel and facile paradigm for preparing highly aligned arrays of lanthanide-doped KMnF 3 (KMnF 3 :Ln) perovskite nanowires, which are good candidates for polarized up-conversion emission studies. These perovskite nanowires, with a width of 10 nm and length of a few micrometers, are formed through the oriented attachment of KMnF 3 :Ln nanocubes along the [001] direction. By the employment of KMnF 3 :Ln nanowire gel as nanoink, a direct-writing method is developed to obtain diverse types of aligned patterns from the nanoscale to the wafer scale. Up-conversion emissions from the highly aligned nanowire arrays are polarized along the array direction with a polarization degree up to 60%. Taking advantage of microscopic nanowire arrays, these polarized up-conversion emissions should offer potential applications in light or information transportation.

  20. Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells.

    PubMed

    Abdi-Jalebi, Mojtaba; Dar, M Ibrahim; Sadhanala, Aditya; Senanayak, Satyaprasad P; Grätzel, Michael; Friend, Richard H

    2017-03-19

    Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical properties. The possibility of doping was investigated by adding monovalent cation halides with similar ionic radii to Pb 2+ , including Cu + , Na + , and Ag + . A shift in the Fermi level and a remarkable decrease of sub-bandgap optical absorption, along with a lower energetic disorder in the perovskite, was achieved. An order-of-magnitude enhancement in the bulk hole mobility and a significant reduction of transport activation energy within an additive-based perovskite device was attained. The confluence of the aforementioned improved properties in the presence of these cations led to an enhancement in the photovoltaic parameters of the perovskite solar cell. An increase of 70 mV in open circuit voltage for AgI and a 2 mA/cm 2 improvement in photocurrent density for NaI- and CuBr-based solar cells were achieved compared to the pristine device. Our work paves the way for further improvements in the optoelectronic quality of CH3NH3PbI3 perovskite and subsequent devices. It highlights a new avenue for investigations on the role of dopant impurities in crystallization and controls the electronic defect density in perovskite structures.

  1. Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells

    PubMed Central

    Abdi-Jalebi, Mojtaba; Dar, M. Ibrahim; Sadhanala, Aditya; Senanayak, Satyaprasad P.; Grätzel, Michael; Friend, Richard H.

    2017-01-01

    Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical properties. The possibility of doping was investigated by adding monovalent cation halides with similar ionic radii to Pb2+, including Cu+, Na+, and Ag+. A shift in the Fermi level and a remarkable decrease of sub-bandgap optical absorption, along with a lower energetic disorder in the perovskite, was achieved. An order-of-magnitude enhancement in the bulk hole mobility and a significant reduction of transport activation energy within an additive-based perovskite device was attained. The confluence of the aforementioned improved properties in the presence of these cations led to an enhancement in the photovoltaic parameters of the perovskite solar cell. An increase of 70 mV in open circuit voltage for AgI and a 2 mA/cm2 improvement in photocurrent density for NaI- and CuBr-based solar cells were achieved compared to the pristine device. Our work paves the way for further improvements in the optoelectronic quality of CH3NH3PbI3 perovskite and subsequent devices. It highlights a new avenue for investigations on the role of dopant impurities in crystallization and controls the electronic defect density in perovskite structures. PMID:28362369

  2. Displacement-type ferroelectric transition with magnetic Mn ions in perovskite Sr1-xBaxMnO3

    NASA Astrophysics Data System (ADS)

    Sakai, Hideaki; Fujioka, Jun; Fukuda, Tatsuo; Okuyama, Daisuke; Hashizume, Daisuke; Kagawa, Fumitaka; Nakao, Hironori; Murakami, Youich; Arima, Takahisa; Baron, Alfred Q. R.; Taguchi, Yasujiro; Tokura, Yoshinori

    2012-02-01

    Almost all the proper ferroelectrics with a perovskite structure discovered so far have no d-electrons in the off-center transition metal site, as exemplified by BaTiO3 and Pb(Zr,Ti)O3. This empirical d^0 rule is incompatible with the emergence of magnetism and has significantly restricted the variety of multiferroic materials. In this work, we have discovered a displacement-type ferroelectric transition originating from off-center Mn^4+ ions in antiferromagnetic Mott insulators Sr1-xBaxMnO3. As Ba concentration increases, the perovskite lattice shows the typical soft mode dynamics, and the ferroelectricity shows up for x .45. In addition to the large polarization and high transition temperature comparable to BaTiO3, we demonstrate that the magnetic order suppresses the ferroelectric lattice dilation by ˜70% and increases the soft-phonon energy by ˜50%, indicating gigantic magnetoelectric effects [1]. This work was supported by the FIRST program on ``Quantum Science on Strong Correlation''. [4pt] [1] H. Sakai et al., Phys. Rev. Lett. 107, 137601 (2011).

  3. Chlorine Incorporation in the CH3NH3PbI3 Perovskite: Small Concentration, Big Effect.

    PubMed

    Quarti, Claudio; Mosconi, Edoardo; Umari, Paolo; De Angelis, Filippo

    2017-01-03

    The role of chlorine doping in CH 3 NH 3 PbI 3 represents an important open issue in the use of hybrid perovskites for photovoltaic applications. In particular, even if a positive role of chlorine doping on perovskite film formation and on material morphology has been demonstrated, an inherent positive effect on the electronic and photovoltaic properties cannot be excluded. Here we carried out periodic density functional theory and Car-Parrinello molecular dynamics simulations, going down to ∼1% doping, to investigate the effect of chlorine on CH 3 NH 3 PbI 3 . We found that such a small doping has important effects on the dynamics of the crystalline structure, both with respect to the inorganic framework and with respect to the cation libration motion. Together, we observe a dynamic spatial localization of the valence and conduction states in separated spatial material regions, which takes place in the 10 -1 ps time scale and which could be the key to ease of exciton dissociation and, likely, to small charge recombination in hybrid perovskites. Moreover, such localization is enhanced by chlorine doping, demonstrating an inherent positive role of chlorine doping on the electronic properties of this class of materials.

  4. Structural, photoluminescence and radioluminescence properties of Eu{sup 3+} doped La{sub 2}Hf{sub 2}O{sub 7} nanoparticles

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wahid, Kareem; Pokhrel, Madhab; Mao, Yuanbing, E-mail: yuanbing.mao@utrgv.edu

    This study presents the structural, optical, and radioluminescent characterization of newly synthesized europium-doped lanthanum hafnate (La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+}, x=0 to 35) nanoparticles (NPs) for use as phosphors and scintillation materials. Samples prepared through a combined co-precipitation and molten salt synthetic process were found to crystalize in the pyrochlore phase, a radiation tolerant structure related to the fluorite structure. These samples exhibit red luminescence under ultraviolet and X-ray excitation. Under these excitations, the optical intensity and quantum yield of the La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+} NPs depend on the Eu{sup 3+} concentration and are maximized at 5%. It ismore » proposed that there is a trade-off between the quenching due to defect states/cross-relaxation and dopant concentration. An optimal dopant concentration allows the La{sub 2}Hf{sub 2}O{sub 7}:5 mol%Eu{sup 3+} NPs to show the best luminescent properties of all the samples. - Graphical abstract: Incident X-ray and UV photons interact with La{sub 2}Hf{sub 2}O{sub 7}: xmol%Eu{sup 3+}(x=1–35) nanoparticles (NPs) to yield strong red luminescence centered at 612 nm. Colored spheres inside NP diagram represent pyrochlore coordination environment of La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+}. Blue, red, yellow, green and black spheres represent hafnium(IV) atoms, lanthanum(III)/europium(III) atoms, oxygen atoms at 48f site, oxygen atoms at 8b site and oxygen vacancies, respectively. - Highlights: • La{sub 2}Hf{sub 2}O{sub 7}:xmol%Eu{sup 3+} (x=0–35) nanoparticles with weakly-ordered pyrochlore structures were synthesized. • Optically and X-ray excited emission spectra showed strong luminescence centered at 612 nm. • Photoluminescence quantum yield increases with doping concentration up to 5% and decreases at higher concentrations.« less

  5. Surface passivation of mixed-halide perovskite CsPb(BrxI1-x)3 nanocrystals by selective etching for improved stability.

    PubMed

    Jing, Qiang; Zhang, Mian; Huang, Xiang; Ren, Xiaoming; Wang, Peng; Lu, Zhenda

    2017-06-08

    In recent years, there has been an unprecedented rise in the research of halide perovskites because of their important optoelectronic applications, including photovoltaic cells, light-emitting diodes, photodetectors and lasers. The most pressing question concerns the stability of these materials. Here faster degradation and PL quenching are observed at higher iodine content for mixed-halide perovskite CsPb(Br x I 1-x ) 3 nanocrystals, and a simple yet effective method is reported to significantly enhance their stability. After selective etching with acetone, surface iodine is partially etched away to form a bromine-rich surface passivation layer on mixed-halide perovskite nanocrystals. This passivation layer remarkably stabilizes the nanocrystals, making their PL intensity improved by almost three orders of magnitude. It is expected that a similar passivation layer can also be applied to various other kinds of perovskite materials with poor stability issues.

  6. Temperature-dependent impedance spectroscopy of La0.8Sr0.2FeO3 nano-crystalline material

    NASA Astrophysics Data System (ADS)

    Kafa, C. A.; Triyono, D.; Laysandra, H.

    2017-04-01

    LaFeO3 is a material with perovskite structure which electrical properties frequently investigated. Research are done due to the exhibition of excellent gas sensing behavior through resistivity comparison from the p-type semiconductor. Sr doping on LaFeO3 or La1-xSrxFeO3 are able to improve the electrical conductivity through structural modification. Using Sr dopant concentration (x) of 0.2, La0.8Sr0.2FeO3 nano-crystal pellet was synthesized. The synthesis used sol-gel method, followed by gradual heat treatment and uniaxial compaction. XRD characterization shows that the structure of the sample is Orthorhombic Perovskite. Topography of the sample by SEM reveals grain and grain boundary existence with emerging agglomeration. The electrical properties of the material, as functions of temperature and frequency, were measured by Impedance Spectroscopy method using RLC meter, for temperatures of 303-373K. Through the Nyquist plot and Bode plot, the electrical conductivity of La0.8Sr0.2FeO3 is contributed by the grain and grain boundary. Finally, the electrical permittivities of La0.8Sr0.2FeO3 are increasing with temperature increase, with the highest achieved when measured at 1 kHz frequency.

  7. Direct experimental evidence for photoinduced strong-coupling polarons in organolead halide perovskite nanoparticles

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zheng, Kaibo; Qatar Univ., Doha; Abdellah, Mohamed

    Echoing the roaring success of their bulk coun-terparts, nano-objects built from organolead halide perov-skites (OLHP) present bright prospects for surpassing the performances of their conventional organic and inorganic analogues in photodriven technologies. Unraveling the pho-toinduced charge dynamics is essential for optimizing OLHP optoelectronic functionalities. However, mapping the carri-er-lattice interactions remains challenging, owing to their manifestations on multiple length scales and time scales. By correlating ultrafast time-resolved optical and X-ray absorp-tion measurements, this work reveals the photoinduced formation of strong-coupling polarons in CH 3NH 3PbBr 3 nanoparticles. Such polarons originate from the self-trapping of electrons in the net Coulombic field causedmore » by the dis-placed inorganic nuclei and the oriented organic cations. The transient structural change detected at the Pb L 3 X-ray ab-sorption edge is well captured by a distortion with average bond elongation in the [PbBr 6] 2- motif. As a result, general implications for designing novel OLHP nanomaterials targeting the active utilization of these quasi-particles are outlined.« less

  8. Direct experimental evidence for photoinduced strong-coupling polarons in organolead halide perovskite nanoparticles

    DOE PAGES

    Zheng, Kaibo; Qatar Univ., Doha; Abdellah, Mohamed; ...

    2016-10-28

    Echoing the roaring success of their bulk coun-terparts, nano-objects built from organolead halide perov-skites (OLHP) present bright prospects for surpassing the performances of their conventional organic and inorganic analogues in photodriven technologies. Unraveling the pho-toinduced charge dynamics is essential for optimizing OLHP optoelectronic functionalities. However, mapping the carri-er-lattice interactions remains challenging, owing to their manifestations on multiple length scales and time scales. By correlating ultrafast time-resolved optical and X-ray absorp-tion measurements, this work reveals the photoinduced formation of strong-coupling polarons in CH 3NH 3PbBr 3 nanoparticles. Such polarons originate from the self-trapping of electrons in the net Coulombic field causedmore » by the dis-placed inorganic nuclei and the oriented organic cations. The transient structural change detected at the Pb L 3 X-ray ab-sorption edge is well captured by a distortion with average bond elongation in the [PbBr 6] 2- motif. As a result, general implications for designing novel OLHP nanomaterials targeting the active utilization of these quasi-particles are outlined.« less

  9. Thermal, optical and vibrational studies of tyrosine doped LaF3:Ce nanoparticles for bioimaging and biotagging

    NASA Astrophysics Data System (ADS)

    Singh, Amit T.

    2018-05-01

    Upconversion quantum dots of tyrosine doped LaF3:Ce nanoparticles have been synthesized by wet chemical route. The thermal studies (TGA/DTA) confirm the crystallinity and stability of different phases of synthesized nanoparticles. The UV-Visible spectra show multiple absorption edges at 215.60 nm and 243.10 nm indicating quantum dot nature of the synthesized nanoparticles. The PL spectra showed upconversion with sharp emission peak at 615 nm (red colour). The FT-RAMAN spectra of the synthesized nanoparticles show the modification of the surface of the nanoparticles in the form of functional groups and skeletal groups. Upconversion nature of the synthesized nanoparticles indicates their potential application in bioimaging and biotagging.

  10. Tuning the metal-insulator transition in d1 and d2 perovskites by epitaxial strain: A first-principles-based study

    NASA Astrophysics Data System (ADS)

    Sclauzero, Gabriele; Dymkowski, Krzysztof; Ederer, Claude

    2016-12-01

    We investigate the effect of epitaxial strain on the Mott metal-insulator transition (MIT) in perovskite systems with d1 and d2 electron configurations of the transition metal (TM) cation. We first discuss the general trends expected from the changes in the crystal-field splitting and in the hopping parameters that are induced by epitaxial strain. We argue that the strain-induced crystal-field splitting generally favors the Mott-insulating state, whereas the strain-induced changes in the hopping parameters favor the metallic state under compressive strain and the insulating state under tensile strain. Thus the two effects can effectively cancel each other under compressive strain, while they usually cooperate under tensile strain, in this case favoring the insulating state. We then validate these general considerations by performing electronic structure calculations for several d1 and d2 perovskites, using a combination of density functional theory (DFT) and dynamical mean-field theory (DMFT). We isolate the individual effects of strain-induced changes in either hopping or crystal-field by performing DMFT calculations where we fix one type of parameter to the corresponding unstrained DFT values. These calculations confirm our general considerations for SrVO3 (d1) and LaVO3 (d2), whereas the case of LaTiO3 (d1) is distinctly different, due to the strong effect of the octahedral tilt distortion in the underlying perovskite crystal structure. Our results demonstrate the possibility to tune the electronic properties of correlated TM oxides by using epitaxial strain, which allows to control the strength of electronic correlations and the vicinity to the Mott MIT.

  11. Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution

    DOE PAGES

    Doane, Tennyson L.; Ryan, Kayla L.; Pathade, Laxmikant; ...

    2016-05-05

    The ability of cesium lead halide (CsPbX 3; X = Cl –, Br –, I –) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. Also, the exchange of CsPbI 3 with Cl – or Br – causes a significant blue-shift in absorption and photoluminescence, whereas reacting I – with CsPbBr 3 causesmore » a red-shift of similar magnitudes. With the high local halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. Finally, the merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites.« less

  12. Efficiency enhancement of perovskite solar cells using structural and morphological improvement of CH3NH3PbI3 absorber layers

    NASA Astrophysics Data System (ADS)

    Alidaei, Maryam; Izadifard, Morteza; Ghazi, Mohammad E.; Ahmadi, Vahid

    2018-01-01

    Perovskite solar cells have been heavily investigated due to their unique properties such as high power conversion efficiency (PCE), low-cost fabrication by solution processes, high diffusion length, large absorption coefficient, and direct and tunable band gap. PCE of perovskite devices is strongly dependent on the absorber layer properties such as morphology, crystallinity, and compactness, which are required to be optimized. In this work, the CH3NH3PbI3 (170-480 nm) absorber layers with various methylammonium iodine (MAI) concentrations (7, 10, 20 and 40 mg ml-1) and perovskite solar cells with the fluorine-doped tin oxide (400 nm)/C-TiO2 (30 nm)/Meso-TiO2 (400 nm)/CH3NH3PbI3 (170-480 nm)/P3HT (30 nm)/Au (100 nm) structure were fabricated. A two-step solution process was used for deposition of the CH3NH3PbI3 absorber layers. The morphology, crystal structure, and optical properties of the perovskite layer grown on glass and also the photovoltaic properties of the fabricated solar cells were studied. The results obtained showed that by controlling the deposition conditions, due to the reduction in charge recombination, PCE enhancement of the perovskite solar cell (up to 11.6%) was accessible.

  13. Tunable plasmon-enhanced broadband light harvesting for perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Que, Meidan; Zhu, Liangliang; Yang, Yawei; Liu, Jie; Chen, Peng; Chen, Wei; Yin, Xingtian; Que, Wenxiu

    2018-04-01

    In this work, we report a reliable method for synthesizing (Au, Au/Ag core)/(TiO2 shell) nanostructures with their plasmonic wavelengths covering the visible light region for perovskite solar cells. The mono- and bi-metallic core-shell nanoparticles exhibit tunable localized surface plasmon resonance wavelength and function as "light tentacle" to improve the photo-electricity conversion efficiency. Plasmonic nanoparticles with different sizes and shapes, different thicknesses of TiO2 shell and Ag interlayer are found to have a strong influence on the localized surface plasmon resonance enhancement effect. The experimental photovoltaic performance of perovskite solar cells is significantly enhanced when the plasmonic nanoparticles are embedded inmesoporous TiO2 scaffolds. A champion photo-electricity conversion efficiency of 17.85% is achieved with nanoparticles (Au/Ag, λLSPR = 650 nm), giving a 18.7% enhancement over that of the pristine device (15.04%). Finite-difference time-domain simulations show that nanorod Au in mesoporus TiO2 scaffold induces the most intense electromagnetic coupling, and provides a novel emitter for photon flux in mesoporous perovskite solar cells. These theoretical results are consistent with the corresponding experimental those. Thus, enhancing the incident light intensities around 650 nm will be most favorable to the improvement of the photo-electricity conversion efficiency of perovskite solar cells.

  14. Correlation between the structural distortions and thermoelectric characteristics in La(1-x)A(x)CoO(3) (A = Ca and Sr).

    PubMed

    Wang, Yang; Sui, Yu; Ren, Peng; Wang, Lan; Wang, Xianjie; Su, Wenhui; Fan, Hong Jin

    2010-04-05

    Detailed structures and thermoelectric (TE) properties are investigated for the perovskite La(1-x)Ca(x)CoO(3) and La(1-x)Sr(x)CoO(3) with 0 3. The monoclinic crystal structures for all samples are refined from powder X-ray diffraction, which reveals that the La(1-x)Sr(x)CoO(3) series has smaller global distortions but larger local distortions. The different structural distortions strongly influence the transport and TE properties in terms of resistivity, thermopower, thermal conductivity, bandwidth, and effective mass as well as electronic correlation. These results unambiguously demonstrate a close correlation between the structural distortions and TE characteristics in this family. Furthermore, a new approach is suggested to improve the TE performance by controlling the structure factors in such strongly correlated oxide systems. The effects of the spin-state transition of Co ions on the TE properties are also discussed.

  15. Mixed-Organic-Cation (FA)x(MA)1-xPbI3 Planar Perovskite Solar Cells with 16.48% Efficiency via a Low-Pressure Vapor-Assisted Solution Process.

    PubMed

    Chen, Jing; Xu, Jia; Xiao, Li; Zhang, Bing; Dai, Songyuan; Yao, Jianxi

    2017-01-25

    Compared to that of methylammonium lead iodide perovskite (MAPbI 3 ), formamidinium lead iodide perovskite (FAPbI 3 ) has a smaller energy band gap and greater potential efficiency. To prevent the transformation of α-FAPbI 3 to δ-FAPbI 3 , preparation of (FA) x (MA) 1-x PbI 3 was regarded as an effective route. Usually, the planar (FA) x (MA) 1-x PbI 3 perovskite solar cells are fabricated by a solution process. Herein, we report a low-pressure vapor-assisted solution process (LP-VASP) for the growth of (FA) x (MA) 1-x PbI 3 perovskite solar cells that features improved electron transportation, uniform morphology, high power conversion efficiency (PCE), and better crystal stability. In LP-VASP, the (FA) x (MA) 1-x PbI 3 films were formed by the reaction between the PbI 2 film with FAI and MAI vapor in a very simple vacuum oven. LP-VASP is an inexpensive way to batch-process solar cells, avoiding the repeated deposition solution process for PbI 2 films, and the device had a low cost. We demonstrate that, with an increase in the MAI content, the (101) peak position of FAPbI 3 shifts toward the (110) peak position of MAPbI 3 , the (FA) x (MA) 1-x PbI 3 perovskites are stable, and no decomposition or phase transition is observed after 14 days. The photovoltaic performance was effectively improved by the introduction of MA + with the highest efficiency being 16.48% under conditions of 40 wt % MAI. The carrier lifetime of (FA) x (MA) 1-x PbI 3 perovskite films is approximately three times longer than that of pure FAPbI 3 . Using this process, solar cells with a large area of 1.00 cm 2 were fabricated with the PCE of 8.0%.

  16. Size effect on the magnetic properties of antiferromagnetic La0.2Ca0.8MnO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Markovich, V.; Fita, I.; Wisniewski, A.; Mogilyansky, D.; Puzniak, R.; Titelman, L.; Martin, C.; Gorodetsky, G.

    2010-03-01

    Magnetic properties of electron-doped La0.2Ca0.8MnO3 manganite nanoparticles with average particle size ranging from 15 to 37 nm, prepared by the glycine-nitrate method, have been investigated in temperature range 5-300 K and in magnetic fields up to 90 kOe. A monotonous enhancement of weak ferromagnetism linked to the reduction in the particle size was observed for all nanoparticles. Magnetic hysteresis loops also indicate size-dependent exchange bias effect displayed by horizontal and vertical shifts in field-cooled processes. The magnetization data reveal two ferromagnetic components: first one appears at T˜200K and may be attributed to surface magnetization and second one appears as a result of spin canting of antiferromagnetic core or is developed at some interfaces inside nanoparticles. Time evolution of magnetization recorded in magnetic fields after the field cooling to low temperatures exhibits a very noisy behavior that may be caused by formation of collective state of nanoparticles with no clear tendency to reach equilibrium state. Magnetic properties of the nanoparticle samples are compared with those of the bulk La0.2Ca0.8MnO3 .

  17. Sn2+-Stabilization in MASnI3 perovskites by superhalide incorporation.

    PubMed

    Xiang, Junxiang; Wang, Kan; Xiang, Bin; Cui, Xudong

    2018-03-28

    Sn-based hybrid halide perovskites are a potential solution to replace Pb and thereby reduce Pb toxicity in MAPbI 3 perovskite-based solar cells. However, the instability of Sn 2+ in air atmosphere causes a poor reproducibility of MASnI 3 , hindering steps towards this goal. In this paper, we propose a new type of organic metal-superhalide perovskite of MASnI 2 BH 4 and MASnI 2 AlH 4 . Through first-principles calculations, our results reveal that the incorporation of BH 4 and AlH 4 superhalides can realize an impressive enhancement of oxidation resistance of Sn 2+ in MASnI 3 perovskites because of the large electron transfer between Sn 2+ and [BH 4 ] - /[AlH 4 ] - . Meanwhile, the high carrier mobility is preserved in these superhalide perovskites and only a slight decrease is observed in the optical absorption strength. Our studies provide a new path to attain highly stable performance and reproducibility of Sn-based perovskite solar cells.

  18. Depletion region effect of highly efficient hole conductor free CH3NH3PbI3 perovskite solar cells.

    PubMed

    Aharon, Sigalit; Gamliel, Shany; El Cohen, Bat; Etgar, Lioz

    2014-06-14

    The inorganic-organic perovskite is currently attracting a lot of attention due to its use as a light harvester in solar cells. The large absorption coefficients, high carrier mobility and good stability of organo-lead halide perovskites present good potential for their use as light harvesters in mesoscopic heterojunction solar cells. This work concentrated on a unique property of the lead halide perovskite, its function simultaneously as a light harvester and a hole conductor in the solar cell. A two-step deposition technique was used to optimize the perovskite deposition and to enhance the solar cell efficiency. It was revealed that the photovoltaic performance of the hole conductor free perovskite solar cell is strongly dependent on the depletion layer width which was created at the TiO2-CH3NH3PbI3 junction. X-ray diffraction measurements indicate that there were no changes in the crystallographic structure of the CH3NH3PbI3 perovskite over time, which supports the high stability of these hole conductor free perovskite solar cells. Furthermore, the power conversion efficiency of the best cells reached 10.85% with a fill factor of 68%, a Voc of 0.84 V, and a Jsc of 19 mA cm(-2), the highest efficiency to date of a hole conductor free perovskite solar cell.

  19. Generalizable, Electroless, Template-Assisted Synthesis and Electrocatalytic Mechanistic Understanding of Perovskite LaNiO3 Nanorods as Viable, Supportless Oxygen Evolution Reaction Catalysts in Alkaline Media.

    PubMed

    McBean, Coray L; Liu, Haiqing; Scofield, Megan E; Li, Luyao; Wang, Lei; Bernstein, Ashley; Wong, Stanislaus S

    2017-07-26

    The oxygen evolution reaction (OER) is a key reaction for water electrolysis cells and air-powered battery applications. However, conventional metal oxide catalysts, used for high-performing OER, tend to incorporate comparatively expensive and less abundant precious metals such as Ru and Ir, and, moreover, suffer from poor stability. To attempt to mitigate for all of these issues, we have prepared one-dimensional (1D) OER-active perovskite nanorods using a unique, simple, generalizable, and robust method. Significantly, our work demonstrates the feasibility of a novel electroless, seedless, surfactant-free, wet solution-based protocol for fabricating "high aspect ratio" LaNiO 3 and LaMnO 3 nanostructures. As the main focus of our demonstration of principle, we prepared as-synthesized LaNiO 3 rods and correlated the various temperatures at which these materials were annealed with their resulting OER performance. We observed generally better OER performance for samples prepared with lower annealing temperatures. Specifically, when annealed at 600 °C, in the absence of a conventional conductive carbon support, our as-synthesized LaNiO 3 rods not only evinced (i) a reasonable level of activity toward OER but also displayed (ii) an improved stability, as demonstrated by chronoamperometric measurements, especially when compared with a control sample of commercially available (and more expensive) RuO 2 .

  20. Generalizable, Electroless, Template-Assisted Synthesis and Electrocatalytic Mechanistic Understanding of Perovskite LaNiO 3 Nanorods as Viable, Supportless Oxygen Evolution Reaction Catalysts in Alkaline Media

    DOE PAGES

    McBean, Coray L.; Liu, Haiqing; Scofield, Megan E.; ...

    2017-07-17

    We present that the oxygen evolution reaction (OER) is a key reaction for water electrolysis cells and air-powered battery applications. However, conventional metal oxide catalysts, used for high-performing OER, tend to incorporate comparatively expensive and less abundant precious metals such as Ru and Ir, and, moreover, suffer from poor stability. To attempt to mitigate for all of these issues, we have prepared one-dimensional (1D) OER-active perovskite nanorods using a unique, simple, generalizable, and robust method. Significantly, our work demonstrates the feasibility of a novel electroless, seedless, surfactant-free, wet solution-based protocol for fabricating “high aspect ratio” LaNiO 3 and LaMnO 3more » nanostructures. As the main focus of our demonstration of principle, we prepared as-synthesized LaNiO 3 rods and correlated the various temperatures at which these materials were annealed with their resulting OER performance. In addition, we observed generally better OER performance for samples prepared with lower annealing temperatures. Specifically, when annealed at 600 °C, in the absence of a conventional conductive carbon support, our as-synthesized LaNiO 3 rods not only evinced (i) a reasonable level of activity toward OER but also displayed (ii) an improved stability, as demonstrated by chronoamperometric measurements, especially when compared with a control sample of commercially available (and more expensive) RuO 2.« less

  1. Investigation of Thermally Induced Degradation in CH3NH3PbI3 Perovskite Solar Cells using In-situ Synchrotron Radiation Analysis.

    PubMed

    Kim, Nam-Koo; Min, Young Hwan; Noh, Seokhwan; Cho, Eunkyung; Jeong, Gitaeg; Joo, Minho; Ahn, Seh-Won; Lee, Jeong Soo; Kim, Seongtak; Ihm, Kyuwook; Ahn, Hyungju; Kang, Yoonmook; Lee, Hae-Seok; Kim, Donghwan

    2017-07-05

    In this study, we employ a combination of various in-situ surface analysis techniques to investigate the thermally induced degradation processes in MAPbI 3 perovskite solar cells (PeSCs) as a function of temperature under air-free conditions (no moisture and oxygen). Through a comprehensive approach that combines in-situ grazing-incidence wide-angle X-ray diffraction (GIWAXD) and high-resolution X-ray photoelectron spectroscopy (HR-XPS) measurements, we confirm that the surface structure of MAPbI 3 perovskite film changes to an intermediate phase and decomposes to CH 3 I, NH 3 , and PbI 2 after both a short (20 min) exposure to heat stress at 100 °C and a long exposure (>1 hour) at 80 °C. Moreover, we observe clearly the changes in the orientation of CH 3 NH 3 + organic cations with respect to the substrate in the intermediate phase, which might be linked directly to the thermal degradation processes in MAPbI 3 perovskites. These results provide important progress towards improved understanding of the thermal degradation mechanisms in perovskite materials and will facilitate improvements in the design and fabrication of perovskite solar cells with better thermal stability.

  2. Dry (Mg,Fe)SiO 3 perovskite in the Earth's lower mantle

    DOE PAGES

    Panero, Wendy R.; Pigott, Jeffrey S.; Reaman, Daniel M.; ...

    2015-02-26

    Combined synthesis experiments and first-principles calculations show that MgSiO 3-perovskite with minor Al or Fe does not incorporate significant OH under lower mantle conditions. Perovskite, stishovite, and residual melt were synthesized from natural Bamble enstatite samples (Mg/(Fe+Mg) = 0.89 and 0.93; Al 2O 3 < 0.1 wt% with 35 and 2065 ppm wt H 2O, respectively) in the laser-heated diamond anvil cell at 1600-2000 K and 25-65 GPa. Combined Fourier transform infrared (FTIR) spectroscopy, x-ray diffraction, and ex-situ transmission electron microscopy (TEM) analysis demonstrates little difference in the resulting perovskite as a function of initial water content. Four distinct OHmore » vibrational stretching bands are evident upon cooling below 100 K (3576, 3378, 3274, and 3078 cm -1), suggesting 4 potential bonding sites for OH in perovskite with a maximum water content of 220 ppm wt H 2O, and likely no more than 10 ppm wt H 2O. Complementary, Fe-free, first-principles calculations predict multiple potential bonding sites for hydrogen in perovskite, each with significant solution enthalpy (0.2 eV/defect). We calculate that perovskite can dissolve less than 37 ppm wt H 2O (400 ppm H/Si) at the top of the lower mantle, decreasing to 31 ppm wt H 2O (340 ppm H/Si) at 125 GPa and 3000 K in the absence of a melt or fluid phase. Here, we propose that these results resolve a long-standing debate of the perovskite melting curve and explain the order of magnitude increase in viscosity from upper to lower mantle.« less

  3. CSP ELEMENTS: High-Temperature Thermochemical Storage with Redox-Stable Perovskites for Concentrating Solar Power

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Jackson, Gregory S; Braun, Robert J; Ma, Zhiwen

    This project was motivated by the potential of reducible perovskite oxides for high-temperature, thermochemical energy storage (TCES) to provide dispatchable renewable heat for concentrating solar power (CSP) plants. This project sought to identify and characterize perovskites from earth-abundant cations with high reducibility below 1000 °C for coupling TCES of solar energy to super-critical CO2 (s-CO2) plants that operate above temperature limits (< 600 °C) of current molten-salt storage. Specific TCES > 750 kJ/kg for storage cycles between 500 and 900 °C was targeted with a system cost goal of $15/kWhth. To realize feasibility of TCES systems based on reducible perovskites,more » our team focused on designing and testing a lab-scale concentrating solar receiver, wherein perovskite particles capture solar energy by fast O2 release and sensible heating at a thermal efficiency of 90% and wall temperatures below 1100 °C. System-level models of the receiver and reoxidation reactor coupled to validated thermochemical materials models can assess approaches to scale-up a full TCES system based on reduction/oxidation cycles of perovskite oxides at large scales. After characterizing many Ca-based perovskites for TCES, our team identified strontium-doped calcium manganite Ca1-xSrxMnO3-δ (with x ≤ 0.1) as a composition with adequate stability and specific TCES capacity (> 750 kJ/kg for Ca0.95Sr0.05MnO3-δ) for cycling between air at 500 °C and low-PO2 (10-4 bar) N2 at 900 °C. Substantial kinetic tests demonstrated that resident times of several minutes in low-PO2 gas were needed for these materials to reach the specific TCES goals with particles of reasonable size for large-scale transport (diameter dp > 200 μm). On the other hand, fast reoxidation kinetics in air enables subsequent rapid heat release in a fluidized reoxidation reactor/ heat recovery unit for driving s-CO2 power plants. Validated material thermochemistry coupled to radiation and convective

  4. Nb and Pd co-doped La0.57Sr0.38Co0.19Fe0.665Nb0.095Pd0.05O3-δ as a stable, high performance electrode for barrier-layer-free Y2O3-ZrO2 electrolyte of solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Chen, Kongfa; He, Shuai; Li, Na; Cheng, Yi; Ai, Na; Chen, Minle; Rickard, William D. A.; Zhang, Teng; Jiang, San Ping

    2018-02-01

    La0.6Sr0.2Co0.2Fe0.8O3-δ (LSCF) is the most intensively investigated high performance cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs), but strontium segregation and migration at the electrode/electrolyte interface is a critical issue limiting the electrocatalytic activity and stability of LSCF based cathodes. Herein, we report a Nb and Pd co-doped LSCF (La0.57Sr0.38Co0.19Fe0.665Nb0.095Pd0.05O3-δ, LSCFNPd) perovskite as stable and active cathode on a barrier-layer-free anode-supported yttria-stabilized zirconia (YSZ) electrolyte cell using direct assembly method without pre-sintering at high temperatures. The cell exhibits a peak power density of 1.3 W cm-2 at 750 °C and excellent stability with no degradation during polarization at 500 mA cm-2 and 750 °C for 175 h. Microscopic and spectroscopic analysis show that the electrochemical polarization promotes the formation of electrode/electrolyte interface in operando and exsolution of Pd/PdO nanoparticles. The Nb doping in the B-site of LSCF significantly reduces the Sr surface segregation, enhancing the stability of the cathode, while the exsoluted Pd/PdO nanoparticles increases the electrocatalytic activity for the oxygen reduction reaction. The present study opens up a new route for the development of cobaltite-based perovskite cathodes with high activity and stability for barrier-layer-free YSZ electrolyte based IT-SOFCs.

  5. Performance of La 0.75Sr 0.25Cr 0.5Mn 0.5O 3- δ perovskite-structure anode material at lanthanum gallate electrolyte for IT-SOFC running on ethanol fuel

    NASA Astrophysics Data System (ADS)

    Huang, Bo; Wang, S. R.; Liu, R. Z.; Ye, X. F.; Nie, H. W.; Sun, X. F.; Wen, T. L.

    Perovskite-structure La 0.75Sr 0.25Cr 0.5Mn 0.5O 3- δ (LSCM) powders were prepared using a simple combustion process. Thermal analysis was carried out on the perovskite precursor to investigate the oxide-phase formation. The structural phase of the powders was determined by X-ray diffraction. These results showed that the decomposition of the precursors occurs in a two-step reaction and temperatures higher than 1100 °C are required for these decomposition reactions. For the electrochemical characterization, LSCM anode materials and (Pr 0.7Ca 0.3) 0.9MnO 3 (PCM) cathode materials were screen-printed on two sides of dense La 0.8Sr 0.2Ga 0.8Mg 0.2O 3 (LSGM) electrolyte layers prepared by tape casting with a thickness of about 600 μm, respectively. The morphology of the screen-printed La 0.75Sr 0.25Cr 0.5Mn 0.5O 3- δ perovskite thick films (65 μm) was investigated by field emission scanning electron microscope and showed a porous microstructure. In addition, fuel cell tests were carried out using humidified hydrogen or ethanol stream as fuel and oxygen as oxidant. The performance of the conventional electrolyte-supported cell LSCM/LSGM/PCM while operating on humidified hydrogen was modest with a maximum power density of 165, 99 and 62 mW cm -2 at 850, 800 and 750 °C, respectively, the corresponding values for the cell while operating on ethanol stream was 160, 101 and 58 mW cm -2, respectively. Cell stability tests indicate no significant degradation in performance has been observed after 60 h of cell testing when LSCM anode was exposed to ethanol steam at 750 °C, suggesting that carbon deposition was limited during cell operation.

  6. Screened hybrid functional applied to 3d0→3d8 transition-metal perovskites LaMO3 (M = Sc-Cu): Influence of the exchange mixing parameter on the structural, electronic, and magnetic properties

    NASA Astrophysics Data System (ADS)

    He, Jiangang; Franchini, Cesare

    2012-12-01

    We assess the performance of the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid density functional scheme applied to the perovskite family LaMO3 (M = Sc-Cu) and discuss the role of the mixing parameter α [which determines the fraction of exact Hartree-Fock exchange included in the density functional theory (DFT) exchange-correlation functional] on the structural, electronic, and magnetic properties. The physical complexity of this class of compounds, manifested by the largely varying electronic characters (band/Mott-Hubbard/charge-transfer insulators and metals), magnetic orderings, structural distortions (cooperative Jahn-Teller-type instabilities), as well as by the strong competition between localization/delocalization effects associated with the gradual filling of the t2g and eg orbitals, symbolize a critical and challenging case for theory. Our results indicate that HSE is able to provide a consistent picture of the complex physical scenario encountered across the LaMO3 series and significantly improve the standard DFT description. The only exceptions are the correlated paramagnetic metals LaNiO3 and LaCuO3, which are found to be treated better within DFT. By fitting the ground-state properties with respect to α, we have constructed a set of “optimum” values of α from LaScO3 to LaCuO3: it is found that the optimum mixing parameter decreases with increasing filling of the d manifold (LaScO3: 0.25; LaTiO3 and LaVO3: 0.10-0.15; LaCrO3, LaMnO3, and LaFeO3: 0.15; LaCoO3: 0.05; LaNiO3 and LaCuO3: 0). This trend can be nicely correlated with the modulation of the screening and dielectric properties across the LaMO3 series, thus providing a physical justification to the empirical fitting procedure. Finally, we show that by using this set of optimum mixing parameter, HSE predict dielectric constants in very good agreement with the experimental ones.

  7. LaF3 core/shell nanoparticles for subcutaneous heating and thermal sensing in the second biological-window

    NASA Astrophysics Data System (ADS)

    Ximendes, Erving Clayton; Rocha, Uéslen; Kumar, Kagola Upendra; Jacinto, Carlos; Jaque, Daniel

    2016-06-01

    We report on Ytterbium and Neodymium codoped LaF3 core/shell nanoparticles capable of simultaneous heating and thermal sensing under single beam infrared laser excitation. Efficient light-to-heat conversion is produced at the Neodymium highly doped shell due to non-radiative de-excitations. Thermal sensing is provided by the temperature dependent Nd3+ → Yb3+ energy transfer processes taking place at the core/shell interface. The potential application of these core/shell multifunctional nanoparticles for controlled photothermal subcutaneous treatments is also demonstrated.

  8. Electron Transfer from Triplet State of TIPS-Pentacene Generated by Singlet Fission Processes to CH3NH3PbI3 Perovskite.

    PubMed

    Lee, Sangsu; Hwang, Daesub; Jung, Seok Il; Kim, Dongho

    2017-02-16

    To reveal the applicability of singlet fission processes in perovskite solar cell, we investigated electron transfer from TIPS-pentacene to CH 3 NH 3 PbI 3 (MAPbI 3 ) perovskite in film phase. Through the observation of the shorter fluorescence lifetime in TIPS-pentacene/MAPbI 3 perovskite bilayer film (5 ns) compared with pristine MAPbI 3 perovskite film (20 ns), we verified electron-transfer processes between TIPS-pentacene and MAPbI 3 perovskite. Furthermore, the observation of singlet fission processes, a faster decay rate, TIPS-pentacene cations, and the analysis of kinetic profiles of the intensity ratio between 500 and 525 nm in the TA spectra of the TIPS-pentacene/MAPbI 3 perovskite bilayer film indicate that electron transfer occurs from triplet state of TIPS-pentacene generated by singlet fission processes to MAPbI 3 perovskite conduction band. We believe that our results can provide useful information on the design of solar cells sensitized by singlet fission processes and pave the way for new types of perovskite solar cells.

  9. Calcium doped MAPbI3 with better energy state alignment in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Lu, Chaojie; Zhang, Jing; Hou, Dagang; Gan, Xinlei; Sun, Hongrui; Zeng, Zhaobing; Chen, Renjie; Tian, Hui; Xiong, Qi; Zhang, Ying; Li, Yuanyuan; Zhu, Yuejin

    2018-05-01

    The organic-inorganic perovskite material with better energy alignment in the solar cell device will have a profound impact on the solar cell performance. It is valuable to tune the energy states by element substitution and doping in perovskites. Here, we present that Ca2+ is incorporated into CH3NH3PbI3, which up-shifts the valence band maximum and the conduction band minimum, leading to a difference between the bandgap and the Fermi level in the device. Consequently, Ca2+ incorporation results in an enhancement of the photovoltage and photocurrent, achieving a summit efficiency of 18.3% under standard 1 sun (AM 1.5). This work reveals the doped perovskite to improve the solar cell performance by tuning the energy state.

  10. Novel catalytic properties of quadruple perovskites

    PubMed Central

    Yamada, Ikuya

    2017-01-01

    ABSTRACT Quadruple perovskite oxides AA′3 B 4O12 demonstrate a rich variety of structural and electronic properties. A large number of constituent elements for A/A′/B-site cations can be introduced using the ultra-high-pressure synthesis method. Development of novel functional materials consisting of earth-abundant elements plays a crucial role in current materials science. In this paper, functional properties, especially oxygen reaction catalysis, for quadruple perovskite oxides CaCu3Fe4O12 and AMn7O12 (A = Ca, La) composed of earth-abundant elements are reviewed. PMID:28970864

  11. STUDY OF BIFERROIC PROPERTIES IN THE La0.37Ca0.17Ba0.43Mn0.52Ti0.44Zr0.04O3 COMPLEX PEROVSKITE

    NASA Astrophysics Data System (ADS)

    Cardona-Vásquez, J. A.; Gómez, M. E.; Landínez-Téllez, D. A.; Roa-Rojas, J.

    2013-10-01

    In this paper, details of synthesis and structural, morphological, electrical, and magnetic characterization of the new La0.37Ca0.17Ba0.43Mn0.52Ti0.44Zr0.04O3 multiferroic complex perovskite are reported. Mixtures with 50% mass of ferromagnetic lanthanum calcium manganite La0.67Ca0.33MnO3 and ferroelectric barium-lanthanum zirconate titanate Ba0.9La0.067Ti0.91Zr0.09 O3 were prepared by the solid state reaction technique. Patterns of X-ray diffraction showed that the materials have reacted resulting in a new perovskite-like structure with tetragonal symmetry, space group P4mm(#99). The structure of the material was refined using the Rietveld method through the GSAS code. ZFC and FC magnetization curves show the occurrence of two phase transitions at 42.25 K and 203.9 K which have been associated with two different magnetic regimes. Hysteresis curves measured confirm that the relationship between the applied field and the magnetization does not evidence a linear behavior. These curves also show that in the low temperature regime the magnetic memory of the material is greater than in the high temperature region. AC impedance as a function of temperature measurements show the same two regions observed in the magnetization curves. The ferroelectric behavior with relative permittivity of 153.12 is observed by polarization curves performed at room temperature in the synthesized materials.

  12. High-Performance CH3NH3PbI3-Inverted Planar Perovskite Solar Cells with Fill Factor Over 83% via Excess Organic/Inorganic Halide.

    PubMed

    Jahandar, Muhammad; Khan, Nasir; Lee, Hang Ken; Lee, Sang Kyu; Shin, Won Suk; Lee, Jong-Cheol; Song, Chang Eun; Moon, Sang-Jin

    2017-10-18

    The reduction of charge carrier recombination and intrinsic defect density in organic-inorganic halide perovskite absorber materials is a prerequisite to achieving high-performance perovskite solar cells with good efficiency and stability. Here, we fabricated inverted planar perovskite solar cells by incorporation of a small amount of excess organic/inorganic halide (methylammonium iodide (CH 3 NH 3 I; MAI), formamidinium iodide (CH(NH 2 ) 2 I; FAI), and cesium iodide (CsI)) in CH 3 NH 3 PbI 3 perovskite film. Larger crystalline grains and enhanced crystallinity in CH 3 NH 3 PbI 3 perovskite films with excess organic/inorganic halide reduce the charge carrier recombination and defect density, leading to enhanced device efficiency (MAI+: 14.49 ± 0.30%, FAI+: 16.22 ± 0.38% and CsI+: 17.52 ± 0.56%) compared to the efficiency of a control MAPbI 3 device (MAI: 12.63 ± 0.64%) and device stability. Especially, the incorporation of a small amount of excess CsI in MAPbI 3 perovskite film leads to a highly reproducible fill factor of over 83%, increased open-circuit voltage (from 0.946 to 1.042 V), and short-circuit current density (from 18.43 to 20.89 mA/cm 2 ).

  13. Characterization of magnetic and dielectric properties of Bi(1-x)Gd(x)FeO3 nanoparticles by local structure analyses.

    PubMed

    Yanoh, Takuya; Kurokawa, Akinobu; Takeuchi, Hiromasa; Yano, Shinya; Onuma, Kazuki; Kondo, Takaya; Miike, Kazunari; Miyasaka, Toshiki; Mibu, Ko; Ichiyanagi, Yuko

    2014-03-01

    Bi(1-x)Gd(x)FeO3 (0 < or = x < or = 1.0) nanoparticles were synthesized by a wet chemical method. The annealing temperatures were controlled to obtain single-phase Bi(1-x)Gd(x)FeO3 nanoparticles. The crystal diameters decreased as the number of doped Gd ions increased. The crystal structure changed, as the number of Gd ions increased, from rhombohedral to orthorhombic perovskite, at x = 0.2. The behavior of the magnetization curves observed at various values of x (x = 0.05, 0.1, 0.15) of the rhombohedral structure suggested that the canted antiferromagnetism and remanent magnetization (M(r)) drastically increased, compared with those at x = 0 (BiFeO3). It is suggested that the spin-canting angle of the Fe ions increased with the increase in the number of Gd ions. The dielectric properties at x = 0.1 showed that the dielectric loss (tan delta) was improved, compared with that at x = 0 (BiFeO3), by approximately 90%, while the real part of the dielectric constant epsilon' was reduced by approximately 15%. The reason is that the doping impurities restrained the reduction in the leakage current. It was found, from the X-ray absorption fine structure (XAFS) spectra, that Gd ions were doped accurately and that the symmetry of the B site was improved. The Mössbauer analysis suggested the existence of magnetic cycloid spiral ordering.

  14. Phase transitions of BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} perovskite-type oxides under reducing environments

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Rodríguez, G.C.Mondragón, E-mail: guillermo.mondragon-rodriguez@dlr.de; Gönüllü, Y.; Ferri, Davide

    2015-01-15

    Highlights: • Solid solution formation BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} with a new wet chemical synthesis method. • Rhodium in the BaTiO{sub 3} perovskite stabilizes the hexagonal structure. • New Rh segregation mechanism for hexagonal BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} upon reduction. - Abstract: Perovskite-type oxides of composition BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} were prepared following a new chemical route that avoids the formation of hydroxyl species and precipitation, and allows the homogeneous distribution of Rh in the final mixed metal oxide. The high dispersion of Rh and the formation of the solid solution between Rh and the BaTiO{sub 3} perovskite is confirmedmore » by means of X-ray diffraction (XRD) and extended X-ray absorption fine structure spectroscopy (EXAFS). The presence of Rh stabilized the hexagonal BaTi{sub 0.9}Rh{sub 0.1}O{sub 3±δ} phase, which decomposes into barium orthotitanate (BaTi{sub 2}O{sub 4}) and metallic Rh° in reducing environment. This phase transition starts already at 700 °C and is only partially completed at 900 °C suggesting that part of the Rh present in the perovskite lattice might not be easily reduced by hydrogen. These aspects and further open questions are discussed.« less

  15. Thermoelectric properties and figure of merit of perovskite-type Ba1-xLaxSnO3 with x=0.002-0.008

    NASA Astrophysics Data System (ADS)

    Yasukawa, Masahiro; Kono, Toshio; Ueda, Kazushige; Yanagi, Hiroshi; Wng Kim, Sung; Hosono, Hideo

    2013-10-01

    Thermoelectric properties and figure of merit were evaluated from the Seebeck coefficient S, electrical conductivity σ, and thermal conductivity κ measured at high temperatures for perovskite-type ceramics of Ba1-xLaxSnO3 with x=0.002, 0.005, and 0.008, which were prepared by a polymerized complex method and a subsequent spark plasma sintering technique. All the polycrystalline dense ceramics showed n-type degenerate semiconducting behavior in the temperature range of 373-1073 K. The La content dependence of the S values revealed successful increase in the electron carriers with the La doping in this x range. The κ values remained almost unchanged with x showing ~9.6 Wm-1 K-1 at room temperature and decreased with increasing temperature. The electronic thermal conductivities calculated by the Wiedemann-Franz law as well as the T-1 dependence of the κ values indicate that the phonon thermal conductivity was dominant. The dimensionless figure of merit ZT increased with increasing temperature for all the ceramics and showed ~0.1 at 1073 K for the ceramics with x=0.002 and 0.005.

  16. Phase constitution in Sr and Mg doped LaGaO{sub 3} system

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Zheng Feng; Bordia, Rajendra K.; Pederson, Larry R

    2004-01-03

    Sr and Mg doped lanthanum gallate perovskites (La{sub 1-x}Sr{sub x}Ga{sub 1-y}Mg{sub y}O{sub 3-{delta}}, shortened as LSGM-XY where X and Y are the doping levels in mole percentage (mol%) at the La- or A-site and the Ga- or B-site, respectively) are promising electrolyte materials for intermediate temperature solid oxide fuel cells (SOFCs). In this study, we have investigated the primary perovskites as well as the secondary phases formed in terms of doping content changes and A/B ratio variations in these materials. Fifteen powder compositions (three doping levels, X=Y=0, 0.1, and 0.2 mol; and five A/B ratios 0.95, 0.98, 1.00, 1.02, andmore » 1.05) were synthesized by the glycine-nitrate combustion process (GNP). These powders were equilibrated by calcining at 1500 deg. C for 9 h prior to crystalline phase characterization by X-ray powder diffraction (XRD). From the results of this study and the available phase diagrams in the literature on constituent binary oxide systems, we propose a crystalline phase diagram of the La{sub 2}O{sub 3}-SrO-Ga{sub 2}O{sub 3}-MgO quaternary system at elevated temperature (1500 deg. C)« less

  17. Highly Efficient 2D/3D Hybrid Perovskite Solar Cells via Low-Pressure Vapor-Assisted Solution Process.

    PubMed

    Li, Ming-Hsien; Yeh, Hung-Hsiang; Chiang, Yu-Hsien; Jeng, U-Ser; Su, Chun-Jen; Shiu, Hung-Wei; Hsu, Yao-Jane; Kosugi, Nobuhiro; Ohigashi, Takuji; Chen, Yu-An; Shen, Po-Shen; Chen, Peter; Guo, Tzung-Fang

    2018-06-08

    The fabrication of multidimensional organometallic halide perovskite via a low-pressure vapor-assisted solution process is demonstrated for the first time. Phenyl ethyl-ammonium iodide (PEAI)-doped lead iodide (PbI 2 ) is first spin-coated onto the substrate and subsequently reacts with methyl-ammonium iodide (MAI) vapor in a low-pressure heating oven. The doping ratio of PEAI in MAI-vapor-treated perovskite has significant impact on the crystalline structure, surface morphology, grain size, UV-vis absorption and photoluminescence spectra, and the resultant device performance. Multiple photoluminescence spectra are observed in the perovskite film starting with high PEAI/PbI 2 ratio, which suggests the coexistence of low-dimensional perovskite (PEA 2 MA n -1 Pb n I 3 n +1 ) with various values of n after vapor reaction. The dimensionality of the as-fabricated perovskite film reveals an evolution from 2D, hybrid 2D/3D to 3D structure when the doping level of PEAI/PbI 2 ratio varies from 2 to 0. Scanning electron microscopy images and Kelvin probe force microscopy mapping show that the PEAI-containing perovskite grain is presumably formed around the MAPbI 3 perovskite grain to benefit MAPbI 3 grain growth. The device employing perovskite with PEAI/PbI 2 = 0.05 achieves a champion power conversion efficiency of 19.10% with an open-circuit voltage of 1.08 V, a current density of 21.91 mA cm -2 , and a remarkable fill factor of 80.36%. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Electrical Stress Influences the Efficiency of CH3 NH3 PbI3 Perovskite Light Emitting Devices.

    PubMed

    Zhao, Lianfeng; Gao, Jia; Lin, YunHui L; Yeh, Yao-Wen; Lee, Kyung Min; Yao, Nan; Loo, Yueh-Lin; Rand, Barry P

    2017-06-01

    Organic-inorganic hybrid perovskite materials are emerging as semiconductors with potential application in optoelectronic devices. In particular, perovskites are very promising for light-emitting devices (LEDs) due to their high color purity, low nonradiative recombination rates, and tunable bandgap. Here, using pure CH 3 NH 3 PbI 3 perovskite LEDs with an external quantum efficiency (EQE) of 5.9% as a platform, it is shown that electrical stress can influence device performance significantly, increasing the EQE from an initial 5.9% to as high as 7.4%. Consistent with the enhanced device performance, both the steady-state photoluminescence (PL) intensity and the time-resolved PL decay lifetime increase after electrical stress, indicating a reduction in nonradiative recombination in the perovskite film. By investigating the temperature-dependent characteristics of the perovskite LEDs and the cross-sectional elemental depth profile, it is proposed that trap reduction and resulting device-performance enhancement is due to local ionic motion of excess ions, likely excess mobile iodide, in the perovskite film that fills vacancies and reduces interstitial defects. On the other hand, it is found that overstressed LEDs show irreversibly degraded device performance, possibly because ions initially on the perovskite lattice are displaced during extended electrical stress and create defects such as vacancies. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Tailored Engineering of an Unusual (C4 H9 NH3 )2 (CH3 NH3 )2 Pb3 Br10 Two-Dimensional Multilayered Perovskite Ferroelectric for a High-Performance Photodetector.

    PubMed

    Li, Lina; Sun, Zhihua; Wang, Peng; Hu, Weida; Wang, Sasa; Ji, Chengmin; Hong, Maochun; Luo, Junhua

    2017-09-25

    Two-dimensional (2D) layered hybrid perovskites have shown great potential in optoelectronics, owing to their unique physical attributes. However, 2D hybrid perovskite ferroelectrics remain rare. The first hybrid ferroelectric with unusual 2D multilayered perovskite framework, (C 4 H 9 NH 3 ) 2 (CH 3 NH 3 ) 2 Pb 3 Br 10 (1), has been constructed by tailored alloying of the mixed organic cations into 3D prototype of CH 3 NH 3 PbBr 3 . Ferroelectricity is created through molecular reorientation and synergic ordering of organic moieties, which are unprecedented for the known 2D multilayered hybrid perovskites. Single-crystal photodetectors of 1 exhibit fascinating performances, including extremely low dark currents (ca. 10 -12  A), large on/off current ratios (ca. 2.5×10 3 ), and very fast response rate (ca. 150 μs). These merits are superior to integrated detectors of other 2D perovskites, and compete with the most active CH 3 NH 3 PbI 3 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Local structural distortion and electrical transport properties of Bi(Ni1/2Ti1/2)O3 perovskite under high pressure.

    PubMed

    Zhu, Jinlong; Yang, Liuxiang; Wang, Hsiu-Wen; Zhang, Jianzhong; Yang, Wenge; Hong, Xinguo; Jin, Changqing; Zhao, Yusheng

    2015-12-16

    Perovskite-structure materials generally exhibit local structural distortions that are distinct from long-range, average crystal structure. The characterization of such distortion is critical to understanding the structural and physical properties of materials. In this work, we combined Pair Distribution Function (PDF) technique with Raman spectroscopy and electrical resistivity measurement to study Bi(Ni1/2Ti1/2)O3 perovskite under high pressure. PDF analysis reveals strong local structural distortion at ambient conditions. As pressure increases, the local structure distortions are substantially suppressed and eventually vanish around 4 GPa, leading to concurrent changes in the electronic band structure and anomalies in the electrical resistivity. Consistent with PDF analysis, Raman spectroscopy data suggest that the local structure changes to a higher ordered state at pressures above 4 GPa.

  1. Laser-induced down-conversion and infrared phosphorescence emissivity of novel ligand-free perovskite nanomaterials

    NASA Astrophysics Data System (ADS)

    Ahmed, M. A.; Khafagy, Rasha M.; El-sayed, O.

    2014-03-01

    For the first time, standalone and ligand-free series of novel rare-earth-based perovskite nanomaterials are used as near infrared (NIR) and mid infrared (MIR) emitters. Nano-sized La0.7Sr0.3M0.1Fe0.9O3; where M = 0, Mn2+, Co2+ or Ni2+ were synthesized using the flash auto-combustion method and characterized using FTIR, FT-Raman, SEM and EDX. Photoluminescence spectra were spontaneously recorded during pumping the samples with 0.5 mW of green laser emitting continuously at 532 nm. La0.7Sr0.3FeO3 (where M = 0) did not result in any infrared emissivity, while intense near and mid infrared down-converted phosphorescence was released from the M-doped samples. The released phosphorescence greatly shifted among the infrared spectral region with changing the doping cation. Ni2+-doped perovskite emitted at the short-wavelength near-infrared region, while Mn2+ and Co2+-doped perovskites emitted at the mid-wavelength infrared region. The detected laser-induced spontaneous parametric down-conversion phosphorescence (SPDC) occurred through a two-photon process by emitting two NIR or MIR photons among a cooperative energy transfer between the La3+ cations and the M2+ cations. Combining SrFeO3 ceramic with both a rare earth cation (RE3+) and a transition metal cation (Mn2+, Co2+ or Ni2+), rather than introducing merely RE3+ cations, greatly improved and controlled the infrared emissivity properties of synthesized perovskites through destroying their crystal symmetry and giving rise to asymmetrical lattice vibration and the nonlinear optical character. The existence of SPDC in the M2+-doped samples verifies their nonlinear character after the absence of this character in La0.7Sr0.3FeO3. Obtained results verify that, for the first time, perovskite nanomaterials are considered as nonlinear optical crystals with intense infrared emissivity at low pumping power of visible wavelengths, which nominates them for photonic applications and requires further studies regarding their lasing

  2. Epitaxial structure and transport in LaTiO3+x films on (001) SrTiO3

    NASA Astrophysics Data System (ADS)

    Kim, K. H.; Norton, D. P.; Budai, J. D.; Chisholm, M. F.; Sales, B. C.; Christen, D. K.; Cantoni, C.

    2003-12-01

    The structure and transport properties of LaTiO3+x epitaxial thin films grown on (001) SrTiO3 by pulsed-laser deposition is examined. Four-circle X-ray diffraction indicates that the films possess the defect perovskite LaTiO3 structure when deposited in vacuum, with the higher X compounds forming at moderate oxygen pressures. The crystal structure of the LaTiO3 films is tetragonal in the epitaxial films, in contrast to the orthorhombic structure observed in bulk materials. A domain structure is observed in the films, consisting of LaTiO3 oriented either with the [110] or [001] directions perpendicular to the substrate surface. Z-contrast scanning transmission electron microscopy reveals that this domain structure is not present in the first few unit cells of the film, but emerges approximately 2-3 nm from the SrTiO3/LaTiO3 interface. Upon increasing the oxygen pressure during growth, a shift in the lattice d-spacing parallel to the substrate surface is observed, and is consistent with the growth of the La2Ti2O7 phase. However, van der Pauw measurements show that the films with the larger d-spacing remain conductive, albeit with a resistivity that is significantly higher than that for the perovskite LaTiO3 films. The transport behavior suggests that the films grown at higher oxygen pressures are LaTiO3+x with 0.4 < x < 0.5. (

  3. Bication lead iodide 2D perovskite component to stabilize inorganic α-CsPbI3 perovskite phase for high-efficiency solar cells

    PubMed Central

    Zhang, Taiyang; Dar, M. Ibrahim; Li, Ge; Xu, Feng; Guo, Nanjie; Grätzel, Michael; Zhao, Yixin

    2017-01-01

    Among various all-inorganic halide perovskites exhibiting better stability than organic-inorganic halide perovskites, α-CsPbI3 with the most suitable band gap for tandem solar cell application faces an issue of phase instability under ambient conditions. We discovered that a small amount of two-dimensional (2D) EDAPbI4 perovskite containing the ethylenediamine (EDA) cation stabilizes the α-CsPbI3 to avoid the undesirable formation of the nonperovskite δ phase. Moreover, not only the 2D perovskite of EDAPbI4 facilitate the formation of α-CsPbI3 perovskite films exhibiting high phase stability at room temperature for months and at 100°C for >150 hours but also the α-CsPbI3 perovskite solar cells (PSCs) display highly reproducible efficiency of 11.8%, a record for all-inorganic lead halide PSCs. Therefore, using the bication EDA presents a novel and promising strategy to design all-inorganic lead halide PSCs with high performance and reliability. PMID:28975149

  4. Transport, Optical, and Magnetic Properties of the Conducting Halide Perovskite CH 3NH 3SnI 3

    NASA Astrophysics Data System (ADS)

    Mitzi, D. B.; Feild, C. A.; Schlesinger, Z.; Laibowitz, R. B.

    1995-01-01

    A low-temperature ( T ≤ 100°C) solution technique is described for the preparation of polycrystalline and single crystal samples of the conducting halide perovskite, CH 3NH 3SnI 3. Transport, Hall effect, magnetic, and optical properties are examined over the temperature range 1.8-300 K, confirming that this unusual conducting halide perovskite is a low carrier density p-type metal with a Hall hole density, 1/ RHe ≃ 2 × 10 19 cm -3. The resistivity of pressed pellet samples decreases with decreasing temperature with resistivity ratio ρ(300 K)/ρ(2 K) ≃ 3 and room temperature resistivity ρ(300 K) ≃ 7 mΩ-cm. A free-carrier infrared reflectivity spectrum with a plasma edge observed at approximately 1600 cm -1 further attests to the metallic nature of this compound and suggests a small optical effective mass, m* ≃ 0.2.

  5. Strain-induced metal-insulator transitions in d1 perovskites within DFT+DMFT

    NASA Astrophysics Data System (ADS)

    Dymkowski, Krzysztof; Ederer, Claude

    2014-03-01

    We present results of combined density functional theory plus dynamical mean-field theory (DFT+DMFT) calculations, assessing the effect of epitaxial strain on the electronic properties of the Mott insulator LaTiO3 and the correlated metal SrVO3. In particular, we take into account the effect of strain on the collective tilts and rotations of the oxygen octahedra in the orthorhombically distorted Pbnm perovskite structure of LaTiO3. We find that LaTiO3 undergoes an insulator-to-metal transition under a compressive strain of about - 2 %, consistent with recent experimental observations. We show that this transition is driven mainly by strain-induced changes in the crystal-field splitting between the Ti t2 g orbitals, which in turn are related to changes in the octahedral tilt distortion. We compare this with the case of SrVO3, without octahedral tilts, where we find a metal-to-insulator transition under tensile epitaxial strain. Similar to LaTiO3, this metal-insulator transition is linked to the strain-induced change in the crystal-field splitting within the t2 g orbitals.

  6. Neutron and electron diffraction studies of La(Zn1/2Ti1/2)O3 perovskite.

    PubMed

    Ubic, Rick; Hu, Yi; Abrahams, Isaac

    2006-08-01

    The crystallography and microwave dielectric properties of La(Zn(1/2)Ti(1/2))O(3) (LZT) ceramics prepared via the mixed-oxide route were investigated in this study. While samples were largely single phase, small amounts of ZnO impurity were detected in sintered pellets. Observed reflections in electron and neutron diffraction patterns indicate that the symmetry of LZT is P2(1)/n. The B site is ordered on {110} or pseudocubic {111}, but the presence of the pseudocubic 1/2(111) reflection is in itself insufficient to indicate the existence of such order. Rietveld refinements of the neutron diffraction data yield an excellent fit for such a model. The structure is highly twinned, with variants related through common {211} composition planes and 90 degrees rotations about <011>. The microwave dielectric properties measured were epsilon(r) = 34, Qf = 36,090 and tau(f) = -70 MK(-1).

  7. Anisotropic plasticity of MgSiO3 post-perovskite from atomic scale modeling

    NASA Astrophysics Data System (ADS)

    Goryaeva, Alexandra; Carrez, Philippe; Cordier, Patrick

    2016-04-01

    In contrast to the lower mantle, the D″ layer exhibits significant seismic anisotropy both at the global and local scale [1]. Located right above the CMB, the D'' represents a very complex region and the causes of its pronounced anisotropy are still debated (CPO, oriented inclusions, layering, thermo-chemical heterogeneities etc). Among them, contribution of the post-perovskite rheology is commonly considered to be substantial. However, for this high-pressure phase, information about mechanical properties, probable slip systems, dislocations and their behavior under stress are still extremely challenging to obtain directly from experiments [3, 4]. Thus, we propose employing full atomistic modeling (based on the pairwise potential previously derived by [2]) to access the ability of MgSiO3 post-perovskite to deform by dislocation glide at 120 GPa. Lattice friction opposed to the dislocation glide in MgSiO3 post-perovskite is shown to be highly anisotropic. Thus, remarkably low values of Peierls stress (1 GPa) are found for the glide of [100] screw dislocations in (010), while glide in (001) requires almost 18 times larger stress values. In general, (010) plane is characterized by the lowest lattice friction which suggests (010) deformation textures. Comparison of our results with previous study of MgSiO3 perovskite (bridgmanite) [5], based on similar simulation approach, clearly shows that monotonous increase in Peierls stress of bridgmanite will be followed by a dramatic drop after the phase transition to the post-perovskite phase, which consequently suggests the D'' located at the CMB to be weaker than the overlying mantle. In addition to that, the observed evolution of CRSS with temperature clearly demonstrates that post-perovskite deforms in the athermal regime which backs up it to be a very weak phase and indicates its deformation by dislocation glide in contrast to high-lattice friction perovskite (bridgmanite) phase deformed by climb only. References [1

  8. Long-range ordering in the Bi 1-xAe xFeO 3-x/2 perovskites: Bi 1/3Sr 2/3FeO 2.67 and Bi 1/2Ca 1/2FeO 2.75

    NASA Astrophysics Data System (ADS)

    Lepoittevin, C.; Malo, S.; Barrier, N.; Nguyen, N.; Van Tendeloo, G.; Hervieu, M.

    2008-10-01

    Two-ordered perovskites, Bi 1/3Sr 2/3FeO 2.67 and Bi 1/2Ca 1/2FeO 2.75, have been stabilized and characterized by transmission electron microscopy, Mössbauer spectroscopy and X-ray powder diffraction techniques. They both exhibit orthorhombic superstructures, one with a≈ b≈2 ap and c≈3 ap (S.G.: Pb2 n or Pbmn) for the Sr-based compound and one with a≈ b≈2 ap and c≈8 ap (S.G.: B222, Bmm2, B2 mm or Bmmm) for the Ca-based one. The high-resolution transmission electron microscopy (HRTEM) images evidence the existence of one deficient [FeO x] ∞ layer, suggesting that Bi 1/3Sr 2/3FeO 2.67 and Bi 1/2Ca 1/2FeO 2.75 behave differently compared to their Ln-based homolog. The HAADF-STEM images allow to propose a model of cation ordering on the A sites of the perovskite. The Mössbauer analyses confirm the trivalent state of iron and its complex environment with three types of coordination. Both compounds exhibit a high value of resistivity and the inverse molar susceptibility versus temperature curves evidence a magnetic transition at about 730 K for the Bi 1/3Sr 2/3FeO 2.67 and a smooth reversible transition between 590 and 650 K for Bi 1/2Ca 1/2FeO 2.75.

  9. Structural, transport and elastic properties of LaTiO3

    NASA Astrophysics Data System (ADS)

    Choithrani, Renu; Bhat, Masroor Ahmad; Gaur, N. K.

    2013-02-01

    The thermophysical properties such as structural, transport and elastic properties of the orthorhombic perovskite-type titanate system, LaTiO3 have been explored in detail for the first time by applying extended rigid ion model (ERIM). LaTiO3 has been subject of recent interest because of the variety of attractive behaviors, including a metal-insulator transition, spin-charge-orbital ordering and high-temperature superconductivity. LaTiO3 has been suggested to have promising scientific and technological applications. The theoretically computed thermophysical properties of LaTiO3 compound are in good agreement with the available results.

  10. Investigation of microstructural and optical properties of La0.8Ca0.2FeO3 nanostructure synthesized via gel combustion method

    NASA Astrophysics Data System (ADS)

    Naseem, Swaleha; Ali, S. Asad; Khan, Wasi; Khan, Shakeel

    2018-05-01

    Ca substituted LaFeO3 orthoferrite nanostructure perovskite has been synthesized by gel combustion method using citric acid as a fuel. The structural and optical properties were investigated by various tools. The structural analysis through Rietveld refinement of the XRD data revealed single phase of orthorhombic structure in R-3c space group of the sample without presence of any other impurity phase. Scanning electron microscopy (SEM) image exhibits non-uniform distribution of the nanoparticles in agglomerated form. The purity of the sample and stoichiometric ratio of the elements were established through energy dispersive x-ray spectroscopy (EDS). FTIR spectroscopy measurement predicts the presence of various band relation of the chemical species of Ca with LaFeO3. Optical properties were explored through UV-visible absorption spectroscopy that showed absorption edge at 347 nm and energy band gap was estimated as 3.47eV using Tauc's relation.

  11. A Long-Term View on Perovskite Optoelectronics.

    PubMed

    Docampo, Pablo; Bein, Thomas

    2016-02-16

    Recently, metal halide perovskite materials have become an exciting topic of research for scientists of a wide variety of backgrounds. Perovskites have found application in many fields, starting from photovoltaics and now also making an impact in light-emitting applications. This new class of materials has proven so interesting since it can be easily solution processed while exhibiting materials properties approaching the best inorganic optoelectronic materials such as GaAs and Si. In photovoltaics, in only 3 years, efficiencies have rapidly increased from an initial value of 3.8% to over 20% in recent reports for the commonly employed methylammonium lead iodide (MAPI) perovskite. The first light emitting diodes and light-emitting electrochemical cells have been developed already exhibiting internal quantum efficiencies exceeding 15% for the former and tunable light emission spectra. Despite their processing advantages, perovskite optoelectronic materials suffer from several drawbacks that need to be overcome before the technology becomes industrially relevant and hence achieve long-term application. Chief among these are the sensitivity of the structure toward moisture and crystal phase transitions in the device operation regime, unreliable device performance dictated by the operation history of the device, that is, hysteresis, the inherent toxicity of the structure, and the high cost of the employed charge selective contacts. In this Account, we highlight recent advances toward the long-term viability of perovskite photovoltaics. We identify material decomposition routes and suggest strategies to prevent damage to the structure. In particular, we focus on the effect of moisture upon the structure and stabilization of the material to avoid phase transitions in the solar cell operating range. Furthermore, we show strategies to achieve low-cost chemistries for the development of hole transporters for perovskite solar cells, necessary to be able to compete with other

  12. The investigation of smart magnetic nanoparticles for use in the hyperthermia treatment of cancer

    NASA Astrophysics Data System (ADS)

    Allyn, Megan; Kharel, Parashu; Vaishnava, Prem; Tackett, Ronald

    The magnetic fluid hyperthermia (MFH) treatment of cancer has emerged as a possible low-side-effect alternative to traditional chemotherapy- and radiation-based therapy. As the nanoparticles absorb energy from a low amplitude RF magnetic field they heat up; however, currently used hyperthermia systems require external temperature monitoring as the nanoparticles can easily heat to temperature greater than the desired window between 42C and 46C. To combat this, we are investigating ``smart'' magnetic nanoparticles whose Curie temperatures fall within the desired range. In order to do this, we have doped non-magnetic cations onto the structure of the AFM LaMnO3. We report synthesis of LaxM1-xMnO3 (M = Ba, Ca, Sr; x = 0.10 - 0.25) nanoparticles via sol-gel method for use in temperature-controlled MFH. These nanoparticles were characterized via powder x-ray diffraction and found to have the expected R -3 c perovskite structure. For elemental analysis, energy dispersive spectroscopy was performed using scanning electron microscopy. The temperature dependence of the magnetization was investigated using vibrating sample magnetometry (VSM) to determine the Curie temperature of the ensembles. The results of the change in temperature vs time and SAR values will be presented.

  13. Sn2+—Stabilization in MASnI3 perovskites by superhalide incorporation

    NASA Astrophysics Data System (ADS)

    Xiang, Junxiang; Wang, Kan; Xiang, Bin; Cui, Xudong

    2018-03-01

    Sn-based hybrid halide perovskites are a potential solution to replace Pb and thereby reduce Pb toxicity in MAPbI3 perovskite-based solar cells. However, the instability of Sn2+ in air atmosphere causes a poor reproducibility of MASnI3, hindering steps towards this goal. In this paper, we propose a new type of organic metal-superhalide perovskite of MASnI2BH4 and MASnI2AlH4. Through first-principles calculations, our results reveal that the incorporation of BH4 and AlH4 superhalides can realize an impressive enhancement of oxidation resistance of Sn2+ in MASnI3 perovskites because of the large electron transfer between Sn2+ and [BH4]-/[AlH4]-. Meanwhile, the high carrier mobility is preserved in these superhalide perovskites and only a slight decrease is observed in the optical absorption strength. Our studies provide a new path to attain highly stable performance and reproducibility of Sn-based perovskite solar cells.

  14. Determination of Debye temperatures and Lamb-Mössbauer factors for LnFeO3 orthoferrite perovskites (Ln  =  La, Nd, Sm, Eu, Gd)

    NASA Astrophysics Data System (ADS)

    Scrimshire, A.; Lobera, A.; Bell, A. M. T.; Jones, A. H.; Sterianou, I.; Forder, S. D.; Bingham, P. A.

    2018-03-01

    Lanthanide orthoferrites have wide-ranging industrial uses including solar, catalytic and electronic applications. Here a series of lanthanide orthoferrite perovskites, LnFeO3 (Ln  =  La Nd; Sm; Eu; Gd), prepared through a standard stoichiometric wet ball milling route using oxide precursors, has been studied. Characterisation through x-ray diffraction and x-ray fluorescence confirmed the synthesis of phase-pure or near-pure LnFeO3 compounds. 57Fe Mössbauer spectroscopy was performed over a temperature range of 10 K-293 K to observe hyperfine structure and to enable calculation of the recoil-free fraction and Debye temperature (θ D) of each orthoferrite. Debye temperatures (Ln  =  La 474 K Nd 459 K Sm 457 K Eu 452 K Gd 473 K) and recoil-free fractions (Ln  =  La 0.827; Nd 0.817; Sm 0.816; Eu 0.812; Gd 0.826) were approximated through minimising the difference in the temperature dependent experimental centre shift and theoretical isomer shift, by allowing the Debye temperature and isomer shift values to vary. This method of minimising the difference between theoretical and actual values yields Debye temperatures consistent with results from other studies determined through thermal analysis methods. This displays the ability of variable-temperature Mössbauer spectroscopy to approximate Debye temperatures and recoil-free fractions, whilst observing temperature induced transitions over the temperature range observed. X-ray diffraction and Rietveld refinement show an inverse relationship between FeO6 octahedral volume and approximated Debye temperatures. Raman spectroscopy show an increase in the band positions attributed to soft modes of Ag symmetry, Ag(3) and Ag(5) from La to GdFeO3 corresponding to octahedral rotations and tilts in the [0 1 0] and [1 0 1] planes respectively.

  15. Thin film nano-photocatalyts with low band gap energy for gas phase degradation of p-xylene: TiO2 doped Cr, UiO66-NH2 and LaBO3 (B  =  Fe, Mn, and Co)

    NASA Astrophysics Data System (ADS)

    Loc Luu, Cam; Thuy Van Nguyen, Thi; Nguyen, Tri; Nguyen, Phung Anh; Hoang, Tien Cuong; Ha, Cam Anh

    2018-03-01

    By dip-coating technique the thin films of nano-photocatalysts TiO2, Cr-doped TiO2, LaBO3 perovskites (B  =  Fe, Mn, and Co) prepared by sol-gel method, and UiO66-NH2 prepared by a solvothermal were obtained and employed for gas phase degradation of p-xylene. Physicochemical characteristics of the catalysts were examined by the methods of BET, SEM, TEM, XRD, FT-IR, TGA, Raman and UV-vis spectroscopies. The thickness of film was determined by a Veeco-American Dektek 6M instrument. The activity of catalysts was evaluated in deep photooxidation of p-xylene in a microflow reactor at room temperature with the radiation sources of a UV (λ  =  365 nm) and LED lamps (λ  =  400-510 nm). The obtained results showed that TiO2 and TiO2 doped Cr thin films was featured by an anatase phase with nanoparticles of 10-100 nm. Doping TiO2 with 0.1%mol Cr2O3 led to reduce band gap energy from 3.01 down to 1.99 eV and extend the spectrum of photon absorption to the visible region (λ  =  622 nm). LaBO3 perovkite thin films were also featured by a crystal phase with average particle nanosize of 8-40 nm, a BET surface area of 17.6-32.7 m2 g-1 and band gap energy of 1.87-2.20 eV. UiO66-NH2 was obtained in the ball shape of 100-200 nm, a BET surface area of 576 m2 g-1 and a band gap energy of 2.83 eV. The low band gap energy nano-photocatalysts based on Cr-doped TiO2 and LaBO3 perovskites exhibited highly stable and active for photo-degradation of p-xylene in the gas phase under radiation of UV-vis light. Perovskite LaFeO3 and Cr-TiO2 thin films were the best photocatalysts with a decomposition yield being reached up to 1.70 g p-xylene/g cat.

  16. Multiferroic Double Perovskites ScFe1-xCrxO3 (1 /6 ≤x ≤5 /6 ) for Highly Efficient Photovoltaics and Spintronics

    NASA Astrophysics Data System (ADS)

    Cai, Tian-Yi; Liu, Shi-Chen; Ju, Sheng; Liu, Cheng-You; Guo, Guang-Yu

    2017-09-01

    Ferroelectric oxides are attractive materials for constructing efficient solar cells. Nevertheless, a wide band gap of nearly 3.0 eV in these ferroelectric oxides would result in poor overall sunlight absorption and, hence, low energy conversion efficiency. Here, by systematic first-principles density-functional calculations, we demonstrate that double-perovskite semiconductors ScFe1-xCrxO3 (1 /6 ≤x ≤5 /6 ) with a narrow band gap of approximately 1.8 eV would simultaneously exhibit large ferroelectric polarization (100 μ C /cm2 ) and ferrimagnetic magnetization (170 emu/cm3 ). Within a Schottky-based model for a typical sandwich solar-cell structure, a power-conversion efficiency of 9.0% can be reached by neglecting all other sources of photovoltaicity in ferroelectric materials. This value is larger than the largest value of 8.1% observed in ferroelectric oxides. Furthermore, these double perovskites are found to be single-spin semiconductors, and the obtained photocurrent is fully spin polarized over almost the entire Sun spectrum. These fascinating advantages would make ScFex Cr1 -xO3 (1 /6 ≤x ≤5 /6 ) semiconductors promising candidates for highly efficient solar cells and spin photovoltaic devices.

  17. Local structural distortion and electrical transport properties of Bi(Ni 1/2Ti 1/2)O 3 perovskite under high pressure

    DOE PAGES

    Zhu, Jinlong; Yang, Liuxiang; Wang, Hsiu -Wen; ...

    2015-12-16

    Perovskite-structure materials generally exhibit local structural distortions that are distinct from long-range, average crystal structure. The characterization of such distortion is critical to understanding the structural and physical properties of materials. In this work, we combined Pair Distribution Function (PDF) technique with Raman spectroscopy and electrical resistivity measurement to study Bi(Ni 1/2Ti 1/2)O 3 perovskite under high pressure. PDF analysis reveals strong local structural distortion at ambient conditions. As pressure increases, the local structure distortions are substantially suppressed and eventually vanish around 4 GPa, leading to concurrent changes in the electronic band structure and anomalies in the electrical resistivity. Wemore » find, consistent with PDF analysis, Raman spectroscopy data suggest that the local structure changes to a higher ordered state at pressures above 4 GPa.« less

  18. La-Sr-Ni-Co-O based perovskite-type solid solutions as catalyst precursors in the CO 2 reforming of methane

    NASA Astrophysics Data System (ADS)

    Valderrama, Gustavo; Kiennemann, Alain; Goldwasser, Mireya R.

    La 1- xSr xNi 0.4Co 0.6O 3 and La 0.8Sr 0.2Ni 1- yCo yO 3 solid solutions with perovskite-type structure were synthesized by the sol-gel resin method and used as catalytic precursors in the dry reforming of methane with CO 2 to syngas, between 873 and 1073 K at atmospheric pressure under continuous flow of reactant gases with CH 4/CO 2 = 1 ratio. These quaternary oxides were characterized by X-ray diffraction (XRD), BET specific surface area and temperature-programmed reduction (TPR) techniques. XRD analyses of the more intense diffraction peaks and cell parameter measurements showed formation of La-Sr-Ni-Co-O solid solutions with La 0.9Sr 0.1CoO 3 and/or La 0.9Sr 0.1NiO 3 as the main crystallographic phases present on the solids depending on the degree of substitution. TPR analyses showed that Sr doping decreases the temperature of reduction via formation of intermediary species producing Ni 0, Co 0 with particle sizes in the range of nanometers over the SrO and La 2O 3 phases. These metallic nano particles highly dispersed in the solid matrix are responsible for the high activity shown during the reaction and avoid carbon formation. The presence of Sr in doping quantities also promotes the secondary reactions of carbon formation and water-gas shift in a very small extension during the dry reforming reaction.

  19. Photoluminescence characterisations of a dynamic aging process of organic-inorganic CH3NH3PbBr3 perovskite

    NASA Astrophysics Data System (ADS)

    Sheng, R.; Wen, X.; Huang, S.; Hao, X.; Chen, S.; Jiang, Y.; Deng, X.; Green, M. A.; Ho-Baillie, A. W. Y.

    2016-01-01

    After unprecedented development of organic-inorganic lead halide perovskite solar cells over the past few years, one of the biggest barriers towards their commercialization is the stability of the perovskite material. It is thus important to understand the interaction between the perovskite material and oxygen and/or humidity and the associated degradation process in order to improve device and encapsulation design for better durability. Here we characterize the dynamic aging process in vapour-assisted deposited (VASP) CH3NH3PbBr3 perovskite thin films using advanced optical techniques, such as time-resolved photoluminescence and fluorescence lifetime imaging microscopy (FLIM). Our investigation reveals that the perovskite grains grow spontaneously and the larger grains are formed at room temperature in the presence of moisture and oxygen. This crystallization process leads to a higher density of defects and a shorter carrier lifetime, specifically in the larger grains. Excitation-intensity-dependent steady-state photoluminescence shows both N2 stored and aged perovskite exhibit a super-linear increase of photoluminescence intensity with increasing excitation intensity; and the larger slope in aged sample suggests a larger density of defects is generated, consistent with time-resolved PL measurements.

  20. Electrically Variable or Programmable Nonvolatile Capacitors

    NASA Technical Reports Server (NTRS)

    Shangqing, Liu; NaiJuan, Wu; Ignatieu, Alex; Jianren, Li

    2009-01-01

    Electrically variable or programmable capacitors based on the unique properties of thin perovskite films are undergoing development. These capacitors show promise of overcoming two important deficiencies of prior electrically programmable capacitors: Unlike in the case of varactors, it is not necessary to supply power continuously to make these capacitors retain their capacitance values. Hence, these capacitors may prove useful as components of nonvolatile analog and digital electronic memories. Unlike in the case of ferroelectric capacitors, it is possible to measure the capacitance values of these capacitors without changing the values. In other words, whereas readout of ferroelectric capacitors is destructive, readout of these capacitors can be nondestructive. A capacitor of this type is a simple two terminal device. It includes a thin film of a suitable perovskite as the dielectric layer, sandwiched between two metal or metal oxide electrodes (for example, see Figure 1). The utility of this device as a variable capacitor is based on a phenomenon, known as electrical-pulse-induced capacitance (EPIC), that is observed in thin perovskite films and especially in those thin perovskite films that exhibit the colossal magnetoresistive (CMR) effect. In EPIC, the application of one or more electrical pulses that exceed a threshold magnitude (typically somewhat less than 1 V) gives rise to a nonvolatile change in capacitance. The change in capacitance depends on the magnitude duration, polarity, and number of pulses. It is not necessary to apply a magnetic field or to cool the device below (or heat it above) room temperature to obtain EPIC. Examples of suitable CMR perovskites include Pr(1-x)Ca(x)MnO3, La(1-x)S-r(x)MnO3,and Nb(1-x)Ca(x)MnO3. Figure 2 is a block diagram showing an EPIC capacitor connected to a circuit that can vary the capacitance, measure the capacitance, and/or measure the resistance of the capacitor.

  1. ZnO nanostructures as electron extraction layers for hybrid perovskite thin films

    NASA Astrophysics Data System (ADS)

    Nikolaidou, Katerina; Sarang, Som; Tung, Vincent; Lu, Jennifer; Ghosh, Sayantani

    Optimum interaction between light harvesting media and electron transport layers is critical for the efficient operation of photovoltaic devices. In this work, ZnO layers of different morphologies are implemented as electron extraction and transport layers for hybrid perovskite CH3NH3PbI3 thin films. These include nanowires, nanoparticles, and single crystalline film. Charge transfer at the ZnO/perovskite interface is investigated and compared through ultra-fast characterization techniques, including temperature and power dependent spectroscopy, and time-resolved photoluminescence. The nanowires cause an enhancement in perovskite emission, which may be attributed to increased scattering and grain boundary formation. However, the ZnO layers with decreasing surface roughness exhibit better electron extraction, as inferred from photoluminescence quenching, reduction in the number of bound excitons, and reduced exciton lifetime in CH3NH3PbI3 samples. This systematic study is expected to provide an understanding of the fundamental processes occurring at the ZnO-CH3NH3PbI3 interface and ultimately, provide guidelines for the ideal configuration of ZnO-based hybrid Perovskite devices. This research was supported by National Aeronautics and Space administration (NASA) Grant No: NNX15AQ01A.

  2. A new ferroelectric solid solution system of LaCrO 3-BiCrO 3

    NASA Astrophysics Data System (ADS)

    Chen, J. I. L.; Kumar, M. Mahesh; Ye, Z.-G.

    2004-04-01

    A new perovskite solid solution system of (1- x)LaCrO 3- xBiCrO 3 has been prepared by conventional solid-state reaction and sintering processes at 1200°C in a sealed Pt tube or a Bi 2O 3-rich environment. A clean orthorhombic phase of LaCrO 3-type structure is established at room temperature for compositions with 0⩽ x⩽0.35. The relative density, lattice parameters, sintering mechanism, microstructure and ferroelectricity of the compounds are investigated. The substitution of Bi 2O 3 for La 2O 3 is found to decrease the unit cell volume and increase the grain size of the ceramics. The relative density of the ceramics sintered at 1200°C is significantly improved from 40% for LaCrO 3 up to about 90% for La 0.65Bi 0.35CrO 3 through a liquid phase sintering mechanism. The ferroelectricity is revealed in La 1- xBi xCrO 3 with 0.1⩽ x⩽0.35 by dielectric hysteresis loops displayed at 77 K. The remnant polarization is found to increase with increasing Bi 3+ content. The origin of the ferroelectricity is attributed to the structural distortion induced by the stereochemically active Bi 3+ ion on the A site.

  3. Controlling CH3NH3PbI(3-x)Cl(x) Film Morphology with Two-Step Annealing Method for Efficient Hybrid Perovskite Solar Cells.

    PubMed

    Liu, Dong; Wu, Lili; Li, Chunxiu; Ren, Shengqiang; Zhang, Jingquan; Li, Wei; Feng, Lianghuan

    2015-08-05

    The methylammonium lead halide perovskite solar cells have become very attractive because they can be prepared with low-cost solution-processable technology and their power conversion efficiency have been increasing from 3.9% to 20% in recent years. However, the high performance of perovskite photovoltaic devices are dependent on the complicated process to prepare compact perovskite films with large grain size. Herein, a new method is developed to achieve excellent CH3NH3PbI3-xClx film with fine morphology and crystallization based on one step deposition and two-step annealing process. This method include the spin coating deposition of the perovskite films with the precursor solution of PbI2, PbCl2, and CH3NH3I at the molar ratio 1:1:4 in dimethylformamide (DMF) and the post two-step annealing (TSA). The first annealing is achieved by solvent-induced process in DMF to promote migration and interdiffusion of the solvent-assisted precursor ions and molecules and realize large size grain growth. The second annealing is conducted by thermal-induced process to further improve morphology and crystallization of films. The compact perovskite films are successfully prepared with grain size up to 1.1 μm according to SEM observation. The PL decay lifetime, and the optic energy gap for the film with two-step annealing are 460 ns and 1.575 eV, respectively, while they are 307 and 327 ns and 1.577 and 1.582 eV for the films annealed in one-step thermal and one-step solvent process. On the basis of the TSA process, the photovoltaic devices exhibit the best efficiency of 14% under AM 1.5G irradiation (100 mW·cm(-2)).

  4. ESR and dielectric studies on superparamagnetic LaFeO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Kumar, A. Sendil; Bhatnagar, Anil K.

    2017-05-01

    Superparamagnetic LaFeO3 nanoparticles are synthesized through sol gel method. Structural, magnetic and dielectric studies are carried out. Temperature dependent ESR studies show that the intensity of the ESR spectra increases at higher temperatures. The line shape at low temperature has inhomogeneous broadening and at higher temperature more symmetry is developed and it fits better with the Lorentzian. Resonance field decreases when temperature is lowered due to dipolar interactions and there are no extrema in linewidth are observed. Single semi-circular arc in the Cole-Cole plot shows that the AC conductivity is from grains only.

  5. Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 perovskites for solar cell applications.

    PubMed

    Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo

    2014-03-26

    Hybrid AMX3 perovskites (A = Cs, CH3NH3; M = Sn, Pb; X = halide) have revolutionized the scenario of emerging photovoltaic technologies, with very recent results demonstrating 15% efficient solar cells. The CH3NH3PbI3/MAPb(I(1-x)Cl(x))3 perovskites have dominated the field, while the similar CH3NH3SnI3 has not been exploited for photovoltaic applications. Replacement of Pb by Sn would facilitate the large uptake of perovskite-based photovoltaics. Despite the extremely fast progress, the materials electronic properties which are key to the photovoltaic performance are relatively little understood. Density Functional Theory electronic structure methods have so far delivered an unbalanced description of Pb- and Sn-based perovskites. Here we develop an effective GW method incorporating spin-orbit coupling which allows us to accurately model the electronic, optical and transport properties of CH3NH3SnI3 and CH3NH3PbI3, opening the way to new materials design. The different CH3NH3SnI3 and CH3NH3PbI3 electronic properties are discussed in light of their exploitation for solar cells, and found to be dominantly due to relativistic effects. These effects stabilize the CH3NH3PbI3 material towards oxidation, by inducing a deeper valence band edge. Relativistic effects, however, also increase the material band-gap compared to CH3NH3SnI3, due to the valence band energy downshift (~0.7 eV) being only partly compensated by the conduction band downshift (~0.2 eV).

  6. Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 Perovskites for Solar Cell Applications

    PubMed Central

    Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo

    2014-01-01

    Hybrid AMX3 perovskites (A = Cs, CH3NH3; M = Sn, Pb; X = halide) have revolutionized the scenario of emerging photovoltaic technologies, with very recent results demonstrating 15% efficient solar cells. The CH3NH3PbI3/MAPb(I1−xClx)3 perovskites have dominated the field, while the similar CH3NH3SnI3 has not been exploited for photovoltaic applications. Replacement of Pb by Sn would facilitate the large uptake of perovskite-based photovoltaics. Despite the extremely fast progress, the materials electronic properties which are key to the photovoltaic performance are relatively little understood. Density Functional Theory electronic structure methods have so far delivered an unbalanced description of Pb- and Sn-based perovskites. Here we develop an effective GW method incorporating spin-orbit coupling which allows us to accurately model the electronic, optical and transport properties of CH3NH3SnI3 and CH3NH3PbI3, opening the way to new materials design. The different CH3NH3SnI3 and CH3NH3PbI3 electronic properties are discussed in light of their exploitation for solar cells, and found to be dominantly due to relativistic effects. These effects stabilize the CH3NH3PbI3 material towards oxidation, by inducing a deeper valence band edge. Relativistic effects, however, also increase the material band-gap compared to CH3NH3SnI3, due to the valence band energy downshift (~0.7 eV) being only partly compensated by the conduction band downshift (~0.2 eV). PMID:24667758

  7. New rare earth hafnium oxynitride perovskites with photocatalytic activity in water oxidation and reduction.

    PubMed

    Black, Ashley P; Suzuki, Hajime; Higashi, Masanobu; Frontera, Carlos; Ritter, Clemens; De, Chandan; Sundaresan, A; Abe, Ryu; Fuertes, Amparo

    2018-02-06

    RHfO 2 N perovskites with R = La, Nd and Sm show a GdFeO 3 -type structure and are semiconductors with band gaps of 3.35, 3.40 and 2.85 eV and relative dielectric constants of 30, 16 and 28 respectively. These compounds have adequate reduction and oxidation potentials to conduct the overall water splitting reaction, and the analogous perovskite LaZrO 2 N with a band gap of 2.8 eV shows photocatalytic activity under visible light irradiation for O 2 evolution.

  8. Structural chemistry and magnetic properties of the perovskite Sr{sub 3}Fe{sub 2}TeO{sub 9}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Tang, Yawei; Hunter, Emily C.; Battle, Peter D., E-mail: peter.battle@chem.ox.ac.uk

    2016-10-15

    A polycrystalline sample of perovskite-like Sr{sub 3}Fe{sub 2}TeO{sub 9} has been prepared in a solid-state reaction and studied by a combination of electron microscopy, Mössbauer spectroscopy, magnetometry, X-ray diffraction and neutron diffraction. The majority of the reaction product is shown to be a trigonal phase with a 2:1 ordered arrangement of Fe{sup 3+} and Te{sup 6+} cations. However, the sample is prone to nano-twinning and tetragonal domains with a different pattern of cation ordering exist within many crystallites. Antiferromagnetic ordering exists in the trigonal phase at 300 K and Sr{sub 3}Fe{sub 2}TeO{sub 9} is thus the first example of amore » perovskite with 2:1 trigonal cation ordering to show long-range magnetic order. At 300 K the antiferromagnetic phase coexists with two paramagnetic phases which show spin-glass behaviour below ~80 K. - Graphical abstract: Sr{sub 3}Fe{sub 2}TeO{sub 9} has a 2:1 ordered arrangement of Fe{sup 3+} and Te{sup 6+} cations over the octahedral sites of a perovskite structure and is antiferromagnetic at room temperature. - Highlights: • 2:1 Cation ordering in a trigonal perovskite. • Magnetically ordered trigonal perovskite. • Intergrowth of nanodomains in perovskite microstructure.« less

  9. Magnetic Susceptibility and Spin Exchange Interactions of the Hexagonal Perovskite-Type Oxides Sr 4/3(Mn 2/3Ni 1/3)O 3

    NASA Astrophysics Data System (ADS)

    El Abed, A.; Gaudin, E.; Darriet, J.; Whangbo, M.-H.

    2002-02-01

    Magnetic susceptibility measurements were carried out for two hexagonal perovskite-type oxides Sr1+x(Mn1-xNix)O3 with slightly different compositions (i.e., x={1}/{3} and 0.324). A significant difference in the susceptibilities of the two phases demonstrates the need to control phase compositions accurately. Sr4/3(Mn2/3Ni1/3)O3 consists of two spin sublattices, i.e., the Mn4+ and the Ni2+ ion sublattices. Spin dimer analysis was carried out to examine the relative strengths in the spin exchange interactions of the Mn4+ ion sublattice. The temperature dependence of the magnetic susceptibility of Sr4/3(Mn2/3Ni1/3)O3 was found consistent with a picture in which the Mn4+ ion sublattice has weakly interacting antiferromagnetically coupled (Mn4+)2 dimers, the Ni2+ ion sublattice acts as a paramagnetic system, and the two sublattices are nearly independent.

  10. Carrier injection and recombination processes in perovskite CH3NH3PbI3 solar cells studied by electroluminescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Handa, Taketo; Okano, Makoto; Tex, David M.; Shimazaki, Ai; Aharen, Tomoko; Wakamiya, Atsushi; Kanemitsu, Yoshihiko

    2016-02-01

    Organic-inorganic hybrid perovskite materials, CH3NH3PbX3 (X = I and Br), are considered as promising candidates for emerging thin-film photovoltaics. For practical implementation, the degradation mechanism and the carrier dynamics during operation have to be clarified. We investigated the degradation mechanism and the carrier injection and recombination processes in perovskite CH3NH3PbI3 solar cells using photoluminescence (PL) and electroluminescence (EL) imaging spectroscopies. By applying forward bias-voltage, an inhomogeneous distribution of the EL intensity was clearly observed from the CH3NH3PbI3 solar cells. By comparing the PL- and EL-images, we revealed that the spatial inhomogeneity of the EL intensity is a result of the inhomogeneous luminescence efficiency in the perovskite layer. An application of bias-voltage for several tens of minutes in air caused a decrease in the EL intensity and the conversion efficiency of the perovskite solar cells. The degradation mechanism of perovskite solar cells under bias-voltage in air is discussed.

  11. Tailoring Electronic Properties in Semiconducting Perovskite Materials through Octahedral Control

    NASA Astrophysics Data System (ADS)

    Choquette, Amber K.

    Perovskite oxides, which take the chemical formula ABO 3, are a very versatile and interesting materials family, exhibiting properties that include ferroelectricity, ferromagnetism, mixed ionic/electronic conductivity, metal-insulator behavior and multiferroicity. Key to these functionalities is the network of BO6 corner-connected octahedra, which are known to distort and rotate, directly altering electronic and ferroic properties. By controlling the BO6 octahedral distortions and rotations through cationic substitutions, the use of strain engineering, or through the formation of superlattice structures, the functional properties of perovskites can be tuned. Motivating the use of structure-driven design in oxide heterostructures is the prediction of hybrid improper ferroelectricity in A'BO3/ABO3 superlattices. Two key design rules to realizing hybrid improper ferroelectricity are the growth of high quality superlattice structures with odd periodicities of the A / A' layers, and the control of the octahedral rotation pattern. My work explores the rotational response in perovskite oxides to strain and interface effects in thin films of RFeO3 ( R = La, Eu). I demonstrate a synchrotron x-ray diffraction technique to identify the rotation pattern that is present in the films. I then establish substrate imprinting as a key tool for controlling the rotation patterns in heterostructures, providing a means to realize the necessary structural variants of the predicted hybrid improper ferroelectricity in superlattices. In addition, by pairing measured diffraction data with a structure factor calculation, I demonstrate how one can extract both A-site and oxygen atomic positions in single crystal perovskite oxide films. Finally, I show results from (LaFeO 3)n/(EuFeO3)n superlattices (n = 1-5), synthesized to test the motivating predictions of hybrid improper ferroelectricity in oxide superlattices.

  12. Copolymers of poly(3-thiopheneacetic acid) with poly(3-hexylthiophene) as hole-transporting material for interfacially engineered perovskite solar cell by modulating band positions for higher efficiency.

    PubMed

    Shit, Arnab; Chal, Pousali; Nandi, Arun K

    2018-06-13

    In order to tune the band positions of the hole-transporting material (HTM) in an interfacially engineered perovskite solar cell (PSC), random copolymers of poly(3-thiopheneacetic acid) and poly(3-hexylthiophene) (P3TAA-co-P3HT) with different compositions were produced by oxidative polymerization. The copolymers were characterized using 1H NMR, FTIR, and UV-vis spectroscopy and gel permeation chromatography. Here, ZnO nanoparticles were used as the electron-transporting material (ETM) and methylammonium lead iodide (MAPbI3) perovskite was used as the light-absorbing material to form an FTO/ZnO/MAPbI3/copolymer/Ag device, of which the power conversion efficiency (PCE) was found to be dependent on the copolymer composition and reached a maximum (∼10%) at a P3TAA content of 43 mol% in the copolymer (P3). The band gaps of the copolymers as determined from UV-vis spectroscopy and cyclic voltammetry exhibit a staggered-gap hetero-interface configuration in which the HOMO and LUMO of P3 closely match those of MAPbI3 and give rise to the maximum PCE. Time-resolved photoluminescence spectra of MAPbI3/HTM samples indicate that charge transfer across the perovskite/copolymer interface was faster with a reduced recombination rate for a P3 sample. The electrochemical impedance spectra (EIS) of the PSCs exhibit Nyquist plots with two semicircles, which correspond to an equivalent circuit consisting of two parallel R-C and R-CPE circuits connected in series. Analysis of the data indicates that the effective electron lifetime was longest for the P3 copolymer, which indicates that the charge recombination was lower than that in the components and other copolymers. The copolymers exhibited an intermediate stability with respect to their components, and amongst the copolymers P3 exhibited the highest stability.

  13. Light-Independent Ionic Transport in Inorganic Perovskite and Ultrastable Cs-Based Perovskite Solar Cells.

    PubMed

    Zhou, Wenke; Zhao, Yicheng; Zhou, Xu; Fu, Rui; Li, Qi; Zhao, Yao; Liu, Kaihui; Yu, Dapeng; Zhao, Qing

    2017-09-07

    Due to light-induced effects in CH 3 NH 3 -based perovskites, such as ion migration, defects formation, and halide segregation, the degradation of CH 3 NH 3 -based perovskite solar cells under maximum power point is generally implicated. Here we demonstrated that the effect of light-enhanced ion migration in CH 3 NH 3 PbI 3 can be eliminated by inorganic Cs substitution, leading to an ultrastable perovskite solar cell. Quantitatively, the ion migration barrier for CH 3 NH 3 PbI 3 is 0.62 eV under dark conditions, larger than that of CsPbI 2 Br (0.45 eV); however, it reduces to 0.07 eV for CH 3 NH 3 PbI 3 under illumination, smaller than that for CsPbI 2 Br (0.43 eV). Meanwhile, photoinduced halide segregation is also suppressed in Cs-based perovskites. Cs-based perovskite solar cells retained >99% of the initial efficiency (10.3%) after 1500 h of maximum power point tracking under AM1.5G illumination, while CH 3 NH 3 PbI 3 solar cells degraded severely after 50 h of operation. Our work reveals an uncovered mechanism for stability improvement by inorganic cation substitution in perovskite-based optoelectronic devices.

  14. Effect of sintering time on structural, microstructural and chemical composition of Ni-doped lanthanum gallate perovskites

    NASA Astrophysics Data System (ADS)

    Colomer, M. T.; Kilner, J. A.

    2015-08-01

    This work reports the effect of two different sintering times, 6 and 48 h on the structural, microstructural, and chemical features of Ni-doped La0.90Sr0.10GaO3.00-δ. Independently of the sintering time, La0.90Sr0.10Ga1-xNixO3.00-δ (where x=0.10, and 0.20 (mol)) presents a rhombohedral symmetry with a lattice volume that decreases when NiO dopant increases. Besides the perovskite, LaSrGa3.00O7.00 (nominal composition) is present as second phase in all cases. When the samples are doped with NiO, the peaks of this second phase are shifted with respect to the peaks of the pure phase. These shifts suggest that this second phase could admit some Ni ions in its structure. According to the XRD patterns, the amount of the latter phase is larger when sintering time is increased. Electron probe microanalysis (EPMA) indicated that the matrix of the samples sintered for 6 h is constituted by a perovskite with an experimental composition very close to the nominal one. However, when the samples are sintered for 48 h the matrix of each sample is constituted by two perovskites; both with compositional deviations with respect to their nominal one. In particular, a significant Sr depletion compensated by a La increment in the A site is observed. Those compositional deviations could be mainly due to the diffusion of the cations in the bulk and/or from the bulk to the surface of the samples. That diffusion can favour the formation, not only, of a second perovskite with a different composition in relation with the first one formed, but also, the formation of second phases. In addition, a very slight broadening of Bragg peaks of the perovskites sintered for 48 h is observed by XRD and can be related to the presence of two different perovskites in each sample according to EPMA results. By BSEM and EPMA analyses La4.00Ga2.00O9.00 (nominal composition) is also observed as second phase when samples are treated for 48 h.

  15. Water soluble (Ln3+) doped nanoparticle: Retention of strong luminescence

    NASA Astrophysics Data System (ADS)

    Attar, Tarannum Vahid; Khandpekar, Mahendra M.

    2018-04-01

    This paper deals with the synthesis of hexagonal nanoparticles of LaF3: Nd, Ho (LFNH) in the presence of LaCl3.7H2O and NH4F by precipitation method using deionized water as solvent. The nanoparticles have a nearly hexagonal shape with cell parameters, a = b = 7.0980 AU and c = 7.2300 AU and confirms with the JCPDS standard card (32-0483) of pure LaF3 crystals. The TEM results show that the average sizes of these nanoparticles are 15nm which is consistent with the sizes obtained from XRD measurements. The SEM image shows uniform size distribution of the nanoparticles. Detection of Second harmonic generation (SHG) signal together with the presence of wide transparency window (UV studies) makes LFNH suitable for optoelectronic applications. The Photoluminescence of the nanocrystals has been observed by excitation and emission spectra. The peak at 629nm indicates red up conversion fluorescence useful in applications like bioimaging and biolabelling.

  16. Crystal structure study of dielectric oxynitride perovskites La{sub 1−x}Sr{sub x}TiO{sub 2+x}N{sub 1−x} (x=0, 0.2)

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Habu, Daiki; Masubuchi, Yuji; Torii, Shuki

    As is the case with SrTaO{sub 2}N, both cis-ordering of nitride anions and octahedral titling are also preferable in La{sub 1−x}Sr{sub x}TiO{sub 2+x}N{sub 1−x} (x=0, 0.2) oxynitride perovskites. A larger dielectric constant of ε{sub r}≈5.0×10{sup 3} was estimated for the pure oxynitride with x=0.2, compared with ε{sub r}≈750 for the product with x=0, by extrapolating the ε{sub r} values obtained from powders mixed with paraffin at various mixing ratios. The crystal structure of x=0.2 with larger tolerance factor than x=0 increased the octahedral tilting, which contributes to the increased dielectric constant. The increased dielectric constant supports the exchange mechanism formore » the dielectric property between two kinds of –Ti–N– helical coils (clockwise and anticlockwise) derived from the above cis-ordering of nitride anions. - Graphical abstract: Very large dielectric constant values were estimated for La{sub 1−x}Sr{sub x}TiO{sub 2+x}N{sub 1−x}; ε{sub r}≈5.0×10{sup 3} in x=0.2 and ε{sub r}≈750 in x=0. - Highlights: • Cis-configuration of nitride anions was confirmed in La{sub 1−x}Sr{sub x}TiO{sub 2+x}N{sub 1−x} (x=0, 0.2). • Dielectric constant values were estimated to be 750 for x=0 and 5.0×10{sup 3} for x=0.2, respectively. • The large dielectric property is to the exchange mechanism between clockwise and anticlockwise –Ti–N– coil motifs.« less

  17. Magnetism in nanoparticle LaCoO3

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Durand, A. M.; Belanger, D. P.; Booth, C. H.

    2014-06-24

    Neutron scattering and magnetometry measurements have been used to study phase transitions in LaCoO3 (LCO). For H <= 100 Oe, evidence for a ferromagnetic (FM) transition is observed at T-c approximate to 87 K. For 1 kOe <= H <= 60 kOe, no transition is apparent. For all H, Curie-Weiss analysis shows predominantly antiferromagnetic (AFM) interactions for T > T-c, but the lack of long-range AFM order indicates magnetic frustration. We argue that the weak ferromagnetism in bulk LCO is induced by lattice strain, as is the case with thin films and nanoparticles. The lattice strain is present at themore » bulk surfaces and at the interfaces between the LCO and a trace cobalt oxide phase. The ferromagnetic ordering in the LCO bulk is strongly affected by the Co-O-Co angle (gamma), in agreement with recent band calculations which predict that ferromagnetic long-range order can only take place above a critical value, gamma C. Consistent with recent thin film estimations, we find gamma C = 162.8 degrees. For gamma > gamma C, we observe power-law behavior in the structural parameters. gamma decreases with T until the critical temperature, T-o approximate to 37 K; below T-o the rate of change becomes very small. For T < T-o, FM order appears to be confined to regions close to the surfaces, likely due to the lattice strain keeping the local Co-O-Co angle above gamma C.« less

  18. Large anisotropic thermoelectricity in perovskite related layered structure: SrnNbnO3n+2 (n=4,5)

    NASA Astrophysics Data System (ADS)

    Sakai, Akihiro; Kanno, Tsutomu; Takahashi, Kouhei; Yamada, Yuka; Adachi, Hideaki

    2010-11-01

    We measured the thermal and charge transport properties of perovskite-related layered structures. Strontium-Niobates, which were expressed as SrnNbnO3n+2 (n =4: Sr1.8La0.2Nb2O7, n =5: Sr5Nb5O17), to explore their thermoelectricities and thermal anisotropies. The behaviors of the thermoelectric parameters (thermal conductivity, Seebeck coefficient, resistivity) were strongly anisotropic in all crystallographic axes (a, b, and c) and large anisotropy exists even in the in-plane direction of the layered structure. Especially, along the a-axis in which corner-sharing NbO6 octahedra aligned straightly, contrastive properties were observed between Sr1.8La0.2Nb2O7 and Sr5Nb5O17. For Sr1.8La0.2Nb2O7, a thermally activated charge conduction is pronounced in the temperature dependence of Seebeck coefficient and resistivity, on the other hand, it was a metallic nature for Sr5Nb5O17. In both compounds, ZT results in anisotropic due to the anisotropic properties of thermoelectric parameters, the best performance is commonly observed in the a-axis. The respective ZT values at room temperature are 3.5×10-2 and 3.6×10-3.

  19. High-pressure studies on Ba-doped cobalt perovskites by neutron diffraction

    NASA Astrophysics Data System (ADS)

    Cao, Huibo; Garlea, Vasile; Wang, Fangwei; Dos Santos, Antonio; Cheng, Zhaohua

    2012-02-01

    Cobalt perovskite possess rich structural, magnetic and electrical properties depending on the subtle balance of the interactions among the spin, charge, and orbital degrees of freedom. Divalent hole-doped cobalt perovskites LaA^2+CoO3 exhibit structural phase transitions, metal-insulator transitions, and multi-magnetic phase transitions. High-pressure measurement is believed to mimic the size effects of the doped ions. We performed neutron diffraction experiments on selected Ba-doped LaCoO3 under pressures up to 6.3 GPa at SNAP at Spallation Neutron Source of ORNL. This work focuses on the high-pressure effects of the selected Ba-doped samples and the change of the phase diagram with pressure.

  20. Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water.

    PubMed

    Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

    2018-06-08

    CH 3 NH 3 PbBr 3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH 3 NH 3 PbBr 3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH 3 NH 3 PbBr 3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

  1. Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water

    NASA Astrophysics Data System (ADS)

    Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

    2018-06-01

    CH3NH3PbBr3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH3NH3PbBr3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH3NH3PbBr3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

  2. Bismuth Based Hybrid Perovskites A3Bi2 I9 (A: Methylammonium or Cesium) for Solar Cell Application.

    PubMed

    Park, Byung-Wook; Philippe, Bertrand; Zhang, Xiaoliang; Rensmo, Håkan; Boschloo, Gerrit; Johansson, Erik M J

    2015-11-18

    Low-toxic bismuth-based perovskites are prepared for the possible replacement of lead perovskite in solar cells. The perovskites have a hexagonal crystalline phase and light absorption in the visible region. A power conversion efficiency of over 1% is obtained for a solar cell with Cs3 Bi2 I9 perovskite, and it is concluded that bismuth perovskites have very promising properties for further development in solar cells. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Fabrication of Lead-Free (CH3 NH3 )3 Bi2 I9 Perovskite Photovoltaics in Ethanol Solvent.

    PubMed

    Li, Haijin; Wu, Congcong; Yan, Yongke; Chi, Bo; Pu, Jian; Li, Jian; Priya, Shashank

    2017-10-23

    The toxicity of lead present in organohalide perovskites and the hazardous solvent systems used for their synthesis hinder the deployment of perovskite solar cells (PSCs). Herein, an environmentally friendly route toward bismuth-based, lead-free (CH 3 NH 3 ) 3 Bi 2 I 9 perovskites that utilize ethanol as the solvent is described. Using this method, dense and homogeneous microstructures were obtained, compared to the porous, rough microstructures obtained using dimethylformamide. Photovoltaic performances were enhanced, with an open-circuit voltage of 0.84 V measured. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Structural and Optical Properties of La1−xSrxTiO3

    PubMed Central

    Gao, Lihong; Ma, Zhuang; Wang, Song; Wang, Fuchi; Yang, Cai

    2014-01-01

    La1−xSrxTiO3+δ has attracted much attention as an important perovskite oxide. However, there are rare reports on its optical properties, especially reflectivity. In this paper, its structural and optical properties were studied. The X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and spectrophotometer were used to characterize the sample. The results show that with increasing Sr concentration, the number of TiO6 octahedral layers in each “slab” increases and the crystal structure changes from layered to cubic structure. A proper Sr doping (x = 0.1) can increase the reflectivity, reaching 95% in the near infrared range, which is comparable with metal Al measured in the same condition. This indicates its potential applications as optical protective coatings or anti-radiation materials at high temperatures. PMID:28788115

  5. CH3NH3PbI3 perovskites: Ferroelasticity revealed.

    PubMed

    Strelcov, Evgheni; Dong, Qingfeng; Li, Tao; Chae, Jungseok; Shao, Yuchuan; Deng, Yehao; Gruverman, Alexei; Huang, Jinsong; Centrone, Andrea

    2017-04-01

    Ferroelectricity has been proposed as a plausible mechanism to explain the high photovoltaic conversion efficiency in organic-inorganic perovskites; however, convincing experimental evidence in support of this hypothesis is still missing. Identifying and distinguishing ferroelectricity from other properties, such as piezoelectricity, ferroelasticity, etc., is typically nontrivial because these phenomena can coexist in many materials. In this work, a combination of microscopic and nanoscale techniques provides solid evidence for the existence of ferroelastic domains in both CH 3 NH 3 PbI 3 polycrystalline films and single crystals in the pristine state and under applied stress. Experiments show that the configuration of CH 3 NH 3 PbI 3 ferroelastic domains in single crystals and polycrystalline films can be controlled with applied stress, suggesting that strain engineering may be used to tune the properties of this material. No evidence of concomitant ferroelectricity was observed. Because grain boundaries have an impact on the long-term stability of organic-inorganic perovskite devices, and because the ferroelastic domain boundaries may differ from regular grain boundaries, the discovery of ferroelasticity provides a new variable to consider in the quest for improving their stability and enabling their widespread adoption.

  6. Magnetic Modes in Rare Earth Perovskites: A Magnetic-Field-Dependent Inelastic Light Scattering study.

    PubMed

    Saha, Surajit; Cao, Bing-Chen; Motapothula, M; Cong, Chun-Xiao; Sarkar, Tarapada; Srivastava, Amar; Sarkar, Soumya; Patra, Abhijeet; Ghosh, Siddhartha; Ariando; Coey, J M D; Yu, Ting; Venkatesan, T

    2016-11-15

    Here, we report the presence of defect-related states with magnetic degrees of freedom in crystals of LaAlO 3 and several other rare-earth based perovskite oxides using inelastic light scattering (Raman spectroscopy) at low temperatures in applied magnetic fields of up to 9 T. Some of these states are at about 140 meV above the valence band maximum while others are mid-gap states at about 2.3 eV. No magnetic impurity could be detected in LaAlO 3 by Proton-Induced X-ray Emission Spectroscopy. We, therefore, attribute the angular momentum-like states in LaAlO 3 to cationic/anionic vacancies or anti-site defects. Comparison with the other rare earth perovskites leads to the empirical rule that the magnetic-field-sensitive transitions require planes of heavy elements (e.g. lanthanum) and oxygen without any other light cations in the same plane. These magnetic degrees of freedom in rare earth perovskites with useful dielectric properties may be tunable by appropriate defect engineering for magneto-optic applications.

  7. La interstitial defect-induced insulator-metal transition in the oxide heterostructures LaAl O3 /SrTi O3

    NASA Astrophysics Data System (ADS)

    Zhou, Jun; Yang, Ming; Feng, Yuan Ping; Rusydi, Andrivo

    2017-11-01

    Perovskite oxide interfaces have attracted tremendous research interest for their fundamental physics and promising all-oxide electronic applications. Here, based on first-principles calculations, we propose a surface La interstitial promoted interface insulator-metal transition in LaAl O3 /SrTi O3 (110). Compared with surface oxygen vacancies, which play a determining role on the insulator-metal transition of LaAl O3 /SrTi O3 (001) interfaces, we find that surface La interstitials can be more experimentally realistic and accessible for manipulation and more stable in an ambient atmospheric environment. Interestingly, these surface La interstitials also induce significant spin-splitting states with a Ti dy z/dx z character at a conducting LaAl O3 /SrTi O3 (110) interface. On the other hand, for insulating LaAl O3 /SrTi O3 (110) (<4 unit cells LaAl O3 thickness), a distortion between La (Al) and O atoms is found at the LaAl O3 side, partially compensating the polarization divergence. Our results reveal the origin of the metal-insulator transition in LaAl O3 /SrTi O3 (110) heterostructures, and also shed light on the manipulation of the superior properties of LaAl O3 /SrTi O3 (110) for different possibilities in electronic and magnetic applications.

  8. Structural, transport and thermoelectric properties of Nb-doped CaLaMnO perovskite

    NASA Astrophysics Data System (ADS)

    Villa, J. I.; Rodríguez, J. E.

    2014-12-01

    Poly-crystalline perovskite-type (CaLaMnO) Ca0.95La0.05Mn1-xNbxO3 (0.0 ≤ x ≤ 0.10) was synthesized using the conventional solid-state reaction method. Structural and morphological properties were studied by X-ray diffraction analysis (XRD) and scanning electron microscopy (SEM), respectively. Their transport and thermoelectric properties were studied from electrical resistivity ρ(T) and Seebeck coefficient S(T) measurements as a function of temperature and niobium content. The Rietveld analysis revealed a compound with orthorhombic structure, where their lattice parameters increase with the niobium content which is given by a distortion in octahedra MnO6. Electrical resistivity exhibits a semiconducting-like behavior, for low niobium contents (Nb ≤ 0.03) the magnitude of the electrical resistivity decreases, reaching minimum values close to 0.1 Ω - cm. Seebeck coefficient is negative in all studied temperature range. The temperature behavior of S(T) is interpreted in terms of variable range hopping (VRH) and Heikes model. From ρ(T) and S(T) measurements it was possible to calculate the thermoelectric power factor (PF), which reaches maximum values around 0.4 μW /K2 -cm. These values make these ceramics promising electronic thermoelectric materials.

  9. Two symmetric n-type interfaces SrTiO{sub 3}/LaAlO{sub 3} in perovskite: Electronic properties from density functional theory

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Reshak, A. H., E-mail: maalidph@yahoo.co.uk, E-mail: mabujafar@najah.edu; Center of Excellence Geopolymer and Green Technology, School of Material Engineering, University Malaysia Perlis, 01007 Kangar, Perlis; Abu-Jafar, M. S., E-mail: maalidph@yahoo.co.uk, E-mail: mabujafar@najah.edu

    2016-06-28

    The first principles study of the (001) two symmetric n-type interfaces between two insulating perovskites, the nonpolar SrTiO{sub 3} (STO), and the polar LaAlO{sub 3} (LAO) was performed. We have analyzed the formation of metallic interface states between the STO and LAO heterointerfaces by using the all-electron full-potential linearized augmented plane-wave approach based on the density functional theory, within the local density approximation, the Perdew-Burke-Ernzerhof generalized gradient approximation (PBE-GGA), and the Engel-Vosko GGA (EVGGA) formalism. It has been found that some bands cross the Fermi energy level (E{sub F}), forming a metallic nature of two symmetric n-type 6.5STO/1.5LAO interfaces withmore » density of states at E{sub F}, N(E{sub F}) of about 3.56 (state/eV/unit cell), and bare electronic specific heat coefficient (γ) of about 0.62 mJ/(mol cell K{sup 2}). The electronic band stature and the partial density of states in the vicinity of E{sub F} are mainly originated from Ti1,2,3,4-3dxy orbitals. These bands are responsible for the metallic behavior and the forming of the Fermi surface of the two symmetric n-type 6.5STO/1.5LAO interfaces. To obtain a clear map of the valence band electronic charge density distribution of the two symmetric n-type 6.5STO/1.5LAO interfaces, we have investigated the bond's nature and the interactions between the atoms. It reveals that the charge is attracted towards O atoms as it is clear that the O atoms are surrounded by uniform blue spheres which indicate the maximum charge accumulation.« less

  10. Miscellaneous Lasing Actions in Organo-Lead Halide Perovskite Films.

    PubMed

    Duan, Zonghui; Wang, Shuai; Yi, Ningbo; Gu, Zhiyuan; Gao, Yisheng; Song, Qinghai; Xiao, Shumin

    2017-06-21

    Lasing actions in organo-lead halide perovskite films have been heavily studied in the past few years. However, due to the disordered nature of synthesized perovskite films, the lasing actions are usually understood as random lasers that are formed by multiple scattering. Herein, we demonstrate the miscellaneous lasing actions in organo-lead halide perovskite films. In addition to the random lasers, we show that a single or a few perovskite microparticles can generate laser emissions with their internal resonances instead of multiple scattering among them. We experimentally observed and numerically confirmed whispering gallery (WG)-like microlasers in polygon shaped and other deformed microparticles. Meanwhile, owing to the nature of total internal reflection and the novel shape of the nanoparticle, the size of the perovskite WG laser can be significantly decreased to a few hundred nanometers. Thus, wavelength-scale lead halide perovskite lasers were realized for the first time. All of these laser behaviors are complementary to typical random lasers in perovskite film and will help the understanding of lasing actions in complex lead halide perovskite systems.

  11. Low-temperature synthesis and investigations on photocatalytic activity of nanoparticles BiFeO3 for methylene blue and methylene orange degradation and some toxic organic compounds

    NASA Astrophysics Data System (ADS)

    Nhiem Dao, Ngoc; Luu, Minh Dai; Chuc Pham, Ngoc; Dung Doan, Trung; Nguyen, Thi Ha Chi; Bac Nguyen, Quang; Lim Duong, Thi

    2016-12-01

    The photocatalytic BiFeO3 perovskite nanoparticles were fabricated by gel combustion method using polyvinyl alcohol and corresponding metal nitrate precursors under the optimum mild conditions such as pH 2, gel formation temperature of 80 °C, metal/polyvinyl alcohol molar ratio of 1/3, metal molar ratio Bi/Fe of 1/1 and calcination temperature at 500 °C for 2 h. The prepared sample was characterized by x-ray diffraction, field scanning electron microscopy, transmission electron microscopy, Brunauer-Emmetl-Teller nitrogen adsorption method at 77 K, energy dispersive x-ray spectroscopy, ultraviolet-visible light spectrophotometry, and thermal analysis. The effects of molar ratios of starting material and calcination temperature on phase formation and morphology were investigated. The degradation of methylene blue, methylene orange and some toxic organic compounds such as phenol and diazinon under visible light irradiation by photocatalytic BiFeO3 nanoparticles were evaluated at different parameters and conditions such as the light intensity determined from the light source to the measured sample, the addition H2O2, reaction time and the regeneration performance. Obtained results showed that the synthesized perovskite BiFeO3 nanoparticles for the optimized sample have a size smaller than 50 nm and the high mean surface area of 50 m2 g-1. Degradation efficiency was almost 90.0% for methylene blue and 80.0% for methylene orange with added H2O2 after 30 min of reaction. After the 3rd time of regeneration, the BiFeO3 nanoparticles still have 92.8% of the degradation performance for removing methylene blue. Phenol and diazinon toxic compound were degraded with the performance of 92.42% and 85.7%, respectively, for 150 min

  12. Reduced thermal conductivity by nanoscale intergrowths in perovskite like layered structure La{sub 2}Ti{sub 2}O{sub 7}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Khaliq, Jibran; Chen, Kan; Li, Chunchun

    2015-02-21

    The effect of substitution and oxidation-reduction on the thermal conductivity of perovskite-like layered structure (PLS) ceramics was investigated in relation to mass contrast and non-stoichiometry. Sr (acceptor) was substituted on the A site, while Ta (donor) was substituted on the B site of La{sub 2}Ti{sub 2}O{sub 7}. Substitution in PLS materials creates atomic scale disorders to accommodate the non-stoichiometry. High resolution transmission electron microscopy and X ray diffraction revealed that acceptor substitution in La{sub 2}Ti{sub 2}O{sub 7} produced nanoscale intergrowths of n = 5 layered phase, while donor substitution produced nanoscale intergrowths of n = 3 layered phase. As a result of these nanoscalemore » intergrowths, the thermal conductivity value reduced by as much as ∼20%. Pure La{sub 2}Ti{sub 2}O{sub 7} has a thermal conductivity value of ∼1.3 W/m K which dropped to a value of ∼1.12 W/m K for Sr doped La{sub 2}Ti{sub 2}O{sub 7} and ∼0.93 W/m K for Ta doped La{sub 2}Ti{sub 2}O{sub 7} at 573 K.« less

  13. A new silver metaniobate semiconductor of Ag0.5La0.5Nb2O6 with defect-perovskite structure

    NASA Astrophysics Data System (ADS)

    Mi, Longqing; Feng, Yongyi; Cao, Lei; Xue, Mingqiang; Huang, Yanlin; Qin, Lin; Seo, Hyo Jin

    2018-03-01

    Silver-containing lanthanum metaniobate Ag0.5La0.5Nb2O6 nanoparticles were synthesized by sol-gel polymerized complex method. A typical defect-perovskite structure was confirmed by XRD Rietveld refinements. The surface characteristics of the sample were tested by SEM, TEM and EDS measurements. SEM and TEM show that the sample presents ball-like particles with the diameters of 100 nm to 400 nm. The sample shows both self-activated luminescence and photocatalytic activities. Ag0.5La0.5Nb2O6 has a direct transition with band energy of 2.85 eV. The Ag4d-O2p hybridization in the valence band contributes to the narrowed band gap. The luminescence properties of Ag0.5La0.5Nb2O6 have been investigated for the first time. The luminescence is characterized by two emission centers with maximum wavelength near 460 and 530 nm. The emission and excitation spectra, decay curves and the thermal quenching mechanism were discussed. Ag0.5La0.5Nb2O6 shows the efficient photocatalytic activities and the photodegradation rate for methylene blue dye (MB) can reach about 95% under visible light (> 420 nm) irradiation in 5 h. The trapped experiments for the active species were tested and discussed, which verified that rad OH radicals could be the major active species in photocatalysis.

  14. Enhancement of photoresponse property of perovskite solar cell by aluminium chloride (AlCl3)

    NASA Astrophysics Data System (ADS)

    Ghosh, S. S.; Sil, A.

    2018-05-01

    The fabrication of a three layer solar cell device is a new area of research. The formation of perovskite phase is evident from x-ray diffraction and its particle size is observed by microstructural analysis. A thin layer of gold coating over the device increases the surface conductivity. Direct contact between a SnCl2 or AlCl3 based perovskite with the gold coating increases the durability of the film but decreases the hole transport properties due to absence of an organic hole transport material. The absorbance spectroscopy analysis gives characteristic peaks showing the evidence of ITO, TiO2 (rutile) and Sn2+ complexes present in the Sn-perovskite film or Al3+ complexes present within the Al-perovskite cell. The desired absorbance near 550 nm due to Al3+ complexes causes a much higher flow of current on illumination and thus is also evidenced by the presence of comparatively high intensity PL spectra in the Al-perovskite system which occurred due to free exciton formation near band edge excitation. The fill factor of the devices is estimated as ∼0.83 and ∼0.65 for Sn-perovskite and Al-perovskite devices respectively. The PCE values of Sn-perovskite and Al-perovskite devices are calculated 0.39% and 0.96% respectively, which establish Al-perovskite film as a useful component for future solar cell device manufacturing.

  15. Graded bandgap perovskite solar cells.

    PubMed

    Ergen, Onur; Gilbert, S Matt; Pham, Thang; Turner, Sally J; Tan, Mark Tian Zhi; Worsley, Marcus A; Zettl, Alex

    2017-05-01

    Organic-inorganic halide perovskite materials have emerged as attractive alternatives to conventional solar cell building blocks. Their high light absorption coefficients and long diffusion lengths suggest high power conversion efficiencies, and indeed perovskite-based single bandgap and tandem solar cell designs have yielded impressive performances. One approach to further enhance solar spectrum utilization is the graded bandgap, but this has not been previously achieved for perovskites. In this study, we demonstrate graded bandgap perovskite solar cells with steady-state conversion efficiencies averaging 18.4%, with a best of 21.7%, all without reflective coatings. An analysis of the experimental data yields high fill factors of ∼75% and high short-circuit current densities up to 42.1 mA cm -2 . The cells are based on an architecture of two perovskite layers (CH 3 NH 3 SnI 3 and CH 3 NH 3 PbI 3-x Br x ), incorporating GaN, monolayer hexagonal boron nitride, and graphene aerogel.

  16. Energetics of magnesium, strontium, and barium doped lanthanum gallate perovskites

    NASA Astrophysics Data System (ADS)

    Cheng, Jihong; Navrotsky, Alexandra

    2004-01-01

    LaGaO 3 perovskites doped with Sr or Ba at the La site and Mg at the Ga site were prepared by solid-state reaction or sol-gel method and characterized. Enthalpies of formation from constituent oxides at 298 K were determined by high-temperature oxide melt solution calorimetry. Energetic trends are discussed in terms of defect chemistry. As oxygen deficiency increases, formation enthalpies define three trends, LaGa 1- yMg yO 3- δ (LGM), La 1- xSr xGa 1- yMg yO 3- δ (LSGM), and La 1- xBa xGa 1- yMg yO 3- δ (LBGM). They become less exothermic with increasing doping, suggesting a dominant destabilization effect from oxygen vacancies. The endothermic enthalpy of vacancy formation is 275±37, 166±18 and 138±12 kJ/mol of VO·· for LGM, LBGM and LSGM, respectively. Tolerance factor and ion size mismatch also affect enthalpies. In terms of energetics, Sr is the best dopant for the La site and Mg for the Ga site, supporting earlier studies, including oxygen ion conductivity and computer modeling.

  17. Competing interactions in ferromagnetic/antiferromagnetic perovskite superlattices

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Takamura, Y.; Biegalski, M.B.; Christen, H.M.

    2009-10-22

    Soft x-ray magnetic dichroism, magnetization, and magnetotransport measurements demonstrate that the competition between different magnetic interactions (exchange coupling, electronic reconstruction, and long-range interactions) in La{sub 0.7}Sr{sub 0.3}FeO{sub 3}(LSFO)/La{sub 0.7}Sr{sub 0.3}MnO{sub 3}(LSMO) perovskite oxide superlattices leads to unexpected functional properties. The antiferromagnetic order parameter in LSFO and ferromagnetic order parameter in LSMO show a dissimilar dependence on sublayer thickness and temperature, illustrating the high degree of tunability in these artificially layered materials.

  18. Double perovskites with strong spin-orbit coupling

    NASA Astrophysics Data System (ADS)

    Cook, Ashley M.

    We first present theoretical analysis of powder inelastic neutron scattering experiments in Ba2FeReO6 performed by our experimental collaborators. Ba2FeReO6, a member of the double perovskite family of materials, exhibits half-metallic behavior and high Curie temperatures Tc, making it of interest for spintronics applications. To interpret the experimental data, we develop a local moment model, which incorporates the interaction of Fe spins with spin-orbital locked magnetic moments on Re, and show that it captures the experimental observations. We then develop a tight-binding model of the double perovskite Ba 2FeReO6, a room temperature ferrimagnet with correlated and spin-orbit coupled Re t2g electrons moving in the background of Fe moments stabilized by Hund's coupling. We show that for such 3d/5d double perovskites, strong correlations on the 5d-element (Re) are essential in driving a half-metallic ground state. Incorporating both strong spin-orbit coupling and the Hubbard repulsion on Re leads to a band structure consistent with ab initio calculations. The uncovered interplay of strong correlations and spin-orbit coupling lends partial support to our previous work, which used a local moment description to capture the spin wave dispersion found in neutron scattering measurements. We then adapt this tight-binding model to study {111}-grown bilayers of half-metallic double perovskites such as Sr2FeMoO6. The combination of spin-orbit coupling, inter-orbital hybridization and symmetry-allowed trigonal distortion leads to a rich phase diagram with tunable ferromagnetic order, topological C= +/-1, +/-2 Chern bands, and a C = +/-2 quantum anomalous Hall insulator regime. We have also performed theoretical analysis of inelastic neutron scattering (INS) experiments to investigate the magnetic excitations in the weakly distorted face-centered-cubic (fcc) iridate double perovskites La2ZnIrO 6 and La2MgIrO6. Models with dominant Kitaev exchange seem to most naturally

  19. Origin of giant dielectric permittivity and weak ferromagnetic behavior in (1-x)LaFeO3-xBaTiO3 (0.0 ≤ x ≤ 0.25) solid solutions

    NASA Astrophysics Data System (ADS)

    Sreenivasu, T.; Tirupathi, P.; Prabahar, K.; Suryanarayana, B.; Chandra Mouli, K.

    The solid solutions of (1-x) LaFeO3-xBaTiO3 (0.0≤x≤0.25) have been synthesized successfully by the conventional solid-state reaction method. Room temperature (RT) X-ray diffraction studies reveal the stabilization of orthorhombic phase with Pbnm space group. Complete solubility in the perovskite series was demonstrated up to x=0.25. The dielectric permittivity shows colossal dielectric constant (CDC) at RT. The doping of BaTiO3 in LaFeO3 exhibit pronounced CDC up to a composition x=0.15, further it starts to decrease. The frequency-dependent dielectric loss exhibits polaronic conduction, which can attribute to presence of multiple valence of iron. The relaxation frequency and polaronic conduction mechanism was shifted towards RT as function of x. Moreover, large magnetic moment with weak ferromagnetic behavior is observed in doped LaFeO3 solid solution, which might be the destruction of spin cycloid structure due to insertion of Ti in Fe-O-Fe network of LaFeO3.

  20. CH3 NH3 PbBr3 Perovskite Nanocrystals as Efficient Light-Harvesting Antenna for Fluorescence Resonance Energy Transfer.

    PubMed

    Muthu, Chinnadurai; Vijayan, Anuja; Nair, Vijayakumar C

    2017-05-04

    Hybrid perovskites have created enormous research interest as a low-cost material for high-performance photovoltaic devices, light-emitting diodes, photodetectors, memory devices and sensors. Perovskite materials in nanocrystal form that display intense luminescence due to the quantum confinement effect were found to be particularly suitable for most of these applications. However, the potential use of perovskite nanocrystals as a light-harvesting antenna for possible applications in artificial photosynthesis systems is not yet explored. In the present work, we study the light-harvesting antenna properties of luminescent methylammonium lead bromide (CH 3 NH 3 PbBr 3 )-based perovskite nanocrystals using fluorescent dyes (rhodamine B, rhodamine 101, and nile red) as energy acceptors. Our studies revealed that CH 3 NH 3 PbBr 3 nanocrystals are an excellent light-harvesting antenna, and efficient fluorescence resonance energy transfer occurs from the nanocrystals to fluorescent dyes. Further, the energy transfer efficiency is found to be highly dependent on the number of anchoring groups and binding ability of the dyes to the surface of the nanocrystals. These observations may have significant implications for perovskite-based light-harvesting devices and their possible use in artificial photosynthesis systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Structural analysis of LaVO3 thin films under epitaxial strain

    NASA Astrophysics Data System (ADS)

    Meley, H.; Karandeep, Oberson, L.; de Bruijckere, J.; Alexander, D. T. L.; Triscone, J.-M.; Ghosez, Ph.; Gariglio, S.

    2018-04-01

    Rare earth vanadate perovskites exhibit a phase diagram in which two different types of structural distortions coexist: the strongest, the rotation of the oxygen octahedra, comes from the small tolerance factor of the perovskite cell (t = 0.88 for LaVO3) and the smaller one comes from inter-site d-orbital interactions manifesting as a cooperative Jahn-Teller effect. Epitaxial strain acts on octahedral rotations and crystal field symmetry to alter this complex lattice-orbit coupling. In this study, LaVO3 thin film structures have been investigated by X-ray diffraction and scanning transmission electron microscopy. The analysis shows two different orientations of octahedral tilt patterns, as well as two distinct temperature behaviors, for compressive and tensile film strain states. Ab initio calculations capture the strain effect on the tilt pattern orientation in agreement with experimental data.

  2. Influence of chromium hyperdoping on the electronic structure of CH3NH3PbI3 perovskite: a first-principles insight.

    PubMed

    García, Gregorio; Palacios, Pablo; Menéndez-Proupin, Eduardo; Montero-Alejo, Ana L; Conesa, José C; Wahnón, Perla

    2018-02-06

    Organic-inorganic hybrid halide perovskites compounds are emerging as new materials with great potential for efficient solar cells. This paper explores the possibility of increasing their photovoltaic efficiency through sub-bandgap absorption by way of the in gap band (IGB) concept. Thus, we assess the formation of an in gap band as well as its effect on the absorption features of Organic-inorganic hybrid halide perovskites CH 3 NH 3 PbI 3 (MAPI). For this task, we use density functional theory (DFT) as well as many-body perturbation methods along to spin-orbit coupling (SOC) to study structural, energetic and electronic properties of partially Cr-substituted MAPI perovskites (CH 3 NH 3 Pb 1-x Cr x I 3 ). Our results reveal that Cr replacement does not lead to an important cell distortion, while the energetic of the substitution process evidences the possibility of obtaining Cr-substituted perovskite. The analysis of the electronic structure shows that Cr 3d-orbitals induce new electronic states in the host semiconductor bandgap, which fulfill the requirements to be considered as an IGB. Precise many-body perturbation methods in G 0 W 0 approach provided an accurate description on the electronic structures as well as the position of the IGB. In short, Pb replacement by Cr could be useful for improved absorption features through new sub-bandgap transitions across the in gap band.

  3. An effective model for LaTiO3 using first principles quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Williams, Kiel; Wagner, Lucas

    The rare earth perovskites have long been of interest due in part to the interplay of their geometries and electronic properties. The perovskite LaTiO3 in particular is an antiferromagnetic insulator with a small 0.2 eV band gap that displays the GdFeO3 distortion at ambient pressure. We apply a new technique to derive an effective model for LaTiO3 as a function of the distortion. Since this technique treats one and two-body degrees of freedom on an equal footing, we use it to evaluate the evolution of effective model parameters with changes in the lattice. We will report on the progress in assessing whether the insulating nature is due to the distortion, or vice versa.

  4. In vitro cell imaging using multifunctional small sized KGdF4:Yb3+,Er3+ upconverting nanoparticles synthesized by a one-pot solvothermal process

    NASA Astrophysics Data System (ADS)

    Wong, Hon-Tung; Tsang, Ming-Kiu; Chan, Chi-Fai; Wong, Ka-Leung; Fei, Bin; Hao, Jianhua

    2013-03-01

    Multifunctional KGdF4:18%Yb3+,2%Er3+ nanoparticles with upconversion fluorescence and paramagnetism are synthesized. The average sizes of the nanoparticles capped with branched polyethyleneimine (PEI) and 6-aminocaproic acid (6AA) are ~14 and ~13 nm, respectively. Our KGdF4 host does not exhibit any phase change with the decrease of particle size, which can prevent the detrimental significant decrease in upconversion luminescence caused by this effect observed in the well-known NaYF4 host. The branched PEI and 6AA capping ligands endow our nanoparticles with water-dispersibility and biocompatibility, which can favor internalization of our nanoparticles into the cytoplasm of HeLa cells and relatively high cell viability. The strong upconversion luminescence detected at the cytoplasm of HeLa cells incubated with the branched PEI-capped nanoparticles is probably attributed to the reported high efficiency of cellular uptake. The magnetic mass susceptibility of our nanoparticle is 8.62 × 10-5 emu g-1 Oe-1. This is the highest value ever reported in trivalent rare-earth ion-doped KGdF4 nanoparticles of small size (<=14 nm), and is very close to that of nanoparticles used as T1 contrast agents in magnetic resonance imaging. These suggest the potential of our KGdF4:Yb3+,Er3+ nanoparticles as small-sized multifunctional bioprobes.

  5. Composition-dependent surface chemistry of colloidal Ba xSr 1-xTiO 3 perovskite nanocrystals

    DOE PAGES

    Margossian, Tigran; Culver, Sean P.; Larmier, Kim; ...

    2016-11-01

    Ba xSr 1-xTiO 3 perovskite nanocrystals, prepared by the vapor diffusion sol-gel method and characterized by state of the art surface techniques, display significantly different O-H stretching frequencies and adsorption properties towards CO 2 as a function of the alkaline earth composition (Ba vs. Sr). Lastly, the difference of properties can be associated with the more basic nature of BaO-rich than SrO-rich surfaces.

  6. Single-crystal perovskite CH3NH3PbBr3 prepared by cast capping method for light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Nguyen, Van-Cao; Katsuki, Hiroyuki; Sasaki, Fumio; Yanagi, Hisao

    2018-04-01

    In this study, electroluminescence from single crystals of CH3NH3PbBr3 perovskite is explored. The cast capping method was applied to fabricate simple devices with an ITO/CH3NH3PbBr3/ITO structure. The devices showed a low operation voltage of 2 V and a pure green luminescence with full width at half maximum of ∼20 nm. However, the emission occurring at the crystal edges demonstrated blinking with a subsecond time interval, which is similar to the previously reported photoluminescence behavior of nanocrystal perovskites. This electroluminescence blinking may provide new insight into the recombination processes depending on the carrier traps and defects of emission layers in perovskite light-emitting devices.

  7. Magnetocaloric effect and its modulation by electric field in La0.325Pr0.3Ca0.375MnO3 films grown on (0 1 1)-PMN-PT substrates

    NASA Astrophysics Data System (ADS)

    Qiao, K. M.; Li, J.; Liu, Y.; Kuang, H.; Wang, J.; Hu, F. X.; Sun, J. R.; Shen, B. G.

    2018-06-01

    In this paper, we have investigated the magnetocaloric effect (MCE) and its modulation by electric field in La0.325Pr0.3Ca0.375MnO3 (LPCMO) films grown on (0 1 1)-oriented PMN-PT substrates. As a typical perovskite manganite with phase separation, the LPCMO bulk shows a considerable MCE, but the MCE of the LPCMO films has never been investigated. We found that the LPCMO films exhibit a MCE over a wide temperature range. A modulation of magnetization by electric field has been observed in the temperature dependent (M-T) and magnetic field dependent (M-H) curves. As a result, enhanced magnetic entropy change and refrigeration capacity by about 4% under an electric field of +6 kV/cm has been demonstrated.

  8. Enhanced optoelectronic quality of perovskite films with excess CH3NH3I for high-efficiency solar cells in ambient air

    NASA Astrophysics Data System (ADS)

    Zhang, Yunhai; Lv, Huiru; Cui, Can; Xu, Lingbo; Wang, Peng; Wang, Hao; Yu, Xuegong; Xie, Jiangsheng; Huang, Jiabin; Tang, Zeguo; Yang, Deren

    2017-05-01

    Solution-processed polycrystalline perovskite films contribute critically to the high photovoltaic performance of perovskite-based solar cells (PSCs). The inevitable electronic trap states at grain boundaries and intrinsic defects such as metallic lead (Pb0) and halide vacancies in perovskite films cause serious carrier recombination loss. Furthermore, the film can easily decompose into PbI2 in a moist atmosphere. Here, we introduce a simple strategy, through a small increase in methylammonium iodide (CH3NH3I, MAI), molar proportion (5%), for perovskite fabrication in ambient air with ˜50% relative humidity. Analysis of the morphology and crystallography demonstrates that excess MAI significantly promotes grain growth without decomposition. X-ray photoemission spectroscopy shows that no metallic Pb0 exists in the perovskite film and the I/Pb ratio is improved. A time-resolved photoluminescence measurement indicates efficient suppression of non-radiative recombination in the perovskite layer. As a result, the device yields improved power conversion efficiency from 14.06% to 18.26% with reduced hysteresis and higher stability under AM1.5G illumination (100 mW cm-2). This work strongly provides a feasible and low-cost way to develop highly efficient PSCs in ambient air.

  9. Magnetic properties of electron-doped La0.23Ca0.77MnO3 nanoparticles

    NASA Astrophysics Data System (ADS)

    Markovich, V.; Jung, G.; Wisniewski, A.; Mogilyansky, D.; Puzniak, R.; Kohn, A.; Wu, X. D.; Suzuki, K.; Gorodetsky, G.

    2012-09-01

    Magnetic properties of electron-doped La0.23Ca0.77MnO3 manganite nanoparticles, with average size of 12 and 60 nm, prepared by the glycine-nitrate method, have been investigated in the temperature range 5-300 K and magnetic fields up to 90 kOe. It is suggested that weak ferromagnetic moment results from ferromagnetic shells of the basically antiferromagnetic nanoparticles and from domains of frustrated disordered phase in the core. Assumption of two distinct sources of ferromagnetism is supported by the appearance of two independent ferromagnetic contributions in the fit of the T 3/2 Bloch law to spontaneous magnetization. The ferromagnetic components, which are more pronounced in smaller particles, occupy only a small fraction of the nanoparticle volume and the antiferromagnetic ground state remains stable. It is found that the magnetic hysteresis loops following field cooled processes, display size-dependent horizontal and vertical shifts, namely, exhibiting exchange bias effect. Time-dependent magnetization dynamics demonstrating two relaxation rates were observed at constant magnetic fields upon cooling to T < 100 K.

  10. Correlation between magnetocaloric and electrical properties based on phenomenological models in La0.47Pr0.2Pb0.33MnO3 perovskite

    NASA Astrophysics Data System (ADS)

    Mechi, Nesrine; Alzahrani, Bandar; Hcini, Sobhi; Bouazizi, Mohamed Lamjed; Dhahri, Abdessalem

    2018-06-01

    We have investigated the correlation between magnetocaloric and electrical properties of La0.47Pr0.2Pb0.33MnO3 perovskite prepared using the sol-gel method. Rietveld analysis of X-ray diffraction (XRD) pattern shows pure crystalline phase with rhombohedral ? structure. Magnetic entropy change, relative cooling power (RCP) and specific heat were predicted from M(T, μ0H) data at different magnetic fields with the help of the phenomenological model. The magnetic entropy change reaches a maximum value ? of about 3.96 J kg-1 K-1 for μ0H = 5 T corresponding to RCP of 183 J kg-1. These values are relatively higher, making our sample a promising candidate for the magnetic refrigeration. Electrical-resistivity measurements were well fitted with the phenomenological percolation model, which is based on the phase segregation of ferromagnetic-metallic clusters and paramagnetic-semiconductor regions. The temperature and magnetic field dependences of resistivity data, ρ(T, μ0H), allowed us to determine the magnetic entropy change ?. Results show that the as-obtained magnetic entropy change values are similar to those determined from the phenomenological model.

  11. [C6 H14 N]PbBr3 : An ABX3 -Type Semiconducting Perovskite Hybrid with Above-Room-Temperature Phase Transition.

    PubMed

    Zhang, Jing; Liu, Xitao; Li, Xianfeng; Han, Shiguo; Tao, Kewen; Wang, Yuyin; Ji, Chengmin; Sun, Zhihua; Luo, Junhua

    2018-04-16

    Organic-inorganic hybrid perovskites, with the formula ABX 3 (A=organic cation, B=metal cation, and X=halide; for example, CH 3 NH 3 PbI 3 ), have diverse and intriguing physical properties, such as semiconduction, phase transitions, and optical properties. Herein, a new ABX 3 -type semiconducting perovskite-like hybrid, (hexamethyleneimine)PbBr 3 (1), consisting of one-dimensional inorganic frameworks and cyclic organic cations, is reported. Notably, the inorganic moiety of 1 adopts a perovskite-like architecture and forms infinite columns composed of face-sharing PbBr 6 octahedra. Strikingly, the organic cation exhibits a highly flexible molecular configuration, which triggers an above-room-temperature phase transition, at T c =338.8 K; this is confirmed by differential scanning calorimetry (DSC), specific heat capacity (C p ), and dielectric measurements. Further structural analysis reveals that the phase transition originates from the molecular configurational distortion of the organic cations coupled with small-angle reorientation of the PbBr 6 octahedra inside the inorganic components. Moreover, temperature-dependent conductivity and UV/Vis absorption measurements reveal that 1 also displays semiconducting behavior below T c . It is believed that this work will pave a potential way to design multifeatured perovskite hybrids by utilizing cyclic organic amines. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Mixed Sn-Ge Perovskite for Enhanced Perovskite Solar Cell Performance in Air.

    PubMed

    Ito, Nozomi; Kamarudin, Muhammad Akmal; Hirotani, Daisuke; Zhang, Yaohong; Shen, Qing; Ogomi, Yuhei; Iikubo, Satoshi; Minemoto, Takashi; Yoshino, Kenji; Hayase, Shuzi

    2018-04-05

    Lead-based perovskite solar cells have gained ground in recent years, showing efficiency as high as 20%, which is on par with that of silicon solar cells. However, the toxicity of lead makes it a nonideal candidate for use in solar cells. Alternatively, tin-based perovskites have been proposed because of their nontoxic nature and abundance. Unfortunately, these solar cells suffer from low efficiency and stability. Here, we propose a new type of perovskite material based on mixed tin and germanium. The material showed a band gap around 1.4-1.5 eV as measured from photoacoustic spectroscopy, which is ideal from the perspective of solar cells. In a solar cell device with inverted planar structure, pure tin perovskite solar cell showed a moderate efficiency of 3.31%. With 5% doping of germanium into the perovskite, the efficiency improved up to 4.48% (6.90% after 72 h) when measured in air without encapsulation.

  13. Magnetic dynamic properties of electron-doped La(0.23)Ca(0.77)MnO3 nanoparticles.

    PubMed

    Dolgin, B; Puzniak, R; Mogilyansky, D; Wisniewski, A; Markovich, V; Jung, G

    2013-02-20

    Magnetic properties of basically antiferromagnetic La(0.23)Ca(0.77)MnO(3) particles with average sizes of 12 and 60 nm have been investigated in a wide range of magnetic fields and temperature. Particular attention has been paid to magnetization dynamics through measurements of the temperature dependence of ac-susceptibility at various frequencies, the temperature and field dependence of thermoremanent and isothermoremanent magnetization originating from nanoparticles shells, and the time decay of the remanent magnetization. Experimental results and their analysis reveal the major role in magnetic behaviour of investigated antiferromagnetic nanoparticles played by the glassy component, associated mainly with the formation of the collective state formed by ferromagnetic clusters in frustrated coordination at the surfaces of interacting antiferromagnetic nanoparticles. Magnetic behaviour of nanoparticles has been ascribed to a core-shell scenario. Magnetic transitions have been found to play an important role in determining the dynamic properties of the phase separated state of coexisting different magnetic phases.

  14. Anisotropic magnetic structures of the Mn R MnSbO6 high-pressure doubly ordered perovskites (R =La , Pr, and Nd)

    NASA Astrophysics Data System (ADS)

    Solana-Madruga, Elena; Arévalo-López, Ángel M.; Dos santos-García, Antonio J.; Ritter, Clemens; Cascales, Concepción; Sáez-Puche, Regino; Attfield, J. Paul

    2018-04-01

    A new type of doubly ordered perovskite (also reported as double double perovskite, DDPv) structure combining columnar and rock-salt orders of the cations at the A and B sites, respectively, was recently found at high pressure for Mn R MnSb O6 (R =La -Sm ). Here we report further magnetic structures of these compounds. M n2 + spins align into antiparallel ferromagnetic sublattices along the x axis for MnLaMnSb O6 , while the magnetic anisotropy of P r3 + magnetic moments induces their preferential order along the z direction for MnPrMnSb O6 . The magnetic structure of MnNdMnSb O6 was reported to show a spin-reorientation transition of M n2 + spins from the z axis towards the x axis driven by the ordering of N d3 + magnetic moments. The crystal-field parameters for P r3 + and N d3 + at the 4 e C2 site of their DDPv structure have been semiempirically estimated and used to derive their energy levels and associated wave functions. The results demonstrate that the spin-reorientation transition in MnNdMnSb O6 arises as a consequence of the crystal-field-induced magnetic anisotropy of N d3 + .

  15. Improvement of electron mobility in La:BaSnO{sub 3} thin films by insertion of an atomically flat insulating (Sr,Ba)SnO{sub 3} buffer layer

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shiogai, Junichi, E-mail: junichi.shiogai@imr.tohoku.ac.jp; Nishihara, Kazuki; Sato, Kazuhisa

    One perovskite oxide, ASnO{sub 3} (A = Sr, Ba), is a candidate for use as a transparent conductive oxide with high electron mobility in single crystalline form. However, the electron mobility of films grown on SrTiO{sub 3} substrates does not reach the bulk value, probably because of dislocation scattering that originates from the large lattice mismatch. This study investigates the effect of insertion of bilayer BaSnO{sub 3} / (Sr,Ba)SnO{sub 3} for buffering this large lattice mismatch between La:BaSnO{sub 3} and SrTiO{sub 3} substrate. The insertion of 200-nm-thick BaSnO{sub 3} on (Sr,Ba)SnO{sub 3} bilayer buffer structures reduces the number of dislocationsmore » and improves surface smoothness of the films after annealing as proved respectively by scanning transmission electron microscopy and atomic force microscopy. A systematic investigation of BaSnO{sub 3} buffer layer thickness dependence on Hall mobility of the electron transport in La:BaSnO{sub 3} shows that the highest obtained value of mobility is 78 cm{sup 2}V{sup −1}s{sup −1} because of its fewer dislocations. High electron mobility films based on perovskite BaSnO{sub 3} can provide a good platform for transparent-conducting-oxide electronic devices and for creation of fascinating perovskite heterostructures.« less

  16. Planar structured perovskite solar cells by hybrid physical chemical vapor deposition with optimized perovskite film thickness

    NASA Astrophysics Data System (ADS)

    Wei, Xiangyang; Peng, Yanke; Jing, Gaoshan; Cui, Tianhong

    2018-05-01

    The thickness of perovskite absorber layer is a critical parameter to determine a planar structured perovskite solar cell’s performance. By modifying the spin coating speed and PbI2/N,N-dimethylformamide (DMF) solution concentration, the thickness of perovskite absorber layer was optimized to obtain high-performance solar cells. Using a PbI2/DMF solution of 1.3 mol/L, maximum power conversion efficiency (PCE) of a perovskite solar cell is 15.5% with a perovskite film of 413 nm at 5000 rpm, and PCE of 14.3% was also obtained for a solar cell with a perovskite film of 182 nm thick. It is derived that higher concentration of PbI2/DMF will result in better perovskite solar cells. Additionally, these perovskite solar cells are highly uniform. In 14 sets of solar cells, standard deviations of 11 sets of solar cells were less than 0.50% and the smallest standard deviation was 0.25%, which demonstrates the reliability and effectiveness of hybrid physical chemical vapor deposition (HPCVD) method.

  17. Structural characterization of a new vacancy ordered perovskite modification found for Ba{sub 3}Fe{sub 3}O{sub 7}F (BaFeO{sub 2.333}F{sub 0.333}): Towards understanding of vacancy ordering for different perovskite-type ferrites

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Clemens, Oliver, E-mail: oliver.clemens@kit.edu; Karlsruher Institut für Technologie, Institut für Nanotechnologie, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen

    2015-05-15

    The new vacancy ordered perovskite-type compound Ba{sub 3}Fe{sub 3}O{sub 7}F (BaFeO{sub 2.33}F{sub 0.33}) was prepared by topochemical low-temperature fluorination of Ba{sub 2}Fe{sub 2}O{sub 5} (BaFeO{sub 2.5}) using stoichiometric amounts of polyvinylidene difluoride (PVDF). The vacancy order was found to be unique so far for perovskite compounds, and the connectivity pattern can be explained by the formula Ba{sub 3}(FeX{sub 6/2}) (FeX{sub 5/2}) (FeX{sub 3/2}X{sub 1/1}), with X=O/F. Mössbauer measurements were used to confirm the structural analysis and agree with the presence of Fe{sup 3+} in the above mentioned coordination environments. Group–subgroup relationships were used to build a starting model for themore » structure solution and to understand the relationship to the cubic perovskite structure. Furthermore, a comparison of a variety of vacancy-ordered iron-containing perovskite-type structures is given, highlighting the factors which favour one structure type over the other depending on the composition. - Graphical abstract: The crystal structure of Ba{sub 3}Fe{sub 3}O{sub 7}F in comparison to other perovskite type ferrites. - Highlights: • The crystal structure of Ba{sub 3}Fe{sub 3}O{sub 7}F in comparison to other perovskite type ferrites. • Ba{sub 3}Fe{sub 3}O{sub 7}F was synthesized by low temperature fluorination of Ba{sub 2}Fe{sub 2}O{sub 5}. • Ba{sub 3}Fe{sub 3}O{sub 7}F shows a unique vacancy order not found for other perovskite type compounds. • The structure of Ba{sub 3}Fe{sub 3}O{sub 7}F was solved using group–subgroup relationships. • A systematic comparison to other ferrite type compounds reveals structural similarities and differences. • The A-site coordination of the cation is shown to play an important role for the type of vacancy order found.« less

  18. Abnormal variation of band gap in Zn doped Bi{sub 0.9}La{sub 0.1}FeO{sub 3} nanoparticles: Role of Fe-O-Fe bond angle and Fe-O bond anisotropy

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xu, Xunling; Liu, Weifang, E-mail: wfliu@tju.edu.cn, E-mail: shouyu.wang@yahoo.com; Wu, Ping

    2015-07-27

    Bi{sub 0.9}La{sub 0.1}FeO{sub 3} (BLFO) and Bi{sub 0.9}La{sub 0.1}Fe{sub 0.99}Zn{sub 0.01}O{sub 3} (BLFZO) nanoparticles were prepared via a sol-gel method. The oxygen vacancies and holes increase with Zn doping analyzed through X-ray photoelectron spectroscopy, which could contribute to the increase of leakage current density. However, with the increase of the defects (oxygen vacancies and holes), the band gap of BLFZO also is increased. To explain the abnormal phenomenon, the bandwidth of occupied and unoccupied bands was analyzed based on the structural symmetry driven by the Fe-O-Fe bond angle and Fe-O bond anisotropy.

  19. Colossal change in thermopower with temperature-driven p-n-type conduction switching in La x Sr2-x TiFeO6 double perovskites

    NASA Astrophysics Data System (ADS)

    Roy, Pinku; Maiti, Tanmoy

    2018-02-01

    Double perovskite materials have been studied in detail by many researchers, as their magnetic and electronic properties can be controlled by the substitution of alkaline earth metals or lanthanides in the A site and transition metals in the B site. Here we report the temperature-driven, p-n-type conduction switching assisted, large change in thermopower in La3+-doped Sr2TiFeO6-based double perovskites. Stoichiometric compositions of La x Sr2-x TiFeO6 (LSTF) with 0  ⩽  x  ⩽  0.25 were synthesized by the solid-state reaction method. Rietveld refinement of room-temperature XRD data confirmed a single-phase solid solution with cubic crystal structure and Pm\\bar{3}m space group. From temperature-dependent electrical conductivity and Seebeck coefficient (S) studies it is evident that all the compositions underwent an intermediate semiconductor-to-metal transition before the semiconductor phase reappeared at higher temperature. In the process of semiconductor-metal-semiconductor transition, LSTF compositions demonstrated temperature-driven p-n-type conduction switching behavior. The electronic restructuring which occurs due to the intermediate metallic phase between semiconductor phases leads to the colossal change in S for LSTF oxides. The maximum drop in thermopower (ΔS ~ 2516 µV K-1) was observed for LSTF with x  =  0.1 composition. Owing to their enormous change in thermopower of the order of millivolts per kelvin, integrated with p-n-type resistance switching, these double perovskites can be used for various high-temperature multifunctional device applications such as diodes, sensors, switches, thermistors, thyristors, thermal runaway monitors etc. Furthermore, the conduction mechanisms of these oxides were explained by the small polaron hopping model.

  20. Insight into the CH3NH3PbI3/C interface in hole-conductor-free mesoscopic perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Li, Jiangwei; Niu, Guangda; Li, Wenzhe; Cao, Kun; Wang, Mingkui; Wang, Liduo

    2016-07-01

    process of CH3NH3PbI3. The derived reaction kinetics allows a quantitative description of the perovskite formation process. In addition, we found that the interfacial contact between carbon and perovskite was dominant for hole extraction efficiency and associated with the photovoltaic parameter of short circuit current density (JSC). Consequently, we conducted a solvent vapor assisted process of PbI2 diffusion to carefully control the CH3NH3PbI3/C interface with less unreacted PbI2 barrier. The improvement of interface conditions thereby contributes to a high hole extraction proved by the charge extraction resistance and PL lifetime change, resulting in the increased JSC valve. Electronic supplementary information (ESI) available: Fig. S1-S11, Tables S1, S2 and details of the Avrami model for reaction kinetics. See DOI: 10.1039/c6nr03359h

  1. Antiferromagnetic defect structure in LaNi O3 -δ single crystals

    NASA Astrophysics Data System (ADS)

    Wang, Bi-Xia; Rosenkranz, S.; Rui, X.; Zhang, Junjie; Ye, F.; Zheng, H.; Klie, R. F.; Mitchell, J. F.; Phelan, D.

    2018-06-01

    The origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, RNiO3 (where R is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of LaNiO3, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced LaNi O3 -δ crystals, we show that both antiferromagnetic and ferromagnetic phases with a Néel temperature of ˜152 K and a Curie temperature of ˜225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of LaNi O3 -δ single crystals; accordingly, the implications of our results for putative oxygen-stoichiometric LaNiO3 are discussed.

  2. Anomalous perovskite PbRuO3 stabilized under high pressure

    PubMed Central

    Cheng, J.-G.; Kweon, K. E.; Zhou, J.-S.; Alonso, J. A.; Kong, P.-P.; Liu, Y.; Jin, Changqing; Wu, Junjie; Lin, Jung-Fu; Larregola, S. A.; Yang, Wenge; Shen, Guoyin; MacDonald, A. H.; Manthiram, Arumugam; Hwang, G. S.; Goodenough, John B.

    2013-01-01

    Perovskite oxides ABO3 are important materials used as components in electronic devices. The highly compact crystal structure consists of a framework of corner-shared BO6 octahedra enclosing the A-site cations. Because of these structural features, forming a strong bond between A and B cations is highly unlikely and has not been reported in the literature. Here we report a pressure-induced first-order transition in PbRuO3 from a common orthorhombic phase (Pbnm) to an orthorhombic phase (Pbn21) at 32 GPa by using synchrotron X-ray diffraction. This transition has been further verified with resistivity measurements and Raman spectra under high pressure. In contrast to most well-studied perovskites under high pressure, the Pbn21 phase of PbRuO3 stabilized at high pressure is a polar perovskite. More interestingly, the Pbn21 phase has the most distorted octahedra and a shortest Pb—Ru bond length relative to the average Pb—Ru bond length that has ever been reported in a perovskite structure. We have also simulated the behavior of the PbRuO3 perovskite under high pressure by first principles calculations. The calculated critical pressure for the phase transition and evolution of lattice parameters under pressure match the experimental results quantitatively. Our calculations also reveal that the hybridization between a Ru:t2g orbital and an sp hybrid on Pb increases dramatically in the Pbnm phase under pressure. This pressure-induced change destabilizes the Pbnm phase to give a phase transition to the Pbn21 phase where electrons in the overlapping orbitals form bonding and antibonding states along the shortest Ru—Pb direction at P > Pc. PMID:24277807

  3. Metal-insulator transition, giant negative magnetoresistance, and ferromagnetism in LaCo1-yNiyO3

    NASA Astrophysics Data System (ADS)

    Hammer, D.; Wu, J.; Leighton, C.

    2004-04-01

    We have investigated the transport and magnetic properties of the perovskite LaCo1-yNiyO3, an alloy of LaCoO3 (a semiconductor that exhibits spin-state transitions) and LaNiO3 (a paramagnetic metal). The metal-insulator transition (MIT) was found to occur at y=0.40. On the insulating side of the transition the conductivity obeys Mott variable range hopping with a characteristic temperature (T0) that varies with y in a manner consistent with the predictions of the scaling theory of electron localization. On the metallic side the low temperature conductivity (down to 0.35 K) varies as T1/2 due to the effects of electron-electron interaction in the presence of disorder. The composition dependence of the low-temperature conductivity in the critical region fits the scaling theory of electron localization with a conductivity critical exponent close to unity, consistent with the scaling of T0 in the insulating phase. A large negative magnetoresistance is observed (up to 70% in 17 T) which increases monotonically with decreasing temperature and is smoothly decreased through the MIT. The magnetic properties show that doping LaCoO3 with Ni leads to a rapid destruction of the low spin-state for Co3+ ions, followed by the onset of distinct ferromagnetic interactions at higher Ni content. Similar to La1-xSrxCoO3, the system shows a smooth evolution from spin-glass to ferromagnetic ground states, which is interpreted in terms of the formation of ferromagnetic clusters. In contrast to La1-xSrxCoO3 further doping does not lead to a bulk ferromagnetlike state with a large TC, despite the clear existence of ferromagnetic interactions. We suggest that this is due to a limitation of the strength of the ferromagnetic interactions, which could be related to the fact that Ni rich clusters are not thermodynamically stable. The ferromagnetic clusters in LaCo1-yNiyO3 do not percolate with increasing y explaining the lack of a high-TC ferromagnetic state and the fact that the MIT is a simple

  4. Room-Temperature Atomic Layer Deposition of Al2 O3 : Impact on Efficiency, Stability and Surface Properties in Perovskite Solar Cells.

    PubMed

    Kot, Malgorzata; Das, Chittaranjan; Wang, Zhiping; Henkel, Karsten; Rouissi, Zied; Wojciechowski, Konrad; Snaith, Henry J; Schmeisser, Dieter

    2016-12-20

    In this work, solar cells with a freshly made CH 3 NH 3 PbI 3 perovskite film showed a power conversion efficiency (PCE) of 15.4 % whereas the one with 50 days aged perovskite film only 6.1 %. However, when the aged perovskite was covered with a layer of Al 2 O 3 deposited by atomic layer deposition (ALD) at room temperature (RT), the PCE value was clearly enhanced. X-ray photoelectron spectroscopy study showed that the ALD precursors are chemically active only at the perovskite surface and passivate it. Moreover, the RT-ALD-Al 2 O 3 -covered perovskite films showed enhanced ambient air stability. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. High-pressure synthesis, crystal chemistry and physics of perovskites with small cations at the A site.

    PubMed

    Belik, Alexei A; Yi, Wei

    2014-04-23

    ABO3 perovskites with small cations at the A site (A = Sc(3+), In(3+) and Mn(2+) and B = Al(3+) and transition metals) are reviewed. They extend the corresponding families of perovskites with A(3+) = Y, La-Lu, and Bi and A(2+) = Cd, Ca, Sr and Ba and exhibit the largest structural distortions. As a result of these large distortions, they show, in many cases, distinct structural and magnetic properties. These are manifested in: B-site-ordered monoclinic structures of ScMnO3 and 'InMnO3'; an unusual superstructure of ScRhO3 and InRhO3; antiferromagnetic ground states and multiferroic properties of Sc2NiMnO6 and In2NiMnO6; two magnetic transitions in ScCrO3 and InCrO3 with very close transition temperatures; a Pnma-to-P-1 structural transition and k = (½, 0, ½) magnetic ordering in ScVO3; and incommensurate magnetic ordering of Mn(2+) spins in metallic MnVO3. A large number of simple ScBO3, InBO3 and MnBO3 perovskites has not been synthesized yet, and the number of experimental and theoretical works on each known ScBO3, InBO3 and MnBO3 perovskites counts to only one or two (except for ScAlO3). The synthesis, crystal chemistry and physics of perovskites with small cations at the A site is an emerging field in perovskite science.

  6. Annealing Induced Re-crystallization in CH3NH3PbI3−xClx for High Performance Perovskite Solar Cells

    PubMed Central

    Yang, Yingguo; Feng, Shanglei; Li, Meng; Xu, Weidong; Yin, Guangzhi; Wang, Zhaokui; Sun, Baoquan; Gao, Xingyu

    2017-01-01

    Using poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) as hole conductor, a series of inverted planar CH3NH3PbI3−xClx perovskite solar cells (PSCs) were fabricated based on perovskite annealed by an improved time-temperature dependent (TTD) procedure in a flowing nitrogen atmosphere for different time. Only after an optimum annealing time, an optimized power conversion efficiency of 14.36% could be achieved. To understand their performance dependence on annealing time, an in situ real-time synchrotron-based grazing incidence X-ray diffraction (GIXRD) was used to monitor a step-by-step gradual structure transformation from distinct mainly organic-inorganic hybrid materials into highly ordered CH3NH3PbI3 crystal during annealing. However, a re-crystallization process of perovskite crystal was observed for the first time during such an annealing procedure, which helps to enhance the perovskite crystallization and preferential orientations. The present GIXRD findings could well explain the drops of the open circuit voltage (Voc) and the fill factor (FF) during the ramping of temperature as well as the optimized power conversion efficiency achieved after an optimum annealing time. Thus, the present study not only illustrates clearly the decisive roles of post-annealing in the formation of solution-processed perovskite to better understand its formation mechanism, but also demonstrates the crucial dependences of device performance on the perovskite microstructure in PSCs. PMID:28429762

  7. Thermoelectric properties of p-type perovskite compounds LaCoO3 systems containing the A-site vacancy

    NASA Astrophysics Data System (ADS)

    Anzai, Mayuka; Kawakami, Hiroshi; Saito, Miwa; Yamamura, Hiroshi

    2011-05-01

    Thermoelectric properties of Sr-doped LaCoO3 system which includes both La1-xSrxCoO3 and La0.95-xSrxsquare0.05CoO3 containing the A-site vacancy were prepared by solid state reaction. The crystal phases of the samples were investigated by X-ray diffraction method. The electrical conductivity, Seebeck coefficient, and thermal conductivity were investigated, focusing the effect of A-site vacancy. Doping of Sr to LaCoO3 improved the electrical conductivity but decreased the seebeck coefficient and increased the thermal conductivity. A-site vacancy of La0.95-xSrxsquare0.05CoO3 system, in comparison with La1-xSrxCoO3 system, increased electrical conductivity, and decreased lattice thermal conductivity. As a result, it was found that the thermoelectric properties of La0.95-xSrxsquare0.05CoO3 containing the A-site vacancy showed the higher values than those of La1-xSrxCoO3. The introduction of A-site vacancy was effective on the improvement of thermoelectric property.

  8. Crack-free CH3NH3PbI3 layer via continuous dripping method for high-performance mesoporous perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Chen, Guo; Zheng, Jianghui; Zheng, LingLing; Yan, Xin; Lin, Huangding; Zhang, Fengyan

    2017-01-01

    The past five years have witnessed the uniquely rapid emergence of the mixed organic-inorganic halide perovskite solar cells. Here, a modified deposition process, continuous dripping method, is reported for fabricating high-performance and reproducible perovskite solar cells. We have systematically investigated the impact of different molar ratio of lead iodide (PbI2) to dimethylsulfoxide (DMSO) on the growth, morphology and crystallinity of CH3NH3PbI3 (MAPbI3) films obtained via this process. The high power conversion efficiency (PCE) perovskite solar cell originates in crack-free and highly crystallographic perovskite films prepared with optimized ratio of PbI2 to DMSO in first precursor solution. The best PCE of 17.76% and an average PCE of 16.37 ± 0.51% were obtained via this process. Moreover, the conventional solution two steps method was also carried out as a comparison to this process. This work provides a new simple solution approach to obtain high quality of perovskite thin films for high-performance and reproducible PSCs.

  9. Spin-Orbital Superstructure in Strained Ferrimagnetic Perovskite Cobalt Oxide

    NASA Astrophysics Data System (ADS)

    Fujioka, J.; Yamasaki, Y.; Nakao, H.; Kumai, R.; Murakami, Y.; Nakamura, M.; Kawasaki, M.; Tokura, Y.

    2013-07-01

    We have investigated the Co-3d spin-orbital state in a thin film of perovskite LaCoO3 to clarify the origin of strain induced spontaneous magnetization (TC=94K) by means of x-ray diffraction, optical spectroscopy, and magnetization measurements. A lattice distortion with the propagation vector (1/4 -​​1/4 1/4) and an anomalous activation of optical phonons coupled to Co-3d orbital are observed below 126 K. Combined with the azimuthal angle analysis of superlattice reflection, we propose that the ordering of Co-3d orbital promoted by an epitaxial strain produces a unique ferrimagnetic structure.

  10. Graphite-like carbon nitride (C3N4) modified N-doped LaTiO3 nanocomposite for higher visible light photocatalytic and photo-electrochemical performance

    NASA Astrophysics Data System (ADS)

    Rakibuddin, Md; Kim, Haekyoung; Ehtisham Khan, Mohammad

    2018-09-01

    A novel g-C3N4/N doped-LaTiO3 organic-inorganic hybrid (CLT) is synthesized via a sol-gel polymerized complex method followed by a facile solid state transformation route. The as synthesized hybrid is characterized using powder X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, UV-visible diffuse reflectance spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis. The results show that the band gap of LaTiO3 is narrowed and also could absorb visible light after doping of N into the LaTiO3 lattice. It is observed that N-doped LaTiO3 nanoparticles are wrapped with the g-C3N4 nano-sheet layers, forming a heterojunction structure, in the CLT hybrid. The CLT hybrid exhibits not only longer wavelength absorption in the visible region but also an enhancement in the photocatalytic and photocurrent activity under visible light compared to pure N-doped LaTiO3 and g-C3N4. Moreover, the hybrid is photo-stable and reusable. The improved visible light photocatalytic activity of the CLT hybrid is ascribed to its suitable band edge potential, better separation of photoinduced charge carriers owing to the heterojunction, and the synergistic effect of g-C3N4 and N-LaTiO3. Based on the results of photoluminescence, electrochemical impedance, and radical scavenger studies, a possible photocatalytic mechanism for the hybrid is also proposed. The g-C3N4/N-LaTiO3 hetero-structure is expected to provide new insight for the application of rare-earth-metal based perovskite oxides in environmental remediation and could be suitable for water splitting and other energy related applications as well.

  11. Photovoltaic performance of textured silicon solar cells with MAPbBr3 perovskite nanophosphors to induce luminescent down-shifting

    NASA Astrophysics Data System (ADS)

    Ho, Wen-Jeng; Li, Guan-Yi; Liu, Jheng-Jie; Lin, Zong-Xian; You, Bang-Jin; Ho, Chun-Hung

    2018-04-01

    This study employed a two-step multi-cycle spin-coating method for the application of MAPbBr3 perovskite nanophosphors on textured silicon solar cells with the aim of enhancing photovoltaic performance through luminescent down-shifting (LDS). The surface morphology and dimensions of the MAPbBr3 perovskite nanophosphors were examined using scanning electron microscopy in conjunction with ImageJ software. The LDS effects of the nanophosphors were revealed by measuring photo-luminance, optical reflectance, and external quantum efficiency. The photovoltaic performance of cells with and without MAPbBr3 perovskite nanophosphors was evaluated according to photovoltaic current density-voltage (J-V) under AM 1.5 G solar illumination. Compared to uncoated cells, two-layer and one-layer coatings of MAPbBr3 perovskite nanophosphors were shown to enhance conversion efficiency by 4.56% and 3.38%, respectively.

  12. New Sulfide Compounds MeXMn1-XS (Me=3d Metal) with the Colossal Magnetoresistance Effect

    DTIC Science & Technology

    2006-05-19

    is to synthesize the new MeXMn1-XS (Me=3d-metal) sulfide compounds and to study the electrical, magnetic and magnetoresistive properties . Recently...oxide compounds of manganese (LaMnO3-type) with perovskite structure have been intensively investigated. This interest is caused by the observation of... properties of the materials with different structure. It is known that alpha - MnS manganese monosulfide, similar to LaMnO3, has the specific

  13. Evolution of Photoluminescence, Raman, and Structure of CH3NH3PbI3 Perovskite Microwires Under Humidity Exposure

    NASA Astrophysics Data System (ADS)

    Segovia, Rubén; Qu, Geyang; Peng, Miao; Sun, Xiudong; Shi, Hongyan; Gao, Bo

    2018-03-01

    Self-assembled organic-inorganic CH3NH3PbI3 perovskite microwires (MWs) upon humidity exposure along several weeks were investigated by photoluminescence (PL) spectroscopy, Raman spectroscopy, and X-ray diffraction (XRD). We show that, in addition to the common perovskite decomposition into PbI2 and the formation of a hydrated phase, humidity induced a gradual PL redshift at the initial weeks that is stabilized for longer exposure ( 21 nm over the degradation process) and an intensity enhancement. Original perovskite Raman band and XRD reflections slightly shifted upon humidity, indicating defects formation and structure distortion of the MWs crystal lattice. By correlating the PL, Raman, and XRD results, it is believed that the redshift of the MWs PL emission was originated from the structural disorder caused by the incorporation of H2O molecules in the crystal lattice and radiative recombination through moisture-induced subgap trap states. Our study provides insights into the optical and structural response of organic-inorganic perovskite materials upon humidity exposure.

  14. As-Deposited (La1-xSrx)(Ga1-y-zMgyCoz)O3-(x+y+z)/2 Crystallized Thin Films Prepared by Pulsed Laser Deposition for Application to Solid Oxide Fuel Cell Electrolyte

    NASA Astrophysics Data System (ADS)

    Mitsugi, Fumiaki; Kanazawa, Seiji; Ohkubo, Toshikazu; Nomoto, Yukiharu; Ishihara, Tatsumi; Takita, Yusaku

    2004-01-01

    Doped lanthanum gallate (La1-xSrx)(Ga1-y-zMgyCoz)O3-(x+y+z)/2 (LSGMCO) perovskite oxide films were deposited on a quartz glass, LaAlO3 single-crystal substrate and porous anode electrode of a solid oxide fuel cell (SOFC) by pulsed laser deposition. It was necessary to increase the substrate temperature up to 800°C for a crystallization of the LSGMCO films. The film deposited on the LaAlO3 single-crystal substrate grew along the c-axis. The as-deposited LSGMCO thick film fabricated on the porous substrate at 800°C and at an oxygen pressure of 20Pa was formed from polycrystal columns and showed a high conductivity of 0.7S/cm at a measurement temperature of 800°C. The activation energies were 0.72 eV at 600-800°C and 1.05 eV at 400-600°C.

  15. Role of bromine doping on the photovoltaic properties and microstructures of CH{sub 3}NH{sub 3}PbI{sub 3} perovskite solar cells

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Suzuki, Atsushi; Okada, Hiroshi; Oku, Takeo

    Organic-inorganic hybrid heterojunction solar cells containing CH{sub 3}NH{sub 3}PbI{sub 3} perovskite compound were fabricated using mesoporous TiO{sub 2} as the electronic transporting layer and spirobifluorence as the hole-transporting layer. The purpose of the present study is to investigate role of bromine (Br) doping on the photovoltaic properties and microstructure of CH{sub 3}NH{sub 3}PbI{sub 3} perovskite solar cells. Photovoltaic, optical properties and microstructures of perovskite-based solar cells were investigated. The X-ray diffraction identified crystal structure of the perovskite layer doped with Br in the solar cell. Scanning electron microscopy observation showed a different behavior of surface morphology and the perovskite crystalmore » structure on the TiO{sub 2} mesoporous structure depending on extent amount of hydrogen doping of Br. The role of bromide halogen doping on the perovskite crystal structure and photovoltaic properties was due to improvement of carrier mobility, optimization of electron structure, band gap related with the photovoltaic parameters of V{sub oc}, J{sub sc} and η. Energy diagram and photovoltaic mechanism of the perovskite solar cells varied with halogen doping was discussed by experimental results.« less

  16. Large anisotropic thermoelectricity in perovskite related layered structure: SrnNbnO3n+2 (n = 4,5)

    NASA Astrophysics Data System (ADS)

    Sakai, Akihiro; Takahashi, Kouhei; Kanno, Tsutomu; Adachi, Hideaki

    2011-05-01

    We have systematically synthesized a series of perovskite related layered structures, Strontium-Niobates expressed as SrnNbnO3n+2 (n = 4 ~ 5) and focused on the thermoelectricity in n = 4 and 5 type materials here. To explore their thermoelectricities and anisotropic properties, we have measured the thermal and charge transport properties along all crystallographic axes. The values of thermoelectric parameters were strongly anisotropic and there exists a large anisotropy even in in-plane direction of the layered structure. As a result, the best performance of thermoelectricity is commonly observed in the a-axis. The respective ZT for Sr1.8La0.2Nb2O7 and Sr5Nb5O17 at room temperature is 3.5×10-2 and 3.6×10-3.

  17. The effect of rare earth ions on structural, morphological and thermoelectric properties of nanostructured tin oxide based perovskite materials

    NASA Astrophysics Data System (ADS)

    Rajasekaran, P.; Alagar Nedunchezhian, A. S.; Yalini Devi, N.; Sidharth, D.; Arivanandhan, M.; Jayavel, R.

    2017-11-01

    Metal oxide based materials are promising for thermoelectric applications especially at elevated temperature due to their high thermal stability. Recently, perovskite based oxide materials have been focused as a novel thermoelectric material due to their tunable electrical conductivity. Thermoelectric properties of BaSnO3 has been extensively investigated. However, the effect of various rare earth doping on the thermoelectric properties of BaSnO3 is not studied in detail. In the present work, Ba1-x RE x SnO3 (RE  =  La and Sr) materials with x  =  0.05 were prepared by polymerization complex (PC) method in order to study the effect of RE incorporation on the structural, morphological and thermoelectric characteristics of BaSnO3. The structural and morphological properties of the synthesized materials were studied by XRD and TEM analysis. XRD analysis confirmed the mixed phases of the synthesized samples. The TEM images of Ba1-x Sr x SnO3 shows hexagonal and cubic morphology while, Ba1-x La x SnO3 exhibit rod like morphology. Various functional groups of the perovskite material were identified using FTIR analysis. Formation of the perovskite material was further confirmed by XPS analysis. The Seebeck coefficient of Ba0.95La0.05SnO3 was relatively higher than that of Ba0.95Sr0.05SnO3, especially at high temperature. The rod like morphology of Ba0.95La0.05SnO3 may facilitate fast electron transport which results high thermal power compared to Ba0.95Sr0.05SnO3 despite of its poor crystalline nature. The substitution of La3+ on the Ba2+ site could vary the carrier density which results high Seebeck coefficient of Ba0.95La0.05SnO3 compared to Ba0.95Sr0.05SnO3. From the experimental results, it is obvious that Ba0.95La0.05SnO3 could be a promising thermoelectric material for high temperature application.

  18. Low-voltage all-inorganic perovskite quantum dot transistor memory

    NASA Astrophysics Data System (ADS)

    Chen, Zhiliang; Zhang, Yating; Zhang, Heng; Yu, Yu; Song, Xiaoxian; Zhang, Haiting; Cao, Mingxuan; Che, Yongli; Jin, Lufan; Li, Yifan; Li, Qingyan; Dai, Haitao; Yang, Junbo; Yao, Jianquan

    2018-05-01

    An all-inorganic cesium lead halide quantum dot (QD) based Au nanoparticle (NP) floating-gate memory with a solution processed layer-by-layer method is demonstrated. Easy synthesis at room temperature and excellent stability make all-inorganic CsPbBr3 perovskite QDs suitable as a semiconductor layer in low voltage nonvolatile transistor memory. The bipolarity of QDs has both electrons and holes stored in the Au NP floating gate, resulting in bidirectional shifts of initial threshold voltage according to the applied programing and erasing pulses. Under low operation voltage (±5 V), the memory achieved a great memory window (˜2.4 V), long retention time (>105 s), and stable endurance properties after 200 cycles. So the proposed memory device based on CsPbBr3 perovskite QDs has a great potential in the flash memory market.

  19. Dynamic Optoelectronic Properties in Perovskite Oxide Thin Films Measured with Ultrafast Transient Absorption & Reflectance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Smolin, Sergey Y.

    -dependent, variable-angle spectroscopic ellipsometry and time-resolved ultrafast optical spectroscopy on a type I heterostructure, we clarify thermal and electronic contributions to spectral transients in LaFeO3. Upon comparison to thermally-derived static spectra of LaFeO3, we find that thermal contributions dominate the transient absorption and reflectance spectra above the band gap. A transient photoinduced absorption feature below the band gap at 1.9 eV is not reproduced in the thermally derived spectra and has significantly longer decay kinetics from the thermallyinduced features; therefore, this long lived photoinduced absorption is likely derived, at least partially, from photoexcited carriers with lifetimes much longer than 3 nanoseconds. LaFeO3 has a wide band gap of 2.4 eV but its absorption can be decreased with chemical substitution of Sr for Fe to make it more suitable for various applications. This type of A-site substitution is a common route to change static optical absorption in perovskite oxides, but there are no systematic studies looking at how A-site substitution changes dynamic optoelectronic properties. To understand the relationship between composition and static and dynamic optical properties we worked with the model system of La1-xSrxFeO 3-delta epitaxial films grown on LSAT, uncovering the effects of A-site cation substitution and oxygen stoichiometry. Variable-angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and a red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy with broadband visible (1.6 eV to 4 eV) and near-infrared (0.9 eV to 1.5 eV) probes. The sign of the reflectance

  20. Non-invasive Photodynamic Therapy in Brain Cancer by Use of Tb3+-Doped LaF3 Nanoparticles in Combination with Photosensitizer Through X-ray Irradiation: A Proof-of-Concept Study

    NASA Astrophysics Data System (ADS)

    Chen, Min-Hua; Jenh, Yi-Jhen; Wu, Sheng-Kai; Chen, Yo-Shen; Hanagata, Nobutaka; Lin, Feng-Huei

    2017-01-01

    The use of photodynamic therapy (PDT) in the treatment of brain cancer has produced exciting results in clinical trials over the past decade. PDT is based on the concept that a photosensitizer exposed to a specific light wavelength produces the predominant cytotoxic agent, to destroy tumor cells. However, delivering an efficient light source to the brain tumor site is still a challenge. The light source should be delivered by placing external optical fibers into the brain at the time of surgical debulking of the tumor. Consequently, there exists the need for a minimally invasive treatment for brain cancer PDT. In this study, we investigated an attractive non-invasive option on glioma cell line by using Tb3+-doped LaF3 scintillating nanoparticles (LaF3:Tb) in combination with photosensitizer, meso-tetra(4-carboxyphenyl)porphyrin (MTCP), followed by activation with soft X-ray (80 kVp). Scintillating LaF3:Tb nanoparticles, with sizes of approximately 25 nm, were fabricated. The particles have a good dispersibility in aqueous solution and possess high biocompatibility. However, significant cytotoxicity was observed in the glioma cells while the LaF3:Tb nanoparticles with MTCP were exposed under X-ray irradiation. The study has demonstrated a proof of concept as a non-invasive way to treat brain cancer in the future.

  1. Luminescence lifetime enhanced by exciton-plasmon couple in hybrid CsPbBr3 perovskite/Pt nanostructure

    NASA Astrophysics Data System (ADS)

    Liu, Chunxu; Zhang, Jisen; Chen, Yongyi; Jing, Pengtao; Zhang, Ligong; Zhao, Haifeng; Fu, Xihong; Wang, Lijun

    2018-02-01

    Photoluminescence (PL) and time-resolved spectroscopic studies on plasmonically coupled semiconductor nanoparticles (SNPs) have demonstrated the PL quenched and lifetime enhanced of SNPs in the presence of metal nanoparticles (MNPs). The hybrid colloidal CsPbBr3 perovskite SNPs/Pt MNPs (S-M) structures exhibit novel optical properties due to the synergetic interaction between the individual components. In hybrid S-M nanostructures colloidal chemistry incorporates SNP and MNP into a single unit resulting in the formation of plexciton (or excimon) which has now been established in a series of hybrid structures. The experimental results of femtosecond transient absorption (TA) spectroscopy based on the time-resolved pump-probe confirm the transformation from excitons to plexcitons. It was found that the experimental data can’t be well described by the theory based on conventional Fӧster resonance energy transfer (FRET). The differences between theory and experiment may be due to the missing some PbBr2 PL peaks, the reason will be revealed further.

  2. Fabrication and characterization of perovskite-based CH{sub 3}NH{sub 3}Pb{sub 1-x}Ge{sub x}I{sub 3}, CH{sub 3}NH{sub 3}Pb{sub 1-x}Tl{sub x}I{sub 3} and CH{sub 3}NH{sub 3}Pb{sub 1-x}In{sub x}I{sub 3} photovoltaic devices

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ohishi, Yuya; Oku, Takeo, E-mail: oku@mat.usp.ac.jp; Suzuki, Atsushi

    2016-02-01

    Perovskite-type CH{sub 3}NH{sub 3}PbI{sub 3}-based photovoltaic devices were fabricated and characterized. Doping effects of thallium (Tl), indium (In), or germanium (Ge) element on the photovoltaic properties and surface structures of the perovskite phase were investigated. The open circuit voltage increased by Ge addition, and fill factors were improved by adding a small amount of Ge, Tl or In. In addition, the wavelength range of incident photon conversion efficiencies was expanded by the Tl addition.

  3. Structural, ferroelectric and magnetic study of lead free (Na{sub 0.5}Bi{sub 0.5}){sub 1-x}La{sub x}Ti{sub 0.988}Fe{sub 0.012}O{sub 3} (x=0,0.01,0.03,0.05) ceramic

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Parmar, Kusum, E-mail: prmrkusum@gmail.com; Sharma, Anshu; Sharma, Hakikat

    2015-05-15

    Lead free (Na{sub 0.5}Bi{sub 0.5}){sub 1-x}La{sub x}Ti{sub 0.988}Fe{sub 0.012}O{sub 3} ceramic having compositions (x=0, 0.01, 0.03, 0.05) has been prepared by sol gel method using citric acid. Structural analysis has been done by X-ray diffraction and FTIR measurements. XRD patterns have been confirmed perovskite structure for all samples. FTIR absorption band at around ∼630 cm{sup −1} is observed for all samples which confirm perovskite phase formation in samples. With increasing La concentration, shifting in XRD peaks and FTIR absorption bands is observed which suggests incorporation of La on A-site in prepared (Na{sub 0.5}Bi{sub 0.5}){sub 1-x}La{sub x}Ti{sub 0.988}Fe{sub 0.012}O{sub 3} samples. Effectmore » of La substitution on Ferroelectric (Polarization vs. Electric field) and Magnetic (Magnetization vs. Magnetic field) properties have been studied at room temperature. All samples exhibit weak ferromagnetic order and also possess ferroelectric behavior which provides new insight to lead free single phase multiferroic materials.« less

  4. Low-temperature route to metal titanate perovskite nanoparticles for photocatalytic applications

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Alammar, Tarek; Hamm, Ines; Wark, Michael

    MTiO 3 (M = Ca, Sr, Ba) nanoparticles were synthesized by a one-step room-temperature ultrasound synthesis in ionic liquid. The samples we gathered are characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption, UV–vis diffuse reflectance, Raman and IR spectroscopy and their capability in photocatalytic hydrogen evolution and methylene blue degradation was tested. Powder X-ray diffraction and Raman spectroscopic investigations revealed the products to crystallize in the cubic perovskite structure. SEM observations showed that the obtained CaTiO 3 consists of nanospheres, BaTiO 3 of raspberry-like shaped particles of 20 nm in diameter. SrTiO 3 particles have cubic-like morphology with anmore » edge length varying from 100 to 300 nm. SrTiO 3 exhibited the highest catalytic activity for photocatalytic H 2 evolution using only 0.025 wt.% Rh as co-catalyst and for the degradation of methylene blue under UV irradiation. The influence of parameters such as synthesis method, calcination temperature, and doping with nitrogen on the morphology, crystallinity, chemical composition, and photocatalytic acivity of SrTiO 3 was studied. Heating the as-prepared SrTiO 3 to 700 °C for extended time leads to a decrease in surface area and catalytic activity. Ionothermal prepared SrTiO 3 exhibits a higher activity than sonochemically prepared one without co-catalyst due to a synergistic effect of anatase which is present in small amount as a by-phase. Furthermore, after photodeposition of Rh, however, the activity is lower than that of the sonochemically prepared SrTiO 3. Nitrogen-doped SrTiO 3 showed photocatalytic acivity under visible light irradiation.« less

  5. Low-temperature route to metal titanate perovskite nanoparticles for photocatalytic applications

    DOE PAGES

    Alammar, Tarek; Hamm, Ines; Wark, Michael; ...

    2014-11-13

    MTiO 3 (M = Ca, Sr, Ba) nanoparticles were synthesized by a one-step room-temperature ultrasound synthesis in ionic liquid. The samples we gathered are characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption, UV–vis diffuse reflectance, Raman and IR spectroscopy and their capability in photocatalytic hydrogen evolution and methylene blue degradation was tested. Powder X-ray diffraction and Raman spectroscopic investigations revealed the products to crystallize in the cubic perovskite structure. SEM observations showed that the obtained CaTiO 3 consists of nanospheres, BaTiO 3 of raspberry-like shaped particles of 20 nm in diameter. SrTiO 3 particles have cubic-like morphology with anmore » edge length varying from 100 to 300 nm. SrTiO 3 exhibited the highest catalytic activity for photocatalytic H 2 evolution using only 0.025 wt.% Rh as co-catalyst and for the degradation of methylene blue under UV irradiation. The influence of parameters such as synthesis method, calcination temperature, and doping with nitrogen on the morphology, crystallinity, chemical composition, and photocatalytic acivity of SrTiO 3 was studied. Heating the as-prepared SrTiO 3 to 700 °C for extended time leads to a decrease in surface area and catalytic activity. Ionothermal prepared SrTiO 3 exhibits a higher activity than sonochemically prepared one without co-catalyst due to a synergistic effect of anatase which is present in small amount as a by-phase. Furthermore, after photodeposition of Rh, however, the activity is lower than that of the sonochemically prepared SrTiO 3. Nitrogen-doped SrTiO 3 showed photocatalytic acivity under visible light irradiation.« less

  6. High-pressure synthesis and structural, physical properties of CaIr1-xPtxO3 and CaIr1-xRhxO3

    NASA Astrophysics Data System (ADS)

    Hirai, S.; Bromiley, G. D.; Klemme, S.; Irifune, T.; Ohfuji, H.; Attfield, P.; Nishiyama, N.

    2010-12-01

    in terms of materials science applications. To our knowledge, this will be the first report on structural, magnetic and charge-transport properties of B-site substituted solid solutions of post-perovskite oxides with 4d/5d transition metals. High-quality polycrystalline samples of CaIr1-xPtxO3 and CaIr1-xRhxO3 have been obtained at high pressures, and structural, magnetic and charge-transport properties of the compounds will be reported. ODF analysis reveals that solutions of CaIrO3, CaPtO3 and CaRhO3 exhibit similar grain growth features to the mother compound, although growth in [0 1 0] plays a more dominant role than the growth in [0 0 1] for the solid solutions. CaIrO3 is a characteristic hard magnet suitable for applications such as magnetic recording, with TN = 108K. A new phase of CaIr1-xPtxO3 synthesized at a high P/T condition has Raman modes which resemble those of CaIrO3 perovskite, suggesting this phase has a perovskite structure.The instability of the perovskite phase of CaIr1-xPtxO3 reveals why the post-perovskite to peovskite phase transition has not been observed for CaPtO3 unlike the case for CaIrO3, CaRhO3 and CaRuO3.

  7. Specific heat of new perovskite-type cobaltates Pr{sub 1-x}Nd{sub x}CoO{sub 3}

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Thakur, Rasna, E-mail: rasnarishu@gmail.com; Thakur, Rajesh K.; Gaur, N. K.

    2016-05-23

    Specific heat and Bulk modulus (B) of new perovskite-type cobaltates Pr{sub 1-x}Nd{sub x}CoO{sub 3} has been studied by means of a Modified Rigid Ion Model (MRIM) and Atoms in Molecules (AIM) theory in a wide temperature range (1 K ≤ T ≤1000 K). The effect of Nd doping on the elastic, cohesive and thermal properties of PrCoO{sub 3} have been studied probably for the first time by an atomistic approach. The computed results are in good agreement with the available experimental data.

  8. Overcoming Short-Circuit in Lead-Free CH 3 NH 3 SnI 3 Perovskite Solar Cells via Kinetically Controlled Gas–Solid Reaction Film Fabrication Process

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yokoyama, Takamichi; Cao, Duyen H.; Stoumpos, Constantinos C.

    2016-02-17

    The development of Sn-based perovskite solar cells has been challenging because devices often show short-circuit behavior due to poor morphologies and undesired electrical properties of the thin films. A low-temperature vapor-assisted solution process (LT-VASP) has been employed as a novel kinetically controlled gas–solid reaction film fabrication method to prepare lead-free CH3NH3SnI3 thin films. We show that the solid SnI2 substrate temperature is the key parameter in achieving perovskite films with high surface coverage and excellent uniformity. The resulting high-quality CH3NH3SnI3 films allow the successful fabrication of solar cells with drastically improved reproducibility, reaching an efficiency of 1.86%. Furthermore, our Kelvinmore » probe studies show the VASP films have a doping level lower than that of films prepared from the conventional one-step method, effectively lowering the film conductivity. Above all, with (LT)-VASP, the short-circuit behavior often obtained from the conventional one-step-fabricated Sn-based perovskite devices has been overcome. This study facilitates the path to more successful Sn-perovskite photovoltaic research.« less

  9. Overcoming Short-Circuit in Lead-Free CH3NH3SnI3 Perovskite Solar Cells via Kinetically Controlled Gas-Solid Reaction Film Fabrication Process.

    PubMed

    Yokoyama, Takamichi; Cao, Duyen H; Stoumpos, Constantinos C; Song, Tze-Bin; Sato, Yoshiharu; Aramaki, Shinji; Kanatzidis, Mercouri G

    2016-03-03

    The development of Sn-based perovskite solar cells has been challenging because devices often show short-circuit behavior due to poor morphologies and undesired electrical properties of the thin films. A low-temperature vapor-assisted solution process (LT-VASP) has been employed as a novel kinetically controlled gas-solid reaction film fabrication method to prepare lead-free CH3NH3SnI3 thin films. We show that the solid SnI2 substrate temperature is the key parameter in achieving perovskite films with high surface coverage and excellent uniformity. The resulting high-quality CH3NH3SnI3 films allow the successful fabrication of solar cells with drastically improved reproducibility, reaching an efficiency of 1.86%. Furthermore, our Kelvin probe studies show the VASP films have a doping level lower than that of films prepared from the conventional one-step method, effectively lowering the film conductivity. Above all, with (LT)-VASP, the short-circuit behavior often obtained from the conventional one-step-fabricated Sn-based perovskite devices has been overcome. This study facilitates the path to more successful Sn-perovskite photovoltaic research.

  10. Perovskite photonic sources

    NASA Astrophysics Data System (ADS)

    Sutherland, Brandon R.; Sargent, Edward H.

    2016-05-01

    The field of solution-processed semiconductors has made great strides; however, it has yet to enable electrically driven lasers. To achieve this goal, improved materials are required that combine efficient (>50% quantum yield) radiative recombination under high injection, large and balanced charge-carrier mobilities in excess of 10 cm2 V-1 s-1, free-carrier densities greater than 1017 cm-3 and gain coefficients exceeding 104 cm-1. Solid-state perovskites are -- in addition to galvanizing the field of solar electricity -- showing great promise in photonic sources, and may be the answer to realizing solution-cast laser diodes. Here, we discuss the properties of perovskites that benefit light emission, review recent progress in perovskite electroluminescent diodes and optically pumped lasers, and examine the remaining challenges in achieving continuous-wave and electrically driven lasing.

  11. Smart Pd Catalyst with Improved Thermal Stability Supported on High-Surface-Area LaFeO3 Prepared by Atomic Layer Deposition.

    PubMed

    Onn, Tzia Ming; Monai, Matteo; Dai, Sheng; Fonda, Emiliano; Montini, Tiziano; Pan, Xiaoqing; Graham, George W; Fornasiero, Paolo; Gorte, Raymond J

    2018-04-11

    The concept of self-regenerating or "smart" catalysts, developed to mitigate the problem of supported metal particle coarsening in high-temperature applications, involves redispersing large metal particles by incorporating them into a perovskite-structured support under oxidizing conditions and then exsolving them as small metal particles under reducing conditions. Unfortunately, the redispersion process does not appear to work in practice because the surface areas of the perovskite supports are too low and the diffusion lengths for the metal ions within the bulk perovskite too short. Here, we demonstrate reversible activation upon redox cycling for CH 4 oxidation and CO oxidation on Pd supported on high-surface-area LaFeO 3 , prepared as a thin conformal coating on a porous MgAl 2 O 4 support using atomic layer deposition. The LaFeO 3 film, less than 1.5 nm thick, was shown to be initially stable to at least 900 °C. The activated catalysts exhibit stable catalytic performance for methane oxidation after high-temperature treatment.

  12. Small polarons and point defects in LaFeO3

    NASA Astrophysics Data System (ADS)

    Zhu, Zhen; Peelaers, Hartwin; van de Walle, Chris G.

    The proton-conductive perovskite-type LaFeO3 is a promising negative-electrode material for Ni/metal-hydride (Ni-MH) batteries. It has a discharge capacity up to 530 mAhg-1 at 333 K, which is significantly higher than commercialized AB5-type alloys. To elucidate the underlying mechanism of this performance, we have investigated the structural and electronic properties of bulk LaFeO3, as well as the effect of point defects, using hybrid density functional methods. LaFeO3 is antiferromagnetic in the ground state with a band gap of 3.54 eV. Small hole and electron polarons can form through self- or point-defect-assisted trapping. We find that La vacancies and Sr substitutional on La sites are shallow acceptors with the induced holes trapped as small polarons, while O and Fe vacancies are deep defect centers. Hydrogen interstitials behave like shallow donors, with the donor electrons localized on nearby iron sites as electron polarons. With a large trapping energy, these polarons can act as electron or hole traps and affect the electrical performance of LaFeO3 as the negative electrode for Ni-MH batteries. We acknowledge DOE for financial support.

  13. Structural, magnetic and impedance spectroscopic analysis of LaFeO3 nano-particles

    NASA Astrophysics Data System (ADS)

    Rao, T. Lakshmana; Pradhan, M. K.; Dash, S.

    2018-04-01

    Physical properties are known to be drastically varied with crystallite size and in a multifunctional material this size reduction is seem to be interesting. One such material is chosen as LaFeO3 nanoparticles which have been prepared by wet-chemical route. The average particle size found to be in the order of 45nm in which the chemical content of the unit cell has been verified. A distorted orthorhombic structure with Pbnm space group is possessed by this nanoparticle. From the bifurcation of ZFC and FC in low field, behavior of inverse susceptibility and the small hysteresis loop favors the material to be in a weak FM state well below the Neel temperature. The electrical behavior and the conduction mechanism above room temperature have been studied by cole-cole plot of the Impedance spectra. The high frequency depressed semi circles represent the grain conduction while the intermediate frequency semi circles appear may be due to grain boundary effect.

  14. Synthesis and equation of state of post-perovskites in the (Mg,Fe)[subscript 3]Al[subscript 2]Si[subscript 3]O[subscript 12] system

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Shieh, Sean R.; Dorfman, Susannah M.; Kubo, Atsushi

    The formation and properties of the post-perovskite (CaIrO{sub 3}-type) phase were studied in Fe-rich compositions along the pyrope-almandine ((Mg,Fe){sub 3}Al{sub 2}Si{sub 3}O{sub 12}) join. Natural and synthetic garnet starting materials with almandine fractions from 38 to 90 mol% were studied using synchrotron X-ray diffraction in the laser-heated diamond anvil cell. Single-phase post-perovskite could be successfully synthesized from garnet compositions at pressures above 148 GPa and temperatures higher than 1600 K. In some cases, evidence for a minor amount of Al{sub 2}O{sub 3} post-perovskite was observed for Alm38 and Alm54 compositions in the perovskite + post-perovskite two-phase region. Pressure-volume data formore » the post-perovskite phases collected during decompression show that incorporation of Fe leads to a systematic increase of unit cell volume broadly similar to the variation observed in the (Mg,Fe)SiO{sub 3} system. The presence of Al{sub 2}O{sub 3} increases the stability of perovskite relative to post-perovskite, requiring higher pressures (> 148 GPa) for synthesis of pure post-perovskites. Our data together with those of Tateno et al. (2005) also suggest that in the Al-rich system the presence of Fe has no strong effect on the pressure required to synthesize the pure post-perovskite phase, but the two-phase perovskite and post-perovskite region may be broad and its width dependent on Fe content. Our results suggest that any regions highly enriched in Al{sub 2}O{sub 3} may consist of either the perovskite phase or a mixture of perovskite and post-perovskite phases throughout the entire thickness of the D* region. The observed synthesis pressures (> 148 GPa) for a pure post-perovskite phase are beyond that at the Earth's core-mantle boundary ({approx} 135 GPa).« less

  15. Local surrounding of Mn in LaMn 1-xCo xO 3 compounds by means of EXAFS on Mn-K

    NASA Astrophysics Data System (ADS)

    Procházka, Vít; Sikora, Marcin; Kapusta, Czeslaw; Štěpánková, Helena; Chlan, Vojtěch; Knížek, Karel; Jirák, Zdeněk

    2010-05-01

    A systematic study of LaMn 1-xCo xO 3 perovskite series by means of X-ray absorption spectroscopy in the extended X-ray absorption fine structure (EXAFS) range of the K-absorption edge of Mn is reported. The Mn-K edge absorption measurements in the EXAFS region were performed to study the local surrounding of Mn ions. Polycrystalline powder samples of LaMn 1-xCo xO 3 ( x=0, 0.02; 0.2; 0.4; 0.5; 0.6; 0.8) prepared by solid-state reaction were used. The EXAFS spectra were analyzed with the FEFF8 computer program. The Mn-O distances of Mn to the nearest oxygen surroundings were evaluated for the samples in the series and compared with the Co-O distances obtained by EXAFS in V. Procházka et al., JMMM 310 (2007) 197 and with results of X-ray powder diffraction in C. Autret, J. Phys. Condens. Matter 17 (2005) 1601.

  16. Enhancing the Performance of Perovskite Solar Cells by Hybridizing SnS Quantum Dots with CH3 NH3 PbI3.

    PubMed

    Han, Jianhua; Yin, Xuewen; Nan, Hui; Zhou, Yu; Yao, Zhibo; Li, Jianbao; Oron, Dan; Lin, Hong

    2017-08-01

    The combination of perovskite solar cells and quantum dot solar cells has significant potential due to the complementary nature of the two constituent materials. In this study, solar cells (SCs) with a hybrid CH 3 NH 3 PbI 3 /SnS quantum dots (QDs) absorber layer are fabricated by a facile and universal in situ crystallization method, enabling easy embedding of the QDs in perovskite layer. Compared with SCs based on CH 3 NH 3 PbI 3 , SCs using CH 3 NH 3 PbI 3 /SnS QDs hybrid films as absorber achieves a 25% enhancement in efficiency, giving rise to an efficiency of 16.8%. The performance improvement can be attributed to the improved crystallinity of the absorber, enhanced photo-induced carriers' separation and transport within the absorber layer, and improved incident light utilization. The generality of the methods used in this work paves a universal pathway for preparing other perovskite/QDs hybrid materials and the synthesis of entire nontoxic perovskite/QDs hybrid structure. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Field emission of silicon emitter arrays coated with sol-gel (Ba0.65Sr0.35)1-xLaxTiO3 thin films

    NASA Astrophysics Data System (ADS)

    Lu, H.; Pan, J. S.; Chen, X. F.; Zhu, W. G.

    2007-07-01

    (Ba0.65Sr0.35)1-xLaxTiO3 (BSLT) thin films with different La concentrations have been deposited on Si field emitter arrays (FEAs) using sol-gel technology for field electron emission applications. The films exhibit the perovskite structure at low La substitution level (x ≤0.5) and the pyrochlore phase at high La concentration (x ≥0.75). The 30-nm-thick BSLT (x =0.25) thin film has higher crystallinity of perovskite structure in the surface region. An x-ray photoelectron spectroscopy study indicates that the oxygen vacancy concentration decreases with La substitution. With respect to the undoped Ba0.65Sr0.35TiO3 thin film, the Fermi level shifts down for the BSLT sample with x =0.1 ascribed to the decreasing oxygen vacancy concentration, and then shifts up for the BSLT sample with x =0.25 attributed to the increasing La substitution level. In highly doped films with an x value over 0.5, it shifts down again associated with the second pyrochlore phase formation. The best enhancement in field emission is found for the BSLT-coated (x =0.25) Si FEAs due to the improved perovskite structure in the surface region and up-moved Fermi level of the coating.

  18. Enhanced photovoltaic performance and stability with a new type of hollow 3D perovskite {en}FASnI 3

    DOE PAGES

    Ke, Weijun; Stoumpos, Constantinos C.; Zhu, Menghua; ...

    2017-08-30

    Perovskite solar cells have revolutionized the fabrication of solution-processable solar cells. The presence of lead in the devices makes this technology less attractive, and alternative metals in perovskites are being researched as suitable alternatives. We demonstrate a new type of tin-based perovskite absorber that incorporates both ethylenediammonium (en) and formamidinium (FA), forming new materials of the type {en}FASnI 3. The three-dimensional ASnI 3 structure is stable only with methylammonium, FA, and Cs cations, and the bandgap can be tuned with solid solutions, such as ASnI 3-xBr x. We show that en can serve as a new A cation capable ofmore » achieving marked increases in the bandgap without the need for solid solutions. The en introduces a new bandgap tuning mechanism that arises from massive Schottky style defects. In addition, incorporation of the en cation in the structure markedly increases the air stability and improves the photoelectric properties of the tin-based perovskite absorbers. Our best-performing {en}FASnI 3 solar cell has the highest efficiency of 7.14%, which is achieved for a lead-free perovskite cell, and retains 96% of its initial efficiency after aging over 1000 hours with encapsulation. Our results introduce a new approach for improving the performance and stability of tin-based, lead-free perovskite solar cells.« less

  19. Enhanced photovoltaic performance and stability with a new type of hollow 3D perovskite {en}FASnI 3

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ke, Weijun; Stoumpos, Constantinos C.; Zhu, Menghua

    Perovskite solar cells have revolutionized the fabrication of solution-processable solar cells. The presence of lead in the devices makes this technology less attractive, and alternative metals in perovskites are being researched as suitable alternatives. We demonstrate a new type of tin-based perovskite absorber that incorporates both ethylenediammonium (en) and formamidinium (FA), forming new materials of the type {en}FASnI 3. The three-dimensional ASnI 3 structure is stable only with methylammonium, FA, and Cs cations, and the bandgap can be tuned with solid solutions, such as ASnI 3-xBr x. We show that en can serve as a new A cation capable ofmore » achieving marked increases in the bandgap without the need for solid solutions. The en introduces a new bandgap tuning mechanism that arises from massive Schottky style defects. In addition, incorporation of the en cation in the structure markedly increases the air stability and improves the photoelectric properties of the tin-based perovskite absorbers. Our best-performing {en}FASnI 3 solar cell has the highest efficiency of 7.14%, which is achieved for a lead-free perovskite cell, and retains 96% of its initial efficiency after aging over 1000 hours with encapsulation. Our results introduce a new approach for improving the performance and stability of tin-based, lead-free perovskite solar cells.« less

  20. Enhanced photovoltaic performance and stability with a new type of hollow 3D perovskite {en}FASnI3

    PubMed Central

    Ke, Weijun; Stoumpos, Constantinos C.; Zhu, Menghua; Mao, Lingling; Spanopoulos, Ioannis; Liu, Jian; Kontsevoi, Oleg Y.; Chen, Michelle; Sarma, Debajit; Zhang, Yongbo; Wasielewski, Michael R.; Kanatzidis, Mercouri G.

    2017-01-01

    Perovskite solar cells have revolutionized the fabrication of solution-processable solar cells. The presence of lead in the devices makes this technology less attractive, and alternative metals in perovskites are being researched as suitable alternatives. We demonstrate a new type of tin-based perovskite absorber that incorporates both ethylenediammonium (en) and formamidinium (FA), forming new materials of the type {en}FASnI3. The three-dimensional ASnI3 structure is stable only with methylammonium, FA, and Cs cations, and the bandgap can be tuned with solid solutions, such as ASnI3−xBrx. We show that en can serve as a new A cation capable of achieving marked increases in the bandgap without the need for solid solutions. The en introduces a new bandgap tuning mechanism that arises from massive Schottky style defects. In addition, incorporation of the en cation in the structure markedly increases the air stability and improves the photoelectric properties of the tin-based perovskite absorbers. Our best-performing {en}FASnI3 solar cell has the highest efficiency of 7.14%, which is achieved for a lead-free perovskite cell, and retains 96% of its initial efficiency after aging over 1000 hours with encapsulation. Our results introduce a new approach for improving the performance and stability of tin-based, lead-free perovskite solar cells. PMID:28875173

  1. Semitransparent Fully Air Processed Perovskite Solar Cells.

    PubMed

    Bu, Lingling; Liu, Zonghao; Zhang, Meng; Li, Wenhui; Zhu, Aili; Cai, Fensha; Zhao, Zhixin; Zhou, Yinhua

    2015-08-19

    Semitransparent solar cells are highly attractive for application as power-generating windows. In this work, we present semitransparent perovskite solar cells that employ conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) ( PSS) film as the transparent counter electrode. The PSS electrode is prepared by transfer lamination technique using plastic wrap as the transfer medium. The use of the transfer lamination technique avoids the damage of the CH3NH3PbI3 perovskite film by direct contact of PSS aqueous solution. The semitransparent perovskite solar cells yield a power conversion efficiency of 10.1% at an area of about 0.06 cm(2) and 2.9% at an area of 1 cm(2). The device structure and the fabrication technique provide a facile way to produce semitransparent perovskite solar cells.

  2. Crystal structure, stability, and optoelectronic properties of the organic-inorganic wide-band-gap perovskite CH3NH3BaI3 : Candidate for transparent conductor applications

    NASA Astrophysics Data System (ADS)

    Kumar, Akash; Balasubramaniam, K. R.; Kangsabanik, Jiban; Vikram, Alam, Aftab

    2016-11-01

    Structural stability, electronic structure, and optical properties of CH3NH3BaI3 hybrid perovskite are examined from theory as well as experiment. Solution-processed thin films of CH3NH3BaI3 exhibited a high transparency in the wavelength range of 400-825 nm (1.5-3.1 eV for which the photon current density is highest in the solar spectrum) which essentially justifies a high band gap of 4 eV obtained by theoretical estimation. Also, the x-ray diffraction patterns of the thin films match well with the {00 l } peaks of the simulated pattern obtained from the relaxed unit cell of CH3NH3BaI3 , crystallizing in the I 4 /m c m space group, with lattice parameters, a =9.30 Å, c =13.94 Å. Atom projected density of state and band structure calculations reveal the conduction and valence band edges to be comprised primarily of barium d orbitals and iodine p orbitals, respectively. The larger band gap of CH3NH3BaI3 compared to CH3NH3PbI3 can be attributed to the lower electronegativity coupled with the lack of d orbitals in the valence band of Ba2 +. A more detailed analysis reveals the excellent chemical and mechanical stability of CH3NH3BaI3 against humidity, unlike its lead halide counterpart, which degrades under such conditions. We propose La to be a suitable dopant to make this compound a promising candidate for transparent conductor applications, especially for all perovskite solar cells. This claim is supported by our calculated results on charge concentration, effective mass, and vacancy formation energies.

  3. Monoclinic Sr(1-x)Na(x)SiO(3-0.5x): new superior oxide ion electrolytes.

    PubMed

    Singh, Preetam; Goodenough, John B

    2013-07-10

    Oxide ion electrolytes determine the temperature of operation of solid oxide fuel cells, oxygen separation membranes, and oxygen sensors. There is a strong incentive to lower their operating temperatures, in a solid oxide fuel cell, for example, from Top > 800 °C to Top ≈ 500 °C. The use of low-cost Na(+) rather than K(+) as the dopant in monoclinic SrSiO3 (C12/C1) is shown to provide a larger solid solution range (0 < x ≤ 0.45) in Sr1-xNaxSiO3-0.5x and to achieve an oxide ion conductivity σo ≥ 10(-2) S·cm(-1) by 525 °C as a result of lowering the temperature of a smooth transition to full disorder of the mobile oxide ions. The Sr1-xNaxSiO3-0.5x electrolytes are much less hygroscopic than Sr1-xKxSiO3-0.5x and are stable with a nickel composite anode in 5% H2/Ar as well as with cathodes such as La1-xSrxMnO3-δ and Sr0.7Y0.3CoO3-δ in air, which makes them candidate electrolytes for intermediate-temperature solid oxide fuel cells or for other applications of oxide ion electrolytes.

  4. CH3 NH3 PbI3 and HC(NH2 )2 PbI3 Powders Synthesized from Low-Grade PbI2 : Single Precursor for High-Efficiency Perovskite Solar Cells.

    PubMed

    Zhang, Yong; Kim, Seul-Gi; Lee, Do-Kyoung; Park, Nam-Gyu

    2018-05-09

    High-efficiency perovskite solar cells are generally fabricated by using highly pure (>99.99 %) PbI 2 mixed with an organic iodide in polar aprotic solvents. However, the use of such an expensive chemical may impede progress toward large-scale industrial applications. Here, we report on the synthesis of perovskite powders by using inexpensive low-grade (99 %) PbI 2 and on the photovoltaic performance of perovskite solar cells prepared from a powder-based single precursor. Pure APbI 3 [A=methylammonium (MA) or formamidinium (FA)] perovskite powders were synthesized by treating low-grade PbI 2 with MAI or FAI in acetonitrile at ambient temperature. The structural phase purity was confirmed by X-ray diffraction. The solar cell with a MAPbI 3 film prepared from the synthesized perovskite powder demonstrated a power conversion efficiency (PCE) of 17.14 %, which is higher than the PCE of MAPbI 3 films prepared by using both MAI and PbI 2 as precursors (PCE=13.09 % for 99 % pure PbI 2 and PCE=16.39 % for 99.9985 % pure PbI 2 ). The synthesized powder showed better absorption and photoluminescence, which were responsible for the better photovoltaic performance. For the FAPbI 3 powder, a solution with a yellow non-perovskite δ-FAPbI 3 powder synthesized at room temperature was found to lead to a black perovskite film, whereas a solution with the black perovskite α-FAPbI 3 powder synthesized at 150 °C was not transformed into a black perovskite film. The α↔δ transition between the powder and film was assumed to correlate with the difference in the iodoplumbates in the powder-dissolved solution. An average PCE of 17.21 % along with a smaller hysteresis [ΔPCE=PCE reverse -PCE forward )=1.53 %] was demonstrated from the perovskite solar cell prepared by using δ-FAPbI 3 powder; this PCE is higher than the average PCE of 17.05 % with a larger hysteresis (ΔPCE=2.71 %) for a device based on a conventional precursor solution dissolving MAI with high

  5. Influence of samarium doping on electronic and magneto-transport properties of La{sub 0.9−x}Sm{sub x}Sr{sub 0.1}MnO{sub 3} (0.1≤x≤0.5) nanoparticles

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Das, Proloy T., E-mail: dasproloy@phy.iitkgp.ernet.in; Nath, Tapan Kumar; Gupta, Kajal

    2014-04-24

    We report detailed field dependent electronic- (ρ-T) and magneto- transport (MR-H) studies of La{sub 1−x}Sm{sub x}Sr{sub 0.1}MnO{sub 3} (0.1≤x≤0.5) nanoparticles. Doping induced disorder at La site is observed in field dependent ρ-T measurements of the sample. At low doping side, nice metal to insulator transition (MIT) peak appears in ρ-T data whereas with increasing of Sm{sup +3} contents, metallic behavior is suppressed under the insulating background although a weak signature of MIT is found. Anomalous resistive nature of the samples with increasing of x can be explained in such a way that doping at nonmagnetic La site with magnetic Sm+3more » ion induces an extra magnetic coupling in the system which changes the long range ferromagnetic ordering to spin glass/cluster glass state in antiferromagnetic background. The field dependent magneto resistance (MR) mechanism at different temperatures is investigated using spin polarized tunneling model of conduction electrons between two adjacent grains at the grain boundaries. For the sample of x=0.5, maximum 83 % change in MR is found at 8 T near MIT which leads the colossal magneto resistance effect.« less

  6. Tuning charge transfer in the LaTiO3/RO/LaNiO3 (R = rare-earth) superlattices by the rare-earth oxides interfaces from a first-principles calculation

    NASA Astrophysics Data System (ADS)

    Yao, Fen; Zhang, Lifang; Meng, Junling; Liu, Xiaojuan; Zhang, Xiong; Zhang, Wenwen; Meng, Jian; Zhang, Hongjie

    2018-03-01

    We investigate the internal charge transfer at the isopolar interfaces in LaTiO3/RO/LaNiO3 (R = La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu) superlattices by means of density functional theory calculations. The charge transfer from Ti sites to Ni sites in all superlattices is induced by the electronegativity difference between the elements Ti and Ni, and the lanthanide oxides interfaces can modulate the amount of charge transfer. Comparison of the perovskite heterostructures with the different rare-earth interfaces shows that increasing the deviations of bond angles from 180.0° and the oxygen motions near the interfaces enhance charge transfer. The 4f electrons themselves of rare-earth elements have faint influences on charge transfer. In addition, the reasons why our calculated 4f states of Sm and Tm elements disagree with the experimental systems have been provided. It is hoped that all the calculated results could be used to design new functional nanoelectronic devices in perovskite oxides.

  7. Antiferromagnetic defect structure in LaNi O 3 – δ single crystals

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Wang, Bi -Xia; Rosenkranz, Stephan; Rui, X.

    Here, the origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, RNiO 3 (where R is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of LaNiO 3, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced LaNiO 3–δ crystals, wemore » show that both antiferromagnetic and ferromagnetic phases with a Néel temperature of ~152 K and a Curie temperature of ~225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of LaNiO 3–δ single crystals; accordingly, the implications of our results for putative oxygen-stoichiometric LaNiO 3 are discussed.« less

  8. Antiferromagnetic defect structure in LaNi O 3 – δ single crystals

    DOE PAGES

    Wang, Bi -Xia; Rosenkranz, Stephan; Rui, X.; ...

    2018-06-12

    Here, the origins of the metal-insulator and magnetic transitions exhibited by perovskite rare-earth nickelates, RNiO 3 (where R is a rare-earth element), remain open issues, with charge disproportionation, magnetic interactions, and lattice response across multiple length scales being among the many possible origins. Recently, growth of single crystals of LaNiO 3, which is the only member of these compounds that remains metallic in its ground state, has been reported, opening a new chapter in the investigation of the perovskite nickelates. Here, using a combination of magnetometry, heat capacity, and neutron scattering on as-grown and purposely reduced LaNiO 3–δ crystals, wemore » show that both antiferromagnetic and ferromagnetic phases with a Néel temperature of ~152 K and a Curie temperature of ~225 K can be induced by reduction of the oxygen content. Transmission electron microscopy shows that these phases are characterized by ordered oxygen vacancy defect structures that exist as dilute secondary phases in as-grown crystals despite growth in partial oxygen pressures up to at least 130 bar. The demonstration of antiferromagnetism resulting from oxygen vacancy ordered structures implies that stoichiometry must be explicitly considered when interpreting the bulk properties of LaNiO 3–δ single crystals; accordingly, the implications of our results for putative oxygen-stoichiometric LaNiO 3 are discussed.« less

  9. Growth and Transport Studies of LaTiO3 / KTaO3 Heterostructures

    NASA Astrophysics Data System (ADS)

    Zou, K.; Walker, F. J.; Ahn, C. H.

    2014-03-01

    Perovskite oxide heterostructures provide a rich platform for exploring emergent electronic properties, such as 2D electron gases (2DEGs) at interfaces. In this talk, we present results on the growth of LaTiO3 / KTaO3 heterostructures by molecular beam epitaxy and subsequent measurements of transport properties. Although both oxide materials are insulating in the bulk, metallic conduction is observed from T = 2 - 300 K. We achieve a room temperature carrier mobility of ~ 25 cm2 /Vs at a carrier density of ~ 1014 /cm2. By comparison, 2DEGs in LaTiO3 / SrTiO3 and LaAlO3 / SrTiO3 have lower carrier mobility, but the same carrier density. We attribute some of the increase in mobility to the smaller band effective mass of the Ta 4d electrons compared to the Ti 3d electrons.

  10. Probing the electronic and defect structure of perovskite superconductors

    NASA Astrophysics Data System (ADS)

    Fluss, M. J.; Wachs, A. L.; Turchi, P. E. A.; Howell, R. H.; Jean, Y. C.; Kyle, J.; Nakanishi, H.; Chu, C. W.; Meng, R. L.; Hor, H. P.

    1988-02-01

    Positrons, either localized or delocalized, in the perovskite superconductors are sensitive to changes in electron density accompanying the normal-to-superconducting transition. We have been using this probe in our laboratory to study the nature of this new phenomena. Our work to date, which is briefly reviewed here, has consisted of a series of lifetime studies on La(sub 1.85)Sr(sub 0.15)CuO4 and YBa2Cu3O(sub 7-d) superconducting samples, the determination of the positron wave function in the perfect crystal, and a direct measurement of the electron momentum density in single crystal La2CuO4. Several important observations have resulted from this early work: the similar response of the positron annihilation lifetime to superconductivity in both La(sub 1.85)Sr(sub 0.15)CuO4 and YBa2Cu3O7, and a quantitative description of the electronic structure for La(sub 1.85)Sr(sub 0.15)CuO4 in terms of a linear combination of atomic orbital-molecular orbital (LCAO-MO) model.

  11. Two-Photon Absorption in Organometallic Bromide Perovskites.

    PubMed

    Walters, Grant; Sutherland, Brandon R; Hoogland, Sjoerd; Shi, Dong; Comin, Riccardo; Sellan, Daniel P; Bakr, Osman M; Sargent, Edward H

    2015-09-22

    Organometallic trihalide perovskites are solution-processed semiconductors that have made great strides in third-generation thin film light-harvesting and light-emitting optoelectronic devices. Recently, it has been demonstrated that large, high-purity single crystals of these perovskites can be synthesized from the solution phase. These crystals' large dimensions, clean bandgap, and solid-state order have provided us with a suitable medium to observe and quantify two-photon absorption in perovskites. When CH3NH3PbBr3 single crystals are pumped with intense 800 nm light, we observe band-to-band photoluminescence at 572 nm, indicative of two-photon absorption. We report the nonlinear absorption coefficient of CH3NH3PbBr3 perovskites to be 8.6 cm GW(-1) at 800 nm, comparable to epitaxial single-crystal semiconductors of similar bandgap. We have leveraged this nonlinear process to electrically autocorrelate a 100 fs pulsed laser using a two-photon perovskite photodetector. This work demonstrates the viability of organometallic trihalide perovskites as a convenient and low-cost nonlinear absorber for applications in ultrafast photonics.

  12. Structural and magnetic study of La0.7Sr0.3MnO3 nanoparticles and AC magnetic heating characteristics for hyperthermia applications

    NASA Astrophysics Data System (ADS)

    Manh, D. H.; Phong, P. T.; Nam, P. H.; Tung, D. K.; Phuc, N. X.; Lee, In-Ja

    We investigated structural and magnetic properties and alternating current magnetic heating characteristics of La0.7Sr0.3MnO3 nanoparticles with respect to the possible application for magnetic hyperthermia treatments. Using Rietveld Profile refinement of powder X-ray diffraction data, the hexagonal structure has been observed. The particle sizes varied from 20 to 50 nm as the annealing temperature increases from 700 to 900 °C. The hysteresis loop is not observed and the good fit of Langevin function with magnetization data reveals the superparamagnetic nature at room temperature for all samples. Characteristic magnetic parameters of the particles including saturation magnetization in the temperature range 10-300 K, an effective anisotropy constant and a magnetocrystalline anisotropy constant have been determined. The Specific Absorption Rate for 15 mg/mL sample concentration was measured in alternating magnetic fields of 50-80 Oe at a fixed frequency of 236 kHz. In addition, the intrinsic loss power (ILP) has been calculated from SAR values. It is believed that La0.7Sr0.3MnO3 nanoparticles with a high ILP will be useful for the in situ hyperthermia treatment of cancer.

  13. Conducting Layered Organic-inorganic Halides Containing <110>-Oriented Perovskite Sheets.

    PubMed

    Mitzi, D B; Wang, S; Feild, C A; Chess, C A; Guloy, A M

    1995-03-10

    Single crystals of the layered organic-inorganic perovskites, [NH(2)C(I=NH(2)](2)(CH(3)NH(3))m SnmI3m+2, were prepared by an aqueous solution growth technique. In contrast to the recently discovered family, (C(4)H(9)NH(3))(2)(CH(3)NH(3))n-1SnnI3n+1, which consists of (100)-terminated perovskite layers, structure determination reveals an unusual structural class with sets of m <110>-oriented CH(3)NH(3)SnI(3) perovskite sheets separated by iodoformamidinium cations. Whereas the m = 2 compound is semiconducting with a band gap of 0.33 +/- 0.05 electron volt, increasing m leads to more metallic character. The ability to control perovskite sheet orientation through the choice of organic cation demonstrates the flexibility provided by organic-inorganic perovskites and adds an important handle for tailoring and understanding lower dimensional transport in layered perovskites.

  14. Thermoelectric properties of the electron-doped perovskites Sr1-xCaxTi1-yNbyO3

    NASA Astrophysics Data System (ADS)

    Fukuyado, J.; Narikiyo, K.; Akaki, M.; Kuwahara, H.; Okuda, T.

    2012-02-01

    We have investigated thermoelectric (TE) properties for single crystals of perovskites Sr1-xCaxTi1-yNbyO3 for 0 ⩽ x ⩽ 0.4 and 0 ⩽ y ⩽ 0.03 below room temperature (RT). We found that SrTi0.99Nb0.01O3 shows a large power factor at low temperature (PF=50 μW/K2 cm at 100 K ˜ 90 μW/K2 cm at 50 K) and the largest dimensionless TE figure-of-merit below 40 K (ZT ˜ 0.07) among the ever-reported materials. Such a large low-temperature TE response around a carrier concentration of 1020 cm-3 is due to a distinct electron-phonon interaction, which could relate to the superconducting state. We also found that the Ca2+ substitution for Sr2+ increases ZT at 300 K for Sr1-xCaxTi0.97Nb0.03O3 from 0.08 to 0.105. The enhancement of ZT around RT originates both in a large reduction of a thermal conductivity due to an introduced randomness into the crystal structure and in an unexpected enhancement of a Seebeck coefficient.

  15. Efficient Sky-Blue Perovskite Light-Emitting Devices Based on Ethylammonium Bromide Induced Layered Perovskites.

    PubMed

    Wang, Qi; Ren, Jie; Peng, Xue-Feng; Ji, Xia-Xia; Yang, Xiao-Hui

    2017-09-06

    Low-dimensional organometallic halide perovskites are actively studied for the light-emitting applications due to their properties such as solution processability, high luminescence quantum yield, large exciton binding energy, and tunable band gap. Introduction of large-group ammonium halides not only serves as a convenient and versatile method to obtain layered perovskites but also allows the exploitation of the energy-funneling process to achieve a high-efficiency light emission. Herein, we investigate the influence of the addition of ethylammonium bromide on the morphology, crystallite structure, and optical properties of the resultant perovskite materials and report that the phase transition from bulk to layered perovskite occurs in the presence of excess ethylammonium bromide. On the basis of this strategy, we report green perovskite light-emitting devices with the maximum external quantum efficiency of ca. 3% and power efficiency of 9.3 lm/W. Notably, blue layered perovskite light-emitting devices with the Commission Internationale de I'Eclairage coordinates of (0.16, 0.23) exhibit the maximum external quantum efficiency of 2.6% and power efficiency of 1 lm/W at 100 cd/m 2 , representing a large improvement over the previously reported analogous devices.

  16. One-Year stable perovskite solar cells by 2D/3D interface engineering

    NASA Astrophysics Data System (ADS)

    Grancini, G.; Roldán-Carmona, C.; Zimmermann, I.; Mosconi, E.; Lee, X.; Martineau, D.; Narbey, S.; Oswald, F.; de Angelis, F.; Graetzel, M.; Nazeeruddin, Mohammad Khaja

    2017-06-01

    Despite the impressive photovoltaic performances with power conversion efficiency beyond 22%, perovskite solar cells are poorly stable under operation, failing by far the market requirements. Various technological approaches have been proposed to overcome the instability problem, which, while delivering appreciable incremental improvements, are still far from a market-proof solution. Here we show one-year stable perovskite devices by engineering an ultra-stable 2D/3D (HOOC(CH2)4NH3)2PbI4/CH3NH3PbI3 perovskite junction. The 2D/3D forms an exceptional gradually-organized multi-dimensional interface that yields up to 12.9% efficiency in a carbon-based architecture, and 14.6% in standard mesoporous solar cells. To demonstrate the up-scale potential of our technology, we fabricate 10 × 10 cm2 solar modules by a fully printable industrial-scale process, delivering 11.2% efficiency stable for >10,000 h with zero loss in performances measured under controlled standard conditions. This innovative stable and low-cost architecture will enable the timely commercialization of perovskite solar cells.

  17. One-Year stable perovskite solar cells by 2D/3D interface engineering

    PubMed Central

    Grancini, G.; Roldán-Carmona, C.; Zimmermann, I.; Mosconi, E.; Lee, X.; Martineau, D.; Narbey, S.; Oswald, F.; De Angelis, F.; Graetzel, M.; Nazeeruddin, Mohammad Khaja

    2017-01-01

    Despite the impressive photovoltaic performances with power conversion efficiency beyond 22%, perovskite solar cells are poorly stable under operation, failing by far the market requirements. Various technological approaches have been proposed to overcome the instability problem, which, while delivering appreciable incremental improvements, are still far from a market-proof solution. Here we show one-year stable perovskite devices by engineering an ultra-stable 2D/3D (HOOC(CH2)4NH3)2PbI4/CH3NH3PbI3 perovskite junction. The 2D/3D forms an exceptional gradually-organized multi-dimensional interface that yields up to 12.9% efficiency in a carbon-based architecture, and 14.6% in standard mesoporous solar cells. To demonstrate the up-scale potential of our technology, we fabricate 10 × 10 cm2 solar modules by a fully printable industrial-scale process, delivering 11.2% efficiency stable for >10,000 h with zero loss in performances measured under controlled standard conditions. This innovative stable and low-cost architecture will enable the timely commercialization of perovskite solar cells. PMID:28569749

  18. One-Year stable perovskite solar cells by 2D/3D interface engineering.

    PubMed

    Grancini, G; Roldán-Carmona, C; Zimmermann, I; Mosconi, E; Lee, X; Martineau, D; Narbey, S; Oswald, F; De Angelis, F; Graetzel, M; Nazeeruddin, Mohammad Khaja

    2017-06-01

    Despite the impressive photovoltaic performances with power conversion efficiency beyond 22%, perovskite solar cells are poorly stable under operation, failing by far the market requirements. Various technological approaches have been proposed to overcome the instability problem, which, while delivering appreciable incremental improvements, are still far from a market-proof solution. Here we show one-year stable perovskite devices by engineering an ultra-stable 2D/3D (HOOC(CH 2 ) 4 NH 3 ) 2 PbI 4 /CH 3 NH 3 PbI 3 perovskite junction. The 2D/3D forms an exceptional gradually-organized multi-dimensional interface that yields up to 12.9% efficiency in a carbon-based architecture, and 14.6% in standard mesoporous solar cells. To demonstrate the up-scale potential of our technology, we fabricate 10 × 10 cm 2 solar modules by a fully printable industrial-scale process, delivering 11.2% efficiency stable for >10,000 h with zero loss in performances measured under controlled standard conditions. This innovative stable and low-cost architecture will enable the timely commercialization of perovskite solar cells.

  19. Enhanced Crystalline Phase Purity of CH3NH3PbI3-xClx Film for High-Efficiency Hysteresis-Free Perovskite Solar Cells.

    PubMed

    Yang, Yingguo; Feng, Shanglei; Xu, Weidong; Li, Meng; Li, Li; Zhang, Xingmin; Ji, Gengwu; Zhang, Xiaonan; Wang, Zhaokui; Xiong, Yimin; Cao, Liang; Sun, Baoquan; Gao, Xingyu

    2017-07-12

    Despite rapid successful developments toward promising perovskite solar cells (PSCs) efficiency, they often suffer significant hysteresis effects. Using synchrotron-based grazing incidence X-ray diffraction (GIXRD) with different probing depths by varying the incident angle, we found that the perovskite films consist of dual phases with a parent phase dominant in the interior and a child phase with a smaller (110) interplanar space (d (110) ) after rapid thermal annealing (RTA), which is a widely used post treatment to improve the crystallization of solution-processed perovskite films for high-performance planar PSCs. In particular, the child phase composition gradually increases with decreasing depth till it becomes the majority on the surface, which might be one of the key factors related to hysteresis in fabricated PSCs. We further improve the crystalline phase purity of the solution-processed CH 3 NH 3 PbI 3-x Cl x perovskite film (referred as g-perovskite) by using a facile gradient thermal annealing (GTA), which shows a uniformly distributed phase structure in pinhole-free morphology with less undercoordinated Pb and I ions determined by synchrotron-based GIXRD, grazing incidence small-angle X-ray scattering, scanning electron microscopy, and X-ray photoelectron spectroscopy. Regardless of device structures (conventional and inverted types), the planar heterojunction PSCs employing CH 3 NH 3 PbI 3-x Cl x g-perovskite films exhibit negligible hysteresis with a champion power conversion efficiency of 17.04% for TiO 2 -based conventional planar PSCs and 14.83% for poly(3,4-ethylenedioxythiophene:poly(styrenesulfonate) (PEDOT:PSS)-based inverted planar PSCs. Our results indicate that the crystalline phase purity in CH 3 NH 3 PbI 3-x Cl x perovskite film, especially in the surface region, plays a crucial role in determining the hysteresis effect and device performance.

  20. Luminescence and magnetic properties of novel nanoparticle-sheathed 3D Micro-Architectures of Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) for bifunctional application

    NASA Astrophysics Data System (ADS)

    Krishnan, Rajagopalan; Thirumalai, Jagannathan; Kathiravan, Arunkumar

    2015-01-01

    For the first time, we report the successful synthesis of novel nanoparticle-sheathed bipyramid-like and almond-like Fe0.5R0.5(MoO4)1.5:Ln3+ (R = Gd3+, La3+), (Ln = Eu, Tb, Dy) 3D hierarchical microstructures through a simple disodium ethylenediaminetetraacetic acid (Na2EDTA) facilitated hydrothermal method. Interestingly, time-dependent experiments confirm that the assembly-disassembly process is responsible for the formation of self-aggregated 3D architectures via Ostwald ripening phenomena. The resultant products are characterized by x-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), photoluminescence (PL), and magnetic measurements. The growth and formation mechanisms of the self-assembled 3D micro structures are discussed in detail. To confirm the presence of all the elements in the microstructure, the energy loss induced by the K, L shell electron ionization is observed in order to map the Fe, Gd, Mo, O, and Eu components. The photo luminescence properties of Fe0.5R0.5(MoO4)1.5 doped with Eu3+, Tb3+, Dy3+ are investigated. The room temperature and low temperature magnetic properties suggest that the interaction between the local-fields introduced by the magnetic Fe3+ ions and the R3+ (La, Gd) ions in the dodecahedral sites determine the magnetism in Fe0.5R0.5(MoO4)1.5:Eu3+. This work provides a new approach to synthesizing the novel Fe0.5R0.5(MoO4)1.5:Ln3+ for bi-functional magnetic and luminescence applications.

  1. Adjusting the introduction of cations (MA, Cs or Rb) to obtain highly efficient and stable perovskite solar cells based on (FAPbI3)0.9(FAPbBr3)0.1.

    PubMed

    Liu, Guozhen; Zheng, Haiying; Zhu, Liangzheng; Alsaedi, Ahmed; Hayat, Tasawar; Pan, Xu; Mo, Li'e; Dai, Songyuan

    2018-05-29

    Although power conversion efficiency (PCE) of perovskite solar cells (PSCs) has increased to 22.7%, the instability when exposed to moisture and heat hindered their further practical development. In this study, to gain highly efficient and stable perovskite component, MA, Cs and Rb cations are respectively introduced into the (FAPbI3)0.9(FAPbBr3)0.1 film which is rarely used due to the poor photovoltaic performance. The effects of different contents of MA, Cs or Rb cations on the performance of (FAPbI3)0.9(FAPbBr3)0.1 films and devices are systematically studied. The results show that the devices with Cs cation exhibit markedly improved photovoltaic performance and stability, attributing to the obviously enhanced quality of films and their intrinsic stability. The (FAPbI3)0.9(FAPbBr3)0.1 devices with 10% Cs obtain a PCE as high as 19.94%. More importantly, the unsealed devices retain about 80% and 90% of the initial PCE at 85 °C after 260 h and under 45±5% relative humidity (RH) after 1440 h, respectively, which are more brilliant than that with 15% MA and 5% Rb under the same condition. It indicates that a highly efficient and stable perovskite component has been achieved and the PSCs based on this component will expect to promote the further development. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Enhanced photovoltaic properties of perovskite solar cells by TiO2 homogeneous hybrid structure.

    PubMed

    Su, Pengyu; Fu, Wuyou; Yao, Huizhen; Liu, Li; Ding, Dong; Feng, Fei; Feng, Shuang; Xue, Yebin; Liu, Xizhe; Yang, Haibin

    2017-10-01

    In this paper, we fabricated a TiO 2 homogeneous hybrid structure for application in perovskite solar cells (PSCs) under ambient conditions. Under the standard air mass 1.5 global (AM 1.5G) illumination, PSCs based on homogeneous hybrid structure present a maximum power conversion efficiency of 5.39% which is higher than that of pure TiO 2 nanosheets. The enhanced properties can be explained by the better contact of TiO 2 nanosheets/nanoparticles with CH 3 NH 3 PbI 3 and fewer pinholes in electron transport materials. The advent of such unique structure opens up new avenues for the future development of high-efficiency photovoltaic cells.

  3. Alkali Metal Doping for Improved CH3NH3PbI3 Perovskite Solar Cells.

    PubMed

    Zhao, Wangen; Yao, Zhun; Yu, Fengyang; Yang, Dong; Liu, Shengzhong Frank

    2018-02-01

    Organic-inorganic hybrid halide perovskites are proven to be a promising semiconductor material as the absorber layer of solar cells. However, the perovskite films always suffer from nonuniform coverage or high trap state density due to the polycrystalline characteristics, which degrade the photoelectric properties of thin films. Herein, the alkali metal ions which are stable against oxidation and reduction are used in the perovskite precursor solution to induce the process of crystallization and nucleation, then affect the properties of the perovskite film. It is found that the addition of the alkali metal ions clearly improves the quality of perovskite film: enlarges the grain sizes, reduces the defect state density, passivates the grain boundaries, increases the built-in potential ( V bi ), resulting to the enhancement in the power conversion efficiency of perovskite thin film solar cell.

  4. Low energy spin dynamics of rare-earth orthoferrites YFeO3 and LaFeO3

    NASA Astrophysics Data System (ADS)

    Park, Kisoo; Sim, Hasung; Leiner, Jonathan; Yoshida, Yoshiyuki; Eisaki, Hiroshi; Yano, Shinichiro; Gardner, Jason; Park, Je-Geun

    YFeO3 and LaFeO3\\ are members of the rare-earth orthoferrites (RFeO3) family with Pbnm space group. With the strong superexchange interaction between Fe3 + ions, both compounds exhibit the room temperature antiferromagnetic order (TN >600 K) with a slight spin canting. Here we report low-energy magnetic excitation of YFeO3 and LaFeO3 using inelastic neutron scattering measurements, showing evidence of magnon mode splitting and a spin anisotropy gap at the zone center. Spin wave calculations with the spin Hamiltonian including both Dzyaloshinsky-Moriya interaction and single-ion anisotropy accounts for the observed features well. Our results offer insight into the underlying physics of other RFeO3\\ with magnetic rare-earth ions or related Fe3+-based multiferroic perovskites such as BiFeO3. The work at the IBS CCES (South Korea) was supported by the research program of the Institute for Basic Science (IBS-R009-G1).

  5. Two-Dimensional CH3NH3PbI3 Perovskite Nanosheets for Ultrafast Pulsed Fiber Lasers.

    PubMed

    Li, Pengfei; Chen, Yao; Yang, Tieshan; Wang, Ziyu; Lin, Han; Xu, Yanhua; Li, Lei; Mu, Haoran; Shivananju, Bannur Nanjunda; Zhang, Yupeng; Zhang, Qinglin; Pan, Anlian; Li, Shaojuan; Tang, Dingyuan; Jia, Baohua; Zhang, Han; Bao, Qiaoliang

    2017-04-12

    Even though the nonlinear optical effects of solution processed organic-inorganic perovskite films have been studied, the nonlinear optical properties in two-dimensional (2D) perovskites, especially their applications for ultrafast photonics, are largely unexplored. In comparison to bulk perovskite films, 2D perovskite nanosheets with small thicknesses of a few unit cells are more suitable for investigating the intrinsic nonlinear optical properties because bulk recombination of photocarriers and the nonlinear scattering are relatively small. In this research, we systematically investigated the nonlinear optical properties of 2D perovskite nanosheets derived from a combined solution process and vapor phase conversion method. It was found that 2D perovskite nanosheets have stronger saturable absorption properties with large modulation depth and very low saturation intensity compared with those of bulk perovskite films. Using an all dry transfer method, we constructed a new type of saturable absorber device based on single piece 2D perovskite nanosheet. Stable soliton state mode-locking was achieved, and ultrafast picosecond pulses were generated at 1064 nm. This work is likely to pave the way for ultrafast photonic and optoelectronic applications based on 2D perovskites.

  6. The thermal expansion of ScAlO3 — A silicate perovskite analogue

    NASA Astrophysics Data System (ADS)

    Hill, R. J.; Jackson, Ian

    1990-01-01

    The crystal structure of ScAlO3 has been refined at temperatures up to 1100° C on the basis of x-ray powder diffraction data. The thermal expansion is adequately described by a Grüneisen-Debye model with the elastic Debye temperature and an effective Grüneisen parameter of 1.6. The volumetric thermal expansion of 3.0% between 10 and 1100° C, corresponding to a mean thermal expansion coefficient of 2.7 × 10-5 K-1, is entirely attributable to the expansion of the AlO6 octahedra. The interoctahedral angles, though not fixed by symmetry, do not vary significantly with temperature —indicating that the expansivities of the constituent AlO6 and distorted ScO8 polyhedra are well matched. Similar considerations of polyhedral expansivity suggest thermal expansion coefficients of ˜2 × 10-5K-1 for cubic CaSiO3 perovskite and a value between 2 × 10-5 K-1 and 4 × 10-5 K-1 for MgSiO3 perovskite. The lower value is consistent with the reconnaissance measurements for Mg0.9Fe0.1SiO3 (Knittle et al. 1986) below 350° C, with low-temperature measurements of single-crystal MgSiO3 (Ross and Hazen 1989), and with the results of some recent calculations. The markedly greater expansivity ˜4 × 10-5 K-1 measured at higher temperatures (350 570° C) by Knittle et al. is inconsistent with the simple Grüneisen-Debye quasiharmonic model and may reflect the marginal metastability of the orthorhombic perovskite phase. Under these circumstances, extrapolation of the measured expansivity is hazardous and may result in the under-estimation of lower mantle densities and the drawing of inappropriate inferences concerning the need for chemical stratification of the Earth's mantle.

  7. Alloying n-Butylamine into CsPbBr3 to Give a Two-Dimensional Bilayered Perovskite Ferroelectric Material.

    PubMed

    Wu, Zhenyue; Ji, Chengmin; Li, Lina; Kong, Jintao; Sun, Zhihua; Zhao, Sangen; Wang, Sasa; Hong, Maochun; Luo, Junhua

    2018-05-11

    Cesium-lead halide perovskites (e.g. CsPbBr 3 ) have gained attention because of their rich physical properties, but their bulk ferroelectricity remains unexplored. Herein, by alloying flexible organic cations into the cubic CsPbBr 3 , we design the first cesium-based two-dimensional (2D) perovskite ferroelectric material with both inorganic alkali metal and organic cations, (C 4 H 9 NH 3 ) 2 CsPb 2 Br 7 (1). Strikingly, 1 shows a high Curie temperature (T c =412 K) above that of BaTiO 3 (ca. 393 K) and notable spontaneous polarization (ca. 4.2 μC cm -2 ), triggered by not only the ordering of organic cations but also atomic displacement of inorganic Cs + ions. To our knowledge, such a 2D bilayered Cs + -based metal-halide perovskite ferroelectric material with inorganic and organic cations is unprecedented. 1 also shows photoelectric semiconducting behavior with large "on/off" ratios of photoconductivity (>10 3 ). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Enhanced photovoltaic performance of CH3NH3PbBrXI3-X-based perovskite solar cells via anti-solvent extraction

    NASA Astrophysics Data System (ADS)

    Jiang, Zhaoyi; Zhang, Weijia; Lu, Chaoqun; Ma, Denghao; Liu, Haixu; Yu, Wei; Zhang, Yu; Ma, Qiang; Zhang, Yulong

    2018-06-01

    In this paper, the two-step sequential deposition method was used to prepare the CH3NH3PbBrXI3-X films by introducing CH3NH3Br in the precursors. The surface morphology of the PbI2 films was controlled by anti-solvent extraction (ASE) to improve the microstructure and photo-physical properties of the perovskite films. It was noteworthy that, compared to the compact PbI2 films, the porous PbI2 films facilitated the growth of crystals and bromine incorporation in films, and the prepared perovskite films exhibited enlarged grain size, increased light absorption, enhanced Br incorporation and prolonged carrier lifetime, which resulted in excellent photo-electrical properties of the CH3NH3PbBrXI3-X films. With porous PbI2 templates, the inverted planar perovskite solar cells based on films with appropriate Br incorporation (CH3NH3Br/CH3NH3I mole ratio = 3/7) showed a photovoltaic conversion efficiency (PCE) of 14.9%, and the stability of the devices in air was elevated. Consequently, the high-quality CH3NH3PbBrXI3-X films can be obtained with porous PbI2 templates for improving the performance of the perovskite solar cells.

  9. Band Gap Tuning of CH₃NH₃Pb(Br(1-x)Clx)₃ Hybrid Perovskite for Blue Electroluminescence.

    PubMed

    Kumawat, Naresh K; Dey, Amrita; Kumar, Aravindh; Gopinathan, Sreelekha P; Narasimhan, K L; Kabra, Dinesh

    2015-06-24

    We report on the structural, morphological and optical properties of AB(Br(1-x)Cl(x))3 (where, A = CH3NH3(+), B = Pb(2+) and x = 0 to 1) perovskite semiconductor and their successful demonstration in green and blue emissive perovskite light emitting diodes at room temperature. The bandgap of perovskite thin film is tuned from 2.42 to 3.16 eV. The onset of optical absorption is dominated by excitonic effects. The coulomb field of the exciton influences the absorption at the band edge. Hence, it is necessary to explicitly account for the enhancement of the absorption through the Sommerfield factor. This enables us to correctly extract the exciton binding energy and the electronic bandgap. We also show that the lattice constant varies linearly with the fractional chlorine content satisfying Vegards law.

  10. Structural manipulation and tailoring of dielectric properties in SrTi1−xFexTaxO3 perovskites: Design of new lead free relaxors

    PubMed Central

    Shukla, R.; Patwe, S. J.; Deshpande, S. K.; Achary, S. N.; Krishna, P. S. R.; Shinde, A. B.; Gopalakrishnan, J.; Tyagi, A. K.

    2016-01-01

    We report composition dependent structure evolution from SrTiO3 to SrFe0.5Ta0.5O3 by powder X-ray and neutron diffraction studies of SrTi1−2xFexTaxO3 (0.00 ≤ × ≤ 0.50) compositions. Structural studies reveal cubic (Pm3m) perovskite-type structure of the parent SrTiO3 for x up to 0.075 and cation disordered orthorhombic (Pbnm) perovskite-type structure for x ≥ 0.33. A biphasic region consisting of a mixture of cubic and orthorhombic structures is found in the range for 0.10 ≤ × ≤ 0.25. Dielectric studies reveal transformation from a normal dielectric to relaxor like properties with increasing Fe3+ and Ta5+ concentration. Dielectric response is maximum at x = 0.33 in the series. The results establish a protocol for designing new lead-free relaxor materials based on the co-substitution of Fe3+ and Ta5+ for Ti4+ in SrTiO3. A complex interplay of strain effects arising from distribution of cations at the octahedral sites of the perovskite structure controls the dielectric properties. PMID:27514668

  11. Polyvinyl alcohol: an efficient fuel for synthesis of superparamagnetic LSMO nanoparticles for biomedical application.

    PubMed

    Thorat, N D; Shinde, K P; Pawar, S H; Barick, K C; Betty, C A; Ningthoujam, R S

    2012-03-14

    La(0.7)Sr(0.3)MnO(3) (LSMO) nanoparticles have been prepared using glycine and polyvinyl alcohol (PVA) as fuels. Their crystal structure, particle morphology and compositions are characterized using X-ray diffraction, transmission electron microscopy, field-emission electron microscopy and energy dispersive analysis of X-ray. They show a pseudo-cubic perovskite structure. The spherical particle sizes of 30 and 20 nm have been obtained from samples prepared by glycine and PVA respectively. The field cooled (FC) and zero field cooled (ZFC) magnetizations have been recorded from 5 to 375 K at 500 Oe and superparamagnetic blocking temperatures (T(B)) of 75 and 30 K are obtained from samples prepared by glycine and PVA respectively. Particle size distribution is observed from dynamic light scattering measurements. Dispersion stability of the particles in water is studied by measuring the Zeta potential with varying the pH of the medium from 1 to 12. Under induction heating experiments, a hyperthermia temperature (42-43 °C) is achieved by both the samples (3-6 mg mL(-1)) at magnetic fields of 167-335 Oe and at a frequency of 267 kHz. The bio-compatibility of the LSMO nanoparticles is studied on the L929 and HeLa cell lines by MTT assay for up to 48 h. The present work reveals the importance of synthesis technique and fuel choice on structural, morphological, magnetic, hyperthermia and biocompatible properties of LSMO and predicts the suitability for biomedical applications.

  12. Investigation on the grain boundaries electrical characteristics of perovskite lithium ion conductors by derivative of tanδ approach

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mariappan, C.R., E-mail: crmari2005@yahoo.com; Bohnke, O.

    2016-02-15

    Graphical abstract: Cole–Cole impedance spectra for Li{sub 0.30}La{sub 0.56}TiO{sub 3}-SSR and Li{sub 0.30}La{sub 0.56}TiO{sub 3}-PC at 310 K and for Li{sub 0.30}Ca{sub 0.35}TaO{sub 3}-SSR and Li{sub 0.30}Ca{sub 0.35}TaO{sub 3}-PC at 473 K. - Highlights: • Li{sub 0.30}La{sub 0.56}TiO{sub 3} & Li{sub 0.30}Ca{sub 0.35}TaO{sub 3} perovskites made by Pechini polymerization route. • Relaxation processes of perovskites are analyzed by derivative of tanδ (α{sub θ}) method. • α{sub θ} (ν) graph resolves the two closer relaxation processes at grain boundary region. • SEM/TEM study supports the resolving ability of α{sub θ} vs log (ν) method. • χ{sup 2} improves from ∼10{sup −3}more » to ∼10{sup −5} for equivalent circuit fitting based on α{sub θ} peaks. - Abstract: We report on the grain boundaries electrical relaxation processes of Li{sub 0.30}La{sub 0.56}TiO{sub 3} and Li{sub 0.30}Ca{sub 0.35}TaO{sub 3} perovskites by derivative of the tanδ (α{sub θ}) method. The α{sub θ} vs log(ν) representation is clearly resolved the two grain boundary relaxation processes at grain boundary region for perovskites synthesized via the modified Pechini-type polymerization complex route in comparison to perovskites obtained by solid state reaction method. The resolving ability of α{sub θ} vs log(ν) representation is much higher than other complex impedance spectroscopic representations. The goodness of the fitting χ{sup 2} is improved from ∼10{sup −3} to ∼10{sup −5} for the electrical equivalent circuit fitting based on α{sub θ} vs log(ν) peaks.« less

  13. Synergic nature of dielectric relaxation process in the layered perovskite halide salts: The case of 1,3- diammoniumpropylenetetrabromocadmate compound

    NASA Astrophysics Data System (ADS)

    Staśkiewicz, Beata

    2018-06-01

    The negative thermal expansion (NTE) property was a prototype to discuss the origin of difference between classical Debye relaxation process and the non-Debye behavior in the layered perovskite halide salt of chemical formula NH3(CH2)3NH3CdBr4. The analysis has been taken by dielectric relaxation spectroscopy measurements in almost six decades in frequency 5 × 102 ≤ f(ω) ≤ 1.2 × 108 and in the temperature range 315 ≤ T(K) ≤ 390. It was shown that the investigated sample exhibit an antiferrodistortive nature of phase transition between two orthorhombic structural modifications i.e. Pnma (phase I) and Ima2 (phase II) at Tc1(I → II) = 326 K, leading from an antiferroelectric to a paraelectric phase. The involvement of an odd number of carbon atoms in the alkylammonium chains in dielectric properties of examined sample is proved. Higher structural modifications, i.e. Ima2 (phase II) and P21/m (phase III), have shown significant deviations from a regular circle on the Cole-Cole diagram. Presented experimental observations are essentially important for the theoretical explanation of relaxation processes in analyzed organic - inorganic compound crystallizing in a perovskite-like topology and may provide new perspective on the fundamental aspect of relaxation response in "diammonium" series.

  14. The structural and magnetic investigation of ( x) BiFe0.95Co0.05O3: (1- x) La0.7Ca0.3MnO3 composites

    NASA Astrophysics Data System (ADS)

    Zhang, Hongguang; Fu, Dexiang; Wang, Yang; Xie, Liang; Li, Yongtao; Chen, Wei

    2017-12-01

    The structural and magnetic behaviors are studied in the composites ( x) BiFe0.95Co0.05O3: (1- x) La0.7Ca0.3MnO3. An influence on the lattice parameters and magnetic states of BiFe0.95Co0.05O3 (BFCO) to the La0.7Ca0.3MnO3 (LCMO) are investigated. Although the variation of the relative X-ray intensity of LCMO to BFCO with composition ( x) in XRD patterns and the randomly distributed small nanoparticle of LCMO ( 200 nm) mixed in the large nanoparticle of BFCO ( 900 nm) given by SEM images indicate an almost immiscibility of BFCO and LCMO in composites obtained by solid solution method, an obvious change of lattice parameters indicates their mutual influence on lattice structure. A detail magnetic investigation of the composites shows that the Griffiths phase is increased with increase of composition x due to the incorporation of ferromagnetism of BFCO to the paramagnetic phase of LCMO. An approximate magnetic phase diagram for the composites is established, which would be helpful for understanding the magnetic singularity of the composites with colossal magnetoresistance and multiferroics.

  15. Covalency and the metal-insulator transition in titanate and vanadate perovskites

    NASA Astrophysics Data System (ADS)

    Dang, Hung T.; Millis, Andrew J.; Marianetti, Chris A.

    2014-04-01

    A combination of density functional and dynamical mean-field theory is applied to the perovskites SrVO3, LaTiO3, and LaVO3. We show that DFT + DMFT in conjunction with the standard fully localized-limit (FLL) double-counting predicts that LaTiO3 and LaVO3 are metals even though experimentally they are correlation-driven ("Mott") insulators. In addition, the FLL double counting implies a splitting between oxygen p and transition metal d levels, which differs from experiment. Introducing into the theory an ad hoc double counting correction, which reproduces the experimentally measured insulating gap leads also to a p-d splitting consistent with experiment if the on-site interaction U is chosen in a relatively narrow range (˜6±1 eV). The results indicate that these early transition metal oxides will serve as critical test for the formulation of a general ab initio theory of correlated electron metals.

  16. A New Lead Iodide Perovskite based on Large Organic Cation for Solar Cell Application.

    PubMed

    Ma, Chunqing; Shen, Dong; Lo, Ming Fai; Lee, Chun-Sing

    2018-06-06

    Methylammonium (CH3NH3+) and formamidinium ((NH2)2CH+) based lead iodide perovskites are currently the two commonly used organic-inorganic lead iodide perovskites for solar cell application. Till now, there is still no alternative organic cations, which can produce perovskites with bandgaps spanning the visible spectrum (i.e. < 1.7 eV) for solar cell application. Here, a new perovskite using large propane-1,3-diammonium cation (n-Pr(NH3)22+) with a chemical structure of (n-Pr(NH3)2)0.5PbI3 is demonstrated. X-ray diffraction (XRD) result shows that the new perovskite exhibits a three-dimensional (3D), tetragonal phase. The bandgap of the new perovskite is ~ 1.6 eV, which is desirable for photovoltaic application. A (n-Pr(NH3)2)0.5PbI3 perovskite solar cell (PSC) yields a power conversion efficiency (PCE) of 5.1%. More importantly, this new perovskite is composed of larger hydrophobic cation that provides a better moisture resistance compared to CH3NH3PbI3 perovskite. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Perovskite Oxide Thin Film Growth, Characterization, and Stability

    NASA Astrophysics Data System (ADS)

    Izumi, Andrew

    Studies into a class of materials known as complex oxides have evoked a great deal of interest due to their unique magnetic, ferroelectric, and superconducting properties. In particular, materials with the ABO3 perovskite structure have highly tunable properties because of the high stability of the structure, which allows for large scale doping and strain. This also allows for a large selection of A and B cations and valences, which can further modify the material's electronic structure. Additionally, deposition of these materials as thin films and superlattices through techniques such as pulsed laser deposition (PLD) results in novel properties due to the reduced dimensionality of the material. The novel properties of perovskite oxide heterostructures can be traced to a several sources, including chemical intermixing, strain and defect formation, and electronic reconstruction. The correlations between microstructure and physical properties must be investigated by examining the physical and electronic structure of perovskites in order to understand this class of materials. Some perovskites can undergo phase changes due to temperature, electrical fields, and magnetic fields. In this work we investigated Nd0.5Sr 0.5MnO3 (NSMO), which undergoes a first order magnetic and electronic transition at T=158K in bulk form. Above this temperature NSMO is a ferromagnetic metal, but transitions into an antiferromagnetic insulator as the temperature is decreased. This rapid transition has interesting potential in memory devices. However, when NSMO is deposited on (001)-oriented SrTiO 3 (STO) or (001)-oriented (LaAlO3)0.3-(Sr 2AlTaO6)0.7 (LSAT) substrates, this transition is lost. It has been reported in the literature that depositing NSMO on (110)-oriented STO allows for the transition to reemerge due to the partial epitaxial growth, where the NSMO film is strained along the [001] surface axis and partially relaxed along the [11¯0] surface axis. This allows the NSMO film enough

  18. Crystal Chemistry, Magnetic and Electrical Properties of La(2-X)BaXNiO4

    DTIC Science & Technology

    1989-02-01

    alternating rock-salt, AO, and perovskite , ABe 3 , layers, with the separation between layers being almost twice the intraplanar distance between two B...t c 1.02, and it is most stable for t - 1.0. The 2 factor arises because the {110 planes of the perovskite layers are stacked alternately with the...a result of Ba 2 + substitution for La3 +.° This is easily understood with respect to the K2 NiF4 structure. The alternating perovskite and rock-salt

  19. Biosynthesis, Antimicrobial and Cytotoxic Effect of Silver Nanoparticles Using a Novel Nocardiopsis sp. MBRC-1

    PubMed Central

    Manivasagan, Panchanathan; Senthilkumar, Kalimuthu; Sivakumar, Kannan; Kim, Se-Kwon

    2013-01-01

    The biosynthesis of nanoparticles has been proposed as a cost effective environmental friendly alternative to chemical and physical methods. Microbial synthesis of nanoparticles is under exploration due to wide biomedical applications, research interest in nanotechnology and microbial biotechnology. In the present study, an ecofriendly process for the synthesis of nanoparticles using a novel Nocardiopsis sp. MBRC-1 has been attempted. We used culture supernatant of Nocardiopsis sp. MBRC-1 for the simple and cost effective green synthesis of silver nanoparticles. The reduction of silver ions occurred when silver nitrate solution was treated with the Nocardiopsis sp. MBRC-1 culture supernatant at room temperature. The nanoparticles were characterized by UV-visible, TEM, FE-SEM, EDX, FTIR, and XRD spectroscopy. The nanoparticles exhibited an absorption peak around 420 nm, a characteristic surface plasmon resonance band of silver nanoparticles. They were spherical in shape with an average particle size of 45 ± 0.15 nm. The EDX analysis showed the presence of elemental silver signal in the synthesized nanoparticles. The FTIR analysis revealed that the protein component in the form of enzyme nitrate reductase produced by the isolate in the culture supernatant may be responsible for reduction and as capping agents. The XRD spectrum showed the characteristic Bragg peaks of 1 2 3, 2 0 4, 0 4 3, 1 4 4, and 3 1 1 facets of the face centered cubic silver nanoparticles and confirms that these nanoparticles are crystalline in nature. The prepared silver nanoparticles exhibited strong antimicrobial activity against bacteria and fungi. Cytotoxicity of biosynthesized AgNPs against in vitro human cervical cancer cell line (HeLa) showed a dose-response activity. IC50 value was found to be 200 μg/mL of AgNPs against HeLa cancer cells. Further studies are needed to elucidate the toxicity and the mechanism involved with antimicrobial and anticancer activity of the synthesized Ag

  20. Biosynthesis, antimicrobial and cytotoxic effect of silver nanoparticles using a novel Nocardiopsis sp. MBRC-1.

    PubMed

    Manivasagan, Panchanathan; Venkatesan, Jayachandran; Senthilkumar, Kalimuthu; Sivakumar, Kannan; Kim, Se-Kwon

    2013-01-01

    The biosynthesis of nanoparticles has been proposed as a cost effective environmental friendly alternative to chemical and physical methods. Microbial synthesis of nanoparticles is under exploration due to wide biomedical applications, research interest in nanotechnology and microbial biotechnology. In the present study, an ecofriendly process for the synthesis of nanoparticles using a novel Nocardiopsis sp. MBRC-1 has been attempted. We used culture supernatant of Nocardiopsis sp. MBRC-1 for the simple and cost effective green synthesis of silver nanoparticles. The reduction of silver ions occurred when silver nitrate solution was treated with the Nocardiopsis sp. MBRC-1 culture supernatant at room temperature. The nanoparticles were characterized by UV-visible, TEM, FE-SEM, EDX, FTIR, and XRD spectroscopy. The nanoparticles exhibited an absorption peak around 420 nm, a characteristic surface plasmon resonance band of silver nanoparticles. They were spherical in shape with an average particle size of 45 ± 0.15 nm. The EDX analysis showed the presence of elemental silver signal in the synthesized nanoparticles. The FTIR analysis revealed that the protein component in the form of enzyme nitrate reductase produced by the isolate in the culture supernatant may be responsible for reduction and as capping agents. The XRD spectrum showed the characteristic Bragg peaks of 1 2 3, 2 0 4, 0 4 3, 1 4 4, and 3 1 1 facets of the face centered cubic silver nanoparticles and confirms that these nanoparticles are crystalline in nature. The prepared silver nanoparticles exhibited strong antimicrobial activity against bacteria and fungi. Cytotoxicity of biosynthesized AgNPs against in vitro human cervical cancer cell line (HeLa) showed a dose-response activity. IC50 value was found to be 200 μg/mL of AgNPs against HeLa cancer cells. Further studies are needed to elucidate the toxicity and the mechanism involved with antimicrobial and anticancer activity of the synthesized AgNPs as