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Sample records for perovskite molybdates ba1-xkxmoo3

  1. Vanadate, molybdate and tungstate for orthomolecular medicine.

    PubMed

    Matsumoto, J

    1994-09-01

    Recent studies indicate that oxyanions, such as vanadate (V) or vanadyl (IV), cause insulin-like effects on rats by stimulating the insulin receptor tyrosine kinase. Tungstate (VI) and molybdate (VI) show the same effects on rat adipocytes and hepatocytes. Results of uncontrolled trials on volunteers accumulated in Japan also suggest that tungstate effectively regulates diabetes mellitus without detectable side effects. Since these oxyanions naturally exist in organisms, oxyanion therapy, the oral administration of vanadate, vanadyl, molybdate, or tungstate, can be considered to be orthomolecular medicine. Therefore, these oxyanions may provide a viable alternative to chemotherapy. Many diseases in addition to diabetes mellitus might also be treated since the implication of these results is that tyrosine kinases are involved in a variety of diseases. PMID:7815975

  2. Antimony promoted bismuth cerium molybdate catalysts

    SciTech Connect

    Brazdil, J.F.; Glaeser, L.C.; Grasselli, R.K.

    1990-05-01

    This patent describes an improvement in antimony-promoted bismuth cerium molybdate whereby the tendency of the catalyst to lose efectiveness over time is significantly reduced. This patent describes new catalysts which are also useful in other oxidation-type reactions such as the oxidation of acrolein and methacrolein to produce the corresponding unsaturated aldehydes and acids and the oxydehydrogenation of various olefins such as isoamylenes to produce the corresponding diolefins such as isoprene.

  3. Study of multiphasic molybdate-based catalysts. II. Synergy effect between bismuth molybdates and mixed iron and cobalt molybdates in mild oxidation of propene

    SciTech Connect

    Millet, J.M.M.; Ponceblanc, H.; Coudurier, G.; Vedrine, J.C. ); Herrmann, J.M. )

    1993-08-01

    Results are reported concerning the synergy effect observed in the oxidation of propene to acrolein over bismuth and mixed iron and cobalt molybdates. The pure bismuth, iron, and cobalt molybdates and mixed cobalt and iron molybdates (solid solutions) have been prepared and individually tested as catalysts. Mechanical mixtures of these phases have been prepared and tested as catalysts. All the catalysts have been characterized before and after the catalytic reaction by several techniques such as ESR, XPS, EDX-STEM, TEM, XRD, and Moessbauer and UV spectroscopies. The synergy effect observed is tentatively explained as due to the deposition on the large bismuth molybdate particles of smaller mixed iron and cobalt molybdate particles with spreading of the bismuth molybdate over the latter particles. It is proposed that the Fe[sub x]Co[sub 1-x]MoO[sub 4] phase plays the role of the fast electron conducting material which enhances the electron mobility and the efficiency of the redox mechanism, the active and selective phase being the overlying bismuth molybdate compounds. 27 refs., 5 figs., 7 tabs.

  4. Acquisition and role of molybdate in Pseudomonas aeruginosa.

    PubMed

    Pederick, Victoria G; Eijkelkamp, Bart A; Ween, Miranda P; Begg, Stephanie L; Paton, James C; McDevitt, Christopher A

    2014-11-01

    In microaerophilic or anaerobic environments, Pseudomonas aeruginosa utilizes nitrate reduction for energy production, a process dependent on the availability of the oxyanionic form of molybdenum, molybdate (MoO4 (2-)). Here, we show that molybdate acquisition in P. aeruginosa occurs via a high-affinity ATP-binding cassette permease (ModABC). ModA is a cluster D-III solute binding protein capable of interacting with molybdate or tungstate oxyanions. Deletion of the modA gene reduces cellular molybdate concentrations and results in inhibition of anaerobic growth and nitrate reduction. Further, we show that conditions that permit nitrate reduction also cause inhibition of biofilm formation and an alteration in fatty acid composition of P. aeruginosa. Collectively, these data highlight the importance of molybdate for anaerobic growth of P. aeruginosa and reveal novel consequences of nitrate reduction on biofilm formation and cell membrane composition.

  5. Acquisition and Role of Molybdate in Pseudomonas aeruginosa

    PubMed Central

    Pederick, Victoria G.; Eijkelkamp, Bart A.; Ween, Miranda P.; Begg, Stephanie L.; Paton, James C.

    2014-01-01

    In microaerophilic or anaerobic environments, Pseudomonas aeruginosa utilizes nitrate reduction for energy production, a process dependent on the availability of the oxyanionic form of molybdenum, molybdate (MoO42−). Here, we show that molybdate acquisition in P. aeruginosa occurs via a high-affinity ATP-binding cassette permease (ModABC). ModA is a cluster D-III solute binding protein capable of interacting with molybdate or tungstate oxyanions. Deletion of the modA gene reduces cellular molybdate concentrations and results in inhibition of anaerobic growth and nitrate reduction. Further, we show that conditions that permit nitrate reduction also cause inhibition of biofilm formation and an alteration in fatty acid composition of P. aeruginosa. Collectively, these data highlight the importance of molybdate for anaerobic growth of P. aeruginosa and reveal novel consequences of nitrate reduction on biofilm formation and cell membrane composition. PMID:25172858

  6. Light deflection in gadolinium molybdate ferroelastic crystals

    NASA Astrophysics Data System (ADS)

    Staniorowski, Piotr; Bornarel, Jean

    2000-02-01

    The deflection of a He-Ne light beam by polydomain gadolinium molybdate (GMO) crystals has been studied with respect to incidence angle icons/Journals/Common/alpha" ALT="alpha" ALIGN="TOP"/> i on the sample at room temperature. The A and B deflected beams do not cross each other during the icons/Journals/Common/alpha" ALT="alpha" ALIGN="TOP"/> i variation, in contrast to results and calculations previously published. The model using the Fresnel equation confirms this result. The model presented is more accurate for numerical calculation than that using the Huygens construction.

  7. Method for controlling corrosion using molybdate compositions

    SciTech Connect

    Boffardi, B.P.; Rey, S.P.

    1989-01-17

    A method is described for inhibiting corrosion in an aqueous system comprising adding to the system an effective amount of a corrosion inhibiting composition comprising: (a) a molybdate ion source; and (b) a water-soluble component selected from the group consisting of polymaleic anhydride; amine adducts of polymaleic anhydride; polymers prepared by polymerizing maleic anhydride with dimethyl diallyl ammonium chloride or homologs thereof; polymers prepared from 50-70%, by weight, acrylic acid or methacrylic acid, 10-40%, by weight, 2-acrylamido-2-methylpropyl sulfonic acid or 2-methyacrylamido-2-methylpropyl sulfonic acid and 10-30%, by weight, of a polyalkyleneoxide compound; salts of the above described polymers; phosphonates selected from the group consisting of 2-phosnphonobutane-1,2,4 tricarboxylic acid and hydroxyphosphono acetic acid; phosphino carboxylic acids; polyphosphoric acid and polyhydroxy esters of polyphosphoric acid; wherein the weight of (a):(b), on an active basis, ranges from about 10:1 to about 1:10.

  8. Mechanism of formation of. gamma. -bismuth molybdate

    SciTech Connect

    Kustova, G.N.; Yurchenko, E.N.; Odegova, G.V.; Lazarenko, T.P.; Tarasova, D.V.; Aleshina, G.I.

    1986-04-01

    Infrared and Raman spectroscopic methods were used to study the mechanism of the formation of a Bi-Mo catalyst. X-ray-amorphous Bi/sub 2/MoO/sub 6/ is formed upon precipitation from solutions of bismuth nitrate and ammonium heptamolybdate at pH 2, which, after removal of the NH/sub 4/NO/sub 3/ side product by filtration and heating, crystallizes to the ..gamma..-phase. The presence of NH/sub 4/NO/sub 3/ causes a change in the nature of the solid-phase transformations upon heat treatment leading to decomposition of Bi/sub 2/MoO/sub 6/ into the ..cap alpha..-molybdate and a basic bismuth salt which react upon a further increase in temperature to form the ..gamma..-phase. This difference in the generation process leads to a change in the state of the catalyst surface.

  9. Aggregate stability of silicon dioxide hydrosols modified by molybdates

    SciTech Connect

    Valyukhov, A.A.; Frolov, Y.G.; Nazarov, V.V.

    1986-03-01

    Modification of the surface of silica hydrosol by molybdates changes the relationship between structural and electrostatic contributions to the disjoining pressure, which maintains the aggregate stability of the sol.

  10. Molybdate binding by ModA, the periplasmic component of the Escherichia coli mod molybdate transport system.

    PubMed

    Imperial, J; Hadi, M; Amy, N K

    1998-03-13

    ModA, the periplasmic-binding protein of the Escherichia coli mod transport system was overexpressed and purified. Binding of molybdate and tungstate to ModA was found to modify the UV absorption and fluorescence emission spectra of the protein. Titration of these changes showed that ModA binds molybdate and tungstate in a 1:1 molar ratio. ModA showed an intrinsic fluorescence emission spectrum attributable to its three tryptophanyl residues. Molybdate binding caused a conformational change in the protein characterized by: (i) a shift of tryptophanyl groups to a more hydrophobic environment; (ii) a quenching (at pH 5.0) or enhancement (at pH 7.8) of fluorescence; and (iii) a higher availability of tryptophanyl groups to the polar quencher acrylamide. The tight binding of molybdate did not allow an accurate estimation of the binding constants by these indirect methods. An isotopic binding method with 99MoO42- was used for accurate determination of KD (20 nM) and stoichiometry (1:1 molar ratio). ModA bound tungstate with approximately the same affinity, but did not bind sulfate or phosphate. These KDs are 150- to 250-fold lower than those previously reported, and compatible with the high molybdate transport affinity of the mod system. The affinity of ModA for molybdate was also determined in vivo and found to be similar to that determined in vitro.

  11. Comparative study of the synthesis of layered transition metal molybdates

    SciTech Connect

    Mitchell, S.; Gomez-Aviles, A.; Gardner, C.; Jones, W.

    2010-01-15

    Mixed metal oxides (MMOs) prepared by the mild thermal decomposition of layered double hydroxides (LDHs) differ in their reactivity on exposure to aqueous molybdate containing solutions. In this study, we investigate the reactivity of some T-Al containing MMOs (T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates (LTMs) possessing the general formula AT{sub 2}(OH)(MoO{sub 4}){sub 2}.H{sub 2}O, where A=NH{sub 4}{sup +}, Na{sup +} or K{sup +}. The phase selectivity of the reaction was studied with respect to the source of molybdate, the ratio of T to Mo and the reaction pH. LTMs were obtained on reaction of Cu-Al and Zn-Al containing MMOs with aqueous solutions of ammonium heptamolybdate. Rehydration of these oxides in the presence of sodium or potassium molybdate yielded a rehydrated LDH phase as the only crystalline product. The LTM products obtained by the rehydration of MMO precursors were compared with LTMs prepared by direct precipitation from the metal salts in order to study the influence of preparative route on their chemical and physical properties. Differences were noted in the composition, morphology and thermal properties of the resulting products. - Graphical abstract: Mixed metal oxides (MMOs) derived from layered double hydroxide precursors differ in their reactivity on exposure to aqueous molybdate containing solutions. We investigate the influence of the molybdate source, the rehydration pH and the ratio of T/Mo on the reactivity of some T-Al containing MMOs (T=Co, Ni, Cu or Zn) towards the formation of layered transition metal molybdates of general formula AT{sub 2}(OH)(MoO{sub 4}){sub 2}.H{sub 2}O (where A{sup +}=NH{sub 4}{sup +}, K{sup +} or Na{sup +}).

  12. Interaction of sodium molybdate with the thyroid hormone receptor.

    PubMed

    Faure, R; Dussault, J H

    1990-03-01

    The 3,5,3'-triiodothyronine (T3) binding activity of solubilized nuclear proteins from rat liver was decreased when molybdate (10 mM) was present in the incubation medium in the absence of thiol reagents. The equilibrium affinity constant was reduced by 40%. The rate of degradation of T3-receptor complexes at 37 degrees C remained unchanged, but when the extracts were further reincubated in the presence of beta-mercaptoethanol, molybdate had a protective effect after 5 h incubation at 37 degrees C. In contrast, the thyroxine (T4) binding activity was not affected by heating at 37 degrees C or by molybdate. Ion-exchange chromatography confirmed the existence of a molybdate-receptor interaction: the T3-receptor complexes shifted from elution at 0.22 to 0.20 M NaCl with the progressive appearance of a small leader peak, whereas the T4-receptor complexes eluted in a large and split peak (0.22-0.4 M NaCl). The destabilizing effect on T3 binding induced by exogenous dephosphorylation is more efficiently reversed by beta-mercaptoethanol when the extracts were pretreated by molybdate. In controls, the loss of saturable T3 binding activity was recovered by 50% at a 10 mM concentration of beta-mercaptoethanol, but in the presence of molybdate, the loss of T3 binding activity was recovered by 50% at a 5 mM concentration of beta-mercaptoethanol. This molybdate-receptor interaction is similar to that with nuclear receptor models in term of (i) stabilization of hormone binding, (ii) dependency on a thiol, and (iii) reversibility of the destabilizing effect by exogenous dephosphorylation.

  13. Study of multiphasic molybdate-based catalysts

    SciTech Connect

    Ponceblanc, H.; Millet, J.M.M.; Coudurier, G.; Vedrine, J.C. ); Herrmann, J.M. )

    1993-08-01

    The electrical conductivity of a series of iron-cobalt molybdates has been measured at 370[degrees]C, as a function of the iron content. An important increase of the electrical conductivity occurred when small amounts of iron were substituted for cobalt. This takes place because iron is partially in the 3+ oxidation state. This species, which is stabilized into the CoMoO[sub 4] structure, creates a valence induction effect which is responsible for the drastic variation of the electrical conductivity with compounds whose iron content ranges from 0 to 20%. UV spectroscopy allows the authors to propose that the ferric species involved in this valence induction phenomenon are those giving rise to the intervalence charge transfer between iron cations (Fe[sup 2+]-O-Fe[sup 3+]). By contrast, ESR spectroscopy is silent for such a phenomenon (too short relaxation time) and shows two typical Fe[sup 3+] (d[sup 5] ion) spectra for Fe[sup 3+] engaged either in a different manner in the solid solution (strongly distorted octahedral site) or a given compound such as Fe[sub 2](MoO[sub 4])[sub 3] observed at high iron content. 7 refs., 5 figs., 1 tab.

  14. Molybdate Reduction to Molybdenum Blue by an Antarctic Bacterium

    PubMed Central

    Ahmad, S. A.; Shukor, M. Y.; Shamaan, N. A.; Mac Cormack, W. P.; Syed, M. A.

    2013-01-01

    A molybdenum-reducing bacterium from Antarctica has been isolated. The bacterium converts sodium molybdate or Mo6+ to molybdenum blue (Mo-blue). Electron donors such as glucose, sucrose, fructose, and lactose supported molybdate reduction. Ammonium sulphate was the best nitrogen source for molybdate reduction. Optimal conditions for molybdate reduction were between 30 and 50 mM molybdate, between 15 and 20°C, and initial pH between 6.5 and 7.5. The Mo-blue produced had a unique absorption spectrum with a peak maximum at 865 nm and a shoulder at 710 nm. Respiratory inhibitors such as antimycin A, sodium azide, potassium cyanide, and rotenone failed to inhibit the reducing activity. The Mo-reducing enzyme was partially purified using ion exchange and gel filtration chromatography. The partially purified enzyme showed optimal pH and temperature for activity at 6.0 and 20°C, respectively. Metal ions such as cadmium, chromium, copper, silver, lead, and mercury caused more than 95% inhibition of the molybdenum-reducing activity at 0.1 mM. The isolate was tentatively identified as Pseudomonas sp. strain DRY1 based on partial 16s rDNA molecular phylogenetic assessment and the Biolog microbial identification system. The characteristics of this strain would make it very useful in bioremediation works in the polar and temperate countries. PMID:24381945

  15. Molybdate reduction to molybdenum blue by an Antarctic bacterium.

    PubMed

    Ahmad, S A; Shukor, M Y; Shamaan, N A; Mac Cormack, W P; Syed, M A

    2013-01-01

    A molybdenum-reducing bacterium from Antarctica has been isolated. The bacterium converts sodium molybdate or Mo⁶⁺ to molybdenum blue (Mo-blue). Electron donors such as glucose, sucrose, fructose, and lactose supported molybdate reduction. Ammonium sulphate was the best nitrogen source for molybdate reduction. Optimal conditions for molybdate reduction were between 30 and 50 mM molybdate, between 15 and 20°C, and initial pH between 6.5 and 7.5. The Mo-blue produced had a unique absorption spectrum with a peak maximum at 865 nm and a shoulder at 710 nm. Respiratory inhibitors such as antimycin A, sodium azide, potassium cyanide, and rotenone failed to inhibit the reducing activity. The Mo-reducing enzyme was partially purified using ion exchange and gel filtration chromatography. The partially purified enzyme showed optimal pH and temperature for activity at 6.0 and 20°C, respectively. Metal ions such as cadmium, chromium, copper, silver, lead, and mercury caused more than 95% inhibition of the molybdenum-reducing activity at 0.1 mM. The isolate was tentatively identified as Pseudomonas sp. strain DRY1 based on partial 16s rDNA molecular phylogenetic assessment and the Biolog microbial identification system. The characteristics of this strain would make it very useful in bioremediation works in the polar and temperate countries. PMID:24381945

  16. Molybdate adsorption from steel slag eluates by subsoils.

    PubMed

    Matern, K; Rennert, T; Mansfeldt, T

    2013-11-01

    Steel slags are industrial by-products which are generated in large amounts worldwide, e.g. 150-230×10(6) Mg in 2012, and which are partly used for construction. Molybdenum (Mo) can be added during steel processing in order to harden the steel. The objective of this study was to evaluate the adsorption behaviour of molybdate (MoO4(2-)) from slag eluates in subsoils. Molybdate batch adsorption experiments were carried out with eluates obtained from two different kinds of steel slags (i) LD slag (Linz-Donawitz operation, LDS) and (ii) electric arc furnace slag (EAF) to assess the risk that may arise from the contamination of groundwater by the leaching of molybdate. Six different subsoils were chosen in order to provide a wide range of chemical properties (pH 4.0-7.6; dithionite-extractable Fe 0.73-14.7 g kg(-1)). Molybdate adsorption experiments were carried out at the pH of the steel slag eluates (pH 11-12) as well as at pH values adjusted to the soil pH. The data were evaluated with the Freundlich equation. Molybdate adsorption exhibited a maximum near pH 4 for steel slag eluates adjusted to the soil pH, and decreased rapidly with increasing pH until adsorption was virtually zero at pH>11. Adsorption was greater for soils with high amounts of dithionite-extractable Fe oxides. The extent and behaviour of molybdate adsorption from both eluates was similar. After a reaction time of 24h, the pH of the EAF slag eluate was lower than that of the LD steel slag eluate, which was caused by different acid buffer capacities. Some soils were able to decrease the pH of the EAF slag eluates by about 4 pH units, enhancing the adsorption of molybdate. Transport simulations indicated that molybdate discharge is low in acidic soils.

  17. Sulfiding of cobalt molybdate catalysts: characterization by Raman spectroscopy

    SciTech Connect

    Schrader, G.L.; Cheng, C.P.

    1984-02-01

    In situ laser Raman spectroscopic studies of the sulfiding of cobalt molybdate hydrodesulfurization catalysts were performed. Sulfiding in 10% H/sub 2/S/H/sub 2/ at 400/sup 0/C resulted in the formation of stable MoS/sub 2/ structures after 2h. However, the Raman spectra indicated that small crystallites or surface layers of perhaps distorted MoS/sub 2/ were present. Stepwise sulfiding of samples to 150, 250, and 350/sup 0/C permitted intermediate stages of sulfiding to be examined. Differences were observed for the relative rates of reduction versus sulfur incorporation for CoMoO/sub 4/, Co/sub 3/O/sub 4/, MoO/sub 3/, and aggregated or polymeric molybdate phases. Cobalt tended to increase the extent of reduction of the catalyst. A previously described model is extended to include the role of cobalt.

  18. Some thermochemical studies of cesium uranate, molybdate and chromate

    NASA Astrophysics Data System (ADS)

    Bose, O. K.; Sundaresan, M.; Tangri, R. P.; Kalyanaraman, R.; Schumacher, G.

    1985-02-01

    The present paper deals with studies on vaporisation of cesium monouranate and enthalpies of formation of cesium molybdate and cesium chromate. Vaporization studies of cesium monouranate using Knudsen cell in combination with quadrupole mass spectrometer at the temperature range of 1000-1573 K have indicated that at a temperature above 1223 K it decomposes to cesium polyuranate and cesium vapour. Cesium ion current vs temperature graphs have been plotted. The slope has thus been experimentally found to be -4.1 × 10 4 which compares well with the calculated value of the temperature co-efficient of the decomposition reaction. The enthalpies of formation of cesium molybdate and cesium chromate have been determined by static bomb calorimetry by reacting cesium carbonate with respective oxide in ultra pure oxygen.

  19. Synthesis of silver molybdate clusters driven by laser-annealing

    SciTech Connect

    Brechignac, C.; Cahuzac, Ph.; Kebaili, N.; Lando, A.; Masson, A.; Schmidt, M.

    2004-11-15

    The synthesis of silver rich molybdate clusters is achieved by laser induced chemical reaction of coadsorbed MoO{sub 3} and O{sub 2} molecules on free silver clusters. The reactants MoO{sub 3} and/or O{sub 2} molecules condensed at low temperature (77 K-175 K) on free silver clusters. Then, the silver clusters together with their adsorbed molecules are flashed either ionized with a discharge or ionized and heated by a laser. Then they are cooled down by evaporation. The synthesized chemical compounds are analyzed by a high-resolution time-of-flight mass spectrometer. If only one type of reactant is adsorbed on the cluster, only one oxide molecule is stabilized on the metallic core after the heating and cooling cycle. On the contrary, the coadsorption of the two types of molecules MoO{sub 3} and O{sub 2} on Ag{sub n}{sup +}, at 77 K, leads to complex aggregates that transform, after laser heating, into a molybdate rich metal clusters. These synthesized species cool down by evaporating silver atoms showing evidence of a binary oxide that is more stable than the metallic core. Moreover we demonstrate that for small size molybdate clusters, a stoichiometric composition may differ from the bulk one.

  20. Corrosion study of stainless steel SS304L in molten molybdates

    NASA Astrophysics Data System (ADS)

    Usami, T.; Uruga, K.; Tsukada, T.; Miura, Y.; Komamine, S.; Ochi, E.

    2016-04-01

    Depending on operating conditions of the vitrification process of high-level liquid waste, molten salt mainly composed of sodium and molybdenum can be generated, and poured into stainless steel canisters. In this work, the possible reaction between the molten molybdate and stainless steel was investigated using multi-component molybdate and simple Na2MoO4 - MoO3 molybdate. In the experiments using multi-component molybdates, no significant reaction is observed between the mixed molybdates and the stainless steel specimens at 700 °C in 4 h. The reaction rate of the stainless steel with the multi-component molybdate increases in proportion to exp(-1/T). The depth of the most reacted area is about 300 μm even at 1000 °C, and was much smaller than the 6 mm thickness of the canister. In the simple Na2MoO4 - MoO3 molybdate, the reaction rate was proportional to the MoO3 concentration. The essence of the reaction is oxidation of metals by Mo6+ - > Mo4+. Part of the reaction product mainly composed of Fe is dissolved into the molybdate, while the other part mainly composed of Cr sloughs and forms a banded layer.

  1. Dielectric and conducting behaviour of polycrystalline holmium octa-molybdate

    NASA Astrophysics Data System (ADS)

    Want, Basharat; Zahoor Ahmad, Bhat; Bhat, Bilal Hamid

    2014-09-01

    Polycrystalline holmium octa-molybdate spherulites have been obtained by using gel diffusion technique and characterized by different physio-chemical techniques. The surfaces of these spherulites are composed of nano-rod with an average diameter of about 80 nm. At room temperature the initial crystal structure is triclinic, space group P1. Thermal studies suggested a phase transition occurring in holmium octa-molybdate crystals at about 793 K. The electrical properties of the system have been studied as a function of frequency and temperature in the ranges of 20 Hz-3 MHz and 290-570 K, respectively. A giant dielectric constant and two loss peaks have been observed in the permittivity formalism. The conducting behaviour of the material is also discussed. The conductivity was found to be 1572 μ Ω-1 m-1 at room temperature and 3 MHz frequency. The conductivity of the polycrystalline material was attributed to the fact that it arises due to the migration of defects on the oxygen sub-lattice. Impedance studies were also performed in the frequency domain to infer the bulk and grain boundary contributions to the overall electric response of the material. The electrical responses have been attributed to the grain, grain-boundary, and interfacial effects.

  2. Role of Molybdate and Other Transition Metals in the Accumulation of Protochelin by Azotobacter vinelandii

    PubMed Central

    Cornish, Anthony S.; Page, William J.

    2000-01-01

    Both molybdate and iron are metals that are required by the obligately aerobic organism Azotobacter vinelandii to survive in the nutrient-limited conditions of its natural soil environment. Previous studies have shown that a high concentration of molybdate (1 mM) affects the formation of A. vinelandii siderophores such that the tricatecholate protochelin is formed to the exclusion of the other catecholate siderophores, azotochelin and aminochelin. It has been shown previously that molybdate combines readily with catecholates and interferes with siderophore function. In this study, we found that the manner in which each catecholate siderophore interacted with molybdate was consistent with the structure and binding potential of the siderophore. The affinity that each siderophore had for molybdate was high enough that stable molybdo-siderophore complexes were formed but low enough that the complexes were readily destabilized by Fe3+. Thus, competition between Fe3+ and molybdate did not appear to be the primary cause of protochelin accumulation; in addition, we determined that protochelin accumulated in the presence of vanadate, tungstate, Zn2+, and Mn2+. We found that all five of these metal ions partially inhibited uptake of 55Fe-protochelin and 55Fe-azotochelin complexes. Also, each of these metal ions partially inhibited the activity of ferric reductase, an enzyme important in the deferration of ferric siderophores. Our results suggest that protochelin accumulates in the presence of molybdate because protochelin uptake and conversion into its component parts, azotochelin and aminochelin, are inhibited by interference with ferric reductase. PMID:10742245

  3. Molybdate/phosphate composite conversion coating on magnesium alloy surface for corrosion protection

    NASA Astrophysics Data System (ADS)

    Yong, Zhiyi; Zhu, Jin; Qiu, Cheng; Liu, Yali

    2008-12-01

    In this paper, a new conversion coating—molybdate/phosphate (Mo/P) coating on magnesium alloy was prepared and investigated by electrochemical impedance spectra (EIS), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and salt-water immersion experiments, respectively. The results demonstrated that the Mo/P coating contained composite phases, which were consisted of metaphosphate as well as molybdate oxide with an "alveolate-crystallized" structure. The composite Mo/P conversion coating had better corrosion resistance performance than molybdate (Mo) coating, and even had almost comparable corrosion protection for Mg alloy to the traditional chromate-based coating.

  4. EFFECT OF TUNGSTATE ON THE UPTAKE AND FUNCTION OF MOLYBDATE IN AZOTOBACTER AGILIS

    PubMed Central

    Bulen, William A.

    1961-01-01

    Bulen, William A. (Charles F. Kettering Foundation, Yellow Springs, Ohio). Effect of tungstate on the uptake and function of molybdate in Azotobacter agilis. J. Bacteriol. 82:130–134. 1961.—The reported competitive inhibition of molybdate by tungstate was investigated in an effort to elucidate molybdenum functions associated with nitrogen fixation by Azotobacter agilis (A. vinelandii). Growth, respiration, and N215-incorporation experiments with normal and molybdenum-deficient cells indicated that tungstate inhibits the uptake of molybdate but does not compete with the metabolically functional molybdenum of cells metabolizing N2. Neither a molybdenum requirement nor a tungstate inhibition was observed with cells metabolizing urea. PMID:16561910

  5. Polymerization and photochromism of ammonium molybdate in porous glass

    NASA Astrophysics Data System (ADS)

    Pak, V. N.; Borisov, A. N.

    2016-08-01

    Modification of porous glass (PG) plates is carried out by impregnation with aqueous solutions of ammonium molybdate (NH4)2MoO4 with subsequent removal of water at 120°C. A long-wavelength shift of absorption spectra upon accumulation of the salt in PG indicates polymerization of MoO 4 2- anions at low concentrations of the encapsulated salt. Photochromism manifests itself as the anionic forms in PG become larger. UV irradiation of the modified plates causes enhancement of continuous absorption in the visible range. The proposed mechanism of photoreduction of the polianions in PG involves the removal of oxygen atoms from the bridging-Mo-O-Mo-bonds and stabilization of the colored forms by means of conjugation of the electrons released from the 4 d-levels of pentavalent molybdenum.

  6. Ferroelectric ultrathin perovskite films

    DOEpatents

    Rappe, Andrew M; Kolpak, Alexie Michelle

    2013-12-10

    Disclosed herein are perovskite ferroelectric thin-film. Also disclosed are methods of controlling the properties of ferroelectric thin films. These films can be used in a variety materials and devices, such as catalysts and storage media, respectively.

  7. Perovskite ferroelectric nanomaterials

    NASA Astrophysics Data System (ADS)

    Nuraje, Nurxat; Su, Kai

    2013-09-01

    In this review, the main concept of ferroelectricity of perovskite oxides and related materials at nanometer scale and existing difficulties in the synthesis of those nanocrystals are discussed. Important effects, such as depolarization field and size effect, on the existence of ferroelectricity in perovskite nanocrystals are deliberated. In the discussion of modeling works, different theoretical calculations are pinpointed focusing on their studies of lattice dynamics, phase transitions, new origin of ferroelectricity in nanostructures, etc. As the major part of this review, recent research progress in the facile synthesis, characterization and various applications of perovskite ferroelectric nanomaterials, such as BaTiO3, PbTiO3, PbZrO3, and BiFeO3, are also scrutinized. Perspectives concerning the future direction of ferroelectric nanomaterials research and its potential applications in renewable energy, etc., are presented. This review provides an overview in this area and guidance for further studies in perovskite ferroelectric nanomaterials and their applications.In this review, the main concept of ferroelectricity of perovskite oxides and related materials at nanometer scale and existing difficulties in the synthesis of those nanocrystals are discussed. Important effects, such as depolarization field and size effect, on the existence of ferroelectricity in perovskite nanocrystals are deliberated. In the discussion of modeling works, different theoretical calculations are pinpointed focusing on their studies of lattice dynamics, phase transitions, new origin of ferroelectricity in nanostructures, etc. As the major part of this review, recent research progress in the facile synthesis, characterization and various applications of perovskite ferroelectric nanomaterials, such as BaTiO3, PbTiO3, PbZrO3, and BiFeO3, are also scrutinized. Perspectives concerning the future direction of ferroelectric nanomaterials research and its potential applications in renewable

  8. Elucidation of molybdosilicate complexes in the molybdate yellow method by ESI-MS.

    PubMed

    Takahashi, Mariko; Abe, Yoshihiro; Tanaka, Miho

    2015-01-01

    The formation of molybdosilicate in the molybdate yellow method is elucidated by ESI-MS. Polymeric silicic acids were hydrolyzed to monomers, and molybdosilicates with a Keggin structure were formed. Each step of the formation reaction of molybdosilicate from molybdic and silicic acids between pH 1 and 2 was clarified by ESI-MS at the molecular level. In a solution below pH 0.5, the polymers of the molybdic acids were decomposed because of the high concentration of sulfuric acid. Excess sulfuric acid prevented the formation of molybdosilicate. Thus, none of the silicic acids reacted to form molybdosilicate at this pH, despite the presence of silicic acid and sulfate ions in the solution. Above pH 2, the condensation of molybdic acids occurred to form α-molybdosilicate. ESI-MS provides information on the formation of molybdosilicate and the individual reaction species present in the reaction mixture.

  9. Perovskite solid electrolytes for SOFC

    SciTech Connect

    Sammells, A.F.

    1992-09-01

    Selected perovskite solid electrolytes incorporated into research size fuel cells have shown stability for > 4000 hours at 600{degrees}C. Perovskite lattice requirements which favor low E{sub a} for ionic conduction include (i) that the perovskite lattice possess a moderate enthalpy of formation, (ii) perovskite lattice possess large free volumes, (iii) that the lattice minimally polarizes the mobile ion and (iv) that the crystallographic saddle point r{sub c} for ionic conduction is {approx_equal} 1.

  10. Perovskite solid electrolytes for SOFC

    SciTech Connect

    Sammells, A.F.

    1992-01-01

    Selected perovskite solid electrolytes incorporated into research size fuel cells have shown stability for > 4000 hours at 600{degrees}C. Perovskite lattice requirements which favor low E{sub a} for ionic conduction include (i) that the perovskite lattice possess a moderate enthalpy of formation, (ii) perovskite lattice possess large free volumes, (iii) that the lattice minimally polarizes the mobile ion and (iv) that the crystallographic saddle point r{sub c} for ionic conduction is {approx equal} 1.

  11. Control of post-harvest decay of apples by pre-harvest and post-harvest application of ammonium molybdate.

    PubMed

    Nunes, C; Usall, J; Teixidó, N; Ochoa de Eribe, X O; Viñas, I

    2001-12-01

    Ammonium molybdate was tested as a potential fungicide for use in apples (cv Golden Delicious) against blue and grey mould, important post-harvest diseases of pome fruits. In tests in vivo at 20 degrees C, ammonium molybdate (15 mM) reduced lesion diameters of Penicillium expansum, Botrytis cinerea and Rhizopus stolonifer by 84%, 88% and 100% respectively. When apples treated with ammonium molybdate were stored at 1 degree C for three months, a significant reduction in severity and incidence of P expansum and B cinerea was observed in both years of study (1998 and 1999). In the second year of the experiment the reduction in disease severity was greater than 88% for both pathogens, and the level of control was similar to, or greater than, that observed with the fungicide imazalil. When ammonium molybdate was applied as a pre-harvest treatment, a significant reduction in blue mould decay was observed after three months in cold storage. In vitro, ammonium molybdate greatly inhibited spore germination of P expansum and B cinerea, although better inhibition was obtained against grey mould. Ammonium dimolybdate, sodium molybdate and potassium molybdate were also tested in vitro in comparison with ammonium molybdate as inhibitors of spore germination, but only ammonium molybdate inhibited spore germination by more than 50%.

  12. In vivo detection of molybdate-binding proteins using a competition assay with ModE in Escherichia coli.

    PubMed

    Kuper, Jochen; Meyer zu Berstenhorst, Sonja; Vödisch, Bernd; Mendel, Ralf R; Schwarz, Günter; Boxer, David H

    2003-01-21

    Molybdenum is an important trace element as it forms the essential part of the active site in all molybdenum-containing enzymes. We have designed an assay for the in vivo detection of molybdate binding to proteins in Escherichia coli. The assay is based on (i). the molybdate-dependent transcriptional regulation of the moa operon by the ModE protein, and (ii). the competition for molybdate between ModE and other molybdate-binding proteins in the cytoplasm of E. coli. We were able to verify in vivo molybdate binding to three different bacterial proteins that are known to bind molybdate. This sensitive in vivo system allows the testing of different proteins for molybdate binding under in vivo conditions and will facilitate the identification of other cellular factors needed for molybdate binding. As a first example, we examined the eukaryotic protein Cnx1 that is involved in the last step of molybdenum cofactor biosynthesis in plants, and show that it is able to compete with ModE for molybdate in a molybdopterin-dependent fashion.

  13. 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.

  14. Identification of a new gene, molR, essential for utilization of molybdate by Escherichia coli.

    PubMed Central

    Lee, J H; Wendt, J C; Shanmugam, K T

    1990-01-01

    A mutation in a new gene, molR, prevented the synthesis in Escherichia coli of molybdoenzymes, including the two formate dehydrogenase isoenzymes, nitrate reductase and trimethylamine-N-oxide reductase. This phenotype was suppressed by supplementing the media with molybdate. Thus, the molR mutant was phenotypically similar to previously described chlD mutants, thought to be defective in molybdate transport. The molR gene is located at 65.3 min in the E. coli chromosome, in contrast to the chlD gene, which maps at 17 min and thus can be readily distinguished. The molR gene is also cotransducible with a hitherto unidentified gene essential for the production of 2-oxoglutarate from isocitrate, designated icdB (located at 66 min). The molR mutant strain SE1100 also failed to produce the hydrogenase component of formate hydrogenlyase (HYD3) in molybdate-unsupplemented media. The amount of molybdate required by strain SE1100 for the production of parental levels of formate hydrogenlyase activity was dependent on the growth medium. In Luria-Bertani medium, this value was about 100 microM, and in glucose-minimal medium, 1.0 microM was sufficient. In low-sulfur medium, this value decreased to about 50 nM. The addition of sulfate or selenite increased the amount of molybdate needed for the production of formate hydrogenlyase activity. These data suggest that in the absence of the high-affinity molybdate transport system, E. coli utilizes sulfate and selenite transport systems for transporting molybdate, preferring sulfate transport over the selenite transport system. PMID:2156810

  15. Properties of the periplasmic ModA molybdate-binding protein of Escherichia coli.

    PubMed

    Rech, S; Wolin, C; Gunsalus, R P

    1996-02-01

    The modABCD operon, located at 17 min on the Escherichia coli chromosome, encodes the protein components of a high affinity molybdate uptake system. Sequence analysis of the modA gene (GenBank L34009) predicts that it encodes a periplasmic binding protein based on the presence of a leader-like sequence at its N terminus. To examine the properties of the ModA protein, the modA structural gene was overexpressed, and its product was purified. The ModA protein was localized to the periplasmic space of the cell, and it was released following a gentle osmotic shock. The N-terminal sequence of ModA confirmed that a leader region of 24 amino acids was removed upon export from the cell. The apparent size of ModA is 31.6 kDa as determined by gel sieve chromatography, whereas it is 22.5 kDa when examined by SDS-polyacrylamide gel electrophoresis. A ligand-dependent protein mobility shift assay was devised using a native polyacrylamide gel electrophoresis protocol to examine binding of molybdate and other anions to the ModA periplasmic protein. Whereas molybdate and tungstate were bound with high affinity (approximately 5 microM), sulfate, chromate, selenate, phosphate, and chlorate did not bind even when tested at 2 mM. A UV spectral assay revealed apparent Kd values of binding for molybdate and tungstate of 3 and 7 microM, respectively. Strains defective in the modA gene were unable to transport molybdate unless high levels of the anion were supplied in the medium. Therefore the modA gene product is essential for high affinity molybdate uptake by the cell. Tungstate interference of molybdate acquisition by the cell is apparently due in part to the high affinity of the ModA protein for this anion.

  16. Molybdate transport in a chemically complex aquifer: Field measurements compared with solute-transport model predictions

    USGS Publications Warehouse

    Stollenwerk, K.G.

    1998-01-01

    A natural-gradient tracer test was conducted in an unconfined sand and gravel aquifer on Cape Cod, Massachusetts. Molybdate was included in the injectate to study the effects of variable groundwater chemistry on its aqueous distribution and to evaluate the reliability of laboratory experiments for identifying and quantifying reactions that control the transport of reactive solutes in groundwater. Transport of molybdate in this aquifer was controlled by adsorption. The amount adsorbed varied with aqueous chemistry that changed with depth as freshwater recharge mixed with a plume of sewage-contaminated groundwater. Molybdate adsorption was strongest near the water table where pH (5.7) and the concentration of the competing solutes phosphate (2.3 micromolar) and sulfate (86 micromolar) were low. Adsorption of molybdate decreased with depth as pH increased to 6.5, phosphate increased to 40 micromolar, and sulfate increased to 340 micromolar. A one-site diffuse-layer surface-complexation model and a two-site diffuse-layer surface-complexation model were used to simulate adsorption. Reactions and equilibrium constants for both models were determined in laboratory experiments and used in the reactive-transport model PHAST to simulate the two-dimensional transport of molybdate during the tracer test. No geochemical parameters were adjusted in the simulation to improve the fit between model and field data. Both models simulated the travel distance of the molybdate cloud to within 10% during the 2-year tracer test; however, the two-site diffuse-layer model more accurately simulated the molybdate concentration distribution within the cloud.

  17. Directed synthesis of noncentrosymmetric molybdates using composition space analysis.

    PubMed

    Veltman, Thomas R; Stover, Adam K; Narducci Sarjeant, Amy; Ok, Kang Min; Halasyamani, P Shiv; Norquist, Alexander J

    2006-07-10

    A systematic investigation of the factors governing the reaction product composition, hydrogen bonding, and symmetry was conducted in the MoO3/3-aminoquinuclidine/H2O system. Composition space analysis was performed through 36 individual reactions under mild hydrothermal conditions using racemic 3-aminoquinuclidine. Single crystals of three new compounds, [C7H16N2][Mo3O10] x H2O, [C7H16N2]2[Mo8O26] x H2O, and [C7H16N2]2[Mo8O26] x 4 H2O, were grown. The relative phase stabilities for these products are dependent upon the reactant mole fractions in the initial reaction gel. This phase stability information was used to direct the synthesis of two new noncentrosymmetric compounds, using either (S)-(-)-3-aminoquinuclidine dihydrochloride or (R)-(+)-3-aminoquinuclidine dihydrochloride. [(R)-C7H16N2]2[Mo8O26] and [(S)-C7H16N2]2[Mo8O26] both crystallize in the noncentrosymmetric space group P2(1) (No. 4), which has the polar crystal class 2 (C2). The second-harmonic generation activities were measured on sieved powders. The structure-directing properties of the molybdate components in each compound were determined using bond valence sums. The structures of all five compounds were determined using single-crystal X-ray diffraction. PMID:16813416

  18. Structural and spectral investigation of terbium molybdate nanophosphor

    NASA Astrophysics Data System (ADS)

    Mani, Kamal P.; Vimal, G.; Biju, P. R.; Joseph, Cyriac; Unnikrishnan, N. V.; Ittyachen, M. A.

    2015-09-01

    Terbium molybdate nanophosphors were synthesized through a facile sol-gel route. The structure of the phosphors was characterized by X-ray diffraction, Raman spectra and Fourier transform infrared spectroscopy analysis. The X-ray diffraction studies revealed that the structure of the nanophosphor gradually changes from monoclinic to orthorhombic phase as heated from 700 to 900 °C. High resolution transmission electron microscopy, SAED and EDS were also employed to characterize the size, crystallinity and composition of the samples. Detailed spectroscopic investigations were carried out by Judd-Ofelt analysis based on UV-Visible-NIR absorption and emission spectra. The luminescence spectra suggest that phosphors with orthorhombic structure have better luminescence properties than the monoclinic structure. The phosphors showed intense green emission under near-UV excitation due to the energy transfer from the host lattice to Tb3+ ions. The CIE coordinates suggest enhanced color purity for green emission and short fluorescence decay values proposes the suitability for LED applications. These phosphors can be applied as promising candidates for blue and near-UV excited WLEDs.

  19. Partial oxidation of methane on supported potassium molybdate

    SciTech Connect

    Erdohelyi, A.; Fodor, K.; Solymosi, F.

    1997-03-01

    The partial oxidation of methane to formaldehyde was studied on K{sub 2}MoO{sub 4}, deposited on various supports, in a fixed-bed continuous-flow reactor at 860-923 K using O{sub 2} as oxidant. The catalysts were characterized by Raman and XPS spectroscopies. It was found that the composition of molybdates deposited by impregnation depended sensitively on the pH value of the slurry containing the support. At low pH values a significant amount of K{sub 2}Mo{sub 2}O{sub 7} was formed. The product distribution of the oxidation reaction was markedly influenced by the nature of the support. The highest activity was measured for magnesia-supported catalyst. In this case, however, only the complete oxidation of methane occurred. Formaldehyde, in a larger quantity, was produced on silica-supported catalyst containing a greater amount of K{sub 2}Mo{sub 2}O{sub 7} and on K{sub 2}MoO{sub 4}/ZSM-5. It was observed that at very low oxygen content, {approximately}0.1%, the reaction pathway of methane conversion was basically different: in this case the main hydrocarbon products were ethylene, ethane, and benzene. Formaldehyde was not detected. A possible mechanism for the reaction of methane is discussed. 37 refs., 7 figs., 3 tabs.

  20. Classification of a Haemophilus influenzae ABC Transporter HI1470/71 through Its Cognate Molybdate Periplasmic Binding Protein, MolA

    SciTech Connect

    Tirado-Lee, Leidamarie; Lee, Allen; Rees, Douglas C.; Pinkett, Heather W.

    2014-10-02

    molA (HI1472) from H. influenzae encodes a periplasmic binding protein (PBP) that delivers substrate to the ABC transporter MolB{sub 2}C{sub 2} (formerly HI1470/71). The structures of MolA with molybdate and tungstate in the binding pocket were solved to 1.6 and 1.7 {angstrom} resolution, respectively. The MolA-binding protein binds molybdate and tungstate, but not other oxyanions such as sulfate and phosphate, making it the first class III molybdate-binding protein structurally solved. The {approx}100 {mu}M binding affinity for tungstate and molybdate is significantly lower than observed for the class II ModA molybdate-binding proteins that have nanomolar to low micromolar affinity for molybdate. The presence of two molybdate loci in H. influenzae suggests multiple transport systems for one substrate, with molABC constituting a low-affinity molybdate locus.

  1. Protection of aluminium foil AA8021 by molybdate-based conversion coatings

    NASA Astrophysics Data System (ADS)

    Liang, Chang-Sheng; Lv, Zhong-Fei; Zhu, Ye-Ling; Xu, Shi-Ai; Wang, Hong

    2014-01-01

    A quick method for surface treatment of aluminium foil with environment-friendly and effective molybdate-based coating was developed in this study. Aluminium foil samples were treated with molybdate-based solution. The microstructure and composition of the resulting molybdate-based conversion coatings were explored by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray photoelectric spectroscopy (XPS). We found that the molybdate-based conversion coating was composed mainly of MoO3, (MoO3)x(P2O5)y and Al2(MoO4)3 compounds. Furthermore, corrosion resistance of the treated aluminium foil was evaluated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization. Our results show that all of the aluminium foils with molybdate-based conversion coatings have much better corrosion resistance than bare aluminium foil. Notably, the sample treated at 40 °C exhibited the best corrosion resistance. The new method is very suitable for continuous processing.

  2. Behavior of silver molybdate at high-pressure

    SciTech Connect

    Arora, A.K.; Nithya, R.; Misra, Sunasira; Yagi, Takehiko

    2012-12-15

    Behavior of cubic spinel phase of Ag{sub 2}MoO{sub 4} is investigated at high pressure using X-ray diffraction and Raman spectroscopy. The P-V data are fitted to a third order Birch-Murnaghan equation of state using a value of B{sub 0}=113 GPa and B Prime {sub 0}=4. The compound is also found to exhibit a phase transition around 5 GPa to a tetragonal structure and the two phases are found to coexist over a range of pressures. Raman spectra exhibit dramatic changes across the phase transition. Increase of X-ray background scattering and broadening of the Raman peaks associated with MoO{sub 4} tetrahedral ions in the high pressure phase suggest evolution of positional disorder. However, no evidence of pressure-induced amorphization was found up to 47 GPa. - Graphical abstract: Evolution of the integrated intensity of all the diffraction peaks between 12 and 18 degree 2{theta} as a function of pressure. The rapid decrease of the intensity suggests evolution of positional disorder in the high-pressure tetragonal phase. Highlights: Black-Right-Pointing-Pointer First in-situ X-ray diffraction and Raman study of cubic silver molybdate at high pressure. Black-Right-Pointing-Pointer Commencement of a structural transition to a tetragonal phase is found at 2.3 GPa. Black-Right-Pointing-Pointer The high-pressure phase is found to have positional disorder. Black-Right-Pointing-Pointer A bulk modulus of 113 GPa is obtained from the equation of state.

  3. Luminescence and electrical behavior of lead molybdate nanoparticles

    NASA Astrophysics Data System (ADS)

    Singh, B. P.; Parchur, A. K.; Rai, S. B.; Singh, P.

    2013-02-01

    We report our investigation on photoluminescence and electrical behavior of lead molybdate (PbMoO4) nanoparticles by spanning the solvent of reaction medium. The PbMoO4 nanoparticles were prepared in different solvents like ethylene glycol (EG), dimethyl sulfonic acid (DMSO) and 50% EG + 50% DMSO at room temperature. The crystallite size and strain acting on nanoparticles were characterized by X-ray diffraction (XRD) study and microstructure was studied by transmission electron microscope (TEM). The average crystallite sizes and strain were found to be ˜22, 24 and 25 nm and ˜0.0028, 0.0039 and 0.0048 for EG, DMSO and EG+DMSO solvents, respectively. The XRD peak corresponding to (112) were found to shift to lower angle by 0.02° for DMSA solvent as compared to EG. This confirmed the lattice expansion in the unit cell. The particle sizes measured from TEM measurements were found to be slightly greater than that obtained from XRD analysis. The photoluminescence (PL) measurements were carried out by using 266 nm Nd-YAG laser excitation (Mo-O CTB). The samples depicted strong BLUE color. The order of emission intensity in the samples was obtained in EG+DMSO > DMSO > EG order. This may be related to the formation of [MoO4] and [PbO8] clusters in PbMoO4 host. The electrical conductivity study were carried out for these samples and from this study, we concluded that the conduction mechanism in this system were polaronic in nature.

  4. Optical filtering and luminescence property of some molybdates prepared by combustion synthesis

    SciTech Connect

    Yadav, P. J.; Joshi, C. P.; Moharil, S. V.

    2014-10-15

    As an important class of lanthanide inorganic compounds, rare earth ions doped molybdates have gained much attention due to their attractive luminescence and structural properties, supporting various promising applications as phosphor materials in the fields such as white light-emitting diodes, optical fibers, biolabel, lasers, and so on. The molybdate family has promising trivalent cation conducting properties and most of the optical properties result from electron transitions of the 4f shell, which are greatly affected by the composition and structures of rare-earth compounds. In this paper we report the molybdate CaMoO{sub 4}:Eu{sup 3+} for red SSL and Bi{sub 1.4}Y{sub 0.6}MoO{sub 6}, Y{sub 6}MoO{sub 12} for optical filtering, prepared by one step combustion synthesis.

  5. In vivo molybdate inhibition of sulfate transfer to porphyridium capsular polysaccharide.

    PubMed

    Ramus, J

    1974-12-01

    Active transport of exogenous sulfate into log phase cells of Porphyridium aerueineum followed Michaelis-Menten kinetics, and the apparent Km for sulfate transport is approximately 2.5 x 10(-6)m. Molybdate, also a group VI anion, is a competitive inhibitor of sulfate transport, and the inhibition is freely reversible. Once in the cell, molybdate depresses the rate of sulfate pool utilization by blocking sulfate transfer to polysaccharides destined for secretion to the cell surface. Specifically, molybdate inhibits the formation of adenosine 5'-phosphosulfate and in turn the formation of adenosine 3'-phosphate 5'-phosphosulfate, the activated donor for sulfate transfer reactions. Combined with the previous identification of adenosine 3'-phosphate 5'-phosphosulfate, this is taken as evidence that the adenosine 5'-phosphosulfate/adenosine 3'-phosphate 5'-phosphosulfate enzymatic sequence for sulfate activation and sulfate donor reactions is operating in Porphyridium. Thiosulfate is utilized as effectively as sulfate as both a sulfur source for growth and polysaccharide synthesis.

  6. Metal molybdate nanorods as non-precious electrocatalysts for the oxygen reduction

    NASA Astrophysics Data System (ADS)

    Wu, Tian; Zhang, Lieyu

    2015-12-01

    Development of non-precious electrocatalysts with applicable electrocatalytic activity towards the oxygen reduction reaction (ORR) is important to fulfill broad-based and large-scale applications of metal/air batteries and fuel cells. Herein, nickel and cobalt molybdates with uniform nanorod morphology are synthesized using a facile one-pot hydrothermal method. The ORR activity of the prepared metal molybdate nanorods in alkaline media are investigated by using cyclic voltammetry (CV), linear sweep voltammetry (LSV) and chronoamperomety in rotating disk electrode (RDE) techniques. The present study suggests that the prepared metal molybdate nanorods exhibit applicable electrocatalytic activities towards the ORR in alkaline media, promising the applications as non-precious cathode in fuel cells and metal-air batteries.

  7. Mo enrichment in black shale and reduction of molybdate by sulfate-reducing bacteria (SRB) (Invited)

    NASA Astrophysics Data System (ADS)

    Xu, H.; Barton, L. L.

    2010-12-01

    The Lower Cambrian Black shale in Zunyi area of Guizhou Province, Southern China contains significant amount of Mo, As, and sulfide minerals. Additionally, Mo and sulfides are closely associated with organic matter of kerogen. Transmission electron microscopy (TEM) results show pyrite micro-crystals and Mo-As-S-bearing carbon (kerogen). High-resolution TEM image shows that Mo-rich areas are Mo-sulfide (molybdenite) layers that form poorly crystalline structures in organic carbon matrix. X-ray energy-dispersive spectra (EDS) indicate composition from the pyrite and the Mo-rich area. The black shale is very unique because of its high Mo concentration. One possible mechanism for enriching Mo from paleo-seawater is the involvement of SRB. Molybdate is an essential trace element required by biological systems including the anaerobic sulfate-reducing bacteria (SRB); however, detrimental consequences may occur if molybdate is present in high concentrations in the environment. We followed the growth of Desulfovibrio gigas ATCC 19364, D. vulgaris Hildenborough, D. desulfuricans DSM 642, and D. desulfuricans DSM 27774 in media containing sub-lethal levels of molybdate and observed a red-brown color in the culture fluid. Spectral analysis of the culture fluid revealed absorption peaks at 467 nm, 395 nm and 314 nm and this color is proposed to be a molybdate-sulfide complex. Reduction of molybdate with the formation of molybdate disulfide occurs in the periplasm D. gigas and D. desulfuricans DSM 642. From these results we suggest that the occurrence of poorly crystalline Mo-sulfides in black shale may be a result from SRB reduction and selective enrichment of Mo in paleo-seawater. We suggest that similar SRB mechanism could cause the Mo enrichment in a ~ 2.5 billion years old late Archean McRae Shale, which is related to the great oxidation event of early earth atmosphere.

  8. Study of the redox properties of bismuth-molybdate and uranium-antimonate catalysts

    SciTech Connect

    Paz-Pujalt, G.R.

    1985-01-01

    The oxidation/reduction properties of various bismuth molybdates, molybdenum trioxide, bismuth oxide, uranium antimonate, and iron antimonate have been studied in an effort to correlate them to their catalytic properties. The temperature at which ..gamma..-phase bismuth molybdate is prereduced plays an important role in the behavior the catalyst exhibits under reoxidation conditions. The overall behavior of ..gamma..-phase bismuth molybdate under catalytic conditions may be divided into two temperature regimes: below 360/sup 0/C the catalyst shows a higher rate of propylene adsorption than product desorption, and above 360/sup 0/C where produced desorption is dominant. This temperature is the same at which the Arrhenius plot for the reaction has a break. Several reduction of ..gamma..-bismuth molybdate results in the formation of clusters of bismuth metal and crystallites of molybdenum dioxide. This is irreversible. The reoxidation of the bismuth molybdate catalysts shows the presence of two oxygen incorporation temperatures. The ratios of the areas under these peaks are not the same for the three catalysts. Uranium antimonate shows a lesser degree of lattice oxygen participation. During several reduction the catalyst decomposes partially and an excess of antimony is evident. The isothermal reduction profiles of the catalysts permitted their classification into either of two reduction models: (A) ..cap alpha..-, ..beta..-, ..gamma..-phase bismuth molybdates, molybdenum trioxide, bismuth oxide, and the equimolar mixture follow the nucleation model, (B) uranium antimonate, and iron antimonate following the shrinking sphere model. These models have been correlated to certain characteristics of these catalysts. Group A catalysts show a high degree of lattice oxygen participation (migration of bulk oxygen to surface nuclei). In contrast in group B catalysts only a few layers of oxygen are peeled off during catalysis.

  9. High Performance Perovskite Solar Cells

    PubMed Central

    Tong, Xin; Lin, Feng; Wu, Jiang

    2015-01-01

    Perovskite solar cells fabricated from organometal halide light harvesters have captured significant attention due to their tremendously low device costs as well as unprecedented rapid progress on power conversion efficiency (PCE). A certified PCE of 20.1% was achieved in late 2014 following the first study of long‐term stable all‐solid‐state perovskite solar cell with a PCE of 9.7% in 2012, showing their promising potential towards future cost‐effective and high performance solar cells. Here, notable achievements of primary device configuration involving perovskite layer, hole‐transporting materials (HTMs) and electron‐transporting materials (ETMs) are reviewed. Numerous strategies for enhancing photovoltaic parameters of perovskite solar cells, including morphology and crystallization control of perovskite layer, HTMs design and ETMs modifications are discussed in detail. In addition, perovskite solar cells outside of HTMs and ETMs are mentioned as well, providing guidelines for further simplification of device processing and hence cost reduction.

  10. Molybdic acid ionisation under hydrothermal conditions to 300 °C

    NASA Astrophysics Data System (ADS)

    Minubayeva, Z.; Seward, T. M.

    2010-08-01

    This UV spectrophotometric study was aimed at providing precise, experimentally derived thermodynamic data for the ionisation of molybdic acid (H 2MoO 4) from 30 to 300 °C and at equilibrium saturated vapour pressures. The determination of the equilibrium constants and associated thermodynamic parameters were facilitated by spectrophotometric measurements using a specially designed high temperature optical Ti-Pd flow-through cell with silica glass windows. The following van't Hoff isochore equations describe the temperature dependence of the first and second ionisation constants of molybdic acid up to 300 °C:

  11. Metal halide perovskite light emitters

    PubMed Central

    Kim, Young-Hoon; Cho, Himchan; Lee, Tae-Woo

    2016-01-01

    Twenty years after layer-type metal halide perovskites were successfully developed, 3D metal halide perovskites (shortly, perovskites) were recently rediscovered and are attracting multidisciplinary interest from physicists, chemists, and material engineers. Perovskites have a crystal structure composed of five atoms per unit cell (ABX3) with cation A positioned at a corner, metal cation B at the center, and halide anion X at the center of six planes and unique optoelectronic properties determined by the crystal structure. Because of very narrow spectra (full width at half-maximum ≤20 nm), which are insensitive to the crystallite/grain/particle dimension and wide wavelength range (400 nm ≤ λ ≤ 780 nm), perovskites are expected to be promising high-color purity light emitters that overcome inherent problems of conventional organic and inorganic quantum dot emitters. Within the last 2 y, perovskites have already demonstrated their great potential in light-emitting diodes by showing high electroluminescence efficiency comparable to those of organic and quantum dot light-emitting diodes. This article reviews the progress of perovskite emitters in two directions of bulk perovskite polycrystalline films and perovskite nanoparticles, describes current challenges, and suggests future research directions for researchers to encourage them to collaborate and to make a synergetic effect in this rapidly emerging multidisciplinary field. PMID:27679844

  12. The Molybdate-Responsive Escherichia coli ModE Transcriptional Regulator Coordinates Periplasmic Nitrate Reductase (napFDAGHBC) Operon Expression with Nitrate and Molybdate Availability

    PubMed Central

    McNicholas, Paul M.; Gunsalus, Robert P.

    2002-01-01

    Expression of the Escherichia coli napFDAGHBC operon (also known as aeg46.5), which encodes the periplasmic molybdoenzyme for nitrate reduction, is increased in response to anaerobiosis and further stimulated by the addition of nitrate or to a lesser extent by nitrite to the cell culture medium. These changes are mediated by the transcription factors Fnr and NarP, respectively. Utilizing a napF-lacZ operon fusion, we demonstrate that napF gene expression is impaired in strain defective for the molybdate-responsive ModE transcription factor. This control abrogates nitrate- or nitrite-dependent induction during anaerobiosis. Gel shift and DNase I footprinting analyses establish that ModE binds to the napF promoter with an apparent Kd of about 35 nM at a position centered at −133.5 relative to the start of napF transcription. Although the ModE binding site sequence is similar to other E. coli ModE binding sites, the location is atypical, because it is not centered near the start of transcription. Introduction of point mutations in the ModE recognition site severely reduced or abolished ModE binding in vitro and conferred a modE phenotype (i.e., loss of molybdate-responsive gene expression) in vivo. In contrast, deletion of the upstream ModE region site rendered napF expression independent of modE. These findings indicate the involvement of an additional transcription factor to help coordinate nitrate- and molybdate-dependent napF expression by the Fnr, NarP, NarL, and ModE proteins. The upstream ModE regulatory site functions to override nitrate control of napF gene expression when the essential enzyme component, molybdate, is limiting in the cell environment. PMID:12029041

  13. Intercalation-controlled cyclodehydration of sorbitol in water over layered-niobium-molybdate solid acid.

    PubMed

    Morita, Yuya; Furusato, Shogo; Takagaki, Atsushi; Hayashi, Shigenobu; Kikuchi, Ryuji; Oyama, S Ted

    2014-03-01

    Layered niobium molybdate (HNbMoO6 ) was used in the aqueous-phase dehydration of sorbitol and was found to exhibit remarkable selectivity toward its monomolecular-dehydrated intermediate 1,4-sorbitan. This was attributed to the selective intercalation of sorbitol within the interlayers with strong Brønsted acid sites.

  14. The molybdate-binding protein (ModA) of the plant pathogen Xanthomonas axonopodis pv. citri.

    PubMed

    Balan, Andrea; Santacruz, Carolina P; Moutran, Alexandre; Ferreira, Rita C C; Medrano, Francisco J; Pérez, Carlos A; Ramos, Carlos H I; Ferreira, Luís C S

    2006-12-01

    The modABC operon of phytopathogen Xanthomonas axonopodis pv. citri (X. citri) encodes a putative ABC transporter involved in the uptake of the molybdate and tungstate anions. Sequence analyses showed high similarity values of ModA orthologs found in X. campestris pv. campestris (X. campestris) and Escherichia coli. The X. citri modA gene was cloned in pET28a and the recombinant protein, expressed in the E. coli BL21 (DE3) strain, purified by immobilized metal affinity chromatography. The purified protein remained soluble and specifically bound molybdate and tungstate with K(d) 0.29+/-0.12 microM and 0.58+/-0.14 microM, respectively. Additionally binding of molybdate drastically enhanced the thermal stability of the recombinant ModA as compared to the apoprotein. This is the first characterization of a ModA ortholog expressed by a phytopathogen and represents an important tool for functional, biochemical and structural analyses of molybdate transport in Xanthomonas species.

  15. An analysis of the binding of repressor protein ModE to modABCD (molybdate transport) operator/promoter DNA of Escherichia coli.

    PubMed

    Grunden, A M; Self, W T; Villain, M; Blalock, J E; Shanmugam, K T

    1999-08-20

    Expression of the modABCD operon in Escherichia coli, which codes for a molybdate-specific transporter, is repressed by ModE in vivo in a molybdate-dependent fashion. In vitro DNase I-footprinting experiments identified three distinct regions of protection by ModE-molybdate on the modA operator/promoter DNA, GTTATATT (-15 to -8; region 1), GCCTACAT (-4 to +4; region 2), and GTTACAT (+8 to +14; region 3). Within the three regions of the protected DNA, a pentamer sequence, TAYAT (Y = C or T), can be identified. DNA-electrophoretic mobility experiments showed that the protected regions 1 and 2 are essential for binding of ModE-molybdate to DNA, whereas the protected region 3 increases the affinity of the DNA to the repressor. The stoichiometry of this interaction was found to be two ModE-molybdate per modA operator DNA. ModE-molybdate at 5 nM completely protected the modABCD operator/promoter DNA from DNase I-catalyzed hydrolysis, whereas ModE alone failed to protect the DNA even at 100 nM. The apparent K(d) for the interaction between the modA operator DNA and ModE-molybdate was 0.3 nM, and the K(d) increased to 8 nM in the absence of molybdate. Among the various oxyanions tested, only tungstate replaced molybdate in the repression of modA by ModE, but the affinity of ModE-tungstate for modABCD operator DNA was 6 times lower than with ModE-molybdate. A mutant ModE(T125I) protein, which repressed modA-lac even in the absence of molybdate, protected the same region of modA operator DNA in the absence of molybdate. The apparent K(d) for the interaction between modA operator DNA and ModE(T125I) was 3 nM in the presence of molybdate and 4 nM without molybdate. The binding of molybdate to ModE resulted in a decrease in fluorescence emission, indicating a conformational change of the protein upon molybdate binding. The fluorescence emission spectra of mutant ModE proteins, ModE(T125I) and ModE(Q216*), were unaffected by molybdate. The molybdate-independent mutant Mod

  16. The Escherichia coli modE gene: effect of modE mutations on molybdate dependent modA expression.

    PubMed

    McNicholas, P M; Chiang, R C; Gunsalus, R P

    1996-11-15

    The Escherichia coli modABCD operon, which encodes a high-affinity molybdate uptake system, is transcriptionally regulated in response to molybdate availability by ModE. Here we describe a highly effective enrichment protocol, applicable to any gene with a repressor role, and establish its application in the isolation of transposon mutations in modE. In addition we show that disruption of the ModE C-terminus abolishes derepression in the absence of molybdate, implying this region of ModE controls the repressor activity. Finally, a mutational analysis of a proposed molybdate binding motif indicates that this motif does not function in regulating the repressor activity of ModE.

  17. Methodologies for high efficiency perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Park, Nam-Gyu

    2016-06-01

    Since the report on long-term durable solid-state perovskite solar cell in 2012, perovskite solar cells based on lead halide perovskites having organic cations such as methylammonium CH3NH3PbI3 or formamidinium HC(NH2)2PbI3 have received great attention because of superb photovoltaic performance with power conversion efficiency exceeding 22 %. In this review, emergence of perovskite solar cell is briefly introduced. Since understanding fundamentals of light absorbers is directly related to their photovoltaic performance, opto-electronic properties of organo lead halide perovskites are investigated in order to provide insight into design of higher efficiency perovskite solar cells. Since the conversion efficiency of perovskite solar cell is found to depend significantly on perovskite film quality, methodologies for fabricating high quality perovskite films are particularly emphasized, including various solution-processes and vacuum deposition method.

  18. Advances in Perovskite Solar Cells

    PubMed Central

    Zuo, Chuantian; Bolink, Henk J.; Han, Hongwei; Huang, Jinsong

    2016-01-01

    Organolead halide perovskite materials possess a combination of remarkable optoelectronic properties, such as steep optical absorption edge and high absorption coefficients, long charge carrier diffusion lengths and lifetimes. Taken together with the ability for low temperature preparation, also from solution, perovskite‐based devices, especially photovoltaic (PV) cells have been studied intensively, with remarkable progress in performance, over the past few years. The combination of high efficiency, low cost and additional (non‐PV) applications provides great potential for commercialization. Performance and applications of perovskite solar cells often correlate with their device structures. Many innovative device structures were developed, aiming at large‐scale fabrication, reducing fabrication cost, enhancing the power conversion efficiency and thus broadening potential future applications. This review summarizes typical structures of perovskite solar cells and comments on novel device structures. The applications of perovskite solar cells are discussed. PMID:27812475

  19. Synthesis and spectroscopy of new plutonium(III) and -(IV) molybdates: comparisons of electronic characteristics.

    PubMed

    Cross, Justin N; Cary, Samantha K; Stritzinger, Jared T; Polinski, Matthew J; Albrecht Schmitt, Thomas E

    2014-03-17

    Synthesis of a plutonium(III) molybdate bromide, PuMoO4Br(H2O), has been accomplished using hydrothermal techniques in an inert-atmosphere glovebox. The compound is green in color, which is in stark contrast to the typical blue color of plutonium(III) complexes. The unusual color arises from the broad charge transfer (CT) spanning from approximately 300 to 500 nm in the UV-vis-near-IR spectra. Repeating the synthesis with an increase in the reaction temperature results in the formation of a plutonium(IV) molybdate, Pu3Mo6O24(H2O)2, which also has a broad CT band and red-shifted f-f transitions. Performing an analogous reaction with neodymium produced a completely different product, [Nd(H2O)3][NdMo12O42]·2H2O, which is built of Silverton-type polyoxometallate clusters.

  20. The surface of iron molybdate catalysts used for the selective oxidation of methanol

    NASA Astrophysics Data System (ADS)

    Yeo, Benjamin R.; Pudge, Geoffrey J. F.; Bugler, Keith G.; Rushby, Alice V.; Kondrat, Simon; Bartley, Jonathan; Golunski, Stanislaw; Taylor, Stuart H.; Gibson, Emma; Wells, Peter. P.; Brookes, Catherine; Bowker, Michael; Hutchings, Graham J.

    2016-06-01

    The oxidation of methanol to formaldehyde is a major chemical process carried out catalytically and iron molybdate is one of the major catalysts for this process. In this paper we explore the nature of the active and selective surfaces of iron molybdate catalysts and show that the effective catalysts comprise molybdenum rich surfaces. We conclude that it is therefore important to maximise the surface area of these active catalysts and to this end we have studied catalysts made using a new physical grinding method with oxalic acid. For super-stoichiometric materials (Fe:Mo = 1:2.2) the reaction data show that physical mixing produces effective catalysts, possibly offering an improvement over the conventional co-precipitation method.

  1. Characterization of ligno-cellulosic materials bleached with oxo-diperoxo-molybdates.

    PubMed

    Sîrghie, Cecilia; Bodescu, Adina-Maria; Botar, Alexandru; Cavaco-Paulo, Artur; Munteanu, Florentina-Daniela

    2013-10-15

    A newly effective system was used to bleach ligno-cellulosic textile materials. This system is based on two different newly synthesized natrium oxo-diperoxo molybdates, Na2[MoO (O2)2(C2O4)] and Na2[MoO (O2)2(C6H6O7)]. These two compounds were characterized by means of cyclic voltammetry, and the bleached fabrics were fully characterized by measuring their whiteness index, percent loss in fabric weight and the content of lignin in the fabric. The obtained results revealed that good whiteness index of the bleached linen-cotton fabrics (50% linen and 50% cotton) and low content of lignin could be obtained by soaking the fabric for 55 min at 90 °C in a solution containing 3.5% of molybdate complex and 3.5% H2O2.

  2. 2-Bromoethanesulfonate, sulfate, molybdate, and ethanesulfonate inhibit anaerobic dechlorination of polychlorobiphenyls by pasteurized microorganisms

    SciTech Connect

    Ye, D. |; Quensen, J.F. III; Boyd, S.A.; Tiedje, J.M.

    1999-01-01

    Dechlorination of (PCB Aroclor 1242) by pasteurized microorganisms was inhibited by 2-bromoethanesulfonate (BES), sulfate, molybdate, and ethanesulfonate. Consumption of these anions and production of sulfide from BES were detected. The inhibition could not be relieved by hydrogen. Taken together these results suggest that pattern M dechlorination is mediated by spore-forming sulfidogenic bacteria. These results also suggest that BES may inhibit anaerobic dechlorination by nonmethanogens by more than one mechanism.

  3. Effect of chlorate, molybdate, and shikimic acid on Salmonella Typhimurium in aerobic and anaerobic cultures

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Two studies were conducted to examine the effects of shikimic acid (60 µg/mL) and(or) molybdate (1 mM) on the sensitivity of Salmonella enterica serovar Typhimurium to sodium chlorate (5 mM) during anaerobic (90% N2:5% CO2:5% H2) or aerobic growth in brain heart infusion broth supplemented with 5 mM...

  4. Ultrasensitive Visual Sensing of Molybdate Based on Enzymatic-like Etching of Gold Nanorods.

    PubMed

    Zhang, Zhiyang; Chen, Zhaopeng; Chen, Lingxin

    2015-08-25

    Here, we have developed a novel approach to the visual detection of molybdate with high sensitivity and selectivity in aqueous media based on the combination of catalytic formation of iodine and iodine-mediated etching of gold nanorods. In weak acid solution, like peroxidase, molybdate can catalyze the reaction between H2O2 and I(-) to produce I2, a moderate oxidant, which then etches gold nanorods preferentially along the longitudinal direction in the presence of hexadecyltrimethylammonium bromide. The etching results in the longitudinal localized surface plasmon resonance extinction peak shifts to short wavelength, accompanied by a color change from blue to red. Under optimal conditions, this sensor exhibits good sensitivity with a detection limit of 1.0 nM. The approach is highlighted by its high selectivity and tolerance to interference, which enables the sensor to detect molybdate directly in real samples, such as tap water, drinking water, and seawater. In addition, perhaps the proposed sensing strategy can be also used for other targets that can selectively regulate the formation of I2 under given conditions. PMID:26226196

  5. Effect of solid-phase amorphization on the spectral characteristics of europium-doped gadolinium molybdate

    NASA Astrophysics Data System (ADS)

    Shmurak, S. Z.; Kiselev, A. P.; Kurmasheva, D. M.; Red'Kin, B. S.; Sinitsyn, V. V.

    2010-05-01

    A method is proposed for detecting spectral characteristics of optically inactive molybdates of rare-earth elements by their doping with rare-earth ions whose luminescence lies in the transparency region of all structural modifications of the sample. Gadolinium molybdate is chosen as the object of investigations, while europium ions are used as an optically active and structurally sensitive admixture. It is shown that after the action of a high pressure under which gadolinium molybdate passes to the amorphous state, the spectral characteristics of Gd1.99Eu0.01(MoO4)3 (GMO:Eu) change radically; namely, considerable line broadening is observed in the luminescence spectra and the luminescence excitation spectra, while the long-wave threshold of optical absorption is shifted considerably (by approximately 1.1 eV) towards lower energies. It is found that by changing the structural state of GMO:Eu by solid-state amorphization followed by annealing, the spectral characteristics of the sample can be purposefully changed. This is extremely important for solving the urgent problem of designing high-efficiency light-emitting diodes producing “white” light.

  6. Organometal Trihalide Perovskite Spintronics

    NASA Astrophysics Data System (ADS)

    Sun, Dali

    The family of organometal trihalide perovskite (OTP), CH3NH3PbX3 (where X is halogen) has recently revolutionized the photovoltaics field, and shows promise in applications such as solar energy harnessing, light emitting diodes, field effect transistors and laser action. The OTP spin characteristic properties are influenced by the large spin-orbit-coupling of the Pb atoms, and thus may offer a new class of semiconductors for spin-based applications. In this talk we will summarize the `magnetic field effect' on photocurrent and electroluminescence in OTP optoelectronic devices, and photoluminescence from OTP films; and report more recent studies of pure spin-current and spin-aligned carrier injection in OTP spintronics devices using `spin-pumping' and `spin-injection', respectively. We measured relatively large inverse-spin-Hall effect using pulsed microwave excitation in OTP devices at resonance with a ferromagnetic (FM) layer, and giant magnetoresistance in OTP-based spin-valves. Our studies launch the field of OTP spintronics. Research sponsored by the DOE, Office of Science, Grant DE-SC0014579. Work done in collaboration with Chuang Zhang, Marzieh Kavand, Kipp J. van Schooten, Hans Malissa, Matthew Groesbeck, Ryan Mclaughlin, Christoph Boehme, and Z. Valy Vardeny.

  7. Purification of molybdenum oxide, growth and characterization of medium size zinc molybdate crystals for the LUMINEU program

    NASA Astrophysics Data System (ADS)

    Shlegel, V. N.; Berge, L.; Boiko, R. S.; Chapellier, M.; Chernyak, D. M.; Coron, N.; Danevich, F. A.; Decourt, R.; Degoda, V. Ya.; Devoyon, L.; Drillien, A.; Dumoulin, L.; Enss, C.; Fleischmann, A.; Gastaldo, L.; Giuliani, A.; Gros, M.; Herve, S.; Ivanov, I. M.; Kobychev, V. V.; Kogut, Ya. P.; Koskas, F.; Loidl, M.; Magnier, P.; Makarov, E. P.; Mancuso, M.; de Marcillac, P.; Marnieros, S.; Marrache-Kikuchi, C.; Nasonov, S. G.; Navick, X. F.; Nones, C.; Olivieri, E.; Paul, B.; Penichot, Y.; Pessina, G.; Plantevin, O.; Poda, D. V.; Redon, T.; Rodrigues, M.; Strazzer, O.; Tenconi, M.; Torres, L.; Tretyak, V. I.; Vasiliev, Ya. V.; Velazquez, M.; Viraphong, O.; Zhdankov, V. N.

    2014-01-01

    The LUMINEU program aims at performing a pilot experiment on neutrinoless double beta decay of 100Mo using radiopure ZnMoO4 crystals operated as scintillating bolometers. Growth of high quality radiopure crystals is a complex task, since there are no commercially available molybdenum compounds with the required levels of purity and radioactive contamination. This paper discusses approaches to purify molybdenum and synthesize compound for high quality radiopure ZnMoO4 crystal growth. A combination of a double sublimation (with addition of zinc molybdate) with subsequent recrystallization in aqueous solutions (using zinc molybdate as a collector) was used. Zinc molybdate crystals up to 1.5 kg were grown by the low-thermal-gradient Czochralski technique, their optical, luminescent, diamagnetic, thermal and bolometric properties were tested.

  8. Synthesis and characterization of carbon nanotubes/titanium molybdate nanocomposite and assessment of its photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Singh, Sneha; Singh, Braj Raj; Khan, Wasi; Naqvi, Alim H.

    2014-01-01

    In this study we have synthesized carbon nanotubes/titanium molybdate nanocomposite (CNT@Tm-NC), the structural, optical, thermal and dielectric properties of the as synthesized CNT@Tm-NC were studied. The XRD analysis ensures that CNT@Tm-NC has the nanostructure structure and confirmed that the titanium molybdate nanoparticles (NPs) were successfully incorporated in the CNT matrix. The thermal analysis (TGA) exhibited an enhanced thermal stability of the CNT@Tm-NC as compare with CNT owing to the strong interaction between the titanium molybdate NPs and CNT matrix. The energy band gaps as calculated through the Tauc relation were found to be higher in the CNT@Tm-NC. The impedance, dielectric constants (ɛ‧, ɛ‧‧), dielectric loss (tan δ) and AC conductivity (σac) were studied as the function of frequency, which have been explained by 'Maxwell Wagner Model'. Moreover, CNT@Tm-NC exhibited the promising photocatalytic activity for the photo-decoloration of the methyl orange (MO) dye under UV light irradiation. Results also showed protection of photo-decoloration of the MO dye by the disodium ethylenediaminetetraacetate dehydrate (EDTA-Na2; C10H14N2Na2O8ṡ2H2O) (hole scavenger) and tert-butyl alcohol (C4H10O) (radical scavenger) clearly suggested the implication of reactive oxygen species in the photocatalytic activity of CNT@Tm-NC. It is encouraging to conclude that CNT@Tm-NC bears the potential of it is applications in photocatalysis.

  9. Molybdate uptake by Agrobacterium tumefaciens correlates with the cellular molybdenum cofactor status.

    PubMed

    Hoffmann, Marie-Christine; Ali, Koral; Sonnenschein, Marleen; Robrahn, Laura; Strauss, Daria; Narberhaus, Franz; Masepohl, Bernd

    2016-09-01

    Many enzymes require the molybdenum cofactor, Moco. Under Mo-limiting conditions, the high-affinity ABC transporter ModABC permits molybdate uptake and Moco biosynthesis in bacteria. Under Mo-replete conditions, Escherichia coli represses modABC transcription by the one-component regulator, ModE, consisting of a DNA-binding and a molybdate-sensing domain. Instead of a full-length ModE protein, many bacteria have a shorter ModE protein, ModE(S) , consisting of a DNA-binding domain only. Here, we asked how such proteins sense the intracellular molybdenum status. We show that the Agrobacterium tumefaciens ModE(S) protein Atu2564 is essential for modABC repression. ModE(S) binds two Mo-boxes in the modA promoter as shown by electrophoretic mobility shift assays. Northern analysis revealed cotranscription of modE(S) with the upstream gene, atu2565, which was dispensable for ModE(S) activity. To identify genes controlling ModE(S) function, we performed transposon mutagenesis. Tn5 insertions resulting in derepressed modA transcription mapped to the atu2565-modE(S) operon and several Moco biosynthesis genes. We conclude that A. tumefaciens ModE(S) activity responds to Moco availability rather than to molybdate concentration directly, as is the case for E. coli ModE. Similar results in Sinorhizobium meliloti suggest that Moco dependence is a common feature of ModE(S) regulators.

  10. Molybdate uptake by Agrobacterium tumefaciens correlates with the cellular molybdenum cofactor status.

    PubMed

    Hoffmann, Marie-Christine; Ali, Koral; Sonnenschein, Marleen; Robrahn, Laura; Strauss, Daria; Narberhaus, Franz; Masepohl, Bernd

    2016-09-01

    Many enzymes require the molybdenum cofactor, Moco. Under Mo-limiting conditions, the high-affinity ABC transporter ModABC permits molybdate uptake and Moco biosynthesis in bacteria. Under Mo-replete conditions, Escherichia coli represses modABC transcription by the one-component regulator, ModE, consisting of a DNA-binding and a molybdate-sensing domain. Instead of a full-length ModE protein, many bacteria have a shorter ModE protein, ModE(S) , consisting of a DNA-binding domain only. Here, we asked how such proteins sense the intracellular molybdenum status. We show that the Agrobacterium tumefaciens ModE(S) protein Atu2564 is essential for modABC repression. ModE(S) binds two Mo-boxes in the modA promoter as shown by electrophoretic mobility shift assays. Northern analysis revealed cotranscription of modE(S) with the upstream gene, atu2565, which was dispensable for ModE(S) activity. To identify genes controlling ModE(S) function, we performed transposon mutagenesis. Tn5 insertions resulting in derepressed modA transcription mapped to the atu2565-modE(S) operon and several Moco biosynthesis genes. We conclude that A. tumefaciens ModE(S) activity responds to Moco availability rather than to molybdate concentration directly, as is the case for E. coli ModE. Similar results in Sinorhizobium meliloti suggest that Moco dependence is a common feature of ModE(S) regulators. PMID:27196733

  11. Analysis of solid solutions stability in scheelite-type molybdates and tungstates

    SciTech Connect

    Zhuravlev, V.D.; Reznitskikh, O.G.; Velikodnyi, Yu.A.; Patrusheva, T.A.; Sivtsova, O.V.

    2011-10-15

    Mutual solubility of bivalent metal molybdates and tungstates with scheelite structure was theoretically estimated by calculating formation enthalpies and the maximal decomposition temperatures of solid solutions at different temperatures. The theoretical stability of continuous solid solutions in binary systems of bivalent metal molybdates and tungstates was found to be higher than reported literature data. After cooling down continuous substitution solid solution should remain in following systems: CaMoO{sub 4}-CdMoO{sub 4}, SrMoO{sub 4}-MMoO{sub 4} (M=Ba, Pb), BaMoO{sub 4}-PbMoO{sub 4}, SrWO{sub 4}-MWO{sub 4} (M=Ca, Pb), and BaWO{sub 4}-PbWO{sub 4}. There is a probability that at room temperature in systems CaMoO{sub 4}-SrMoO{sub 4,} CaWO{sub 4}-PbWO{sub 4}, and BaWO{sub 4}-SrWO{sub 4} the single homogeneity region may decompose to limited solid solutions. It was shown experimentally that a continuous series of scheelite-structure solid solutions M{sub 1-x}M{sup I}{sub x}TO{sub 4} can be formed via citrate synthesis at temperatures below 500 deg. S. - Graphical abstract: Calculated boundaries of solid solutions in BaWO{sub 4}-CaWO{sub 4} (1) and PbMoO{sub 4}-CaMoO{sub 4} (2) systems. Highlights: > Stability of solid solutions molybdates and tungstates has been investigated. > The ionic model for isovalent substitutions was used. > In 'polyhedral substitution model' enthalphies of mixing were calculated. > Most of the examined series of solid solutions is stable at room temperatures. > Solid solutions M{sub 1-x}M{sup I}{sub x}Mo(W)O{sub 4} (x=0-1) were formed via citrate synthesis below 500 S.

  12. Electrical and mechanical properties of ZnO doped silver-molybdate glass-nanocomposite system

    NASA Astrophysics Data System (ADS)

    Kundu, Ranadip; Roy, Debasish; Bhattacharya, Sanjib

    2016-05-01

    Zno doped silver-molybdate glass-nanocomposites, 0.3 Ag2O - 0.7 [0.075 ZnO - 0.925 MoO3] have been prepared by melt-quenching method. Ionic conductivity of these glass-nanocomposites has been measured in wide temperature and frequency windows. Vicker's hardness methods have been employed to study micro-hardness of the as-prepared samples. Heat-treated counterparts for this glass-nanocomposites system has been analyzed in different temperature to observe the changes in conductivity as well as micro-hardness for that system.

  13. The chronic toxicity of molybdate to freshwater organisms. I. Generating reliable effects data.

    PubMed

    De Schamphelaere, K A C; Stubblefield, W; Rodriguez, P; Vleminckx, K; Janssen, C R

    2010-10-15

    The European Union regulation on Registration, Evaluation, Authorization and Restriction of Chemical substances (REACH) (EC, 2006) requires the characterization of the chronic toxicity of many chemicals in the aquatic environment, including molybdate (MoO(4)(2-)). Our literature review on the ecotoxicity of molybdate revealed that a limited amount of reliable chronic no observed effect concentrations (NOECs) for the derivation of a predicted no-effect concentration (PNEC) existed. This paper presents the results of additional ecotoxicity experiments that were conducted in order to fulfill the requirements for the derivation of a PNEC by means of the scientifically most robust species sensitivity distribution (SSD) approach (also called the statistical extrapolation approach). Ten test species were chronically exposed to molybdate (added as sodium molybdate dihydrate, Na(2)MoO(4)·2H(2)O) according to internationally accepted standard testing guidelines or equivalent. The 10% effective concentrations (EC10, expressed as measured dissolved molybdenum) for the most sensitive endpoint per species were 62.8-105.6 (mg Mo)/L for Daphnia magna (21day-reproduction), 78.2 (mg Mo)/L for Ceriodaphnia dubia (7day-reproduction), 61.2-366.2 (mg Mo)/L for the green alga Pseudokirchneriella subcapitata (72h-growth rate), 193.6 (mg Mo)/L for the rotifer Brachionus calyciflorus (48h-population growth rate), 121.4 (mg Mo)/L for the midge Chironomus riparius (14day-growth), 211.3 (mg Mo)/L for the snail Lymnaea stagnalis (28day-growth rate), 115.9 (mg Mo)/L for the frog Xenopus laevis (4day-larval development), 241.5 (mg Mo)/L for the higher plant Lemna minor (7day-growth rate), 39.3 (mg Mo)/L for the fathead minnow Pimephales promelas (34day-dry weight/biomass), and 43.2 (mg Mo)/L for the rainbow trout Oncorhynchus mykiss (78day-biomass). These effect concentrations are in line with the few reliable data currently available in the open literature. The data presented in this study can

  14. Activation energies to characterize ease of removal of various kinds of oxygen from bismuth molybdate

    SciTech Connect

    Dadyburjor, D.B.; Ruckenstein, E.

    1980-06-01

    Calculations by the method of minimum energy paths showed that oxygen(-2) anions are more easily displaced from molybdenum(VI) or from the layer between molybdenum and bismuth than from bismuth(III) of a 2:1 bismuth molybdate (Bi/sub 2/MoO/sub 6/). However, available experimental evidence suggests that the oxygen of the bismuth layer is active in the selective oxidation of hydrocarbons; apparently the presence of the hydrocarbon decreases the energy barrier required for transfer of the oxygen anion, and anion vacancies generated, e.g., in a prereduction of the catalyst, also decrease the energy barrier.

  15. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, K.D.

    1991-06-25

    Perovskites of the structure A[sub 2]B[sub 2]C[sub 3]O[sub 10] are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  16. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, Kenneth D.

    1991-01-01

    Perovskites of the structure A.sub.2 B.sub.2 C.sub.3 O.sub.10 are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  17. Sonochemical Process for the Preparation of Novel Calcium Zinc Molybdate Nanoparticles

    NASA Astrophysics Data System (ADS)

    Bhanvase, B. A.; Kadam, V. B.; Rode, T. D.; Jadhao, P. R.

    2015-06-01

    The present work deals with the use of sonochemical and conventional mixing process for the preparation of calcium zinc molybdate (CZM) nanoparticles using calcium chloride and sodium zinc molybdate as a precursor material without addition of any emulsifying agent. This new process is useful to control the size and shape of the CZM nanoparticles. The formed product was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and differential thermal analysis (DTA). The formation of CZM was confirmed through XRD, FTIR and elemental analysis. The pH and conductivity results show that sonochemical process takes less time compared to conventional process for the preparation of CZM nanoparticles. The use of sonochemical process during the preparation of CZM nanoparticles results in reduction of the size and nearly the cubic shape is obtained due to the improved solute transfer rate, rapid nucleation, and formation of a large number of nuclei in the presence of cavitation.

  18. An attempt to prepare nonchromate, self-healing protective films containing molybdate on iron

    SciTech Connect

    Aramaki, K.

    1999-11-01

    Preparation of a nonchromate, self-healing protective film on an Fe surface was attempted. A protective film of 1,2-bis(triethoxysilyl)ethane ([C{sub 2}H{sub 5}O]{sub 3} Si[CH{sub 2}]{sub 2} Si[OC{sub 2}H{sub 5}]{sub 3}) polymer containing a fine powder of ammonium heptamolybdate tetrahydrate ([NH{sub 4}]{sub 6}Mo{sub 7}O{sub 24} {center{underscore}dot} 4H{sub 2}O) was prepared on a surface of Fe electrode passivated in aerated 0.1-M sodium molybdate (Na{sub 2}MoO{sub 4}). The protective ability of this film was examined on the covered electrode in an aerated 0.1-M sodium chloride (NaCl) solution at 30 C by polarization measurement. The protection efficiency (P) of the film was significantly high, 99.0%. After the electrode coated with the film was scratched with a knife edge, the self-healing ability of the film was estimated on the electrode in the NaCl solution by polarization measurement. The P value of the film on the scratched electrode was still high, 98.8%. The anodic process of Fe corrosion markedly was suppressed by the formation of a passive film at the scratched surface with molybdate ion (MoO{sub 4}{sup {minus}}) incorporated in the polymer film, resulting in a self-healing activity of the film.

  19. Effect of chlorate, molybdate, and shikimic acid on Salmonella enterica serovar Typhimurium in aerobic and anaerobic cultures

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Chlorate is a bactericide that has potential as a pre-slaughter feed additive to improve food safety of meat products. The aims of the present study were to examine the effects of chlorate (5mM), molybdate (1 mM), and shikimate (0.34 mM) on the growth and chlorate-resistance of Salmonella enterica ...

  20. Crystallization, data collection and phasing of the molybdate-binding protein of the phytopathogen Xanthomonas axonopodis pv. citri

    SciTech Connect

    Santacruz, C. P.; Balan, A.; Ferreira, L. C. S.; Barbosa, J. A. R. G.

    2006-03-01

    The molybdate-binding protein (ModA) from X. axonopodis pv. citri was crystallized with sodium molybdate in the presence of PEG or sulfate. The crystal diffracted to a maximum resolution of 1.7 Å and belongs to the orthorhombic space group C222{sub 1,} with unit-cell parameters a = 68.15, b = 172.14, c = 112.04 Å. Xanthomonas axonopodis pv. citri ModA protein is the ABC periplasmic binding component responsible for the capture of molybdate. The protein was crystallized with sodium molybdate using the hanging-drop vapour-diffusion method in the presence of PEG or sulfate. X-ray diffraction data were collected to a maximum resolution of 1.7 Å using synchrotron radiation. The crystal belongs to the orthorhombic space group C222{sub 1}, with unit-cell parameters a = 68.15, b = 172.14, c = 112.04 Å. The crystal structure was solved by molecular-replacement methods and structure refinement is in progress.

  1. Simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate in welding fume alkaline extracts by HPLC-ICP-MS.

    PubMed

    Ščančar, Janez; Berlinger, Balázs; Thomassen, Yngvar; Milačič, Radmila

    2015-09-01

    A novel analytical procedure was developed for the simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate by anion-exchange high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Linear gradient elution from 100% water to 100% 0.7 M NaCl was applied for chromatographic separation of metal species. In standard aqueous solution at neutral pH molybdate, tungstate and vanadate exist in several aqueous species, while chromate is present as a single CrO4(2-) species. Consequently, only chromate can be separated from this solution in a sharp chromatographic peak. For obtaining sharp chromatographic peaks for molybdate, tungstate and vanadate, the pH of aqueous standard solutions was raised to 12. At highly alkaline conditions single CrO4(2-), MoO4(2-) and WO4(2-) are present and were eluted in sharp chromatographic peaks, while VO4(3-) species, which predominates at pH 12 was eluted in slightly broaden peak. In a mixture of aqueous standard solutions (pH 12) chromate, molybdate, tungstate and vanadate were eluted at retention times from 380 to 420 s, 320 to 370 s, 300 to 350 s and 240 to 360 s, respectively. Eluted species were simultaneously detected on-line by ICP-MS recording m/z 52, 95, 182 and 51. The developed procedure was successfully applied to the analysis of leachable concentrations of chromate, molybdate, tungstate and vanadate in alkaline extracts (2% NaOH+3% Na2CO3) of manual metal arc (MMA) welding fumes loaded on filters. Good repeatability and reproducibility of measurement (RSD±3.0%) for the investigated species were obtained in both aqueous standard solutions (pH 12) and in alkaline extracts of welding fumes. Low limits of detection (LODs) were found for chromate (0.02 ng Cr mL(-1)), molybdate (0.1 ng Mo mL(-1)), tungstate (0.1 ng W mL(-1)) and vanadate (0.2 ng V mL(-1)). The accuracy of analytical procedure for the determination of chromate was checked by analysis of

  2. Simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate in welding fume alkaline extracts by HPLC-ICP-MS.

    PubMed

    Ščančar, Janez; Berlinger, Balázs; Thomassen, Yngvar; Milačič, Radmila

    2015-09-01

    A novel analytical procedure was developed for the simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate by anion-exchange high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Linear gradient elution from 100% water to 100% 0.7 M NaCl was applied for chromatographic separation of metal species. In standard aqueous solution at neutral pH molybdate, tungstate and vanadate exist in several aqueous species, while chromate is present as a single CrO4(2-) species. Consequently, only chromate can be separated from this solution in a sharp chromatographic peak. For obtaining sharp chromatographic peaks for molybdate, tungstate and vanadate, the pH of aqueous standard solutions was raised to 12. At highly alkaline conditions single CrO4(2-), MoO4(2-) and WO4(2-) are present and were eluted in sharp chromatographic peaks, while VO4(3-) species, which predominates at pH 12 was eluted in slightly broaden peak. In a mixture of aqueous standard solutions (pH 12) chromate, molybdate, tungstate and vanadate were eluted at retention times from 380 to 420 s, 320 to 370 s, 300 to 350 s and 240 to 360 s, respectively. Eluted species were simultaneously detected on-line by ICP-MS recording m/z 52, 95, 182 and 51. The developed procedure was successfully applied to the analysis of leachable concentrations of chromate, molybdate, tungstate and vanadate in alkaline extracts (2% NaOH+3% Na2CO3) of manual metal arc (MMA) welding fumes loaded on filters. Good repeatability and reproducibility of measurement (RSD±3.0%) for the investigated species were obtained in both aqueous standard solutions (pH 12) and in alkaline extracts of welding fumes. Low limits of detection (LODs) were found for chromate (0.02 ng Cr mL(-1)), molybdate (0.1 ng Mo mL(-1)), tungstate (0.1 ng W mL(-1)) and vanadate (0.2 ng V mL(-1)). The accuracy of analytical procedure for the determination of chromate was checked by analysis of

  3. Polarization twist in perovskite ferrielectrics

    PubMed Central

    Kitanaka, Yuuki; Hirano, Kiyotaka; Ogino, Motohiro; Noguchi, Yuji; Miyayama, Masaru; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

    2016-01-01

    Because the functions of polar materials are governed primarily by their polarization response to external stimuli, the majority of studies have focused on controlling polar lattice distortions. In some perovskite oxides, polar distortions coexist with nonpolar tilts and rotations of oxygen octahedra. The interplay between nonpolar and polar instabilities appears to play a crucial role, raising the question of how to design materials by exploiting their coupling. Here, we introduce the concept of ‘polarization twist’, which offers enhanced control over piezoelectric responses in polar materials. Our experimental and theoretical studies provide direct evidence that a ferrielectric perovskite exhibits a large piezoelectric response because of extended polar distortion, accompanied by nonpolar octahedral rotations, as if twisted polarization relaxes under electric fields. The concept underlying the polarization twist opens new possibilities for developing alternative materials in bulk and thin-film forms. PMID:27586824

  4. Polarization twist in perovskite ferrielectrics.

    PubMed

    Kitanaka, Yuuki; Hirano, Kiyotaka; Ogino, Motohiro; Noguchi, Yuji; Miyayama, Masaru; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

    2016-09-02

    Because the functions of polar materials are governed primarily by their polarization response to external stimuli, the majority of studies have focused on controlling polar lattice distortions. In some perovskite oxides, polar distortions coexist with nonpolar tilts and rotations of oxygen octahedra. The interplay between nonpolar and polar instabilities appears to play a crucial role, raising the question of how to design materials by exploiting their coupling. Here, we introduce the concept of 'polarization twist', which offers enhanced control over piezoelectric responses in polar materials. Our experimental and theoretical studies provide direct evidence that a ferrielectric perovskite exhibits a large piezoelectric response because of extended polar distortion, accompanied by nonpolar octahedral rotations, as if twisted polarization relaxes under electric fields. The concept underlying the polarization twist opens new possibilities for developing alternative materials in bulk and thin-film forms.

  5. Polarization twist in perovskite ferrielectrics.

    PubMed

    Kitanaka, Yuuki; Hirano, Kiyotaka; Ogino, Motohiro; Noguchi, Yuji; Miyayama, Masaru; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

    2016-01-01

    Because the functions of polar materials are governed primarily by their polarization response to external stimuli, the majority of studies have focused on controlling polar lattice distortions. In some perovskite oxides, polar distortions coexist with nonpolar tilts and rotations of oxygen octahedra. The interplay between nonpolar and polar instabilities appears to play a crucial role, raising the question of how to design materials by exploiting their coupling. Here, we introduce the concept of 'polarization twist', which offers enhanced control over piezoelectric responses in polar materials. Our experimental and theoretical studies provide direct evidence that a ferrielectric perovskite exhibits a large piezoelectric response because of extended polar distortion, accompanied by nonpolar octahedral rotations, as if twisted polarization relaxes under electric fields. The concept underlying the polarization twist opens new possibilities for developing alternative materials in bulk and thin-film forms. PMID:27586824

  6. Multiferroic crossover in perovskite oxides

    NASA Astrophysics Data System (ADS)

    Weston, L.; Cui, X. Y.; Ringer, S. P.; Stampfl, C.

    2016-04-01

    The coexistence of ferroelectricity and magnetism in A B O3 perovskite oxides is rare, a phenomenon that has become known as the ferroelectric "d0 rule." Recently, the perovskite BiCoO3 has been shown experimentally to be isostructural with PbTiO3, while simultaneously the d6Co3 + ion has a high-spin ground state with C -type antiferromagnetic ordering. It has been suggested that the hybridization of Bi 6 s states with the O 2 p valence band stabilizes the polar phase, however, we have recently demonstrated that Co3 + ions in the perovskite structure can facilitate a ferroelectric distortion via the Co 3 d -O 2 p covalent interaction [L. Weston, et al., Phys. Rev. Lett. 114, 247601 (2015), 10.1103/PhysRevLett.114.247601]. In this paper, using accurate hybrid density functional calculations, we investigate the atomic, electronic, and magnetic structure of BiCoO3 to elucidate the origin of the multiferroic state. To begin with, we perform a more general first-principles investigation of the role of d electrons in affecting the tendency for perovskite materials to exhibit a ferroelectric distortion; this is achieved via a qualitative trend study in artificial cubic and tetragonal La B O3 perovskites. We choose La as the A cation so as to remove the effects of Bi 6 s hybridization. The lattice instability is identified by the softening of phonon modes in the cubic phase, as well as by the energy lowering associated with a ferroelectric distortion. For the La B O3 series, where B is a d0-d8 cation from the 3 d block, the trend study reveals that increasing the d orbital occupation initially removes the tendency for a polar distortion, as expected. However, for high-spin d5-d7 and d8 cations a strong ferroelectric instability is recovered. This effect is explained in terms of increased pseudo-Jahn-Teller (PJT) p -d vibronic coupling. The PJT effect is described by the competition between a stabilizing force (K0) that favors the cubic phase, and a vibronic term that

  7. High-performance perovskite light-emitting diodes via morphological control of perovskite films.

    PubMed

    Yu, Jae Choul; Kim, Da Bin; Jung, Eui Dae; Lee, Bo Ram; Song, Myoung Hoon

    2016-04-01

    Solution-processable perovskite materials have garnered tremendous attention because of their excellent charge carrier mobility, possibility of a tunable optical bandgap, and high photoluminescence quantum efficiency (PLQE). In particular, the uniform morphology of a perovskite film is the most important factor in realizing perovskite light-emitting diodes (PeLEDs) with high efficiency and full-coverage electroluminescence (EL). In this study, we demonstrate highly efficient PeLEDs that contain a perovskite film with a uniform morphology by introducing HBr into the perovskite precursor. The introduction of HBr into the perovskite precursor results in a perovskite film with a uniform, continuous morphology because the HBr increases the solubility of the inorganic component in the perovskite precursor and reduces the crystallization rate of the perovskite film upon spin-coating. Moreover, PeLEDs fabricated using perovskite films with a uniform, continuous morphology, which were deposited using 6 vol% HBr in a dimethylformamide (DMF)/hydrobromic acid (HBr) cosolvent, exhibited full coverage of the green EL emission. Finally, the optimized PeLEDs fabricated with perovskite films deposited using the DMF/HBr cosolvent exhibited a maximum luminance of 3490 cd m(-2) (at 4.3 V) and a luminous efficiency of 0.43 cd A(-1) (at 4.3 V). PMID:26607474

  8. Controllable synthesis and characterization of cadmium molybdate octahedral nanocrystals by coprecipitation method

    SciTech Connect

    Shahri, Zahra; Sobhani, Azam; Salavati-Niasari, Masoud

    2013-10-15

    Graphical abstract: CdMoO{sub 4} nanocrystals have been synthesized via coprecipitation method by using Cd(Sal){sub 2} and (NH{sub 4}){sub 6}Mo{sub 7}O{sub 24}·4H{sub 2}O as starting materials in water. Effects of temperature, reaction time, solvent, surfactant, cadmium and molybdate sources were investigated to reach optimum condition. It was found that particle size, morphology and phase of the final products could be greatly influenced via these parameters. - Highlights: • A facile coprecipitation method was successfully employed to prepare CdMoO{sub 4}. • The effects of some parameters were investigated. • PEG600, PVP, SDS and CTAB were used as surfactant. • Optimum condition for preparation CdMoO{sub 4} nanocrystals was investigated. - Abstract: Cadmium molybdate (CdMoO{sub 4}) nanocrystals have been successfully synthesized via coprecipitation method by using Cd(Sal){sub 2} (Sal = salicylidene) and (NH{sub 4}){sub 6}Mo{sub 7}O{sub 24}·4H{sub 2}O as starting materials in water as solvent. Effects of temperature, reaction time, solvent, surfactant and cadmium source were investigated to reach optimum condition. It was found that particle size, morphology and phase of the final products could be greatly influenced via these parameters. The products were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectra, photoluminescence (PL) spectroscopy, energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM) and transmission electron microscopy (TEM)

  9. Characterization of Molybdate Conversion Coatings for Aluminum Alloys by Electrochemical Impedance Spectroscopy

    NASA Technical Reports Server (NTRS)

    Calle, Luz Marina

    2000-01-01

    Electrochemical impedance spectroscopy (EIS) was used to investigate the corrosion inhibiting properties of newly developed proprietary molybdate conversion coatings on aluminum alloy 2024-T3 under immersion in aerated 5% (w/w) NaCl. Corrosion potential and EIS measurements were gathered for six formulations of the coating at several immersion times for two weeks. Nyquist as well as Bode plots of the data were obtained. The conversion-coated alloy panels showed an increase in the corrosion potential during the first 24 hours of immersion that later subsided and approached a steady value. Corrosion potential measurements indicated that formulations A, D, and F exhibit a protective effect on aluminum 2024-T3. The EIS spectra of the conversion-coated alloy were characterized by an impedance that is higher than the impedance of the bare alloy at all the immersion times. The low frequency impedance, Z(sub lf) (determined from the value at 0.05 Hz) for the conversion-coated alloy was higher at all the immersion times than that of the bare panel. This indicates improvement of corrosion resistance with addition of the molybdate conversion coating. Scanning electron microscopy (SEM) revealed the presence of cracks in the coating and the presence of cubic crystals believed to be calcium carbonate. Energy dispersive spectroscopy (EDS) of the test panels revealed the presence of high levels of aluminum, oxygen, and calcium but did not detect the presence of molybdenum on the test panels. X-ray photoelectron spectroscopy (XPS) indicated the presence of less than 0.01 atomic percent molybdenum on the surface of the coating.

  10. Lasing properties of new Nd 3+-doped tungstate, molybdate, and fluoride materials under selective optical pumping

    NASA Astrophysics Data System (ADS)

    Šulc, Jan; Jelínkova, Helena; Basiev, Tolstoban T.; Doroschenko, Maxim E.; Ivleva, Ludmila I.; Osiko, Vyacheslav V.; Zverev, Peter G.

    2006-02-01

    The purpose of this work was to determine the relative efficiencies of new Nd 3+-doped laser active/Raman - tungstate, molybdate, and fluoride - materials (SrWO 4, PbWO 4, BaWO 4, SrMoO 4, PbMoO 4, SrF II, and LaF 3) under selective longitudinal optical pumping by the alexandrite (~750nm), or diode (~800nm) laser. Crystals with various length, orientations and active ions concentrations were tested. To optimize the output of the tested lasers a set of input dichroic and output dielectric mirrors with different reflectivities were used. For realized lasers operating at pulsed free-running regime, threshold energy, slope efficiency, emission wavelength, and radiation polarization were determined. For each crystal, fluorescence lifetime and absorption coefficient under given pumping were established. The slope efficiency in case of Nd 3+:PbMoO 4 laser at wavelength 1054nm was measured to be 54.3% with total efficiency of 46% which is the best result obtained for all new tested crystals. For Nd 3+ doped SrWO 4, PbWO 4, and BaWO 4 crystals simultaneous laser and self-Raman emission were demonstrated in Q-switched regime. Thus newly proposed laser Raman crystals demonstrate high efficiency for Nd 3+ laser oscillations comparable with well known and widely used Nd:KGW crystal. Further improvement in the quality of tungstate and molybdate type crystals should result in further increase in lasing efficiency at 1.06μm wavelength. Self Raman frequency conversion of Nd 3+-laser oscillations in these crystals should result in high efficient pulse shortening, high peak power and new wavelengths in 1.2-1.5μm wavelength region.

  11. From Spin Glass to Spin Liquid Ground States in Pyrochlore Molybdates

    NASA Astrophysics Data System (ADS)

    Clark, Lucy

    Magnetic pyrochlores continue to generate intense interest due to the wealth of interesting behaviours that they can display as a result of their highly frustrated nature. Here we will present our study of the molybdate pyrochlore Lu2Mo2O7, which contains non-magnetic Lu3+ and an antiferromagnetic network of corner-sharing tetrahedra of Mo4+ 4d2 S = 1 ions. Magnetic susceptibility data show that Lu2Mo2O7 enters an unconventional spin glass state at Tf ~ 16 K that displays a quadratic dependence of the low temperature magnetic heat capacity, akin to that observed for its well-studied sister compound Y2Mo2O7. This spin glass transition is also clearly marked in our inelastic (CNCS, SNS) and diffuse elastic magnetic (D7, ILL) neutron scattering data. Furthermore, we will show that it is possible to topochemically substitute the oxide, O2-, ions within Lu2Mo2O7 for nitride, N3-, to produce an oxynitride molybdate pyrochlore of composition Lu2Mo2O5N2. Magnetic susceptibility measurements confirm that strong antiferromagnetic correlations persist within the oxynitride, which contains Mo5+ 4d1 S =1/2 ions and is thus a prime candidate to host exotic quantum spin liquid behavior. We will discuss how the enhanced quantum spin fluctuations in Lu2Mo2O5N2 appear to suppress the spin freezing transition observed in its parent oxide and instead support the formation of a gapless spin liquid phase that displays a linear dependence of the low temperature magnetic heat capacity.

  12. Flexible Hybrid Organic-Inorganic Perovskite Memory.

    PubMed

    Gu, Chungwan; Lee, Jang-Sik

    2016-05-24

    Active research has been done on hybrid organic-inorganic perovskite materials for application to solar cells with high power conversion efficiency. However, this material often shows hysteresis, which is undesirable, shift in the current-voltage curve. The hysteresis may come from formation of defects and their movement in perovskite materials. Here, we utilize the defects in perovskite materials to be used in memory operations. We demonstrate flexible nonvolatile memory devices based on hybrid organic-inorganic perovskite as the resistive switching layer on a plastic substrate. A uniform perovskite layer is formed on a transparent electrode-coated plastic substrate by solvent engineering. Flexible nonvolatile memory based on the perovskite layer shows reproducible and reliable memory characteristics in terms of program/erase operations, data retention, and endurance properties. The memory devices also show good mechanical flexibility. It is suggested that resistive switching is done by migration of vacancy defects and formation of conducting filaments under the electric field in the perovskite layer. It is believed that organic-inorganic perovskite materials have great potential to be used in high-performance, flexible memory devices. PMID:27093096

  13. Achieving High Performance Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Yang, Yang

    2015-03-01

    Recently, metal halide perovskite based solar cell with the characteristics of rather low raw materials cost, great potential for simple process and scalable production, and extreme high power conversion efficiency (PCE), have been highlighted as one of the most competitive technologies for next generation thin film photovoltaic (PV). In UCLA, we have realized an efficient pathway to achieve high performance pervoskite solar cells, where the findings are beneficial to this unique materials/devices system. Our recent progress lies in perovskite film formation, defect passivation, transport materials design, interface engineering with respect to high performance solar cell, as well as the exploration of its applications beyond photovoltaics. These achievements include: 1) development of vapor assisted solution process (VASP) and moisture assisted solution process, which produces perovskite film with improved conformity, high crystallinity, reduced recombination rate, and the resulting high performance; 2) examination of the defects property of perovskite materials, and demonstration of a self-induced passivation approach to reduce carrier recombination; 3) interface engineering based on design of the carrier transport materials and the electrodes, in combination with high quality perovskite film, which delivers 15 ~ 20% PCEs; 4) a novel integration of bulk heterojunction to perovskite solar cell to achieve better light harvest; 5) fabrication of inverted solar cell device with high efficiency and flexibility and 6) exploration the application of perovskite materials to photodetector. Further development in film, device architecture, and interfaces will lead to continuous improved perovskite solar cells and other organic-inorganic hybrid optoelectronics.

  14. Stability of organometal perovskites with organic overlayers

    SciTech Connect

    Tran, Catherine D. T.; Liu, Yi; Thibau, Emmanuel S.; Llanos, Adrian; Lu, Zheng-Hong

    2015-08-15

    The air-stability of vapour-phase-deposited methylammonium lead triiodide (CH{sub 3}NH{sub 3}PbI{sub 3}) perovskite thin films has been studied using X-ray diffraction. It is found that the perovskite structure without organic coating decomposes completely within a short period of time (∼two days) upon exposure to ambient environment. The degradation of the perovskite structure is drastically reduced when the perovskite films are capped with thin N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) films. We discovered that the amount of lead iodide (PbI{sub 2}), a product of the degradation, grows as a function of time in a sigmoidal manner. Further mathematical modeling analysis shows that the perovskite degradation follows the Avrami equation, a kinetics theory developed for quantifying phase transformations in solid-state materials.

  15. Non-collinear magnetism in multiferroic perovskites.

    PubMed

    Bousquet, Eric; Cano, Andrés

    2016-03-31

    We present an overview of the current interest in non-collinear magnetism in multiferroic perovskite crystals. We first describe the different microscopic mechanisms giving rise to the non-collinearity of spins in this class of materials. We discuss, in particular, the interplay between non-collinear magnetism and ferroelectric and antiferrodistortive distortions of the perovskite structure, and how this can promote magnetoelectric responses. We then provide a literature survey on non-collinear multiferroic perovskites. We discuss numerous examples of spin cantings driving weak ferromagnetism in transition metal perovskites, and of spin-induced ferroelectricity as observed in the rare-earth based perovskites. These examples are chosen to best illustrate the fundamental role of non-collinear magnetism in the design of multiferroicity.

  16. Organohalide Lead Perovskites for Photovoltaic Applications.

    PubMed

    Yusoff, Abd Rashid Bin Mohd; Nazeeruddin, Mohammad Khaja

    2016-03-01

    Perovskite solar cells have recently exhibited a significant leap in efficiency due to their broad absorption, high optical absorption coefficient, very low exciton binding energy, long carrier diffusion lengths, efficient charge collection, and very high open-circuit potential, similar to that of III-IV semiconductors. Unlike silicon solar cells, perovskite solar cells can be developed from a variety of low-temperature solutions processed from inexpensive raw materials. When the perovskite absorber film formation is optimized using solvent engineering, a power conversion efficiency of over 21% has been demonstrated, highlighting the unique photovoltaic properties of perovskite materials. Here, we review the current progress in perovskite solar cells and charge transport materials. We highlight crucial challenges and provide a summary and prospects. PMID:26885884

  17. Non-destructive analysis of didymium and praseodymium molybdate crystals using energy dispersive X-ray fluorescence technique

    NASA Astrophysics Data System (ADS)

    Bhat, C. K.; Joseph, Daisy; Pandita, Sanjay; Kotru, P. N.

    2016-08-01

    Analysis of didymium (Di) and praseodymium molybdate crystals were carried out using energy dispersive X-ray fluorescence (EDXRF). The assigned empirical chemical formulae of the composites were tested and verified by the EDXRF technique by estimating experimental major elemental concentration ratios. On the Basis of these ratios, the established formulae for some of the composite materials have been verified and suggestions made for their refinement. Non-destructive technique used in this analysis enables to retain the original crystal samples and makes rapid simultaneous scan of major elements such as La, Pr, Ned and Mo as well as impurities such as Ce. Absence of samarium(Sm) in the spectrum during analysis of didymium molybdate crystals indicated an incomplete growth of mixed rare earth single crystal. These crystals (e.g.,Di) are shown to be of modified stoichiometry with Ce as trace impurity.

  18. Large Grained Perovskite Solar Cells Derived from Single-Crystal Perovskite Powders with Enhanced Ambient Stability.

    PubMed

    Yen, Hung-Ju; Liang, Po-Wei; Chueh, Chu-Chen; Yang, Zhibin; Jen, Alex K-Y; Wang, Hsing-Lin

    2016-06-15

    In this study, we demonstrate the large grained perovskite solar cells prepared from precursor solution comprising single-crystal perovskite powders for the first time. The resultant large grained perovskite thin film possesses a negligible physical (structural) gap between each large grain and is highly crystalline as evidenced by its fan-shaped birefringence observed under polarized light, which is very different from the thin film prepared from the typical precursor route (MAI + PbI2).

  19. Formation of gas-phase. pi. -allyl radicals from propylene over bismuth oxide and. gamma. -bismuth molybdate catalysts

    SciTech Connect

    Martir, W.; Lunsford, J.H.

    1981-07-01

    Gas-phase ..pi..-allyl radicals were produced when propylene reacted over Bi/sub 2/O/sub 3/ and ..gamma..-bismuth molybdate catalysts at 723 K. The pressure in the catalyst zone was varied between 5 x 10/sup -3/ and 1 torr. The radicals were detected by EPR spectroscopy together with a matrix isolation technique in which argon was used as the diluent. The matrix was formed on a sapphire rod at 12 K which was located 33-cm downstream from the catalyst. Bismuth oxide was more effective in the production of gas-phase allyl radicals than ..gamma..-bismuth molybdate. By contrast ..cap alpha..-bismuth molybdate was ineffective in forming allyl radicals and MoO/sub 3/ acted as a sink for radicals which were produced elsewhere in the system. Comparison of the ..pi..-allyl radical and the stable product concentrations over Bi/sub 2/O/sub 3/ revealed that gas-phase radical recombination reactions served as a major pathway for the formation of 1,5-hexadiene. Addition of small amounts of gas-phase oxygen increased the concentration of allyl radicals, and at greater oxygen levels allyl peroxy radicals were detected. Because of the effect of temperature on the equilibrium between allyl and allyl peroxy radicals, the latter product must be formed in the cooler part of the system.

  20. Surface properties of AZ91 magnesium alloy after PEO treatment using molybdate salts and low current densities

    NASA Astrophysics Data System (ADS)

    Pezzato, Luca; Brunelli, Katya; Napolitani, Enrico; Magrini, Maurizio; Dabalà, Manuele

    2015-12-01

    Plasma electrolytic oxidation (PEO) process is a recently developed electrochemical method used to produce on the surface of various metals oxide ceramic coatings that improve corrosion and wear properties of the substrate. In this work, PEO process was applied on AZ91 magnesium alloy using low current densities (0.05 A/cm2) and an alkaline solution of silicates with different concentrations of sodium molybdate (0.3-3 g/l). The effect of the low current densities of process and of molybdate salts on the corrosion resistance of the coatings was studied with potentiodynamic polarization tests and electrochemical impedance spectroscopy (EIS) in chloride and sulfate environment. The morphology, the phases and the chemical composition of the coatings were examined using a scanning electron microscope equipped with EDS, X-ray diffraction, secondary ion mass spectrometry and X-ray photoelectron spectroscopy. The corrosion properties of the PEO coated samples were remarkably improved if compared with the uncoated samples. The addition of sodium molybdate, in determinate conditions, had a positive effect on the characteristics of the coatings in terms of corrosion resistance.

  1. Perovskites: transforming photovoltaics, a mini-review

    DOE PAGESBeta

    Chilvery, Ashwith Kumar; Batra, Ashok K.; Yang, Bin; Xiao, Kai; Guggilla, Padmaja; Aggarwal, Mohan D.; Surabhi, Raja; Lal, Ravi B.; Currie, James R.; Penn, Benjamin G.

    2015-01-06

    The recent power-packed advent of perovskite solar cells is transforming photovoltaics (PV) with their superior efficiencies, ease of fabrication, and cost. This perovskite solar cell further boasts of many unexplored features that can further enhance its PV properties and lead to it being branded as a successful commercial product. This paper provides a detailed insight of the organometal halide based perovskite structure, its unique stoichiometric design, and its underlying principles for PV applications. Finally, the compatibility of various PV layers and its fabrication methods is also discussed.

  2. Templated Synthesis of Uniform Perovskite Nanowire Arrays.

    PubMed

    Ashley, Michael J; O'Brien, Matthew N; Hedderick, Konrad R; Mason, Jarad A; Ross, Michael B; Mirkin, Chad A

    2016-08-17

    While the chemical composition of semiconducting metal halide perovskites can be precisely controlled in thin films for photovoltaic devices, the synthesis of perovskite nanostructures with tunable dimensions and composition has not been realized. Here, we describe the templated synthesis of uniform perovskite nanowires with controlled diameter (50-200 nm). Importantly, by providing three examples (CH3NH3PbI3, CH3NH3PbBr3, and Cs2SnI6), we show that this process is composition general and results in oriented nanowire arrays on transparent conductive substrates. PMID:27501464

  3. Strongly correlated perovskite fuel cells

    NASA Astrophysics Data System (ADS)

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

    2016-06-01

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

  4. Strongly correlated perovskite fuel cells.

    PubMed

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

    2016-05-16

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

  5. Strongly correlated perovskite fuel cells.

    PubMed

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

    2016-06-01

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations. PMID:27279218

  6. Decomposition of molybdate-hexamethylenetetramine complex: One single source route for different catalytic materials

    SciTech Connect

    Chouzier, Sandra; Czeri, Tivadar; Roy-Auberger, Magalie; Pichon, Christophe; Geantet, Christophe; Vrinat, Michel; Afanasiev, Pavel

    2011-10-15

    Decomposition of ammonium heptamolybdate-hexamethylentetramine (HMTA) complex (HMTA){sub 2}(NH{sub 4}){sub 4}Mo{sub 7}O{sub 24}.2H{sub 2}O was studied as a function of treatment conditions in the range 300-1173 K. The evolution of solid products during decomposition was studied by thermal analysis and in situ EXAFS. Depending on the nature of the gas used for treatment, single phases of highly dispersed nitrides Mo{sub 2}N, carbide Mo{sub 2}C, or oxide MoO{sub 2} can be obtained. The nature of the products obtained was explained by qualitative thermodynamical considerations. Morphology of the solids considerably depends on such preparation parameters as temperature and mass velocity of the gas flow. For the nitride-based materials, catalytic activity was evaluated in the model thiophene HDS reaction. It was demonstrated that NH{sub 3}-treated samples showed better catalytic activity than N{sub 2}-treated ones due to cleaner surface and better morphology. Transmission microscopy, XRD and XPS studies showed that MoS{sub 2} is formed on the surface during HDS reaction or sulfidation with H{sub 2}S. Optimized nitride-derived catalysts showed mass activity several times higher than unsupported MoS{sub 2} or MoS{sub 2}/Al{sub 2}O{sub 3} reference catalyst. - Graphical Abstract: Depending on the conditions, decomposition of molybdate-HTMA complex yields highly dispersed molybdenum nitride, carbide or oxide. Research Highlights: > Decomposition of molybdate-HTMA complex yields highly dispersed Mo{sub 2}N, Mo{sub 2}C or MoO{sub 2}. > In situ EXAFS shows formation of common amorphous product MoC{sub x}N{sub y}O{sub z} at 673 K. > Crystalline Mo{sub 2}N with surface area near 200 m{sup 2}/g was obtained at 823 K. > High mass activity in thiophene HDS was observed.

  7. High-performance perovskite light-emitting diodes via morphological control of perovskite films

    NASA Astrophysics Data System (ADS)

    Yu, Jae Choul; Kim, Da Bin; Jung, Eui Dae; Lee, Bo Ram; Song, Myoung Hoon

    2016-03-01

    Solution-processable perovskite materials have garnered tremendous attention because of their excellent charge carrier mobility, possibility of a tunable optical bandgap, and high photoluminescence quantum efficiency (PLQE). In particular, the uniform morphology of a perovskite film is the most important factor in realizing perovskite light-emitting diodes (PeLEDs) with high efficiency and full-coverage electroluminescence (EL). In this study, we demonstrate highly efficient PeLEDs that contain a perovskite film with a uniform morphology by introducing HBr into the perovskite precursor. The introduction of HBr into the perovskite precursor results in a perovskite film with a uniform, continuous morphology because the HBr increases the solubility of the inorganic component in the perovskite precursor and reduces the crystallization rate of the perovskite film upon spin-coating. Moreover, PeLEDs fabricated using perovskite films with a uniform, continuous morphology, which were deposited using 6 vol% HBr in a dimethylformamide (DMF)/hydrobromic acid (HBr) cosolvent, exhibited full coverage of the green EL emission. Finally, the optimized PeLEDs fabricated with perovskite films deposited using the DMF/HBr cosolvent exhibited a maximum luminance of 3490 cd m-2 (at 4.3 V) and a luminous efficiency of 0.43 cd A-1 (at 4.3 V).Solution-processable perovskite materials have garnered tremendous attention because of their excellent charge carrier mobility, possibility of a tunable optical bandgap, and high photoluminescence quantum efficiency (PLQE). In particular, the uniform morphology of a perovskite film is the most important factor in realizing perovskite light-emitting diodes (PeLEDs) with high efficiency and full-coverage electroluminescence (EL). In this study, we demonstrate highly efficient PeLEDs that contain a perovskite film with a uniform morphology by introducing HBr into the perovskite precursor. The introduction of HBr into the perovskite precursor results in

  8. Use of molybdate as novel complex-forming selector in the analysis of polyhydric phenols by capillary zone electrophoresis.

    PubMed

    Polásek, Miroslav; Petriska, Ivan; Pospísilová, Marie; Jahodár, Ludek

    2006-03-15

    Molybdate was examined as a complex-forming additive to the CE background electrolytes (BGE) to affect the selectivity of separation of polyhydric phenols such as flavonoids (apigenin, hyperoside, luteolin, quercetin and rutin) and hydroxyphenylcarboxylic acids (ferulic, caffeic, p-coumaric and chlorogenic acid). Effects of the buffer concentrations and pH and the influence of molybdate concentration on the migration times of the analytes were investigated. In contrast to borate (which is a buffering and complex-forming agent generally used in CE at pH > or =9) molybdate forms more stable complexes with aromatic o-dihydroxy compounds and hence the complex-formation effect is observed at considerably lower pH. Model mixtures of cinnamic acid, ferulic acid, caffeic acid and 3-hydroxycinnamic acid were separated with 25 mM morpholinoethanesulfonic acid of pH 5.4 (adjusted with Tris) containing 0.15 mM sodium molybdate as the BGE (25 kV, silica capillary effective length 45 cm x 0.1mm I.D., UV-vis detection at 280 nm). With 25 mM 2-hydroxy-3-[4-(2-hydroxyethyl)-1-piperazinyl]propanesulphonic acid/Tris of pH* 7.4 containing 2mM sodium molybdate in aqueous 25% (v/v) methanol as the BGE mixtures of all the above mentioned flavonoids, p-coumaric acid and chlorogenic acid could be separated (the same capillary as above, UV-vis detection at 263 nm). The calibration curves (analyte peak area versus concentration) were rectilinear (r>0.998) for approximately 8-35 microg/ml of an analyte (with 1-nitroso-2-naphthol as internal standard). The limit of quantification values ranged between 1.1 mg l(-1) for p-coumaric acid and 2.8 mg l(-1) for quercetin. The CE method was employed for the assay of flavonoids in medicinal plant extracts. The R.S.D. values ranged between 0.9 and 4.7% (n=3) when determining luteolin (0.08%) and apigenin (0.92%) in dry Matricaria recutita flowers and rutin (1.03%) and hyperoside (0.82%) in dry Hypericum perforatum haulm. The recoveries were >96%. PMID

  9. New double molybdate Na9Fe(MoO4)6: Synthesis, structure, properties

    NASA Astrophysics Data System (ADS)

    Savina, Aleksandra A.; Solodovnikov, Sergey F.; Basovich, Olga M.; Solodovnikova, Zoya A.; Belov, Dmitry A.; Pokholok, Konstantin V.; Gudkova, Irina A.; Stefanovich, Sergey Yu.; Lazoryak, Bogdan I.; Khaikina, Elena G.

    2013-09-01

    A new double molybdate Na9Fe(MoO4)6 was synthesized using solid state reactions and studied with X-ray powder diffraction, second harmonic generation (SHG) technique, differential scanning calorimetry, X-ray fluorescence analysis, Mössbauer and dielectric impedance spectroscopy. Single crystals of Na9Fe(MoO4)6 were obtained and its structure was solved (the space group R3¯, a=14.8264(2), c=19.2402(3) Å, V=3662.79(9) Å3, Z=6, R=0.0132). The structure is related to that of sodium ion conductor II-Na3Fe2(AsO4)3. The basic structure units are polyhedral clusters composed of central FeО6 octahedron sharing edges with three Na(1)О6 octahedra. The clusters share common vertices with bridging МоО4 tetrahedra to form an open 3D framework where the cavities are occupied by Na(2) and Na(3) atoms. The compound melts incongruently at 904.7±0.2 K. Arrhenius type temperature dependence of electric conductivity σ has been registered in solid state (σ=6.8×10-2 S сm-1 at 800 K), thus allowing considering Na9Fe(MoO4)6 as a new sodium ion conductor.

  10. Black lead molybdate nanoparticles: Facile synthesis and photocatalytic properties responding to visible light

    NASA Astrophysics Data System (ADS)

    Du, Weimin; Liu, Lixin; Zhou, Keke; Ma, Xiaodan; Hao, Yaming; Qian, Xuefeng

    2015-02-01

    Black lead molybdate (PbMoO4) nanoparticles were first synthesized by the glycol-solvothermal method. Phase, morphology, crystal lattice, and specific surface of products were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and Brunauer-Emmett-Teller nitrogen adsorption-desorption, respectively. Results revealed that the as-synthesized PbMoO4 nanoparticles are the scheelite-type tetragonal structure with 30-50 nm in size. Also, glycol played a dual function in present synthetic system: solvent and surface modification agent. Optical properties reveal glycol-modification on the surface of PbMoO4 nanoparticles can generate new energy level between the original conduction band and valence band, leading to better absorption of visible light and the black appearance. Photocatalytic experimental results demonstrate that black PbMoO4 nanoparticles synthesized in glycol medium have pretty visible-light-responsive photocatalytic degradation performance on methylene blue and phenol solution. Reaction mechanism investigations show that the excellent photocatalytic activities of black PbMoO4 nanoparticles derive from the novel energy band structure, smaller size, and larger specific surface area. Hence one can see that black PbMoO4 nanoparticles are a type of visible-light-responsive photocatalysts with excellent photocatalytic activities and potentially applied prospects in dye wastewater treatment and environmental protection. Meanwhile, the present work provides an innovative strategy for adjusting the energy band structure of wide band-gap semiconductors.

  11. Kinetics and mechanism of reaction between silver molybdate and mercuric iodide in solid state

    SciTech Connect

    Beg, M.A.; Rafiuddin

    1987-05-01

    The kinetics and the mechanism of the reaction between silver molybdate and mercuric iodide were studied in the solid state by X-ray, chemical analysis, and electrical conductivity measurements. This is a multistep reaction where Ag/sub 2/HgI/sub 4/ is formed as an intermediate. In an equimolar mixture of Ag/sub 2/MoO/sub 4/ and HgI/sub 2/, AgI an HgMoO/sub 4/ are formed, whereas in a 1:2 molar mixture Ag/sub 2/HgI/sub 4/ and HgMoO/sub 4/ are formed. The data for lateral diffusion best fit the equation X/sup n/ = kt, where X is the product thickness, t is time, and k and n are constants. This is a multistep solid state ionic reaction initiated by the diffusion of HgI/sub 2/ molecules as such and not through counterdiffusion of cations.

  12. Removal of molybdate anions from water by adsorption on zeolite-supported magnetite.

    PubMed

    Verbinnen, Bram; Block, Chantal; Hannes, Dries; Lievens, Patrick; Vaclavikova, Miroslava; Stefusova, Katarina; Gallios, Georgios; Vandecasteele, Carlo

    2012-09-01

    Industrial wastewater may contain high molybdenum concentrations, making treatment before discharge necessary. In this paper, the removal of molybdate anions from water is presented, using clinoptilolite zeolite coated with magnetite nanoparticles. In batch experiments the influence of pH, ionic strength, possible interfering (oxy)anions, temperature and contact time is investigated. Besides determination of kinetic parameters and adsorption isotherms, thermodynamic modeling is performed to get better insight into the adsorption mechanism; molybdenum is assumed to be adsorbed as a FeOMoO2(OH).2H2O inner-sphere complex. At the optimum pH of 3, the adsorption capacity is around 18 mg molybdenum per gram adsorbent. The ionic strength of the solution has no influence on the adsorption capacity. Other anions, added to the molybdenum solution in at least a tenfold excess, only have a minor influence on the adsorption of molybdenum, with the exception of phosphate. Adsorption increases when temperature is increased. It is demonstrated that the adsorbent can be used to remove molybdenum from industrial wastewater streams, and that the limitations set by the World Health Organization (residual concentration of 70 microg/l Mo) can easily be met.

  13. Catalytic oxidation of propylene--7. Use of temperature programmed reoxidation to characterize. gamma. -bismuth molybdate

    SciTech Connect

    Uda, T.; Lin, T.T.; Keulks, G.W.

    1980-03-01

    Temperature-programed reoxidation of propylene-reduced ..gamma..-Bi/sub 2/MoO/sub 6/ revealed a low-temperature peak (LTP) at 158/sup 0/C and a high-temperature peak (HTP) at 340/sup 0/C. Auger spectroscopy and X-ray diffraction of reduced and partially or completely reoxidized bismuth molybdate showed that at the LTP, molybdenum(IV) is oxidized to molybdenum(VI) and bismuth, from the metallic state to an oxidation state between zero and three, and that the HTP is associated with the complete oxidation of bismuth to bismuth(III). Activity tests for propylene oxidation showed lower acrolein formation on the catalyst, on which only the LTP was reoxidized than on catalysts on which both peaks were reoxidized. The reoxidation kinetics of the catalyst under conditions corresponding to the LTP showed an activation energy of 22.9 kcal/mole below 170/sup 0/C and near zero above 170/sup 0/C; the break in the Arrhenius plot of reoxidation of the catalyst under conditions corresponding to the HTP was at 400/sup 0/C, with activation energies of 46 kcal/mole at lower and near zero at higher temperatures. Propylene oxidation was apparently rate-limited by the HTP reoxidation process below 400/sup 0/C and by allylic hydrogen abstraction above 400/sup 0/C.

  14. Kinetics and characterization of bismuth molybdate catalysts. 1. A gradientless partial oxidation reactor

    SciTech Connect

    Burban, P.M.; Schuit, G.C.A.; Bicschoff, K.B. ); Koch, T.A. Du Pont Experimental Station, Wilmington, DE )

    1990-12-01

    A gradientless laboratory fixed bed reactor was designed for studying the partial oxidation of 1-butene to 1,3-butadiene over bismuth-molybdate catalysts. By dilution of the catalyst bed with inert silicon carbide, axial catalyst bed temperature gradients were routinely reduced to 2 K or less over the temperature range 650-740 K for the exothermic model reaction. A systematic experimental procedure was developed and used to show that potential transport 'disguises' did not significantly influence the intrinsic rate of butadiene formation measured under both integral and differential conditions. For one Bi{sub 2}MoO{sub 6} catalyst system, rate of butadiene formation data over the temperature range 700-740 K were fit to pseudo first-order (in butene) kinetics. Analytical solutions of the governing equations describing fixed bed reactor transport disguises for first-order catalytic reactions were used to confirm that the reactor operated in a near gradientless fashion, in agreement with experiment.

  15. Perovskite thin films via atomic layer deposition.

    PubMed

    Sutherland, Brandon R; Hoogland, Sjoerd; Adachi, Michael M; Kanjanaboos, Pongsakorn; Wong, Chris T O; McDowell, Jeffrey J; Xu, Jixian; Voznyy, Oleksandr; Ning, Zhijun; Houtepen, Arjan J; Sargent, Edward H

    2015-01-01

    A new method to deposit perovskite thin films that benefit from the thickness control and conformality of atomic layer deposition (ALD) is detailed. A seed layer of ALD PbS is place-exchanged with PbI2 and subsequently CH3 NH3 PbI3 perovskite. These films show promising optical properties, with gain coefficients of 3200 ± 830 cm(-1) .

  16. Modeling Anomalous Hysteresis in Perovskite Solar Cells.

    PubMed

    van Reenen, Stephan; Kemerink, Martijn; Snaith, Henry J

    2015-10-01

    Organic-inorganic lead halide perovskites are distinct from most other semiconductors because they exhibit characteristics of both electronic and ionic motion. Accurate understanding of the optoelectronic impact of such properties is important to fully optimize devices and be aware of any limitations of perovskite solar cells and broader optoelectronic devices. Here we use a numerical drift-diffusion model to describe device operation of perovskite solar cells. To achieve hysteresis in the modeled current-voltage characteristics, we must include both ion migration and electronic charge traps, serving as recombination centers. Trapped electronic charges recombine with oppositely charged free electronic carriers, of which the density depends on the bias-dependent ion distribution in the perovskite. Our results therefore show that reduction of either the density of mobile ionic species or carrier trapping at the perovskite interface will remove the adverse hysteresis in perovskite solar cells. This gives a clear target for ongoing research effort and unifies previously conflicting experimental observations and theories.

  17. Ambipolar solution-processed hybrid perovskite phototransistors

    PubMed Central

    Li, Feng; Ma, Chun; Wang, Hong; Hu, Weijin; Yu, Weili; Sheikh, Arif D.; Wu, Tom

    2015-01-01

    Organolead halide perovskites have attracted substantial attention because of their excellent physical properties, which enable them to serve as the active material in emerging hybrid solid-state solar cells. Here we investigate the phototransistors based on hybrid perovskite films and provide direct evidence for their superior carrier transport property with ambipolar characteristics. The field-effect mobilities for triiodide perovskites at room temperature are measured as 0.18 (0.17) cm2 V−1 s−1 for holes (electrons), which increase to 1.24 (1.01) cm2 V−1 s−1 for mixed-halide perovskites. The photoresponsivity of our hybrid perovskite devices reaches 320 A W−1, which is among the largest values reported for phototransistors. Importantly, the phototransistors exhibit an ultrafast photoresponse speed of less than 10 μs. The solution-based process and excellent device performance strongly underscore hybrid perovskites as promising material candidates for photoelectronic applications. PMID:26345730

  18. Perovskite solar cells: from materials to devices.

    PubMed

    Jung, Hyun Suk; Park, Nam-Gyu

    2015-01-01

    Perovskite solar cells based on organometal halide light absorbers have been considered a promising photovoltaic technology due to their superb power conversion efficiency (PCE) along with very low material costs. Since the first report on a long-term durable solid-state perovskite solar cell with a PCE of 9.7% in 2012, a PCE as high as 19.3% was demonstrated in 2014, and a certified PCE of 17.9% was shown in 2014. Such a high photovoltaic performance is attributed to optically high absorption characteristics and balanced charge transport properties with long diffusion lengths. Nevertheless, there are lots of puzzles to unravel the basis for such high photovoltaic performances. The working principle of perovskite solar cells has not been well established by far, which is the most important thing for understanding perovksite solar cells. In this review, basic fundamentals of perovskite materials including opto-electronic and dielectric properties are described to give a better understanding and insight into high-performing perovskite solar cells. In addition, various fabrication techniques and device structures are described toward the further improvement of perovskite solar cells.

  19. Multiferroicity in Perovskite Manganite Superlattice

    NASA Astrophysics Data System (ADS)

    Tao, Yong-Mei; Jiang, Xue-Fan; Liu, Jun-Ming

    2016-08-01

    Multiferroic properties of short period perovskite type manganite superlattice ((R1MnO3)n/(R2MnO3)n (n=1,2,3)) are considered within the framework of classical Heisenberg model using Monte Carlo simulation. Our result revealed the interesting behaviors in Mn spins structure in superlattice. Apart from simple plane spin cycloid structure which is shown in all manganites including bulk, film, and superlattice here in low temperature, a non-coplanar spiral spin structure is exhibited in a certain temperature range when n equals 1, 2 or 3. Specific heat, spin-helicity vector, spin correlation function, spin-helicity correlation function, and spin configuration are calculated to confirm this non-coplanar spiral spin structure. These results are associated with the competition among exchange interaction, magnetic anisotropy, and Dzyaloshinskii-Moriya interaction. Supported by the National Natural Science Foundation of China (NSFC) under Grant No. 11447136

  20. Effect of Perovskite Overlayers on TiO2 Electrodes in Perovskite-Sensitized Solar Cells.

    PubMed

    Kim, Kang-Pil; Kim, Jeong-Hwa; Hwang, Dae-Kue

    2016-05-01

    In this paper, we have studied the effect of the thickness of a CH3NH3PbI3 perovskite overlayer on mesoporous TiO2 electrodes in perovskite solar cells. The overlayers were prepared by spin coating PbI2 films on the electrodes, which were subsequently exposed to a CH3NH3I/2-propanol solution. We controlled the thickness of the perovskite overlayer by changing the PbI2 solution concentration. The thicknesses of the overlayers spin-coated from 0.5, 0.75, 0.9, and 1 M PbI2 solutions were approximately 179, 262, 316, and 341 nm, respectively. Perovskite solar cells with an approximately 316-nm-thick overlayer showed the highest efficiency of 9.11%. We conclude that optimization of the perovskite overlayer thickness in the solar cell structure is necessary to improve the cell efficiency. PMID:27483921

  1. Making and Breaking of Lead Halide Perovskites.

    PubMed

    Manser, Joseph S; Saidaminov, Makhsud I; Christians, Jeffrey A; Bakr, Osman M; Kamat, Prashant V

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  2. X-ray imaging: Perovskites target X-ray detection

    NASA Astrophysics Data System (ADS)

    Heiss, Wolfgang; Brabec, Christoph

    2016-05-01

    Single crystals of perovskites are currently of interest to help fathom fundamental physical parameters limiting the performance of perovskite-based polycrystalline solar cells. Now, such perovskites offer a technology platform for optoelectronic devices, such as cheap and sensitive X-ray detectors.

  3. Efficient Visible Quasi-2D Perovskite Light-Emitting Diodes.

    PubMed

    Byun, Jinwoo; Cho, Himchan; Wolf, Christoph; Jang, Mi; Sadhanala, Aditya; Friend, Richard H; Yang, Hoichang; Lee, Tae-Woo

    2016-09-01

    Efficient quasi-2D-structure perovskite light-emitting diodes (4.90 cd A(-1) ) are demonstrated by mixing a 3D-structured perovskite material (methyl ammonium lead bromide) and a 2D-structured perovskite material (phenylethyl ammonium lead bromide), which can be ascribed to better film uniformity, enhanced exciton confinement, and reduced trap density. PMID:27334788

  4. Efficient Visible Quasi-2D Perovskite Light-Emitting Diodes.

    PubMed

    Byun, Jinwoo; Cho, Himchan; Wolf, Christoph; Jang, Mi; Sadhanala, Aditya; Friend, Richard H; Yang, Hoichang; Lee, Tae-Woo

    2016-09-01

    Efficient quasi-2D-structure perovskite light-emitting diodes (4.90 cd A(-1) ) are demonstrated by mixing a 3D-structured perovskite material (methyl ammonium lead bromide) and a 2D-structured perovskite material (phenylethyl ammonium lead bromide), which can be ascribed to better film uniformity, enhanced exciton confinement, and reduced trap density.

  5. Surface Raman excitation and enhancement profiles for chromate, molybdate, and tungstate on colloidal silver

    SciTech Connect

    Feilchenfeld, H.; Siiman, O.

    1986-05-08

    The surface-enhanced Raman scattering (SERS) excitation profiles of chromate, molybdate, and tungstate ions on colloidal silver were obtained by using excitation wavelengths between 457.9 and 676.4 nm. The intensity of the strongest SERS band between 800 and 900 cm/sup -1/, assignable to nu/sub s/(M-O), was in each case referenced to the 1020-cm/sup -1/ band of the internal standard, methanol, in silver hydrosols. These relative SERS intensities were compared against similar intensity ratios for each oxo anion in solution and then appropriately scaled for the concentration of MO/sub 4//sup 2 -/ in solution and on the surface of the silver particles in the sols. Peak SERS enhancements occurred at 560 nm for CrO/sub 4//sup 2 -/ and at 600 nm for both MoO/sub 4//sup 2 -/ and WO/sub 4//sup 2 -/. The latter peak positions matched the secondary absorption band maxima that originate from aggregates of silver particles in the sols. The numerical values of the SERS enhancements were 5 x 10/sup 4/-l x 10/sup 5/ for CrO/sub 4//sup 2 -/, 9 x 10/sup 5/ for MoO/sub 4//sup 2 -/, and about 2 x 10/sup 5/ for WO/sub 4//sup 2 -/ on colloidal silver. The somewhat lower SERS enhancements for the chromophoric adsorbate, CrO/sub 4//sup 2 -/, which adsorbs maximally at 370 nm in aqueous solution, are attributed to a lower degree of aggregation for the sols with added CrO/sub 4//sup 2 -/, rather than to partial quenching of its resonant excited state on the heavy metal (silver) surface. 34 references, 4 figures, 5 tables.

  6. Sodium molybdate prevents hypertension and vascular prostanoid imbalance in fructose-overloaded rats.

    PubMed

    Peredo, H A; Andrade, V; Donoso, A S; Lee, H J; Puyó, A M

    2013-10-01

    (1) Fructose (F) overload produces elevated blood pressure (BP), hyperglycaemia, hypertriglyceridemia and insulin resistance, resembling human metabolic syndrome. Previously, we found altered vascular prostanoid (PR) production in this model. (2) Sodium molybdate (Mo), as well as sodium tungstate, causes insulin-like effects and normalizes plasma glucose levels in streptozotocin-treated diabetic rats. We studied the effects of Mo on BP, metabolic parameters and release of PR from the mesenteric vascular bed (MVB) in F-overloaded rats. (3) Four groups of male Sprague-Dawley rats were analysed: Control, tap water to drink; F, F solution 10% W/V to drink; CMo, Mo 100 mg kg day(-1) and FMo, both treatments. After 9 weeks, the animals were killed and MVBs removed and the released PRs measured. (4) F increased BP, glycemia, triglyceridemia and insulinemia. Mo treatment prevented the increases in BP and glycemia, but did not modify triglyceridemia or insulinemia. In addition, Mo decreased BP in controls. (5) Prostaglandins (PG) F2 alpha and E2, PG 6-ketoF1 alpha and thromboxane (TX) B2 , as well as inactive metabolites of prostacyclin (PGI2 ) and TXA2 were detected. F decreased the production of vasodilator PRs PGI2 and PGE2 in MVB. Mo prevented these alterations and increased PGE2 in controls. Vasoconstrict or PRs PGF2 alpha and TXA2 release was not modified. (6) Mo treatment, beyond its known lowering effect on glycemia, prevents the reduction in the vascular release of vasodilator PR observed in this model. This could be one of the mechanisms by which Mo avoids the increase in BP caused by F overload in the rat.

  7. From yellow to black: dramatic changes between cerium(IV) and plutonium(IV) molybdates.

    PubMed

    Cross, Justin N; Duncan, Patrick M; Villa, Eric M; Polinski, Matthew J; Babo, Jean-Marie; Alekseev, Evgeny V; Booth, Corwin H; Albrecht-Schmitt, Thomas E

    2013-02-20

    Hydrothermal reactions of CeCl(3) and PuCl(3) with MoO(3) and Cs(2)CO(3) yield surprisingly different results. Ce(3)Mo(6)O(24)(H(2)O)(4) crystallizes as bright yellow plates (space group C2/c, a = 12.7337(7) Å, b = 22.1309(16) Å, c = 7.8392(4) Å, β = 96.591(4)°, V = 2194.6(2) Å(3)), whereas CsPu(3)Mo(6)O(24)(H(2)O) crystallizes as semiconducting black-red plates (space group C2/c, a = 12.633(5) Å, b = 21.770(8) Å, c = 7.743(7) Å, β = 96.218(2)°, V = 2117(2) Å(3)). The topologies of the two compounds are similar, with channel structures built from disordered Mo(VI) square pyramids and (RE)O(8) square antiprisms (RE = Ce(IV), Pu(IV)). However, the Pu(IV) compound contains Cs(+) in its channels, while the channels in Ce(3)Mo(6)O(24)(H(2)O)(4) contain water molecules. Disorder and an ambiguous oxidation state of Mo lead to the formula CsPu(3)Mo(6)O(24)(H(2)O), where one Mo site is Mo(V) and the rest are Mo(VI). X-ray absorption near-edge structure (XANES) experiments were performed to investigate the source of the black color of CsPu(3)Mo(6)O(24)(H(2)O). These experiments revealed Pu to be tetravalent, while the strong pre-edge absorption from the distorted molybdate anions leaves the oxidation state ambiguous between Mo(V) and Mo(VI). PMID:23360299

  8. Syntheses, crystal structures and biological relevance of glycolato and S-lactato molybdates.

    PubMed

    Zhou, Zhao-Hui; Hou, Shu-Ya; Cao, Ze-Xing; Wan, Hui-Lin; Ng, Seik-Weng

    2004-06-01

    Glycolato and S-lactato complexes containing the dioxomolybdenum(VI) moiety have been synthesized for studies on the role of the alpha-hydroxycarboxylato anion in the iron molybdenum cofactor of nitrogenase. The ligands in these complexes, vis K2[MoO2(glyc)2].H2O (H2glyc=glycolic acid, C2H4O3) (1) and (Na2[MoO2(S-lact)2])3.13H2O (H2lact=lactic acid, C3H6O3) (2) chelate through their alpha-alkoxyl and alpha-carboxyl oxygen atoms. In contrast, octanuclear K6[(MoO2)8(glyc)6(Hglyc)2].10H2O (3) formed by the reduction of the glycolato complex (1), features three different ligand binding modes: (i) non-bridging and bridging bidentate coordination of alpha-alkoxyl and alpha-carboxyl groups, and (ii) bidentate bridging using alpha-carboxyl group, leaving the alpha-alkoxyl group free. The octanuclear skeleton shows strong metal-metal interactions. The coordination modes in (1) and (2) mimic that of homocitrate to the iron molybdenum cofactor (FeMo-co) of nitrogenase. The bidentate coordination of alpha-alkoxyl and alpha-carboxyl groups shows that bond of alpha-carboxyl group to Mo is less susceptible to the oxidation state of molybdenum compared with the Mo-alpha-alkoxyl bond. This is supported by the dinuclear coordination of alpha-carboxyl group with free alpha-alkoxyl group in glycolato molybdate(V) (3).

  9. Rational Strategies for Efficient Perovskite Solar Cells.

    PubMed

    Seo, Jangwon; Noh, Jun Hong; Seok, Sang Il

    2016-03-15

    A long-standing dream in the large scale application of solar energy conversion is the fabrication of solar cells with high-efficiency and long-term stability at low cost. The realization of such practical goals depends on the architecture, process and key materials because solar cells are typically constructed from multilayer heterostructures of light harvesters, with electron and hole transporting layers as a major component. Recently, inorganic-organic hybrid lead halide perovskites have attracted significant attention as light absorbers for the fabrication of low-cost and high-efficiency solar cells via a solution process. This mainly stems from long-range ambipolar charge transport properties, low exciton binding energies, and suitable band gap tuning by managing the chemical composition. In our pioneering work, a new photovoltaic platform for efficient perovskite solar cells (PSCs) was proposed, which yielded a high power conversion efficiency (PCE) of 12%. The platform consisted of a pillared architecture of a three-dimensional nanocomposite of perovskites fully infiltrating mesoporous TiO2, resulting in the formation of continuous phases and perovskite domains overlaid with a polymeric hole conductor. Since then, the PCE of our PSCs has been rapidly increased from 3% to over 20% certified efficiency. The unprecedented increase in the PCE can be attributed to the effective integration of the advantageous attributes of the refined bicontinuous architecture, deposition process, and composition of perovskite materials. Specifically, the bicontinuous architectures used in the high efficiency comprise a layer of perovskite sandwiched between mesoporous metal-oxide layer, which is a very thinner than that of used in conventional dye-sensitized solar cells, and hole-conducting contact materials with a metal back contact. The mesoporous scaffold can affect the hysteresis under different scan direction in measurements of PSCs. The hysteresis also greatly depends on

  10. Perovskites with the Framework-Forming Xenon.

    PubMed

    Britvin, Sergey N; Kashtanov, Sergei A; Krzhizhanovskaya, Maria G; Gurinov, Andrey A; Glumov, Oleg V; Strekopytov, Stanislav; Kretser, Yury L; Zaitsev, Anatoly N; Chukanov, Nikita V; Krivovichev, Sergey V

    2015-11-23

    The Group 18 elements (noble gases) were the last ones in the periodic system to have not been encountered in perovskite structures. We herein report the synthesis of a new group of double perovskites KM(XeNaO6) (M = Ca, Sr, Ba) containing framework-forming xenon. The structures of the new compounds, like other double perovskites, are built up of the alternating sequence of corner-sharing (XeO6) and (NaO6) octahedra arranged in a three-dimensional rocksalt order. The fact that xenon can be incorporated into the perovskite structure provides new insights into the problem of Xe depletion in the atmosphere. Since octahedrally coordinated Xe(VIII) and Si(IV) exhibit close values of ionic radii (0.48 and 0.40 Å, respectively), one could assume that Xe(VIII) can be incorporated into hyperbaric frameworks such as MgSiO3 perovskite. The ability of Xe to form stable inorganic frameworks can further extend the rich and still enigmatic chemistry of this noble gas. PMID:26429762

  11. A Heteroepitaxial Perovskite Metal-Base Transistor

    SciTech Connect

    Yajima, T.; Hikita, Y.; Hwang, H.Y.; /Tokyo U. /JST, PRESTO /SLAC

    2011-08-11

    'More than Moore' captures a concept for overcoming limitations in silicon electronics by incorporating new functionalities in the constituent materials. Perovskite oxides are candidates because of their vast array of physical properties in a common structure. They also enable new electronic devices based on strongly-correlated electrons. The field effect transistor and its derivatives have been the principal oxide devices investigated thus far, but another option is available in a different geometry: if the current is perpendicular to the interface, the strong internal electric fields generated at back-to-back heterojunctions can be used for oxide electronics, analogous to bipolar transistors. Here we demonstrate a perovskite heteroepitaxial metal-base transistor operating at room temperature, enabled by interface dipole engineering. Analysis of many devices quantifies the evolution from hot-electron to permeable-base behaviour. This device provides a platform for incorporating the exotic ground states of perovskite oxides, as well as novel electronic phases at their interfaces.

  12. Autothermal reforming catalyst having perovskite structure

    DOEpatents

    Krumpel, Michael; Liu, Di-Jia

    2009-03-24

    The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

  13. Machine learning bandgaps of double perovskites

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam; Mannodi-Kanakkithodi, Arun; Uberuaga, Blas; Ramprasad, Rampi; Gubernatis, James; Lookman, Turab

    The ability to make rapid and accurate predictions of bandgaps for double perovskites is of much practical interest for a range of applications. While quantum mechanical computations for high-fidelity bandgaps are enormously computation-time intensive and thus impractical in high throughput studies, informatics-based statistical learning approaches can be a promising alternative. Here we demonstrate a systematic feature-engineering approach and a robust learning framework for efficient and accurate predictions of electronic bandgaps for double perovskites. After evaluating a set of nearly 1.2 million features, we identify several elemental features of the constituent atomic species as the most crucial and relevant predictors. The developed models are validated and tested using the best practices of data science (on a dataset of more than 1300 double perovskite bandgaps) and further analyzed to rationalize their prediction performance. Los Alamos National Laboratory LDRD program and the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

  14. Nanoimprinted Perovskite Solar Cells With Enhanced Photocurrent

    NASA Astrophysics Data System (ADS)

    Haroldson, Ross; Balachandran, Balasubramaniam?; Ren, Yixin; Zakhidov, Anvar; Hu, Wenchuang; UTD Nanoimprint Team

    We have developed a new method of Nanoimprint Lithography (NIL) to shape the morphology of organolead trihalide perovskite. With this hot stamping process we created ordered gratings or other micro or nanostructures of perovskite resembling 2D photonic crytals on the scale of 200 to 600 nm from a starting small grain spin-coated film of the same scale. With this new method of nanoimprinting, we demonstrate that perovskite PV device performance can be improved and controlled. Initial results comparing flat vs. NIL-PV structure devices show dramatic increase in photocurrent as well as better crystallinity. The origin of Isc enhancement is explained in terms of better morphology and larger grains, resulting in longer diffusion length of carriers, while better light absorption by photonic crystal nanopatterns cannot be excluded.

  15. Metal halide perovskites for energy applications

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.

    2016-06-01

    Exploring prospective materials for energy production and storage is one of the biggest challenges of this century. Solar energy is one of the most important renewable energy resources, due to its wide availability and low environmental impact. Metal halide perovskites have emerged as a class of semiconductor materials with unique properties, including tunable bandgap, high absorption coefficient, broad absorption spectrum, high charge carrier mobility and long charge diffusion lengths, which enable a broad range of photovoltaic and optoelectronic applications. Since the first embodiment of perovskite solar cells showing a power conversion efficiency of 3.8%, the device performance has been boosted up to a certified 22.1% within a few years. In this Perspective, we discuss differing forms of perovskite materials produced via various deposition procedures. We focus on their energy-related applications and discuss current challenges and possible solutions, with the aim of stimulating potential new applications.

  16. Electronic and Ionic Transport Dynamics in Organolead Halide Perovskites.

    PubMed

    Li, Dehui; Wu, Hao; Cheng, Hung-Chieh; Wang, Gongming; Huang, Yu; Duan, Xiangfeng

    2016-07-26

    Ion migration has been postulated as the underlying mechanism responsible for the hysteresis in organolead halide perovskite devices. However, the electronic and ionic transport dynamics and how they impact each other in organolead halide perovskites remain elusive to date. Here we report a systematic investigation of the electronic and ionic transport dynamics in organolead halide perovskite microplate crystals and thin films using temperature-dependent transient response measurements. Our study reveals that thermally activated ionic and electronic conduction coexist in perovskite devices. The extracted activation energies suggest that the electronic transport is easier, but ions migrate harder in microplates than in thin films, demonstrating that the crystalline quality and grain boundaries can fundamentally modify electronic and ionic transport in perovskites. These findings offer valuable insight on the electronic and ionic transport dynamics in organolead halide perovskites, which is critical for optimizing perovskite devices with reduced hysteresis and improved stability and efficiency.

  17. Functionalization of perovskite thin films with moisture-tolerant molecules

    NASA Astrophysics Data System (ADS)

    Yang, Shuang; Wang, Yun; Liu, Porun; Cheng, Yi-Bing; Zhao, Hui Jun; Yang, Hua Gui

    2016-02-01

    Organic-inorganic hybrid perovskites are particularly suited as light-harvesting materials in photovoltaic devices. The power conversion efficiency of perovskite solar cells has reached certified values of over 20% in just a few years. However, one of the major hindrances for application of these materials in real-world devices is the performance degradation in humid conditions, leading to a rapid loss of photovoltaic response. Here, we demonstrate that hydrophobic tertiary and quaternary alkyl ammonium cations can be successfully assembled on the perovskite surface as efficient water-resisting layers via a facile surface functionalization technique. Such layers can protect the perovskite film under high relative humidity (90 ± 5%) over 30 days. More importantly, devices based on such films can retain the photovoltaic capacities of bulk perovskites, with power conversion efficiencies over 15%. Improving the humidity tolerance of perovskite materials is a necessary step towards large-scale production of high-performance perovskite-based devices under ambient humidity.

  18. Effects of Molybdate, Tungstate, and Selenium Compounds on Formate Dehydrogenase and Other Enzyme Systems in Escherichia coli1

    PubMed Central

    Enoch, Harry G.; Lester, Robert L.

    1972-01-01

    The role of selenium and molybdenum in the metabolism of Escherichia coli was explored by growing cells in a simple salts medium and examining the metabolic consequences of altering the concentration of molybdenum and selenium compounds in the medium. The addition of tungstate increased the molybdate deficiency of this medium, as reflected by lowered levels of enzyme systems previously recognized to require compounds of molybdenum and selenium for their formation [formate-dependent oxygen reduction, formate dehydrogenase (FDH) (EC 1.2.2.1), and nitrate reductase (EC 1.9.6.1)]. The requirement for selenium and molybdenum appears to be unique to the enzymes of formate and nitrate metabolism since molybdate- and selenite-deficient medium had no effect on the level of several dehydrogenase and oxidase systems, for which the electron donors were reduced nicotinamide adenine dinucleotide, succinate, d- or l-lactate, and glycerol. In addition, no effect was observed on the growth rate or cell yield with any carbon source tested (glucose, glycerol, dl-lactate, acetate, succinate, and l-malate) when the medium was deficient in molybdenum and selenium. dl-Selenocystine was about as effective as selenite in stimulating the formation of formate dehydrogenase, whereas dl-selenomethionine was only 1% as effective. In aerobic cells, an amount of FDH was formed such that 3,200 or 3,800 moles of formate were oxidized per min per mole of added selenium (added as dl-selenocystine or selenite, respectively). PMID:4555402

  19. Intensification of ultrasound-assisted process for the preparation of spindle-shape sodium zinc molybdate nanoparticles.

    PubMed

    Bhanvase, B A; Patel, M A; Sonawane, S H; Pandit, A B

    2016-01-01

    In the present work, sodium zinc molybdate (SZM) nanoparticles were prepared using conventional and an innovative ultrasound assisted co-precipitation of sodium molybdate, zinc oxide and HNO3 at different temperatures. Prepared product was characterized by XRD, TEM, FT-IR, particle size distribution (PSD), TGA and DTA techniques. TEM analysis shows the spindle-shaped morphology of the formed SZM nanoparticles. The average particle size of SZM nanoparticles is found to be lower in case of sonochemical method (78.3 nm) compared to conventional method (340.2 nm) which is attributed to faster solute transfer rate due to ultrasonic irradiation leading to rapid nucleation and restricted growth of SZM nanoparticles. Further, the kinetics of synthesis of SZM nanoparticles are studied using the sonochemical method at different operating temperature and conventional method at 80°C. It is shown that the rate of reaction is significantly faster at 40°C compared to other temperatures and also conventional method. This can be attributed to intense cavity collapse at lower temperature (low vapour pressure) compared to higher temperature (high vapour pressure) of the reaction mixture.

  20. Simulation of the inhibition of microbial sulfate reduction in a two-compartment upflow bioreactor subjected to molybdate injection.

    PubMed

    de Jesus, E B; de Andrade Lima, L R P

    2016-08-01

    Souring of oil fields during secondary oil recovery by water injection occurs mainly due to the action of sulfate-reducing bacteria (SRB) adhered to the rock surface in the vicinity of injection wells. Upflow packed-bed bioreactors have been used in petroleum microbiology because of its similarity to the oil field near the injection wells or production. However, these reactors do not realistically describe the regions near the injection wells, which are characterized by the presence of a saturated zone and a void region close to the well. In this study, the hydrodynamics of the two-compartment packing-free/packed-bed pilot bioreactor that mimics an oil reservoir was studied. The packed-free compartment was modeled using a continuous stirred tank model with mass exchange between active and stagnant zones, whereas the packed-bed compartment was modeled using a piston-dispersion-exchange model. The proposed model adequately represents the hydrodynamic of the packed-free/packed-bed bioreactor while the simulations provide important information about the characteristics of the residence time distribution (RTD) curves for different sets of model parameters. Simulations were performed to represent the control of the sulfate-reducing bacteria activity in the bioreactor with the use of molybdate in different scenarios. The simulations show that increased amounts of molybdate cause an effective inhibition of the souring sulfate-reducing bacteria activity. PMID:27126499

  1. A structural and thermodynamic basis for the catalytic behavior of single phase and multiphase bismuth cerium molybdate ammoxidation catalysts

    SciTech Connect

    Brazdil, J.F.; Glaeser, L.C.; Grasselli, R.K.; Teller, R.G.

    1983-09-01

    The vast majority of fundamental studies of metal oxide selective oxidation catalysts have been performed with single phase systems. These investigations established the basic tenents of the redox mechanism of selective oxidation and ammoxidation catalysis. By comparison, structural and kinetic investigations of multiphase oxide catalysts are less numerous because of the inherent difficulties in understanding the relative contributions of separate phases to the catalytic behavior of the composite catalyst. Some attempts have been made in the past to understand the complex chemistry of multiphase catalysts and additional important insights have been realized more recently. However, a clear understanding of the most significant catalytic interactions between individual phases of a multiphase multicomponent redox catalyst is still lacking. In an effort to provide an understanding and a physical basis for the observed synergism in multiphase oxide catalysts, the structural and chemical features which dictate the catalytic behavior of bismuth cerium molybdate catalysts were assessed. Bismuth cerium molybdates are known to be active catalysts for the selective oxidation and ammoxidation of olefins. Compositions with superior catalytic performance have been identified in both the single phase and two phase regions of the Bi/sub 2/(MoO/sub 4/)/sub 3/ - Ce/sub 2/(MoO/sub 4/)/sub 3/ phase diagram. Hence, this catalyst system serves as a useful model for determining key structural and thermodynamic aspects of the catalytic behavior of multicomponent single phase and multiphase redox catalysts.

  2. Research Update: Luminescence in lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Srimath Kandada, Ajay Ram; Petrozza, Annamaria

    2016-09-01

    Efficiency and dynamics of radiative recombination of carriers are crucial figures of merit for optoelectronic materials. Following the recent success of lead halide perovskites in efficient photovoltaic and light emitting technologies, here we review some of the noted literature on the luminescence of this emerging class of materials. After outlining the theoretical formalism that is currently used to explain the carrier recombination dynamics, we review a few significant works which use photoluminescence as a tool to understand and optimize the operation of perovskite based optoelectronic devices.

  3. Nanoscale investigation of organic - inorganic halide perovskites

    NASA Astrophysics Data System (ADS)

    Cacovich, S.; Divitini, G.; Vrućinić, M.; Sadhanala, A.; Friend, R. H.; Sirringhaus, H.; Deschler, F.; Ducati, C.

    2015-10-01

    Over the last few years organic - inorganic halide perovskite-based solar cells have exhibited a rapid evolution, reaching certified power conversion efficiencies now surpassing 20%. Nevertheless the understanding of the optical and electronic properties of such systems on the nanoscale is still an open problem. In this work we investigate two model perovskite systems (based on iodine - CH3NH3PbI3 and bromine - CH3NH3PbBr3), analysing the local elemental composition and crystallinity and identifying chemical inhomogeneities.

  4. Stability of tetravalent actinides in perovskites

    SciTech Connect

    Williams, C.W.; Morss, L.R.; Choi, I.K.

    1983-01-01

    This paper reports the first determination of the enthalpy of formation of a complex actinide(IV) oxide: ..delta..H/sup 0//sub f/ (BaUO/sub 3/, s, 298 K) = -1690 +- 10 kJ mol/sup -1/. The preparation and properties of this and other actinide(IV) complex oxides are described and are compared with other perovskites BaMO/sub 3/. The relative stabilities of tetravalent and hexavalent uranium in various environments are compared in terms of the oxidation-reduction behavior of uranium in geological nuclear waste storage media; in perovskite, uranium(IV) is very unstable in comparison with uranium(VI).

  5. Excited State Properties of Hybrid Perovskites.

    PubMed

    Saba, Michele; Quochi, Francesco; Mura, Andrea; Bongiovanni, Giovanni

    2016-01-19

    Metal halide perovskites have come to the attention of the scientific community for the progress achieved in solar light conversion. Energy sustainability is one of the priorities of our society, and materials advancements resulting in low-cost but efficient solar cells and large-area lighting devices represent a major goal for applied research. From a basic point of view, perovskites are an exotic class of hybrid materials combining some merits of organic and inorganic semiconductors: large optical absorption, large mobilities, and tunable band gap together with the possibility to be processed in solution. When a novel class of promising semiconductors comes into the limelight, lively discussions ensue on the photophysics of band-edge excitations, because just the states close to the band edge are entailed in energy/charge transport and light emission. This was the case several decades ago for III-V semiconductors, it has been up to 10 years ago for organics, and it is currently the case for perovskites. Our aim in this Account is to rationalize the body of experimental evidence on perovskite photophysics in a coherent theoretical framework, borrowing from the knowledge acquired over the years in materials optoelectronics. A crucial question is whether photon absorption leads to a population of unbound, conductive free charges or instead excitons, neutral and insulating bound states created by Coulomb interaction just below the energy of the band gap. We first focus on the experimental estimates of the exciton binding energy (Eb): at room temperature, Eb is comparable to the thermal energy kBT in MAPbI3 and increases up to values 2-3kBT in wide band gap MAPbBr3 and MAPbCl3. Statistical considerations predict that these values, even though comparable to or larger than thermal energy, let free carriers prevail over bound excitons for all levels of excitation densities relevant for devices. The analysis of photophysics evidence confirms that all hybrid halide

  6. Kinetics and characterization of bismuth molybdate catalysts. 2. Reaction studies over various bimolybdates

    SciTech Connect

    Burban, P.M.; Schuit, G.C.A.; Bischoff, K.B. ); Koch, T.A. Du Pont Experimental Station, Wilmington, DE )

    1990-12-01

    The model reaction, 1-butene to 1,3-butadiene, was studied over various compositions of unsupported bismuth molybdates to rank the catalysts' reactivities. The authors confirmed that {gamma}-Bi{sub 2}MoO{sub 6} doped with bismuth to yield a surface Bi/Mo > 2.0 is unselective: selective catalyst species need a few mole% excess MoO{sub 3}. All catalysts with a surface Bi/Mo {le} 1.5 show selectivities to butadiene greater than 95%. As the amount of MoO{sub 3} increases, reducing the surface Bi/Mo ratio, the activity increases down to Bi/Mo = 1.5, then remains constant down to Bi/Mo = 1, and then decreases steadily down to Bi/Mo = 2/3. Characteristics of the partial oxidation catalysis change drastically going from {gamma}-Bi{sub 2}MoO{sub 6} to {alpha}-Bi{sub 2}MoO{sub 12}catalysts. For the model reaction, Bi{sub 2}MoO{sub 6} + 4% MoO{sub 3}exhibits an E{alpha} = 40 kJ/mol(9.5 kcal/mol) at temperatures above 673 K. This catalyst is completely poisoned by its product butadiene below 673 K, while the inhibition is lifted above this temperature. The authors suggest that the pores of this catalyst, estimated to be 24 nm in diameter, become filled with polybutadiene; the heat of butadiene adsorption was estimated to be 375 kJ/mol. In contrast, {alpha}-Bi{sub 2}MoO{sub 12} is not inhibited by butadiene, and has a lower activity (even calculated per unit surface) with an activation energy of 93 kJ/mol over the entire temperature range 660-713 K, studied. The authors propose models which describe two distinct ensemble effects operative in determining the kinetics over selective {gamma}-Bi{sub 2}MoO{sub 6} and {alpha}-Bi{sub 2}Mo{sub 3}O{sub 12} catalysts.

  7. Novel Solvent-free Perovskite Deposition in Fabrication of Normal and Inverted Architectures of Perovskite Solar Cells.

    PubMed

    Nejand, Bahram Abdollahi; Gharibzadeh, Saba; Ahmadi, Vahid; Shahverdi, H Reza

    2016-01-01

    We introduced a new approach to deposit perovskite layer with no need for dissolving perovskite precursors. Deposition of Solution-free perovskite (SFP) layer is a key method for deposition of perovskite layer on the hole or electron transport layers that are strongly sensitive to perovskite precursors. Using deposition of SFP layer in the perovskite solar cells would extend possibility of using many electron and hole transport materials in both normal and invert architectures of perovskite solar cells. In the present work, we synthesized crystalline perovskite powder followed by successful deposition on TiO2 and cuprous iodide as the non-sensitve and sensitive charge transport layers to PbI2 and CH3NH3I solution in DMF. The post compressing step enhanced the efficiency of the devices by increasing the interface area between perovskite and charge transport layers. The 9.07% and 7.71% cell efficiencies of the device prepared by SFP layer was achieved in respective normal (using TiO2 as a deposition substrate) and inverted structure (using CuI as deposition substrate) of perovskite solar cell. This method can be efficient in large-scale and low cost fabrication of new generation perovskite solar cells.

  8. Novel Solvent-free Perovskite Deposition in Fabrication of Normal and Inverted Architectures of Perovskite Solar Cells

    PubMed Central

    Nejand, Bahram Abdollahi; Gharibzadeh, Saba; Ahmadi, Vahid; Shahverdi, H. Reza

    2016-01-01

    We introduced a new approach to deposit perovskite layer with no need for dissolving perovskite precursors. Deposition of Solution-free perovskite (SFP) layer is a key method for deposition of perovskite layer on the hole or electron transport layers that are strongly sensitive to perovskite precursors. Using deposition of SFP layer in the perovskite solar cells would extend possibility of using many electron and hole transport materials in both normal and invert architectures of perovskite solar cells. In the present work, we synthesized crystalline perovskite powder followed by successful deposition on TiO2 and cuprous iodide as the non-sensitve and sensitive charge transport layers to PbI2 and CH3NH3I solution in DMF. The post compressing step enhanced the efficiency of the devices by increasing the interface area between perovskite and charge transport layers. The 9.07% and 7.71% cell efficiencies of the device prepared by SFP layer was achieved in respective normal (using TiO2 as a deposition substrate) and inverted structure (using CuI as deposition substrate) of perovskite solar cell. This method can be efficient in large-scale and low cost fabrication of new generation perovskite solar cells. PMID:27640991

  9. Novel Solvent-free Perovskite Deposition in Fabrication of Normal and Inverted Architectures of Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Nejand, Bahram Abdollahi; Gharibzadeh, Saba; Ahmadi, Vahid; Shahverdi, H. Reza

    2016-09-01

    We introduced a new approach to deposit perovskite layer with no need for dissolving perovskite precursors. Deposition of Solution-free perovskite (SFP) layer is a key method for deposition of perovskite layer on the hole or electron transport layers that are strongly sensitive to perovskite precursors. Using deposition of SFP layer in the perovskite solar cells would extend possibility of using many electron and hole transport materials in both normal and invert architectures of perovskite solar cells. In the present work, we synthesized crystalline perovskite powder followed by successful deposition on TiO2 and cuprous iodide as the non-sensitve and sensitive charge transport layers to PbI2 and CH3NH3I solution in DMF. The post compressing step enhanced the efficiency of the devices by increasing the interface area between perovskite and charge transport layers. The 9.07% and 7.71% cell efficiencies of the device prepared by SFP layer was achieved in respective normal (using TiO2 as a deposition substrate) and inverted structure (using CuI as deposition substrate) of perovskite solar cell. This method can be efficient in large-scale and low cost fabrication of new generation perovskite solar cells.

  10. Novel Solvent-free Perovskite Deposition in Fabrication of Normal and Inverted Architectures of Perovskite Solar Cells.

    PubMed

    Nejand, Bahram Abdollahi; Gharibzadeh, Saba; Ahmadi, Vahid; Shahverdi, H Reza

    2016-01-01

    We introduced a new approach to deposit perovskite layer with no need for dissolving perovskite precursors. Deposition of Solution-free perovskite (SFP) layer is a key method for deposition of perovskite layer on the hole or electron transport layers that are strongly sensitive to perovskite precursors. Using deposition of SFP layer in the perovskite solar cells would extend possibility of using many electron and hole transport materials in both normal and invert architectures of perovskite solar cells. In the present work, we synthesized crystalline perovskite powder followed by successful deposition on TiO2 and cuprous iodide as the non-sensitve and sensitive charge transport layers to PbI2 and CH3NH3I solution in DMF. The post compressing step enhanced the efficiency of the devices by increasing the interface area between perovskite and charge transport layers. The 9.07% and 7.71% cell efficiencies of the device prepared by SFP layer was achieved in respective normal (using TiO2 as a deposition substrate) and inverted structure (using CuI as deposition substrate) of perovskite solar cell. This method can be efficient in large-scale and low cost fabrication of new generation perovskite solar cells. PMID:27640991

  11. Study of ammonium molybdate to minimize the phosphate interference in the selenium determination by electrothermal atomic absorption spectrometry with deuterium background correction

    NASA Astrophysics Data System (ADS)

    Bermejo-Barrera, Pilar; Moreda-Piñeiro, Antonio; Bermejo-Barrera, Adela

    2002-02-01

    The use of ammonium molybdate to minimize the phosphate interference when measuring selenium by electrothermal atomic absorption spectrometry (ETAAS) with deuterium background correction was evaluated. Ammonium molybdate did not produce a selenium thermal stabilization; however, the presence of ammonium molybdate decreased the phosphate interference. The study was carried out with mussel acid digests and mussel slurries. Pd-Mg(NO 3) 2 was used as a chemical modifier at optimum concentrations of 300 and 250 mg l -1, respectively, yielding optimum pyrolysis and atomization temperatures of 1200 and 2100 °C, respectively. A yellow solid (ammonium molybdophosphate) was obtained when adding ammonium molybdate to mussel acid digest solutions. This precipitate can be removed after centrifugation prior to ETAAS determination. Additionally, studies on the sampling of the solid ammonium molybdophosphate (AMP) together with the liquid phase, as a slurry, were also developed. The volatilization of the solid AMP was not reached at temperatures lower than 2500 °C. By this way, phosphate, as AMP, is not present in the vapor phase at the atomization temperature (2100 °C), yielding a reduction of the spectral interference by phosphate. The proposed method was validated analyzing three reference materials of marine origin (DORM-1, DOLT-1 and TORT-1). Good agreement with the certified selenium contents was reached for all cases.

  12. - and Perovskite-Sensitised Mesoscopic Solar Cells

    NASA Astrophysics Data System (ADS)

    Grätzel, Michael; Durrant, James R.

    2015-10-01

    The following sections are included: * Introduction * Historical background * Mode of function of dye-sensitised solar cells * DSSC research and development * Solid-state mesoscopic cells based on molecular dyes or perovskite pigments as sensitisers * Pilot production of modules, field tests and commercial DSSC development * Outlook * Acknowledgements * References

  13. Perovskite solar cells: Different facets of performance

    NASA Astrophysics Data System (ADS)

    Eperon, Giles E.; Ginger, David S.

    2016-08-01

    The electronic properties of halide perovskites vary significantly between crystalline grains, but the impact of this heterogeneity on solar cell performance is unclear. Now, this variability is shown to limit the photovoltaic properties of solar cells, and its origins are linked to differing properties between crystal facets.

  14. Improving the Stability and Performance of Perovskite Light-Emitting Diodes by Thermal Annealing Treatment.

    PubMed

    Yu, Jae Choul; Kim, Dae Woo; Kim, Da Bin; Jung, Eui Dae; Park, Jong Hyun; Lee, Ah-Young; Lee, Bo Ram; Di Nuzzo, Daniele; Friend, Richard H; Song, Myoung Hoon

    2016-08-01

    A perovskite LED with a perovskite film treated under optimum thermal annealing conditions exhibits a significantly enhanced long-term stability with full coverage of the green electroluminescence emission due to the highly uniform morphology of the perovskite film.

  15. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    PubMed

    Chen, Kun; Tüysüz, Harun

    2015-11-01

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. PMID:26376773

  16. Band gap engineering strategy via polarization rotation in perovskite ferroelectrics

    SciTech Connect

    Wang, Fenggong Grinberg, Ilya; Rappe, Andrew M.

    2014-04-14

    We propose a strategy to engineer the band gaps of perovskite oxide ferroelectrics, supported by first principles calculations. We find that the band gaps of perovskites can be substantially reduced by as much as 1.2 eV through local rhombohedral-to-tetragonal structural transition. Furthermore, the strong polarization of the rhombohedral perovskite is largely preserved by its tetragonal counterpart. The B-cation off-center displacements and the resulting enhancement of the antibonding character in the conduction band give rise to the wider band gaps of the rhombohedral perovskites. The correlation between the structure, polarization orientation, and electronic structure lays a good foundation for understanding the physics of more complex perovskite solid solutions and provides a route for the design of photovoltaic perovskite ferroelectrics.

  17. Neutral- and Multi-Colored Semitransparent Perovskite Solar Cells.

    PubMed

    Lee, Kyu-Tae; Guo, L Jay; Park, Hui Joon

    2016-04-11

    In this review, we summarize recent works on perovskite solar cells with neutral- and multi-colored semitransparency for building-integrated photovoltaics and tandem solar cells. The perovskite solar cells exploiting microstructured arrays of perovskite "islands" and transparent electrodes-the latter of which include thin metallic films, metal nanowires, carbon nanotubes, graphenes, and transparent conductive oxides for achieving optical transparency-are investigated. Moreover, the perovskite solar cells with distinctive color generation, which are enabled by engineering the band gap of the perovskite light-harvesting semiconductors with chemical management and integrating with photonic nanostructures, including microcavity, are discussed. We conclude by providing future research directions toward further performance improvements of the semitransparent perovskite solar cells.

  18. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    PubMed

    Chen, Kun; Tüysüz, Harun

    2015-11-01

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites.

  19. One-step synthesis of bismuth molybdate catalysts via flame spray pyrolysis for the selective oxidation of propylene to acrolein.

    PubMed

    Schuh, K; Kleist, W; Høj, M; Trouillet, V; Jensen, A D; Grunwaldt, J-D

    2014-12-18

    Flame spray pyrolysis (FSP) of Bi(III)- and Mo(VI)-2-ethylhexanoate dissolved in xylene resulted in various nanocrystalline bismuth molybdate phases depending on the Bi/Mo ratio. Besides α-Bi2Mo3O12 and γ-Bi2MoO6, FSP gave direct access to the metastable β-Bi2Mo2O9 phase with high surface area (19 m(2) g(-1)). This phase is normally only obtained at high calcination temperatures (>560 °C) resulting in lower surface areas. The β-phase was stable up to 400 °C and showed superior catalytic performance compared to α- and γ-phases in selective oxidation of propylene to acrolein at temperatures relevant for industrial applications (360 °C). PMID:25350295

  20. Molecular orientation of molybdate ions adsorbed on goethite nanoparticles revealed by polarized in situ ATR-IR spectroscopy

    NASA Astrophysics Data System (ADS)

    Davantès, Athénaïs; Lefèvre, Grégory

    2016-11-01

    The speciation of species adsorbed on nanoparticles is a major concern for several fields, as environmental pollution and remediation, surface functionalization, or catalysis. Attenuated total reflectance infrared spectroscopy (ATR-IR) was amongst the rare methods able to give in situ information about the geometry of surface complexes on nanoparticles. A new possibility using this technique is illustrated here with the MoO42 -/goethite system. Using deuterated goethite to avoid spectral interferences, adsorption of molybdate ions on a spontaneous oriented film of nanoparticles has been followed using a polarized infrared beam. From the decomposition of spectra in the x, y and z directions, a monodentate surface complex on the {101} faces has been found as the most probable geometry. This result demonstrates that polarized ATR-IR allows to characterize in more details adsorption mode at the atomic scale, in comparison with usual ATR-IR spectroscopy.

  1. Photovoltaic Performance of Perovskite Solar Cells with Different Grain Sizes.

    PubMed

    Kim, Hyung Do; Ohkita, Hideo; Benten, Hiroaki; Ito, Shinzaburo

    2016-02-01

    Perovskite solar cells exhibit improved photovoltaic parameters with increasing perovskite grain size. The larger photocurrent is due to the enhanced absorption efficiency for thicker perovskite layers. The larger open-circuit voltage (VOC ) is ascribed to the reduced trap-assisted recombination for the larger grains. As a result, the power conversion efficiency exceeds 19% at best. Further improvement in VOC would be possible if the trap density were reduced.

  2. Predominant Intermediate-Spin Ferrous Iron in Lowermost Mantle Post-Perovskite and Perovskite

    NASA Astrophysics Data System (ADS)

    Lin, J.; Watson, H. C.; Vanko, G.; Alp, E. E.; Prakapenka, V.; Dera, P.; Struzhkin, V. V.; Kubo, A.; Zhao, J.; McCammon, C.; Evans, W. J.

    2008-12-01

    Silicate post-perovskite and perovskite are believed to be the dominant minerals of the lowermost mantle and the lower mantle, respectively, and their properties, which can be strongly influenced by the electronic state of iron in these phases, affect our understanding of the nature of the deep Earth. To date, in these minerals the electronic spin state of iron remains unknown under lowermost-mantle pressure-temperature conditions, although recent studies have showed an electronic spin crossover from high-spin to low-spin in ferropericlase over an extended pressure-temperature range of the lower mantle (i.e., Lin et al., Science, 2007) and from high-spin to intermediate-spin in silicate perovskite near the top of the lower mantle (McCammon et al., Nature Geoscience, 2008). Here we report the spin and valence states of iron in post-perovskite and perovskite at pressure-temperature conditions relevant to the lowermost mantle using in situ X-ray emission, X-ray diffraction, and synchrotron Mossbauer spectroscopies in a laser-heated diamond cell. Perovskite and post-perovskite display extremely high quadrupole splitting (QS) of approximately 4 mm/s and relatively high center shift in the synchrotron Mossbauer spectra at 110 GPa and 134 GPa, respectively. Our results show that Fe2+ exists predominantly in the intermediate-spin state with a total spin number of one in both phases (Lin et al., Nature Geoscience, 2008). Together with recent results on the effects of the spin transition in the lower-mantle ferropericlase (see a recent review by Lin and Tsuchiya, PEPI, 2008), here we will address how the electronic spin states in lower-mantle phases and their associated effects affect our understanding on the composition, geophysics, and dynamics of the lower mantle.. References: 1. Lin, J. F., H. C. Watson, G. Vanko, E. E. Alp, V. B. Prakapenka, P. Dera, V. V. Struzhkin, A. Kubo, J. Zhao, C. McCammon, W. J. Evans, Intermediate-spin ferrous iron in lowermost mantle post-perovskite

  3. Organohalide Perovskites for Solar Energy Conversion.

    PubMed

    Lin, Qianqian; Armin, Ardalan; Burn, Paul L; Meredith, Paul

    2016-03-15

    Lead-based organohalide perovskites have recently emerged as arguably the most promising of all next generation thin film solar cell technologies. Power conversion efficiencies have reached 20% in less than 5 years, and their application to other optoelectronic device platforms such as photodetectors and light emitting diodes is being increasingly reported. Organohalide perovskites can be solution processed or evaporated at low temperatures to form simple thin film photojunctions, thus delivering the potential for the holy grail of high efficiency, low embedded energy, and low cost photovoltaics. The initial device-driven "perovskite fever" has more recently given way to efforts to better understand how these materials work in solar cells, and deeper elucidation of their structure-property relationships. In this Account, we focus on this element of organohalide perovskite chemistry and physics in particular examining critical electro-optical, morphological, and architectural phenomena. We first examine basic crystal and chemical structure, and how this impacts important solar-cell related properties such as the optical gap. We then turn to deeper electronic phenomena such as carrier mobilities, trap densities, and recombination dynamics, as well as examining ionic and dielectric properties and how these two types of physics impact each other. The issue of whether organohalide perovskites are predominantly nonexcitonic at room temperature is currently a matter of some debate, and we summarize the evidence for what appears to be the emerging field consensus: an exciton binding energy of order 10 meV. Having discussed the important basic chemistry and physics we turn to more device-related considerations including processing, morphology, architecture, thin film electro-optics and interfacial energetics. These phenomena directly impact solar cell performance parameters such as open circuit voltage, short circuit current density, internal and external quantum efficiency

  4. Organohalide Perovskites for Solar Energy Conversion.

    PubMed

    Lin, Qianqian; Armin, Ardalan; Burn, Paul L; Meredith, Paul

    2016-03-15

    Lead-based organohalide perovskites have recently emerged as arguably the most promising of all next generation thin film solar cell technologies. Power conversion efficiencies have reached 20% in less than 5 years, and their application to other optoelectronic device platforms such as photodetectors and light emitting diodes is being increasingly reported. Organohalide perovskites can be solution processed or evaporated at low temperatures to form simple thin film photojunctions, thus delivering the potential for the holy grail of high efficiency, low embedded energy, and low cost photovoltaics. The initial device-driven "perovskite fever" has more recently given way to efforts to better understand how these materials work in solar cells, and deeper elucidation of their structure-property relationships. In this Account, we focus on this element of organohalide perovskite chemistry and physics in particular examining critical electro-optical, morphological, and architectural phenomena. We first examine basic crystal and chemical structure, and how this impacts important solar-cell related properties such as the optical gap. We then turn to deeper electronic phenomena such as carrier mobilities, trap densities, and recombination dynamics, as well as examining ionic and dielectric properties and how these two types of physics impact each other. The issue of whether organohalide perovskites are predominantly nonexcitonic at room temperature is currently a matter of some debate, and we summarize the evidence for what appears to be the emerging field consensus: an exciton binding energy of order 10 meV. Having discussed the important basic chemistry and physics we turn to more device-related considerations including processing, morphology, architecture, thin film electro-optics and interfacial energetics. These phenomena directly impact solar cell performance parameters such as open circuit voltage, short circuit current density, internal and external quantum efficiency

  5. Post-perovskite transitions in CaB4+O3 at high pressure

    NASA Astrophysics Data System (ADS)

    Akaogi, M.; Shirako, Y.; Kojitani, H.; Takamori, S.; Yamaura, K.; Takayama-Muromachi, E.

    2010-03-01

    High-pressure phase transitions in CaRhO3 were examined using a multianvil apparatus up to 27 GPa and 1930 oC. CaRhO3 perovskite transforms to post-perovskite via a monoclinic intermediate phase with increasing pressure. Volume changes for the transitions of perovskite - intermediate phase and of intermediate phase - post-perovskite are -1.1 and -0.7 %, respectively. CaRhO3 post-perovskite is the fourth quenchable post-perovskite oxide found so far. By high-temperature calorimetric experiments, enthalpy of the perovskite - post-perovskite transition in CaRuO3 was measured as 15.2±3.3 kJ/mol. Combining the datum with those of CaIrO3, it is shown that CaIrO3 perovskite is energetically less stable than CaRuO3 perovskite. This is consistent with the fact that orthorhombic distortion of CaIrO3 perovskite is larger than CaRuO3, as indicated with the tilt-angle of octahedral framework of perovskite structure. The transition pressure from perovskite to post-perovskite in CaBO3 (B = Ru, Rh, Ir) increases almost linearly with decreasing the tilt-angle, suggesting that the perovskite - post-perovskite transition may result from instability of the perovskite structure with pressure.

  6. Machine learning bandgaps of double perovskites

    NASA Astrophysics Data System (ADS)

    Pilania, G.; Mannodi-Kanakkithodi, A.; Uberuaga, B. P.; Ramprasad, R.; Gubernatis, J. E.; Lookman, T.

    2016-01-01

    The ability to make rapid and accurate predictions on bandgaps of double perovskites is of much practical interest for a range of applications. While quantum mechanical computations for high-fidelity bandgaps are enormously computation-time intensive and thus impractical in high throughput studies, informatics-based statistical learning approaches can be a promising alternative. Here we demonstrate a systematic feature-engineering approach and a robust learning framework for efficient and accurate predictions of electronic bandgaps of double perovskites. After evaluating a set of more than 1.2 million features, we identify lowest occupied Kohn-Sham levels and elemental electronegativities of the constituent atomic species as the most crucial and relevant predictors. The developed models are validated and tested using the best practices of data science and further analyzed to rationalize their prediction performance.

  7. Machine learning bandgaps of double perovskites

    DOE PAGESBeta

    Pilania, G.; Mannodi-Kanakkithodi, A.; Uberuaga, B. P.; Ramprasad, R.; Gubernatis, J. E.; Lookman, T.

    2016-01-19

    The ability to make rapid and accurate predictions on bandgaps of double perovskites is of much practical interest for a range of applications. While quantum mechanical computations for high-fidelity bandgaps are enormously computation-time intensive and thus impractical in high throughput studies, informatics-based statistical learning approaches can be a promising alternative. Here we demonstrate a systematic feature-engineering approach and a robust learning framework for efficient and accurate predictions of electronic bandgaps of double perovskites. After evaluating a set of more than 1.2 million features, we identify lowest occupied Kohn-Sham levels and elemental electronegativities of the constituent atomic species as the mostmore » crucial and relevant predictors. As a result, the developed models are validated and tested using the best practices of data science and further analyzed to rationalize their prediction performance.« less

  8. Machine learning bandgaps of double perovskites

    PubMed Central

    Pilania, G.; Mannodi-Kanakkithodi, A.; Uberuaga, B. P.; Ramprasad, R.; Gubernatis, J. E.; Lookman, T.

    2016-01-01

    The ability to make rapid and accurate predictions on bandgaps of double perovskites is of much practical interest for a range of applications. While quantum mechanical computations for high-fidelity bandgaps are enormously computation-time intensive and thus impractical in high throughput studies, informatics-based statistical learning approaches can be a promising alternative. Here we demonstrate a systematic feature-engineering approach and a robust learning framework for efficient and accurate predictions of electronic bandgaps of double perovskites. After evaluating a set of more than 1.2 million features, we identify lowest occupied Kohn-Sham levels and elemental electronegativities of the constituent atomic species as the most crucial and relevant predictors. The developed models are validated and tested using the best practices of data science and further analyzed to rationalize their prediction performance. PMID:26783247

  9. The photophysics of perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Sum, Tze Chien

    2014-09-01

    Solution-processed hybrid organic-inorganic perovskite solar cells, a newcomer to the photovoltaic arena, have taken the field by storm with their extraordinary power conversion efficiencies exceeding 17%. In this paper, the photophysics and the latest findings on the carrier dynamics and charge transfer mechanisms in this new class of photovoltaic material will be examined and distilled. Some open photophysics questions will also be discussed.

  10. Resistance switching memory in perovskite oxides

    SciTech Connect

    Yan, Z.B. Liu, J.-M.

    2015-07-15

    The resistance switching behavior has recently attracted great attentions for its application as resistive random access memories (RRAMs) due to a variety of advantages such as simple structure, high-density, high-speed and low-power. As a leading storage media, the transition metal perovskite oxide owns the strong correlation of electrons and the stable crystal structure, which brings out multifunctionality such as ferroelectric, multiferroic, superconductor, and colossal magnetoresistance/electroresistance effect, etc. The existence of rich electronic phases, metal–insulator transition and the nonstoichiometric oxygen in perovskite oxide provides good platforms to insight into the resistive switching mechanisms. In this review, we first introduce the general characteristics of the resistance switching effects, the operation methods and the storage media. Then, the experimental evidences of conductive filaments, the transport and switching mechanisms, and the memory performances and enhancing methods of perovskite oxide based filamentary RRAM cells have been summarized and discussed. Subsequently, the switching mechanisms and the performances of the uniform RRAM cells associating with the carrier trapping/detrapping and the ferroelectric polarization switching have been discussed. Finally, the advices and outlook for further investigating the resistance switching and enhancing the memory performances are given.

  11. Light-trapping in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Du, Qing Guo; Shen, Guansheng; John, Sajeev

    2016-06-01

    We numerically demonstrate enhanced light harvesting efficiency in both CH3NH3PbI3 and CH(NH2)2PbI3-based perovskite solar cells using inverted vertical-cone photonic-crystal nanostructures. For CH3NH3PbI3 perovskite solar cells, the maximum achievable photocurrent density (MAPD) reaches 25.1 mA/cm2, corresponding to 92% of the total available photocurrent in the absorption range of 300 nm to 800 nm. Our cell shows 6% absorption enhancement compared to the Lambertian limit (23.7 mA/cm2) and has a projected power conversion efficiency of 12.9%. Excellent solar absorption is numerically demonstrated over a broad angular range from 0 to 60 degree for both S- and P- polarizations. For the corresponding CH(NH2)2PbI3 based perovskite solar cell, with absorption range of 300 nm to 850 nm, we find a MAPD of 29.1 mA/cm2, corresponding to 95.4% of the total available photocurrent. The projected power conversion efficiency of the CH(NH2)2PbI3 based photonic crystal solar cell is 23.4%, well above the current world record efficiency of 20.1%.

  12. Perovskite-related oxynitrides in photocatalysis.

    PubMed

    Pokrant, Simone; Maegli, Alexandra E; Chiarello, Gian Luca; Weidenkaff, Anke

    2013-01-01

    Over the last decades photocatalytic water splitting has become of increasing importance for fundamental and applied research, since the direct conversion of sunlight into chemical energy via the production of H2 has the potential to contribute to the world's energy needs without CO2 generation. One of the unsolved challenges consists of finding a highly efficient photocatalyst that is cheap, environmentally friendly, contains exclusively abundant elements, is (photo)chemically stable and absorbs visible light. Photocatalytic efficiency is closely connected to both structural properties like crystallinity, particle size and surface area and to electronic properties like the band gap and the quantum efficiency. Hence extensive control over a large parameter field is necessary to design a good photocatalyst. A material class where the structure-composition-property relations and the influence of substitution effects are well studied is the perovskite-type family of compounds. The perovskite-related oxynitrides belong to this very flexible compound family where many of the necessary characteristics for a photocatalyst are already given and some of the intrinsic properties like the band gap can be tuned within the same crystal structure by substitution. In this work we present materials' design concepts to improve the photocatalytic efficiency of a perovskite-type catalyst and describe their effects on the photocatalytic activity. PMID:23574956

  13. 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).

  14. Two Dimensional Organometal Halide Perovskite Nanorods with Tunable Optical Properties.

    PubMed

    Aharon, Sigalit; Etgar, Lioz

    2016-05-11

    Organo-metal halide perovskite is an efficient light harvester in photovoltaic solar cells. Organometal halide perovskite is used mainly in its "bulk" form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halide perovskite, as well as the nanoscale properties. In this paper, we present facile low-temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g., octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. The 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light-emitting diodes, lasing, solar cells, and sensors. PMID:27089497

  15. Solution Chemistry Engineering toward High-Efficiency Perovskite Solar Cells.

    PubMed

    Zhao, Yixin; Zhu, Kai

    2014-12-01

    Organic and inorganic hybrid perovskites (e.g., CH3NH3PbI3) have emerged as a revolutionary class of light-absorbing semiconductors that has demonstrated a rapid increase in efficiency within a few years of active research. Controlling perovskite morphology and composition has been found critical to developing high-performance perovskite solar cells. The recent development of solution chemistry engineering has led to fabrication of greater than 15-17%-efficiency solar cells by multiple groups, with the highest certified 17.9% efficiency that has significantly surpassed the best-reported perovskite solar cell by vapor-phase growth. In this Perspective, we review recent progress on solution chemistry engineering processes and various control parameters that are critical to the success of solution growth of high-quality perovskite films. We discuss the importance of understanding the impact of solution-processing parameters and perovskite film architectures on the fundamental charge carrier dynamics in perovskite solar cells. The cost and stability issues of perovskite solar cells will also be discussed.

  16. Solution Chemistry Engineering toward High-Efficiency Perovskite Solar Cells.

    PubMed

    Zhao, Yixin; Zhu, Kai

    2014-12-01

    Organic and inorganic hybrid perovskites (e.g., CH3NH3PbI3) have emerged as a revolutionary class of light-absorbing semiconductors that has demonstrated a rapid increase in efficiency within a few years of active research. Controlling perovskite morphology and composition has been found critical to developing high-performance perovskite solar cells. The recent development of solution chemistry engineering has led to fabrication of greater than 15-17%-efficiency solar cells by multiple groups, with the highest certified 17.9% efficiency that has significantly surpassed the best-reported perovskite solar cell by vapor-phase growth. In this Perspective, we review recent progress on solution chemistry engineering processes and various control parameters that are critical to the success of solution growth of high-quality perovskite films. We discuss the importance of understanding the impact of solution-processing parameters and perovskite film architectures on the fundamental charge carrier dynamics in perovskite solar cells. The cost and stability issues of perovskite solar cells will also be discussed. PMID:26278951

  17. Self-Assembled PbSe Nanowire:Perovskite Hybrids.

    PubMed

    Yang, Zhenyu; Yassitepe, Emre; Voznyy, Oleksandr; Janmohamed, Alyf; Lan, Xinzheng; Levina, Larissa; Comin, Riccardo; Sargent, Edward H

    2015-12-01

    Inorganic semiconductor nanowires are of interest in nano- and microscale photonic and electronic applications. Here we report the formation of PbSe nanowires based on directional quantum dot alignment and fusion regulated by hybrid organic-inorganic perovskite surface ligands. All material synthesis is carried out at mild temperatures. Passivation of PbSe quantum dots was achieved via a new perovskite ligand exchange. Subsequent in situ ammonium/amine substitution by butylamine enables quantum dots to be capped by butylammonium lead iodide, and this further drives the formation of a PbSe nanowire superlattice in a two-dimensional (2D) perovskite matrix. The average spacing between two adjacent nanowires agrees well with the thickness of single atomic layer of 2D perovskite, consistent with the formation of a new self-assembled semiconductor nanowire:perovskite heterocrystal hybrid.

  18. Highly efficient light management for perovskite solar cells

    PubMed Central

    Wang, Dong-Lin; Cui, Hui-Juan; Hou, Guo-Jiao; Zhu, Zhen-Gang; Yan, Qing-Bo; Su, Gang

    2016-01-01

    Organic-inorganic halide perovskite solar cells have enormous potential to impact the existing photovoltaic industry. As realizing a higher conversion efficiency of the solar cell is still the most crucial task, a great number of schemes were proposed to minimize the carrier loss by optimizing the electrical properties of the perovskite solar cells. Here, we focus on another significant aspect that is to minimize the light loss by optimizing the light management to gain a high efficiency for perovskite solar cells. In our scheme, the slotted and inverted prism structured SiO2 layers are adopted to trap more light into the solar cells, and a better transparent conducting oxide layer is employed to reduce the parasitic absorption. For such an implementation, the efficiency and the serviceable angle of the perovskite solar cell can be promoted impressively. This proposal would shed new light on developing the high-performance perovskite solar cells. PMID:26733112

  19. Highly efficient light management for perovskite solar cells.

    PubMed

    Wang, Dong-Lin; Cui, Hui-Juan; Hou, Guo-Jiao; Zhu, Zhen-Gang; Yan, Qing-Bo; Su, Gang

    2016-01-06

    Organic-inorganic halide perovskite solar cells have enormous potential to impact the existing photovoltaic industry. As realizing a higher conversion efficiency of the solar cell is still the most crucial task, a great number of schemes were proposed to minimize the carrier loss by optimizing the electrical properties of the perovskite solar cells. Here, we focus on another significant aspect that is to minimize the light loss by optimizing the light management to gain a high efficiency for perovskite solar cells. In our scheme, the slotted and inverted prism structured SiO2 layers are adopted to trap more light into the solar cells, and a better transparent conducting oxide layer is employed to reduce the parasitic absorption. For such an implementation, the efficiency and the serviceable angle of the perovskite solar cell can be promoted impressively. This proposal would shed new light on developing the high-performance perovskite solar cells.

  20. Perovskite-fullerene hybrid materials suppress hysteresis in planar diodes.

    PubMed

    Xu, Jixian; Buin, Andrei; Ip, Alexander H; Li, Wei; Voznyy, Oleksandr; Comin, Riccardo; Yuan, Mingjian; Jeon, Seokmin; Ning, Zhijun; McDowell, Jeffrey J; Kanjanaboos, Pongsakorn; Sun, Jon-Paul; Lan, Xinzheng; Quan, Li Na; Kim, Dong Ha; Hill, Ian G; Maksymovych, Peter; Sargent, Edward H

    2015-05-08

    Solution-processed planar perovskite devices are highly desirable in a wide variety of optoelectronic applications; however, they are prone to hysteresis and current instabilities. Here we report the first perovskite-PCBM hybrid solid with significantly reduced hysteresis and recombination loss achieved in a single step. This new material displays an efficient electrically coupled microstructure: PCBM is homogeneously distributed throughout the film at perovskite grain boundaries. The PCBM passivates the key PbI3(-) antisite defects during the perovskite self-assembly, as revealed by theory and experiment. Photoluminescence transient spectroscopy proves that the PCBM phase promotes electron extraction. We showcase this mixed material in planar solar cells that feature low hysteresis and enhanced photovoltage. Using conductive AFM studies, we reveal the memristive properties of perovskite films. We close by positing that PCBM, by tying up both halide-rich antisites and unincorporated halides, reduces electric field-induced anion migration that may give rise to hysteresis and unstable diode behaviour.

  1. Study of ternary-component bismuth molybdate catalysts by /sup 18/O/sub 2/ tracer in the oxidation of propylene to acrolein

    SciTech Connect

    Ueda, W.; Moro-oka, Y.; Ikawa, T.

    1981-08-01

    Participation of lattice oxide ions of ternary-component bismuth molybdate catalysts M-Bi-Mo-O (M = Ni, Co, Mg, Mn, Ca, Sr, Ba, and Pb) was investigated using the /sup 18/O/sub 2/ tracer in the selective oxidation of propylene to acrolein. The participation of the lattice oxide ions in the oxidation is prominent on every catalyst but the extent of the participation varies significantly depending on the structure of the catalyst. Only lattice oxide ions in the bismuth molybdate phase are incorporated into the oxidized products on the catalysts (M = Ni, Co, Mg, and Mn) where M have smaller ionic radius than Bi/sup 3 +/; catalyst particles are composed of a shell of bismuth molybdates and a core of MMoO/sub 4/. On the other hand, whole oxide ions in the active particles are involved in the oxidation on catalysts having a scheelite-type structure (M = Ca, Sr, Ba, and Pb) where M has a comparable ionic radius to Bi/sup 3 +/.

  2. Weakening of Calcium Iridate During its Transformation from Perovskite to Post-Perovskite

    SciTech Connect

    Hunt, S.; Weidner, D; Li, L; Wang, L; Walte, N; Brodholt, J; Dobson, D

    2009-01-01

    The lowermost part of the Earth's mantle - the {approx}200-km-thick D{double_prime} layer - shows anomalous seismic properties, and is rheologically distinct from the rest of the lower mantle. The difference is thought to result from a phase transition from silicate perovskite to silicate post-perovskite. However, the rheology of the latter phase remains to be documented owing to experimental difficulties in reproducing pressures equivalent to those in the lowermost mantle. Here we address this problem by conducting laboratory experiments that use calcium iridate, which has been shown to be an appropriate low-pressure analogue. We find that the post-perovskite phase of this analogue is approximately five times weaker than its perovskite phase, and that it further weakens by a factor of two during the phase transformation; these are minimum estimates. If, as is likely, a similar weakening occurs in lower-mantle magnesium - silicate compositions, this could provide an explanation for the behaviour of the lowermost mantle as inferred from geophysical data.

  3. Generalized trends in the formation energies of perovskite oxides.

    PubMed

    Zeng, ZhenHua; Calle-Vallejo, Federico; Mogensen, Mogens B; Rossmeisl, Jan

    2013-05-28

    Generalized trends in the formation energies of several families of perovskite oxides (ABO3) and plausible explanations to their existence are provided in this study through a combination of DFT calculations, solid-state physics analyses and simple physical/chemical descriptors. The studied elements at the A site of perovskites comprise rare-earth, alkaline-earth and alkaline metals, whereas 3d and 5d metals were studied at the B site. We also include ReO3-type compounds, which have the same crystal structure of cubic ABO3 perovskites except without A-site elements. From the observations we extract the following four conclusions for the perovskites studied in the present paper: for a given cation at the B site, (I) perovskites with cations of identical oxidation state at the A site possess close formation energies; and (II) perovskites with cations of different oxidation states at the A site usually have quite different but ordered formation energies. On the other hand, for a given A-site cation, (III) the formation energies of perovskites vary linearly with respect to the atomic number of the elements at the B site within the same period of the periodic table, and the slopes depend systematically on the oxidation state of the A-site cation; and (IV) the trends in formation energies of perovskites with elements from different periods at the B site depend on the oxidation state of A-site cations. Since the energetics of perovskites is shown to be the superposition of the individual contributions of their constituent oxides, the trends can be rationalized in terms of A-O and B-O interactions in the ionic crystal. These findings reveal the existence of general systematic trends in the formation energies of perovskites and provide further insight into the role of ion-ion interactions in the properties of ternary compounds.

  4. Generalized trends in the formation energies of perovskite oxides.

    PubMed

    Zeng, ZhenHua; Calle-Vallejo, Federico; Mogensen, Mogens B; Rossmeisl, Jan

    2013-05-28

    Generalized trends in the formation energies of several families of perovskite oxides (ABO3) and plausible explanations to their existence are provided in this study through a combination of DFT calculations, solid-state physics analyses and simple physical/chemical descriptors. The studied elements at the A site of perovskites comprise rare-earth, alkaline-earth and alkaline metals, whereas 3d and 5d metals were studied at the B site. We also include ReO3-type compounds, which have the same crystal structure of cubic ABO3 perovskites except without A-site elements. From the observations we extract the following four conclusions for the perovskites studied in the present paper: for a given cation at the B site, (I) perovskites with cations of identical oxidation state at the A site possess close formation energies; and (II) perovskites with cations of different oxidation states at the A site usually have quite different but ordered formation energies. On the other hand, for a given A-site cation, (III) the formation energies of perovskites vary linearly with respect to the atomic number of the elements at the B site within the same period of the periodic table, and the slopes depend systematically on the oxidation state of the A-site cation; and (IV) the trends in formation energies of perovskites with elements from different periods at the B site depend on the oxidation state of A-site cations. Since the energetics of perovskites is shown to be the superposition of the individual contributions of their constituent oxides, the trends can be rationalized in terms of A-O and B-O interactions in the ionic crystal. These findings reveal the existence of general systematic trends in the formation energies of perovskites and provide further insight into the role of ion-ion interactions in the properties of ternary compounds. PMID:23579382

  5. CH3 NH3 PbBr3 -CH3 NH3 PbI3 Perovskite-Perovskite Tandem Solar Cells with Exceeding 2.2 V Open Circuit Voltage.

    PubMed

    Heo, Jin Hyuck; Im, Sang Hyuk

    2016-07-01

    Perovskite-perovskite tandem solar cells with open-circuit voltages of over 2.2 V are reported. These cost-effective, solution-processible perovskite hybrid tandem solar cells with high open-circuit voltages are fabricated by the simple lamination of a front planar MAPbBr3 perovskite cell and a back MAPbI3 planar perovskite solar cell.

  6. New double molybdate Na{sub 9}Fe(MoO{sub 4}){sub 6}: Synthesis, structure, properties

    SciTech Connect

    Savina, Aleksandra A.; Solodovnikov, Sergey F.; Basovich, Olga M.; Solodovnikova, Zoya A.; Belov, Dmitry A.; Pokholok, Konstantin V.; Gudkova, Irina A.; Stefanovich, Sergey Yu.; Lazoryak, Bogdan I.; Khaikina, Elena G.

    2013-09-15

    A new double molybdate Na{sub 9}Fe(MoO{sub 4}){sub 6} was synthesized using solid state reactions and studied with X-ray powder diffraction, second harmonic generation (SHG) technique, differential scanning calorimetry, X-ray fluorescence analysis, Mössbauer and dielectric impedance spectroscopy. Single crystals of Na{sub 9}Fe(MoO{sub 4}){sub 6} were obtained and its structure was solved (the space group R3{sup ¯}, a=14.8264(2), c=19.2402(3) Å, V=3662.79(9) Å{sup 3}, Z=6, R=0.0132). The structure is related to that of sodium ion conductor II-Na{sub 3}Fe{sub 2}(AsO{sub 4}){sub 3}. The basic structure units are polyhedral clusters composed of central FeO{sub 6} octahedron sharing edges with three Na(1)O{sub 6} octahedra. The clusters share common vertices with bridging MoO{sub 4} tetrahedra to form an open 3D framework where the cavities are occupied by Na(2) and Na(3) atoms. The compound melts incongruently at 904.7±0.2 K. Arrhenius type temperature dependence of electric conductivity σ has been registered in solid state (σ=6.8×10{sup −2} S cm{sup −1} at 800 K), thus allowing considering Na{sub 9}Fe(MoO{sub 4}){sub 6} as a new sodium ion conductor. - Graphical abstract: A new double molybdate Na{sub 9}Fe(MoO{sub 4}){sub 6} was synthesized and structurally characterized, its physicochemical properties were studied. Display Omitted - Highlights: • A new compound Na{sub 9}Fe(MoO{sub 4}){sub 6} was synthesized as ceramics and single crystals. • Na{sub 9}Fe(MoO{sub 4}){sub 6} structure is related to that of sodium-ion conductor II-Na{sub 3}Fe{sub 2}(AsO{sub 4}){sub 3}. • Physicochemical properties of the compound were studied. • Arrhenius plot for conductivity showed 6.8×10{sup −2} S cm{sup −1} at 800 K, E{sub a}∼0.8 eV. • Thus, Na{sub 9}Fe(MoO{sub 4}){sub 6} may be considered as a new sodium ion conductor.

  7. The structures and properties of the new two-dimensional inorganic–organic hybrid materials based on the molybdate chains

    SciTech Connect

    Li, Na; Mu, Bao; Cao, Xinyu; Huang, Rudan

    2014-09-15

    A series of inorganic organic hybrid materials based on polyoxometalates(POMs), namely, [M{sup II}(HL){sub 2}(H{sub 2}O){sub 2}][Mo{sup VI}{sub 6}O{sub 20}] [M=Co (1), Ni (2), Cu (3), Zn (4)], [Mn{sup IV}L{sub 2}(H{sub 2}O){sub 2}][Mo{sup VI}{sub 6}O{sub 20}] (5), and (HL){sub 3}PMO{sub 12}O{sub 40} (6) [L=3-(4-pyridyl)pyrazole], have been synthesized. The compounds have been characterized by elemental analysis, powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. The results from single-crystal X-ray diffraction indicate that 1–5 are isostructural. It is worth noting that the polyanions are bridged by Mo–O–Mo to form 1D inorganic chains, which are further connected via M ions to form 2D nets. In compound 6, the ligands are used as the positive ions to balance the charge of the compound. Moreover, the magnetic properties of compound 5 have also been investigated in detail. - Graphical abstract: In complex 1, The Co ion is six coordinated by four oxygen atoms from two Mo{sub 6}O{sub 20} and two water molecules, and two N atoms from two different ligand. It is noticeable that there is an one-dimensional chain molybdate, which is combined by O–Mo–O, then the chain parallel with each other, the Mo{sub 6} anion acts as a bidentate ligand providing O7 atoms to bridge CoII ions to form a 2D inorganic layer. Finally every nets become 3D structure by hydrogen bond. - Highlights: • Novel inorganic–organic hybrid materials have been prepared. • Compounds 1–5 contain the 1D molybdate chains composed of (MoO{sub 6}) octahedra. • The 1D chains parallel with each other to form a 2D inorganic layer.

  8. Ferroelectricity in d0 double perovskite fluoroscandates

    NASA Astrophysics Data System (ADS)

    Charles, Nenian; Rondinelli, James M.

    2015-08-01

    Ferroelectricity in strain-free and strained double perovskite fluorides, Na3ScF6 and K2NaScF6 , is investigated using first-principles density functional theory. Although the experimental room temperature crystal structures of these fluoroscandates are centrosymmetric, i.e., Na3ScF6 (P 21/n ) and K2NaScF6 (F m 3 ¯m ), lattice dynamical calculations reveal that soft polar instabilities exist in each prototypical cubic phase and that the modes harden as the tolerance factor approaches unity. Thus the double fluoroperovskites bear some similarities to A B O3 perovskite oxides; however, in contrast, these fluorides exhibit large acentric displacements of alkali metal cations (Na, K) rather than polar displacements of the transition metal cations. Biaxial strain investigations of the centrosymmetric and polar Na3ScF6 and K2NaScF6 phases reveal that the paraelectric structures are favored under compressive strain, whereas polar structures with in-plane electric polarizations (˜5 -18 μ C cm-2 ) are realized at sufficiently large tensile strains. The electric polarization and stability of the polar structures for both chemistries are found to be further enhanced and stabilized by a coexisting single octahedral tilt system. Our results suggest that polar double perovskite fluorides may be realized by suppression of octahedral rotations about more than one Cartesian axis; structures exhibiting in- or out-of-phase octahedral rotations about the c axis are more susceptible to polar symmetries.

  9. Piezoelectric activity in Perovskite ferroelectric crystals.

    PubMed

    Li, Fei; Wang, Linghang; Jin, Li; Lin, Dabin; Li, Jinglei; Li, Zhenrong; Xu, Zhuo; Zhang, Shujun

    2015-01-01

    Perovskite ferroelectrics (PFs) have been the dominant piezoelectric materials for various electromechanical applications, such as ultrasonic transducers, sensors, and actuators, to name a few. In this review article, the development of PF crystals is introduced, focusing on the crystal growth and piezoelectric activity. The critical factors responsible for the high piezoelectric activity of PFs (i.e., phase transition, monoclinic phase, domain size, relaxor component, dopants, and piezoelectric anisotropy) are surveyed and discussed. A general picture of the present understanding on the high piezoelectricity of PFs is described. At the end of this review, potential approaches to further improve the piezoelectricity of PFs are proposed.

  10. Lasing properties of selectively pumped Raman-active Nd{sup 3+}-doped molybdate and tungstate crystals

    SciTech Connect

    Basiev, Tasoltan T; Doroshenko, Maxim E; Ivleva, Lyudmila I; Osiko, Vyacheslav V; Kosmyna, M B; Komar', V K; Sulc, J; Jelinkova, H

    2006-08-31

    The lasing efficiency of Nd{sup 3+} ions is studied in laser materials capable of self-Raman frequency conversion. The lasing properties of tungstate and molybdate crystals with the scheelite structure (SrWO{sub 4}, BaWO{sub 4}, PbWO{sub 4}, SrMoO{sub 4}, PbMoO{sub 4}) activated with neodymium ions are investigated upon longitudinal pumping by a 750-nm alexandrite laser or a 800-nm diode laser. The slope lasing efficiency obtained for a Nd{sup 3+}:PbMoO{sub 4} laser emitting at 1054 nm is 54.3% for the total lasing efficiency of 46%, which is the best result for all the crystals with the scheelite structure studied so far. The simultaneous Q-switched lasing and self-Raman frequency conversion were demonstrated in neodymium-doped SrWO{sub 4}, PbWO{sub 4}, and BaWO{sub 4} crystals. (papers devoted to the 90th anniversary of a.m.prokhorov)

  11. Network structure of molybdate glasses by neutron and X-ray diffraction and reverse Monte Carlo modelling

    NASA Astrophysics Data System (ADS)

    Fabian, M.; Svab, E.; Krezhov, K.

    2016-09-01

    Rare-earth molybdate glasses have been prepared by rapid quench technique, the network structure was investigated by neutron and high-energy X-ray diffraction. For data evaluation the reverse Monte Carlo simulation technique was applied to obtain a possible 3dimensional network configuration, which is consistent with the experimental data. From the modelling the partial atomic correlation functions giJ(r) and the coordination number distributions CNij have been revealed. Formation of MoO4 (55%) and MoO6 (25%) units was established for the binary 90MoO3-10Nd2O3 glass. The B-O first neighbour distribution show a relatively broad first neighbour distance at 1.40A, the average coordination numbers show the presents of trigonal BO3 and tetrahedral BO4 groups. For 50MoO3-25Nd2O3-25B2O3 sample mixed MoO4-BO4 and MoO4-BO3 linkages form pronounced intermediate-range order.

  12. Synthesis, structural and spectroscopic properties of acentric triple molybdate Cs2NaBi(MoO4)3

    NASA Astrophysics Data System (ADS)

    Savina, A. A.; Atuchin, V. V.; Solodovnikov, S. F.; Solodovnikova, Z. A.; Krylov, A. S.; Maximovskiy, E. A.; Molokeev, M. S.; Oreshonkov, A. S.; Pugachev, A. M.; Khaikina, E. G.

    2015-05-01

    New ternary molybdate Cs2NaBi(MoO4)3 is synthesized in the system Na2MoO4-Cs2MoO4-Bi2(MoO4)3. The structure of Cs2NaBi(MoO4)3 of a new type is determined in noncentrosymmetric space group R3c, a=10.6435(2), c=40.9524(7) Å, V=4017.71(13) Å3, Z=12 in anisotropic approximation for all atoms taking into account racemic twinning. The structure is completely ordered, Mo atoms are tetrahedrally coordinated, Bi(1) and Bi(2) atoms are in octahedra, and Na(1) and Na(2) atoms have a distorted trigonal prismatic coordination. The Cs(1) and Cs(2) atoms are in the framework cavities with coordination numbers 12 and 10, respectively. No phase transitions were found in Cs2NaBi(MoO4)3 up to the melting point at 826 K. The compound shows an SHG signal, I2w/I2w(SiO2)=5 estimated by the powder method. The vibrational properties are evaluated by Raman spectroscopy, and 26 narrow lines are measured.

  13. Characterisation of heterogeneous molybdate and chromate phase assemblages in model nuclear waste glasses by multinuclear magnetic resonance spectroscopy.

    PubMed

    Greer, Brandon J; Kroeker, Scott

    2012-05-28

    A series of sodium borosilicate glasses containing cesium, molybdenum, and chromium was prepared to investigate the partitioning of chromium amongst the glass and phase-separated crystalline molybdates. The precipitates were examined by (133)Cs, (23)Na, and (95)Mo MAS NMR, revealing a phase assemblage consisting of Na(2)MoO(4), Na(2)MoO(4)·2H(2)O, Cs(2)MoO(4), Cs(2)CrO(4), CsNaMoO(4)·2H(2)O, and Cs(3)Na(MoO(4))(2). (133)Cs MAS NMR indicates random substitution of Cr into the Mo sites of Cs(3)Na(MoO(4))(2) and provides a quantitative assessment of Cr incorporation. The sample compositions were verified by various analytical techniques and highlight the centrality of NMR in the identification and quantification of heterogeneous crystalline composites, including sensitivity to cationic substitution. The observation and facile interconversion of hydrated phases invites careful consideration of these materials for nuclear waste disposal.

  14. Molten-salt synthesis and composition-dependent luminescent properties of barium tungsto-molybdate-based solid solution phosphors

    NASA Astrophysics Data System (ADS)

    Xiang-Hong, He; Zhao-Lian, Ye; Ming-Yun, Guan; Ning, Lian; Jian-Hua, Sun

    2016-02-01

    Pr3+-activated barium tungsto-molybdate solid solution phosphor Ba(Mo1-zWz)O4:Pr3+ is successfully fabricated via a facile molten-salt approach. The as-synthesized microcrystal is of truncated octahedron and exhibits deep-red-emitting upon blue light excitation. Powder x-ray diffraction and Raman spectroscopy techniques are utilized to investigate the formation of solid solution phosphor. The luminescence behaviors depend on the resulting composition of the microcrystals with fixed Pr3+-doping concentration, while the host lattices remain in a scheelite structure. The forming solid solution via the substitution of [WO4] for [MoO4] can significantly enhance its luminescence, which may be due to the fact that Ba(Mo1-zWz)O4:Pr3+ owns well-defined facets and uniform morphologies. Owing to its properties of high phase purity, well-defined facets, highly uniform morphologies, exceptional chemical and thermal stabilities, and stronger emission intensity, the resulting solid solution phosphor is expected to find potential applications in phosphor-converted white light-emitting diodes (LEDs). Project supported by the Construction Fund for Science and Technology Innovation Group from Jiangsu University of Technology, China, the Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, China (Grant No. KHK1409), the Priority Academic Program Development of Jiangsu Higher Education Institutions, China, and the National Natural Science Foundation of China (Grant No. 21373103).

  15. High-temperature behavior of dicesium molybdate Cs2MoO4: Implications for fast neutron reactors

    NASA Astrophysics Data System (ADS)

    Wallez, Gilles; Raison, Philippe E.; Smith, Anna L.; Clavier, Nicolas; Dacheux, Nicolas

    2014-07-01

    Dicesium molybdate (Cs2MoO4)'s thermal expansion and crystal structure have been investigated herein by high temperature X ray diffraction in conjunction with Raman spectroscopy. This first crystal-chemical insight at high temperature is aimed at predicting the thermostructural and thermomechanical behavior of this oxide formed by the accumulation of Cs and Mo fission products at the periphery of nuclear fuel rods in sodium-cooled fast reactors. Within the temperature range of the fuel's rim, Cs2MoO4 becomes hexagonal P63/mmc, with disordered MoO4 tetrahedra and 2D distribution of Cs-O bonds that makes thermal axial expansion both large (50≤αl≤70 10-6 °C-1, 500-800 °C) and highly anisotropic (αc-αa=67×10-6 °C-1, hexagonal form). The difference with the fuel's expansion coefficient is of potential concern with respect to the cohesion of the Cs2MoO4 surface film and the possible release of cesium radionuclides in accidental situations.

  16. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth.

    PubMed

    Yang, Bin; Keum, Jong; Ovchinnikova, Olga S; Belianinov, Alex; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

    2016-04-20

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films, a major unresolved question is the competition between multiple halide species (e.g., I(-), Cl(-), Br(-)) in the formation of the mixed-halide perovskite crystals. Whether Cl(-) ions are successfully incorporated into the perovskite crystal structure or, alternatively, where they are located is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br(-) or Cl(-) ions can promote crystal growth, yet reactive I(-) ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl(-) ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performing and cost-effective optoelectronic devices. PMID:26931634

  17. Anion order in perovskites: a group-theoretical analysis.

    PubMed

    Talanov, M V; Shirokov, V B; Talanov, V M

    2016-03-01

    Anion ordering in the structure of cubic perovskite has been investigated by the group-theoretical method. The possibility of the existence of 261 ordered low-symmetry structures, each with a unique space-group symmetry, is established. These results include five binary and 14 ternary anion superstructures. The 261 idealized anion-ordered perovskite structures are considered as aristotypes, giving rise to different derivatives. The structures of these derivatives are formed by tilting of BO6 octahedra, distortions caused by the cooperative Jahn-Teller effect and other physical effects. Some derivatives of aristotypes exist as real substances, and some as virtual ones. A classification of aristotypes of anion superstructures in perovskite is proposed: the AX class (the simultaneous ordering of A cations and anions in cubic perovskite structure), the BX class (the simultaneous ordering of B cations and anions) and the X class (the ordering of anions only in cubic perovskite structure). In most perovskites anion ordering is accompanied by cation ordering. Therefore, the main classes of anion order in perovskites are the AX and BX classes. The calculated structures of some anion superstructures are reported. Comparison of predictions and experimentally investigated anion superstructures shows coherency of theoretical and experimental results. PMID:26919374

  18. Modeling of optical losses in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Taghavi, M. Javad; Houshmand, Mohammad; Zandi, M. Hossein; Gorji, Nima E.

    2016-09-01

    The optical losses within the structure of hybrid perovskite solar cells are investigated using only the optical properties of each layer e.g. refractive index and extinction coefficient. This model allows calculating the transmission/reflection rates at the interfaces and absorption loss within any layer. Then, the short circuit current density and loss percentage are calculated versus the perovskite and TiO2 thicknesses from 50 nm to 150 nm. To make our calculations closer to reality, we extracted the optical properties of each device component from the literature reports on glass/TCO/TiO2/perovskite/metal. The simulations were fitted with the experimental results of some relevant references. Our simulations show that ITO transmits the light better than SnO2 as the TCO front electrode, and the light reflection at both sides of the perovskite layer, e.g. at TiO2/perovskite and perovskite/Spiro-OMeTAD, is lower than 25%. The light interference and multiple reflections have been accounted in our calculations and finally we showed that a thicker TiO2 and perovskite cause more optical loss in current density due to stronger absorption.

  19. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    DOE PAGESBeta

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher; Geohegan, David B.; Xiao, Kai

    2016-03-01

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films a major unresolved question is the competition between multiple halide species (e.g. I-, Cl-, Br-) in the formation of the mixed halide perovskite crystals. Whether Cl- ions are successfully incorporated into the perovskite crystal structure or alternatively, where they are located, is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br- or Cl- ions can promote crystal growth, yet reactive I- ionsmore » prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl- ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites, and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performance and cost-effective optoelectronic devices.« less

  20. Perovskite Materials for Light-Emitting Diodes and Lasers.

    PubMed

    Veldhuis, Sjoerd A; Boix, Pablo P; Yantara, Natalia; Li, Mingjie; Sum, Tze Chien; Mathews, Nripan; Mhaisalkar, Subodh G

    2016-08-01

    Organic-inorganic hybrid perovskites have cemented their position as an exceptional class of optoelectronic materials thanks to record photovoltaic efficiencies of 22.1%, as well as promising demonstrations of light-emitting diodes, lasers, and light-emitting transistors. Perovskite materials with photoluminescence quantum yields close to 100% and perovskite light-emitting diodes with external quantum efficiencies of 8% and current efficiencies of 43 cd A(-1) have been achieved. Although perovskite light-emitting devices are yet to become industrially relevant, in merely two years these devices have achieved the brightness and efficiencies that organic light-emitting diodes accomplished in two decades. Further advances will rely decisively on the multitude of compositional, structural variants that enable the formation of lower-dimensionality layered and three-dimensional perovskites, nanostructures, charge-transport materials, and device processing with architectural innovations. Here, the rapid advancements in perovskite light-emitting devices and lasers are reviewed. The key challenges in materials development, device fabrication, operational stability are addressed, and an outlook is presented that will address market viability of perovskite light-emitting devices.

  1. 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.

  2. Perovskite Materials for Light-Emitting Diodes and Lasers.

    PubMed

    Veldhuis, Sjoerd A; Boix, Pablo P; Yantara, Natalia; Li, Mingjie; Sum, Tze Chien; Mathews, Nripan; Mhaisalkar, Subodh G

    2016-08-01

    Organic-inorganic hybrid perovskites have cemented their position as an exceptional class of optoelectronic materials thanks to record photovoltaic efficiencies of 22.1%, as well as promising demonstrations of light-emitting diodes, lasers, and light-emitting transistors. Perovskite materials with photoluminescence quantum yields close to 100% and perovskite light-emitting diodes with external quantum efficiencies of 8% and current efficiencies of 43 cd A(-1) have been achieved. Although perovskite light-emitting devices are yet to become industrially relevant, in merely two years these devices have achieved the brightness and efficiencies that organic light-emitting diodes accomplished in two decades. Further advances will rely decisively on the multitude of compositional, structural variants that enable the formation of lower-dimensionality layered and three-dimensional perovskites, nanostructures, charge-transport materials, and device processing with architectural innovations. Here, the rapid advancements in perovskite light-emitting devices and lasers are reviewed. The key challenges in materials development, device fabrication, operational stability are addressed, and an outlook is presented that will address market viability of perovskite light-emitting devices. PMID:27214091

  3. NREL Studies Carrier Separation and Transport in Perovskite Solar Cells

    SciTech Connect

    2016-01-01

    NREL scientists studied charge separation and transport in perovskite solar cells by determining the junction structure across the solar device using the nanoelectrical characterization technique of Kelvin probe force microscopy. The distribution of electrical potential across both planar and porous devices demonstrates a p-n junction structure at the interface between titanium dioxide and perovskite. In addition, minority-carrier transport within the devices operates under diffusion/drift. Clarifying the fundamental junction structure provides significant guidance for future research and development. This NREL study points to the fact that improving carrier mobility is a critical factor for continued efficiency gains in perovskite solar cells.

  4. Electronic spin state of iron in lower mantle perovskite

    SciTech Connect

    Li, J.; Struzhkin, V.; Mao, H.-k.; Shu, J.; Hemley, R.; Fei, Y.; Mysen, B.; Dera, P.; Parapenka, V.; Shen, G.

    2010-11-16

    The electronic spin state of iron in lower mantle perovskite is one of the fundamental parameters that governs the physics and chemistry of the most voluminous and massive shell in the Earth. We present experimental evidence for spin-pairing transition in aluminum-bearing silicate perovskite (Mg,Fe)(Si,Al)O{sub 3} under the lower mantle pressures. Our results demonstrate that as pressure increases, iron in perovskite transforms gradually from the initial high-spin state toward the final low-spin state. At 100 GPa, both aluminum-free and aluminum-bearing samples exhibit a mixed spin state. The residual magnetic moment in the aluminum-bearing perovskite is significantly higher than that in its aluminum-free counterpart. The observed spin evolution with pressure can be explained by the presence of multiple iron species and the occurrence of partial spin-paring transitions in the perovskite. Pressure-induced spin-pairing transitions in the perovskite would have important bearing on the magnetic, thermoelastic, and transport properties of the lower mantle, and on the distribution of iron in the Earth's interior. The lower mantle constitutes more than half of the Earth's interior by volume (1), and it is believed to consist predominantly (80-100%) of (Mg,Fe)(Si,Al)O{sub 3} perovskite (hereafter called perovskite), with up to 20% (Mg,Fe)O ferropericlase (2). The electronic spin state of iron has direct influence on the physical properties and chemical behavior of its host phase. Hence, knowledge on the spin state of iron is important for the interpretation of seismic observations, geochemical modeling, and geodynamic simulation of the Earth's deep interior (3, 4). Crystal field theory (4, 5) and band theory (6) predicted that a high-spin to low-spin transition would occur as a result of compression. To date, no experimental data exist on the spin sate of iron in Al-bearing perovskite. To detect possible spinpairing transition of iron in perovskite under the lower mantle

  5. Finding New Perovskite Halides via Machine learning

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-01

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning) via building a support vector machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  6. Perovskite oxides: Oxygen electrocatalysis and bulk structure

    NASA Technical Reports Server (NTRS)

    Carbonio, R. E.; Fierro, C.; Tryk, D.; Scherson, D.; Yeager, Ernest

    1987-01-01

    Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

  7. Finding new perovskite halides via machine learning

    DOE PAGESBeta

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-26

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach toward rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning, henceforth referred to as ML) via building a support vectormore » machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br, or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 185 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor, and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. As a result, the trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.« less

  8. Topological Phases in Perovskite Oxide Heterostructures

    NASA Astrophysics Data System (ADS)

    Kim, Rokyeon; Yu, Jaejun; Jin, Hosub

    Quantum spin Hall (QSH) insulator is a new state of matter characterized by gapless edge states and insulating bulk states. Because the edge states are topologically protected and therefore robust against non-magnetic perturbations, it has a potential to be utilized in spintronics devices. Quauntum vally Hall (QVH) phase, on the other hand, is another class of topological state exhibiting valley-contrasting Berry curvature and spin splitting, which could yield novel transport properties, such as valley Hall effect and valley spin Hall effect. We propose a new kind of perovskite (111) heterostructures which can host both QSH and QVH phases with appropriate choices of composing elements. By carrying out first-principles calculations, we demonstrate that a Dirac cone emerges in a particular choice of heterostructure, and a sizable spin-orbit coupling turns the system into the QSH phase. In addition, the QVH phase with different Berry phases and spin textures in each valley is shown to be realized in the heterostructure with broken inversion symmetry. We porpose that these perovskite heterostructures can provide a feasible platform for spintronics, valleytronics, and topological engineering of the two-dimensional electron system.

  9. Neutral color semitransparent microstructured perovskite solar cells.

    PubMed

    Eperon, Giles E; Burlakov, Victor M; Goriely, Alain; Snaith, Henry J

    2014-01-28

    Neutral-colored semitransparent solar cells are commercially desired to integrate solar cells into the windows and cladding of buildings and automotive applications. Here, we report the use of morphological control of perovskite thin films to form semitransparent planar heterojunction solar cells with neutral color and comparatively high efficiencies. We take advantage of spontaneous dewetting to create microstructured arrays of perovskite "islands", on a length-scale small enough to appear continuous to the eye yet large enough to enable unattenuated transmission of light between the islands. The islands are thick enough to absorb most visible light, and the combination of completely absorbing and completely transparent regions results in neutral transmission of light. Using these films, we fabricate thin-film solar cells with respectable power conversion efficiencies. Remarkably, we find that such discontinuous films still have good rectification behavior and relatively high open-circuit voltages due to the inherent rectification between the n- and p-type charge collection layers. Furthermore, we demonstrate the ease of "color-tinting" such microstructured perovksite solar cells with no reduction in performance, by incorporation of a dye within the hole transport medium.

  10. Perovskite Solar Cells: High Efficiency Pb-In Binary Metal Perovskite Solar Cells (Adv. Mater. 31/2016).

    PubMed

    Wang, Zhao-Kui; Li, Meng; Yang, Ying-Guo; Hu, Yun; Ma, Heng; Gao, Xing-Yu; Liao, Liang-Sheng

    2016-08-01

    On page 6695, X. Y. Gao, L.-S. Liao, and co-workers describe the fabrication of mixed Pb-In perovskite solar cells, using indium (III) chloride and lead (II) chloride with methylammonium iodide. A maximum power conversion efficiency as high as 17.55% is achieved owing to the high quality of the perovskites with multiple ordered crystal orientations. This work demonstrates the possibility of substituting the Pb (II) by using In (III), which opens a broad route to fabricating alloy perovskite solar cells with mitigated ecological impact.

  11. Perovskite Solar Cells: High Efficiency Pb-In Binary Metal Perovskite Solar Cells (Adv. Mater. 31/2016).

    PubMed

    Wang, Zhao-Kui; Li, Meng; Yang, Ying-Guo; Hu, Yun; Ma, Heng; Gao, Xing-Yu; Liao, Liang-Sheng

    2016-08-01

    On page 6695, X. Y. Gao, L.-S. Liao, and co-workers describe the fabrication of mixed Pb-In perovskite solar cells, using indium (III) chloride and lead (II) chloride with methylammonium iodide. A maximum power conversion efficiency as high as 17.55% is achieved owing to the high quality of the perovskites with multiple ordered crystal orientations. This work demonstrates the possibility of substituting the Pb (II) by using In (III), which opens a broad route to fabricating alloy perovskite solar cells with mitigated ecological impact. PMID:27511533

  12. Rain on Methylammonium Lead Iodide Based Perovskites: Possible Environmental Effects of Perovskite Solar Cells.

    PubMed

    Hailegnaw, Bekele; Kirmayer, Saar; Edri, Eran; Hodes, Gary; Cahen, David

    2015-05-01

    The great promise of hybrid organic-inorganic lead halide perovskite (HOIP)-based solar cells is being challenged by its Pb content and its sensitivity to water. Here, the impact of rain on methylammonium lead iodide perovskite films was investigated by exposing such films to water of varying pH values, simulating exposure of the films to rain. The amount of Pb loss was determined using both gravimetric and inductively coupled plasma mass spectrometry measurements. Using our results, the extent of Pb loss to the environment, in the case of catastrophic module failure, was evaluated. Although very dependent on module siting, even total destruction of a large solar electrical power generating plant, based on HOIPs, while obviously highly undesirable, is estimated to be far from catastrophic for the environment.

  13. Investigation of perovskite-sensitized nanoporous titanium dioxide photoanodes with different thicknesses in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Xiao, Yaoming; Han, Gaoyi; Chang, Yunzhen; Zhang, Ying; Li, Yanping; Li, Miaoyu

    2015-07-01

    Perovskite-sensitized nanoporous TiO2 films with different thicknesses are prepared by an in situ method, which are employed as photoanodes in perovskite solar cells (PSCs). The photoelectrochemical properties of different photoanodes are quantified by the ultraviolet to visible reflectance spectra, incident monochromatic photon-to-current conversion efficiency, and electrochemical impedance spectroscopy measurements. Results demonstrate that the thin photoanode has high electron lifetime for recombination, which can enhance the separation and transmission of the electron and hole. However, the sunlight utilization will decrease with reducing the photoanode thickness due to the small quantity of CH3NH3PbI3 filled into the photoanode to absorb sunlight. After optimization, PSC with 0.80 μm of the photoanode thickness shows a superior cell efficiency of 12.22% without a hole transporting material.

  14. Perovskite as light harvester: a game changer in photovoltaics.

    PubMed

    Kazim, Samrana; Nazeeruddin, Mohammad Khaja; Grätzel, Michael; Ahmad, Shahzada

    2014-03-10

    It is not often that the scientific community is blessed with a material, which brings enormous hopes and receives special attention. When it does, it expands at a rapid pace and its every dimension creates curiosity. One such material is perovskite, which has triggered the development of new device architectures in energy conversion. Perovskites are of great interest in photovoltaic devices due to their panchromatic light absorption and ambipolar behavior. Power conversion efficiencies have been doubled in less than a year and over 15% is being now measured in labs. Every digit increment in efficiency is being celebrated widely in the scientific community and is being discussed in industry. Here we provide a summary on the use of perovskite for inexpensive solar cells fabrication. It will not be unrealistic to speculate that one day perovskite-based solar cells can match the capability and capacity of existing technologies. PMID:24519832

  15. The Coulombic Lattice Potential of Ionic Compounds: The Cubic Perovskites.

    ERIC Educational Resources Information Center

    Francisco, E.; And Others

    1988-01-01

    Presents coulombic models representing the particles of a system by point charges interacting through Coulomb's law to explain coulombic lattice potential. Uses rubidium manganese trifluoride as an example of cubic perovskite structure. Discusses the effects on cluster properties. (CW)

  16. Oxyanions in perovskites: from superconductors to solid oxide fuel cells.

    PubMed

    Hancock, C A; Porras-Vazquez, J M; Keenan, P J; Slater, P R

    2015-06-21

    In this article we review work on oxyanion (carbonate, borate, nitrate, phosphate, sulphate, silicate) doping in perovskite materials beginning with early work on doping studies in superconducting cuprates, and extending to more recent work on doping into perovskite-type solid oxide fuel cell materials. In this doping strategy, the central atom of the oxyanion group occupies the perovskite B cation site, with the associated oxide ions filling 3 (carbonate, nitrate, borate) or 4 (phosphate, sulphate, silicate) of the available 6 anion sites around this site, albeit displaced so as to achieve the required geometry for the oxyanion. We highlight the potential of this doping strategy to prepare new systems, stabilize phases that cannot be prepared under ambient pressure conditions, and lead to modifications to the electronic and ionic conductivity. We also highlight the need for further work in this area, in particular to evaluate the carbonate content of perovskite phases in general. PMID:25407324

  17. Two-Dimensional Organic-Inorganic Hybrid Perovskite Photonic Films.

    PubMed

    Meng, Ke; Gao, Shanshan; Wu, Longlong; Wang, Geng; Liu, Xin; Chen, Gang; Liu, Zhou; Chen, Gang

    2016-07-13

    Organic-inorganic hybrid perovskites have created enormous expectations for low-cost and high-performance optoelectronic devices. In prospect, future advancements may derive from reaping novel electrical and optical properties beyond pristine perovskites through microscopic structure design and engineering. Herein, we report the successful preparation of two-dimensional inverse-opal perovskite (IOP) photonic films, featuring unique nanostructures and vivid colors. Further compositional and structural managements promise optical property and energy level tunability of the IOP films. They are further functionalized in solar cells, resulting in colorful devices with respectable power conversion efficiency. Such concept has not been previously applied for perovskite-based solar cells, which could open a route for more versatile optoelectronic devices.

  18. Two-Dimensional Organic-Inorganic Hybrid Perovskite Photonic Films.

    PubMed

    Meng, Ke; Gao, Shanshan; Wu, Longlong; Wang, Geng; Liu, Xin; Chen, Gang; Liu, Zhou; Chen, Gang

    2016-07-13

    Organic-inorganic hybrid perovskites have created enormous expectations for low-cost and high-performance optoelectronic devices. In prospect, future advancements may derive from reaping novel electrical and optical properties beyond pristine perovskites through microscopic structure design and engineering. Herein, we report the successful preparation of two-dimensional inverse-opal perovskite (IOP) photonic films, featuring unique nanostructures and vivid colors. Further compositional and structural managements promise optical property and energy level tunability of the IOP films. They are further functionalized in solar cells, resulting in colorful devices with respectable power conversion efficiency. Such concept has not been previously applied for perovskite-based solar cells, which could open a route for more versatile optoelectronic devices. PMID:27267266

  19. Perovskite-Fullerene Hybrid Materials Eliminate Hysteresis In Planar Diodes

    SciTech Connect

    Xu, Jixian; Buin, Andrei; Ip, Alexander H.; Li, Wei; Voznyy, Oleksandr; Comin, Riccardo; Yuan, Mingjian; Jeon, Seokmin; Ning, Zhijun; McDowell, Jeffrey; Kanjanaboos, Pongsakorn; Sun, Jon-Paul; Lan, Xinzheng; Quan, Li Na; Kim, Dong Ha; Hill, Ian; Maksymovych, Petro; Sargent, Edward H.

    2015-03-31

    Solution-processed planar perovskite devices are highly desirable in a wide variety of optoelectronic applications; however, they are prone to hysteresis and current instabilities. Here we report the first perovskite–PCBM hybrid solid with significantly reduced hysteresis and recombination loss achieved in a single step. This new material displays an efficient electrically coupled microstructure: PCBM is homogeneously distributed throughout the film at perovskite grain boundaries. The PCBM passivates the key PbI3 antisite defects during the perovskite self-assembly, as revealed by theory and experiment. Photoluminescence transient spectroscopy proves that the PCBM phase promotes electron extraction. We showcase this mixed material in planar solar cells that feature low hysteresis and enhanced photovoltage. Using conductive AFM studies, we reveal the memristive properties of perovskite films. We close by positing that PCBM, by tying up both halide-rich antisites and unincorporated halides, reduces electric field-induced anion migration that may give rise to hysteresis and unstable diode behaviour.

  20. Tetravalent dysprosium in a perovskite-type oxide.

    PubMed

    Han, Donglin; Uda, Tetsuya; Nose, Yoshitaro; Okajima, Toshihiro; Murata, Hidenobu; Tanaka, Isao; Shinoda, Kozo

    2012-04-17

    The existence of tetravalent dysprosium in perovskite-type oxide barium zirconate is confirmed in this work. This discovery will stimulate many researchers in diverse fields such as catalysts, solid state ionics, sensors, and fluorescent materials.

  1. Highly Efficient Perovskite Solar Cells with Tunable Structural Color

    PubMed Central

    2015-01-01

    The performance of perovskite solar cells has been progressing over the past few years and efficiency is likely to continue to increase. However, a negative aspect for the integration of perovskite solar cells in the built environment is that the color gamut available in these materials is very limited and does not cover the green-to-blue region of the visible spectrum, which has been a big selling point for organic photovoltaics. Here, we integrate a porous photonic crystal (PC) scaffold within the photoactive layer of an opaque perovskite solar cell following a bottom-up approach employing inexpensive and scalable liquid processing techniques. The photovoltaic devices presented herein show high efficiency with tunable color across the visible spectrum. This now imbues the perovskite solar cells with highly desirable properties for cladding in the built environment and encourages design of sustainable colorful buildings and iridescent electric vehicles as future power generation sources. PMID:25650872

  2. Recent advances of lanthanum-based perovskite oxides for catalysis

    SciTech Connect

    Zhu, Huiyuan; Zhang, Pengfei; Dai, Sheng

    2015-09-21

    There is a need to reduce the use of noble metal elements especially in the field of catalysis, where noble metals are ubiquitously applied. To this end, perovskite oxides, an important class of mixed oxide, have been attracting increasing attention for decades as potential replacements. Benefiting from the extraordinary tunability of their compositions and structures, perovskite oxides can be rationally tailored and equipped with targeted physical and chemical properties e.g. redox behavior, oxygen mobility, and ion conductivity for enhanced catalysis. Recently, the development of highly efficient perovskite oxide catalysts has been extensively studied. This review article summarizes the recent development of lanthanum-based perovskite oxides as advanced catalysts for both energy conversion applications and traditional heterogeneous reactions.

  3. Recent advances of lanthanum-based perovskite oxides for catalysis

    DOE PAGESBeta

    Zhu, Huiyuan; Zhang, Pengfei; Dai, Sheng

    2015-09-21

    There is a need to reduce the use of noble metal elements especially in the field of catalysis, where noble metals are ubiquitously applied. To this end, perovskite oxides, an important class of mixed oxide, have been attracting increasing attention for decades as potential replacements. Benefiting from the extraordinary tunability of their compositions and structures, perovskite oxides can be rationally tailored and equipped with targeted physical and chemical properties e.g. redox behavior, oxygen mobility, and ion conductivity for enhanced catalysis. Recently, the development of highly efficient perovskite oxide catalysts has been extensively studied. This review article summarizes the recent developmentmore » of lanthanum-based perovskite oxides as advanced catalysts for both energy conversion applications and traditional heterogeneous reactions.« less

  4. Highly efficient perovskite solar cells with tunable structural color.

    PubMed

    Zhang, Wei; Anaya, Miguel; Lozano, Gabriel; Calvo, Mauricio E; Johnston, Michael B; Míguez, Hernán; Snaith, Henry J

    2015-03-11

    The performance of perovskite solar cells has been progressing over the past few years and efficiency is likely to continue to increase. However, a negative aspect for the integration of perovskite solar cells in the built environment is that the color gamut available in these materials is very limited and does not cover the green-to-blue region of the visible spectrum, which has been a big selling point for organic photovoltaics. Here, we integrate a porous photonic crystal (PC) scaffold within the photoactive layer of an opaque perovskite solar cell following a bottom-up approach employing inexpensive and scalable liquid processing techniques. The photovoltaic devices presented herein show high efficiency with tunable color across the visible spectrum. This now imbues the perovskite solar cells with highly desirable properties for cladding in the built environment and encourages design of sustainable colorful buildings and iridescent electric vehicles as future power generation sources.

  5. Origin of “memory glass” effect in pressure-amorphized rare-earth molybdate single crystals

    SciTech Connect

    Willinger, Elena; Sinitsyn, Vitaly; Khasanov, Salavat; Redkin, Boris; Shmurak, Semeon; Ponyatovsky, Eugeny

    2015-02-15

    The memory glass effect (MGE) describes the ability of some materials to recover the initial structure and crystallographic orientation after pressure-induced amorphization (PIA). In spite of numerous studies the nature and underlying mechanisms of this phenomenon are still not clear. Here we report investigations of MGE in β′-Eu{sub 2}(MoO{sub 4}){sub 3} single crystal samples subjected to high pressure amorphization. Using the XRD and TEM techniques we carried out detailed analysis of the structural state of high pressure treated single crystal samples as well as structural transformations due to subsequent annealing at atmospheric pressure. The structure of the sample has been found to be complex, mainly amorphous, however, the amorphous medium contains evenly distributed nanosize inclusions of a paracrystalline phase. The inclusions are highly correlated in orientation and act as “memory units” in the MGE. - Graphical abstract: Schematic representation of pressure-induced amorphization and “memory glass” effect in rare-earth molybdate single crystals. The XRD and TEM measurements have revealed the presence of the residual identically oriented paracrystalline nanodomains in the pressure-amorphized state. These domains preserve the information about initial structure and orientation of the sample. They act as memory units and crystalline seeds during transformation of the amorphous phase back to the starting single crystalline one. - Highlights: • Pressure-amorphized Eu{sub 2}(MoO4){sub 3} single crystals were studied ex-situ by XRD and TEM. • Tiny residual crystalline inclusions were found in amorphous matrix of sample. • The inclusions keep in memory the parent crystal structure and orientation. • The inclusions account for “memory glass” effect in rare-earth molibdates.

  6. 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.

  7. High Performance Tandem Perovskite/Polymer Solar Cells

    NASA Astrophysics Data System (ADS)

    Liu, Yao; Bag, Monojit; Page, Zachariah; Renna, Lawrence; Kim, Paul; Choi, Jaewon; Emrick, Todd; Venkataraman, D.; Russell, Thomas

    Combining perovskites with other inorganic materials, such as copper indium gallium diselenide (CIGS) or silicon, is enabling significant improvement in solar cell device performance. Here, we demonstrate a highly efficient hybrid tandem solar cell fabricated through a facile solution deposition approach to give a perovskite front sub-cell and a polymer:fullerene blend back sub-cell. This methodology eliminates the adverse effects of thermal annealing during perovskite fabrication on polymer solar cells. The record tandem solar cell efficiency of 15.96% is 40% greater than the corresponding perovskite-based single junction device and 65% greater than the polymer-based single junction device, while mitigating deleterious hysteresis effects often associated with perovskite solar cells. The hybrid tandem devices demonstrate the synergistic effects arising from the combination of perovskite and polymer-based materials for solar cells. This work was supported by the Department of Energy-supported Energy Frontier Research Center at the University of Massachusetts (DE-SC0001087). The authors acknowledge the W.M. Keck Electron Microscopy.

  8. Iodomethane-Mediated Organometal Halide Perovskite with Record Photoluminescence Lifetime.

    PubMed

    Xu, Weidong; McLeod, John A; Yang, Yingguo; Wang, Yimeng; Wu, Zhongwei; Bai, Sai; Yuan, Zhongcheng; Song, Tao; Wang, Yusheng; Si, Junjie; Wang, Rongbin; Gao, Xingyu; Zhang, Xinping; Liu, Lijia; Sun, Baoquan

    2016-09-01

    Organometallic lead halide perovskites are excellent light harvesters for high-efficiency photovoltaic devices. However, as the key component in these devices, a perovskite thin film with good morphology and minimal trap states is still difficult to obtain. Herein we show that by incorporating a low boiling point alkyl halide such as iodomethane (CH3I) into the precursor solution, a perovskite (CH3NH3PbI3-xClx) film with improved grain size and orientation can be easily achieved. More importantly, these films exhibit a significantly reduced amount of trap states. Record photoluminescence lifetimes of more than 4 μs are achieved; these lifetimes are significantly longer than that of pristine CH3NH3PbI3-xClx films. Planar heterojunction solar cells incorporating these CH3I-mediated perovskites have demonstrated a dramatically increased power conversion efficiency compared to the ones using pristine CH3NH3PbI3-xClx. Photoluminescence, transient absorption, and microwave detected photoconductivity measurements all provide consistent evidence that CH3I addition increases the number of excitons generated and their diffusion length, both of which assist efficient carrier transport in the photovoltaic device. The simple incorporation of alkyl halide to enhance perovskite surface passivation introduces an important direction for future progress on high efficiency perovskite optoelectronic devices. PMID:27529636

  9. Laser Crystallization of Organic-Inorganic Hybrid Perovskite Solar Cells.

    PubMed

    Jeon, Taewoo; Jin, Hyeong Min; Lee, Seung Hyun; Lee, Ju Min; Park, Hyung Il; Kim, Mi Kyung; Lee, Keon Jae; Shin, Byungha; Kim, Sang Ouk

    2016-08-23

    Organic-inorganic hybrid perovskites attract enormous research interest for next generation solar energy harvest. Synergistic crystalline structures comprising organic and inorganic components enable solution processing of perovskite films. A reliable crystallization method for perovskites, compatible with fast continuous process over large-area flexible substrates, is crucial for high performance solar cell production. Here, we present laser crystallization of hybrid perovskite solar cells using near-infrared (NIR) laser (λ = 1064 nm). Crystalline morphology of CH3NH3PbI3 (MAPbI3) perovskite films are widely controllable with laser irradiation condition while maintaining film uniformity. Photothermal heating effectively assisted by interfacial photoconversion layers is critical for phase transformation without beam damage of multilayered device structures. Notably, laser crystallization attains higher device performances than conventional thermal annealing. Fast laser crystallization with manufacture level scan rate (1 m min(-1)) demonstrates inverted-type perovskite solar cells with 11.3 and 8.0% efficiencies on typical glass and flexible polymer substrates, respectively, without rigorous device optimization.

  10. Tracking the formation of methylammonium lead triiodide perovskite

    NASA Astrophysics Data System (ADS)

    Liu, Lijia; McLeod, John A.; Wang, Rongbin; Shen, Pengfei; Duhm, Steffen

    2015-08-01

    The formation mechanism of perovskite methylammonium lead triiodide (CH3NH3PbI3) was studied with in situ X-ray photoelectron spectroscopy (XPS) on successive depositions of thermally evaporated methylammonium iodide (CH3NH3I) on a lead iodide (PbI2) film. This deposition method mimics the "two-step" synthesis method commonly used in device fabrication. We find that several competing processes occur during the formation of perovskite CH3NH3PbI3. Our most important finding is that during vapour deposition of CH3NH3I onto PbI2, at least two carbon species are present in the resulting material, while only one nitrogen species is present. This suggests that CH3NH3I can dissociate during the transition to a perovskite phase, and some of the resulting molecules can be incorporated into the perovskite. The effect of partial CH3NH3 substitution with CH3 was evaluated, and electronic structure calculations show that CH3 defects would impact the photovoltaic performance in perovskite solar cells. The possibility that not all A sites in the APbI3 perovskite are occupied by CH3NH3 is therefore an important consideration when evaluating the performance of organometallic trihalide solar cells synthesized using typical approaches.

  11. Laser Crystallization of Organic-Inorganic Hybrid Perovskite Solar Cells.

    PubMed

    Jeon, Taewoo; Jin, Hyeong Min; Lee, Seung Hyun; Lee, Ju Min; Park, Hyung Il; Kim, Mi Kyung; Lee, Keon Jae; Shin, Byungha; Kim, Sang Ouk

    2016-08-23

    Organic-inorganic hybrid perovskites attract enormous research interest for next generation solar energy harvest. Synergistic crystalline structures comprising organic and inorganic components enable solution processing of perovskite films. A reliable crystallization method for perovskites, compatible with fast continuous process over large-area flexible substrates, is crucial for high performance solar cell production. Here, we present laser crystallization of hybrid perovskite solar cells using near-infrared (NIR) laser (λ = 1064 nm). Crystalline morphology of CH3NH3PbI3 (MAPbI3) perovskite films are widely controllable with laser irradiation condition while maintaining film uniformity. Photothermal heating effectively assisted by interfacial photoconversion layers is critical for phase transformation without beam damage of multilayered device structures. Notably, laser crystallization attains higher device performances than conventional thermal annealing. Fast laser crystallization with manufacture level scan rate (1 m min(-1)) demonstrates inverted-type perovskite solar cells with 11.3 and 8.0% efficiencies on typical glass and flexible polymer substrates, respectively, without rigorous device optimization. PMID:27377145

  12. Optical properties of trigonal single crystals (Yb,Tm)Al{sub 3}(BO{sub 3}){sub 4} grown from fluxes based on the bismuth and lithium molybdates

    SciTech Connect

    Temerov, V. L. Sokolov, A. E.; Sukhachev, A. L.; Bovina, A. F.; Edel'man, I. S.; Malakhovskii, A. V.

    2008-12-15

    The conditions for synthesis of Yb{sub x}Tm{sub 1-x}Al{sub 3}(BO{sub 3}){sub 4} (x = 0, 0.1, 0.2, 1.0) single crystals from fluxes based on bismuth trimolybdate Bi{sub 2}Mo{sub 3}O{sub 12} and lithium molybdate Li{sub 2}MoO{sub 4} are investigated. It is proposed to grow them by the group method on seeds. The polarized optical absorption spectra are measured for two mutually orthogonal linear polarizations at temperatures of 100 and 300 K.

  13. Topological crystalline metal in orthorhombic perovskite iridates.

    PubMed

    Chen, Yige; Lu, Yuan-Ming; Kee, Hae-Young

    2015-03-16

    Since topological insulators were theoretically predicted and experimentally observed in semiconductors with strong spin-orbit coupling, increasing attention has been drawn to topological materials that host exotic surface states. These surface excitations are stable against perturbations since they are protected by global or spatial/lattice symmetries. Following the success in achieving various topological insulators, a tempting challenge now is to search for metallic materials with novel topological properties. Here we predict that orthorhombic perovskite iridates realize a new class of metals dubbed topological crystalline metals, which support zero-energy surface states protected by certain lattice symmetry. These surface states can be probed by photoemission and tunnelling experiments. Furthermore, we show that by applying magnetic fields, the topological crystalline metal can be driven into other topological metallic phases, with different topological properties and surface states.

  14. Perovskites for use as sulfur tolerant anodes

    NASA Astrophysics Data System (ADS)

    Howell, Thomas G.

    One of the major obstacles encountered when using solid oxide fuel cells with hydrocarbon fuels is sulfur poisoning. The current anode material used is Ni/YSZ and Ni is not sulfur tolerant; therefore, the performance of the cell will degrade over time due to the formation of NiS. Perovskites have demonstrated superior sulfur tolerance but lack the high conductivity and catalytic activity of Ni/YSZ cermets. One of the objectives of this effort is to explore the substitution of the A-site in an A2MgMoO 6 perovskite with Sr and Ba, to create Sr2MgMoO6 (SMMO) and Ba2MgMoO6 (BMMO), respectively, to improve the sulfur tolerance of solid oxide fuel cells (SOFCs). Sr2MgMoO 6, a double perovskite, has been previously studied and is suggested as a material of interest because of its relatively high conductivity and catalytic potential. Barium has not been previously studied and was selected as the dopant because the ionic radii (1.61 A) resulted in a calculated tolerance factor of 1.036 for BMMO when compared to SMMO, which has an ionic radii of 1.44 A and a calculated tolerance factor of 0.978. The tolerance factor for BaSrMgMoO6, a bi-substituted material synthesized for comparison as an intermediate formulation, was calculated to be 1.00. Another objective is to synthesize and characterize a series of lanthanum (La) doped Sr2MgMoO6 (SMMO) or La doped Sr2MgNbO 6 (SMNO) anode materials, which can be used in combination with electrolytes containing lanthanum to mitigate the effects of lanthanum poisoning in SOFCs. Currently, a La0.4Ce0.6O1.8 (LDC) transition layer is used with many perovskite-based anode materials to prevent La diffusion into the anode from the La0.8Sr0.2Ga0.8Mg 0.2O2.8 (LSGM) electrolyte, which can create a resistive La species that impedes electrochemical performance. To accomplish this, a new class of anode materials was synthesized with the goal of balancing La chemical potential between these neighboring materials. It was hypothesized that by

  15. Superconductivity and magnetism in rapidly solidified perovskites

    SciTech Connect

    O'Handley, R.C.; Kalonji, G.

    1991-01-01

    The report is divided into six parts, reflecting major thrusts of our work since 1987. The six areas are: molecular orbital theory of high {Tc} superconductivity; rapid solidification processing of oxide superconductors; time dependent magnetic and superconducting properties of these inhomogeneous materials; excess Gd in Gd{sub 1+x}Ba{sub 2-x}Cu{sub 3}O{sub 7-{delta}} perovskites; rapid solidification and directional annealing to achieve high Jc; and Mossbauer studies of T = Fe, Co and Ni site selection in YBa{sub 2}(CuT){sub 3}O{sub 7-{delta}} and GdBa{sub 2}(CuT){sub 3}O{sub 7-{delta}}.

  16. New Generation Perovskite Thermal Barrier Coating Materials

    NASA Astrophysics Data System (ADS)

    Ma, W.; Jarligo, M. O.; Mack, D. E.; Pitzer, D.; Malzbender, J.; Vaßen, R.; Stöver, D.

    2008-12-01

    Advanced ceramic materials of perovskite structure have been developed for potential application in thermal barrier coating systems, in an effort to improve the properties of the pre-existing ones like yttria-stabilized zirconia. Yb2O3 and Gd2O3 doped strontium zirconate (SrZrO3) and barium magnesium tantalate (Ba(Mg1/3Ta2/3)O3) of the ABO3 and complex A(B'1/3B''2/3)O3 systems, respectively, have been synthesized using ball milling prior to solid state sintering. Thermal and mechanical investigations show desirable properties for high-temperature coating applications. On atmospheric plasma spraying, the newly developed thermal barrier coatings reveal promising thermal cycle lifetime up to 1350 °C.

  17. The interaction between hybrid organic-inorganic halide perovskite and selective contacts in perovskite solar cells: an infrared spectroscopy study.

    PubMed

    Idígoras, J; Todinova, A; Sánchez-Valencia, J R; Barranco, A; Borrás, A; Anta, J A

    2016-05-11

    The interaction of hybrid organic-inorganic halide perovskite and selective contacts is crucial to get efficient, stable and hysteresis-free perovskite-based solar cells. In this report, we analyze the vibrational properties of methylammonium lead halide perovskites deposited on different substrates by infrared absorption (IR) measurements (4000-500 cm(-1)). The materials employed as substrates are not only characterized by different chemical natures (TiO2, ZnO and Al2O3), but also by different morphologies. For all of them, we have investigated the influence of these substrate properties on perovskite formation and its degradation by humidity. The effect of selective-hole contact (Spiro-OmeTad and P3HT) layers on the degradation rate by moisture has also been studied. Our IR results reveal the existence of a strong interaction between perovskite and all ZnO materials considered, evidenced by a shift of the peaks related to the N-H vibrational modes. The interaction even induces a morphological change in ZnO nanoparticles after perovskite deposition, pointing to an acid-base reaction that takes place through the NH3(+) groups of the methylammonium cation. Our IR and X-ray diffraction results also indicate that this specific interaction favors perovskite decomposition and PbI2 formation for ZnO/perovskite films subjected to humid conditions. Although no interaction is observed for TiO2, Al2O3, and the hole selective contact, the morphology and chemical nature of both contacts appear to play an important role in the rate of degradation upon exposure to moisture.

  18. Special quasirandom structures for perovskite solid solutions.

    PubMed

    Jiang, Zhijun; Nahas, Yousra; Xu, Bin; Prosandeev, Sergey; Wang, Dawei; Bellaiche, Laurent

    2016-11-30

    Special quasirandom structures (SQS) are presently generated for disordered (A'1-x [Formula: see text] x )BX3 and A(B'1-x [Formula: see text] x )X3 perovskite solid solutions, with x  =  1/2 as well as 1/3 and 2/3. These SQS configurations are obtained by imposing that the so-called Cowley parameters are as close to zero as possible for the three nearest neighboring shells. Moreover, these SQS configurations are slightly larger in size than those available in the literature for x  =  1/2, mostly because of the current capabilities of atomistic techniques. They are used here within effective Hamiltonian schemes to predict various properties, which are then compared to those associated with large random supercells, in a variety of compounds, namely (Ba1-x Sr x )TiO3, Pb(Zr1-x Ti x )O3, Pb(Sc0.5Nb0.5)O3, Ba(Zr1-x Ti x )O3, Pb(Mg1/3Nb2/3)O3 and (Bi1-x Nd x )FeO3. It is found that these SQS configurations can reproduce many properties of large random supercells of most of these disordered perovskite alloys, below some finite material-dependent temperature. Examples of these properties are electrical polarization, anti-phase and in-phase octahedral tiltings, antipolar motions, antiferromagnetism, strain, piezoelectric coefficients, dielectric response, specific heat and even the formation of polar nanoregions (PNRs) in some relaxors. Some limitations of these SQS configurations are also pointed out and explained. PMID:27661191

  19. Special quasirandom structures for perovskite solid solutions

    NASA Astrophysics Data System (ADS)

    Jiang, Zhijun; Nahas, Yousra; Xu, Bin; Prosandeev, Sergey; Wang, Dawei; Bellaiche, Laurent

    2016-11-01

    Special quasirandom structures (SQS) are presently generated for disordered (A‧1-x {{\\text{A}}\\prime \\prime} x )BX3 and A(B‧1-x {{\\text{B}}\\prime \\prime} x )X3 perovskite solid solutions, with x  =  1/2 as well as 1/3 and 2/3. These SQS configurations are obtained by imposing that the so-called Cowley parameters are as close to zero as possible for the three nearest neighboring shells. Moreover, these SQS configurations are slightly larger in size than those available in the literature for x  =  1/2, mostly because of the current capabilities of atomistic techniques. They are used here within effective Hamiltonian schemes to predict various properties, which are then compared to those associated with large random supercells, in a variety of compounds, namely (Ba1-x Sr x )TiO3, Pb(Zr1-x Ti x )O3, Pb(Sc0.5Nb0.5)O3, Ba(Zr1-x Ti x )O3, Pb(Mg1/3Nb2/3)O3 and (Bi1-x Nd x )FeO3. It is found that these SQS configurations can reproduce many properties of large random supercells of most of these disordered perovskite alloys, below some finite material-dependent temperature. Examples of these properties are electrical polarization, anti-phase and in-phase octahedral tiltings, antipolar motions, antiferromagnetism, strain, piezoelectric coefficients, dielectric response, specific heat and even the formation of polar nanoregions (PNRs) in some relaxors. Some limitations of these SQS configurations are also pointed out and explained.

  20. Fine control of perovskite-layered morphology and composition via sequential deposition crystallization process towards improved perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Luo, Yi; Meng, Fanli; Zhao, Erfei; Zheng, Yan-Zhen; Zhou, Yali; Tao, Xia

    2016-04-01

    The ability to prepare high coverage and compact perovskite films via solution-based crystallization manipulation processes still represents a vital issue towards improving the ultimate photoelectric conversion efficiency of devices. In this work, we prepare the active perovskite layer by means of sequential deposition crystallization process i.e. dipping PbI2-infiltrated TiO2 film within CH3NH3I solution from 20s to 60s. The morphology and thickness of the as-prepared perovskite layer, and its overall performance superiority are investigated. X-ray diffraction (XRD) reveals that a maximum conversion of PbI2 to perovskite is completed upon applying a sequential deposition crystallization process of 40s. Field emission scanning electron microscope (FESEM) demonstrates that the coverage of the perovskite capping layer exhibits a trend from rise to decline in the whole dipping time from 20s to 60s. By fine control of the dipping time, a 620 nm-thickness compact perovskite active layer is obtained at the optimized dipping time of 40s and is verified to possess strong light absorption and high electron extraction efficiency, leading to a higher photocurrent. By further optimizing the mesoporous TiO2 film thickness, a high photocurrent of 23.98 mA cm-2 and an efficiency of 13.47% are achieved.

  1. Selective dissolution of halide perovskites as a step towards recycling solar cells

    NASA Astrophysics Data System (ADS)

    Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee; Park, So Yeon; Li, Zhen; Zhu, Kai; Jung, Hyun Suk

    2016-05-01

    Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Herein, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easily decomposed in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb2+ cations. After 10 cycles of recycling, a mesoporous TiO2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells.

  2. Selective dissolution of halide perovskites as a step towards recycling solar cells

    PubMed Central

    Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee; Park, So Yeon; Li, Zhen; Zhu, Kai; Jung, Hyun Suk

    2016-01-01

    Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Herein, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easily decomposed in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb2+ cations. After 10 cycles of recycling, a mesoporous TiO2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells. PMID:27211006

  3. Low-temperature fabrication of efficient wide-bandgap organolead trihalide perovskite solar cells

    DOE PAGESBeta

    Bi, Cheng; Yuan, Yongbo; Fang, Yanjun; Huang, Jinsong

    2014-11-25

    A mixed halide perovskite solar cell with a 1.72 eV bandgap is developed by incorporating Br into perovskite through a low-temperature solution process. A high efficiency of 13.1% is achieved by carefully tuning the thickness, morphology, and surface passivation of the perovskite layers. Furthermore, the fabrication techniques and conditions are compatible with future perovskite/Si tandem cell studies.

  4. Research Update: Overview of progress about efficiency and stability on perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Ito, Seigo

    2016-09-01

    Due to the high conversion efficiency, organic-inorganic hybrid perovskite (CH3NH3PbI3) solar cells are investigated for new practical energy resources for our future society. However, the perovskite solar cells have been quite unstable devices. In this manuscript, the history of perovskite solar cells is introduced, and then, the efforts to improve and understand the stability issue of perovskite solar cells are summarized.

  5. Planar Heterojunction Perovskite Solar Cells Incorporating Metal-Organic Framework Nanocrystals.

    PubMed

    Chang, Ting-Hsiang; Kung, Chung-Wei; Chen, Hsin-Wei; Huang, Tzu-Yen; Kao, Sheng-Yuan; Lu, Hsin-Che; Lee, Min-Han; Boopathi, Karunakara Moorthy; Chu, Chih-Wei; Ho, Kuo-Chuan

    2015-11-25

    Zr-based porphyrin metal-organic framework (MOF-525) nanocrystals with a crystal size of about 140 nm are synthesized and incorporated into perovskite solar cells. The morphology and crystallinity of the perovskite thin film are enhanced since the micropores of MOF-525 allow the crystallization of perovskite to occur inside; this observation results in a higher cell efficiency of the obtained MOF/perovskite solar cell.

  6. Fe-Mg partitioning between perovskite, post-perovskite, and ferropericlase at the lowermost mantle

    NASA Astrophysics Data System (ADS)

    Sakai, T.; Ohtani, E.; Miyahara, M.; Nishijima, M.; Terasaki, H.; Kondo, T.; Kikegawa, T.; Hirao, N.; Ohishi, Y.

    2007-12-01

    The lower mantle consists mainly of iron-bearing magnesium silicate perovskite and ferropericlase. The Fe-Mg partition coefficient between these minerals is important to understand the chemical and physical properties of the mantle. The lowermost 200 km of the mantle is called D" layer and it is considered to be a thermal and chemical boundary layer between the silicate mantle and outer core. Recent high pressure studies [e.g., Murakami et al., 2004] revealed that (Mg, Fe)SiO3 perovskite transformed to post-perovskite phase at the pressure and temperature conditions of D" layer. In this study, high pressure and high temperature partitioning experiments were performed up to 140 GPa at 2000 K using a laser heated diamond anvil cell (LHDAC). Powdered or single crystalline Al-free San Carlos olivine (Mg0.88, Fe0.12)2SiO4 was used as a starting material in order to avoid complicated compositional effects. The starting material was embedded in sodium chloride which is pressure medium. Pressures were determined by both the ruby fluorescence method [Mao et al., 1978] and the Raman shift of the first-order Raman spectra of diamond anvil [Akahama and Kawamura, 2004]. Temperatures were measured by spectroradiometric method. The recovered samples were analyzed using the technique of combination of FIB and ATEM (JEOL JEM-3000F (FEG TEM-STEM)). The result shows that post- perovskite phase exhibits very small iron content, Fe# = 0.01 at 140 GPa and 2000 K. Therefore, the partition coefficient was K = 0.03, which indicates that iron prefers ferropericlase strongly rather than post-perovskite phase, which is consistent with the prediction of the ab initio calculation [Iitaka et al., 2004], and the high-spin/low- spin transition arguments of ferropericlase [Badro et al., 2003]. Kobayashi et al. (2005) showed higher partitioning coefficient of K= 0.30 in spite of the lower temperature condition of 1600 K compared to the present experiment. They reported that significant iron

  7. Influence of void-free perovskite capping layer on the charge recombination process in high performance CH3NH3PbI3 perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Fu, Kunwu; Nelson, Christopher T.; Scott, Mary Cooper; Minor, Andrew; Mathews, Nripan; Wong, Lydia Helena

    2016-02-01

    The stunning rise of methylammonium lead iodide perovskite material as a light harvesting material in recent years has drawn much attention in the photovoltaic community. Here, we investigated in detail the uniform and void-free perovskite capping layer in the mesoscopic perovskite devices and found it to play a critical role in determining device performance and charge recombination process. Compared to the rough surface with voids of the perovskite layer, surface of the perovskite capping layer obtained from sequential deposition process is much more uniform with less void formation and distribution within the TiO2 mesoscopic scaffold is more homogeneous, leading to much improved photovoltaic parameters of the devices. The impact of void free perovskite capping layer surface on the charge recombination processes within the mesoscopic perovskite solar cells is further scrutinized via charge extraction measurement. Modulation of precursor solution concentrations in order to further improve the perovskite layer surface morphology leads to higher efficiency and lower charge recombination rates. Inhibited charge recombination in these solar cells also matches with the higher charge density and slower photovoltage decay profiles measured.The stunning rise of methylammonium lead iodide perovskite material as a light harvesting material in recent years has drawn much attention in the photovoltaic community. Here, we investigated in detail the uniform and void-free perovskite capping layer in the mesoscopic perovskite devices and found it to play a critical role in determining device performance and charge recombination process. Compared to the rough surface with voids of the perovskite layer, surface of the perovskite capping layer obtained from sequential deposition process is much more uniform with less void formation and distribution within the TiO2 mesoscopic scaffold is more homogeneous, leading to much improved photovoltaic parameters of the devices. The impact of

  8. Recent Advances in Interface Engineering for Planar Heterojunction Perovskite Solar Cells.

    PubMed

    Yin, Wei; Pan, Lijia; Yang, Tingbin; Liang, Yongye

    2016-06-25

    Organic-inorganic hybrid perovskite solar cells are considered as one of the most promising next-generation solar cells due to their advantages of low-cost precursors, high power conversion efficiency (PCE) and easy of processing. In the past few years, the PCEs have climbed from a few to over 20% for perovskite solar cells. Recent developments demonstrate that perovskite exhibits ambipolar semiconducting characteristics, which allows for the construction of planar heterojunction (PHJ) perovskite solar cells. PHJ perovskite solar cells can avoid the use of high-temperature sintered mesoporous metal oxides, enabling simple processing and the fabrication of flexible and tandem perovskite solar cells. In planar heterojunction materials, hole/electron transport layers are introduced between a perovskite film and the anode/cathode. The hole and electron transporting layers are expected to enhance exciton separation, charge transportation and collection. Further, the supporting layer for the perovskite film not only plays an important role in energy-level alignment, but also affects perovskite film morphology, which have a great effect on device performance. In addition, interfacial layers also affect device stability. In this review, recent progress in interfacial engineering for PHJ perovskite solar cells will be reviewed, especially with the molecular interfacial materials. The supporting interfacial layers for the optimization of perovskite films will be systematically reviewed. Finally, the challenges remaining in perovskite solar cells research will be discussed.

  9. Improving the Stability and Performance of Perovskite Light-Emitting Diodes by Thermal Annealing Treatment.

    PubMed

    Yu, Jae Choul; Kim, Dae Woo; Kim, Da Bin; Jung, Eui Dae; Park, Jong Hyun; Lee, Ah-Young; Lee, Bo Ram; Di Nuzzo, Daniele; Friend, Richard H; Song, Myoung Hoon

    2016-08-01

    A perovskite LED with a perovskite film treated under optimum thermal annealing conditions exhibits a significantly enhanced long-term stability with full coverage of the green electroluminescence emission due to the highly uniform morphology of the perovskite film. PMID:27239729

  10. Changes in hematology, serum biochemistry, and gastrointestinal nematode infection in lambs fed sericea lespedeza with or without dietary sodium molybdate.

    PubMed

    Acharya, M; Burke, J M; Coffey, K P; Kegley, E B; Miller, J E; Huff, G R; Smyth, E; Terrill, T H; Mosjidis, J A; Rosenkrans, C

    2015-04-01

    Sericea lespedeza (SL; Lespedeza cuneata) is a legume rich in condensed tannins that can be grazed or fed to small ruminants for parasite control. Condensed tannins, a secondary plant compound in SL, may lead to unintended consequences such as changes in production. In our preliminary research, there was consistently a reduction in serum and liver concentrations of Mo. The objective of this study was to determine the effect of SL with or without Mo supplementation on changes in BW, hematology, and serum biochemistry in lambs. Thirty ram lambs weaned in May (84 ± 1.5 d of age; 27 ± 1.1 kg) were blocked by BW, breed type (full or three-fourths Katahdin), and EBV of parasite resistance and randomly assigned to be fed 900 g of alfalfa-based supplement (CON; n = 10) or SL-based supplement (n = 20) for 103 d. Supplements were formulated to be isonitrogenous and isocaloric and to meet trace mineral requirements. Within the SL diet, half of the lambs received 490 mg sodium molybdate weekly (SLMO). Body condition scores and BW were determined every 14 d and blood and feces collected to determine hematological and serum biochemical profiles and fecal egg counts (FEC). Data were analyzed using a mixed model with repeated measures and orthogonal contrasts. The white blood cell counts tended to be reduced in SL- and SLMO-fed lambs compared with CON-fed lambs (P < 0.06), which was associated with a reduction in neutrophils (P < 0.001). Red blood cell counts were also reduced in SL but not SLMO lambs compared with CON lambs (P < 0.04). There was a reduction in blood packed cell volume (P < 0.04) and serum concentrations of albumin (P < 0.001) and creatinine (P < 0.02) in both SL and SLMO lambs compared with CON lambs. Similarly, concentrations of blood urea nitrogen were reduced in both SL and SLMO lambs, but differences among dietary treatments disappeared after 42 d of feeding (treatment × day, P < 0.004). Serum concentrations of total proteins were reduced only in SLMO

  11. Changes in concentrations of trace minerals in lambs fed sericea lespedeza leaf meal pellets with or without dietary sodium molybdate.

    PubMed

    Acharya, M; Burke, J M; Coffey, K P; Kegley, E B; Miller, J E; Smyth, E; Welborn, M G; Terrill, T H; Mosjidis, J A; Rosenkrans, C

    2016-04-01

    Prolonged feeding of sericea lespedeza (SL) previously led to reduced serum concentrations of Mo, a cofactor in an enzyme complex that may be involved in weight gain. The current objective was to determine the effect of Mo supplementation on changes in serum, fecal, urine, and liver concentrations of trace minerals in lambs fed SL leaf meal pellets. Thirty ram lambs weaned in May (84 ± 1.5 d of age and 27 ± 1.1 kg; D 0) were blocked by BW, breed type (full or three-fourths Katahdin), and EBV of parasite resistance and randomly assigned to be fed 900 g/d of an alfalfa-based supplement (CON; = 10) or a SL-based supplement ( = 20) for 103 d. Supplements were formulated to be isonitrogenous and isocaloric and to meet trace mineral requirements. Within the SL group, individual lambs were administered either 5 mL water or 5 mL of water with 163.3 mg of sodium molybdate (SLMO). Serum was collected on d 28, 56, and 104; a liver sample was collected by biopsy on d 104 to determine concentrations of trace minerals. Data were analyzed using a mixed model and orthogonal contrasts. Serum concentrations of Mo increased in response to the drench and were greatest in SLMO lambs and then CON lambs and lowest in SL lambs ( < 0.001). Concentrations of Mo in the liver ( < 0.001) were similar between CON and SLMO lambs and were lower in SL lambs than other groups. Serum ( < 0.001) and liver ( = 0.013) concentrations of zinc (Zn) were reduced in both SL and SLMO lambs compared with CON lambs. Serum concentrations of cobalt (Co) increased in CON lambs compared with SL and SLMO lambs between d 0 and 56 but were similar on d 104 (diet × day, < 0.005) as with concentrations in the liver. Serum and liver concentrations of copper (Cu) were greatest ( < 0.001 and < 0.001, respectively) in CON lambs followed by SL lambs and then SLMO lambs. Serum concentrations of selenium (Se) tended ( = 0.10) to be reduced in SL lambs compared with CON and SLMO lambs, but concentrations in the liver were

  12. Changes in concentrations of trace minerals in lambs fed sericea lespedeza leaf meal pellets with or without dietary sodium molybdate.

    PubMed

    Acharya, M; Burke, J M; Coffey, K P; Kegley, E B; Miller, J E; Smyth, E; Welborn, M G; Terrill, T H; Mosjidis, J A; Rosenkrans, C

    2016-04-01

    Prolonged feeding of sericea lespedeza (SL) previously led to reduced serum concentrations of Mo, a cofactor in an enzyme complex that may be involved in weight gain. The current objective was to determine the effect of Mo supplementation on changes in serum, fecal, urine, and liver concentrations of trace minerals in lambs fed SL leaf meal pellets. Thirty ram lambs weaned in May (84 ± 1.5 d of age and 27 ± 1.1 kg; D 0) were blocked by BW, breed type (full or three-fourths Katahdin), and EBV of parasite resistance and randomly assigned to be fed 900 g/d of an alfalfa-based supplement (CON; = 10) or a SL-based supplement ( = 20) for 103 d. Supplements were formulated to be isonitrogenous and isocaloric and to meet trace mineral requirements. Within the SL group, individual lambs were administered either 5 mL water or 5 mL of water with 163.3 mg of sodium molybdate (SLMO). Serum was collected on d 28, 56, and 104; a liver sample was collected by biopsy on d 104 to determine concentrations of trace minerals. Data were analyzed using a mixed model and orthogonal contrasts. Serum concentrations of Mo increased in response to the drench and were greatest in SLMO lambs and then CON lambs and lowest in SL lambs ( < 0.001). Concentrations of Mo in the liver ( < 0.001) were similar between CON and SLMO lambs and were lower in SL lambs than other groups. Serum ( < 0.001) and liver ( = 0.013) concentrations of zinc (Zn) were reduced in both SL and SLMO lambs compared with CON lambs. Serum concentrations of cobalt (Co) increased in CON lambs compared with SL and SLMO lambs between d 0 and 56 but were similar on d 104 (diet × day, < 0.005) as with concentrations in the liver. Serum and liver concentrations of copper (Cu) were greatest ( < 0.001 and < 0.001, respectively) in CON lambs followed by SL lambs and then SLMO lambs. Serum concentrations of selenium (Se) tended ( = 0.10) to be reduced in SL lambs compared with CON and SLMO lambs, but concentrations in the liver were

  13. Hydrothermal epitaxy of perovskite thin films

    NASA Astrophysics Data System (ADS)

    Chien, Allen T.

    1998-12-01

    This work details the discovery and study of a new process for the growth of epitaxial single crystal thin films which we call hydrothermal epitaxy. Hydrothermal epitaxy is a low temperature solution route for producing heteroepitaxial thin films through the use of solution chemistry and structurally similar substrates. The application of this synthesis route has led to the growth of a variety of epitaxial perovskite (BaTiOsb3, SrTiOsb3, and Pb(Zr,Ti)Osb3 (PZT)) thin films which provides a simple processing pathway for the formation of other materials of technological interest. BaTiOsb3 and PZT heteroepitaxial thin films and powders were produced by the hydrothermal method at 90-200sp°C using various alkali bases. XRD and TEM analysis shows that, in each case, the films and powders form epitaxially with a composition nearly identical to that of the starting precursors. Sequential growth experiments show that film formation initiates by the nucleation of submicron faceted islands at the step edges of the SrTiOsb3 substrates followed by coalescence after longer growth periods. A Ba-rich interfacial layer between the BaTiOsb3 islands and the SrTiOsb3 surface is seen by cross-section TEM during early growth periods. Electrophoretic and Basp{2+} adsorption data provide a chemical basis for the existence of the interfacial layer. Homoepitaxial growth of SrTiOsb3 on SrTiOsb3 also occurs by island growth, suggesting that the growth mode may be a consequence of the aqueous surface chemistry inherent in the process. Film formation is shown to be affected by any number of factors including type of base, pH, temperature, and substrate pretreatments. Different cation bases (Na-, K-, Rb-, Cs-, TMA-OH) demonstrated pronounced changes in powder and film morphology. For example, smaller cation bases (e.g., NaOH, KOH and RbOH) resulted the formation of 1.5 mum \\{100\\} faceted perovskite PbTiOsb3 blocks while larger cation bases (e.g., CsOH and TMA-OH) produced 500 nm sized

  14. Employing Lead Thiocyanate Additive to Reduce the Hysteresis and Boost the Fill Factor of Planar Perovskite Solar Cells.

    PubMed

    Ke, Weijun; Xiao, Chuanxiao; Wang, Changlei; Saparov, Bayrammurad; Duan, Hsin-Sheng; Zhao, Dewei; Xiao, Zewen; Schulz, Philip; Harvey, Steven P; Liao, Weiqiang; Meng, Weiwei; Yu, Yue; Cimaroli, Alexander J; Jiang, Chun-Sheng; Zhu, Kai; Al-Jassim, Mowafak; Fang, Guojia; Mitzi, David B; Yan, Yanfa

    2016-07-01

    Lead thiocyanate in the perovskite precursor can increase the grain size of a perovskite thin film and reduce the conductivity of the grain boundaries, leading to perovskite solar cells with reduced hysteresis and enhanced fill factor. A planar perovskite solar cell with grain boundary and interface passivation achieves a steady-state efficiency of 18.42%.

  15. Elusive Presence of Chloride in Mixed Halide Perovskite Solar Cells.

    PubMed

    Colella, Silvia; Mosconi, Edoardo; Pellegrino, Giovanna; Alberti, Alessandra; Guerra, Valentino L P; Masi, Sofia; Listorti, Andrea; Rizzo, Aurora; Condorelli, Guglielmo Guido; De Angelis, Filippo; Gigli, Giuseppe

    2014-10-16

    The role of chloride in the MAPbI3-xClx perovskite is still limitedly understood, albeit subjected of much debate. Here, we present a combined angle-resolved X-ray photoelectron spectroscopy (AR-XPS) and first-principles DFT modeling to investigate the MAPbI3-xClx/TiO2 interface. AR-XPS analyses carried out on ad hoc designed bilayers of MAPbI3-xClx perovskite deposited onto a flat TiO2 substrate reveal that the chloride is preferentially located in close proximity to the perovskite/TiO2 interface. DFT calculations indicate the preferential location of chloride at the TiO2 interface compared to the bulk perovskite due to an increased chloride-TiO2 surface affinity. Furthermore, our calculations clearly demonstrate an interfacial chloride-induced band bending, creating a directional "electron funnel" that may improve the charge collection efficiency of the device and possibly affecting also recombination pathways. Our findings represent a step forward to the rationalization of the peculiar properties of mixed halide perovskite, allowing one to further address material and device design issues. PMID:26278605

  16. Interface and Composition Analysis on Perovskite Solar Cells.

    PubMed

    Matteocci, Fabio; Busby, Yan; Pireaux, Jean-Jacques; Divitini, Giorgio; Cacovich, Stefania; Ducati, Caterina; Di Carlo, Aldo

    2015-12-01

    Organometal halide (hybrid) perovskite solar cells have been fabricated following four different deposition procedures and investigated in order to find correlations between the solar cell characteristics/performance and their structure and composition as determined by combining depth-resolved imaging with time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and analytical scanning transmission electron microscopy (STEM). The interface quality is found to be strongly affected by the perovskite deposition procedure, and in particular from the environment where the conversion of the starting precursors into the final perovskite is performed (air, nitrogen, or vacuum). The conversion efficiency of the precursors into the hybrid perovskite layer is compared between the different solar cells by looking at the ToF-SIMS intensities of the characteristic molecular fragments from the perovskite and the precursor materials. Energy dispersive X-ray spectroscopy in the STEM confirms the macroscopic ToF-SIMS findings and allows elemental mapping with nanometer resolution. Clear evidence for iodine diffusion has been observed and related to the fabrication procedure.

  17. Robust high-κ response in molecularly thin perovskite nanosheets.

    PubMed

    Osada, Minoru; Akatsuka, Kosho; Ebina, Yasuo; Funakubo, Hiroshi; Ono, Kanta; Takada, Kazunori; Sasaki, Takayoshi

    2010-09-28

    Size-induced suppression of permittivity in perovskite thin films is a fundamental problem that has remained unresolved for decades. This size-effect issue becomes increasingly important due to the integration of perovskite nanofilms into high-κ capacitors, as well as concerns that intrinsic size effects may limit their device performance. Here, we report a new approach to produce robust high-κ nanodielectrics using perovskite nanosheet (Ca2Nb3O10), a new class of nanomaterials that is derived from layered compounds by exfoliation. By a solution-based bottom-up approach using perovskite nanosheets, we have successfully fabricated multilayer nanofilms directly on SrRuO3 or Pt substrates without any interfacial dead layers. These nanofilms exhibit high dielectric constant (>200), the largest value seen so far in perovskite films with a thickness down to 10 nm. Furthermore, the superior high-κ properties are a size-effect-free characteristic with low leakage current density (<10(-7) A cm(-2)). Our work provides a key for understanding the size effect and also represents a step toward a bottom-up paradigm for future high-κ devices.

  18. Halide Perovskites: Poor Man's High-Performance Semiconductors.

    PubMed

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2016-07-01

    Halide perovskites are a rapidly developing class of medium-bandgap semiconductors which, to date, have been popularized on account of their remarkable success in solid-state heterojunction solar cells raising the photovoltaic efficiency to 20% within the last 5 years. As the physical properties of the materials are being explored, it is becoming apparent that the photovoltaic performance of the halide perovskites is just but one aspect of the wealth of opportunities that these compounds offer as high-performance semiconductors. From unique optical and electrical properties stemming from their characteristic electronic structure to highly efficient real-life technological applications, halide perovskites constitute a brand new class of materials with exotic properties awaiting discovery. The nature of halide perovskites from the materials' viewpoint is discussed here, enlisting the most important classes of the compounds and describing their most exciting properties. The topics covered focus on the optical and electrical properties highlighting some of the milestone achievements reported to date but also addressing controversies in the vastly expanding halide perovskite literature. PMID:27174223

  19. Electron–phonon coupling in hybrid lead halide perovskites

    PubMed Central

    Wright, Adam D.; Verdi, Carla; Milot, Rebecca L.; Eperon, Giles E.; Pérez-Osorio, Miguel A.; Snaith, Henry J.; Giustino, Feliciano; Johnston, Michael B.; Herz, Laura M.

    2016-01-01

    Phonon scattering limits charge-carrier mobilities and governs emission line broadening in hybrid metal halide perovskites. Establishing how charge carriers interact with phonons in these materials is therefore essential for the development of high-efficiency perovskite photovoltaics and low-cost lasers. Here we investigate the temperature dependence of emission line broadening in the four commonly studied formamidinium and methylammonium perovskites, HC(NH2)2PbI3, HC(NH2)2PbBr3, CH3NH3PbI3 and CH3NH3PbBr3, and discover that scattering from longitudinal optical phonons via the Fröhlich interaction is the dominant source of electron–phonon coupling near room temperature, with scattering off acoustic phonons negligible. We determine energies for the interacting longitudinal optical phonon modes to be 11.5 and 15.3 meV, and Fröhlich coupling constants of ∼40 and 60 meV for the lead iodide and bromide perovskites, respectively. Our findings correlate well with first-principles calculations based on many-body perturbation theory, which underlines the suitability of an electronic band-structure picture for describing charge carriers in hybrid perovskites. PMID:27225329

  20. Perovskite-fullerene hybrid materials suppress hysteresis in planar diodes.

    PubMed

    Xu, Jixian; Buin, Andrei; Ip, Alexander H; Li, Wei; Voznyy, Oleksandr; Comin, Riccardo; Yuan, Mingjian; Jeon, Seokmin; Ning, Zhijun; McDowell, Jeffrey J; Kanjanaboos, Pongsakorn; Sun, Jon-Paul; Lan, Xinzheng; Quan, Li Na; Kim, Dong Ha; Hill, Ian G; Maksymovych, Peter; Sargent, Edward H

    2015-01-01

    Solution-processed planar perovskite devices are highly desirable in a wide variety of optoelectronic applications; however, they are prone to hysteresis and current instabilities. Here we report the first perovskite-PCBM hybrid solid with significantly reduced hysteresis and recombination loss achieved in a single step. This new material displays an efficient electrically coupled microstructure: PCBM is homogeneously distributed throughout the film at perovskite grain boundaries. The PCBM passivates the key PbI3(-) antisite defects during the perovskite self-assembly, as revealed by theory and experiment. Photoluminescence transient spectroscopy proves that the PCBM phase promotes electron extraction. We showcase this mixed material in planar solar cells that feature low hysteresis and enhanced photovoltage. Using conductive AFM studies, we reveal the memristive properties of perovskite films. We close by positing that PCBM, by tying up both halide-rich antisites and unincorporated halides, reduces electric field-induced anion migration that may give rise to hysteresis and unstable diode behaviour. PMID:25953105

  1. Novel materials for stable perovskite solar cells (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Abate, Antonio

    2015-09-01

    Organic-inorganic perovskites are quickly overrunning research activities in new materials for cost-effective and high-efficiency photovoltaic technologies. Since the first demonstration from Kojima and co-workers in 2009, several perovskite-based solar cells have been reported and certified with rapidly improving power conversion efficiency. Recent reports demonstrate that perovskites can compete with the most efficient inorganic materials, while they still allow processing from solution as potential advantage to deliver a cost-effective solar technology. Compare to the impressive progress in power conversion efficiency, stability studies are rather poor and often controversial. An intrinsic complication comes from the fact that the stability of perovskite solar cells is strongly affected by any small difference in the device architecture, preparation procedure, materials composition and testing procedure. In the present talk we will focus on the stability of perovskite solar cells in working condition. We will discuss a measuring protocol to extract reliable and reproducible ageing data. We will present new materials and preparation procedures which improve the device lifetime without giving up on high power conversion efficiency.

  2. Interface and Composition Analysis on Perovskite Solar Cells.

    PubMed

    Matteocci, Fabio; Busby, Yan; Pireaux, Jean-Jacques; Divitini, Giorgio; Cacovich, Stefania; Ducati, Caterina; Di Carlo, Aldo

    2015-12-01

    Organometal halide (hybrid) perovskite solar cells have been fabricated following four different deposition procedures and investigated in order to find correlations between the solar cell characteristics/performance and their structure and composition as determined by combining depth-resolved imaging with time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and analytical scanning transmission electron microscopy (STEM). The interface quality is found to be strongly affected by the perovskite deposition procedure, and in particular from the environment where the conversion of the starting precursors into the final perovskite is performed (air, nitrogen, or vacuum). The conversion efficiency of the precursors into the hybrid perovskite layer is compared between the different solar cells by looking at the ToF-SIMS intensities of the characteristic molecular fragments from the perovskite and the precursor materials. Energy dispersive X-ray spectroscopy in the STEM confirms the macroscopic ToF-SIMS findings and allows elemental mapping with nanometer resolution. Clear evidence for iodine diffusion has been observed and related to the fabrication procedure. PMID:26523427

  3. Halide Perovskites: Poor Man's High-Performance Semiconductors.

    PubMed

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2016-07-01

    Halide perovskites are a rapidly developing class of medium-bandgap semiconductors which, to date, have been popularized on account of their remarkable success in solid-state heterojunction solar cells raising the photovoltaic efficiency to 20% within the last 5 years. As the physical properties of the materials are being explored, it is becoming apparent that the photovoltaic performance of the halide perovskites is just but one aspect of the wealth of opportunities that these compounds offer as high-performance semiconductors. From unique optical and electrical properties stemming from their characteristic electronic structure to highly efficient real-life technological applications, halide perovskites constitute a brand new class of materials with exotic properties awaiting discovery. The nature of halide perovskites from the materials' viewpoint is discussed here, enlisting the most important classes of the compounds and describing their most exciting properties. The topics covered focus on the optical and electrical properties highlighting some of the milestone achievements reported to date but also addressing controversies in the vastly expanding halide perovskite literature.

  4. Size-Dependent Photon Emission from Organometal Halide Perovskite Nanocrystals Embedded in an Organic Matrix

    PubMed Central

    2015-01-01

    In recent years, organometal halide perovskite materials have attracted significant research interest in the field of optoelectronics. Here, we introduce a simple and low-temperature route for the formation of self-assembled perovskite nanocrystals in a solid organic matrix. We demonstrate that the size and photoluminescence peak of the perovskite nanocrystals can be tuned by varying the concentration of perovskite in the matrix material. The physical origin of the blue shift of the perovskite nanocrystals’ emission compared to its bulk phase is also discussed. PMID:25949773

  5. Review on palladium-containing perovskites: synthesis, physico-chemical properties and applications in catalysis.

    PubMed

    Essoumhi, Abdellatif; El Kazzouli, Saïd; Bousmina, Mosto

    2014-02-01

    This review reports on the recent advances in the synthesis and physico-chemical properties of palladium-containing perovskites. Initially, the perovskite structure is briefly reviewed, then palladium-containing perovskites synthesis and physico-chemical properties are detailed. The applications of palladium-containing perovskites in catalysis; namely, NO reduction, methane combustion, methanol as well as ethanol oxidation, are briefly highlighted. The involvement and the important contribution of palladium-containing perovskites in cross-coupling reactions, especially Suzuki-Miyaura, Sonogashira, Ulmann and Grignard, are discussed. PMID:24749470

  6. Charge carrier mobility in hybrid halide perovskites

    PubMed Central

    Motta, Carlo; El-Mellouhi, Fedwa; Sanvito, Stefano

    2015-01-01

    The charge transport properties of hybrid halide perovskites are investigated with a combination of density functional theory including van der Waals interaction and the Boltzmann theory for diffusive transport in the relaxation time approximation. We find the mobility of electrons to be in the range 5–10 cm2V−1s−1 and that for holes within 1–5 cm2V−1s−1, where the variations depend on the crystal structure investigated and the level of doping. Such results, in good agreement with recent experiments, set the relaxation time to about 1 ps, which is the time-scale for the molecular rotation at room temperature. For the room temperature tetragonal phase we explore two possible orientations of the organic cations and find that the mobility has a significant asymmetry depending on the direction of the current with respect to the molecular axis. This is due mostly to the way the PbI3 octahedral symmetry is broken. Interestingly we find that substituting I with Cl has minor effects on the mobilities. Our analysis suggests that the carrier mobility is probably not a key factor in determining the high solar-harvesting efficiency of this class of materials. PMID:26235910

  7. Exciton localization in solution-processed organolead trihalide perovskites

    NASA Astrophysics Data System (ADS)

    He, Haiping; Yu, Qianqian; Li, Hui; Li, Jing; Si, Junjie; Jin, Yizheng; Wang, Nana; Wang, Jianpu; He, Jingwen; Wang, Xinke; Zhang, Yan; Ye, Zhizhen

    2016-03-01

    Organolead trihalide perovskites have attracted great attention due to the stunning advances in both photovoltaic and light-emitting devices. However, the photophysical properties, especially the recombination dynamics of photogenerated carriers, of this class of materials are controversial. Here we report that under an excitation level close to the working regime of solar cells, the recombination of photogenerated carriers in solution-processed methylammonium-lead-halide films is dominated by excitons weakly localized in band tail states. This scenario is evidenced by experiments of spectral-dependent luminescence decay, excitation density-dependent luminescence and frequency-dependent terahertz photoconductivity. The exciton localization effect is found to be general for several solution-processed hybrid perovskite films prepared by different methods. Our results provide insights into the charge transport and recombination mechanism in perovskite films and help to unravel their potential for high-performance optoelectronic devices.

  8. A polymer scaffold for self-healing perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Zhao, Yicheng; Wei, Jing; Li, Heng; Yan, Yin; Zhou, Wenke; Yu, Dapeng; Zhao, Qing

    2016-01-01

    Advancing of the lead halide perovskite solar cells towards photovoltaic market demands large-scale devices of high-power conversion efficiency, high reproducibility and stability via low-cost fabrication technology, and in particular resistance to humid environment for long-time operation. Here we achieve uniform perovskite film based on a novel polymer-scaffold architecture via a mild-temperature process. These solar cells exhibit efficiency of up to ~16% with small variation. The unencapsulated devices retain high output for up to 300 h in highly humid environment (70% relative humidity). Moreover, they show strong humidity resistant and self-healing behaviour, recovering rapidly after removing from water vapour. Not only the film can self-heal in this case, but the corresponding devices can present power conversion efficiency recovery after the water vapour is removed. Our work demonstrates the value of cheap, long chain and hygroscopic polymer scaffold in perovskite solar cells towards commercialization.

  9. Atomistic mechanism leading to complex antiferroelectric and incommensurate perovskites

    NASA Astrophysics Data System (ADS)

    Patel, Kinnary; Prosandeev, Sergey; Yang, Yurong; Xu, Bin; Íñiguez, Jorge; Bellaiche, L.

    2016-08-01

    An atomic interaction is identified in all perovskite compounds, such as A B O3 oxides, that can potentially result in unconventional structures. The term is harmonic in nature and couples the motions of the A cations with the rotations of the oxygen octahedra in the perovskite lattice. When strong enough, this coupling leads to hybrid normal modes that present both (anti)polar and rotational characters, which are keys to understand a variety of exotic phases. For example, we show that not only does this new coupling explain the long-period soft phonons characterizing prototype antiferroelectric PbZrO3, but it also provides us with an unified description of the complex antipolar structures of a variety of perovskites, including the possible occurrence of incommensurate phases. This coupling is further demonstrated to result, in the continuum limit, in an energy invariant adopting an analytical form that has been previously overlooked, to the best of our knowledge.

  10. Los Alamos Discovers Super Efficient Solar Using Perovskite Crystals

    SciTech Connect

    Mohite, Aditya; Nie, Wanyi

    2015-01-29

    State-of-the-art photovoltaics using high-purity, large-area, wafer-scale single-crystalline semiconductors grown by sophisticated, high temperature crystal-growth processes offer promising routes for developing low-cost, solar-based clean global energy solutions for the future. Solar cells composed of the recently discovered material organic-inorganic perovskites offer the efficiency of silicon, yet suffer from a variety of deficiencies limiting the commercial viability of perovskite photovoltaic technology. In research to appear in Science, Los Alamos National Laboratory researchers reveal a new solution-based hot-casting technique that eliminates these limitations, one that allows for the growth of high-quality, large-area, millimeter-scale perovskite crystals and demonstrates that highly efficient and reproducible solar cells with reduced trap assisted recombination can be realized.

  11. Photon recycling in lead iodide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Pazos-Outón, Luis M.; Szumilo, Monika; Lamboll, Robin; Richter, Johannes M.; Crespo-Quesada, Micaela; Abdi-Jalebi, Mojtaba; Beeson, Harry J.; Vrućinić, Milan; Alsari, Mejd; Snaith, Henry J.; Ehrler, Bruno; Friend, Richard H.; Deschler, Felix

    2016-03-01

    Lead-halide perovskites have emerged as high-performance photovoltaic materials. We mapped the propagation of photogenerated luminescence and charges from a local photoexcitation spot in thin films of lead tri-iodide perovskites. We observed light emission at distances of ≥50 micrometers and found that the peak of the internal photon spectrum red-shifts from 765 to ≥800 nanometers. We used a lateral-contact solar cell with selective electron- and hole-collecting contacts and observed that charge extraction for photoexcitation >50 micrometers away from the contacts arose from repeated recycling between photons and electron-hole pairs. Thus, energy transport is not limited by diffusive charge transport but can occur over long distances through multiple absorption-diffusion-emission events. This process creates high excitation densities within the perovskite layer and allows high open-circuit voltages.

  12. Transparent conducting oxide free backside illuminated perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Li, Jia; Yao, Jiexiong; Xia, Huarong; Sun, Wentao; Liu, Jian; Peng, Lianmao

    2015-07-01

    Recently, hybrid perovskites have attracted great attention because of their promising applications in solar cells. However, perovskite solar devices reported till now are mostly based on transparent conducting oxide (TCO) substrates which account for a large proportion in the total cost. Herein, TCO-free perovskite solar cells are fabricated. A photo-electricity conversion efficiency of 5.27% is obtained with short circuit current density (Jsc) of 10.7 mA/cm2, open circuit voltage (Voc) of 0.837 V, and fill factor of 0.588. This study points a feasible way of replacing TCO substrate by low cost substrates, indicating promising potentials in solar energy conversion applications.

  13. Mixture interlayer for high performance organic-inorganic perovskite photodetectors

    NASA Astrophysics Data System (ADS)

    Tang, Feng; Chen, Qi; Chen, Lei; Ye, Fengye; Cai, Jinhua; Chen, Liwei

    2016-09-01

    Organic-inorganic perovskites are promising light absorbing active materials for photodetectors; however, the performance of current organic-inorganic perovskite-based photodetectors are limited by the high dark current due to hole injection at the cathode interlayer typically composed of fullerene derivatives. We have developed a mixture interlayer by simply blending polymethyl methacrylate (PMMA) with [6,6]-phenyl-C61-butyric acidmethyl ester (PCBM). Scanning Kelvin probe microscopy imaging reveals that the presence of PMMA reduced the work function of the PCBM:PMMA interlayer, which leads to increased energy barrier for hole injection and better hole-blocking property. Optimized perovskite photodetector with PCBM:PMMA hole-blocking interlayer exhibits a high detectivity of 1.1 × 1013 Jones, a broad linear dynamic range of 112 dB, and a fast response time of 2.2 μs.

  14. Specific features of nonvalent interactions in orthorhombic perovskites

    NASA Astrophysics Data System (ADS)

    Serezhkin, V. N.; Pushkin, D. V.; Serezhkina, L. B.

    2014-07-01

    It is established that isostructural orthorhombic perovskites ABO3 (sp. gr. Pnma in different systems, no. 62, Z = 4), depending on the specificity of nonvalent interactions (which determine the combinatorial-topological type of the Voronoi-Dirichlet polyhedra (VDPs) of four basis atoms), are divided into ten different stereotypes. It is shown by the example of 259 perovskites belonging to the DyCrO3 stereotype that VDP characteristics can be used to quantitatively estimate the distortion of BO6 octahedra, including that caused by the Jahn-Teller effect. It is found that one of the causes of the distortion of the coordination polyhedra of atoms in the structure of orthorhombic perovskites is heteroatomic metal-metal interactions, for which the interatomic distances are much shorter than the sum of the Slater radii of A and B atoms.

  15. Ultrafast Extreme Ultraviolet Absorption Spectroscopy of Methylammonium Lead Iodide Perovskite

    NASA Astrophysics Data System (ADS)

    Verkamp, Max A.; Lin, Ming-Fu; Ryland, Elizabeth S.; Vura-Weis, Josh

    2016-06-01

    Methylammonium lead iodide (perovskite) is a leading candidate for use in next-generation solar cell devices. However, the photophysics responsible for its strong photovoltaic qualities are not fully understood. Ultrafast extreme ultraviolet (XUV) absorption was used to investigate electron and hole dynamics in perovskite by observing transitions from a common inner-shell level (I 4d) to the valence and conduction bands. Ultrashort (30 fs) pulses of XUV radiation with a broad spectrum (40-70 eV) were generated via high-harmonic generation using a tabletop instrument. Transient absorption measurements with visible pump and XUV probe directly observed the relaxation of charge carriers in perovskite after above-band excitation in the femtosecond and picosecond time ranges.

  16. Photon recycling in lead iodide perovskite solar cells.

    PubMed

    Pazos-Outón, Luis M; Szumilo, Monika; Lamboll, Robin; Richter, Johannes M; Crespo-Quesada, Micaela; Abdi-Jalebi, Mojtaba; Beeson, Harry J; Vrućinić, Milan; Alsari, Mejd; Snaith, Henry J; Ehrler, Bruno; Friend, Richard H; Deschler, Felix

    2016-03-25

    Lead-halide perovskites have emerged as high-performance photovoltaic materials. We mapped the propagation of photogenerated luminescence and charges from a local photoexcitation spot in thin films of lead tri-iodide perovskites. We observed light emission at distances of ≥50 micrometers and found that the peak of the internal photon spectrum red-shifts from 765 to ≥800 nanometers. We used a lateral-contact solar cell with selective electron- and hole-collecting contacts and observed that charge extraction for photoexcitation >50 micrometers away from the contacts arose from repeated recycling between photons and electron-hole pairs. Thus, energy transport is not limited by diffusive charge transport but can occur over long distances through multiple absorption-diffusion-emission events. This process creates high excitation densities within the perovskite layer and allows high open-circuit voltages.

  17. Exciton localization in solution-processed organolead trihalide perovskites

    PubMed Central

    He, Haiping; Yu, Qianqian; Li, Hui; Li, Jing; Si, Junjie; Jin, Yizheng; Wang, Nana; Wang, Jianpu; He, Jingwen; Wang, Xinke; Zhang, Yan; Ye, Zhizhen

    2016-01-01

    Organolead trihalide perovskites have attracted great attention due to the stunning advances in both photovoltaic and light-emitting devices. However, the photophysical properties, especially the recombination dynamics of photogenerated carriers, of this class of materials are controversial. Here we report that under an excitation level close to the working regime of solar cells, the recombination of photogenerated carriers in solution-processed methylammonium–lead–halide films is dominated by excitons weakly localized in band tail states. This scenario is evidenced by experiments of spectral-dependent luminescence decay, excitation density-dependent luminescence and frequency-dependent terahertz photoconductivity. The exciton localization effect is found to be general for several solution-processed hybrid perovskite films prepared by different methods. Our results provide insights into the charge transport and recombination mechanism in perovskite films and help to unravel their potential for high-performance optoelectronic devices. PMID:26996605

  18. A polymer scaffold for self-healing perovskite solar cells.

    PubMed

    Zhao, Yicheng; Wei, Jing; Li, Heng; Yan, Yin; Zhou, Wenke; Yu, Dapeng; Zhao, Qing

    2016-01-01

    Advancing of the lead halide perovskite solar cells towards photovoltaic market demands large-scale devices of high-power conversion efficiency, high reproducibility and stability via low-cost fabrication technology, and in particular resistance to humid environment for long-time operation. Here we achieve uniform perovskite film based on a novel polymer-scaffold architecture via a mild-temperature process. These solar cells exhibit efficiency of up to ∼ 16% with small variation. The unencapsulated devices retain high output for up to 300 h in highly humid environment (70% relative humidity). Moreover, they show strong humidity resistant and self-healing behaviour, recovering rapidly after removing from water vapour. Not only the film can self-heal in this case, but the corresponding devices can present power conversion efficiency recovery after the water vapour is removed. Our work demonstrates the value of cheap, long chain and hygroscopic polymer scaffold in perovskite solar cells towards commercialization. PMID:26732479

  19. A polymer scaffold for self-healing perovskite solar cells

    PubMed Central

    Zhao, Yicheng; Wei, Jing; Li, Heng; Yan, Yin; Zhou, Wenke; Yu, Dapeng; Zhao, Qing

    2016-01-01

    Advancing of the lead halide perovskite solar cells towards photovoltaic market demands large-scale devices of high-power conversion efficiency, high reproducibility and stability via low-cost fabrication technology, and in particular resistance to humid environment for long-time operation. Here we achieve uniform perovskite film based on a novel polymer-scaffold architecture via a mild-temperature process. These solar cells exhibit efficiency of up to ∼16% with small variation. The unencapsulated devices retain high output for up to 300 h in highly humid environment (70% relative humidity). Moreover, they show strong humidity resistant and self-healing behaviour, recovering rapidly after removing from water vapour. Not only the film can self-heal in this case, but the corresponding devices can present power conversion efficiency recovery after the water vapour is removed. Our work demonstrates the value of cheap, long chain and hygroscopic polymer scaffold in perovskite solar cells towards commercialization. PMID:26732479

  20. Tracking the formation of methylammonium lead triiodide perovskite

    SciTech Connect

    Liu, Lijia E-mail: jmcleod@suda.edu.cn; McLeod, John A. E-mail: jmcleod@suda.edu.cn; Wang, Rongbin; Shen, Pengfei; Duhm, Steffen

    2015-08-10

    The formation mechanism of perovskite methylammonium lead triiodide (CH{sub 3}NH{sub 3}PbI{sub 3}) was studied with in situ X-ray photoelectron spectroscopy (XPS) on successive depositions of thermally evaporated methylammonium iodide (CH{sub 3}NH{sub 3}I) on a lead iodide (PbI{sub 2}) film. This deposition method mimics the “two-step” synthesis method commonly used in device fabrication. We find that several competing processes occur during the formation of perovskite CH{sub 3}NH{sub 3}PbI{sub 3}. Our most important finding is that during vapour deposition of CH{sub 3}NH{sub 3}I onto PbI{sub 2}, at least two carbon species are present in the resulting material, while only one nitrogen species is present. This suggests that CH{sub 3}NH{sub 3}I can dissociate during the transition to a perovskite phase, and some of the resulting molecules can be incorporated into the perovskite. The effect of partial CH{sub 3}NH{sub 3} substitution with CH{sub 3} was evaluated, and electronic structure calculations show that CH{sub 3} defects would impact the photovoltaic performance in perovskite solar cells. The possibility that not all A sites in the APbI{sub 3} perovskite are occupied by CH{sub 3}NH{sub 3} is therefore an important consideration when evaluating the performance of organometallic trihalide solar cells synthesized using typical approaches.

  1. Plasmonic-enhanced perovskite-graphene hybrid photodetectors

    NASA Astrophysics Data System (ADS)

    Sun, Zhenhua; Aigouy, Lionel; Chen, Zhuoying

    2016-03-01

    The surface plasmonic effect of metal nanostructures is a promising method to boost the performance of optoelectronic devices such as solar cells and photodetectors. In this report, gold nanoparticles with surface plasmon resonance localized at about 530 nm were synthesized and integrated into graphene/methylammonium lead iodide perovskite (CH3NH3PbI3) hybrid photodetectors. Compared with pristine graphene-CH3NH3PbI3 devices, a device with gold nanoparticles embedded has a doubly higher photo-responsivity as well as a faster photoresponse speed. The present devices adopt a unique configuration with gold nanoparticles physically separated from the light harvesting component, i.e., the perovskite layer by graphene. Advantages are revealed through a series of characterization techniques and analyses. First, thanks to the tiny thickness of graphene, the plasmonic effect of gold nanoparticles can effectively enhance the near-field of perovskite and thus facilitate light-harvesting. Second, the enhanced light-harvesting in perovskite happens very close to this interface where photo-induced carriers have relatively short paths to diffuse toward graphene, favoring a fast photo-response. This work demonstrates a feasible and inspiring strategy to improve the performance of photodetectors through the surface plasmonic effect of metallic nanostructures.The surface plasmonic effect of metal nanostructures is a promising method to boost the performance of optoelectronic devices such as solar cells and photodetectors. In this report, gold nanoparticles with surface plasmon resonance localized at about 530 nm were synthesized and integrated into graphene/methylammonium lead iodide perovskite (CH3NH3PbI3) hybrid photodetectors. Compared with pristine graphene-CH3NH3PbI3 devices, a device with gold nanoparticles embedded has a doubly higher photo-responsivity as well as a faster photoresponse speed. The present devices adopt a unique configuration with gold nanoparticles physically

  2. The Effect of Al on the Compressibility of Silicate Perovskite

    NASA Astrophysics Data System (ADS)

    Walter, M. J.; Kubo, A.; Yoshino, T.; Koga, K. T.; Ohishi, Y.

    2003-12-01

    Experimental data on compressibility of aluminous silicate perovskite show widely disparate results. Several studies show that Al causes a dramatic increase in compressibility1-3, while another study indicates a mild decrease in compressibility4. Here we report new results for the effect of Al on the room-temperature compressibility of perovskite using in situ X-ray diffraction in the diamond anvil cell from 30 to 100 GPa. We studied compressibility of perovskite in the system MgSiO3-Al2O3 in compositions with 0 to 25 mol% Al. Perovskite was synthesized from starting glasses using laser-heating in the DAC, with KBr as a pressure medium. Diffraction patterns were obtained using monochromatic radiation and an imaging plate detector at beamline BL10XU, SPring8, Japan. Addition of Al into the perovskite structure causes systematic increases in orthorhombic distortion and unit cell volume at ambient conditions (V0). Compression of the perovskite unit cell is anisotropic, with the a axis about 25% and 3% more compressive than the b and c axes, respectively. The magnitude of orthorhombic distortion increases with pressure, but aluminous perovskite remains stable to at least 100 GPa. Our results show that Al causes only a mild increase in compressibility, with the bulk modulus (K0) decreasing at a rate of 0.7 GPa/0.01 XAl. This increase in compressibility is consistent with recent ab initio calculations if Al mixes into both the 6- and 8-coordinated sites by coupled substitution5, where 2 Al3+ = Mg2+ + Si4+. Our results together with those of [4] indicate that this substitution mechanism predominates throughout the lower mantle. Previous mineralogic models indicating the upper and lower mantle are compositionally similar in terms of major elements remain effectively unchanged because solution of 5 mol% Al into perovskite has a minor effect on density. 1. Zhang & Weidner (1999). Science 284, 782-784. 2. Kubo et al. (2000) Proc. Jap. Acad. 76B, 103-107. 3. Daniel et al

  3. Guest-Activated Forbidden Tilts in a Molecular Perovskite Analogue.

    PubMed

    Duyker, Samuel G; Hill, Joshua A; Howard, Christopher J; Goodwin, Andrew L

    2016-09-01

    The manipulation of distortions in perovskite structures is critical to tailoring the properties of these materials for a variety of applications. Here we demonstrate a violation of established octahedral tilt rules in the double perovskite analogue (NH4)2SrFe(CN)6·2H2O. The forbidden tilt pattern we observe arises through coupling to hydration-driven Jahn-Teller-like distortions of the Sr coordination environment. Access to novel distortion mechanisms and the ability to switch these distortions on and off through chemical modification fundamentally expands the toolbox of techniques available for engineering symmetry-breaking processes in solid materials. PMID:27533044

  4. Pathways toward high-performance perovskite solar cells: review of recent advances in organo-metal halide perovskites for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Song, Zhaoning; Watthage, Suneth C.; Phillips, Adam B.; Heben, Michael J.

    2016-04-01

    Organo-metal halide perovskite-based solar cells have been the focus of intense research over the past five years, and power conversion efficiencies have rapidly been improved from 3.8 to >21%. This article reviews major advances in perovskite solar cells that have contributed to the recent efficiency enhancements, including the evolution of device architecture, the development of material deposition processes, and the advanced device engineering techniques aiming to improve control over morphology, crystallinity, composition, and the interface properties of the perovskite thin films. The challenges and future directions for perovskite solar cell research and development are also discussed.

  5. Electrical conductivity of (Mg,Fe)SiO3 Perovskite and a Perovskite-dominated assemblage at lower mantle conditions

    NASA Technical Reports Server (NTRS)

    Li, Xiaoyuan; Jeanloz, Raymond

    1987-01-01

    Electrical conductivity measurements of Perovskite and a Perovskite-dominated assemblage synthesized from pyroxene and olivine demonstrate that these high-pressure phases are insulating to pressures of 82 GPa and temperatures of 4500 K. Assuming an anhydrous upper mantle composition, the result provides an upper bound of 0.01 S/m for the electrical conductivity of the lower mantle between depths of 700 and 1900 km. This is 2 to 4 orders of magnitude lower than previous estimates of lower-mantle conductivity derived from studies of geomagnetic secular variations.

  6. Characterization of arsenic (V) and arsenic (III) in water samples using ammonium molybdate and estimation by graphite furnace atomic absorption spectroscopy.

    PubMed

    Sounderajan, Suvarna; Udas, A C; Venkataramani, B

    2007-10-01

    Arsenic (V) is known to form heteropolyacid with ammonium molybdate in acidic aqueous solutions, which can be quantitatively extracted into certain organic solvents. In the present work, 12-molybdoarsenic acid extracted in butan-1-ol is used for quantification of As (V). Total arsenic is estimated by converting arsenic (III) to arsenic (V) by digesting samples with concentrated nitric acid before extraction. Concentration of As (III) in the sample solutions could be calculated by the difference in total arsenic and arsenic (V). The characterization of arsenic was carried out by GFAAS using Pd as modifier. Optimization of the experimental conditions and instrumental parameters was investigated in detail. Recoveries of (90-110%) were obtained in the spiked samples. The detection limit was 0.2 microg l(-1). The proposed method was successfully applied for the determination of trace amount of arsenic (III) and arsenic (V) in process water samples. PMID:17761387

  7. Interaction of uranyl molybdate with the Na{sub 2}MoO{sub 4}-Na{sub 2}Mo{sub 2}O{sub 4} melt

    SciTech Connect

    Smolenskii, V.V.; Bove, A.L.; Martem`yanova, Z.S.

    1994-06-01

    Behavior of uranyl molybdate in molten Na{sub 2}MoO{sub 4}-Na{sub 2}Mo{sub 2}O{sub 7} salt mixture at 1073 K in air was studied using cyclic linear voltammetry and potentiometric titration techniques. Uranyl complexes of two types ([UO{sub 2}(MoO{sub 4}){sub 2}]{sup 2{minus}} and UO{sub 3}MoO{sub 4}{sup 2{minus}}) were shown to be formed in the solution upon the addition of UO{sub 2}MoO{sub 4}. The composition of a cathodic product was found to be determined by the molar ratio of these two complexes in the melt.

  8. PAPERS DEVOTED TO THE 90TH ANNIVERSARY OF A.M.PROKHOROV: Lasing properties of selectively pumped Raman-active Nd3+-doped molybdate and tungstate crystals

    NASA Astrophysics Data System (ADS)

    Basiev, Tasoltan T.; Doroshenko, Maxim E.; Ivleva, Lyudmila I.; Osiko, Vyacheslav V.; Kosmyna, M. B.; Komar', V. K.; Sulc, J.; Jelinkova, H.

    2006-08-01

    The lasing efficiency of Nd3+ ions is studied in laser materials capable of self-Raman frequency conversion. The lasing properties of tungstate and molybdate crystals with the scheelite structure (SrWO4, BaWO4, PbWO4, SrMoO4, PbMoO4) activated with neodymium ions are investigated upon longitudinal pumping by a 750-nm alexandrite laser or a 800-nm diode laser. The slope lasing efficiency obtained for a Nd3+:PbMoO4 laser emitting at 1054 nm is 54.3% for the total lasing efficiency of 46%, which is the best result for all the crystals with the scheelite structure studied so far. The simultaneous Q-switched lasing and self-Raman frequency conversion were demonstrated in neodymium-doped SrWO4, PbWO4, and BaWO4 crystals.

  9. EPR spectroscopy of MolB2C2-a reveals mechanism of transport for a bacterial type II molybdate importer.

    PubMed

    Rice, Austin J; Alvarez, Frances J D; Schultz, Kathryn M; Klug, Candice S; Davidson, Amy L; Pinkett, Heather W

    2013-07-19

    In bacteria, ATP-binding cassette (ABC) transporters are vital for the uptake of nutrients and cofactors. Based on differences in structure and activity, ABC importers are divided into two types. Type I transporters have been well studied and employ a tightly regulated alternating access mechanism. Less is known about Type II importers, but much of what we do know has been observed in studies of the vitamin B12 importer BtuC2D2. MolB2C2 (formally known as HI1470/71) is also a Type II importer, but its substrate, molybdate, is ∼10-fold smaller than vitamin B12. To understand mechanistic differences among Type II importers, we focused our studies on MolBC, for which alternative conformations may be required to transport its relatively small substrate. To investigate the mechanism of MolBC, we employed disulfide cross-linking and EPR spectroscopy. From these studies, we found that nucleotide binding is coupled to a conformational shift at the periplasmic gate. Unlike the larger conformational changes in BtuCD-F, this shift in MolBC-A is akin to unlocking a swinging door: allowing just enough space for molybdate to slip into the cell. The lower cytoplasmic gate, identified in BtuCD-F as "gate I," remains open throughout the MolBC-A mechanism, and cytoplasmic gate II closes in the presence of nucleotide. Combining our results, we propose a peristaltic mechanism for MolBC-A, which gives new insight in the transport of small substrates by a Type II importer.

  10. EPR Spectroscopy of MolB2C2-A Reveals Mechanism of Transport for a Bacterial Type II Molybdate Importer*♦

    PubMed Central

    Rice, Austin J.; Alvarez, Frances J. D.; Schultz, Kathryn M.; Klug, Candice S.; Davidson, Amy L.; Pinkett, Heather W.

    2013-01-01

    In bacteria, ATP-binding cassette (ABC) transporters are vital for the uptake of nutrients and cofactors. Based on differences in structure and activity, ABC importers are divided into two types. Type I transporters have been well studied and employ a tightly regulated alternating access mechanism. Less is known about Type II importers, but much of what we do know has been observed in studies of the vitamin B12 importer BtuC2D2. MolB2C2 (formally known as HI1470/71) is also a Type II importer, but its substrate, molybdate, is ∼10-fold smaller than vitamin B12. To understand mechanistic differences among Type II importers, we focused our studies on MolBC, for which alternative conformations may be required to transport its relatively small substrate. To investigate the mechanism of MolBC, we employed disulfide cross-linking and EPR spectroscopy. From these studies, we found that nucleotide binding is coupled to a conformational shift at the periplasmic gate. Unlike the larger conformational changes in BtuCD-F, this shift in MolBC-A is akin to unlocking a swinging door: allowing just enough space for molybdate to slip into the cell. The lower cytoplasmic gate, identified in BtuCD-F as “gate I,” remains open throughout the MolBC-A mechanism, and cytoplasmic gate II closes in the presence of nucleotide. Combining our results, we propose a peristaltic mechanism for MolBC-A, which gives new insight in the transport of small substrates by a Type II importer. PMID:23709218

  11. The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation

    DOE PAGESBeta

    Rodriguez, Jose A.; Xu, Wenqian; Ramirez, Pedro J.; Stachiola, Dario; Brito, Joaquin L.

    2015-05-06

    A new approach has been tested for the preparation of metal/Mo₂C catalysts using mixed-metal oxide molybdates as precursors. Synchrotron-based in situ time-resolved X-ray diffraction was used to study the reduction and carburization processes of Cu₃(MoO₄)₂(OH)₂, a-NiMoO₄ and CoMoO₄•nH₂O by thermal treatment under mixtures of hydrogen and methane. In all cases, the final product was β-Mo₂C and a metal phase (Cu, Ni, or Co), but the transition sequence varied with the different metals, and it could be related to the reduction potential of the Cu²⁺, Ni²⁺ and Co²⁺ cations inside each molybdate. The synthesized Cu/Mo₂C, Ni/Mo₂C and Co/Mo₂C catalysts were highlymore » active for the hydrogenation of CO₂. The metal/Mo₂C systems exhibited large variations in the selectivity towards methanol, methane and CnH₂n₊₂ (n > 2) hydrocarbons depending on the nature of the supported metal and its ability to cleave C-O bonds. Cu/Mo₂C displayed a high selectivity for CO and methanol production. Ni/Mo₂C and Co/Mo₂C were the most active catalysts for the activation and full decomposition of CO₂, showing high selectivity for the production of methane (Ni case) and CnH₂n₊₂ (n > 2) hydrocarbons (Co case).« less

  12. The carburization of transition metal molybdates (MxMoO₄, M= Cu, Ni or Co) and the generation of highly active metal/carbide catalysts for CO₂ hydrogenation

    SciTech Connect

    Rodriguez, Jose A.; Xu, Wenqian; Ramirez, Pedro J.; Stachiola, Dario; Brito, Joaquin L.

    2015-05-06

    A new approach has been tested for the preparation of metal/Mo₂C catalysts using mixed-metal oxide molybdates as precursors. Synchrotron-based in situ time-resolved X-ray diffraction was used to study the reduction and carburization processes of Cu₃(MoO₄)₂(OH)₂, a-NiMoO₄ and CoMoO₄•nH₂O by thermal treatment under mixtures of hydrogen and methane. In all cases, the final product was β-Mo₂C and a metal phase (Cu, Ni, or Co), but the transition sequence varied with the different metals, and it could be related to the reduction potential of the Cu²⁺, Ni²⁺ and Co²⁺ cations inside each molybdate. The synthesized Cu/Mo₂C, Ni/Mo₂C and Co/Mo₂C catalysts were highly active for the hydrogenation of CO₂. The metal/Mo₂C systems exhibited large variations in the selectivity towards methanol, methane and CnH₂n₊₂ (n > 2) hydrocarbons depending on the nature of the supported metal and its ability to cleave C-O bonds. Cu/Mo₂C displayed a high selectivity for CO and methanol production. Ni/Mo₂C and Co/Mo₂C were the most active catalysts for the activation and full decomposition of CO₂, showing high selectivity for the production of methane (Ni case) and CnH₂n₊₂ (n > 2) hydrocarbons (Co case).

  13. Synthesis, structural and spectroscopic properties of acentric triple molybdate Cs{sub 2}NaBi(MoO{sub 4}){sub 3}

    SciTech Connect

    Savina, A.A.; Atuchin, V.V.; Solodovnikov, S.F.; Solodovnikova, Z.A.; Krylov, A.S.; Maximovskiy, E.A.; Molokeev, M.S.; Oreshonkov, A.S; Pugachev, A.M.; and others

    2015-05-15

    New ternary molybdate Cs{sub 2}NaBi(MoO{sub 4}){sub 3} is synthesized in the system Na{sub 2}MoO{sub 4}–Cs{sub 2}MoO{sub 4}–Bi{sub 2}(MoO{sub 4}){sub 3}. The structure of Cs{sub 2}NaBi(MoO{sub 4}){sub 3} of a new type is determined in noncentrosymmetric space group R3c, a=10.6435(2), c=40.9524(7) Å, V=4017.71(13) Å{sup 3}, Z=12 in anisotropic approximation for all atoms taking into account racemic twinning. The structure is completely ordered, Mo atoms are tetrahedrally coordinated, Bi(1) and Bi(2) atoms are in octahedra, and Na(1) and Na(2) atoms have a distorted trigonal prismatic coordination. The Cs(1) and Cs(2) atoms are in the framework cavities with coordination numbers 12 and 10, respectively. No phase transitions were found in Cs{sub 2}NaBi(MoO{sub 4}){sub 3} up to the melting point at 826 K. The compound shows an SHG signal, I{sub 2w}/I{sub 2w}(SiO{sub 2})=5 estimated by the powder method. The vibrational properties are evaluated by Raman spectroscopy, and 26 narrow lines are measured. - Graphical abstract: - Highlights: • The crystal structure of Cs{sub 2}NaBi(MoO{sub 4}){sub 3} is defined. • The molybdate Cs{sub 2}NaBi(MoO{sub 4}){sub 3} is stable up to melting point at 826 K. • Vibrational properties of Cs{sub 2}NaBi(MoO{sub 4}){sub 3} are evaluated by Raman spectroscopy.

  14. Emission Enhancement and Intermittency in Polycrystalline Organolead Halide Perovskite Films.

    PubMed

    Li, Cheng; Zhong, Yu; Luna, Carlos Andres Melo; Unger, Thomas; Deichsel, Konstantin; Gräser, Anna; Köhler, Jürgen; Köhler, Anna; Hildner, Richard; Huettner, Sven

    2016-01-01

    Inorganic-organic halide organometal perovskites have demonstrated very promising performance for opto-electronic applications, such as solar cells, light-emitting diodes, lasers, single-photon sources, etc. However, the little knowledge on the underlying photophysics, especially on a microscopic scale, hampers the further improvement of devices based on this material. In this communication, correlated conventional photoluminescence (PL) characterization and wide-field PL imaging as a function of time are employed to investigate the spatially- and temporally-resolved PL in CH₃NH₃PbI3-xClx perovskite films. Along with a continuous increase of the PL intensity during light soaking, we also observe PL blinking or PL intermittency behavior in individual grains of these films. Combined with significant suppression of PL blinking in perovskite films coated with a phenyl-C61-butyric acid methyl ester (PCBM) layer, it suggests that this PL intermittency is attributed to Auger recombination induced by photoionized defects/traps or mobile ions within grains. These defects/traps are detrimental for light conversion and can be effectively passivated by the PCBM layer. This finding paves the way to provide a guideline on the further improvement of perovskite opto-electronic devices. PMID:27548128

  15. Materials processing routes to trap-free halide perovskites.

    PubMed

    Buin, Andrei; Pietsch, Patrick; Xu, Jixian; Voznyy, Oleksandr; Ip, Alexander H; Comin, Riccardo; Sargent, Edward H

    2014-11-12

    Photovoltaic devices based on lead iodide perovskite films have seen rapid advancements, recently achieving an impressive 17.9% certified solar power conversion efficiency. Reports have consistently emphasized that the specific choice of growth conditions and chemical precursors is central to achieving superior performance from these materials; yet the roles and mechanisms underlying the selection of materials processing route is poorly understood. Here we show that films grown under iodine-rich conditions are prone to a high density of deep electronic traps (recombination centers), while the use of a chloride precursor avoids the formation of key defects (Pb atom substituted by I) responsible for short diffusion lengths and poor photovoltaic performance. Furthermore, the lowest-energy surfaces of perovskite crystals are found to be entirely trap-free, preserving both electron and hole delocalization to a remarkable degree, helping to account for explaining the success of polycrystalline perovskite films. We construct perovskite films from I-poor conditions using a lead acetate precursor, and our measurement of a long (600 ± 40 nm) diffusion length confirms this new picture of the importance of growth conditions.

  16. Controlling Octahedral Rotations in a Perovskite via Strain Doping

    PubMed Central

    Herklotz, A.; Wong, A. T.; Meyer, T.; Biegalski, M. D.; Lee, H. N.; Ward, T. Z.

    2016-01-01

    The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film can be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO3 films coherently grown on SrTiO3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. These results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials. PMID:27215804

  17. Controlling octahedral rotations in a perovskite via strain doping

    DOE PAGESBeta

    Herklotz, Andreas; Biegalski, Michael D.; Lee, Ho Nyung; Ward, Thomas Zac; Wong, A. T.; Meyer, T.

    2016-05-24

    The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film canmore » be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO3 films coherently grown on SrTiO3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. Lastly, these results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials.« less

  18. 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.

  19. Comprehensive design of omnidirectional high-performance perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Zhang, Yutao; Xuan, Yimin

    2016-07-01

    The comprehensive design approach is established with coupled optical-electrical simulation for perovskite-based solar cell, which emerged as one of the most promising competitors to silicon solar cell for its low-cost fabrication and high PCE. The selection of structured surface, effect of geometry parameters, incident angle-dependence and polarization-sensitivity are considered in the simulation. The optical modeling is performed via the finite-difference time-domain method whilst the electrical properties are obtained by solving the coupled nonlinear equations of Poisson, continuity, and drift-diffusion equations. The optical and electrical performances of five different structured surfaces are compared to select a best structured surface for perovskite solar cell. The effects of the geometry parameters on the optical and electrical properties of the perovskite cell are analyzed. The results indicate that the light harvesting is obviously enhanced by the structured surface. The electrical performance can be remarkably improved due to the enhanced light harvesting of the designed best structured surface. The angle-dependence for s- and p-polarizations is investigated. The structured surface exhibits omnidirectional behavior and favorable polarization-insensitive feature within a wide incident angle range. Such a comprehensive design approach can highlight the potential of perovskite cell for power conversion in the full daylight.

  20. Degradation mechanism for planar heterojunction perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Yamamoto, Kouhei; Furumoto, Yoshikazu; Shahiduzzaman, M.; Kuwabara, Takayuki; Takahashi, Kohshin; Taima, Tetsuya

    2016-04-01

    Organic-inorganic hybrid perovskite materials have recently emerged as a promising cost- and energy-efficient light absorber material for photovoltaic applications. Unfortunately, perovskite solar cells have a problem with decreasing power conversion efficiency owing to their degradation in air. To clarify the cause of the degradation of perovskite solar cells, we exposed deposited CH3NH3PbI3 and HC(NH2)2PbI3 films to an O2 or (H2O+N2) atmosphere condition. Analysis of these films revealed that a large energy band gap was observed as a result of the influence of the H2O molecule in CH3NH3PbI3 and HC(NH2)2PbI3. Under the (H2O+N2) atmosphere condition, the existence of CH3NH3I and HC(NH2)2I molecules was found to affect the morphology and as well as the crystalline diffraction peak. The resultant perovskite crystalline structure was degraded by H2O molecules under the air exposure condition.

  1. Controlling Octahedral Rotations in a Perovskite via Strain Doping

    NASA Astrophysics Data System (ADS)

    Herklotz, A.; Wong, A. T.; Meyer, T.; Biegalski, M. D.; Lee, H. N.; Ward, T. Z.

    2016-05-01

    The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film can be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO3 films coherently grown on SrTiO3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. These results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials.

  2. Comprehensive design of omnidirectional high-performance perovskite solar cells.

    PubMed

    Zhang, Yutao; Xuan, Yimin

    2016-01-01

    The comprehensive design approach is established with coupled optical-electrical simulation for perovskite-based solar cell, which emerged as one of the most promising competitors to silicon solar cell for its low-cost fabrication and high PCE. The selection of structured surface, effect of geometry parameters, incident angle-dependence and polarization-sensitivity are considered in the simulation. The optical modeling is performed via the finite-difference time-domain method whilst the electrical properties are obtained by solving the coupled nonlinear equations of Poisson, continuity, and drift-diffusion equations. The optical and electrical performances of five different structured surfaces are compared to select a best structured surface for perovskite solar cell. The effects of the geometry parameters on the optical and electrical properties of the perovskite cell are analyzed. The results indicate that the light harvesting is obviously enhanced by the structured surface. The electrical performance can be remarkably improved due to the enhanced light harvesting of the designed best structured surface. The angle-dependence for s- and p-polarizations is investigated. The structured surface exhibits omnidirectional behavior and favorable polarization-insensitive feature within a wide incident angle range. Such a comprehensive design approach can highlight the potential of perovskite cell for power conversion in the full daylight. PMID:27405419

  3. Perovskite-Fullerene Hybrid Materials Eliminate Hysteresis In Planar Diodes

    DOE PAGESBeta

    Xu, Jixian; Buin, Andrei; Ip, Alexander H.; Li, Wei; Voznyy, Oleksandr; Comin, Riccardo; Yuan, Mingjian; Jeon, Seokmin; Ning, Zhijun; McDowell, Jeffrey; et al

    2015-03-31

    Solution-processed planar perovskite devices are highly desirable in a wide variety of optoelectronic applications; however, they are prone to hysteresis and current instabilities. Here we report the first perovskite–PCBM hybrid solid with significantly reduced hysteresis and recombination loss achieved in a single step. This new material displays an efficient electrically coupled microstructure: PCBM is homogeneously distributed throughout the film at perovskite grain boundaries. The PCBM passivates the key PbI3 antisite defects during the perovskite self-assembly, as revealed by theory and experiment. Photoluminescence transient spectroscopy proves that the PCBM phase promotes electron extraction. We showcase this mixed material in planar solarmore » cells that feature low hysteresis and enhanced photovoltage. Using conductive AFM studies, we reveal the memristive properties of perovskite films. We close by positing that PCBM, by tying up both halide-rich antisites and unincorporated halides, reduces electric field-induced anion migration that may give rise to hysteresis and unstable diode behaviour.« less

  4. Comprehensive design of omnidirectional high-performance perovskite solar cells

    PubMed Central

    Zhang, Yutao; Xuan, Yimin

    2016-01-01

    The comprehensive design approach is established with coupled optical-electrical simulation for perovskite-based solar cell, which emerged as one of the most promising competitors to silicon solar cell for its low-cost fabrication and high PCE. The selection of structured surface, effect of geometry parameters, incident angle-dependence and polarization-sensitivity are considered in the simulation. The optical modeling is performed via the finite-difference time-domain method whilst the electrical properties are obtained by solving the coupled nonlinear equations of Poisson, continuity, and drift-diffusion equations. The optical and electrical performances of five different structured surfaces are compared to select a best structured surface for perovskite solar cell. The effects of the geometry parameters on the optical and electrical properties of the perovskite cell are analyzed. The results indicate that the light harvesting is obviously enhanced by the structured surface. The electrical performance can be remarkably improved due to the enhanced light harvesting of the designed best structured surface. The angle-dependence for s- and p-polarizations is investigated. The structured surface exhibits omnidirectional behavior and favorable polarization-insensitive feature within a wide incident angle range. Such a comprehensive design approach can highlight the potential of perovskite cell for power conversion in the full daylight. PMID:27405419

  5. Hysteresis, Stability, and Ion Migration in Lead Halide Perovskite Photovoltaics.

    PubMed

    Miyano, Kenjiro; Yanagida, Masatoshi; Tripathi, Neeti; Shirai, Yasuhiro

    2016-06-16

    Ion migration has been suspected as the origin of various irreproducible and unstable properties, most notably the hysteresis, of lead halide perovskite photovoltaic (PV) cells since the early stage of the research. Although many evidence of ionic movement have been presented both numerically and experimentally, a coherent and quantitative picture that accounts for the observed irreproducible phenomena is still lacking. At the same time, however, it has been noticed that in certain types of PV cells, the hysteresis is absent or at least within the measurement reproducibility. We have previously shown that the electronic properties of hysteresis-free cells are well represented in terms of the conventional inorganic semiconductors. The reproducibility of these measurements was confirmed typically within tens of minutes under the biasing field of -1 V to +1.5 V. In order to probe the effect of ionic motion in the hysteresis-free cells, we extended the time scale and the biasing rage in the electronic measurements, from which we conclude the following: (1) From various evidence, it appears that ion migration is inevitable. However, it does not cause detrimental effects to the PV operation. (2) We propose, based on the quantitative characterization, that the degradation is more likely due to the chemical change at the interfaces between the carrier selective layers and perovskite rather than the compositional change of the lead iodide perovskite bulk. Together, they give much hope in the use of the lead iodide perovskite in the use of actual application.

  6. Krypton irradiation damage in Nd-doped zirconolite and perovskite

    NASA Astrophysics Data System (ADS)

    Davoisne, C.; Stennett, M. C.; Hyatt, N. C.; Peng, N.; Jeynes, C.; Lee, W. E.

    2011-08-01

    Understanding the effect of radiation damage and noble gas accommodation in potential ceramic hosts for plutonium disposition is necessary to evaluate their long-term behaviour during geological disposal. Polycrystalline samples of Nd-doped zirconolite and Nd-doped perovskite were irradiated ex situ with 2 MeV Kr + at a dose of 5 × 10 15 ions cm -2 to simulate recoil of Pu nuclei during alpha decay. The feasibility of thin section preparation of both pristine and irradiated samples by Focused Ion Beam sectioning was demonstrated. After irradiation, the Nd-doped zirconolite revealed a well defined amorphous region separated from the pristine material by a thin (40-60 nm) damaged interface. The zirconolite lattice was lost in the damaged interface, but the fluorite sublattice was retained. The Nd-doped perovskite contained a defined irradiated layer composed of an amorphous region surrounded by damaged but still crystalline layers. The structural evolution of the damaged regions is consistent with a change from orthorhombic to cubic symmetry. In addition in Nd-doped perovskite, the amorphisation dose depended on crystallographic orientation and possibly sample configuration (thin section or bulk). Electron Energy Loss Spectroscopy revealed Ti remained in the 4+ oxidation state but there was a change in Ti coordination in both Nd-doped perovskite and Nd-doped zirconolite associated with the crystalline to amorphous transition.

  7. Multifunctional MgO Layer in Perovskite Solar Cells.

    PubMed

    Guo, Xudong; Dong, Haopeng; Li, Wenzhe; Li, Nan; Wang, Liduo

    2015-06-01

    A multifunctional magnesium oxide (MgO) layer was successfully introduced into perovskite solar cells (PSCs) to enhance their performance. MgO was coated onto the surface of mesoporous TiO(2) by the decomposition of magnesium acetate and, therefore, could block contact between the perovskite and TiO(2). X-ray photoelectron spectroscopy and infrared spectroscopy showed that the amount of H(2)O/hydroxyl absorbed on the TiO(2) decreased after MgO modification. The UV/Vis absorption spectra of the perovskite with MgO modification revealed an enhanced photoelectric performance compared with that of unmodified perovskite after UV illumination. In addition to the photocurrent, the photovoltage and fill factor also showed an enhancement after modification, which resulted in an increase in the overall efficiency of the cell from 9.6 to 13.9 %. Electrochemical impedance spectroscopy (EIS) confirmed that MgO acts as an insulating layer to reduce charge recombination. PMID:25851999

  8. High-performance perovskite-graphene hybrid photodetector.

    PubMed

    Lee, Youngbin; Kwon, Jeong; Hwang, Euyheon; Ra, Chang-Ho; Yoo, Won Jong; Ahn, Jong-Hyun; Park, Jong Hyeok; Cho, Jeong Ho

    2015-01-01

    A high-performance novel photodetector is demonstrated, which consists of graphene and CH3 NH3 PbI3 perovskite layers. The resulting hybrid photodetector exhibits a dramatically enhanced photo responsivity (180 A/W) and effective quantum efficiency (5× 10(4) %) over a broad bandwidth within the UV and visible ranges.

  9. Hysteresis, Stability, and Ion Migration in Lead Halide Perovskite Photovoltaics.

    PubMed

    Miyano, Kenjiro; Yanagida, Masatoshi; Tripathi, Neeti; Shirai, Yasuhiro

    2016-06-16

    Ion migration has been suspected as the origin of various irreproducible and unstable properties, most notably the hysteresis, of lead halide perovskite photovoltaic (PV) cells since the early stage of the research. Although many evidence of ionic movement have been presented both numerically and experimentally, a coherent and quantitative picture that accounts for the observed irreproducible phenomena is still lacking. At the same time, however, it has been noticed that in certain types of PV cells, the hysteresis is absent or at least within the measurement reproducibility. We have previously shown that the electronic properties of hysteresis-free cells are well represented in terms of the conventional inorganic semiconductors. The reproducibility of these measurements was confirmed typically within tens of minutes under the biasing field of -1 V to +1.5 V. In order to probe the effect of ionic motion in the hysteresis-free cells, we extended the time scale and the biasing rage in the electronic measurements, from which we conclude the following: (1) From various evidence, it appears that ion migration is inevitable. However, it does not cause detrimental effects to the PV operation. (2) We propose, based on the quantitative characterization, that the degradation is more likely due to the chemical change at the interfaces between the carrier selective layers and perovskite rather than the compositional change of the lead iodide perovskite bulk. Together, they give much hope in the use of the lead iodide perovskite in the use of actual application. PMID:27227427

  10. Multifunctional MgO Layer in Perovskite Solar Cells.

    PubMed

    Guo, Xudong; Dong, Haopeng; Li, Wenzhe; Li, Nan; Wang, Liduo

    2015-06-01

    A multifunctional magnesium oxide (MgO) layer was successfully introduced into perovskite solar cells (PSCs) to enhance their performance. MgO was coated onto the surface of mesoporous TiO(2) by the decomposition of magnesium acetate and, therefore, could block contact between the perovskite and TiO(2). X-ray photoelectron spectroscopy and infrared spectroscopy showed that the amount of H(2)O/hydroxyl absorbed on the TiO(2) decreased after MgO modification. The UV/Vis absorption spectra of the perovskite with MgO modification revealed an enhanced photoelectric performance compared with that of unmodified perovskite after UV illumination. In addition to the photocurrent, the photovoltage and fill factor also showed an enhancement after modification, which resulted in an increase in the overall efficiency of the cell from 9.6 to 13.9 %. Electrochemical impedance spectroscopy (EIS) confirmed that MgO acts as an insulating layer to reduce charge recombination.

  11. Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects.

    PubMed

    Liu, Yuanyue; Xiao, Hai; Goddard, William A

    2016-05-11

    Two-dimensional (2D) halide perovskites are emerging as promising candidates for nanoelectronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g., transition metal dichalcogenides MX2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gap states. We show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX2. The donors tend to have high formation energies and the harmful defects are difficult to form at a low halide chemical potential. Thus, we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them.

  12. Temperature-independent sensors based on perovskite-type oxides

    NASA Astrophysics Data System (ADS)

    Zaza, F.; Frangini, S.; Leoncini, J.; Luisetto, I.; Masci, A.; Pasquali, M.; Tuti, S.

    2014-06-01

    The need of energy security and environment sustainability drives toward the development of energy technology in order to enhance the performance of internal combustion engines. Gas sensors play a key role for controlling the fuel oxygen ratio and monitoring the pollution emissions. The perovskite-type oxides can be synthesized for an extremely wide variety of combinations of chemical elements, allowing to design materials with suitable properties for sensing application. Lanthanum strontium ferrites, such as La0.7Sr0.3FeO3, are suitable oxygen sensing materials with temperature-independence conductivity, but they have low chemical stability under reducing conditions. The addition of aluminum into the perovskite structure improves the material properties in order to develop suitable oxygen sensing probes for lean burn engine control systems. Perovskite-type oxides with formula (La0.7Sr0.3)(AlxFe1-x)O3 was synthesized by the citrate-nitrate combustion synthesis method. XRD analyses, show that it was synthesized a phase-pure powder belonging to the perovskite structure. Aluminum affects both the unit cell parameters, by shrinking the unit cell, and the powder morphology, by promoting the synthesis of particles with small crystallite size and large specific surface area. The partial substitution of iron with aluminum improves the chemical stability under reducing gas conditions and modulates the oxygen sensitivity by affecting the relative amount of Fe4+ and Fe3+, as confirmed from TPR profiles. In the same time, the addition of aluminum does not affects the temperature-independent properties of lanthanum strontium ferrites. Indeed, the electrical measurements show that (La0.7Sr0.3)(AlxFe1-x)O3 perovskites have temperature-independence conductivity from 900 K.

  13. Temperature-independent sensors based on perovskite-type oxides

    SciTech Connect

    Zaza, F.; Frangini, S.; Masci, A.; Leoncini, J.; Pasquali, M.; Luisetto, I.; Tuti, S.

    2014-06-19

    The need of energy security and environment sustainability drives toward the development of energy technology in order to enhance the performance of internal combustion engines. Gas sensors play a key role for controlling the fuel oxygen ratio and monitoring the pollution emissions. The perovskite-type oxides can be synthesized for an extremely wide variety of combinations of chemical elements, allowing to design materials with suitable properties for sensing application. Lanthanum strontium ferrites, such as La{sub 0.7}Sr{sub 0.3}FeO{sub 3}, are suitable oxygen sensing materials with temperature-independence conductivity, but they have low chemical stability under reducing conditions. The addition of aluminum into the perovskite structure improves the material properties in order to develop suitable oxygen sensing probes for lean burn engine control systems. Perovskite-type oxides with formula (La{sub 0.7}Sr{sub 0.3})(Al{sub x}Fe{sub 1−x})O{sub 3} was synthesized by the citrate-nitrate combustion synthesis method. XRD analyses, show that it was synthesized a phase-pure powder belonging to the perovskite structure. Aluminum affects both the unit cell parameters, by shrinking the unit cell, and the powder morphology, by promoting the synthesis of particles with small crystallite size and large specific surface area. The partial substitution of iron with aluminum improves the chemical stability under reducing gas conditions and modulates the oxygen sensitivity by affecting the relative amount of Fe{sup 4+} and Fe{sup 3+}, as confirmed from TPR profiles. In the same time, the addition of aluminum does not affects the temperature-independent properties of lanthanum strontium ferrites. Indeed, the electrical measurements show that (La{sub 0.7}Sr{sub 0.3})(Al{sub x}Fe{sub 1−x})O{sub 3} perovskites have temperature-independence conductivity from 900 K.

  14. High-performance cadmium sulphide-based planar perovskite solar cell and the cadmium sulphide/perovskite interfaces

    NASA Astrophysics Data System (ADS)

    Peng, Haitao; Sun, Weihai; Li, Yunlong; Yan, Weibo; Yu, Pingrong; Zhou, Huanping; Bian, Zuqiang; Huang, Chunhui

    2016-04-01

    Planar heterojunction perovskite solar cell is one of the most competitive photovoltaic technologies, while charge transport materials play a crucial role. We successfully demonstrated an effective electron transport material, namely chemical bath deposited cadmium sulphide (CdS) film under low temperature, in perovskite-based solar cells. Power conversion efficiency of 16.1% has been achieved, which is comparable to that of devices based on TiO2 film prepared via low-temperature processes. Electronic impedance spectra reveal that the CdS-based device presents a higher recombination resistance than TiO2-based devices, which reduces carrier recombination and increases the open circuit voltage. The interface between CdS and perovskite was characterized with improved characteristics when compared to TiO2, e.g., efficient carrier extraction and reduced surface defect-associated degradation in the devices, which help to alleviate anomalous hysteresis and long-term instability. Furthermore, the entire device was fabricated via solution process with a processing temperature below 100°C, suggesting a promising method of further development of perovskite solar cells and commercial manufacturing.

  15. Elasticity of AlFeO3 and FeAlO3 perovskite and post-perovskite from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Caracas, R.

    2010-10-01

    We use state-of-the-art ab initio calculations based on the generalized gradient approximation of the density functional theory in the planar augmented wavefunction formalism to determine the elastic constants tensor of perovskite and post-perovskite with formulas AlFeO3 and FeAlO3 in which Fe or Al respectively occupy only octahedral sites, for the stable magnetic configurations. The phase transition between perovskite and post-perovskite is associated with a site exchange, during which Fe from the inter-octahedral site in perovskite moves into the octahedral site in post-perovskite. Following this transition path the elastic moduli show positive jumps, considerably larger than for MgSiO3. The phase transition is marked by a positive jump of 0.04 km/s (0.33%) in the velocity of the compressional waves and by a negative jump of -0.15 km/s (-1.87%) in shear wave velocity. We find that the effects of the Mg + Si <=> Al + Fe substitution on the seismic properties of MgSiO3 perovskite and post-perovskite depend on the crystallography of the substitution, namely the position the exchanged cations take in the structure.

  16. Research Update: Challenges for high-efficiency hybrid lead-halide perovskite LEDs and the path towards electrically pumped lasing

    NASA Astrophysics Data System (ADS)

    Li, Guangru; Price, Michael; Deschler, Felix

    2016-09-01

    Hybrid lead-halide perovskites have emerged as promising solution-processed semiconductor materials for thin-film optoelectronics. In this review, we discuss current challenges in perovskite LED performance, using thin-film and nano-crystalline perovskite as emitter layers, and look at device performance and stability. Fabrication of electrically pumped, optical-feedback devices with hybrid lead halide perovskites as gain medium is a future challenge, initiated by the demonstration of optically pumped lasing structures with low gain thresholds. We explain the material parameters affecting optical gain in perovskites and discuss the challenges towards electrically pumped perovskite lasers.

  17. Localized surface plasmon for enhanced lasing performance in solution-processed perovskites.

    PubMed

    Kao, Tsung Sheng; Hong, Kuo-Bin; Chou, Yu-Hsun; Huang, Jiong-Fu; Chen, Fang-Chung; Lu, Tien-Chang

    2016-09-01

    A promising method to promote the lasing performance of solution-processed organic-inorganic lead-halide perovskites has been demonstrated. With the adding Ag and PMMA thin films, the threshold excitation power for low-temperature lasing action in perovskites can be greatly reduced by over two orders of magnitude than that acquired in bare perovskite layers, ascribing to the strong exciton-plasmon coupling between the Ag and perovskite films. Also, the PMMA layer can be exploited to prevent the perovskite degradation from the hydrolysis in ambient environment, achieving long-lasting light-emitting performance. The advantages exhibited by the hybrid perovskite configuration would be very promising in making practical laser devices. PMID:27607673

  18. A two-step route to planar perovskite cells exhibiting reduced hysteresis

    SciTech Connect

    Ip, Alexander H.; Adachi, Michael M.; McDowell, Jeffrey J.; Xu, Jixian; Sargent, Edward H.; Quan, Li Na; Kim, Dong Ha

    2015-04-06

    A simple two-step method was used to produce efficient planar organolead halide perovskite solar cells. Films produced using solely iodine containing precursors resulted in poor morphology and failed devices, whereas addition of chlorine to the process greatly improved morphology and resulted in dense, uniform perovskite films. This process was used to produce perovskite solar cells with a fullerene-based passivation layer. The hysteresis effect, to which planar perovskite devices are otherwise prone, was greatly suppressed through the use of this interface modifier. The combined techniques resulted in perovskite solar cells having a stable efficiency exceeding 11%. This straightforward fabrication procedure holds promise in development of various optoelectronic applications of planar perovskite films.

  19. Enhancing Stability of Perovskite Solar Cells to Moisture by the Facile Hydrophobic Passivation.

    PubMed

    Hwang, Insung; Jeong, Inyoung; Lee, Jinwoo; Ko, Min Jae; Yong, Kijung

    2015-08-12

    In this study, a novel and facile passivation process for a perovskite solar cell is reported. Poor stability in ambient atmosphere, which is the most critical demerit of a perovskite solar cell, is overcome by a simple passivation process using a hydrophobic polymer layer. Teflon, the hydrophobic polymer, is deposited on the top of a perovskite solar cell by a spin-coating method. With the hydrophobic passivation, the perovskite solar cell shows negligible degradation after a 30 day storage in ambient atmosphere. Suppressed degradation of the perovskite film is proved in various ways: X-ray diffraction, light absorption spectrum, and quartz crystal microbalance. This simple but effective passivation process suggests new kind of approach to enhance stability of perovskite solar cells to moisture.

  20. Preface for Special Topic: Perovskite solar cells—A research update

    NASA Astrophysics Data System (ADS)

    Schmidt-Mende, Lukas; Herz, Laura M.

    2016-09-01

    Over the last few years, tremendous progress has been made in the research field of perovskite solar cells. Not only are record power conversion efficiencies now exceeding 20%, but our understanding about the different mechanisms leading to this extraordinary performance has improved phenomenally. The aim of this special issue is to review the current state-of-the-art understanding of perovskite solar cells. Most of the presented articles are research updates giving a succinct overview over different aspects concerning perovskite solar cells.

  1. Humidity versus photo-stability of metal halide perovskite films in a polymer matrix.

    PubMed

    Manshor, Nurul Ain; Wali, Qamar; Wong, Ka Kan; Muzakir, Saifful Kamaluddin; Fakharuddin, Azhar; Schmidt-Mende, Lukas; Jose, Rajan

    2016-08-21

    Despite the high efficiency of over 21% reported for emerging thin film perovskite solar cells, one of the key issues prior to their commercial deployment is to attain their long term stability under ambient and outdoor conditions. The instability in perovskite is widely conceived to be humidity induced due to the water solubility of its initial precursors, which leads to decomposition of the perovskite crystal structure; however, we note that humidity alone is not the major degradation factor and it is rather the photon dose in combination with humidity exposure that triggers the instability. In our experiment, which is designed to decouple the effect of humidity and light on perovskite degradation, we investigate the shelf-lifetime of CH3NH3PbI3 films in the dark and under illumination under high humidity conditions (Rel. H. > 70%). We note minor degradation in perovskite films stored in a humid dark environment whereas upon exposure to light, the films undergo drastic degradation, primarily owing to the reactive TiO2/perovskite interface and also the surface defects of TiO2. To enhance its air-stability, we incorporate CH3NH3PbI3 perovskite in a polymer (poly-vinylpyrrolidone, PVP) matrix which retained its optical and structural characteristics in the dark for ∼2000 h and ∼800 h in room light soaking, significantly higher than a pristine perovskite film, which degraded completely in 600 h in the dark and in less than 100 h when exposed to light. We attribute the superior stability of PVP incorporated perovskite films to the improved structural stability of CH3NH3PbI3 and also to the improved TiO2/perovskite interface upon incorporating a polymer matrix. Charge injection from the polymer embedded perovskite films has also been confirmed by fabricating solar cells using them, thereby providing a promising future research pathway for stable and efficient perovskite solar cells. PMID:27432518

  2. Greater functionality of bismuth and lead based perovskites

    NASA Astrophysics Data System (ADS)

    Suchomel, Matthew R.

    Novel Bi and Pb-based perovskite oxide chemistries have been investigated through bulk solid-state synthesis methods with a goal of increasing the dielectric, ferroelectric, and magnetic functionality of these materials. Although the Pb+2 and Bi+3 canons are chemically similar, Pb-based perovskites have historically received greater commercial and scientific attention. However, recent experimental and theoretical progress in studies of Bi containing systems has prompted a renewed interest in their potential. As such, particular focus was given to the Bi+3 containing systems in the current work. An investigation of the Bi-based perovskite compounds, emphasizing multiferroic BiFeO3 and related solid solutions, has explored the limitations of bulk synthesis methods for these systems. Numerous cation and anion substitution routes are experimentally studied and a comprehensive review of previous work examining B' site cation substitution in Bi-based perovskites is performed. This has resulted in an improved understanding of phase competition within these systems. These findings were used to engineer new chemistries, particularly those of mixed cation site occupancy, with improved perovskite stability. New low tolerance factor Bi-based perovskites with mixed B ' site cation chemistries have been used to induce morphotropic phase boundary (MPB) formation in solid solutions with PbTiO3. Moreover, a new qualitative relationship correlating the tolerance factor of Bi and Pb-based end members in PbTiO3 solid solutions to the compositional position of the system's MPB has been developed and experimentally validated. This relationship has been used to explore novel end members with very low tolerance factors including (Pb1/2Th1/2)ScO 3, for PbTiO3-based MPB solid solutions. A new category of Bi-based chemistries which enhance tetragonality and Curie temperature (Tc) in solid solutions with PbTiO3 has been identified. This effect is particularly dramatic for the (x)PbTiO 3

  3. Cooperative tin oxide fullerene electron selective layers for high-performance planar perovskite solar cells

    SciTech Connect

    Ke, Weijun; Zhao, Dewei; Xiao, Chuanxiao; Wang, Changlei; Cimaroli, Alexander J.; Grice, Corey R.; Yang, Mengjin; Li, Zhen; Jiang, Chun-Sheng; Al-Jassim, Mowafak; Zhu, Kai; Kanatzidis, Mercouri G.; Fang, Guojia; Yan, Yanfa

    2016-01-01

    Both tin oxide (SnO2) and fullerenes have been reported as electron selective layers (ESLs) for producing efficient lead halide perovskite solar cells. Here, we report that SnO2 and fullerenes can work cooperatively to further boost the performance of perovskite solar cells. We find that fullerenes can be redissolved during perovskite deposition, allowing ultra-thin fullerenes to be retained at the interface and some dissolved fullerenes infiltrate into perovskite grain boundaries. The SnO2 layer blocks holes effectively; whereas, the fullerenes promote electron transfer and passivate both the SnO2/perovskite interface and perovskite grain boundaries. With careful device optimization, the best-performing planar perovskite solar cell using a fullerene passivated SnO2 ESL has achieved a steady-state efficiency of 17.75% and a power conversion efficiency of 19.12% with an open circuit voltage of 1.12 V, a short-circuit current density of 22.61 mA cm-2, and a fill factor of 75.8% when measured under reverse voltage scanning. We find that the partial dissolving of fullerenes during perovskite deposition is the key for fabricating high-performance perovskite solar cells based on metal oxide/fullerene ESLs.

  4. Investigating the Effect of Pyridine Vapor Treatment on Perovskite Solar Cells

    SciTech Connect

    Ong, Alison

    2015-08-20

    Perovskite photovoltaics have recently come to prominence as a viable alternative to crystalline silicon based solar cells. In an effort to create consistent and high-quality films, we studied the effect of various annealing conditions as well as the effect of pyridine vapor treatment on mixed halide methylammonium lead perovskite films. Of six conditions tested, we found that annealing at 100°C for 90 minutes followed by 120°C for 15 minutes resulted in the purest perovskite. Perovskite films made using that condition were treated with pyridine for various amounts of time, and the effects on perovskite microstructure were studied using x-ray diffraction, UV-Vis spectroscopy, and time-resolved photoluminescence lifetime analysis (TRPL). A previous study found that pyridine vapor caused perovskite films to have higher photoluminescence intensity and become more homogenous. In this study we found that the effects of pyridine are more complex: while films appeared to become more homogenous, a decrease in bulk photoluminescence lifetime was observed. In addition, the perovskite bandgap appeared to decrease with increased pyridine treatment time. Finally, X-ray diffraction showed that pyridine vapor treatment increased the perovskite (110) peak intensity but also often gave rise to new unidentified peaks, suggesting the formation of a foreign species. It was observed that the intensity of this unknown species had an inverse correlation with the increase in perovskite peak intensity, and also seemed to be correlated with the decrease in TRPL lifetime.

  5. The influence of morphology on charge transport/recombination dynamics in planar perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Yu, Man; Wang, Yi; Wang, Hao-Yi; Han, Jun; Qin, Yujun; Zhang, Jian-Ping; Ai, Xi-Cheng

    2016-10-01

    The photovoltaic performance of planar perovskite solar cell is significantly influenced by the morphology of perovskite film. In this work, five kinds of devices with different perovskite film morphologies were prepared by varying the concentration of CH3NH3Cl in precursor solutions. We found that best morphology of perovskite film results in the excellent photovoltaic performance with an average efficiency of 15.52% and a champion efficiency of 16.38%. Transient photovoltage and photocurrent measurements are performed to elucidate the mechanism of photoelectric conversion processes, which shows that the charge recombination is effectively suppressed and the charge transport is obviously promoted by optimized morphology.

  6. Pyrophanite pseudomorphs after perovskite in Perkupa serpentinites (Hungary): a microtextural study and geological implications

    NASA Astrophysics Data System (ADS)

    Zajzon, N.; Váczi, T.; Fehér, B.; Takács, Á.; Szakáll, S.; Weiszburg, T. G.

    2013-09-01

    Pyrophanite in serpentinite at Perkupa (Hungary) is described in detail for the first time as a replacement product of perovskite. It occurs as a 20- to 30-μm-wide rim, mantling a remnant core composed of perovskite or its alteration products. The pyrophanite rim consists of an inner zone, representing a pseudomorph after perovskite, and an outer overgrowth zone. Raman mapping and electron backscatter diffraction data show that the pyrophanite rims typically represent single crystals rather than being composed of multiple domains in different crystallographic orientations. Perovskite occurs exclusively in the core of pyrophanite and was identified as the orthorhombic CaTiO3 phase, based on Raman spectra. Heterogeneous, polyphase mineral cores, consisting of calcite, anatase and/or brookite, kassite, and Mn-bearing kassite, in some cases in association with relict perovskite, are typical in the larger pyrophanite-rimmed grains. The crystallographically coherent pyrophanite rims could have formed through a process where the precursor perovskite crystal acted as a structural template for the newly forming phase, that is, by interface-coupled dissolution reprecipitation during serpentinization of the precursor rock. This alteration of perovskite to pyrophanite was not complete, resulting in the presence of perovskite fragments enclosed in pyrophanite. During the metamorphic evolution of the rock, some of the remnant perovskite cores further altered to TiO2 polymorphs (anatase and brookite) and calcite, via transitional alteration products.

  7. Reversible Structural Swell-Shrink and Recoverable Optical Properties in Hybrid Inorganic-Organic Perovskite.

    PubMed

    Zhang, Yupeng; Wang, Yusheng; Xu, Zai-Quan; Liu, Jingying; Song, Jingchao; Xue, Yunzhou; Wang, Ziyu; Zheng, Jialu; Jiang, Liangcong; Zheng, Changxi; Huang, Fuzhi; Sun, Baoquan; Cheng, Yi-Bing; Bao, Qiaoliang

    2016-07-26

    Ion migration in hybrid organic-inorganic perovskites has been suggested to be an important factor for many unusual behaviors in perovskite-based optoelectronics, such as current-voltage hysteresis, low-frequency giant dielectric response, and the switchable photovoltaic effect. However, the role played by ion migration in the photoelectric conversion process of perovskites is still unclear. In this work, we provide microscale insights into the influence of ion migration on the microstructure, stability, and light-matter interaction in perovskite micro/nanowires by using spatially resolved optical characterization techniques. We observed that ion migration, especially the migration of MA(+) ions, will induce a reversible structural swell-shrink in perovskites and recoverably affect the reflective index, quantum efficiency, light-harvesting, and photoelectric properties. The maximum ion migration quantity in perovskites was as high as approximately 30%, resulting in lattice swell or shrink of approximately 4.4%. Meanwhile, the evidence shows that ion migration in perovskites could gradually accelerate the aging of perovskites because of lattice distortion in the reversible structural swell-shrink process. Knowledge regarding reversible structural swell-shrink and recoverable optical properties may shed light on the development of optoelectronic and converse piezoelectric devices based on perovskites.

  8. Research Update: Physical and electrical characteristics of lead halide perovskites for solar cell applications

    NASA Astrophysics Data System (ADS)

    Bretschneider, Simon A.; Weickert, Jonas; Dorman, James A.; Schmidt-Mende, Lukas

    2014-04-01

    The field of thin-film photovoltaics has been recently enriched by the introduction of lead halide perovskites as absorber materials, which allow low-cost synthesis of solar cells with efficiencies exceeding 16%. The exact impact of the perovskite crystal structure and composition on the optoelectronic properties of the material are not fully understood. Our progress report highlights the knowledge gained about lead halide perovskites with a focus on physical and optoelectronic properties. We discuss the crystal and band structure of perovskite materials currently implemented in solar cells and the impact of the crystal properties on ferroelectricity, ambipolarity, and the properties of excitons.

  9. Efficient methylammonium lead iodide perovskite solar cells with active layers from 300 to 900 nm

    SciTech Connect

    Momblona, C.; Malinkiewicz, O.; Soriano, A.; Gil-Escrig, L.; Bandiello, E.; Scheepers, M.; Bolink, H. J.; Edri, E.

    2014-08-01

    Efficient methylammonium lead iodide perovskite-based solar cells have been prepared in which the perovskite layer is sandwiched in between two organic charge transporting layers that block holes and electrons, respectively. This configuration leads to stable and reproducible devices that do not suffer from strong hysteresis effects and when optimized lead to efficiencies close to 15%. The perovskite layer is formed by using a dual-source thermal evaporation method, whereas the organic layers are processed from solution. The dual-source thermal evaporation method leads to smooth films and allows for high precision thickness variations. Devices were prepared with perovskite layer thicknesses ranging from 160 to 900 nm. The short-circuit current observed for these devices increased with increasing perovskite layer thickness. The main parameter that decreases with increasing perovskite layer thickness is the fill factor and as a result optimum device performance is obtained for perovskite layer thickness around 300 nm. However, here we demonstrate that with a slightly oxidized electron blocking layer the fill factor for the solar cells with a perovskite layer thickness of 900 nm increases to the same values as for the devices with thin perovskite layers. As a result the power conversion efficiencies for the cells with 300 and 900 nm are very similar, 12.7% and 12%, respectively.

  10. High-Efficiency Flexible Solar Cells Based on Organometal Halide Perovskites.

    PubMed

    Wang, Yuming; Bai, Sai; Cheng, Lu; Wang, Nana; Wang, Jianpu; Gao, Feng; Huang, Wei

    2016-06-01

    Flexible and light-weight solar cells are important because they not only supply power to wearable and portable devices, but also reduce the transportation and installation cost of solar panels. High-efficiency organometal halide perovskite solar cells can be fabricated by a low-temperature solution process, and hence are promising for flexible-solar-cell applications. Here, the development of perovskite solar cells is briefly discussed, followed by the merits of organometal halide perovskites as promising candidates as high-efficiency, flexible, and light-weight photovoltaic materials. Afterward, recent developments of flexible solar cells based on perovskites are reviewed. PMID:26669326

  11. Reversible Structural Swell-Shrink and Recoverable Optical Properties in Hybrid Inorganic-Organic Perovskite.

    PubMed

    Zhang, Yupeng; Wang, Yusheng; Xu, Zai-Quan; Liu, Jingying; Song, Jingchao; Xue, Yunzhou; Wang, Ziyu; Zheng, Jialu; Jiang, Liangcong; Zheng, Changxi; Huang, Fuzhi; Sun, Baoquan; Cheng, Yi-Bing; Bao, Qiaoliang

    2016-07-26

    Ion migration in hybrid organic-inorganic perovskites has been suggested to be an important factor for many unusual behaviors in perovskite-based optoelectronics, such as current-voltage hysteresis, low-frequency giant dielectric response, and the switchable photovoltaic effect. However, the role played by ion migration in the photoelectric conversion process of perovskites is still unclear. In this work, we provide microscale insights into the influence of ion migration on the microstructure, stability, and light-matter interaction in perovskite micro/nanowires by using spatially resolved optical characterization techniques. We observed that ion migration, especially the migration of MA(+) ions, will induce a reversible structural swell-shrink in perovskites and recoverably affect the reflective index, quantum efficiency, light-harvesting, and photoelectric properties. The maximum ion migration quantity in perovskites was as high as approximately 30%, resulting in lattice swell or shrink of approximately 4.4%. Meanwhile, the evidence shows that ion migration in perovskites could gradually accelerate the aging of perovskites because of lattice distortion in the reversible structural swell-shrink process. Knowledge regarding reversible structural swell-shrink and recoverable optical properties may shed light on the development of optoelectronic and converse piezoelectric devices based on perovskites. PMID:27386731

  12. Investigating the Effect of Pyridine Vapor Treatment on Perovskite Solar Cells - Oral Presentation

    SciTech Connect

    Ong, Alison J.

    2015-08-25

    Perovskite photovoltaics have recently come to prominence as a viable alternative to crystalline silicon based solar cells. In an effort to create consistent and high-quality films, we studied the effect of various annealing conditions as well as the effect of pyridine vapor treatment on mixed halide methylammonium lead perovskite films. Of six conditions tested, we found that annealing at 100 degree Celsius for 90 minutes followed by 120 degree Celsius for 15 minutes resulted in the purest perovskite. Perovskite films made using that condition were treated with pyridine for various amounts of time, and the effects on perovskite microstructure were studied using x-ray diffraction, UV-Vis spectroscopy, and time-resolved photoluminescence lifetime analysis (TRPL). A previous study found that pyridine vapor caused perovskite films to have higher photoluminescence intensity and become more homogenous. In this study we found that the effects of pyridine are more complex: while films appeared to become more homogenous, a decrease in bulkphotoluminescence lifetime was observed. In addition, the perovskite bandgap appeared to decrease with increased pyridine treatment time. Finally, X-ray diffraction showed that pyridine vapor treatment increased the perovskite (110) peak intensity but also often gave rise to new unidentified peaks, suggesting the formation of a foreign species. It was observed that the intensity of this unknown species had an inverse correlation with the increase in perovskite peak intensity, and also seemed to be correlated with the decrease in TRPL lifetime.

  13. Life Cycle Assessment of Titania Perovskite Solar Cell Technology for Sustainable Design and Manufacturing.

    PubMed

    Zhang, Jingyi; Gao, Xianfeng; Deng, Yelin; Li, Bingbing; Yuan, Chris

    2015-11-01

    Perovskite solar cells have attracted enormous attention in recent years due to their low cost and superior technical performance. However, the use of toxic metals, such as lead, in the perovskite dye and toxic chemicals in perovskite solar cell manufacturing causes grave concerns for its environmental performance. To understand and facilitate the sustainable development of perovskite solar cell technology from its design to manufacturing, a comprehensive environmental impact assessment has been conducted on titanium dioxide nanotube based perovskite solar cells by using an attributional life cycle assessment approach, from cradle to gate, with manufacturing data from our laboratory-scale experiments and upstream data collected from professional databases and the literature. The results indicate that the perovskite dye is the primary source of environmental impact, associated with 64.77% total embodied energy and 31.38% embodied materials consumption, contributing to more than 50% of the life cycle impact in almost all impact categories, although lead used in the perovskite dye only contributes to about 1.14% of the human toxicity potential. A comparison of perovskite solar cells with commercial silicon and cadmium-tellurium solar cells reveals that perovskite solar cells could be a promising alternative technology for future large-scale industrial applications.

  14. High-Efficiency Flexible Solar Cells Based on Organometal Halide Perovskites.

    PubMed

    Wang, Yuming; Bai, Sai; Cheng, Lu; Wang, Nana; Wang, Jianpu; Gao, Feng; Huang, Wei

    2016-06-01

    Flexible and light-weight solar cells are important because they not only supply power to wearable and portable devices, but also reduce the transportation and installation cost of solar panels. High-efficiency organometal halide perovskite solar cells can be fabricated by a low-temperature solution process, and hence are promising for flexible-solar-cell applications. Here, the development of perovskite solar cells is briefly discussed, followed by the merits of organometal halide perovskites as promising candidates as high-efficiency, flexible, and light-weight photovoltaic materials. Afterward, recent developments of flexible solar cells based on perovskites are reviewed.

  15. Life Cycle Assessment of Titania Perovskite Solar Cell Technology for Sustainable Design and Manufacturing.

    PubMed

    Zhang, Jingyi; Gao, Xianfeng; Deng, Yelin; Li, Bingbing; Yuan, Chris

    2015-11-01

    Perovskite solar cells have attracted enormous attention in recent years due to their low cost and superior technical performance. However, the use of toxic metals, such as lead, in the perovskite dye and toxic chemicals in perovskite solar cell manufacturing causes grave concerns for its environmental performance. To understand and facilitate the sustainable development of perovskite solar cell technology from its design to manufacturing, a comprehensive environmental impact assessment has been conducted on titanium dioxide nanotube based perovskite solar cells by using an attributional life cycle assessment approach, from cradle to gate, with manufacturing data from our laboratory-scale experiments and upstream data collected from professional databases and the literature. The results indicate that the perovskite dye is the primary source of environmental impact, associated with 64.77% total embodied energy and 31.38% embodied materials consumption, contributing to more than 50% of the life cycle impact in almost all impact categories, although lead used in the perovskite dye only contributes to about 1.14% of the human toxicity potential. A comparison of perovskite solar cells with commercial silicon and cadmium-tellurium solar cells reveals that perovskite solar cells could be a promising alternative technology for future large-scale industrial applications. PMID:26489525

  16. Growing perovskite into polymers for easy-processable optoelectronic devices.

    PubMed

    Masi, Sofia; Colella, Silvia; Listorti, Andrea; Roiati, Vittoria; Liscio, Andrea; Palermo, Vincenzo; Rizzo, Aurora; Gigli, Giuseppe

    2015-01-12

    Here we conceive an innovative nanocomposite to endow hybrid perovskites with the easy processability of polymers, providing a tool to control film quality and material crystallinity. We verify that the employed semiconducting polymer, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), controls the self-assembly of CH₃NH₃PbI₃ (MAPbI₃) crystalline domains and favors the deposition of a very smooth and homogenous layer in one straightforward step. This idea offers a new paradigm for the implementation of polymer/perovskite nanocomposites towards versatile optoelectronic devices combined with the feasibility of mass production. As a proof-of-concept we propose the application of such nanocomposite in polymer solar cell architecture, demonstrating a power conversion efficiency up to 3%, to date the highest reported for MEH-PPV. On-purpose designed polymers are expected to suit the nanocomposite properties for the integration in diverse optoelectronic devices via facile processing condition.

  17. Nonlocal quartic interactions and universality classes in perovskite manganites.

    PubMed

    Singh, Rohit; Dutta, Kishore; Nandy, Malay K

    2015-07-01

    A modified Ginzburg-Landau model with a screened nonlocal interaction in the quartic term is treated via Wilson's renormalization-group scheme at one-loop order to explore the critical behavior of the paramagnetic-to-ferromagnetic phase transition in perovskite manganites. We find the Fisher exponent η to be O(ε) and the correlation exponent to be ν=1/2+O(ε) through epsilon expansion in the parameter ε=d(c)-d, where d is the space dimension, d(c)=4+2σ is the upper critical dimension, and σ is a parameter coming from the nonlocal interaction in the model Hamiltonian. The ensuing critical exponents in three dimensions for different values of σ compare well with various existing experimental estimates for perovskite manganites with various doping levels. This suggests that the nonlocal model Hamiltonian contains a wide variety of such universality classes. PMID:26274140

  18. Growing perovskite into polymers for easy-processable optoelectronic devices.

    PubMed

    Masi, Sofia; Colella, Silvia; Listorti, Andrea; Roiati, Vittoria; Liscio, Andrea; Palermo, Vincenzo; Rizzo, Aurora; Gigli, Giuseppe

    2015-01-01

    Here we conceive an innovative nanocomposite to endow hybrid perovskites with the easy processability of polymers, providing a tool to control film quality and material crystallinity. We verify that the employed semiconducting polymer, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), controls the self-assembly of CH₃NH₃PbI₃ (MAPbI₃) crystalline domains and favors the deposition of a very smooth and homogenous layer in one straightforward step. This idea offers a new paradigm for the implementation of polymer/perovskite nanocomposites towards versatile optoelectronic devices combined with the feasibility of mass production. As a proof-of-concept we propose the application of such nanocomposite in polymer solar cell architecture, demonstrating a power conversion efficiency up to 3%, to date the highest reported for MEH-PPV. On-purpose designed polymers are expected to suit the nanocomposite properties for the integration in diverse optoelectronic devices via facile processing condition. PMID:25579988

  19. Photoinduced surface voltage mapping study for large perovskite single crystals

    NASA Astrophysics Data System (ADS)

    Liu, Xiaojing; Liu, Yucheng; Gao, Fei; Yang, Zhou; Liu, Shengzhong Frank

    2016-05-01

    Using a series of illumination sources, including white light (tungsten-halogen lamp), 445-nm, 532-nm, 635-nm, and 730-nm lasers, the surface photovoltage (SPV) images were mapped for centimeter-sized CH3NH3PbX3 (X = Cl, Br, I) perovskite single crystals using Kelvin probe force microscopy. The significant SPV signals were observed to be wavelength-dependent. We attribute the appreciable SPV to the built-in electric field in the space charge region. This study shines light into the understanding of photoinduced charge generation and separation processes at nanoscale to help advance the development of perovskite solar cells, optoelectronics, laser, photodetector, and light-emitting diode (LED).

  20. Origin of J-V Hysteresis in Perovskite Solar Cells.

    PubMed

    Chen, Bo; Yang, Mengjin; Priya, Shashank; Zhu, Kai

    2016-03-01

    High-performance perovskite solar cells (PSCs) based on organometal halide perovskite have emerged in the past five years as excellent devices for harvesting solar energy. Some remaining challenges should be resolved to continue the momentum in their development. The photocurrent density-voltage (J-V) responses of the PSCs demonstrate anomalous dependence on the voltage scan direction/rate/range, voltage conditioning history, and device configuration. The hysteretic J-V behavior presents a challenge for determining the accurate power conversion efficiency of the PSCs. Here, we review the recent progress on the investigation of the origin(s) of J-V hysteresis behavior in PSCs. We discuss the impact of slow transient capacitive current, trapping and detrapping process, ion migrations, and ferroelectric polarization on the hysteresis behavior. The remaining issues and future research required toward the understanding of J-V hysteresis in PSCs will also be discussed.

  1. Extraction of exchange parameters in transition-metal perovskites

    DOE PAGESBeta

    Furrer, A.; Podlesnyak, A.; Krämer, K. W.

    2015-09-15

    When extracting exchange parameters from measured spin-wave dispersion relations there are severe limitations particularly for magnetic compounds such as the transition-metal perovskites, where the nearest-neighbor exchange parameter usually dominates the couplings between the further-distant-neighbor spins. Very precise exchange parameters beyond the nearest-neighbor spins can be obtained by neutron spectroscopic investigations of the magnetic excitation spectra of isolated multimers in magnetically diluted compounds. Moreover, this is exemplified for manganese trimers in the mixed three-and two-dimensional perovskite compounds KMnxZn1-xF3 and K2MnxZn1-xF4, respectively. We show that the small exchange couplings between the second-nearest-neighbor and the third-nearest-neighbor spins can be determined unambiguously and withmore » equal precision as the dominating nearest-neighbor exchange coupling.« less

  2. Bandgap calculations and trends of organometal halide perovskites

    SciTech Connect

    Castelli, Ivano E. Thygesen, Kristian S.; Jacobsen, Karsten W.; García-Lastra, Juan María

    2014-08-01

    Energy production from the Sun requires a stable efficient light absorber. Promising candidates in this respect are organometal perovskites (ABX{sub 3}), which have been intensely investigated during the last years. Here, we have performed electronic structure calculations of 240 perovskites composed of Cs, CH{sub 3}NH{sub 3}, and HC(NH{sub 2}){sub 2} as A-cation, Sn and Pb as B-ion, and a combination of Cl, Br, and I as anions. The calculated gaps span over a region from 0.5 to 5.0 eV. In addition, the trends over bandgaps have been investigated: the bandgap increases with an increase of the electronegativities of the constituent species, while it reduces with an increase of the lattice constants of the system.

  3. Method for fabricating high aspect ratio structures in perovskite material

    DOEpatents

    Karapetrov, Goran T.; Kwok, Wai-Kwong; Crabtree, George W.; Iavarone, Maria

    2003-10-28

    A method of fabricating high aspect ratio ceramic structures in which a selected portion of perovskite or perovskite-like crystalline material is exposed to a high energy ion beam for a time sufficient to cause the crystalline material contacted by the ion beam to have substantially parallel columnar defects. Then selected portions of the material having substantially parallel columnar defects are etched leaving material with and without substantially parallel columnar defects in a predetermined shape having high aspect ratios of not less than 2 to 1. Etching is accomplished by optical or PMMA lithography. There is also disclosed a structure of a ceramic which is superconducting at a temperature in the range of from about 10.degree. K. to about 90.degree. K. with substantially parallel columnar defects in which the smallest lateral dimension of the structure is less than about 5 microns, and the thickness of the structure is greater than 2 times the smallest lateral dimension of the structure.

  4. Electronic structure of the superconducting layered perovskite niobate

    NASA Astrophysics Data System (ADS)

    Hase, Izumi; Nishihara, Yoshikazu

    1998-07-01

    The electronic energy-band structure for RbLaNb2O7, which is closely related to the layered perovskite niobate superconducting KCa2Nb3O10 and metallic KLaNb2O7 with Li intercalation, has been calculated by using the scalar-relativistic full-potential linearized augmented-plane-wave method within the local-density approximation. The result of the calculation shows that this compound is a band insulator with a small gap, and its conduction band is a typical two-dimensional one and the valence band is rather three dimensional. We can conclude that the layered perovskite niobate KCa2Nb3O10 is a band insulator that can be superconducting with electron doping, and have the highly two-dimensional electronic structure.

  5. 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

  6. Colloidal Quantum Dot Photovoltaics Enhanced by Perovskite Shelling.

    PubMed

    Yang, Zhenyu; Janmohamed, Alyf; Lan, Xinzheng; García de Arquer, F Pelayo; Voznyy, Oleksandr; Yassitepe, Emre; Kim, Gi-Hwan; Ning, Zhijun; Gong, Xiwen; Comin, Riccardo; Sargent, Edward H

    2015-11-11

    Solution-processed quantum dots are a promising material for large-scale, low-cost solar cell applications. New device architectures and improved passivation have been instrumental in increasing the performance of quantum dot photovoltaic devices. Here we report photovoltaic devices based on inks of quantum dot on which we grow thin perovskite shells in solid-state films. Passivation using the perovskite was achieved using a facile solution ligand exchange followed by postannealing. The resulting hybrid nanostructure created a more intrinsic CQD film, which, when incorporated into a photovoltaic device with graded bandstructure, achieved a record solar cell performance for single-step-deposited CQD films, exhibiting an AM1.5 solar power conversion efficiency of 8.95%.

  7. Theoretical insights into hybrid perovskites for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Even, Jacky; Boyer-Richard, Soline; Carignano, Marcelo; Pedesseau, Laurent; Jancu, Jean-Marc; Katan, Claudine

    2016-03-01

    In this paper, we examine recent theoretical investigations on 3D hybrid perovskites (HOP) that combine concepts developed for classical bulk solid-state physics and empirical simulations of their optoelectronic properties. In fact, the complexity of HOP calls for a coherent global view that combines usually disconnected concepts. For the pseudocubic high temperature reference perovskite structure that plays a central role for 3D HOP, we introduce a new tight-binding Hamiltonian, which specifically includes spin-orbit coupling. The resultant electronic band structure is compared to that obtained using state of the art density functional theory (DFT). Next, recent experimental investigations of excitonic properties in HOP will be revisited within the scope of theoretical concepts already well implemented in the field of conventional semiconductors. Last, possible plastic crystal and orientational glass behaviors of HOP will be discussed, building on Car-Parrinello molecular dynamics simulations.

  8. Origin of J-V Hysteresis in Perovskite Solar Cells.

    PubMed

    Chen, Bo; Yang, Mengjin; Priya, Shashank; Zhu, Kai

    2016-03-01

    High-performance perovskite solar cells (PSCs) based on organometal halide perovskite have emerged in the past five years as excellent devices for harvesting solar energy. Some remaining challenges should be resolved to continue the momentum in their development. The photocurrent density-voltage (J-V) responses of the PSCs demonstrate anomalous dependence on the voltage scan direction/rate/range, voltage conditioning history, and device configuration. The hysteretic J-V behavior presents a challenge for determining the accurate power conversion efficiency of the PSCs. Here, we review the recent progress on the investigation of the origin(s) of J-V hysteresis behavior in PSCs. We discuss the impact of slow transient capacitive current, trapping and detrapping process, ion migrations, and ferroelectric polarization on the hysteresis behavior. The remaining issues and future research required toward the understanding of J-V hysteresis in PSCs will also be discussed. PMID:26886052

  9. Perovskite electrodes and method of making the same

    DOEpatents

    Seabaugh, Matthew M.; Swartz, Scott L.

    2009-09-22

    The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

  10. Photovoltaic switching mechanism in lateral structure hybrid perovskite solar cells

    DOE PAGESBeta

    Yuan, Yongbo; Chae, Jungseok; Shao, Yuchuan; Wang, Qi; Xiao, Zhengguo; Centrone, Andrea; Huang, Jinsong

    2015-06-05

    In this study, long range electromigration of methylammonium ions (MA+) in methyl ammonium lead tri-iodide (MAPbI3) film is observed directly using the photo­thermal induced resonance technique. The electromigration of MA+ leads to the formation of a lateral p-i-n structure, which is the origin of the switchable photovoltaic effect in MAPbI3 perovskite devices.

  11. Perovskite electrodes and method of making the same

    SciTech Connect

    Seabaugh, Matthew M.; Swartz, Scott L.

    2005-09-20

    The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

  12. Simple characterization of electronic processes in perovskite photovoltaic cells

    SciTech Connect

    Miyano, Kenjiro Yanagida, Masatoshi; Tripathi, Neeti; Shirai, Yasuhiro

    2015-03-02

    Electronic properties of perovskite lead-halide photovoltaic cells have been studied. The dc current/voltage characteristics were found to be well fitted by a standard diode equation under optical excitation and in the dark, while the impedance spectroscopy revealed a pronounced slow process under light illumination, which is absent in the dark. A simple model is proposed, which can explain all aspects of the observed behavior quantitatively and consistently.

  13. Photovoltaic switching mechanism in lateral structure hybrid perovskite solar cells

    SciTech Connect

    Yuan, Yongbo; Chae, Jungseok; Shao, Yuchuan; Wang, Qi; Xiao, Zhengguo; Centrone, Andrea; Huang, Jinsong

    2015-06-05

    In this study, long range electromigration of methylammonium ions (MA+) in methyl ammonium lead tri-iodide (MAPbI3) film is observed directly using the photo­thermal induced resonance technique. The electromigration of MA+ leads to the formation of a lateral p-i-n structure, which is the origin of the switchable photovoltaic effect in MAPbI3 perovskite devices.

  14. Super-ion inspired colorful hybrid perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Fang, Hong; Jena, Puru

    Organic-inorganic hybrid perovskites, with the general formula AMX3 (A =cation; M =metal; X =halogen), have emerged as a new generation of efficient yet inexpensive photovoltaic cells. These materials show record high conversion efficiency as solar cells and have excellent light-emission properties that can also be used in other optoelectronic devices. They can be processed easily from solution with optic band gaps, tunable from visible to infrared regions and are considered to be ``the next big thing in photovoltaics''. However, several important issues such as the relationship between their photoexcitation properties and the chemical structures, their stability under ambient conditions, as well as the possibility to invent their environment-friendly analogues remain unsolved. In this work, our aim is not only to gain a fundamental understanding of the structure-property relationship of organic-inorganic hybrid perovskites, but also to rationally design a new class of hybrid perovskites that have desired electronic band gaps for solar cell applications. This is accomplished by using super-ions that can mimic the properties of elementary alkali and halogen ions as building blocks. These super-ions include superalkalis - CH3NH3+,HC(NH2) 2 + , and Li3O+ as cations and hyperhalogens - Ge(BH4) 3 - and Sn(BH4) 3 - as anions. The results are compared with perovskites composed of GeCl3-,GeBr3-,GeI3-,SnCl3-,SnBr3-,and SnI3-superhalogen anions. We develop a strategy to assemble these super-ions to form environment-friendly solar cells with adjustable band gaps (covering the visible range and beyond) and with improved resistance to moisture.

  15. Ionic transport in hybrid lead iodide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Eames, Christopher; Frost, Jarvist M.; Barnes, Piers R. F.; O'Regan, Brian C.; Walsh, Aron; Islam, M. Saiful

    2015-06-01

    Solar cells based on organic-inorganic halide perovskites have recently shown rapidly rising power conversion efficiencies, but exhibit unusual behaviour such as current-voltage hysteresis and a low-frequency giant dielectric response. Ionic transport has been suggested to be an important factor contributing to these effects; however, the chemical origin of this transport and the mobile species are unclear. Here, the activation energies for ionic migration in methylammonium lead iodide (CH3NH3PbI3) are derived from first principles, and are compared with kinetic data extracted from the current-voltage response of a perovskite-based solar cell. We identify the microscopic transport mechanisms, and find facile vacancy-assisted migration of iodide ions with an activation energy of 0.6 eV, in good agreement with the kinetic measurements. The results of this combined computational and experimental study suggest that hybrid halide perovskites are mixed ionic-electronic conductors, a finding that has major implications for solar cell device architectures.

  16. Magnetic domain wall induced ferroelectricity in double perovskites

    SciTech Connect

    Zhou, Hai Yang; Zhao, Hong Jian E-mail: xmchen59@zju.edu.cn; Chen, Xiang Ming E-mail: xmchen59@zju.edu.cn; Zhang, Wen Qing

    2015-04-13

    Recently, a magnetically induced ferroelectricity occurring at magnetic domain wall of double perovskite Lu{sub 2}CoMnO{sub 6} has been reported experimentally. However, there exists a conflict whether the electric polarization is along b or c direction. Here, by first-principles calculations, we show that the magnetic domain wall (with ↑↑↓↓ spin configuration) can lead to the ferroelectric displacements of R{sup 3+}, Ni{sup 2+}, Mn{sup 4+}, and O{sup 2−} ions in double perovskites R{sub 2}NiMnO{sub 6} (R = rare earth ion) via exchange striction. The resulted electric polarization is along b direction with the P2{sub 1} symmetry. We further reveal the origin of the ferroelectric displacements as that: (1) on a structural point of view, such displacements make the two out-of-plane Ni-O-Mn bond angles as well as Ni-Mn distance unequal, and (2) on an energy point of view, such displacements weaken the out-of-plane Ni-Mn super-exchange interaction obviously. Finally, our calculations show that such a kind of ferroelectric order is general in ferromagnetic double perovskites.

  17. Ionic transport in hybrid lead iodide perovskite solar cells

    PubMed Central

    Eames, Christopher; Frost, Jarvist M.; Barnes, Piers R. F.; O'Regan, Brian C.; Walsh, Aron; Islam, M. Saiful

    2015-01-01

    Solar cells based on organic–inorganic halide perovskites have recently shown rapidly rising power conversion efficiencies, but exhibit unusual behaviour such as current–voltage hysteresis and a low-frequency giant dielectric response. Ionic transport has been suggested to be an important factor contributing to these effects; however, the chemical origin of this transport and the mobile species are unclear. Here, the activation energies for ionic migration in methylammonium lead iodide (CH3NH3PbI3) are derived from first principles, and are compared with kinetic data extracted from the current–voltage response of a perovskite-based solar cell. We identify the microscopic transport mechanisms, and find facile vacancy-assisted migration of iodide ions with an activation energy of 0.6 eV, in good agreement with the kinetic measurements. The results of this combined computational and experimental study suggest that hybrid halide perovskites are mixed ionic–electronic conductors, a finding that has major implications for solar cell device architectures. PMID:26105623

  18. Laser cooling of organic-inorganic lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Ha, Son-Tung; Shen, Chao; Zhang, Jun; Xiong, Qihua

    2016-02-01

    Optical irradiation with suitable energy can cool solids, a phenomenon known as optical refrigeration, first proposed in 1929 and experimentally achieved in ytterbium-doped glasses in 1995. Since then, considerable progress has been made in various rare earth element-doped materials, with a recent record of cooling to 91 K directly from ambient temperatures. For practical use and to suit future applications of optical refrigeration, the discovery of materials with facile and scalable synthesis and high cooling power density will be required. Herein we present the realization of a net cooling of 23.0 K in micrometre-thick 3D CH3NH3PbI3 (MAPbI3) and 58.7 K in exfoliated 2D (C6H5C2H4NH3)2PbI4 (PhEPbI4) perovskite crystals directly from room temperature. We found that the perovskite crystals exhibit strong photoluminescence upconversion and near unity external quantum efficiency, properties that are responsible for the realization of net laser cooling. Our findings indicate that solution-processed perovskite thin films may be a highly suitable candidate for constructing integrated optical cooler devices.

  19. Recycling Perovskite Solar Cells To Avoid Lead Waste.

    PubMed

    Binek, Andreas; Petrus, Michiel L; Huber, Niklas; Bristow, Helen; Hu, Yinghong; Bein, Thomas; Docampo, Pablo

    2016-05-25

    Methylammonium lead iodide (MAPbI3) perovskite based solar cells have recently emerged as a serious competitor for large scale and low-cost photovoltaic technologies. However, since these solar cells contain toxic lead, a sustainable procedure for handling the cells after their operational lifetime is required to prevent exposure of the environment to lead and to comply with international electronic waste disposal regulations. Herein, we report a procedure to remove every layer of the solar cells separately, which gives the possibility to selectively isolate the different materials. Besides isolating the toxic lead iodide in high yield, we show that the PbI2 can be reused for the preparation of new solar cells with comparable performance and in this way avoid lead waste. Furthermore, we show that the most expensive part of the solar cell, the conductive glass (FTO), can be reused several times without any reduction in the performance of the devices. With our simple recycling procedure, we address both the risk of contamination and the waste disposal of perovskite based solar cells while further reducing the cost of the system. This brings perovskite solar cells one step closer to their introduction into commercial systems. PMID:27149009

  20. Coloring Semitransparent Perovskite Solar Cells via Dielectric Mirrors.

    PubMed

    Ramírez Quiroz, César Omar; Bronnbauer, Carina; Levchuk, Ievgen; Hou, Yi; Brabec, Christoph J; Forberich, Karen

    2016-05-24

    While perovskite-based semitransparent solar cells for window applications show competitive levels of transparency and efficiency compared to organic photovoltaics, the color perception of the perovskite films is highly restricted because band gap engineering results in losses in power conversion efficiencies. To overcome the limitation in visual aesthetics, we combined semitransparent perovskite solar cells with dielectric mirrors. This approach enables one to tailor the device appearance to almost any desired color and simultaneously offers additional light harvesting for the solar cell. In the present work, opto-electrical effects are investigated through quantum efficiency and UV-to-visible spectroscopic measurements. Likewise, a detailed chromaticity analysis, featuring the transmissive and reflective color perception of the device including the mirror, from both sides and in different illumination conditions, is presented and analyzed. Photocurrent density enhancement of up to 21% along with overall device transparency values of up to 31% (4.2% efficiency) is demonstrated for cells showing a colored aesthetic appeal. Finally, a series of simulations emulating the device chromaticity, transparency, and increased photocurrent density as a function of the photoactive layer thickness and the design wavelength of the dielectric mirror are presented. Our simulations and their experimental validation enabled us to establish the design rules that consider the color efficiency/transparency interplay for real applications.

  1. Orbital Delocalization and Enhancement of Magnetic Interactions in Perovskite Oxyhydrides

    PubMed Central

    Liu, Kai; Hou, Yusheng; Gong, Xingao; Xiang, Hongjun

    2016-01-01

    Recent experiments showed that some perovskite oxyhydrides have surprisingly high magnetic-transition temperature. In order to unveil the origin of this interesting phenomenon, we investigate the magnetism in SrCrO2H and SrVO2H on the basis of first-principles calculations and Monte Carlo simulations. Our work indicates that the Cr-O-Cr superexchange interaction in SrCrO2H is unexpectedly strong. Different from the previous explanation in terms of the H− ion substitution induced increase of the Cr-O-Cr bond angle, we reveal instead that this is mainly because the 3d orbitals in perovskite oxyhydrides becomes more delocalized since H− ions have weaker electronegativity and less electrons than O2− ions. The delocalized 3d orbitals result in stronger Cr-O interactions and enhance the magnetic-transition temperature. This novel mechanism is also applicable to the case of SrVO2H. Furthermore, we predict that SrFeO2H will have unprecedented high Neel temperature because of the extraordinarily strong Fe-H-Fe σ-type interactions. Our work suggests the anion substitution can be used to effectively manipulate the magnetic properties of perovskite compounds. PMID:26804825

  2. Coloring Semitransparent Perovskite Solar Cells via Dielectric Mirrors.

    PubMed

    Ramírez Quiroz, César Omar; Bronnbauer, Carina; Levchuk, Ievgen; Hou, Yi; Brabec, Christoph J; Forberich, Karen

    2016-05-24

    While perovskite-based semitransparent solar cells for window applications show competitive levels of transparency and efficiency compared to organic photovoltaics, the color perception of the perovskite films is highly restricted because band gap engineering results in losses in power conversion efficiencies. To overcome the limitation in visual aesthetics, we combined semitransparent perovskite solar cells with dielectric mirrors. This approach enables one to tailor the device appearance to almost any desired color and simultaneously offers additional light harvesting for the solar cell. In the present work, opto-electrical effects are investigated through quantum efficiency and UV-to-visible spectroscopic measurements. Likewise, a detailed chromaticity analysis, featuring the transmissive and reflective color perception of the device including the mirror, from both sides and in different illumination conditions, is presented and analyzed. Photocurrent density enhancement of up to 21% along with overall device transparency values of up to 31% (4.2% efficiency) is demonstrated for cells showing a colored aesthetic appeal. Finally, a series of simulations emulating the device chromaticity, transparency, and increased photocurrent density as a function of the photoactive layer thickness and the design wavelength of the dielectric mirror are presented. Our simulations and their experimental validation enabled us to establish the design rules that consider the color efficiency/transparency interplay for real applications. PMID:27070738

  3. Local Time-Dependent Charging in a Perovskite Solar Cell.

    PubMed

    Bergmann, Victor W; Guo, Yunlong; Tanaka, Hideyuki; Hermes, Ilka M; Li, Dan; Klasen, Alexander; Bretschneider, Simon A; Nakamura, Eiichi; Berger, Rüdiger; Weber, Stefan A L

    2016-08-01

    Efficient charge extraction within solar cells explicitly depends on the optimization of the internal interfaces. Potential barriers, unbalanced charge extraction, and interfacial trap states can prevent cells from reaching high power conversion efficiencies. In the case of perovskite solar cells, slow processes happening on time scales of seconds cause hysteresis in the current-voltage characteristics. In this work, we localized and investigated these slow processes using frequency-modulation Kelvin probe force microscopy (FM-KPFM) on cross sections of planar methylammonium lead iodide (MAPI) perovskite solar cells. FM-KPFM can map the charge density distribution and its dynamics at internal interfaces. Upon illumination, space charge layers formed at the interfaces of the selective contacts with the MAPI layer within several seconds. We observed distinct differences in the charging dynamics at the interfaces of MAPI with adjacent layers. Our results indicate that more than one process is involved in hysteresis. This finding is in agreement with recent simulation studies claiming that a combination of ion migration and interfacial trap states causes the hysteresis in perovskite solar cells. Such differences in the charging rates at different interfaces cannot be separated by conventional device measurements.

  4. Interfacial Charge Transfer Anisotropy in Polycrystalline Lead Iodide Perovskite Films.

    PubMed

    Yin, Jun; Cortecchia, Daniele; Krishna, Anurag; Chen, Shi; Mathews, Nripan; Grimsdale, Andrew C; Soci, Cesare

    2015-04-16

    Solar cells based on organic-inorganic lead iodide perovskite (CH3NH3PbI3) exhibit remarkably high power conversion efficiency (PCE). One of the key issues in solution-processed films is that often the polycrystalline domain orientation is not well-defined, which makes it difficult to predict energy alignment and charge transfer efficiency. Here we combine ab initio calculations and photoelectron spectroscopy to unravel the electronic structure and charge redistribution at the interface between different surfaces of CH3NH3PbI3 and typical organic hole acceptor Spiro-OMeTAD and electron acceptor PCBM. We find that both hole and electron interfacial transfer depend strongly on the CH3NH3PbI3 surface orientation: while the (001) and (110) surfaces tend to favor hole injection to Spiro-OMeTAD, the (100) surface facilitates electron transfer to PCBM due to surface delocalized charges and hole/electron accumulation at the CH3NH3PbI3/organic interfaces. Molecular dynamic simulations indicate that this is due to strong orbital interactions under thermal fluctuations at room temperature, suggesting the possibility to further improve charge separation and extraction in perovskite-based solar cells by controlling perovskite film crystallization and surface orientation.

  5. Rapid Topochemical Modification of Layered Perovskites via Microwave Reactions.

    PubMed

    Akbarian-Tefaghi, Sara; Teixeira Veiga, Elaine; Amand, Guillaume; Wiley, John B

    2016-02-15

    An effective microwave approach to the topochemical modification of different layered oxide perovskite hosts is presented where cation exchange, grafting, and intercalation reactions with acid, n-alkyl alcohols, and n-alkylamines, respectively, are successfully carried out. Microwave-assisted proton exchange reactions involving double- and triple-layered Dion-Jacobson and Ruddlesden-Popper perovskite family members, RbLnNb2O7 (Ln = La, Pr), KCa2Nb3O10, Li2CaTa2O7, and Na2La2Ti3O10, were found to be quite efficient, decreasing reaction times from several days to ≤3 h. Grafting and intercalation reactions involving double-layered perovskites were also quite rapid with full conversions occurring in as fast as an hour. Interestingly, triple-layered hosts were found to show different behavior; when complete intercalations were possible, grafting reactions were limited at best. Utilization of this rapid synthetic approach could help facilitate the fabrication of new organic-inorganic hybrids. PMID:26835716

  6. Perovskite phase thin films and method of making

    DOEpatents

    Boyle, Timothy J.; Rodriguez, Mark A.

    2000-01-01

    The present invention comprises perovskite-phase thin films, of the general formula A.sub.x B.sub.y O.sub.3 on a substrate, wherein A is selected from beryllium, magnesium, calcium, strontium, and barium or a combination thereof; B is selected from niobium and tantalum or a combination thereof; and x and y are mole fractions between approximately 0.8 and 1.2. More particularly, A is strontium or barium or a combination thereof and B is niobium or tantalum or a combination thereof. Also provided is a method of making a perovskite-phase thin film, comprising combining at least one element-A-containing compound, wherein A is selected from beryllium, magnesium, calcium, strontium or barium, with at least one element-B-containing compound, wherein B niobium or tantalum, to form a solution; adding a solvent to said solution to form another solution; spin-coating the solution onto a substrate to form a thin film; and heating the film to form the perovskite-phase thin film.

  7. Tunable Near-Infrared Luminescence in Tin Halide Perovskite Devices.

    PubMed

    Lai, May L; Tay, Timothy Y S; Sadhanala, Aditya; Dutton, Siân E; Li, Guangru; Friend, Richard H; Tan, Zhi-Kuang

    2016-07-21

    Infrared emitters are reasonably rare in solution-processed materials. Recently, research into hybrid organo-lead halide perovskite, originally popular in photovoltaics,1-3 has gained traction in light-emitting diodes (LED) due to their low-cost solution processing and good performance.4-9 The lead-based electroluminescent materials show strong colorful emission in the visible region, but lack emissive variants further in the infrared. The concerns with the toxicity of lead may, additionally, limit their wide-scale applications. Here, we demonstrate tunable near-infrared electroluminescence from a lead-free organo-tin halide perovskite, using an ITO/PEDOT:PSS/CH3NH3Sn(Br1-xIx)3/F8/Ca/Ag device architecture. In our tin iodide (CH3NH3SnI3) LEDs, we achieved a 945 nm near-infrared emission with a radiance of 3.4 W sr(-1) m(-2) and a maximum external quantum efficiency of 0.72%, comparable with earlier lead-based devices. Increasing the bromide content in these tin perovskite devices widens the semiconductor bandgap and leads to shorter wavelength emissions, tunable down to 667 nm. These near-infrared LEDs could find useful applications in a range of optical communication, sensing and medical device applications.

  8. Control of Perovskite Crystal Growth by Methylammonium Lead Chloride Templating.

    PubMed

    Binek, Andreas; Grill, Irene; Huber, Niklas; Peters, Kristina; Hufnagel, Alexander G; Handloser, Matthias; Docampo, Pablo; Hartschuh, Achim; Bein, Thomas

    2016-04-20

    State-of-the-art solar cells based on methylammonium lead iodide (MAPbI3 ) now reach efficiencies over 20 %. This fast improvement was possible with intensive research in perovskite processing. In particular, chloride-based precursors are known to have a positive influence on the crystallization of the perovskite. Here, we used a combination of in-situ X-ray diffraction and charge-transport measurements to understand the influence of chloride during perovskite crystallization in planar heterojunction solar cells. We show that MAPbCl3 crystallizes directly after the deposition of the starting solution and acts as a template for the formation of MAPbI3 . Additionally, we show that the charge-carrier mobility doubles by extending the time for the template formation. Our results give a deeper understanding of the influence of chloride in the synthesis of MAPbI3 and illustrate the importance of carefully controlling crystallization for reproducible, high-efficiency solar cells. PMID:26928877

  9. 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.

  10. Rapid Microwave Synthesis of Perovskite Oxide Nanostructures with Enhanced Functionality

    NASA Astrophysics Data System (ADS)

    Salazar, Gregory; Datta, Anuja; Mukherjee, Pritish

    2015-03-01

    Perovskite oxides are an important class of materials having high dielectric and piezoelectric coefficients, switchable ferroelectric (FE) polarization and interesting optical and electrical properties. Realization of functional devices based on classic perovskite oxides such as Pb(Zr0.52Ti0.48) O3 (PZT), and emerging Pb-free noncentrosymmetric (NCS) oxides, such as, ZnSnO3, ZnTiO3 and CaTiO3 have reinforced the investigation of these materials in multiple dimensions and length scales. However, large-scale synthesis and integration of ordered low-dimensional structures is a challenge, due to their complicated methodologies, high-cost and difficulties with phase stability. We discuss a generalized, cost-effective, rapid microwave synthesis route for size and shape selective nanostructure growth of these functional perovskite oxides on industrially viable flexible and hard substrates, stabilized by an enhanced ionic covalence. The rational synthesis approach allowed improved tunability of the size, shape, and orientation of the structures with improved electrical and FE properties. The facile fabrication route of these nanostructures may expand the outreach of probes for understanding the structure-property relationships in these hitherto unexplored and technologically important materials.

  11. Local Time-Dependent Charging in a Perovskite Solar Cell.

    PubMed

    Bergmann, Victor W; Guo, Yunlong; Tanaka, Hideyuki; Hermes, Ilka M; Li, Dan; Klasen, Alexander; Bretschneider, Simon A; Nakamura, Eiichi; Berger, Rüdiger; Weber, Stefan A L

    2016-08-01

    Efficient charge extraction within solar cells explicitly depends on the optimization of the internal interfaces. Potential barriers, unbalanced charge extraction, and interfacial trap states can prevent cells from reaching high power conversion efficiencies. In the case of perovskite solar cells, slow processes happening on time scales of seconds cause hysteresis in the current-voltage characteristics. In this work, we localized and investigated these slow processes using frequency-modulation Kelvin probe force microscopy (FM-KPFM) on cross sections of planar methylammonium lead iodide (MAPI) perovskite solar cells. FM-KPFM can map the charge density distribution and its dynamics at internal interfaces. Upon illumination, space charge layers formed at the interfaces of the selective contacts with the MAPI layer within several seconds. We observed distinct differences in the charging dynamics at the interfaces of MAPI with adjacent layers. Our results indicate that more than one process is involved in hysteresis. This finding is in agreement with recent simulation studies claiming that a combination of ion migration and interfacial trap states causes the hysteresis in perovskite solar cells. Such differences in the charging rates at different interfaces cannot be separated by conventional device measurements. PMID:27377472

  12. Recycling Perovskite Solar Cells To Avoid Lead Waste.

    PubMed

    Binek, Andreas; Petrus, Michiel L; Huber, Niklas; Bristow, Helen; Hu, Yinghong; Bein, Thomas; Docampo, Pablo

    2016-05-25

    Methylammonium lead iodide (MAPbI3) perovskite based solar cells have recently emerged as a serious competitor for large scale and low-cost photovoltaic technologies. However, since these solar cells contain toxic lead, a sustainable procedure for handling the cells after their operational lifetime is required to prevent exposure of the environment to lead and to comply with international electronic waste disposal regulations. Herein, we report a procedure to remove every layer of the solar cells separately, which gives the possibility to selectively isolate the different materials. Besides isolating the toxic lead iodide in high yield, we show that the PbI2 can be reused for the preparation of new solar cells with comparable performance and in this way avoid lead waste. Furthermore, we show that the most expensive part of the solar cell, the conductive glass (FTO), can be reused several times without any reduction in the performance of the devices. With our simple recycling procedure, we address both the risk of contamination and the waste disposal of perovskite based solar cells while further reducing the cost of the system. This brings perovskite solar cells one step closer to their introduction into commercial systems.

  13. Selective Precipitation and Concentrating of Perovskite Crystals from Titanium-Bearing Slag Melt in Supergravity Field

    NASA Astrophysics Data System (ADS)

    Gao, Jintao; Zhong, Yiwei; Guo, Zhancheng

    2016-08-01

    Selective precipitation and concentrating of perovskite crystals from titanium-bearing slag melt in the supergravity field was investigated in this study. Since perovskite was the first precipitated phase from the slag melt during the cooling process, and a greater precipitation quantity and larger crystal sizes of perovskite were obtained at 1593 K to 1563 K (1320 °C to 1290 °C), concentrating of perovskite crystals from the slag melt was carried out at this temperature range in the supergravity field, at which the perovskite transforms into solid particles while the other minerals remain in the liquid melt. The layered structures appeared significantly in the sample obtained by supergravity treatment, and all the perovskite crystals moved along the supergravity direction and concentrated as the perovskite-rich phase in the bottom area, whereas the molten slag concentrated in the upper area along the opposite direction, in which it was impossible to find any perovskite crystals. With the gravity coefficient of G = 750, the mass fraction of TiO2 in the perovskite-rich phase was up to 34.65 wt pct, whereas that of the slag phase was decreased to 12.23 wt pct, and the recovery ratio of Ti in the perovskite-rich phase was up to 75.28 pct. On this basis, an amplification experimental centrifugal apparatus was exploited and the continuous experiment with larger scale was further carried out, the results confirming that selective precipitation and concentrating of perovskite crystals from the titanium-bearing slag melt by supergravity was a feasible method.

  14. The electronic structure of metal oxide/organo metal halide perovskite junctions in perovskite based solar cells

    PubMed Central

    Dymshits, Alex; Henning, Alex; Segev, Gideon; Rosenwaks, Yossi; Etgar, Lioz

    2015-01-01

    Cross-sections of a hole-conductor-free CH3NH3PbI3 perovskite solar cell were characterized with Kelvin probe force microscopy. A depletion region width of about 45 nm was determined from the measured potential profiles at the interface between CH3NH3PbI3 and nanocrystalline TiO2, whereas a negligible depletion was measured at the CH3NH3PbI3/Al2O3 interface. A complete solar cell can be realized with the CH3NH3PbI3 that functions both as light harvester and hole conductor in combination with a metal oxide. The band diagrams were estimated from the measured potential profile at the interfaces, and are critical findings for a better understanding and further improvement of perovskite based solar cells. PMID:25731963

  15. Structure and Growth Control of Organic–Inorganic Halide Perovskites for Optoelectronics: From Polycrystalline Films to Single Crystals

    PubMed Central

    Chen, Yani; He, Minhong; Peng, Jiajun; Sun, Yong

    2016-01-01

    Recently, organic–inorganic halide perovskites have sparked tremendous research interest because of their ground‐breaking photovoltaic performance. The crystallization process and crystal shape of perovskites have striking impacts on their optoelectronic properties. Polycrystalline films and single crystals are two main forms of perovskites. Currently, perovskite thin films have been under intensive investigation while studies of perovskite single crystals are just in their infancy. This review article is concentrated upon the control of perovskite structures and growth, which are intimately correlated for improvements of not only solar cells but also light‐emitting diodes, lasers, and photodetectors. We begin with the survey of the film formation process of perovskites including deposition methods and morphological optimization avenues. Strategies such as the use of additives, thermal annealing, solvent annealing, atmospheric control, and solvent engineering have been successfully employed to yield high‐quality perovskite films. Next, we turn to summarize the shape evolution of perovskites single crystals from three‐dimensional large sized single crystals, two‐dimensional nanoplates, one‐dimensional nanowires, to zero‐dimensional quantum dots. Siginificant functions of perovskites single crystals are highlighted, which benefit fundamental studies of intrinsic photophysics. Then, the growth mechanisms of the previously mentioned perovskite crystals are unveiled. Lastly, perspectives for structure and growth control of perovskites are outlined towards high‐performance (opto)electronic devices. PMID:27812463

  16. Modelling dislocation cores in MgSiO3 perovskite

    NASA Astrophysics Data System (ADS)

    Cordier, P.; Carrez, P.; Gouriet, K.; Kraych, A.

    2012-12-01

    MgSiO3 perovskite is the most abundant mineral of the Earth's lower mantle (i.e. between 700 and 2900 km depth) and accounts for half of Earth's mass. At lower mantle pressures (25-135 GPa) MgSiO3 crystallises in a distorted (orthorhombic) perovskite structure (described in the following using the Pbnm space group). In this structure, SiO6 octahedra are tilted with tilt angles increasing with increasing pressure. Since it is very difficult to perform deformation experiments under the extreme P, T conditions of the lower mantle, little is known about plastic deformation of MgSiO3 perovskite and its slip systems are still a matter of debate. To overcome this difficulty, we model dislocation core structures in this mineral taking into account the influence of pressure. In this study, we focus on dislocation core structures of dislocations with [100] and [010] Burgers vectors (which derive from <110> Burgers vectors of the underlying pseudo-cubic structure). Atomistic calculations are performed using pair-wise potentials as implemented in the LAMMPS code. The choice of potentials was initially validated by comparing generalized stacking fault (GSF) energies to similar calculations performed with the density functional theory (DFT). The core structures of screw dislocations are calculated using two independent methods. The first one is based on Peierls-Nabarro-Galerkin simulations involving GSF as an input. Direct calculations have also bee performed using cluster approach. It turns out that screw dislocations with [100] Burgers vector are characterised by a core mostly spread in the (010) plane. The core exhibits two edge-sharing octahedra in a configuration very similar to that modelled in SrTiO3 cubic perovskite. The structure of [010] screw dislocations is more complex with dissociation into two, non-collinear partial dislocations with a significant non-screw component. Both dislocations exhibit high Peierls stresses. This illustrates the effect of orthorhombic

  17. Photophysics of Hybrid Lead Halide Perovskites: The Role of Microstructure.

    PubMed

    Srimath Kandada, Ajay Ram; Petrozza, Annamaria

    2016-03-15

    Since the first reports on high efficiency, solution processed solar cells based on hybrid lead halide perovskites, there has been an explosion of activities on these materials. Researchers with interests spanning the full range from conventional inorganic to emerging organic and hybrid optoelectronic technologies have been contributing to the prolific research output. This has led to solar cell power conversion efficiencies now exceeding 20% and the demonstration of proofs of concept for electroluminescent and lasing devices. Hybrid perovskites can be self-assembled by a simple chemical deposition of the constituent units, with the possibility of integrating the useful properties of organic and inorganic compounds at the molecular scale within a single crystalline material, thus enabling a fine-tuning of the electronic properties. Tellingly, the fundamental properties of these materials may make us think of a new, solution processable, GaAs-like semiconductor. While this can be true to a first approximation, hybrid perovskites are intrinsically complex materials, where the presence of various types of interactions and structural disorder may strongly affect their properties. In particular, a clear understanding and control of the relative interactions between the organic and inorganic moieties is of paramount importance to properly disentangle their innate physics. In this Account we review our recent studies which aim to clarify the relationship between structural and electronic properties from a molecular to mesoscopic level. First we identify the markers for local disorder at the molecular level by using Raman spectroscopy as a probe. Then, we exploit such a tool to explore the role of microstructure on the absorption and luminescence properties of the semiconductor. Finally we address the controversy surrounding electron-hole interactions and excitonic effects. We show that in hybrid lead-halide perovskites dielectric screening also depends on the local

  18. Impact of a Mesoporous Titania-Perovskite Interface on the Performance of Hybrid Organic-Inorganic Perovskite Solar Cells.

    PubMed

    Abdi-Jalebi, Mojtaba; Dar, M Ibrahim; Sadhanala, Aditya; Senanayak, Satyaprasad P; Giordano, Fabrizio; Zakeeruddin, Shaik Mohammed; Grätzel, Michael; Friend, Richard H

    2016-08-18

    We report on the optimization of the interfacial properties of titania in mesoscopic CH3NH3PbI3 solar cells. Modification of the mesoporous TiO2 film by TiCl4 treatment substantially reduced the surface traps, as is evident from the sharpness of the absorption edge with a significant reduction in Urbach energy (from 320 to 140 meV) determined from photothermal deflection spectroscopy, and led to an order of magnitude enhancement in the bulk electron mobility and corresponding decrease in the transport activation energy (from 170 to 90 meV) within a device. After optimization of the photoanode-perovskite interface using various sizes of TiO2 nanoparticles, the best photovoltaic efficiency of 16.3% was achieved with the mesoporous TiO2 composed of 36 nm sized nanoparticles. The improvement in device performance can be attributed to the enhanced charge collection efficiency that is driven by improved charge transport in the mesoporous TiO2 layer. Also, the decreased recombination at the TiO2-perovskite interface and better perovskite coverage play important roles. PMID:27472458

  19. Impact of a Mesoporous Titania-Perovskite Interface on the Performance of Hybrid Organic-Inorganic Perovskite Solar Cells.

    PubMed

    Abdi-Jalebi, Mojtaba; Dar, M Ibrahim; Sadhanala, Aditya; Senanayak, Satyaprasad P; Giordano, Fabrizio; Zakeeruddin, Shaik Mohammed; Grätzel, Michael; Friend, Richard H

    2016-08-18

    We report on the optimization of the interfacial properties of titania in mesoscopic CH3NH3PbI3 solar cells. Modification of the mesoporous TiO2 film by TiCl4 treatment substantially reduced the surface traps, as is evident from the sharpness of the absorption edge with a significant reduction in Urbach energy (from 320 to 140 meV) determined from photothermal deflection spectroscopy, and led to an order of magnitude enhancement in the bulk electron mobility and corresponding decrease in the transport activation energy (from 170 to 90 meV) within a device. After optimization of the photoanode-perovskite interface using various sizes of TiO2 nanoparticles, the best photovoltaic efficiency of 16.3% was achieved with the mesoporous TiO2 composed of 36 nm sized nanoparticles. The improvement in device performance can be attributed to the enhanced charge collection efficiency that is driven by improved charge transport in the mesoporous TiO2 layer. Also, the decreased recombination at the TiO2-perovskite interface and better perovskite coverage play important roles.

  20. Synthesis, crystal structure and properties of alluaudite-like triple molybdate Na25Cs8Fe5(MoO4)24

    NASA Astrophysics Data System (ADS)

    Savina, Aleksandra A.; Solodovnikov, Sergey F.; Belov, Dmitry A.; Basovich, Olga M.; Solodovnikova, Zoya A.; Pokholok, Konstantin V.; Stefanovich, Sergey Yu.; Lazoryak, Bogdan I.; Khaikina, Elena G.

    2014-12-01

    A new triple molybdate Na25Cs8Fe5(MoO4)24 was synthesized using solid state reactions and studied with X-ray powder diffraction, second harmonic generation (SHG) technique, differential scanning calorimetry, Mössbauer and dielectric impedance spectroscopy. Single crystals of Na25Cs8Fe5(MoO4)24 were obtained and its structure was solved (the space group P1bar, a=12.5814(5), b=13.8989(5), c=28.4386(9) Å, α=90.108(2), β=90.064(2), γ=90.020(2)°, V=4973.0(3) Å3, Z=2, R=0.0440). Characteristic features of the structure are polyhedral layers composed of pairs of edge-shared FeO6 and (Fe, Na)O6 octahedra, which are connected by bridging МоО4 tetrahedra. The layers share common vertices with bridging МоО4 tetrahedra to form an open 3D framework with the cavities occupied by the Cs+ and Na+ cations. The compound undergoes first-order phase transformation at 642 K and above this phase transition, electrical conductivity reaches 10-3-10-2 S cm-1. Thus, Na25Cs8Fe5(MoO4)24 may be considered as a promising compound for developing new materials with high ionic conductivity.

  1. Effects of molybdenum deficiency and defects in molybdate transporter MOT1 on transcript accumulation and nitrogen/sulphur metabolism in Arabidopsis thaliana.

    PubMed

    Ide, Yoko; Kusano, Miyako; Oikawa, Akira; Fukushima, Atsushi; Tomatsu, Hajime; Saito, Kazuki; Hirai, Masami Yokota; Fujiwara, Toru

    2011-02-01

    Molybdenum (Mo) is a micronutrient essential for plant growth, as several key enzymes of plant metabolic pathways contain Mo cofactor in their catalytic centres. Mo-containing oxidoreductases include nitrate reductase, sulphite oxidase, xanthine dehydrogenase, and aldehyde oxidase. These are involved in nitrate assimilation, sulphite detoxification, purine metabolism or the synthesis of abscisic acid, auxin and glucosinolates in plants. To understand the effects of Mo deficiency and a mutation in a molybdate transporter, MOT1, on nitrogen and sulphur metabolism in Arabidopsis thaliana, transcript and metabolite profiling of the mutant lacking MOT1 was conducted in the presence or absence of Mo. Transcriptome analysis revealed that Mo deficiency had impacts on genes involved in metabolisms, transport, stress responses, and signal transductions. The transcript level of a nitrate reductase NR1 was highly induced under Mo deficiency in mot1-1. The metabolite profiles were analysed further by using gas chromatography time-of-flight mass spectrometry, capillary electrophoresis time-of-flight mass spectrometry, and ultra high performance liquid chromatography. The levels of amino acids, sugars, organic acids, and purine metabolites were altered significantly in the Mo-deficient plants. These results are the first investigation of the global effect of Mo nutrition and MOT1 on plant gene expressions and metabolism. PMID:21131548

  2. Electronic paramagnetic resonance or rare-earth ions Yb3+, Pr3+, Dy3+, and Nd3+ in double molybdates and tungstenates

    NASA Astrophysics Data System (ADS)

    Kobets, M. I.; Khats'ko, E. N.; Dergachev, K. G.; Kalinin, P. S.

    2010-07-01

    The particulars of the EPR spectrum of magnetically concentrated crystals of double molybdates and tungstenates with a crystal structure of low symmetry were studied at liquid-helium temperatures in the frequency range 15-120GHz. The directions of the principal magnetic axes were determined and the principal values of the g tensors were obtained for all experimental crystals KYb(MoO4)2, CsPr(MoO4)2, RbDy(MoO4)2, and RbNd(WO4)2. Two non-equivalent geometric centers were found in KYb(MoO4)2 and RbDy(MoO4)2 crystals; the local axes of the centers were turned in different directions relative to the crystallographic axes a and c by 34° and 25°. The dipole-dipole interaction energy was estimated as Edd˜0.1cm-1 for KYb(MoO4)2. It was shown that the lowest states of CsPr(MoO4)2 are close-lying singlets (quasidoublet) with splitting Δ ˜0.2cm-1.

  3. Tunable quasi-cw two-micron lasing in diode-pumped crystals of mixed Tm{sup 3+}-doped sodium - lanthanum - gadolinium molybdates and tungstates

    SciTech Connect

    Bol'shchikov, F A; Ryabochkina, P A; Zharikov, Evgeny V; Lis, Denis A; Subbotin, Kirill A; Zakharov, N G; Antipov, Oleg L

    2010-12-09

    Two-micron lasing is obtained for the first time on the {sup 3}F{sub 4} {yields} {sup 3}H{sub 6} transition of Tm{sup 3+} ions in diode-pumped crystals of mixed sodium - lanthanum - gadolinium tungstate Tm:NaLa{sub 1/2}Gd{sub 1/2}(WO{sub 4}){sub 2} (C{sub Tm} = 3.6 at %) (3.6Tm : NLGW) and molybdate Tm:NaLa{sub 1/3}Gd{sub 2/3}(MoO{sub 4}){sub 2} (C{sub Tm} = 4.8 at %) (4.8Tm : NLGM). For the 3.6Tm : NLGW crystal, the quasi-cw laser output power exceeded 200 mW and the slope efficiency (with respect to absorbed pump power) for the {pi}- and {sigma}-polarisations at wavelengths of 1908 and 1918 nm was 34% and 30%, respectively. The laser wavelength of this crystal was continuously tuned within the spectral range of 1860 - 1935 nm. For the 4.8Tm : NLGM crystal, the slope efficiency for the {pi}- and {sigma}-polarisations at wavelengths of 1910 and 1918 nm was 27% and 23%, respectively, and the laser wavelength was tunable within the spectral range of 1870 - 1950 nm. (lasers)

  4. Unraveling the Role of Monovalent Halides in Mixed-Halide Organic-Inorganic Perovskites.

    PubMed

    Deepa, Melepurath; Ramos, F Javier; Shivaprasad, S M; Ahmad, Shahzada

    2016-03-16

    The performance of perovskite solar cells is strongly influenced by the composition and microstructure of the perovskite. A recent approach to improve the power conversion efficiencies utilized mixed-halide perovskites, but the halide ions and their roles were not directly studied. Unraveling their precise location in the perovskite layer is of paramount importance. Here, we investigated four different perovskites by using X-ray photoelectron spectroscopy, and found that among the three studied mixed-halide perovskites, CH3 NH3 Pb(I0.74 Br0.26 )3 and CH3 NH3 PbBr3-x Clx show peaks that unambiguously demonstrate the presence of iodide and bromide in the former, and bromide and chloride in the latter. The CH3 NH3 PbI3-x Clx perovskite shows anomalous behavior, the iodide content far outweighs that of the chloride; a small proportion of chloride, in all likelihood, resides deep within the TiO2 /absorber layer. Our study reveals that there are many distinguishable structural differences between these perovskites, and that these directly impact the photovoltaic performances. PMID:26717046

  5. Artificial Synapses: Organometal Halide Perovskite Artificial Synapses (Adv. Mater. 28/2016).

    PubMed

    Xu, Wentao; Cho, Himchan; Kim, Young-Hoon; Kim, Young-Tae; Wolf, Christoph; Park, Chan-Gyung; Lee, Tae-Woo

    2016-07-01

    A synapse-emulating electronic device based on organometal halide perovskite thin films is described by T.-W. Lee and co-workers on page 5916. The device successfully emulates important characteristics of a biological synapse. This work extends the application of organometal halide perovskites to bioinspired electronic devices, and contributes to the development of neuromorphic electronics. PMID:27442971

  6. Degradation of Methylammonium Lead Iodide Perovskite Structures through Light and Electron Beam Driven Ion Migration

    PubMed Central

    2016-01-01

    Organometal halide perovskites show promising features for cost-effective application in photovoltaics. The material instability remains a major obstacle to broad application because of the poorly understood degradation pathways. Here, we apply simultaneous luminescence and electron microscopy on perovskites for the first time, allowing us to monitor in situ morphology evolution and optical properties upon perovskite degradation. Interestingly, morphology, photoluminescence (PL), and cathodoluminescence of perovskite samples evolve differently upon degradation driven by electron beam (e-beam) or by light. A transversal electric current generated by a scanning electron beam leads to dramatic changes in PL and tunes the energy band gaps continuously alongside film thinning. In contrast, light-induced degradation results in material decomposition to scattered particles and shows little PL spectral shifts. The differences in degradation can be ascribed to different electric currents that drive ion migration. Moreover, solution-processed perovskite cuboids show heterogeneity in stability which is likely related to crystallinity and morphology. Our results reveal the essential role of ion migration in perovskite degradation and provide potential avenues to rationally enhance the stability of perovskite materials by reducing ion migration while improving morphology and crystallinity. It is worth noting that even moderate e-beam currents (86 pA) and acceleration voltages (10 kV) readily induce significant perovskite degradation and alter their optical properties. Therefore, attention has to be paid while characterizing such materials using scanning electron microscopy or transmission electron microscopy techniques. PMID:26804213

  7. Fiber-Shaped Perovskite Solar Cells with High Power Conversion Efficiency.

    PubMed

    Qiu, Longbin; He, Sisi; Yang, Jiahua; Deng, Jue; Peng, Huisheng

    2016-05-01

    A perovskite solar cell fiber is created with a high power conversion efficiency of 7.1% through a controllable deposition method. A combination of aligned TiO2 nanotubes, a uniform perovskite layer, and transparent aligned carbon nanotube sheet contributes to the high photovoltaic performance. It is flexible and stable, and can be woven into smart clothes for wearable applications.

  8. Fiber-Shaped Perovskite Solar Cells with High Power Conversion Efficiency.

    PubMed

    Qiu, Longbin; He, Sisi; Yang, Jiahua; Deng, Jue; Peng, Huisheng

    2016-05-01

    A perovskite solar cell fiber is created with a high power conversion efficiency of 7.1% through a controllable deposition method. A combination of aligned TiO2 nanotubes, a uniform perovskite layer, and transparent aligned carbon nanotube sheet contributes to the high photovoltaic performance. It is flexible and stable, and can be woven into smart clothes for wearable applications. PMID:27002590

  9. Selective dissolution of halide perovskites as a step towards recycling solar cells

    DOE PAGESBeta

    Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee; Park, So Yeon; Li, Zhen; Zhu, Kai; Jung, Hyun Suk

    2016-05-23

    Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Here, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easily decomposedmore » in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb2+ cations. After 10 cycles of recycling, a mesoporous TiO2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells.« less

  10. Aluminum-Doped Zinc Oxide as Highly Stable Electron Collection Layer for Perovskite Solar Cells.

    PubMed

    Zhao, Xingyue; Shen, Heping; Zhang, Ye; Li, Xin; Zhao, Xiaochong; Tai, Meiqian; Li, Jingfeng; Li, Jianbao; Li, Xin; Lin, Hong

    2016-03-01

    Although low-temperature, solution-processed zinc oxide (ZnO) has been widely adopted as the electron collection layer (ECL) in perovskite solar cells (PSCs) because of its simple synthesis and excellent electrical properties such as high charge mobility, the thermal stability of the perovskite films deposited atop ZnO layer remains as a major issue. Herein, we addressed this problem by employing aluminum-doped zinc oxide (AZO) as the ECL and obtained extraordinarily thermally stable perovskite layers. The improvement of the thermal stability was ascribed to diminish of the Lewis acid-base chemical reaction between perovskite and ECL. Notably, the outstanding transmittance and conductivity also render AZO layer as an ideal candidate for transparent conductive electrodes, which enables a simplified cell structure featuring glass/AZO/perovskite/Spiro-OMeTAD/Au. Optimization of the perovskite layer leads to an excellent and repeatable photovoltaic performance, with the champion cell exhibiting an open-circuit voltage (Voc) of 0.94 V, a short-circuit current (Jsc) of 20.2 mA cm(-2), a fill factor (FF) of 0.67, and an overall power conversion efficiency (PCE) of 12.6% under standard 1 sun illumination. It was also revealed by steady-state and time-resolved photoluminescence that the AZO/perovskite interface resulted in less quenching than that between perovskite and hole transport material. PMID:26960451

  11. Aluminum-Doped Zinc Oxide as Highly Stable Electron Collection Layer for Perovskite Solar Cells.

    PubMed

    Zhao, Xingyue; Shen, Heping; Zhang, Ye; Li, Xin; Zhao, Xiaochong; Tai, Meiqian; Li, Jingfeng; Li, Jianbao; Li, Xin; Lin, Hong

    2016-03-01

    Although low-temperature, solution-processed zinc oxide (ZnO) has been widely adopted as the electron collection layer (ECL) in perovskite solar cells (PSCs) because of its simple synthesis and excellent electrical properties such as high charge mobility, the thermal stability of the perovskite films deposited atop ZnO layer remains as a major issue. Herein, we addressed this problem by employing aluminum-doped zinc oxide (AZO) as the ECL and obtained extraordinarily thermally stable perovskite layers. The improvement of the thermal stability was ascribed to diminish of the Lewis acid-base chemical reaction between perovskite and ECL. Notably, the outstanding transmittance and conductivity also render AZO layer as an ideal candidate for transparent conductive electrodes, which enables a simplified cell structure featuring glass/AZO/perovskite/Spiro-OMeTAD/Au. Optimization of the perovskite layer leads to an excellent and repeatable photovoltaic performance, with the champion cell exhibiting an open-circuit voltage (Voc) of 0.94 V, a short-circuit current (Jsc) of 20.2 mA cm(-2), a fill factor (FF) of 0.67, and an overall power conversion efficiency (PCE) of 12.6% under standard 1 sun illumination. It was also revealed by steady-state and time-resolved photoluminescence that the AZO/perovskite interface resulted in less quenching than that between perovskite and hole transport material.

  12. Lateral-Structure Single-Crystal Hybrid Perovskite Solar Cells via Piezoelectric Poling.

    PubMed

    Dong, Qingfeng; Song, Jingfeng; Fang, Yanjun; Shao, Yuchuan; Ducharme, Stephen; Huang, Jinsong

    2016-04-13

    Single-crystal perovskite solar cells with a lateral structure yield an efficiency enhancement 44-fold that of polycrystalline thin films, due to the much longer carrier diffusion length. A piezoelectric effect observed in perovskite single-crystal and the strain-generated grain-boundaries enable ion migration to form a p-i-n structure. PMID:26836224

  13. Nanostructuring Mixed-Dimensional Perovskites: A Route Toward Tunable, Efficient Photovoltaics.

    PubMed

    Koh, Teck Ming; Shanmugam, Vignesh; Schlipf, Johannes; Oesinghaus, Lukas; Müller-Buschbaum, Peter; Ramakrishnan, N; Swamy, Varghese; Mathews, Nripan; Boix, Pablo P; Mhaisalkar, Subodh G

    2016-05-01

    2D perovskites is one of the proposed strategies to enhance the moisture resistance, since the larger organic cations can act as a natural barrier. Nevertheless, 2D perovskites hinder the charge transport in certain directions, reducing the solar cell power conversion efficiency. A nanostructured mixed-dimensionality approach is presented to overcome the charge transport limitation, obtaining power conversion efficiencies over 9%.

  14. NaIrO{sub 3}-A pentavalent post-perovskite

    SciTech Connect

    Bremholm, M.; Dutton, S.E.; Stephens, P.W.; Cava, R.J.

    2011-03-15

    Sodium iridium (V) oxide, NaIrO{sub 3,} was synthesized by a high pressure solid state method and recovered to ambient conditions. It is found to be isostructural with CaIrO{sub 3}, the much-studied structural analog of the high-pressure post-perovskite phase of MgSiO{sub 3}. Among the oxide post-perovskites, NaIrO{sub 3} is the first example with a pentavalent cation. The structure consists of layers of corner- and edge-sharing IrO{sub 6} octahedra separated by layers of NaO{sub 8} bicapped trigonal prisms. NaIrO{sub 3} shows no magnetic ordering and resistivity measurements show non-metallic behavior. The crystal structure, electrical and magnetic properties are discussed and compared to known post-perovskites and pentavalent perovskite metal oxides. -- Graphical abstract: Sodium iridium(V) oxide, NaIrO{sub 3}, synthesized by a high pressure solid state method and recovered to ambient conditions is found to crystallize as the post-perovskite structure and is the first example of a pentavalent ABO{sub 3} post-perovskite. Research highlights: {yields} NaIrO{sub 3} post-perovskite stabilized by pressure. {yields} First example of a pentavalent oxide post-perovskite. {yields} Non-metallic and non-magnetic behavior of NaIrO{sub 3}.

  15. Layered hybrid perovskites with micropores created by alkylammonium functional silsesquioxane interlayers.

    PubMed

    Kataoka, Sho; Banerjee, Subhabrata; Kawai, Akiko; Kamimura, Yoshihiro; Choi, Jun-Chul; Kodaira, Tetsuya; Sato, Kazuhiko; Endo, Akira

    2015-04-01

    Layered organic-inorganic hybrid perovskites that consist of metal halides and organic interlayers are a class of low-dimensional materials. Here, we report the fabrication of layered hybrid perovskites using metal halides and silsesquioxane with a cage-like structure. We used a silsesquioxane as an interlayer to produce a rigid structure and improve the functionality of perovskite layers. Propylammonium-functionalized silsesquioxane and metal halide salts (CuCl2, PdCl2, PbCl2, and MnCl2) were self-assembled to form rigid layered perovskite structures with high crystallinity. The rigid silsesquioxane structure produces micropores between the perovskite layers that can potentially be filled with different molecules to tune the dielectric constants of the interlayers. The obtained silsesquioxane-metal halide hybrid perovskites exhibit some characteristic properties of layered perovskites including magnetic ordering (CuCl4(2-) and MnCl4(2-)) and excitonic absorption/emission (PbCl4(2-)). Our results indicate that inserting silsesquioxane interlayers into hybrid perovskites retains and enhances the low-dimensional properties of the materials.

  16. Lateral-Structure Single-Crystal Hybrid Perovskite Solar Cells via Piezoelectric Poling.

    PubMed

    Dong, Qingfeng; Song, Jingfeng; Fang, Yanjun; Shao, Yuchuan; Ducharme, Stephen; Huang, Jinsong

    2016-04-13

    Single-crystal perovskite solar cells with a lateral structure yield an efficiency enhancement 44-fold that of polycrystalline thin films, due to the much longer carrier diffusion length. A piezoelectric effect observed in perovskite single-crystal and the strain-generated grain-boundaries enable ion migration to form a p-i-n structure.

  17. 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

  18. Distinct exciton dissociation behavior of organolead trihalide perovskite and excitonic semiconductors studied in a same device

    DOE PAGESBeta

    Hu, Miao; Bi, Cheng; Yuan, Yongbo; Xiao, Zhengguo; Dong, Qingfeng; Shao, Yuchuan; Huang, Jinsong

    2015-01-15

    The nonexcitonic character for organometal trihalide perovskites is demonstrated by examining the field-dependent exciton dissociation behavior. Moreover, it is found that photogenerated excitons can be effectively dissociated into free charges inside perovskite without the assistance of charge extraction layer or external field, which is a stark contrast to the charge-separation behavior in excitonic materials in the same photovoltaic operation system.

  19. The Synthesis and Characterization of Some Fluoride Perovskites: An Undergraduate Experiment in Solid State Chemistry.

    ERIC Educational Resources Information Center

    Langley, Richard H.; And Others

    1984-01-01

    Describes a senior-level experiment dealing with the synthesis and characterization of a perovskite. Since most perovskites are cubic, their characterization by x-ray diffraction is simplified. In addition, magnetic ordering may be observed and the effects of a Jahn-Teller distortion seen. (JN)

  20. A 2-terminal perovskite/silicon multijunction solar cell enabled by a silicon tunnel junction

    SciTech Connect

    Mailoa, Jonathan P.; Bailie, Colin D.; Johlin, Eric C.; Hoke, Eric T.; Akey, Austin J.; Nguyen, William H.; McGehee, Michael D.; Buonassisi, Tonio

    2015-03-24

    With the advent of efficient high-bandgap metal-halide perovskite photovoltaics, an opportunity exists to make perovskite/silicon tandem solar cells. We fabricate a monolithic tandem by developing a silicon-based interband tunnel junction that facilitates majority-carrier charge recombination between the perovskite and silicon sub-cells. We demonstrate a 1 cm2 2-terminal monolithic perovskite/silicon multijunction solar cell with a VOC as high as 1.65 V. As a result, we achieve a stable 13.7% power conversion efficiency with the perovskite as the current-limiting sub-cell, and identify key challenges for this device architecture to reach efficiencies over 25%.

  1. Perovskite Solar Cells with Large-Area CVD-Graphene for Tandem Solar Cells.

    PubMed

    Lang, Felix; Gluba, Marc A; Albrecht, Steve; Rappich, Jörg; Korte, Lars; Rech, Bernd; Nickel, Norbert H

    2015-07-16

    Perovskite solar cells with transparent contacts may be used to compensate for thermalization losses of silicon solar cells in tandem devices. This offers a way to outreach stagnating efficiencies. However, perovskite top cells in tandem structures require contact layers with high electrical conductivity and optimal transparency. We address this challenge by implementing large-area graphene grown by chemical vapor deposition as a highly transparent electrode in perovskite solar cells, leading to identical charge collection efficiencies. Electrical performance of solar cells with a graphene-based contact reached those of solar cells with standard gold contacts. The optical transmission by far exceeds that of reference devices and amounts to 64.3% below the perovskite band gap. Finally, we demonstrate a four-terminal tandem device combining a high band gap graphene-contacted perovskite top solar cell (Eg = 1.6 eV) with an amorphous/crystalline silicon bottom solar cell (Eg = 1.12 eV). PMID:26266857

  2. Electric-Field-Induced Degradation of Methylammonium Lead Iodide Perovskite Solar Cells.

    PubMed

    Bae, Soohyun; Kim, Seongtak; Lee, Sang-Won; Cho, Kyung Jin; Park, Sungeun; Lee, Seunghun; Kang, Yoonmook; Lee, Hae-Seok; Kim, Donghwan

    2016-08-18

    Perovskite solar cells have great potential for high efficiency generation but are subject to the impact of external environmental conditions such as humidity, UV and sun light, temperature, and electric fields. The long-term stability of perovskite solar cells is an important issue for their commercialization. Various studies on the stability of perovskite solar cells are currently being performed; however, the stability related to electric fields is rarely discussed. Here the electrical stability of perovskite solar cells is studied. Ion migration is confirmed using the temperature-dependent dark current decay. Changes in the power conversion efficiency according to the amount of the external bias are measured in the dark, and a significant drop is observed only at an applied voltage greater than 0.8 V. We demonstrate that perovskite solar cells are stable under an electric field up to the operating voltage. PMID:27462013

  3. Electric-Field-Induced Degradation of Methylammonium Lead Iodide Perovskite Solar Cells.

    PubMed

    Bae, Soohyun; Kim, Seongtak; Lee, Sang-Won; Cho, Kyung Jin; Park, Sungeun; Lee, Seunghun; Kang, Yoonmook; Lee, Hae-Seok; Kim, Donghwan

    2016-08-18

    Perovskite solar cells have great potential for high efficiency generation but are subject to the impact of external environmental conditions such as humidity, UV and sun light, temperature, and electric fields. The long-term stability of perovskite solar cells is an important issue for their commercialization. Various studies on the stability of perovskite solar cells are currently being performed; however, the stability related to electric fields is rarely discussed. Here the electrical stability of perovskite solar cells is studied. Ion migration is confirmed using the temperature-dependent dark current decay. Changes in the power conversion efficiency according to the amount of the external bias are measured in the dark, and a significant drop is observed only at an applied voltage greater than 0.8 V. We demonstrate that perovskite solar cells are stable under an electric field up to the operating voltage.

  4. A numerical model for charge transport and energy conversion of perovskite solar cells.

    PubMed

    Zhou, Yecheng; Gray-Weale, Angus

    2016-02-14

    Based on the continuity equations and Poisson's equation, we developed a numerical model for perovskite solar cells. Due to different working mechanisms, the model for perovskite solar cells differs from that of silicon solar cells and Dye Sensitized Solar Cells. The output voltage and current are calculated differently, and in a manner suited in particular to perovskite organohalides. We report a test of our equations against experiment with good agreement. Using this numerical model, it was found that performances of solar cells increase with charge carrier's lifetimes, mobilities and diffusion lengths. The open circuit voltage (Voc) of a solar cell is dependent on light intensities, and charge carrier lifetimes. Diffusion length and light intensity determine the saturated current (Jsc). Additionally, three possible guidelines for the design and fabrication of perovskite solar cells are suggested by our calculations. Lastly, we argue that concentrator perovskite solar cells are promising.

  5. Crystallization Dynamics of Organolead Halide Perovskite by Real-Time X-ray Diffraction.

    PubMed

    Miyadera, Tetsuhiko; Shibata, Yosei; Koganezawa, Tomoyuki; Murakami, Takurou N; Sugita, Takeshi; Tanigaki, Nobutaka; Chikamatsu, Masayuki

    2015-08-12

    We analyzed the crystallization process of the CH3NH3PbI3 perovskite by observing real-time X-ray diffraction immediately after combining a PbI2 thin film with a CH3NH3I solution. A detailed analysis of the transformation kinetics demonstrated the fractal diffusion of the CH3NH3I solution into the PbI2 film. Moreover, the perovskite crystal was found to be initially oriented based on the PbI2 crystal orientation but to gradually transition to a random orientation. The fluctuating characteristics of the crystallization process of perovskites, such as fractal penetration and orientational transformation, should be controlled to allow the fabrication of high-quality perovskite crystals. The characteristic reaction dynamics observed in this study should assist in establishing reproducible fabrication processes for perovskite solar cells.

  6. A 2-terminal perovskite/silicon multijunction solar cell enabled by a silicon tunnel junction

    DOE PAGESBeta

    Mailoa, Jonathan P.; Bailie, Colin D.; Johlin, Eric C.; Hoke, Eric T.; Akey, Austin J.; Nguyen, William H.; McGehee, Michael D.; Buonassisi, Tonio

    2015-03-24

    With the advent of efficient high-bandgap metal-halide perovskite photovoltaics, an opportunity exists to make perovskite/silicon tandem solar cells. We fabricate a monolithic tandem by developing a silicon-based interband tunnel junction that facilitates majority-carrier charge recombination between the perovskite and silicon sub-cells. We demonstrate a 1 cm2 2-terminal monolithic perovskite/silicon multijunction solar cell with a VOC as high as 1.65 V. As a result, we achieve a stable 13.7% power conversion efficiency with the perovskite as the current-limiting sub-cell, and identify key challenges for this device architecture to reach efficiencies over 25%.

  7. Perovskite Solar Cells with Large-Area CVD-Graphene for Tandem Solar Cells.

    PubMed

    Lang, Felix; Gluba, Marc A; Albrecht, Steve; Rappich, Jörg; Korte, Lars; Rech, Bernd; Nickel, Norbert H

    2015-07-16

    Perovskite solar cells with transparent contacts may be used to compensate for thermalization losses of silicon solar cells in tandem devices. This offers a way to outreach stagnating efficiencies. However, perovskite top cells in tandem structures require contact layers with high electrical conductivity and optimal transparency. We address this challenge by implementing large-area graphene grown by chemical vapor deposition as a highly transparent electrode in perovskite solar cells, leading to identical charge collection efficiencies. Electrical performance of solar cells with a graphene-based contact reached those of solar cells with standard gold contacts. The optical transmission by far exceeds that of reference devices and amounts to 64.3% below the perovskite band gap. Finally, we demonstrate a four-terminal tandem device combining a high band gap graphene-contacted perovskite top solar cell (Eg = 1.6 eV) with an amorphous/crystalline silicon bottom solar cell (Eg = 1.12 eV).

  8. Toward Revealing the Critical Role of Perovskite Coverage in Highly Efficient Electron-Transport Layer-Free Perovskite Solar Cells: An Energy Band and Equivalent Circuit Model Perspective.

    PubMed

    Huang, Like; Xu, Jie; Sun, Xiaoxiang; Du, Yangyang; Cai, Hongkun; Ni, Jian; Li, Juan; Hu, Ziyang; Zhang, Jianjun

    2016-04-20

    Currently, most efficient perovskite solar cells (PVKSCs) with a p-i-n structure require simultaneously electron transport layers (ETLs) and hole transport layers (HTLs) to help collecting photogenerated electrons and holes for obtaining high performance. ETL free planar PVKSC is a relatively new and simple structured solar cell that gets rid of the complex and high temperature required ETL (such as compact and mesoporous TiO2). Here, we demonstrate the critical role of high coverage of perovskite in efficient ETL free PVKSCs from an energy band and equivalent circuit model perspective. From an electrical point of view, we confirmed that the low coverage of perovskite does cause localized short circuit of the device. With coverage optimization, a planar p-i-n(++) device with a power conversion efficiency of over 11% was achieved, implying that the ETL layer may not be necessary for an efficient device as long as the perovskite coverage is approaching 100%. PMID:27020395

  9. Toward Revealing the Critical Role of Perovskite Coverage in Highly Efficient Electron-Transport Layer-Free Perovskite Solar Cells: An Energy Band and Equivalent Circuit Model Perspective.

    PubMed

    Huang, Like; Xu, Jie; Sun, Xiaoxiang; Du, Yangyang; Cai, Hongkun; Ni, Jian; Li, Juan; Hu, Ziyang; Zhang, Jianjun

    2016-04-20

    Currently, most efficient perovskite solar cells (PVKSCs) with a p-i-n structure require simultaneously electron transport layers (ETLs) and hole transport layers (HTLs) to help collecting photogenerated electrons and holes for obtaining high performance. ETL free planar PVKSC is a relatively new and simple structured solar cell that gets rid of the complex and high temperature required ETL (such as compact and mesoporous TiO2). Here, we demonstrate the critical role of high coverage of perovskite in efficient ETL free PVKSCs from an energy band and equivalent circuit model perspective. From an electrical point of view, we confirmed that the low coverage of perovskite does cause localized short circuit of the device. With coverage optimization, a planar p-i-n(++) device with a power conversion efficiency of over 11% was achieved, implying that the ETL layer may not be necessary for an efficient device as long as the perovskite coverage is approaching 100%.

  10. 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

    2016-01-01

    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

  11. 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

  12. 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.

  13. Lattice constant prediction of defective rare earth titanate perovskites

    SciTech Connect

    Letourneau, Steven; Zhen, Zhen; Owens, Josh; Tolman, Kevin; Ubic, Rick; Kriven, Waltraud M.

    2014-11-15

    Engineering defective structures in an attempt to modify properties is an established technique in materials chemistry, yet, no models exist which can predict the structure of perovskite compounds containing extrinsic point defects such as vacancies. An empirically derived predictive model, based solely on chemical composition and published ionic radii has been developed. Effective vacancy sizes were derived both empirically from an existing model for pseudocubic lattice-constants, as well as experimentally, from average bond lengths calculated from neutron diffraction data. Compounds of lanthanum-doped barium titanate and strontium-doped magnesium titanate were synthesized with vacancies engineered on the A and B sites. Effective vacancy sizes were then used in empirical models to predict changes in lattice constants. Experimentally refined bond lengths used in the derivation of an effective vacancy size seemed to overestimate the effect of the point defects. Conversely, using calculated vacancy sizes, derived from a previously reported predictive model, showed significant improvements in the prediction of the pseudocubic perovskite lattice. - Graphical abstract: Atomistic model of Sr{sub 0.3}Nd{sub 0.7}Mg{sub 0.35}Ti{sub 0.65}O{sub 3} and Rietveld refinement of neutron diffraction data. - Highlights: • Defective perovskites were synthesized using the organic steric entrapment method. • Oxygen tilt systems were solved through X-ray, electron, and neutron diffraction. • An effective vacancy size for the cations was calculated from experimental bond lengths. • Discrepancies between Shannon radii and experimental measurements are explored. • An empirical model for predicting a{sub pc}, with an absolute error of 0.20%, was developed.

  14. Luminescence studies of perovskite structured titanates: A review

    NASA Astrophysics Data System (ADS)

    Nag Bhargavi, G.; Khare, Ayush

    2015-06-01

    Apart from widely known dielectric and ferroelectric properties, the perovskite type materials also constitute a class of materials, which are recently investigated for their optical properties. These materials are being used for fabrication of various microelectronics and optoelectronic devices. Photoluminescence (PL), mechanoluminescence (ML) and thermoluminescence (TL) are such phenomena offering numerous applications in different fields like electro-optics, flat panel displays, LED technology, sensors, dynamic visualization etc. This paper briefly reviews the status and new progress in luminescence studies of ferroelectric materials like barium titanate (BT), barium zirconate titanate (BZT), calcium titanate (CT), calcium zirconate titanate (CZT), lead titanate (PT), lead zirconate titanate (PZT), etc., prepared through various methods.

  15. First Principles Studies of ABO3 Perovskite Surfaces and Nanostructures

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam

    Perovskite-type complex oxides, with general formula ABO 3, constitute one of the most prominent classes of metal oxides which finds key applications in diverse technological fields. In recent years, properties of perovskites at reduced dimensions have aroused considerable interest. However, a complete atomic-level understanding of various phenomena is yet to emerge. To fully exploit the materials opportunities provided by nano-structured perovskites, it is important to characterize and understand their bulk and near-surface electronic structure along with the electric, magnetic, elastic and chemical properties of these materials in the nano-regime, where surface and interface effects naturally play a dominant role. In this thesis, state-of-the-art first principles computations are employed to systematically study properties of one- and two-dimensional perovskite systems which are of direct technological significance. Specifically, our bifocal study targets (1) polarization behavior and dielectric response of ABO3 ferroelectric nanowires, and (2) oxygen chemistry relevant for catalytic properties of ABO3 surfaces. In the first strand, we identify presence of novel closure or vortex-like polarization domains in PbTIO3 and BaTiO3 ferroelectric nanowires and explore ways to control the polarization configurations by means of strain and surface chemistry in these prototypical model systems. The intrinsic tendency towards vortex polarization at reduced dimensions and the underlying driving forces are discussed and previously unknown strain induced phase transitions are identified. Furthermore, to compute the dielectric permittivity of nanostructures, a new multiscale model is developed and applied to the PbTiO3 nanowires with conventional and vortex-like polarization configurations. The second part of the work undertaken in this thesis is comprised of a number of ab initio surface studies, targeted to investigate the effects of surface terminations, prevailing chemical

  16. What Is Moving in Hybrid Halide Perovskite Solar Cells?

    PubMed

    Frost, Jarvist M; Walsh, Aron

    2016-03-15

    Organic-inorganic semiconductors, which adopt the perovskite crystal structure, have perturbed the landscape of contemporary photovoltaics research. High-efficiency solar cells can be produced with solution-processed active layers. The materials are earth abundant, and the simple processing required suggests that high-throughput and low-cost manufacture at scale should be possible. While these materials bear considerable similarity to traditional inorganic semiconductors, there are notable differences in their optoelectronic behavior. A key distinction of these materials is that they are physically soft, leading to considerable thermally activated motion. In this Account, we discuss the internal motion of methylammonium lead iodide (CH3NH3PbI3) and formamidinium lead iodide ([CH(NH2)2]PbI3), covering: (i) molecular rotation-libration in the cuboctahedral cavity; (ii) drift and diffusion of large electron and hole polarons; (iii) transport of charged ionic defects. These processes give rise to a range of properties that are unconventional for photovoltaic materials, including frequency-dependent permittivity, low electron-hole recombination rates, and current-voltage hysteresis. Multiscale simulations, drawing from electronic structure, ab initio molecular dynamic and Monte Carlo computational techniques, have been combined with neutron diffraction measurements, quasi-elastic neutron scattering, and ultrafast vibrational spectroscopy to qualify the nature and time scales of the motions. Electron and hole motion occurs on a femtosecond time scale. Molecular libration is a sub-picosecond process. Molecular rotations occur with a time constant of several picoseconds depending on the cation. Recent experimental evidence and theoretical models for simultaneous electron and ion transport in these materials has been presented, suggesting they are mixed-mode conductors with similarities to fast-ion conducting metal oxide perovskites developed for battery and fuel cell

  17. Optical Properties of Photovoltaic Organic-Inorganic Lead Halide Perovskites.

    PubMed

    Green, Martin A; Jiang, Yajie; Soufiani, Arman Mahboubi; Ho-Baillie, Anita

    2015-12-01

    Over the last several years, organic-inorganic lead halide perovskites have rapidly emerged as a new photovoltaic contender. Although energy conversion efficiency above 20% has now been certified, improved understanding of the material properties contributing to these high performance levels may allow the progression to even higher efficiency, stable cells. The optical properties of these new materials are important not only to device design but also because of the insight they provide into less directly accessible properties, including energy-band structures, binding energies, and likely impact of excitons, as well as into absorption and inverse radiative recombination processes.

  18. Competing interactions in ferromagnetic/antiferromagnetic perovskite superlattices

    SciTech Connect

    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.

  19. Magnetic coupling at perovskite and rock-salt structured interfaces

    SciTech Connect

    Matvejeff, M.; Ahvenniemi, E.; Takahashi, R.; Lippmaa, M.

    2015-10-05

    We study magnetic coupling between hole-doped manganite layers separated by either a perovskite or a rock-salt barrier of variable thickness. Both the type and the quality of the interface have a strong impact on the minimum critical barrier thickness where the manganite layers become magnetically decoupled. A rock-salt barrier layer only 1 unit cell (0.5 nm) thick remains insulating and is able to magnetically de-couple the electrode layers. The technique can therefore be used for developing high-performance planar oxide electronic devices such as magnetic tunnel junctions and quantum well structures that depend on magnetically and electronically sharp heterointerfaces.

  20. What Is Moving in Hybrid Halide Perovskite Solar Cells?

    PubMed Central

    2016-01-01

    Conspectus Organic–inorganic semiconductors, which adopt the perovskite crystal structure, have perturbed the landscape of contemporary photovoltaics research. High-efficiency solar cells can be produced with solution-processed active layers. The materials are earth abundant, and the simple processing required suggests that high-throughput and low-cost manufacture at scale should be possible. While these materials bear considerable similarity to traditional inorganic semiconductors, there are notable differences in their optoelectronic behavior. A key distinction of these materials is that they are physically soft, leading to considerable thermally activated motion. In this Account, we discuss the internal motion of methylammonium lead iodide (CH3NH3PbI3) and formamidinium lead iodide ([CH(NH2)2]PbI3), covering: (i) molecular rotation-libration in the cuboctahedral cavity; (ii) drift and diffusion of large electron and hole polarons; (iii) transport of charged ionic defects. These processes give rise to a range of properties that are unconventional for photovoltaic materials, including frequency-dependent permittivity, low electron–hole recombination rates, and current–voltage hysteresis. Multiscale simulations, drawing from electronic structure, ab initio molecular dynamic and Monte Carlo computational techniques, have been combined with neutron diffraction measurements, quasi-elastic neutron scattering, and ultrafast vibrational spectroscopy to qualify the nature and time scales of the motions. Electron and hole motion occurs on a femtosecond time scale. Molecular libration is a sub-picosecond process. Molecular rotations occur with a time constant of several picoseconds depending on the cation. Recent experimental evidence and theoretical models for simultaneous electron and ion transport in these materials has been presented, suggesting they are mixed-mode conductors with similarities to fast-ion conducting metal oxide perovskites developed for battery

  1. Efficient light-emitting diodes based on nanocrystalline perovskite in a dielectric polymer matrix.

    PubMed

    Li, Guangru; Tan, Zhi-Kuang; Di, Dawei; Lai, May Ling; Jiang, Lang; Lim, Jonathan Hua-Wei; Friend, Richard H; Greenham, Neil C

    2015-04-01

    Electroluminescence in light-emitting devices relies on the encounter and radiative recombination of electrons and holes in the emissive layer. In organometal halide perovskite light-emitting diodes, poor film formation creates electrical shunting paths, where injected charge carriers bypass the perovskite emitter, leading to a loss in electroluminescence yield. Here, we report a solution-processing method to block electrical shunts and thereby enhance electroluminescence quantum efficiency in perovskite devices. In this method, a blend of perovskite and a polyimide precursor dielectric (PIP) is solution-deposited to form perovskite nanocrystals in a thin-film matrix of PIP. The PIP forms a pinhole-free charge-blocking layer, while still allowing the embedded perovskite crystals to form electrical contact with the electron- and hole-injection layers. This modified structure reduces nonradiative current losses and improves quantum efficiency by 2 orders of magnitude, giving an external quantum efficiency of 1.2%. This simple technique provides an alternative route to circumvent film formation problems in perovskite optoelectronics and offers the possibility of flexible and high-performance light-emitting displays.

  2. van der Waals Heterojunction Devices Based on Organohalide Perovskites and Two-Dimensional Materials.

    PubMed

    Cheng, Hung-Chieh; Wang, Gongming; Li, Dehui; He, Qiyuan; Yin, Anxiang; Liu, Yuan; Wu, Hao; Ding, Mengning; Huang, Yu; Duan, Xiangfeng

    2016-01-13

    The recently emerged organohalide perovskites (e.g., CH3NH3PbI3) have drawn intense attention for high efficiency solar cells. However, with a considerable solubility in many solvents, these perovskites are not typically compatible with conventional lithography processes for more complicated device fabrications that are important for both fundamental studies and technological applications. Here, we report the creation of novel heterojunction devices based on perovskites and two-dimensional (2D) crystals by taking advantage of the layered characteristic of lead iodide (PbI2) and vapor-phase intercalation. We show that a graphene/perovskite/graphene vertical stack can deliver a highest photoresponsivity of ∼950 A/W and photoconductive gain of ∼2200, and a graphene/WSe2/perovskite/graphene heterojunction can display a high on/off ratio (∼10(6)) transistor behavior with distinct gate-tunable diode characteristics and open-circuit voltages. Such unique perovskite-2D heterostructures have significant potential for future optoelectronic research and can enable broad possibilities with compositional tunability of organohalide perovskites and the versatility offered by diverse 2D materials.

  3. Flexible and Semitransparent Organolead Triiodide Perovskite Network Photodetector Arrays with High Stability.

    PubMed

    Deng, Hui; Yang, Xiaokun; Dong, Dongdong; Li, Bing; Yang, Dun; Yuan, Shengjie; Qiao, Keke; Cheng, Yi-Bing; Tang, Jiang; Song, Haisheng

    2015-12-01

    Organolead triiodide perovskite (CH3NH3PbI3) as a light-sensitive material has attracted extensive attention in optoelectronics. The reported perovskite photodetectors (PDs) mainly focus on the individual, which limits their spatial imaging applications. Uniform perovskite networks combining transparency and device performance were synthesized on poly(ethylene terephthalate) (PET) by controlling perovskite crystallization. Photodetector arrays based on above network were fabricated to demonstrate the potential for image mapping. The trade-off between the PD performance and transparency was systematically investigated and the optimal device was obtained from 30 wt % precursor concentration. The switching ratio, normalized detectivity, and equivalent dark current derived shot noise as the critical parameters of PD arrays reached 300, 1.02 × 10(12) Jones, and 4.73 × 10(-15)A Hz(-1/2), respectively. Furthermore, the PD arrays could clearly detect spatial light intensity distribution, thus demonstrating its preliminary imaging function. The perovskite network PD arrays fabricated on PET substrates could also conduct superior flexibility under wide angle and large number of bending. For the common problem of perovskite optoelectronics in stability, the perovskite networks sheathed with hydrophobic polymers greatly enhanced the device stability due to the improved interface contacts, surface passivation, and moisture isolation. Taking into consideration transparency, flexibility, imaging and stability, the present PD arrays were expected to be widely applied in visualized portable optoelectronic system.

  4. High Efficiency Tandem Thin-Perovskite/Polymer Solar Cells with a Graded Recombination Layer.

    PubMed

    Liu, Yao; Renna, Lawrence A; Bag, Monojit; Page, Zachariah A; Kim, Paul; Choi, Jaewon; Emrick, Todd; Venkataraman, D; Russell, Thomas P

    2016-03-23

    Perovskite-containing tandem solar cells are attracting attention for their potential to achieve high efficiencies. We demonstrate a series connection of a ∼ 90 nm thick perovskite front subcell and a ∼ 100 nm thick polymer:fullerene blend back subcell that benefits from an efficient graded recombination layer containing a zwitterionic fullerene, silver (Ag), and molybdenum trioxide (MoO3). This methodology eliminates the adverse effects of thermal annealing or chemical treatment that occurs during perovskite fabrication on polymer-based front subcells. The record tandem perovskite/polymer solar cell efficiency of 16.0%, with low hysteresis, is 75% greater than that of the corresponding ∼ 90 nm thick perovskite single-junction device and 65% greater than that of the polymer single-junction device. The high efficiency of this hybrid tandem device, achieved using only a ∼ 90 nm thick perovskite layer, provides an opportunity to substantially reduce the lead content in the device, while maintaining the high performance derived from perovskites. PMID:26918708

  5. Organic-inorganic hybrid lead halide perovskites for optoelectronic and electronic applications.

    PubMed

    Zhao, Yixin; Zhu, Kai

    2016-02-01

    Organic and inorganic hybrid perovskites (e.g., CH(3)NH(3)PbI(3)), with advantages of facile processing, tunable bandgaps, and superior charge-transfer properties, have emerged as a new class of revolutionary optoelectronic semiconductors promising for various applications. Perovskite solar cells constructed with a variety of configurations have demonstrated unprecedented progress in efficiency, reaching about 20% from multiple groups after only several years of active research. A key to this success is the development of various solution-synthesis and film-deposition techniques for controlling the morphology and composition of hybrid perovskites. The rapid progress in material synthesis and device fabrication has also promoted the development of other optoelectronic applications including light-emitting diodes, photodetectors, and transistors. Both experimental and theoretical investigations on organic-inorganic hybrid perovskites have enabled some critical fundamental understandings of this material system. Recent studies have also demonstrated progress in addressing the potential stability issue, which has been identified as a main challenge for future research on halide perovskites. Here, we review recent progress on hybrid perovskites including basic chemical and crystal structures, chemical synthesis of bulk/nanocrystals and thin films with their chemical and physical properties, device configurations, operation principles for various optoelectronic applications (with a focus on solar cells), and photophysics of charge-carrier dynamics. We also discuss the importance of further understanding of the fundamental properties of hybrid perovskites, especially those related to chemical and structural stabilities. PMID:26645733

  6. High Efficiency Tandem Thin-Perovskite/Polymer Solar Cells with a Graded Recombination Layer.

    PubMed

    Liu, Yao; Renna, Lawrence A; Bag, Monojit; Page, Zachariah A; Kim, Paul; Choi, Jaewon; Emrick, Todd; Venkataraman, D; Russell, Thomas P

    2016-03-23

    Perovskite-containing tandem solar cells are attracting attention for their potential to achieve high efficiencies. We demonstrate a series connection of a ∼ 90 nm thick perovskite front subcell and a ∼ 100 nm thick polymer:fullerene blend back subcell that benefits from an efficient graded recombination layer containing a zwitterionic fullerene, silver (Ag), and molybdenum trioxide (MoO3). This methodology eliminates the adverse effects of thermal annealing or chemical treatment that occurs during perovskite fabrication on polymer-based front subcells. The record tandem perovskite/polymer solar cell efficiency of 16.0%, with low hysteresis, is 75% greater than that of the corresponding ∼ 90 nm thick perovskite single-junction device and 65% greater than that of the polymer single-junction device. The high efficiency of this hybrid tandem device, achieved using only a ∼ 90 nm thick perovskite layer, provides an opportunity to substantially reduce the lead content in the device, while maintaining the high performance derived from perovskites.

  7. Fabrication of potato-like silver molybdate microstructures for photocatalytic degradation of chronic toxicity ciprofloxacin and highly selective electrochemical detection of H2O2

    PubMed Central

    Kumar, J. Vinoth; Karthik, R.; Chen, Shen-Ming; Muthuraj, V.; Karuppiah, Chelladurai

    2016-01-01

    In the present work, potato-like silver molybdate (Ag2MoO4) microstructures were synthesized through a simple hydrothermal method. The microstructures of Ag2MoO4 were characterized by various analytical and spectroscopic techniques such as XRD, FTIR, Raman, SEM, EDX and XPS. Interestingly, the as-prepared Ag2MoO4 showed excellent photocatalytic and electrocatalytic activity for the degradation of ciprofloxacin (CIP) and electrochemical detection of hydrogen peroxide (H2O2), respectively. The ultraviolet-visible (UV-Vis) spectroscopy results revealed that the potato-like Ag2MoO4 microstructures could offer a high photocatalytic activity towards the degradation of CIP under UV-light illumination, leads to rapid degradation within 40 min with a degradation rate of above 98%. In addition, the cyclic voltammetry (CV) and amperometry studies were realized that the electrochemical performance of Ag2MoO4 modified electrode toward H2O2 detection. Our H2O2 sensor shows a wide linear range and lower detection limit of 0.04–240 μM and 0.03 μM, respectively. The Ag2MoO4 modified electrode exhibits a high selectivity towards the detection of H2O2 in the presence of different biological interferences. These results suggested that the development of potato-like Ag2MoO4 microstructure could be an efficient photocatalyst as well as electrocatalyst in the potential application of environmental, biomedical and pharmaceutical samples. PMID:27671795

  8. High-temperature behavior of dicesium molybdate Cs{sub 2}MoO{sub 4}: Implications for fast neutron reactors

    SciTech Connect

    Wallez, Gilles; Raison, Philippe E.; Smith, Anna L.; Clavier, Nicolas

    2014-07-01

    Dicesium molybdate (Cs{sub 2}MoO{sub 4})'s thermal expansion and crystal structure have been investigated herein by high temperature X ray diffraction in conjunction with Raman spectroscopy. This first crystal-chemical insight at high temperature is aimed at predicting the thermostructural and thermomechanical behavior of this oxide formed by the accumulation of Cs and Mo fission products at the periphery of nuclear fuel rods in sodium-cooled fast reactors. Within the temperature range of the fuel's rim, Cs{sub 2}MoO{sub 4} becomes hexagonal P6{sub 3}/mmc, with disordered MoO{sub 4} tetrahedra and 2D distribution of Cs–O bonds that makes thermal axial expansion both large (50≤α{sub l}≤70 10{sup −6} °C{sup −1}, 500–800 °C) and highly anisotropic (α{sub c}−α{sub a}=67×10{sup −6} °C{sup −1}, hexagonal form). The difference with the fuel's expansion coefficient is of potential concern with respect to the cohesion of the Cs{sub 2}MoO{sub 4} surface film and the possible release of cesium radionuclides in accidental situations. - Graphical abstract: The weakness of the Cs–O bonds and the disordering of the MoO{sub 4} tetrahedra array in the high-temperature form are responsible for the huge thermal expansion of Cs{sub 2}MoO{sub 4} along the c-axis. - Highlights: • Thermomechanical behavior of Cs{sub 2}MoO{sub 4} fission products compound is studied. • High-temperature form of Cs{sub 2}MoO{sub 4} is characterized by XRD and Raman. • Thermal expansion appears very high and anisotropic. • Cohesion between Cs{sub 2}MoO{sub 4} and nuclear fuel seems questionable, and Cs release is expected.

  9. Fabrication of potato-like silver molybdate microstructures for photocatalytic degradation of chronic toxicity ciprofloxacin and highly selective electrochemical detection of H2O2

    NASA Astrophysics Data System (ADS)

    Kumar, J. Vinoth; Karthik, R.; Chen, Shen-Ming; Muthuraj, V.; Karuppiah, Chelladurai

    2016-09-01

    In the present work, potato-like silver molybdate (Ag2MoO4) microstructures were synthesized through a simple hydrothermal method. The microstructures of Ag2MoO4 were characterized by various analytical and spectroscopic techniques such as XRD, FTIR, Raman, SEM, EDX and XPS. Interestingly, the as-prepared Ag2MoO4 showed excellent photocatalytic and electrocatalytic activity for the degradation of ciprofloxacin (CIP) and electrochemical detection of hydrogen peroxide (H2O2), respectively. The ultraviolet-visible (UV-Vis) spectroscopy results revealed that the potato-like Ag2MoO4 microstructures could offer a high photocatalytic activity towards the degradation of CIP under UV-light illumination, leads to rapid degradation within 40 min with a degradation rate of above 98%. In addition, the cyclic voltammetry (CV) and amperometry studies were realized that the electrochemical performance of Ag2MoO4 modified electrode toward H2O2 detection. Our H2O2 sensor shows a wide linear range and lower detection limit of 0.04–240 μM and 0.03 μM, respectively. The Ag2MoO4 modified electrode exhibits a high selectivity towards the detection of H2O2 in the presence of different biological interferences. These results suggested that the development of potato-like Ag2MoO4 microstructure could be an efficient photocatalyst as well as electrocatalyst in the potential application of environmental, biomedical and pharmaceutical samples.

  10. Solvent-Assisted Gel Printing for Micropatterning Thin Organic-Inorganic Hybrid Perovskite Films.

    PubMed

    Jeong, Beomjin; Hwang, Ihn; Cho, Sung Hwan; Kim, Eui Hyuk; Cha, Soonyoung; Lee, Jinseong; Kang, Han Sol; Cho, Suk Man; Choi, Hyunyong; Park, Cheolmin

    2016-09-27

    While tremendous efforts have been made for developing thin perovskite films suitable for a variety of potential photoelectric applications such as solar cells, field-effect transistors, and photodetectors, only a few works focus on the micropatterning of a perovskite film which is one of the most critical issues for large area and uniform microarrays of perovskite-based devices. Here we demonstrate a simple but robust method of micropatterning a thin perovskite film with controlled crystalline structure which guarantees to preserve its intrinsic photoelectric properties. A variety of micropatterns of a perovskite film are fabricated by either microimprinting or transfer-printing a thin spin-coated precursor film in soft-gel state with a topographically prepatterned elastomeric poly(dimethylsiloxane) (PDMS) mold, followed by thermal treatment for complete conversion of the precursor film to a perovskite one. The key materials development of our solvent-assisted gel printing is to prepare a thin precursor film with a high-boiling temperature solvent, dimethyl sulfoxide. The residual solvent in the precursor gel film makes the film moldable upon microprinting with a patterned PDMS mold, leading to various perovskite micropatterns in resolution of a few micrometers over a large area. Our nondestructive micropatterning process does not harm the intrinsic photoelectric properties of a perovskite film, which allows for realizing arrays of parallel-type photodetectors containing micropatterns of a perovskite film with reliable photoconduction performance. The facile transfer of a micropatterned soft-gel precursor film on other substrates including mechanically flexible plastics can further broaden its applications to flexible photoelectric systems.

  11. Additive to regulate the perovskite crystal film growth in planar heterojunction solar cells

    SciTech Connect

    Song, Xin; Sun, Po; Chen, Zhi-Kuan E-mail: iamzkchen@njtech.edu.cn; Wang, Weiwei; Ma, Wanli E-mail: iamzkchen@njtech.edu.cn

    2015-01-19

    We reported a planar heterojunction perovskite solar cell fabricated from MAPbI{sub 3−x}Cl{sub x} perovskite precursor solution containing 1-chloronaphthalene (CN) additive. The MAPbI{sub 3−x}Cl{sub x} perovskite films have been characterized by UV-vis, SEM, XRD, and steady-state photoluminescence (PL). UV-vis absorption spectra measurement shows that the absorbance of the film with CN additive is significantly higher than the pristine film and the absorption peak is red shift by 30 nm, indicating the perovskite film with additive possessing better crystal structures. In-situ XRD study of the perovskite films with additive demonstrated intense diffraction peaks from MAPbI{sub 3−x}Cl{sub x} perovskite crystal planes of (110), (220), and (330). SEM images of the films with additive indicated the films were more smooth and homogenous with fewer pin-holes and voids and better surface coverage than the pristine films. These results implied that the additive CN is beneficial to regulate the crystallization transformation kinetics of perovskite to form high quality crystal films. The steady-state PL measurement suggested that the films with additive contained less charge traps and defects. The planar heterojunction perovskite solar cells fabricated from perovskite precursor solution containing CN additive demonstrated 30% enhancement in performance compared to the devices with pristine films. The improvement in device efficiency is mainly attributed to the good crystal structures, more homogenous film morphology, and also fewer trap centers and defects in the films with the additive.

  12. Solvent-Assisted Gel Printing for Micropatterning Thin Organic-Inorganic Hybrid Perovskite Films.

    PubMed

    Jeong, Beomjin; Hwang, Ihn; Cho, Sung Hwan; Kim, Eui Hyuk; Cha, Soonyoung; Lee, Jinseong; Kang, Han Sol; Cho, Suk Man; Choi, Hyunyong; Park, Cheolmin

    2016-09-27

    While tremendous efforts have been made for developing thin perovskite films suitable for a variety of potential photoelectric applications such as solar cells, field-effect transistors, and photodetectors, only a few works focus on the micropatterning of a perovskite film which is one of the most critical issues for large area and uniform microarrays of perovskite-based devices. Here we demonstrate a simple but robust method of micropatterning a thin perovskite film with controlled crystalline structure which guarantees to preserve its intrinsic photoelectric properties. A variety of micropatterns of a perovskite film are fabricated by either microimprinting or transfer-printing a thin spin-coated precursor film in soft-gel state with a topographically prepatterned elastomeric poly(dimethylsiloxane) (PDMS) mold, followed by thermal treatment for complete conversion of the precursor film to a perovskite one. The key materials development of our solvent-assisted gel printing is to prepare a thin precursor film with a high-boiling temperature solvent, dimethyl sulfoxide. The residual solvent in the precursor gel film makes the film moldable upon microprinting with a patterned PDMS mold, leading to various perovskite micropatterns in resolution of a few micrometers over a large area. Our nondestructive micropatterning process does not harm the intrinsic photoelectric properties of a perovskite film, which allows for realizing arrays of parallel-type photodetectors containing micropatterns of a perovskite film with reliable photoconduction performance. The facile transfer of a micropatterned soft-gel precursor film on other substrates including mechanically flexible plastics can further broaden its applications to flexible photoelectric systems. PMID:27571339

  13. Ion-solvent and ion-ion interactions of sodium molybdate and sodium tungstate in mixtures of acetonitrile and water at 298.15, 308.15, and 318.15 K

    NASA Astrophysics Data System (ADS)

    Sarkar, B. K.; Sinha, B.; Roy, M. N.

    2008-06-01

    The apparent molar volumes ( V ϕ) and viscosity B-coefficients of sodium molybdate and sodium tungstate in aqueous binary mixtures of acetonitrile were determined from solution density and viscosity measurements at 298.15, 308.15 and 318.15 K and various electrolyte concentrations. The experimental density and viscosity data were evaluated by the Masson and Jones-Dole equations, respectively, and the parameters derived were interpreted in terms of ion-solvent and ion-ion interactions. The activation parameters of viscous flow were also determined and discussed using transition state theory.

  14. Molecular Origin of Properties of Organic-Inorganic Hybrid Perovskites: The Big Picture from Small Clusters.

    PubMed

    Fang, Hong; Jena, Puru

    2016-04-21

    We show that the electronic properties, including the band gap, the gap deformation potential, and the exciton binding energy as well as the chemical stability of organic-inorganic hybrid perovskites can be traced back to their corresponding molecular motifs. This understanding allows one to quickly estimate the properties of the bulk semiconductors from their corresponding molecular building blocks. New hybrid perovskite admixtures are proposed by replacing halogens with superhalogens having compatible ionic radii. The mechanism of the boron-hydride based hybrid perovskite reacting with water is investigated by using a cluster model. PMID:27064550

  15. Evidence for reduced charge recombination in carbon nanotube/perovskite-based active layers

    NASA Astrophysics Data System (ADS)

    Bag, Monojit; Renna, Lawrence A.; Jeong, Seung Pyo; Han, Xu; Cutting, Christie L.; Maroudas, Dimitrios; Venkataraman, D.

    2016-10-01

    Using impedance spectroscopy and computation, we show that incorporation of multi-walled carbon nanotubes (MWCNTs) in the bulk of the active layer of perovskite-based solar cells reduces charge recombination and increases the open circuit voltage. An ∼87% reduction in recombination was achieved when MWCNTs were introduced in the planar-heterostructure perovskite solar cell containing mixed counterions. The open circuit voltage (Voc) of perovskite/MWCNTs devices was increased by 70 mV, while the short circuit current density (Jsc) and fill factor (FF) remained unchanged.

  16. Surface coverage enhancement of a mixed halide perovskite film by using an UV-ozone treatment

    NASA Astrophysics Data System (ADS)

    Lee, Hyunho; Rhee, Seunghyun; Kim, Jaeyoul; Lee, Changhee; Kim, Hyeok

    2016-08-01

    Recently, a significant breakthrough in emerging photovoltaics occurred. Now, perovskite solar cells, hybrid types of organic and inorganic solar cells, are considered as reliable next-generation solar cells due to their outstanding photovoltaic performance. Records of the National Renewable Energy Laboratory (NREL) on cell efficiency research indicates a prominent growth in the power conversion efficiency (PCE) of a perovskite solar cells which is now approaching 20.1%. Perovskite solar cells are, in general, classified into three types based on their structures; the mesoporous type with TiO2 nanoparticles, the meso-superstructure type with Al2O3 and the planar hetero-junction type. Among them, planar-structured perovskite solar cells have strong advantages due to their easy processibility and flexibility. We can replace the materials in the electron transport layer (ETL) and the hole transport layer (HTL) with common materials that are available in organic solar cells. However, a great challenge is to fabricate a high-quality perovskite film because the perovskite morphology is highly sensitive to its fabrication conditions. For control of the film's morphology, some experiments, such as changing the annealing temperature or time and adding some additives, have been done to increase the surface coverage of perovskite films. In this work, we introduce normal, planar, perovskite solar cells with a hetero-junction structure based on compact TiO2 and a mixed halide perovskite (CH3NH3PbI3- x Cl x ). To enlarge the surface coverage of perovskite film, we used an UV-ozone treatment on top of the compact TiO2, which made the surface of TiO2 hydrophilic. Because a perovskite precursor is hydrophilic, an UV-ozone treatment is expected to improve the wettability between the compact TiO2 and the perovskite film. Here, we present the photovoltaic performance, along with the surface coverage difference, for various UV-ozone treatment time. In addition, the effect of the UV

  17. Efficient Light Harvester Layer Prepared by Solid/Mist Interface Reaction for Perovskite Solar Cells.

    PubMed

    Xia, Xiang; Li, Hongcui; Wu, Wenyi; Li, Yanhua; Fei, Dehou; Gao, Chunxiao; Liu, Xizhe

    2015-08-12

    A solid/mist reaction method is developed to produce well-crystallized light harvester layers without pinhole defects for perovskite solar cells. The reaction based on mist precursor can be facilely operated with low process temperature. And it can effectively control the volume of CH3NH3I solution and the reaction temperature, which affect the quality of perovskite harvester layers and the performance of perovskite solar cells remarkably. Under optimized condition, the efficiencies of devices reach 16.2% with the average efficiency of 14.9%. The solid/mist reaction is also used to fabricate planar junction solar cells and a PCE of 14.9% is obtained.

  18. Perovskites: transforming photovoltaics, a mini-review

    NASA Astrophysics Data System (ADS)

    Chilvery, Ashwith Kumar; Batra, Ashok K.; Yang, Bin; Xiao, Kai; Guggilla, Padmaja; Aggarwal, Mohan D.; Surabhi, Raja; Lal, Ravi B.; Currie, James R.; Penn, Benjamin G.

    2015-01-01

    The recent power-packed advent of perovskite solar cells is transforming photovoltaics (PV) with their superior efficiencies, ease of fabrication, and cost. This perovskite solar cell further boasts of many unexplored features that can further enhance its PV properties and lead to it being branded as a successful commercial product. This article provides a detailed insight of the organometal halide based perovskite structure, its unique stoichiometric design, and its underlying principles for PV applications. The compatibility of various PV layers and its fabrication methods is also discussed.

  19. Growing perovskite into polymers for easy-processable optoelectronic devices

    NASA Astrophysics Data System (ADS)

    Masi, Sofia; Colella, Silvia; Listorti, Andrea; Roiati, Vittoria; Liscio, Andrea; Palermo, Vincenzo; Rizzo, Aurora; Gigli, Giuseppe

    2015-01-01

    Here we conceive an innovative nanocomposite to endow hybrid perovskites with the easy processability of polymers, providing a tool to control film quality and material crystallinity. We verify that the employed semiconducting polymer, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), controls the self-assembly of CH3NH3PbI3 (MAPbI3) crystalline domains and favors the deposition of a very smooth and homogenous layer in one straightforward step. This idea offers a new paradigm for the implementation of polymer/perovskite nanocomposites towards versatile optoelectronic devices combined with the feasibility of mass production. As a proof-of-concept we propose the application of such nanocomposite in polymer solar cell architecture, demonstrating a power conversion efficiency up to 3%, to date the highest reported for MEH-PPV. On-purpose designed polymers are expected to suit the nanocomposite properties for the integration in diverse optoelectronic devices via facile processing condition.

  20. Perovskite energy funnels for efficient light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Yuan, Mingjian; Quan, Li Na; Comin, Riccardo; Walters, Grant; Sabatini, Randy; Voznyy, Oleksandr; Hoogland, Sjoerd; Zhao, Yongbiao; Beauregard, Eric M.; Kanjanaboos, Pongsakorn; Lu, Zhenghong; Kim, Dong Ha; Sargent, Edward H.

    2016-10-01

    Organometal halide perovskites exhibit large bulk crystal domain sizes, rare traps, excellent mobilities and carriers that are free at room temperature—properties that support their excellent performance in charge-separating devices. In devices that rely on the forward injection of electrons and holes, such as light-emitting diodes (LEDs), excellent mobilities contribute to the efficient capture of non-equilibrium charge carriers by rare non-radiative centres. Moreover, the lack of bound excitons weakens the competition of desired radiative (over undesired non-radiative) recombination. Here we report a perovskite mixed material comprising a series of differently quantum-size-tuned grains that funnels photoexcitations to the lowest-bandgap light-emitter in the mixture. The materials function as charge carrier concentrators, ensuring that radiative recombination successfully outcompetes trapping and hence non-radiative recombination. We use the new material to build devices that exhibit an external quantum efficiency (EQE) of 8.8% and a radiance of 80 W sr‑1 m‑2. These represent the brightest and most efficient solution-processed near-infrared LEDs to date.

  1. Growing perovskite into polymers for easy-processable optoelectronic devices

    PubMed Central

    Masi, Sofia; Colella, Silvia; Listorti, Andrea; Roiati, Vittoria; Liscio, Andrea; Palermo, Vincenzo; Rizzo, Aurora; Gigli, Giuseppe

    2015-01-01

    Here we conceive an innovative nanocomposite to endow hybrid perovskites with the easy processability of polymers, providing a tool to control film quality and material crystallinity. We verify that the employed semiconducting polymer, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), controls the self-assembly of CH3NH3PbI3 (MAPbI3) crystalline domains and favors the deposition of a very smooth and homogenous layer in one straightforward step. This idea offers a new paradigm for the implementation of polymer/perovskite nanocomposites towards versatile optoelectronic devices combined with the feasibility of mass production. As a proof-of-concept we propose the application of such nanocomposite in polymer solar cell architecture, demonstrating a power conversion efficiency up to 3%, to date the highest reported for MEH-PPV. On-purpose designed polymers are expected to suit the nanocomposite properties for the integration in diverse optoelectronic devices via facile processing condition. PMID:25579988

  2. Lead iodide perovskite light-emitting field-effect transistor

    PubMed Central

    Chin, Xin Yu; Cortecchia, Daniele; Yin, Jun; Bruno, Annalisa; Soci, Cesare

    2015-01-01

    Despite the widespread use of solution-processable hybrid organic–inorganic perovskites in photovoltaic and light-emitting applications, determination of their intrinsic charge transport parameters has been elusive due to the variability of film preparation and history-dependent device performance. Here we show that screening effects associated to ionic transport can be effectively eliminated by lowering the operating temperature of methylammonium lead iodide perovskite (CH3NH3PbI3) field-effect transistors. Field-effect carrier mobility is found to increase by almost two orders of magnitude below 200 K, consistent with phonon scattering-limited transport. Under balanced ambipolar carrier injection, gate-dependent electroluminescence is also observed from the transistor channel, with spectra revealing the tetragonal to orthorhombic phase transition. This demonstration of CH3NH3PbI3 light-emitting field-effect transistors provides intrinsic transport parameters to guide materials and solar cell optimization, and will drive the development of new electro-optic device concepts, such as gated light-emitting diodes and lasers operating at room temperature. PMID:26108967

  3. Lead iodide perovskite light-emitting field-effect transistor

    NASA Astrophysics Data System (ADS)

    Chin, Xin Yu; Cortecchia, Daniele; Yin, Jun; Bruno, Annalisa; Soci, Cesare

    2015-06-01

    Despite the widespread use of solution-processable hybrid organic-inorganic perovskites in photovoltaic and light-emitting applications, determination of their intrinsic charge transport parameters has been elusive due to the variability of film preparation and history-dependent device performance. Here we show that screening effects associated to ionic transport can be effectively eliminated by lowering the operating temperature of methylammonium lead iodide perovskite (CH3NH3PbI3) field-effect transistors. Field-effect carrier mobility is found to increase by almost two orders of magnitude below 200 K, consistent with phonon scattering-limited transport. Under balanced ambipolar carrier injection, gate-dependent electroluminescence is also observed from the transistor channel, with spectra revealing the tetragonal to orthorhombic phase transition. This demonstration of CH3NH3PbI3 light-emitting field-effect transistors provides intrinsic transport parameters to guide materials and solar cell optimization, and will drive the development of new electro-optic device concepts, such as gated light-emitting diodes and lasers operating at room temperature.

  4. Classification of ABO3 perovskite solids: a machine learning study.

    PubMed

    Pilania, G; Balachandran, P V; Gubernatis, J E; Lookman, T

    2015-10-01

    We explored the use of machine learning methods for classifying whether a particular ABO3 chemistry forms a perovskite or non-perovskite structured solid. Starting with three sets of feature pairs (the tolerance and octahedral factors, the A and B ionic radii relative to the radius of O, and the bond valence distances between the A and B ions from the O atoms), we used machine learning to create a hyper-dimensional partial dependency structure plot using all three feature pairs or any two of them. Doing so increased the accuracy of our predictions by 2-3 percentage points over using any one pair. We also included the Mendeleev numbers of the A and B atoms to this set of feature pairs. Doing this and using the capabilities of our machine learning algorithm, the gradient tree boosting classifier, enabled us to generate a new type of structure plot that has the simplicity of one based on using just the Mendeleev numbers, but with the added advantages of having a higher accuracy and providing a measure of likelihood of the predicted structure.

  5. Design Principles of Perovskites for Thermochemical Oxygen Separation

    PubMed Central

    Ezbiri, Miriam; Allen, Kyle M.; Gàlvez, Maria E.; Steinfeld, Aldo

    2015-01-01

    Abstract Separation and concentration of O2 from gas mixtures is central to several sustainable energy technologies, such as solar‐driven synthesis of liquid hydrocarbon fuels from CO2, H2O, and concentrated sunlight. We introduce a rationale for designing metal oxide redox materials for oxygen separation through “thermochemical pumping” of O2 against a pO2 gradient with low‐grade process heat. Electronic structure calculations show that the activity of O vacancies in metal oxides pinpoints the ideal oxygen exchange capacity of perovskites. Thermogravimetric analysis and high‐temperature X‐ray diffraction for SrCoO3−δ, BaCoO3−δ and BaMnO3−δ perovskites and Ag2O and Cu2O references confirm the predicted performance of SrCoO3−δ, which surpasses the performance of state‐of‐the‐art Cu2O at these conditions with an oxygen exchange capacity of 44 mmol O 2 mol SrCoO 3−δ −1 exchanged at 12.1 μmol O 2 min−1 g−1 at 600–900 K. The redox trends are understood due to lattice expansion and electronic charge transfer. PMID:25925955

  6. Identification of Trap States in Perovskite Solar Cells.

    PubMed

    Baumann, Andreas; Väth, Stefan; Rieder, Philipp; Heiber, Michael C; Tvingstedt, Kristofer; Dyakonov, Vladimir

    2015-06-18

    Thermally stimulated current (TSC) measurements are used to characterize electronic trap states in methylammonium lead iodide perovsite solar cells. Several TSC peaks were observed over the temperature range from 20 K to room temperature. To elucidate the origins of these peaks, devices with various organic charge transport layers and devices without transport layers were tested. Two peaks appear at very low temperatures, indicating shallow trap states that are mainly attributed to the PCBM/C60 electron transport bilayer. However, two additional peaks appear at higher temperatures, that is, they are deeper in energy, and are assigned to the perovskite layer. At around T = 163 K, a sharp peak, also present in the dark TSC measurements, is assigned to the orthorhombic-tetragonal phase transition in the perovskite. However, a peak at around T = 191 K is assigned to trap states with activation energies of around 500 meV but with a rather low concentration of 1 × 10(21) m(-3). PMID:26266616

  7. Lasing in robust cesium lead halide perovskite nanowires

    PubMed Central

    Eaton, Samuel W.; Lai, Minliang; Gibson, Natalie A.; Wong, Andrew B.; Dou, Letian; Ma, Jie; Wang, Lin-Wang; Leone, Stephen R.; Yang, Peidong

    2016-01-01

    The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic–inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored and handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry–Pérot lasing occurs in CsPbBr3 nanowires with an onset of 5 μJ cm−2 with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 109 excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication. PMID:26862172

  8. Design Principles of Perovskites for Thermochemical Oxygen Separation.

    PubMed

    Ezbiri, Miriam; Allen, Kyle M; Gàlvez, Maria E; Michalsky, Ronald; Steinfeld, Aldo

    2015-06-01

    Separation and concentration of O2 from gas mixtures is central to several sustainable energy technologies, such as solar-driven synthesis of liquid hydrocarbon fuels from CO2 , H2 O, and concentrated sunlight. We introduce a rationale for designing metal oxide redox materials for oxygen separation through "thermochemical pumping" of O2 against a pO2 gradient with low-grade process heat. Electronic structure calculations show that the activity of O vacancies in metal oxides pinpoints the ideal oxygen exchange capacity of perovskites. Thermogravimetric analysis and high-temperature X-ray diffraction for SrCoO3-δ , BaCoO3-δ and BaMnO3-δ perovskites and Ag2 O and Cu2 O references confirm the predicted performance of SrCoO3-δ , which surpasses the performance of state-of-the-art Cu2 O at these conditions with an oxygen exchange capacity of 44 mmol O 2 mol SrCoO 3-δ(-1) exchanged at 12.1 μmol O 2 min(-1)  g(-1) at 600-900 K. The redox trends are understood due to lattice expansion and electronic charge transfer. PMID:25925955

  9. Characterization of perovskite solar cells: Towards a reliable measurement protocol

    NASA Astrophysics Data System (ADS)

    Zimmermann, Eugen; Wong, Ka Kan; Müller, Michael; Hu, Hao; Ehrenreich, Philipp; Kohlstädt, Markus; Würfel, Uli; Mastroianni, Simone; Mathiazhagan, Gayathri; Hinsch, Andreas; Gujar, Tanaji P.; Thelakkat, Mukundan; Pfadler, Thomas; Schmidt-Mende, Lukas

    2016-09-01

    Lead halide perovskite solar cells have shown a tremendous rise in power conversion efficiency with reported record efficiencies of over 20% making this material very promising as a low cost alternative to conventional inorganic solar cells. However, due to a differently severe "hysteretic" behaviour during current density-voltage measurements, which strongly depends on scan rate, device and measurement history, preparation method, device architecture, etc., commonly used solar cell measurements do not give reliable or even reproducible results. For the aspect of commercialization and the possibility to compare results of different devices among different laboratories, it is necessary to establish a measurement protocol which gives reproducible results. Therefore, we compare device characteristics derived from standard current density-voltage measurements with stabilized values obtained from an adaptive tracking of the maximum power point and the open circuit voltage as well as characteristics extracted from time resolved current density-voltage measurements. Our results provide insight into the challenges of a correct determination of device performance and propose a measurement protocol for a reliable characterisation which is easy to implement and has been tested on varying perovskite solar cells fabricated in different laboratories.

  10. Extraction of exchange parameters in transition-metal perovskites

    SciTech Connect

    Furrer, A.; Podlesnyak, A.; Krämer, K. W.

    2015-09-15

    When extracting exchange parameters from measured spin-wave dispersion relations there are severe limitations particularly for magnetic compounds such as the transition-metal perovskites, where the nearest-neighbor exchange parameter usually dominates the couplings between the further-distant-neighbor spins. Very precise exchange parameters beyond the nearest-neighbor spins can be obtained by neutron spectroscopic investigations of the magnetic excitation spectra of isolated multimers in magnetically diluted compounds. Moreover, this is exemplified for manganese trimers in the mixed three-and two-dimensional perovskite compounds KMnxZn1-xF3 and K2MnxZn1-xF4, respectively. We show that the small exchange couplings between the second-nearest-neighbor and the third-nearest-neighbor spins can be determined unambiguously and with equal precision as the dominating nearest-neighbor exchange coupling.

  11. Design Principles of Perovskites for Thermochemical Oxygen Separation.

    PubMed

    Ezbiri, Miriam; Allen, Kyle M; Gàlvez, Maria E; Michalsky, Ronald; Steinfeld, Aldo

    2015-06-01

    Separation and concentration of O2 from gas mixtures is central to several sustainable energy technologies, such as solar-driven synthesis of liquid hydrocarbon fuels from CO2 , H2 O, and concentrated sunlight. We introduce a rationale for designing metal oxide redox materials for oxygen separation through "thermochemical pumping" of O2 against a pO2 gradient with low-grade process heat. Electronic structure calculations show that the activity of O vacancies in metal oxides pinpoints the ideal oxygen exchange capacity of perovskites. Thermogravimetric analysis and high-temperature X-ray diffraction for SrCoO3-δ , BaCoO3-δ and BaMnO3-δ perovskites and Ag2 O and Cu2 O references confirm the predicted performance of SrCoO3-δ , which surpasses the performance of state-of-the-art Cu2 O at these conditions with an oxygen exchange capacity of 44 mmol O 2 mol SrCoO 3-δ(-1) exchanged at 12.1 μmol O 2 min(-1)  g(-1) at 600-900 K. The redox trends are understood due to lattice expansion and electronic charge transfer.

  12. Accessing hidden isosymmetric phase transitions in perovskite thin films

    NASA Astrophysics Data System (ADS)

    Rondinelli, James; Coh, Sinisa

    2011-03-01

    Isosymmetric phase transitions (IPT), which show no change in occupied Wyckoff positions or crystallographic space group, are exceedingly rare in crystalline matter because most condensed systems respond to external stimuli by undergoing ``conventional'' symmetry-lowering displacive, martensitic or reconstructive transitions. In this work, we use first-principles density functional calculations to identify an elusive IPT in orthorhombic AB O3 perovskite oxides with tendency towards rhombohedral symmetry. Using perovskite LaGa O3 as our prototypical system, we show that the latent isosymmetric phase transition, which manifests as an abrupt change in the octahedral rotation axis, is accessible only with an external elastic constraint---bi-axial strain. We show the transition originates from a soft phonon that describes the geometric connectivity and relative phase of the Ga O6 polyhedra. By connecting the origin of IPT to a chemical and structural incompatibility between the lattice and the elastic constraints, we describe how subtle changes in bulk orthorhombic and monoclinic symmetries are critical to the complete engineering of structure-correlated electronic properties in thin films. Because bi-axial strain is the critical parameter controlling the IPT, we suggest heteroepitaxial synthesis of IPT materials is a plausible route to realize high- κ dielectric actuators with variable band gaps and dielectric anisotropies.

  13. Phase transformations in superconducting and non-superconducting perovskites

    SciTech Connect

    Mitchell, T.E.

    1992-01-01

    Most of the high {Tc} superconductors and other perovskite-related cuprates exhibit some kind of structural instability. For example, tetragonal-to-orthorhombic phase transformations occur in the Y-Ba-Cu-O and La-Sr-Cu-O systems while crystal structures in the Bi-Ca-Sr-Cu-O and Tl-Ba-Ca-Cu-O systems have incommensurate periodicities associated with displacements of the heavy cations. In YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}}, the transformation is due to the ordering of oxygen vacancies while in La{sub 2-x}Sr{sub x}CuO{sub 4} the transformation is accompanied by tilting of the (CuO{sub 6}) octahedra. Such tilting and distortion of the co-ordination octahedra commonly occur in perovskite-related compounds and transformations between the structures are frequently martensitic. Phase transformations in the superconducting cuprates have been investigated by transmission electron microscopy but none of them appear to be martensitic. The phase transformations are accompanied by twinning and the resulting configurations are used to calculate twin boundary energies.

  14. Phase transformations in superconducting and non-superconducting perovskites

    SciTech Connect

    Mitchell, T.E.

    1992-07-01

    Most of the high {Tc} superconductors and other perovskite-related cuprates exhibit some kind of structural instability. For example, tetragonal-to-orthorhombic phase transformations occur in the Y-Ba-Cu-O and La-Sr-Cu-O systems while crystal structures in the Bi-Ca-Sr-Cu-O and Tl-Ba-Ca-Cu-O systems have incommensurate periodicities associated with displacements of the heavy cations. In YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}}, the transformation is due to the ordering of oxygen vacancies while in La{sub 2-x}Sr{sub x}CuO{sub 4} the transformation is accompanied by tilting of the [CuO{sub 6}] octahedra. Such tilting and distortion of the co-ordination octahedra commonly occur in perovskite-related compounds and transformations between the structures are frequently martensitic. Phase transformations in the superconducting cuprates have been investigated by transmission electron microscopy but none of them appear to be martensitic. The phase transformations are accompanied by twinning and the resulting configurations are used to calculate twin boundary energies.

  15. Ferroelastic switching in a layered-perovskite thin film

    PubMed Central

    Wang, Chuanshou; Ke, Xiaoxing; Wang, Jianjun; Liang, Renrong; Luo, Zhenlin; Tian, Yu; Yi, Di; Zhang, Qintong; Wang, Jing; Han, Xiu-Feng; Van Tendeloo, Gustaaf; Chen, Long-Qing; Nan, Ce-Wen; Ramesh, Ramamoorthy; Zhang, Jinxing

    2016-01-01

    A controllable ferroelastic switching in ferroelectric/multiferroic oxides is highly desirable due to the non-volatile strain and possible coupling between lattice and other order parameter in heterostructures. However, a substrate clamping usually inhibits their elastic deformation in thin films without micro/nano-patterned structure so that the integration of the non-volatile strain with thin film devices is challenging. Here, we report that reversible in-plane elastic switching with a non-volatile strain of approximately 0.4% can be achieved in layered-perovskite Bi2WO6 thin films, where the ferroelectric polarization rotates by 90° within four in-plane preferred orientations. Phase-field simulation indicates that the energy barrier of ferroelastic switching in orthorhombic Bi2WO6 film is ten times lower than the one in PbTiO3 films, revealing the origin of the switching with negligible substrate constraint. The reversible control of the in-plane strain in this layered-perovskite thin film demonstrates a new pathway to integrate mechanical deformation with nanoscale electronic and/or magnetoelectronic applications. PMID:26838483

  16. Ferroelastic switching in a layered-perovskite thin film

    NASA Astrophysics Data System (ADS)

    Wang, Chuanshou; Ke, Xiaoxing; Wang, Jianjun; Liang, Renrong; Luo, Zhenlin; Tian, Yu; Yi, Di; Zhang, Qintong; Wang, Jing; Han, Xiu-Feng; van Tendeloo, Gustaaf; Chen, Long-Qing; Nan, Ce-Wen; Ramesh, Ramamoorthy; Zhang, Jinxing

    2016-02-01

    A controllable ferroelastic switching in ferroelectric/multiferroic oxides is highly desirable due to the non-volatile strain and possible coupling between lattice and other order parameter in heterostructures. However, a substrate clamping usually inhibits their elastic deformation in thin films without micro/nano-patterned structure so that the integration of the non-volatile strain with thin film devices is challenging. Here, we report that reversible in-plane elastic switching with a non-volatile strain of approximately 0.4% can be achieved in layered-perovskite Bi2WO6 thin films, where the ferroelectric polarization rotates by 90° within four in-plane preferred orientations. Phase-field simulation indicates that the energy barrier of ferroelastic switching in orthorhombic Bi2WO6 film is ten times lower than the one in PbTiO3 films, revealing the origin of the switching with negligible substrate constraint. The reversible control of the in-plane strain in this layered-perovskite thin film demonstrates a new pathway to integrate mechanical deformation with nanoscale electronic and/or magnetoelectronic applications.

  17. Perovskite Photovoltachromic Supercapacitor with All-Transparent Electrodes.

    PubMed

    Zhou, Feichi; Ren, Zhiwei; Zhao, Yuda; Shen, Xinpeng; Wang, Aiwu; Li, Yang Yang; Surya, Charles; Chai, Yang

    2016-06-28

    Photovoltachromic cells (PVCCs) are of great interest for the self-powered smart windows of architectures and vehicles, which require widely tunable transmittance and automatic color change under photostimuli. Organolead halide perovskite possesses high light absorption coefficient and enables thin and semitransparent photovoltaic device. In this work, we demonstrate co-anode and co-cathode photovoltachromic supercapacitors (PVCSs) by vertically integrating a perovskite solar cell (PSC) with MoO3/Au/MoO3 transparent electrode and electrochromic supercapacitor. The PVCSs provide a seamless integration of energy harvesting/storage device, automatic and wide color tunability, and enhanced photostability of PSCs. Compared with conventional PVCC, the counter electrodes of our PVCSs provide sufficient balancing charge, eliminate the necessity of reverse bias voltage for bleaching the device, and realize reasonable in situ energy storage. The color states of PVCSs not only indicate the amount of energy stored and energy consumed in real time, but also enhance the photostability of photovoltaic component by preventing its long-time photoexposure under fully charged state of PVCSs. This work designs PVCS devices for multifunctional smart window applications commonly made of glass.

  18. Giant switchable photovoltaic effect in organometal trihalide perovskite devices

    SciTech Connect

    Xiao, Zhengguo; Yuan, Yongbo; Shao, Yuchuan; Wang, Qi; Dong, Qingfeng; Bi, Cheng; Sharma, Pankaj; Gruverman, Alexei; Huang, Jinsong

    2014-12-08

    Organolead trihalide perovskite (OTP) materials are emerging as naturally abundant materials for low-cost, solution-processed and highly efficient solar cells. Here, we show that, in OTP-based photovoltaic devices with vertical and lateral cell configurations, the photocurrent direction can be switched repeatedly by applying a small electric field of <1 V μm–1. The switchable photocurrent, generally observed in devices based on ferroelectric materials, reached 20.1 mA cm–2 under one sun illumination in OTP devices with a vertical architecture, which is four orders of magnitude larger than that measured in other ferroelectric photovoltaic devices. This field-switchable photovoltaic effect can be explained by the formation of reversible p–i–n structures induced by ion drift in the perovskite layer. Furthermore, the demonstration of switchable OTP photovoltaics and electric-field-manipulated doping paves the way for innovative solar cell designs and for the exploitation of OTP materials in electrically and optically readable memristors and circuits.

  19. Giant switchable photovoltaic effect in organometal trihalide perovskite devices

    DOE PAGESBeta

    Xiao, Zhengguo; Yuan, Yongbo; Shao, Yuchuan; Wang, Qi; Dong, Qingfeng; Bi, Cheng; Sharma, Pankaj; Gruverman, Alexei; Huang, Jinsong

    2014-12-08

    Organolead trihalide perovskite (OTP) materials are emerging as naturally abundant materials for low-cost, solution-processed and highly efficient solar cells. Here, we show that, in OTP-based photovoltaic devices with vertical and lateral cell configurations, the photocurrent direction can be switched repeatedly by applying a small electric field of <1 V μm–1. The switchable photocurrent, generally observed in devices based on ferroelectric materials, reached 20.1 mA cm–2 under one sun illumination in OTP devices with a vertical architecture, which is four orders of magnitude larger than that measured in other ferroelectric photovoltaic devices. This field-switchable photovoltaic effect can be explained by themore » formation of reversible p–i–n structures induced by ion drift in the perovskite layer. Furthermore, the demonstration of switchable OTP photovoltaics and electric-field-manipulated doping paves the way for innovative solar cell designs and for the exploitation of OTP materials in electrically and optically readable memristors and circuits.« less

  20. Perovskite Photovoltachromic Supercapacitor with All-Transparent Electrodes.

    PubMed

    Zhou, Feichi; Ren, Zhiwei; Zhao, Yuda; Shen, Xinpeng; Wang, Aiwu; Li, Yang Yang; Surya, Charles; Chai, Yang

    2016-06-28

    Photovoltachromic cells (PVCCs) are of great interest for the self-powered smart windows of architectures and vehicles, which require widely tunable transmittance and automatic color change under photostimuli. Organolead halide perovskite possesses high light absorption coefficient and enables thin and semitransparent photovoltaic device. In this work, we demonstrate co-anode and co-cathode photovoltachromic supercapacitors (PVCSs) by vertically integrating a perovskite solar cell (PSC) with MoO3/Au/MoO3 transparent electrode and electrochromic supercapacitor. The PVCSs provide a seamless integration of energy harvesting/storage device, automatic and wide color tunability, and enhanced photostability of PSCs. Compared with conventional PVCC, the counter electrodes of our PVCSs provide sufficient balancing charge, eliminate the necessity of reverse bias voltage for bleaching the device, and realize reasonable in situ energy storage. The color states of PVCSs not only indicate the amount of energy stored and energy consumed in real time, but also enhance the photostability of photovoltaic component by preventing its long-time photoexposure under fully charged state of PVCSs. This work designs PVCS devices for multifunctional smart window applications commonly made of glass. PMID:27159013

  1. Planar heterojunction perovskite solar cells with superior reproducibility.

    PubMed

    Jeon, Ye-Jin; Lee, Sehyun; Kang, Rira; Kim, Jueng-Eun; Yeo, Jun-Seok; Lee, Seung-Hoon; Kim, Seok-Soon; Yun, Jin-Mun; Kim, Dong-Yu

    2014-01-01

    Perovskite solar cells (PeSCs) have been considered one of the competitive next generation power sources. To date, light-to-electric conversion efficiencies have rapidly increased to over 10%, and further improvements are expected. However, the poor device reproducibility of PeSCs ascribed to their inhomogeneously covered film morphology has hindered their practical application. Here, we demonstrate high-performance PeSCs with superior reproducibility by introducing small amounts of N-cyclohexyl-2-pyrrolidone (CHP) as a morphology controller into N,N-dimethylformamide (DMF). As a result, highly homogeneous film morphology, similar to that achieved by vacuum-deposition methods, as well as a high PCE of 10% and an extremely small performance deviation within 0.14% were achieved. This study represents a method for realizing efficient and reproducible planar heterojunction (PHJ) PeSCs through morphology control, taking a major step forward in the low-cost and rapid production of PeSCs by solving one of the biggest problems of PHJ perovskite photovoltaic technology through a facile method. PMID:25377945

  2. Planar heterojunction perovskite solar cells with superior reproducibility

    PubMed Central

    Jeon, Ye-Jin; Lee, Sehyun; Kang, Rira; Kim, Jueng-Eun; Yeo, Jun-Seok; Lee, Seung-Hoon; Kim, Seok-Soon; Yun, Jin-Mun; Kim, Dong-Yu

    2014-01-01

    Perovskite solar cells (PeSCs) have been considered one of the competitive next generation power sources. To date, light-to-electric conversion efficiencies have rapidly increased to over 10%, and further improvements are expected. However, the poor device reproducibility of PeSCs ascribed to their inhomogeneously covered film morphology has hindered their practical application. Here, we demonstrate high-performance PeSCs with superior reproducibility by introducing small amounts of N-cyclohexyl-2-pyrrolidone (CHP) as a morphology controller into N,N-dimethylformamide (DMF). As a result, highly homogeneous film morphology, similar to that achieved by vacuum-deposition methods, as well as a high PCE of 10% and an extremely small performance deviation within 0.14% were achieved. This study represents a method for realizing efficient and reproducible planar heterojunction (PHJ) PeSCs through morphology control, taking a major step forward in the low-cost and rapid production of PeSCs by solving one of the biggest problems of PHJ perovskite photovoltaic technology through a facile method. PMID:25377945

  3. Investigation into the Advantages of Pure Perovskite Film without PbI2 for High Performance Solar Cell

    PubMed Central

    Kwon, Uisik; Hasan, Md Mehedi; Yin, Wenping; Kim, Dasom; Ha, Na Young; Lee, Soonil; Ahn, Tae Kyu; Park, Hui Joon

    2016-01-01

    In CH3NH3PbI3-based high efficiency perovskite solar cells (PSCs), tiny amount of PbI2 impurity was often found with the perovskite crystal. However, for two-step solution process-based perovskite films, most of findings have been based on the films having different morphologies between with and without PbI2. This was mainly due to the inferior morphology of pure perovskite film without PbI2, inevitably produced when the remaining PbI2 forced to be converted to perovskite, so advantages of pure perovskite photoactive layer without PbI2 impurity have been overlooked. In this work, we designed a printing-based two-step process, which could not only generate pure perovskite crystal without PbI2, but also provide uniform and full surface coverage perovskite film, of which nanoscale morphology was comparable to that prepared by conventional two-step solution process having residual PbI2. Our results showed that, in two-step solution process-based PSC, pure perovskite had better photon absorption and longer carrier lifetime, leading to superior photocurrent generation with higher power conversion efficiency. Furthermore, this process was further applicable to prepare mixed phase pure perovskite crystal without PbI2 impurity, and we showed that the additional merits such as extended absorption to longer wavelength, increased carrier lifetime and reduced carrier recombination could be secured. PMID:27786257

  4. New Physical Deposition Approach for Low Cost Inorganic Hole Transport Layer in Normal Architecture of Durable Perovskite Solar Cells.

    PubMed

    Nejand, Bahram Abdollahi; Ahmadi, Vahid; Shahverdi, Hamid Reza

    2015-10-01

    In this work we reported sputter deposited NiOx/Ni double layer as an HTM/contact couple in normal architecture of perovskite solar cell. A perovskite solar cell that is durable for more than 60 days was achieved, with increasing efficiency from 1.3% to 7.28% within 6 days. Moreover, low temperature direct deposition of NiOx layer on perovskite layer was introduced as a potential hole transport material for an efficient cost-effective solar cell applicable for various morphologies of perovskite layers, even for perovskite layers containing pinholes, which is a notable challenge in perovskite solar cells. The angular deposition of NiOx layers by dc reactive magnetron sputtering showed uniform and crack-free coverage of the perovskite layer with no negative impact on perovskite structure that is suitable for nickel back contact layer, surface shielding against moisture, and mechanical damages. Replacing the expensive complex materials in previous perovskite solar cells with low cost available materials introduces cost-effective scalable perovskite solar cells.

  5. 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

  6. 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

    2016-07-01

    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

  7. Wire-shaped perovskite solar cell based on TiO2 nanotubes

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoyan; Kulkarni, Sneha A.; Li, Zhen; Xu, Wenjing; Batabyal, Sudip K.; Zhang, Sam; Cao, Anyuan; Wong, Lydia Helena

    2016-05-01

    In this work, a wire-shaped perovskite solar cell based on TiO2 nanotube (TNT) arrays is demonstrated for the first time by integrating a perovskite absorber on TNT-coated Ti wire. Anodization was adopted for the conformal growth of TNTs on Ti wire, together with the simultaneous formation of a compact TiO2 layer. A sequential step dipping process is employed to produce a uniform and compact perovskite layer on top of TNTs with conformal coverage as the efficient light absorber. Transparent carbon nanotube film is wrapped around Ti wire as the hole collector and counter electrode. The integrated perovskite solar cell wire by facile fabrication approaches shows a promising future in portable and wearable textile electronics.

  8. Preparation and characterization of Ni-based perovskite catalyst for steam CO2 reforming of methane.

    PubMed

    Yang, Eun-Hyeok; Kim, Sang Woo; Ahn, Byong Song; Moon, Dong Ju

    2013-06-01

    Steam CO2 reforming of methane was investigated over Ni-based perovskite catalyst to produce desired H2/CO ratio by adjusting the feed ratio of CH4, CO2 and H2O for floating GTL process application. La modified perovskites were prepared by the Pechini method and calcined in air and the Ni-based catalysts were prepared by dispersing Ni on the La modified perovskite by an incipient wetness impregnation. The catalysts before and after the reaction were characterized by N2 physisoprtion, CO chemisoprtion, XRD, TPR and SEM techniques. To control desired H2/CO ratio, simulation for SCR was carried out by Aspen plus, and product distribution for SCR was investigated in a fixed bed reactor system using feed ratio estimated by simulation. The Ni-based perovskite catalysts were found to give CH4 and CO2 conversions of up to 82% and 60% respectively to yield a H2/CO product ratio close to 2.

  9. Electric Field Control of Jahn-Teller Distortions in Bulk Perovskites

    NASA Astrophysics Data System (ADS)

    Varignon, Julien; Bristowe, Nicholas C.; Ghosez, Philippe

    2016-02-01

    The Jahn-Teller distortion, by its very nature, is often at the heart of the various electronic properties displayed by perovskites and related materials. Despite the Jahn-Teller mode being nonpolar, we devise and demonstrate, in the present Letter, an electric field control of Jahn-Teller distortions in bulk perovskites. The electric field control is enabled through an anharmonic lattice mode coupling between the Jahn-Teller distortion and a polar mode. We confirm this coupling and quantify it through first-principles calculations. The coupling will always exist within the P b 21m space group, which is found to be the favored ground state for various perovskites under sufficient tensile epitaxial strain. Intriguingly, the calculations reveal that this mechanism is not only restricted to Jahn-Teller active systems, promising a general route to tune or induce novel electronic functionality in perovskites as a whole.

  10. Morphology control of perovskite light-emitting diodes by using amino acid self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Wang, Nana; Cheng, Lu; Si, Junjie; Liang, Xiaoyong; Jin, Yizheng; Wang, Jianpu; Huang, Wei

    2016-04-01

    Amino acid self-assembled monolayers are used in the fabrication of light-emitting diodes based on organic-inorganic halide perovskites. The monolayers of amino acids provide modified interfaces by anchoring to the surfaces of ZnO charge-transporting layers using carboxyl groups, leaving the amino groups to facilitate the nucleation of MAPbBr3 perovskite films. This surface-modification strategy, together with chlorobenzene-assisted fast crystallization method, results in good surface coverage and reduced defect density of the perovskite films. These efforts lead to green perovskite light emitting diodes with a low turn-on voltage of 2 V and an external quantum efficiency of 0.43% at a brightness of ˜5000 cd m-2.

  11. Relationships between Lead Halide Perovskite Thin-Film Fabrication, Morphology, and Performance in Solar Cells.

    PubMed

    Sharenko, Alexander; Toney, Michael F

    2016-01-20

    Solution-processed lead halide perovskite thin-film solar cells have achieved power conversion efficiencies comparable to those obtained with several commercial photovoltaic technologies in a remarkably short period of time. This rapid rise in device efficiency is largely the result of the development of fabrication protocols capable of producing continuous, smooth perovskite films with micrometer-sized grains. Further developments in film fabrication and morphological control are necessary, however, in order for perovskite solar cells to reliably and reproducibly approach their thermodynamic efficiency limit. This Perspective discusses the fabrication of lead halide perovskite thin films, while highlighting the processing-property-performance relationships that have emerged from the literature, and from this knowledge, suggests future research directions.

  12. Trace Elemental Abundances in an Unusual Hibonite-Perovskite Refractory Inclusion from Allende

    NASA Astrophysics Data System (ADS)

    Mane, P.; Wadhwa, M.; Keller, L. P.

    2013-09-01

    This abstract discusses rare earth elemental abundances of an unusual hibonite- perovskite refractory inclusion (Named a s SHAL) from Allende CV3 meteorite and their implications about its formation history.

  13. Artifacts in Absorption Measurements of Organometal Halide Perovskite Materials: What Are the Real Spectra?

    PubMed

    Tian, Yuxi; Scheblykin, Ivan G

    2015-09-01

    Organometal halide (OMH) perovskites have attracted lots of attention over the last several years due to their very promising performance as the materials for solar cells and light-emitting devices. Photophysical processes in these hybrid organic-inorganic semiconductors are still heavily debated. To know precise absorption spectra is absolutely necessary for quantitative understanding of the fundamental properties of OMH perovskites. We show that to measure the absorption of perovskite materials correctly is a difficult task which could be easily overlooked by the community. Many of the published absorption spectra exhibit a characteristic step-like featureless shape due to light scattering, high optical density of individual perovskite crystals and poor coverage of the substrate. We show how to recognize these artifacts, to avoid them, and to use absorption spectra of films for estimation of the surface coverage ratio. PMID:27120683

  14. Highly Efficient Flexible Perovskite Solar Cells Using Solution-Derived NiOx Hole Contacts.

    PubMed

    Yin, Xingtian; Chen, Peng; Que, Meidan; Xing, Yonglei; Que, Wenxiu; Niu, Chunming; Shao, Jinyou

    2016-03-22

    A solution-derived NiOx film was employed as the hole contact of a flexible organic-inorganic hybrid perovskite solar cell. The NiOx film, which was spin coated from presynthesized NiOx nanoparticles solution, can extract holes and block electrons efficiently, without any other post-treatments. An optimal power conversion efficiency (PCE) of 16.47% was demonstrated in the NiOx-based perovskite solar cell on an ITO-glass substrate, which is much higher than that of the perovskite solar cells using high temperature-derived NiOx film contacts. The low-temperature deposition process made the NiOx films suitable for flexible devices. NiOx-based flexible perovskite solar cells were fabricated on ITO-PEN substrates, and a preliminary PCE of 13.43% was achieved. PMID:26958704

  15. Improved Crystallization of Perovskite Films by Optimized Solvent Annealing for High Efficiency Solar Cell.

    PubMed

    Liu, Jiang; Gao, Cheng; He, Xulin; Ye, Qinyan; Ouyang, Liangqi; Zhuang, Daming; Liao, Cheng; Mei, Jun; Lau, Woonming

    2015-11-01

    Organic-inorganic halide perovskite-based thin film solar cells show excellent light-to-power conversion efficiency. The high performance for the devices requires the preparation of well-crystallized perovskite absorbers. In this paper, we used the postannealing process to treat the perovskite films under different solvent vapors and observed that the solvent vapors have a strong effect on the film growth. A model regarding the perovskite film growth was proposed as well. Intensive characterizations including scanning electron microscopy, electrochemical impedance spectroscopy, and admittance spectroscopy allowed us to attribute the improved performance to reduced recombination loss and defect density. Solar cell based on the DMSO-treated films delivered a power conversion efficiency of over 13% with negligible photocurrent hysteresis.

  16. Wire-shaped perovskite solar cell based on TiO2 nanotubes.

    PubMed

    Wang, Xiaoyan; Kulkarni, Sneha A; Li, Zhen; Xu, Wenjing; Batabyal, Sudip K; Zhang, Sam; Cao, Anyuan; Wong, Lydia Helena

    2016-05-20

    In this work, a wire-shaped perovskite solar cell based on TiO2 nanotube (TNT) arrays is demonstrated for the first time by integrating a perovskite absorber on TNT-coated Ti wire. Anodization was adopted for the conformal growth of TNTs on Ti wire, together with the simultaneous formation of a compact TiO2 layer. A sequential step dipping process is employed to produce a uniform and compact perovskite layer on top of TNTs with conformal coverage as the efficient light absorber. Transparent carbon nanotube film is wrapped around Ti wire as the hole collector and counter electrode. The integrated perovskite solar cell wire by facile fabrication approaches shows a promising future in portable and wearable textile electronics.

  17. High Open-Circuit Voltage Solar Cells Based on Organic-Inorganic Lead Bromide Perovskite.

    PubMed

    Edri, Eran; Kirmayer, Saar; Cahen, David; Hodes, Gary

    2013-03-21

    Mesoscopic solar cells, based on solution-processed organic-inorganic perovskite absorbers, are a promising avenue for converting solar to electrical energy. We used solution-processed organic-inorganic lead halide perovskite absorbers, in conjunction with organic hole conductors, to form high voltage solar cells. There is a dire need for low-cost cells of this type, to drive electrochemical reactions or as the high photon energy cell in a system with spectral splitting. These perovskite materials, although spin-coated from solution, form highly crystalline materials. Their simple synthesis, along with high chemical versatility, allows tuning their electronic and optical properties. By judicious selection of the perovskite lead halide-based absorber, matching organic hole conductor, and contacts, a cell with a ∼ 1.3 V open circuit voltage was made. While further study is needed, this achievement provides a general guideline for additional improvement of cell performance.

  18. Hydrophobic Organic Hole Transporters for Improved Moisture Resistance in Metal Halide Perovskite Solar Cells.

    PubMed

    Leijtens, Tomas; Giovenzana, Tommaso; Habisreutinger, Severin N; Tinkham, Jonathan S; Noel, Nakita K; Kamino, Brett A; Sadoughi, Golnaz; Sellinger, Alan; Snaith, Henry J

    2016-03-01

    Solar cells based on organic-inorganic perovskite semiconductor materials have recently made rapid improvements in performance, with the best cells performing at over 20% efficiency. With such rapid progress, questions such as cost and solar cell stability are becoming increasingly important to address if this new technology is to reach commercial deployment. The moisture sensitivity of commonly used organic-inorganic metal halide perovskites has especially raised concerns. Here, we demonstrate that the hygroscopic lithium salt commonly used as a dopant for the hole transport material in perovskite solar cells makes the top layer of the devices hydrophilic and causes the solar cells to rapidly degrade in the presence of moisture. By using novel, low cost, and hydrophobic hole transporters in conjunction with a doping method incorporating a preoxidized salt of the respective hole transporters, we are able to prepare efficient perovskite solar cells with greatly enhanced water resistance.

  19. Efficiency-Enhanced Planar Perovskite Solar Cells via an Isopropanol/Ethanol Mixed Solvent Process.

    PubMed

    Mao, Peng; Zhou, Qing; Jin, Zhiwen; Li, Hui; Wang, Jizheng

    2016-09-14

    Solution processable perovskite solar cells traditionally employed isopropanol as the solvent of CH3NH3I in a two-step method. One of the largest issues of this technique is the uncontrollable morphology of the perovskite film. In this study, a homogeneous and dense PbI2 film was prepared by introducing DMSO as an additive into DMF and then reacting the mixture with CH3NH3I dissolved in an isopropanol/ethanol solvent to fabricate high-quality perovskite films. Results revealed that ethanol played a crucial role on morphology and components of perovskite films. When the ratio of isopropanol to ethanol was optimized, a power conversion efficiency of 15.76% was achieved, which was on average ∼50% higher than that of PSCs without DMSO and ethanol processing. PMID:27549444

  20. Efficiency-Enhanced Planar Perovskite Solar Cells via an Isopropanol/Ethanol Mixed Solvent Process.

    PubMed

    Mao, Peng; Zhou, Qing; Jin, Zhiwen; Li, Hui; Wang, Jizheng

    2016-09-14

    Solution processable perovskite solar cells traditionally employed isopropanol as the solvent of CH3NH3I in a two-step method. One of the largest issues of this technique is the uncontrollable morphology of the perovskite film. In this study, a homogeneous and dense PbI2 film was prepared by introducing DMSO as an additive into DMF and then reacting the mixture with CH3NH3I dissolved in an isopropanol/ethanol solvent to fabricate high-quality perovskite films. Results revealed that ethanol played a crucial role on morphology and components of perovskite films. When the ratio of isopropanol to ethanol was optimized, a power conversion efficiency of 15.76% was achieved, which was on average ∼50% higher than that of PSCs without DMSO and ethanol processing.

  1. Crystal Structure of a Layered Perovskite Niobate KCa 2Nb 3O 10

    NASA Astrophysics Data System (ADS)

    Fukuoka, Hiroshi; Isami, Toshiyuki; Yamanaka, Shoji

    2000-04-01

    The crystal structure of a layered perovskite niobate KCa2Nb3O10 was investigated through single-crystal X-ray analysis. The niobate crystallized in the orthorhombic system Cmcm with lattice constants of a=3.8802(9) Å, b=29.508(6) Å, c=7.714(1) Å, V=883.2(2) Å3. The final refinement using the 908 independent reflections converged into R=4.1%, and Rw=4.7%. The structure of KCa2Nb3O10 was composed of triple-layered perovskite slabs, potassium ions being situated between the slabs. The adjacent perovskite slabs, stacking along the c axis, were mutually displaced with a displacement vector of a→/2. The potassium ions were coordinated by six oxygen atoms to form two short and four long bonds. Apparent disordering was observed in the equatorial oxygen sites of the central niobium atoms in the triple perovskite slabs.

  2. NaIrO3—A Pentavalent Post-perovskite

    SciTech Connect

    M Bremholm; S Dutton; P Stephens; R Cava

    2011-12-31

    Sodium iridium (V) oxide, NaIrO{sub 3}, was synthesized by a high pressure solid state method and recovered to ambient conditions. It is found to be isostructural with CaIrO{sub 3}, the much-studied structural analog of the high-pressure post-perovskite phase of MgSiO{sub 3}. Among the oxide post-perovskites, NaIrO{sub 3} is the first example with a pentavalent cation. The structure consists of layers of corner- and edge-sharing IrO{sub 6} octahedra separated by layers of NaO{sub 8} bicapped trigonal prisms. NaIrO{sub 3} shows no magnetic ordering and resistivity measurements show non-metallic behavior. The crystal structure, electrical and magnetic properties are discussed and compared to known post-perovskites and pentavalent perovskite metal oxides.

  3. Ultrathin Cu2O as an efficient inorganic hole transporting material for perovskite solar cells.

    PubMed

    Yu, Weili; Li, Feng; Wang, Hong; Alarousu, Erkki; Chen, Yin; Lin, Bin; Wang, Lingfei; Hedhili, Mohamed Nejib; Li, Yangyang; Wu, Kewei; Wang, Xianbin; Mohammed, Omar F; Wu, Tom

    2016-03-21

    We demonstrate that ultrathin P-type Cu2O thin films fabricated by a facile thermal oxidation method can serve as a promising hole-transporting material in perovskite solar cells. Following a two-step method, inorganic-organic hybrid perovskite solar cells were fabricated and a power conversion efficiency of 11.0% was achieved. We found that the thickness and properties of Cu2O layers must be precisely tuned in order to achieve the optimal solar cell performance. The good performance of such perovskite solar cells can be attributed to the unique properties of ultrathin Cu2O, including high hole mobility, good energy level alignment with CH3NH3PbI3, and longer lifetime of photo-excited carriers. Combining the merits of low cost, facile synthesis, and high device performance, ultrathin Cu2O films fabricated via thermal oxidation hold promise for facilitating the developments of industrial-scale perovskite solar cells.

  4. Wire-shaped perovskite solar cell based on TiO2 nanotubes.

    PubMed

    Wang, Xiaoyan; Kulkarni, Sneha A; Li, Zhen; Xu, Wenjing; Batabyal, Sudip K; Zhang, Sam; Cao, Anyuan; Wong, Lydia Helena

    2016-05-20

    In this work, a wire-shaped perovskite solar cell based on TiO2 nanotube (TNT) arrays is demonstrated for the first time by integrating a perovskite absorber on TNT-coated Ti wire. Anodization was adopted for the conformal growth of TNTs on Ti wire, together with the simultaneous formation of a compact TiO2 layer. A sequential step dipping process is employed to produce a uniform and compact perovskite layer on top of TNTs with conformal coverage as the efficient light absorber. Transparent carbon nanotube film is wrapped around Ti wire as the hole collector and counter electrode. The integrated perovskite solar cell wire by facile fabrication approaches shows a promising future in portable and wearable textile electronics. PMID:27070991

  5. Stability of MgSio[subscript 3] Perovskite in the Lower Mantle

    SciTech Connect

    Shim, D.

    2006-01-19

    As it is expected to be the dominant phase in the lower mantle, any pressure-induced phase changes in MgSiO{sub 3} could require significant modifications in current models of the dynamics and structures of Earth's deep mantle. Studies to date have yielded discrepant results regarding the high-pressure stability of MgSiO{sub 3} perovskite. Understanding the source of discrepancy is essential, both to resolving the stability of perovskite and to developing more reliable techniques for understanding the Earth's deep interior. In this report, we give an overview of previous studies on the stability of MgSiO{sub 3} perovskite and recent observations on the post-perovskite transition. We also summarize our measurements on MgSiO{sub 3} perovskite to core-mantle boundary pressure-temperature (P-T) conditions using in-situ X-ray diffraction. Major peaks in our diffraction patterns are best explained by those of MgSiO{sub 3} perovskite at 1200-2500-km depth conditions. No evidence of dissociation to MgO + SiO, and a transition to a cubic perovskite structure has been found to core-mantle boundary P-T conditions. We have also observed a new peak at 2.62-2.57 {angstrom} at 88-145 GPa, the existence of which may be relevant to a modification in perovskite crystal structure. However, the possibility that this peak may be from a chemical reaction among gasket, anvil materials, and sample cannot be ruled out. More significant changes are observed during heating above 2500 K at 135-145 GPa: appearance of new peaks, splitting of a peak, and intensity changes of some diffraction peaks. The recently proposed post-perovskite phase explains dominant new diffraction features. Based on the results available as of May 2005, the post-perovskite transition appears to be relevant to the D seismic discontinuity. Furthermore, depth of the post-perovskite transition may be very sensitive to variations in chemical composition as well as temperature.

  6. The Renaissance of Halide Perovskites and Their Evolution as Emerging Semiconductors.

    PubMed

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2015-10-20

    The recent re-emergence of the halide perovskites, of the type AMX3, derives from a sea-changing breakthrough in the field of photovoltaics that has led to a whole new generation of solar devices with remarkable power conversion efficiency. The success in the field of photovoltaics has led to intense, combined research efforts to better understand these materials both from the fundamental chemistry and physics points of view and for the improvement of applied functional device engineering. This groundswell of activity has breathed new life into this long-known but largely "forgotten" class of perovskites. The impressive achievements of halide perovskites in photovoltaics, as well as other optoelectronic applications, stem from an unusually favorable combination of optical and electronic properties, with the ability to be solution processed into films. This defines them as a brand new class of semiconductors that can rival or exceed the performance of the venerable classes of III-V and II-IV semiconductors, which presently dominate the industries of applied optoelectronics. Our aim in this Account is to highlight the basic pillars that define the chemistry of the halide perovskites and their unconventional electronic properties through the prism of structure-property relationships. We focus on the synthetic requirements under which a halide perovskite can exist and emphasize how the synthetic conditions can determine the structural integrity and the bulk properties of the perovskites. Then we proceed to discuss the origins of the optical and electronic phenomena, using the perovskite crystal structure as a guide. Some of the most remarkable features of the perovskites dealt with in this Account include the evolution of a unique type of defect, which gives rise to superlattices. These can enhance or diminish the fluorescence properties of the perovskites. For example, the exotic self-doping ability of the Sn-based perovskites allows them to adopt electrical

  7. Cuprous Oxide as a Potential Low-Cost Hole-Transport Material for Stable Perovskite Solar Cells.

    PubMed

    Nejand, Bahram Abdollahi; Ahmadi, Vahid; Gharibzadeh, Saba; Shahverdi, Hamid Reza

    2016-02-01

    Inorganic hole-transport materials are commercially desired to decrease the fabrication cost of perovskite solar cells. Here, Cu2O is introduced as a potential hole-transport material for stable, low-cost devices. Considering that Cu2O formation is highly sensitive to the underlying mixture of perovskite precursors and their solvents, we proposed and engineered a technique for reactive magnetron sputtering. The rotational angular deposition of Cu2O yields high surface coverage of the perovskite layer for high rate of charge extraction. Deposition of this Cu2O layer on the pinhole-free perovskite layer produces devices with power conversion efficiency values of up to 8.93%. The engineered Cu2O layers showed uniform, compact, and crack-free surfaces on the perovskite layer without affecting the perovskite structure, which is desired for deposition of the top metal contact and for surface shielding against moisture and mechanical damages. PMID:26748959

  8. Effect of iron content on the electrical conductivity of perovskite and magnesiowuestite assemblages at lower mantle conditions

    NASA Technical Reports Server (NTRS)

    Li, Xiaoyuan; Jeanloz, Raymond

    1991-01-01

    The electrical conductivity of (Mg/0.76/Fe/0.24/)SiO3 perovskite and of an assemblage of (Mg/0.89/Fe/0.11/)SiO3 perovskite + (Mg/0.70/Fe/0.30/)O magnesiowiestite was measured at pressures of 45-80 GPa and temperatures from 295 to 3600 K. The apparent activation energy for electrical conduction is 0.24 (+ or - 0.10) eV for the perovskite and 0.20 (+ or - 0.08) eV for the perovskite + magnesiowuestite assemblage. Comparing present results with those derived previously for Fe-poor samples, it is found that the electrical conductivities of both the silicate perovskite and the perovskite + magnesiowuestite assemblage depend strongly on iron content. Thus, the electrical conductivity distribution inside the earth could provide an important constraint in modeling the composition of the lower mantle.

  9. Structure, Growth Process, and Growth Mechanism of Perovskite in High-Titanium-Bearing Blast Furnace Slag

    NASA Astrophysics Data System (ADS)

    Liu, Lu; Hu, Meilong; Xu, Yuzhou; Bai, Chenguang; Gan, Yunhua

    2015-08-01

    The isothermal crystallization of perovskite in TiO2-CaO-SiO2-Al2O3-MgO high-titanium-bearing blast furnace slag was observed in situ at 1698 K (1425 °C) using a confocal scanning laser microscope. The dendrite structure of perovskite (CaTiO3) thus obtained showed vividly the primary dendrite trunks and secondary dendrite arms. Furthermore, the dendritic growth of perovskite in liquid slag was clearly observed on line. The results showed that the dendrite arrays in which the primary dendrite trunks observed on slag surface were parallel with each other grew toward the same direction. The secondary dendrite arms grew in the perpendicular direction with the primary trucks and stopped growing when they encounter. The perovskite dendrites showed a linear growth at two stages. The dendrites grew faster at early stage at about 5 to 7 μm/s and grew with a lower growth rate at about 1 to 2 μm/s in later stage. Finally, the growth mechanism of perovskite in melt was analyzed with the solidification theory. Based on the theoretical calculation of equilibrium phases in slag, the initial slag could be considered as a binary component system. One component was perovskite and the other component was the sum of all the other species that did not attend the crystallization of perovskite (included SiO2, Al2O3, and MgO, as well as CaO and TiO2 that were not involved in the solid formation). The formation of perovskite required the diffusion of CaO and TiO2 to the solid/liquid interface and the rejection of the other species from the interface. The solid/liquid equilibrium schematic diagram was made based on the calculation.

  10. Low-temperature solution-processed p-type vanadium oxide for perovskite solar cells.

    PubMed

    Sun, Haocheng; Hou, Xiaomeng; Wei, Qiulong; Liu, Huawei; Yang, Kecheng; Wang, Wei; An, Qinyou; Rong, Yaoguang

    2016-06-21

    A low-temperature solution-processed inorganic p-type contact material of vanadium oxide (VOx) was developed to fabricate planar-heterojunction perovskite solar cells. Using a solvent-assisted process, high-quality uniform and compact perovskite (CH3NH3PbI3) films were deposited on VOx coated substrates. Due to the high transmittance and quenching efficiency of VOx layers, a power conversion efficiency of over 14% was achieved.

  11. Highly Efficient Perovskite Nanocrystal Light-Emitting Diodes Enabled by a Universal Crosslinking Method.

    PubMed

    Li, Guangru; Rivarola, Florencia Wisnivesky Rocca; Davis, Nathaniel J L K; Bai, Sai; Jellicoe, Tom C; de la Peña, Francisco; Hou, Shaocong; Ducati, Caterina; Gao, Feng; Friend, Richard H; Greenham, Neil C; Tan, Zhi-Kuang

    2016-05-01

    The preparation of highly efficient perovskite nanocrystal light-emitting diodes is shown. A new trimethylaluminum vapor-based crosslinking method to render the nanocrystal films insoluble is applied. The resulting near-complete nanocrystal film coverage, coupled with the natural confinement of injected charges within the perovskite crystals, facilitates electron-hole capture and give rise to a remarkable electroluminescence yield of 5.7%.

  12. Observation of Enhanced Hole Extraction in Br Concentration Gradient Perovskite Materials.

    PubMed

    Kim, Min-Cheol; Kim, Byeong Jo; Son, Dae-Yong; Park, Nam-Gyu; Jung, Hyun Suk; Choi, Mansoo

    2016-09-14

    Enhancing hole extraction inside the perovskite layer is the key factor for boosting photovoltaic performance. Realization of halide concentration gradient perovskite materials has been expected to exhibit rapid hole extraction due to the precise bandgap tuning. Moreover, a formation of Br-rich region on the tri-iodide perovskite layer is expected to enhance moisture stability without a loss of current density. However, conventional synthetic techniques of perovskite materials such as the solution process have not achieved the realization of halide concentration gradient perovskite materials. In this report, we demonstrate the fabrication of Br concentration gradient mixed halide perovskite materials using a novel and facile halide conversion method based on vaporized hydrobromic acid. Accelerated hole extraction and enhanced lifetime due to Br gradient was verified by observing photoluminescence properties. Through the combination of secondary ion mass spectroscopy and transmission electron microscopy with energy-dispersive X-ray spectroscopy analysis, the diffusion behavior of Br ions in perovskite materials was investigated. The Br-gradient was found to be eventually converted into a homogeneous mixed halide layer after undergoing an intermixing process. Br-substituted perovskite solar cells exhibited a power conversion efficiency of 18.94% due to an increase in open circuit voltage from 1.08 to 1.11 V and an advance in fill-factor from 0.71 to 0.74. Long-term stability was also dramatically enhanced after the conversion process, i.e., the power conversion efficiency of the post-treated device has remained over 97% of the initial value under high humid conditions (40-90%) without any encapsulation for 4 weeks. PMID:27500375

  13. Nanostructuring Mixed-Dimensional Perovskites: A Route Toward Tunable, Efficient Photovoltaics.

    PubMed

    Koh, Teck Ming; Shanmugam, Vignesh; Schlipf, Johannes; Oesinghaus, Lukas; Müller-Buschbaum, Peter; Ramakrishnan, N; Swamy, Varghese; Mathews, Nripan; Boix, Pablo P; Mhaisalkar, Subodh G

    2016-05-01

    2D perovskites is one of the proposed strategies to enhance the moisture resistance, since the larger organic cations can act as a natural barrier. Nevertheless, 2D perovskites hinder the charge transport in certain directions, reducing the solar cell power conversion efficiency. A nanostructured mixed-dimensionality approach is presented to overcome the charge transport limitation, obtaining power conversion efficiencies over 9%. PMID:26990287

  14. Highly Efficient Perovskite Nanocrystal Light-Emitting Diodes Enabled by a Universal Crosslinking Method.

    PubMed

    Li, Guangru; Rivarola, Florencia Wisnivesky Rocca; Davis, Nathaniel J L K; Bai, Sai; Jellicoe, Tom C; de la Peña, Francisco; Hou, Shaocong; Ducati, Caterina; Gao, Feng; Friend, Richard H; Greenham, Neil C; Tan, Zhi-Kuang

    2016-05-01

    The preparation of highly efficient perovskite nanocrystal light-emitting diodes is shown. A new trimethylaluminum vapor-based crosslinking method to render the nanocrystal films insoluble is applied. The resulting near-complete nanocrystal film coverage, coupled with the natural confinement of injected charges within the perovskite crystals, facilitates electron-hole capture and give rise to a remarkable electroluminescence yield of 5.7%. PMID:26990965

  15. From Morphology to Interfaces to Tandem Geometries: Enhancing the Performance of Perovskite/Polymer Solar Cells

    NASA Astrophysics Data System (ADS)

    Russell, Thomas

    We have taken a new approach to develop mesoporous lead iodide scaffolds, using the nucleation and growth of lead iodide crystallites in a wet film. A simple time-dependent growth control enabled the manipulation of the mesoporous lead iodide layer quality in a continuous manner. The morphology of lead iodide is shown to influence the subsequent crystallization of methyamoniumleadiodide film by using angle-dependent grazing incidence x-ray scattering. The morphology of lead iodide film can be fine-tuned, and thus the methyamoniumleadiodide film quality can be effectively controlled, leading to an optimization of the perovskite active layer. Using this strategy, perovskite solar cells with inverted PHJ structure showed a PCE of 15.7 per cent with little hysteresis. Interface engineering is critical for achieving efficient solar cells, yet a comprehensive understanding of the interface between metal electrode and electron transport layer (ETL) is lacking. A significant power conversion efficiency (PCE) improvement of fullerene/perovskite planar heterojunction solar cells was achieved by inserting a fulleropyrrolidine interlayer between the silver electrode and electron transport layer. The interlayer was found to enhance recombination resistance, increases electron extraction rate and prolongs free carrier lifetime. We also uncovered a facile solution-based fabrication of high performance tandem perovskite/polymer solar cells where the front sub-cell consists of perovskite and the back sub-cell is a polymer-based layer. A record maximum PCE of 15.96 per cent was achieved, demonstrating the synergy between the perovskite and semiconducting polymers. This design balances the absorption of the perovskite and the polymer, eliminates the adverse impact of thermal annealing during perovskite fabrication, and affords devices with no hysteresis. This work was performed in collaboration with Y. Liu, Z. Page, D. Venkataraman and T. Emrick (UMASS), F. Liu (LBNL) and Q. Hu and R

  16. Towards optical optimization of planar monolithic perovskite/silicon-heterojunction tandem solar cells

    NASA Astrophysics Data System (ADS)

    Albrecht, Steve; Saliba, Michael; Correa-Baena, Juan-Pablo; Jäger, Klaus; Korte, Lars; Hagfeldt, Anders; Grätzel, Michael; Rech, Bernd

    2016-06-01

    Combining inorganic–organic perovskites and crystalline silicon into a monolithic tandem solar cell has recently attracted increased attention due to the high efficiency potential of this cell architecture. Promising results with published efficiencies above 21% have been reported so far. To further increase the device performance, optical optimizations enabling device related guidelines are highly necessary. Here we experimentally show the optical influence of the ITO thickness in the interconnecting layer and fabricate an efficient monolithic tandem cell with a reduced ITO layer thickness that shows slightly improved absorption within the silicon sub-cell and a stabilized power output of 17%. Furthermore we present detailed optical simulations on experimentally relevant planar tandem stacks to give practical guidelines to reach efficiencies above 25%. By optimizing the thickness of all functional and the perovskite absorber layers, together with the optimization of the perovskite band-gap, we present a tandem stack that can yield ca 17.5 mA cm‑ 2 current in both sub-cells at a perovskite band-gap of 1.73 eV including losses from reflection and parasitic absorption. Assuming that the higher band-gap of the perovskite absorber directly translates into a higher open circuit voltage, the perovskite sub-cell should be able to reach a value of 1.3 V. With that, realistic efficiencies above 28% are within reach for planar monolithic tandem cells in which the thickness of the perovskite top-cell and the perovskite band-gap are highly optimized. When applying light trapping schemes such as textured surfaces and by reducing the parasitic absorption of the functional layers, for example in spiro-OMeTAD, this monolithic tandem can overcome 30% power conversion efficiency.

  17. Oxide-Ion Conduction in Anion-Deficient Perovskites.

    NASA Astrophysics Data System (ADS)

    Feng, Man

    1995-01-01

    Strategies for the design of an improved oxide -ion electrolyte for medium-temperature fuel cells, sensors, and oxygen pumps are outlined. Anion-deficient oxides with the perovskite structure were chosen for study. Stoichiometric oxides contain a high fraction of vacancies, but vacancy ordering suppresses ionic conductivity. Nevertheless, the brownmillerite rm Ba_2In_2O _5 undergoes an order-disorder transition at 930^circC that allows an estimate of the motional enthalpy of the disordered vacancy. Substitution of both aliovalent and isovalent cations were investigated as a means of suppressing the long-range ordering. Substitution of Nb^{5+}, Ti ^{4+}, Sn^{4+ } could be made for In^{3+ } at the B sites of the ABO_ {3-delta} perovskite structure, and this strategy did suppress long-range ordering of the oxygen vacancies for more than 10 mole % dopant. However, it was found that these dopants have a sufficient preference for octahedral anion coordination that water is introduced into the vacancies below 400^circ C; the protons introduced with the water became dominant conductive species below 400^circ C. At high temperature, the oxide-ion conduction is dominant and, below 930^circC, is enhanced by two orders of magnitude for about 20% dopant whether quadravalent or pentavalent dopants are used. Substitution of La^{3+} for Ba ^{2+} suppressed the introduction of water at low temperature, and the best oxide-ion conduction was achieved in rm Ba_{0.6}La _{0.4}InO_{2.7} isovalent doping of Y for In in rm Ba_2In _2O_5<=ad to the discovery of an extremely high ionic conduction in rm Ba _3Y_4O_9 stabilized at room temperature by quenching from above 1200^ circC. On heating in air, it first decomposes into rm Y_2O_3 and a Ba(OH)_2-BaO_2 mix that becomes an immobilized melt and a fast ionic conductor above 370^circC. With time in air, the melt is transformed to BaCO_3 , which is not conductive. Superior oxide-ion conduction was discovered in the Sr and Mg doped perovskite La

  18. Modeling the PbI2 formation in perovskite solar cells using XRD/XPS patterns

    NASA Astrophysics Data System (ADS)

    Sohrabpoor, Hamed; Elyasi, Majid; Aldosari, Marouf; Gorji, Nima E.

    2016-09-01

    The impact of prolonged irradiation and air humidity on the stability of perovskite solar cells is modeled using X-ray diffraction and X-ray photoelectron spectroscopy patterns reported in the literature. Light or air-moisture causes the formation of a thin PbI2 or oxide defective layers (in nanoscale) at the interface of perovskite/hole-transport-layer or at the junction with metallic back contact. This thin layer blocks the carrier transport/passivation at the interfaces and cause degradation of device parameters. Variation in thickness of defective layers, changes the XRD and XPS peaks. This allows detection and estimation of the type, crystallinity and thickness of the defective layer. A simple model is developed here to extract the thickness of such thin defective layers formed in nanometer scale at the back region of several perovskite devices. Based on this information, corrected energy band diagram of every device before and after degradation/aging is drawn and discussed in order to obtain insight into the carrier transport and charge collection at the barrier region. In addition, graphene contacted perovskite devices are investigated showing that honey-comb network of graphene contact reduces the effect of aging leading to formation of a thinner defective layer at the perovskite surface compared to perovskite devices with conventional inorganic contacts i.e. Au, Al.

  19. Wafer-scale growth of large arrays of perovskite microplate crystals for functional electronics and optoelectronics

    PubMed Central

    Wang, Gongming; Li, Dehui; Cheng, Hung-Chieh; Li, Yongjia; Chen, Chih-Yen; Yin, Anxiang; Zhao, Zipeng; Lin, Zhaoyang; Wu, Hao; He, Qiyuan; Ding, Mengning; Liu, Yuan; Huang, Yu; Duan, Xiangfeng

    2015-01-01

    Methylammonium lead iodide perovskite has attracted intensive interest for its diverse optoelectronic applications. However, most studies to date have been limited to bulk thin films that are difficult to implement for integrated device arrays because of their incompatibility with typical lithography processes. We report the first patterned growth of regular arrays of perovskite microplate crystals for functional electronics and optoelectronics. We show that large arrays of lead iodide microplates can be grown from an aqueous solution through a seeded growth process and can be further intercalated with methylammonium iodide to produce perovskite crystals. Structural and optical characterizations demonstrate that the resulting materials display excellent crystalline quality and optical properties. We further show that perovskite crystals can be selectively grown on prepatterned electrode arrays to create independently addressable photodetector arrays and functional field effect transistors. The ability to grow perovskite microplates and to precisely place them at specific locations offers a new material platform for the fundamental investigation of the electronic and optical properties of perovskite materials and opens a pathway for integrated electronic and optoelectronic systems. PMID:26601297

  20. Effect of Mesostructured Layer upon Crystalline Properties and Device Performance on Perovskite Solar Cells.

    PubMed

    Listorti, Andrea; Juarez-Perez, Emilio J; Frontera, Carlos; Roiati, Vittoria; Garcia-Andrade, Laura; Colella, Silvia; Rizzo, Aurora; Ortiz, Pablo; Mora-Sero, Ivan

    2015-05-01

    One of the most fascinating characteristics of perovskite solar cells (PSCs) is the retrieved obtainment of outstanding photovoltaic (PV) performances withstanding important device configuration variations. Here we have analyzed CH3NH3PbI3-xClx in planar or in mesostructured (MS) configurations, employing both titania and alumina scaffolds, fully infiltrated with perovskite material or presenting an overstanding layer. The use of the MS scaffold induces to the perovskite different structural properties, in terms of grain size, preferential orientation, and unit cell volume, in comparison to the ones of the material grown with no constraints, as we have found out by X-ray diffraction analyses. We have studied the effect of the PSC configuration on photoinduced absorption and time-resolved photoluminescence, complementary techniques that allow studying charge photogeneration and recombination. We have estimated electron diffusion length in the considered configurations observing a decrease when the material is confined in the MS scaffold with respect to a planar architecture. However, the presence of perovskite overlayer allows an overall recovering of long diffusion lengths explaining the record PV performances obtained with a device configuration bearing both the mesostructure and a perovskite overlayer. Our results suggest that performance in devices with perovskite overlayer is mainly ruled by the overlayer, whereas the mesoporous layer influences the contact properties. PMID:26263326