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Sample records for lead halides

  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. Ultrafast time-resolved spectroscopy of lead halide perovskite films

    NASA Astrophysics Data System (ADS)

    Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

    2015-09-01

    Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

  3. 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

  4. Lasing in robust cesium lead halide perovskite nanowires.

    PubMed

    Eaton, Samuel W; Lai, Minliang; Gibson, Natalie A; Wong, Andrew B; Dou, Letian; Ma, Jie; Wang, Lin-Wang; Leone, Stephen R; Yang, Peidong

    2016-02-23

    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 10(9) 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

  5. 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. PMID:26560862

  6. Giant photostriction in organic-inorganic lead halide perovskites.

    PubMed

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-01-01

    Among the many materials investigated for next-generation photovoltaic cells, organic-inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge-orbital-lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices. PMID:27044485

  7. Giant photostriction in organic–inorganic lead halide perovskites

    PubMed Central

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-01-01

    Among the many materials investigated for next-generation photovoltaic cells, organic–inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge–orbital–lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices. PMID:27044485

  8. Giant photostriction in organic-inorganic lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-04-01

    Among the many materials investigated for next-generation photovoltaic cells, organic-inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge-orbital-lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices.

  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. 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

  11. Experimental and theoretical optical properties of methylammonium lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Leguy, Aurélien M. A.; Azarhoosh, Pooya; Alonso, M. Isabel; Campoy-Quiles, Mariano; Weber, Oliver J.; Yao, Jizhong; Bryant, Daniel; Weller, Mark T.; Nelson, Jenny; Walsh, Aron; van Schilfgaarde, Mark; Barnes, Piers R. F.

    2016-03-01

    The optical constants of methylammonium lead halide single crystals CH3NH3PbX3 (X = I, Br, Cl) are interpreted with high level ab initio calculations using the relativistic quasiparticle self-consistent GW approximation (QSGW). Good agreement between the optical constants derived from QSGW and those obtained from spectroscopic ellipsometry enables the assignment of the spectral features to their respective inter-band transitions. We show that the transition from the highest valence band (VB) to the lowest conduction band (CB) is responsible for almost all the optical response of MAPbI3 between 1.2 and 5.5 eV (with minor contributions from the second highest VB and the second lowest CB). The calculations indicate that the orientation of [CH3NH3]+ cations has a significant influence on the position of the bandgap suggesting that collective orientation of the organic moieties could result in significant local variations of the optical properties. The optical constants and energy band diagram of CH3NH3PbI3 are then used to simulate the contributions from different optical transitions to a typical transient absorption spectrum (TAS).The optical constants of methylammonium lead halide single crystals CH3NH3PbX3 (X = I, Br, Cl) are interpreted with high level ab initio calculations using the relativistic quasiparticle self-consistent GW approximation (QSGW). Good agreement between the optical constants derived from QSGW and those obtained from spectroscopic ellipsometry enables the assignment of the spectral features to their respective inter-band transitions. We show that the transition from the highest valence band (VB) to the lowest conduction band (CB) is responsible for almost all the optical response of MAPbI3 between 1.2 and 5.5 eV (with minor contributions from the second highest VB and the second lowest CB). The calculations indicate that the orientation of [CH3NH3]+ cations has a significant influence on the position of the bandgap suggesting that collective

  12. Electron-phonon coupling in hybrid lead halide perovskites.

    PubMed

    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

  13. Experimental and theoretical optical properties of methylammonium lead halide perovskites.

    PubMed

    Leguy, Aurélien M A; Azarhoosh, Pooya; Alonso, M Isabel; Campoy-Quiles, Mariano; Weber, Oliver J; Yao, Jizhong; Bryant, Daniel; Weller, Mark T; Nelson, Jenny; Walsh, Aron; van Schilfgaarde, Mark; Barnes, Piers R F

    2016-03-17

    The optical constants of methylammonium lead halide single crystals CH3NH3PbX3 (X = I, Br, Cl) are interpreted with high level ab initio calculations using the relativistic quasiparticle self-consistent GW approximation (QSGW). Good agreement between the optical constants derived from QSGW and those obtained from spectroscopic ellipsometry enables the assignment of the spectral features to their respective inter-band transitions. We show that the transition from the highest valence band (VB) to the lowest conduction band (CB) is responsible for almost all the optical response of MAPbI3 between 1.2 and 5.5 eV (with minor contributions from the second highest VB and the second lowest CB). The calculations indicate that the orientation of [CH3NH3](+) cations has a significant influence on the position of the bandgap suggesting that collective orientation of the organic moieties could result in significant local variations of the optical properties. The optical constants and energy band diagram of CH3NH3PbI3 are then used to simulate the contributions from different optical transitions to a typical transient absorption spectrum (TAS). PMID:26477295

  14. 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

  15. Multigraphene growth on lead-pencil drawn sliver halide print paper irradiated by scanning femtosecond laser

    NASA Astrophysics Data System (ADS)

    Kaneko, Satoru; Shimizu, Yoshitada; Rachi, Takeshi; Kato, Chihiro; Tanaka, Satomi; Naganuma, Yasuhiro; Katakura, Toru; Satoh, Kazuo; Ushiyama, Mikio; Konuma, Seiji; Itou, Yuko; Takikawa, Hirofumi; Tan, Goon; Matsuda, Akifumi; Yoshimoto, Mamoru

    2016-01-01

    Drawings were made on various types of paper using lead pencils of grades from 4H through 10B. Raman spectroscopy verified both G and D peaks on all the drawings on PC print paper, PC photopaper, kent paper, and paper for silver halide print. After irradiation with a scanning femtosecond laser, silver halide paper drawn on with a 10B lead pencil maintained its surface flatness compared with the other types of paper. Raman spectroscopy on silver print paper showed a high-intensity G peak and a low-intensity D peak. After irradiating the scanning femtosecond laser on silver halide paper drawn on with a 10B lead pencil, Raman spectroscopy showed a high-intensity G peak and less intense of D peak together with a 2D peak around 2,700 cm-1 corresponding to the existence of multigraphene.

  16. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions

    PubMed Central

    2015-01-01

    We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles. PMID:26214734

  17. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions.

    PubMed

    Akkerman, Quinten A; D'Innocenzo, Valerio; Accornero, Sara; Scarpellini, Alice; Petrozza, Annamaria; Prato, Mirko; Manna, Liberato

    2015-08-19

    We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl(-) or I(-) ions and reinsertion of Br(-) ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles. PMID:26214734

  18. Quantitative determination of lead in mixtures of lead(II) halides using solid-state 207Pb NMR spectroscopy.

    PubMed

    Glatfelter, Alicia; Stephenson, Nicole; Bai, Shi; Dybowski, Cecil; Perry, Dale L

    2006-11-01

    We demonstrate a multi-spectrum technique for facile, quantitative determination of lead in solid materials using solid-state (207)Pb NMR that avoids the major problem of uniform excitation across a wide spectral range; the method can be employed without chemical separation or other chemical manipulations and without any prior sample preparation, resulting in a non-destructive analysis, and producing results that are in agreement with gravimetric analyses of mixed samples of the lead halides. PMID:17066187

  19. Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites

    PubMed Central

    Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska; Bodnarchuk, Maryna I.; Nedelcu, Georgian; Humer, Markus; De Luca, Gabriele; Fiebig, Manfred; Heiss, Wolfgang; Kovalenko, Maksym V.

    2015-01-01

    Metal halide semiconductors with perovskite crystal structures have recently emerged as highly promising optoelectronic materials. Despite the recent surge of reports on microcrystalline, thin-film and bulk single-crystalline metal halides, very little is known about the photophysics of metal halides in the form of uniform, size-tunable nanocrystals. Here we report low-threshold amplified spontaneous emission and lasing from ∼10 nm monodisperse colloidal nanocrystals of caesium lead halide perovskites CsPbX3 (X=Cl, Br or I, or mixed Cl/Br and Br/I systems). We find that room-temperature optical amplification can be obtained in the entire visible spectral range (440–700 nm) with low pump thresholds down to 5±1 μJ cm−2 and high values of modal net gain of at least 450±30 cm−1. Two kinds of lasing modes are successfully observed: whispering-gallery-mode lasing using silica microspheres as high-finesse resonators, conformally coated with CsPbX3 nanocrystals and random lasing in films of CsPbX3 nanocrystals. PMID:26290056

  20. Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska; Bodnarchuk, Maryna I.; Nedelcu, Georgian; Humer, Markus; de Luca, Gabriele; Fiebig, Manfred; Heiss, Wolfgang; Kovalenko, Maksym V.

    2015-08-01

    Metal halide semiconductors with perovskite crystal structures have recently emerged as highly promising optoelectronic materials. Despite the recent surge of reports on microcrystalline, thin-film and bulk single-crystalline metal halides, very little is known about the photophysics of metal halides in the form of uniform, size-tunable nanocrystals. Here we report low-threshold amplified spontaneous emission and lasing from ~10 nm monodisperse colloidal nanocrystals of caesium lead halide perovskites CsPbX3 (X=Cl, Br or I, or mixed Cl/Br and Br/I systems). We find that room-temperature optical amplification can be obtained in the entire visible spectral range (440-700 nm) with low pump thresholds down to 5+/-1 μJ cm-2 and high values of modal net gain of at least 450+/-30 cm-1. Two kinds of lasing modes are successfully observed: whispering-gallery-mode lasing using silica microspheres as high-finesse resonators, conformally coated with CsPbX3 nanocrystals and random lasing in films of CsPbX3 nanocrystals.

  1. Enhancement of Exciton Emission in Lead Halide-Based Layered Perovskites by Cation Mixing.

    PubMed

    Era, Masanao; Komatsu, Yumeko; Sakamoto, Naotaka

    2016-04-01

    Spin-coated films of a lead halide, PbX: X = I and Br, layered perovskites having cyclohexenylethyl ammonium molecule as an organic layer, which were mixed with other metal halide-based layered perovskites consisting of various divalent metal halides (for example, Ca2, Cdl2, FeI2, SnBr2 and so on), were prepared. The results of X-ray diffraction measurements exhibited that solid solution formation between PbX-based layered perovskite and other divalent metal halide-based layered perovskites was observed up to very high molar concentration of 50 molar% in the mixed film samples when divalent cations having ionic radius close to that of Pb2+ were employed. In the solid solution films, the exciton emission was much enhanced at room temperature. Exciton emission intensity of Pbl-based layered perovskite mixed with Cal-based layered perovskite (20 molar%) is about 5 times large that of the pristine Pbl-based layered perovskite, and that of PbBr-based layered perovskite mixed with SnBr-based layered perovskite (20 molar%) was also about 5 times large that of the pristine PbBr-based layered perovskite at room temperature. PMID:27451628

  2. Spectral Features and Charge Dynamics of Lead Halide Perovskites: Origins and Interpretations.

    PubMed

    Sum, Tze Chien; Mathews, Nripan; Xing, Guichuan; Lim, Swee Sien; Chong, Wee Kiang; Giovanni, David; Dewi, Herlina Arianita

    2016-02-16

    Lead halide perovskite solar cells are presently the forerunner among the third generation solution-processed photovoltaic technologies. With efficiencies exceeding 20% and low production costs, they are prime candidates for commercialization. Critical insights into their light harvesting, charge transport, and loss mechanisms have been gained through time-resolved optical probes such as femtosecond transient absorption spectroscopy (fs-TAS), transient photoluminescence spectroscopy, and time-resolved terahertz spectroscopy. Specifically, the discoveries of long balanced electron-hole diffusion lengths and gain properties in halide perovskites underpin their significant roles in uncovering structure-function relations and providing essential feedback for materials development and device optimization. In particular, fs-TAS is becoming increasingly popular in perovskite characterization studies, with commercial one-box pump-probe systems readily available as part of a researcher's toolkit. Although TAS is a powerful probe in the study of charge dynamics and recombination mechanisms, its instrumentation and data interpretation can be daunting even for experienced researchers. This issue is exacerbated by the sensitive nature of halide perovskites where the kinetics are especially susceptible to pump fluence, sample preparation and handling and even degradation effects that could lead to disparate conclusions. Nonetheless, with end-users having a clear understanding of TAS's capabilities, subtleties, and limitations, cutting-edge work with deep insights can still be performed using commercial setups as has been the trend for ubiquitous spectroscopy instruments like absorption, fluorescence, and transient photoluminescence spectrometers. Herein, we will first briefly examine the photophysical processes in lead halide perovskites, highlighting their novel properties. Next, we proceed to give a succinct overview of the fundamentals of pump-probe spectroscopy in relation

  3. High-Density and Uniform Lead Halide Perovskite Nanolaser Array on Silicon.

    PubMed

    Wang, Kaiyang; Gu, Zhiyuan; Liu, Shuai; Sun, Wenzhao; Zhang, Nan; Xiao, Shumin; Song, Qinghai

    2016-07-01

    The realization of high density and highly uniform nanolaser arrays in lead halide perovskite is quite challenging, especially on silicon. Herein, we demonstrate a simple way to form lead halide nanolaser array on silicon chip with high density and uniform lasing wavelengths. By positioning a perovskite microwire onto a silicon grating, only the suspended parts can hold high quality (Q) resonances and generate laser emissions. As the perovskite microwire is periodically segmented by the silicon grating, the transverse lasers are divided into a periodic nanolaser array and the lasing wavelengths from different subunits are almost the same. The transverse laser has been observed in an air gap as narrow as 420 nm, increasing the density of nanolasers to about 1250 per millimeter (800 nm period in experiment). We believe this research shall shed light on the development of perovskite microlaser and nanolaser arrays on silicon and their applications. PMID:27320490

  4. Tuning the thermal conductivity of methylammonium lead halide by the molecular substructure.

    PubMed

    Caddeo, Claudia; Melis, Claudio; Saba, Maria Ilenia; Filippetti, Alessio; Colombo, Luciano; Mattoni, Alessandro

    2016-09-21

    By using state-of-the-art atomistic methods we provide an accurate estimate of thermal conductivity of methylammonium lead halide as a function of sample size and temperature, in agreement with experimental works. We show that the thermal conductivity of methylammonium lead halide is intrinsically low, due to the low sound velocity of the PbI lattice. Furthermore, by selectively analyzing the effect of different molecular degrees of freedom, we clarify the role of the molecular substructure by showing that the internal modes above 150 cm(-1) (in addition to rotations) are effective in reducing the thermal conductivity of hybrid perovskites. This analysis suggests strategies to tailor the thermal conductivity by modifying the internal structure of organic cations. PMID:27531063

  5. Light-induced defects in hybrid lead halide perovskite

    NASA Astrophysics Data System (ADS)

    Sharia, Onise; Schneider, William

    One of the main challenges facing organohalide perovskites for solar application is stability. Solar cells must last decades to be economically viable alternatives to traditional energy sources. While some causes of instability can be avoided through engineering, light-induced defects can be fundamentally limiting factor for practical application of the material. Light creates large numbers of electron and hole pairs that can contribute to degradation processes. Using ab initio theoretical methods, we systematically explore first steps of light induced defect formation in methyl ammonium lead iodide, MAPbI3. In particular, we study charged and neutral Frenkel pair formation involving Pb and I atoms. We find that most of the defects, except negatively charged Pb Frenkel pairs, are reversible, and thus most do not lead to degradation. Negative Pb defects create a mid-gap state and localize the conduction band electron. A minimum energy path study shows that, once the first defect is created, Pb atoms migrate relatively fast. The defects have two detrimental effects on the material. First, they create charge traps below the conduction band. Second, they can lead to degradation of the material by forming Pb clusters.

  6. Nanowire Lasers of Formamidinium Lead Halide Perovskites and Their Stabilized Alloys with Improved Stability.

    PubMed

    Fu, Yongping; Zhu, Haiming; Schrader, Alex W; Liang, Dong; Ding, Qi; Joshi, Prakriti; Hwang, Leekyoung; Zhu, X-Y; Jin, Song

    2016-02-10

    The excellent intrinsic optoelectronic properties of methylammonium lead halide perovskites (MAPbX3, X = Br, I), such as high photoluminescence quantum efficiency, long carrier lifetime, and high gain coupled with the facile solution growth of nanowires make them promising new materials for ultralow-threshold nanowire lasers. However, their photo and thermal stabilities need to be improved for practical applications. Herein, we report a low-temperature solution growth of single crystal nanowires of formamidinium lead halide perovskites (FAPbX3) that feature red-shifted emission and better thermal stability compared to MAPbX3. We demonstrate optically pumped room-temperature near-infrared (∼820 nm) and green lasing (∼560 nm) from FAPbI3 (and MABr-stabilized FAPbI3) and FAPbBr3 nanowires with low lasing thresholds of several microjoules per square centimeter and high quality factors of about 1500-2300. More remarkably, the FAPbI3 and MABr-stabilized FAPbI3 nanowires display durable room-temperature lasing under ∼10(8) shots of sustained illumination of 402 nm pulsed laser excitation (150 fs, 250 kHz), substantially exceeding the stability of MAPbI3 (∼10(7) laser shots). We further demonstrate tunable nanowire lasers in wider wavelength region from FA-based lead halide perovskite alloys (FA,MA)PbI3 and (FA,MA)Pb(I,Br)3 through cation and anion substitutions. The results suggest that formamidinium lead halide perovskite nanostructures could be more promising and stable materials for the development of light-emitting diodes and continuous-wave lasers. PMID:26727024

  7. Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors.

    PubMed

    Zhu, Haiming; Fu, Yongping; Meng, Fei; Wu, Xiaoxi; Gong, Zizhou; Ding, Qi; Gustafsson, Martin V; Trinh, M Tuan; Jin, Song; Zhu, X-Y

    2015-06-01

    The remarkable performance of lead halide perovskites in solar cells can be attributed to the long carrier lifetimes and low non-radiative recombination rates, the same physical properties that are ideal for semiconductor lasers. Here, we show room-temperature and wavelength-tunable lasing from single-crystal lead halide perovskite nanowires with very low lasing thresholds (220 nJ cm(-2)) and high quality factors (Q ∼ 3,600). The lasing threshold corresponds to a charge carrier density as low as 1.5 × 10(16) cm(-3). Kinetic analysis based on time-resolved fluorescence reveals little charge carrier trapping in these single-crystal nanowires and gives estimated lasing quantum yields approaching 100%. Such lasing performance, coupled with the facile solution growth of single-crystal nanowires and the broad stoichiometry-dependent tunability of emission colour, makes lead halide perovskites ideal materials for the development of nanophotonics, in parallel with the rapid development in photovoltaics from the same materials. PMID:25849532

  8. Random lasing in organo-lead halide perovskite microcrystal networks

    SciTech Connect

    Dhanker, R.; Brigeman, A. N.; Giebink, N. C.; Larsen, A. V.; Stewart, R. J.; Asbury, J. B.

    2014-10-13

    We report optically pumped random lasing in planar methylammonium lead iodide perovskite microcrystal networks that form spontaneously from spin coating. Low thresholds (<200 μJ/cm{sup 2}) and narrow linewidths (Δλ < 0.5 nm) reflect lasing from closed quasi-modes that result from ballistic waveguiding in linear network segments linked by scattering at the junctions. Spatio-spectral imaging indicates that these quasi-modes extend over lateral length scales >100 μm and spatially overlap with one another, resulting in chaotic pulse-to-pulse intensity fluctuations due to gain competition. These results demonstrate this class of hybrid organic-inorganic perovskite as a platform to study random lasing with well-defined, low-level disorder, and support the potential of these materials for use in semiconductor laser applications.

  9. On the Thermal and Thermodynamic (In)Stability of Methylammonium Lead Halide Perovskites

    PubMed Central

    Brunetti, Bruno; Cavallo, Carmen; Ciccioli, Andrea; Gigli, Guido; Latini, Alessandro

    2016-01-01

    The interest of the scientific community on methylammonium lead halide perovskites (MAPbX3, X = Cl, Br, I) for hybrid organic-inorganic solar cells has grown exponentially since the first report in 2009. This fact is clearly justified by the very high efficiencies attainable (reaching 20% in lab scale devices) at a fraction of the cost of conventional photovoltaics. However, many problems must be solved before a market introduction of these devices can be envisaged. Perhaps the most important to be addressed is the lack of information regarding the thermal and thermodynamic stability of the materials towards decomposition, which are intrinsic properties of them and which can seriously limit or even exclude their use in real devices. In this work we present and discuss the results we obtained using non-ambient X-ray diffraction, Knudsen effusion-mass spectrometry (KEMS) and Knudsen effusion mass loss (KEML) techniques on MAPbCl3, MAPbBr3 and MAPbI3. The measurements demonstrate that all the materials decompose to the corresponding solid lead (II) halide and gaseous methylamine and hydrogen halide, and the decomposition is well detectable even at moderate temperatures (~60 °C). Our results suggest that these materials may be problematic for long term operation of solar devices. PMID:27545661

  10. Lead-Free Halide Double Perovskites via Heterovalent Substitution of Noble Metals.

    PubMed

    Volonakis, George; Filip, Marina R; Haghighirad, Amir Abbas; Sakai, Nobuya; Wenger, Bernard; Snaith, Henry J; Giustino, Feliciano

    2016-04-01

    Lead-based halide perovskites are emerging as the most promising class of materials for next-generation optoelectronics; however, despite the enormous success of lead-halide perovskite solar cells, the issues of stability and toxicity are yet to be resolved. Here we report on the computational design and the experimental synthesis of a new family of Pb-free inorganic halide double perovskites based on bismuth or antimony and noble metals. Using first-principles calculations we show that this hitherto unknown family of perovskites exhibits very promising optoelectronic properties, such as tunable band gaps in the visible range and low carrier effective masses. Furthermore, we successfully synthesize the double perovskite Cs2BiAgCl6, perform structural refinement using single-crystal X-ray diffraction, and characterize its optical properties via optical absorption and photoluminescence measurements. This new perovskite belongs to the Fm3̅m space group and consists of BiCl6 and AgCl6 octahedra alternating in a rock-salt face-centered cubic structure. From UV-vis and photoluminescence measurements we obtain an indirect gap of 2.2 eV. PMID:26982118

  11. On the Thermal and Thermodynamic (In)Stability of Methylammonium Lead Halide Perovskites.

    PubMed

    Brunetti, Bruno; Cavallo, Carmen; Ciccioli, Andrea; Gigli, Guido; Latini, Alessandro

    2016-01-01

    The interest of the scientific community on methylammonium lead halide perovskites (MAPbX3, X = Cl, Br, I) for hybrid organic-inorganic solar cells has grown exponentially since the first report in 2009. This fact is clearly justified by the very high efficiencies attainable (reaching 20% in lab scale devices) at a fraction of the cost of conventional photovoltaics. However, many problems must be solved before a market introduction of these devices can be envisaged. Perhaps the most important to be addressed is the lack of information regarding the thermal and thermodynamic stability of the materials towards decomposition, which are intrinsic properties of them and which can seriously limit or even exclude their use in real devices. In this work we present and discuss the results we obtained using non-ambient X-ray diffraction, Knudsen effusion-mass spectrometry (KEMS) and Knudsen effusion mass loss (KEML) techniques on MAPbCl3, MAPbBr3 and MAPbI3. The measurements demonstrate that all the materials decompose to the corresponding solid lead (II) halide and gaseous methylamine and hydrogen halide, and the decomposition is well detectable even at moderate temperatures (~60 °C). Our results suggest that these materials may be problematic for long term operation of solar devices. PMID:27545661

  12. Kinetics of cesium lead halide perovskite nanoparticle growth; focusing and de-focusing of size distribution

    NASA Astrophysics Data System (ADS)

    Koolyk, Miriam; Amgar, Daniel; Aharon, Sigalit; Etgar, Lioz

    2016-03-01

    In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking their growth by high-resolution transmission electron microscopy and size distribution analysis. As a result, we are able to provide a detailed model for the kinetics of their growth. It was observed that the CsPbI3 NPs exhibit focusing of the size distribution in the first 20 seconds of growth, followed by de-focusing over longer growth durations, while the CsPbBr3 NPs show de-focusing of the size distribution starting from the beginning of the growth. The monomer concentration is depleted faster in the case of CsPbBr3 than in the case of CsPbI3, due to faster diffusion of the monomers, which increases the critical radius and results in de-focusing of the population. Accordingly, focusing is not observed within 40 seconds of growth in the case of CsPbBr3. This study provides important knowledge on how to achieve a narrow size distribution of cesium lead halide perovskite NPs when generating large amounts of these promising, highly luminescent NPs.In this work we study the kinetics of cesium lead halide perovskite nanoparticle (NP) growth; the focusing and de-focusing of the NP size distribution. Cesium lead halide perovskite NPs are considered to be attractive materials for optoelectronic applications. Understanding the kinetics of the formation of these all-inorganic perovskite NPs is critical for reproducibly and reliably generating large amounts of uniformly sized NPs. Here we investigate different growth durations for CsPbI3 and CsPbBr3 NPs, tracking

  13. Color-Pure Violet-Light-Emitting Diodes Based on Layered Lead Halide Perovskite Nanoplates.

    PubMed

    Liang, Dong; Peng, Yuelin; Fu, Yongping; Shearer, Melinda J; Zhang, Jingjing; Zhai, Jianyuan; Zhang, Yi; Hamers, Robert J; Andrew, Trisha L; Jin, Song

    2016-07-26

    Violet electroluminescence is rare in both inorganic and organic light-emitting diodes (LEDs). Low-cost and room-temperature solution-processed lead halide perovskites with high-efficiency and color-tunable photoluminescence are promising for LEDs. Here, we report room-temperature color-pure violet LEDs based on a two-dimensional lead halide perovskite material, namely, 2-phenylethylammonium (C6H5CH2CH2NH3(+), PEA) lead bromide [(PEA)2PbBr4]. The natural quantum confinement of two-dimensional layered perovskite (PEA)2PbBr4 allows for photoluminescence of shorter wavelength (410 nm) than its three-dimensional counterpart. By converting as-deposited polycrystalline thin films to micrometer-sized (PEA)2PbBr4 nanoplates using solvent vapor annealing, we successfully integrated this layered perovskite material into LEDs and achieved efficient room-temperature violet electroluminescence at 410 nm with a narrow bandwidth. This conversion to nanoplates significantly enhanced the crystallinity and photophysical properties of the (PEA)2PbBr4 samples and the external quantum efficiency of the violet LED. The solvent vapor annealing method reported herein can be generally applied to other perovskite materials to increase their grain size and, ultimately, improve the performance of optoelectronic devices based on perovskite materials. PMID:27336850

  14. Synthesis of Cesium Lead Halide Perovskite Nanocrystals in a Droplet-Based Microfluidic Platform: Fast Parametric Space Mapping.

    PubMed

    Lignos, Ioannis; Stavrakis, Stavros; Nedelcu, Georgian; Protesescu, Loredana; deMello, Andrew J; Kovalenko, Maksym V

    2016-03-01

    Prior to this work, fully inorganic nanocrystals of cesium lead halide perovskite (CsPbX3, X = Br, I, Cl and Cl/Br and Br/I mixed halide systems), exhibiting bright and tunable photoluminescence, have been synthesized using conventional batch (flask-based) reactions. Unfortunately, our understanding of the parameters governing the formation of these nanocrystals is still very limited due to extremely fast reaction kinetics and multiple variables involved in ion-metathesis-based synthesis of such multinary halide systems. Herein, we report the use of a droplet-based microfluidic platform for the synthesis of CsPbX3 nanocrystals. The combination of online photoluminescence and absorption measurements and the fast mixing of reagents within such a platform allows the rigorous and rapid mapping of the reaction parameters, including molar ratios of Cs, Pb, and halide precursors, reaction temperatures, and reaction times. This translates into enormous savings in reagent usage and screening times when compared to analogous batch synthetic approaches. The early-stage insight into the mechanism of nucleation of metal halide nanocrystals suggests similarities with multinary metal chalcogenide systems, albeit with much faster reaction kinetics in the case of halides. Furthermore, we show that microfluidics-optimized synthesis parameters are also directly transferrable to the conventional flask-based reaction. PMID:26836149

  15. An Explanation of the Photoinduced Giant Dielectric Constant of Lead Halide Perovskite Solar Cells.

    PubMed

    Almond, Darryl P; Bowen, Chris R

    2015-05-01

    A photoinduced giant dielectric constant of ~10(6) has been found in impedance spectroscopy measurements of lead halide perovskite solar cells. We report similar effects in measurements of a porous lead zirconate titanate (PZT) sample saturated with water. The principal effect of the illumination of the solar cell and of the introduction of water into the pore volume of the PZT sample is a significant increase in conductivity and dielectric loss. This is shown to exhibit low frequency power law dispersion. Application of the Kramers-Kronig relationships show the large measured values of permittivity to be related to the power law changes in conductivity and dielectric loss. The power law dispersions in the electrical responses are consistent with an electrical network model of microstructure. It is concluded that the high apparent values of permittivity are features of the microstructural networks and not fundamental effects in the two perovskite materials. PMID:26263342

  16. Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites.

    PubMed

    Nagabhushana, G P; Shivaramaiah, Radha; Navrotsky, Alexandra

    2016-07-12

    Hybrid perovskites, especially methylammonium lead iodide (MAPbI3), exhibit excellent solar power conversion efficiencies. However, their application is plagued by poor chemical and structural stability. Using direct calorimetric measurement of heats of formation, MAPbI3 is shown to be thermodynamically unstable with respect to decomposition to lead iodide and methylammonium iodide, even in the absence of ambient air or light or heat-induced defects, thus limiting its long-term use in devices. The formation enthalpy from binary halide components becomes less favorable in the order MAPbCl3, MAPbBr3, MAPbI3, with only the chloride having a negative heat of formation. Optimizing the geometric match of constituents as measured by the Goldschmidt tolerance factor provides a potentially quantifiable thermodynamic guide for seeking chemical substitutions to enhance stability. PMID:27357677

  17. Polar-solvent-free colloidal synthesis of highly luminescent alkylammonium lead halide perovskite nanocrystals.

    PubMed

    Vybornyi, Oleh; Yakunin, Sergii; Kovalenko, Maksym V

    2016-03-17

    A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm(-2). PMID:26645348

  18. Optical modelling data for room temperature optical properties of organic–inorganic lead halide perovskites

    PubMed Central

    Jiang, Yajie; Green, Martin A.; Sheng, Rui; Ho-Baillie, Anita

    2015-01-01

    The optical properties of perovskites at ambient temperatures are important both to the design of optimised solar cells as well as in other areas such as the refinement of electronic band structure calculations. Limited previous information on the optical modelling has been published. The experimental fitting parameters for optical constants of CH3NH3PbI3−xClx and CH3NH3PbI3 perovskite films are reported at 297 K as determined by detailed analysis of reflectance and transmittance data. The data in this study is related to the research article “Room temperature optical properties of organic–inorganic lead halide perovskites” in Solar Energy Materials & Solar Cells [1]. PMID:26217745

  19. Polar-solvent-free colloidal synthesis of highly luminescent alkylammonium lead halide perovskite nanocrystals

    NASA Astrophysics Data System (ADS)

    Vybornyi, Oleh; Yakunin, Sergii; Kovalenko, Maksym V.

    2016-03-01

    A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2.A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2. Electronic supplementary information (ESI) available: Materials and methods, additional figures. See DOI: 10.1039/c5nr06890h

  20. Pressure-Induced Structural and Optical Properties of Organometal Halide Perovskite-Based Formamidinium Lead Bromide.

    PubMed

    Wang, Lingrui; Wang, Kai; Zou, Bo

    2016-07-01

    Organometal halide perovskites (OMHPs) are attracting an ever-growing scientific interest as photovoltaic materials with moderate cost and compelling properties. In this Letter, pressure-induced optical and structural changes of OMHP-based formamidinium lead bromide (FAPbBr3) were systematically investigated. We studied the pressure dependence of optical absorption and photoluminescence, both of which showed piezochromism. Synchrotron X-ray diffraction indicated that FAPbBr3 underwent two phase transitions and subsequent amorphization, leading directly to the bandgap evolution with redshift followed by blueshift during compression. Raman experiments illustrated the high pressure behavior of organic cation and the surrounding inorganic octahedra. Additionally, the effect of cation size and the different intermolecular interactions between organic cation and inorganic octahedra result in the fact that FAPbBr3 is less compressible than the reported methylammonium lead bromide (MAPbBr3). High pressure studies of the structural evolution and optical properties of OMHPs provide important clues in optimizing photovoltaic performance and help to design novel OMHPs with higher stimuli-resistant ability. PMID:27321024

  1. Synthesis and Optical Properties of Lead-Free Cesium Tin Halide Perovskite Nanocrystals.

    PubMed

    Jellicoe, Tom C; Richter, Johannes M; Glass, Hugh F J; Tabachnyk, Maxim; Brady, Ryan; Dutton, Siân E; Rao, Akshay; Friend, Richard H; Credgington, Dan; Greenham, Neil C; Böhm, Marcus L

    2016-03-01

    Metal halide perovskite crystal structures have emerged as a class of optoelectronic materials, which combine the ease of solution processability with excellent optical absorption and emission qualities. Restricting the physical dimensions of the perovskite crystallites to a few nanometers can also unlock spatial confinement effects, which allow large spectral tunability and high luminescence quantum yields at low excitation densities. However, the most promising perovskite structures rely on lead as a cationic species, thereby hindering commercial application. The replacement of lead with nontoxic alternatives such as tin has been demonstrated in bulk films, but not in spatially confined nanocrystals. Here, we synthesize CsSnX3 (X = Cl, Cl0.5Br0.5, Br, Br0.5I0.5, I) perovskite nanocrystals and provide evidence of their spectral tunability through both quantum confinement effects and control of the anionic composition. We show that luminescence from Sn-based perovskite nanocrystals occurs on pico- to nanosecond time scales via two spectrally distinct radiative decay processes, which we assign to band-to-band emission and radiative recombination at shallow intrinsic defect sites. PMID:26901659

  2. Synthesis of Composition Tunable and Highly Luminescent Cesium Lead Halide Nanowires through Anion-Exchange Reactions.

    PubMed

    Zhang, Dandan; Yang, Yiming; Bekenstein, Yehonadav; Yu, Yi; Gibson, Natalie A; Wong, Andrew B; Eaton, Samuel W; Kornienko, Nikolay; Kong, Qiao; Lai, Minliang; Alivisatos, A Paul; Leone, Stephen R; Yang, Peidong

    2016-06-15

    Here, we demonstrate the successful synthesis of brightly emitting colloidal cesium lead halide (CsPbX3, X = Cl, Br, I) nanowires (NWs) with uniform diameters and tunable compositions. By using highly monodisperse CsPbBr3 NWs as templates, the NW composition can be independently controlled through anion-exchange reactions. CsPbX3 alloy NWs with a wide range of alloy compositions can be achieved with well-preserved morphology and crystal structure. The NWs are highly luminescent with photoluminescence quantum yields (PLQY) ranging from 20% to 80%. The bright photoluminescence can be tuned over nearly the entire visible spectrum. The high PLQYs together with charge transport measurements exemplify the efficient alloying of the anionic sublattice in a one-dimensional CsPbX3 system. The wires increased functionality in the form of fast photoresponse rates and the low defect density suggest CsPbX3 NWs as prospective materials for optoelectronic applications. PMID:27213511

  3. Modulating the Electron-Hole Interaction in a Hybrid Lead Halide Perovskite with an Electric Field.

    PubMed

    Leijtens, Tomas; Srimath Kandada, Ajay Ram; Eperon, Giles E; Grancini, Giulia; D'Innocenzo, Valerio; Ball, James M; Stranks, Samuel D; Snaith, Henry J; Petrozza, Annamaria

    2015-12-16

    Despite rapid developments in both photovoltaic and light-emitting device performance, the understanding of the optoelectronic properties of hybrid lead halide perovskites is still incomplete. In particular, the polarizability of the material, the presence of molecular dipoles, and their influence on the dynamics of the photoexcitations remain an open issue to be clarified. Here, we investigate the effect of an applied external electric field on the photoexcited species of CH3NH3PbI3 thin films, both at room temperature and at low temperature, by monitoring the photoluminescence (PL) yield and PL decays. At room temperature we find evidence for electric-field-induced reduction of radiative bimolecular carrier recombination together with motion of charged defects that affects the nonradiative decay rate of the photoexcited species. At low temperature (190 K), we observe a field-induced enhancement of radiative free carrier recombination rates that lasts even after the removal of the field. We assign this to field-induced alignment of the molecular dipoles, which reduces the vibrational freedom of the lattice and the associated local screening and hence results in a stronger electron-hole interaction. PMID:26579724

  4. DFT +U Modeling of Hole Polarons in Organic Lead Halide Perovskites

    NASA Astrophysics Data System (ADS)

    Welch, Eric; Erhart, Paul; Scolfaro, Luisa; Zakhidov, Alex

    Due to the ever present drive towards improved efficiencies in solar cell technology, new and improved materials are emerging rapidly. Organic halide perovskites are a promising prospect, yet a fundamental understanding of the organic perovskite structure and electronic properties is missing. Particularly, explanations of certain physical phenomena, specifically a low recombination rate and high mobility of charge carriers still remain controversial. We theoretically investigate possible formation of hole polarons adopting methodology used for oxide perovskites. The perovskite studied here is the ABX3structure, with A being an organic cation, B lead and C a halogen; the combinations studied allow for A1,xA2 , 1 - xBX1,xX2 , 3 - xwhere the alloy convention is used to show mixtures of the organic cations and/or the halogens. Two organic cations, methylammonium and formamidinium, and three halogens, iodine, chlorine and bromine are studied. Electronic structures and polaron behavior is studied through first principle density functional theory (DFT) calculations using the Vienna Ab Initio Simulation Package (VASP). Local density approximation (LDA) pseudopotentials are used and a +U Hubbard correction of 8 eV is added; this method was shown to work with oxide perovskites. It is shown that a localized state is realized with the Hubbard correction in systems with an electron removed, residing in the band gap of each different structure. Thus, hole polarons are expected to be seen in these perovskites.

  5. Multicolor fluorescent light-emitting diodes based on cesium lead halide perovskite quantum dots

    NASA Astrophysics Data System (ADS)

    Wang, Peng; Bai, Xue; Sun, Chun; Zhang, Xiaoyu; Zhang, Tieqiang; Zhang, Yu

    2016-08-01

    High quantum yield, narrow full width at half-maximum and tunable emission color of perovskite quantum dots (QDs) make this kind of material good prospects for light-emitting diodes (LEDs). However, the relatively poor stability under high temperature and air condition limits the device performance. To overcome this issue, the liquid-type packaging structure in combination with blue LED chip was employed to fabricate the fluorescent perovskite quantum dot-based LEDs. A variety of monochromatic LEDs with green, yellow, reddish-orange, and red emission were fabricated by utilizing the inorganic cesium lead halide perovskite quantum dots as the color-conversion layer, which exhibited the narrow full width at half-maximum (<35 nm), the relatively high luminous efficiency (reaching 75.5 lm/W), and the relatively high external quantum efficiency (14.6%), making it the best-performing perovskite LEDs so far. Compared to the solid state LED device, the liquid-type LED devices exhibited excellent color stability against the various working currents. Furthermore, we demonstrated the potential prospects of all-inorganic perovskite QDs for the liquid-type warm white LEDs.

  6. Incorporation of Cl into sequentially deposited lead halide perovskite films for highly efficient mesoporous solar cells

    NASA Astrophysics Data System (ADS)

    Dharani, Sabba; Dewi, Herlina Arianita; Prabhakar, Rajiv Ramanujam; Baikie, Tom; Shi, Chen; Yonghua, Du; Mathews, Nripan; Boix, Pablo P.; Mhaisalkar, Subodh G.

    2014-10-01

    Organic-inorganic lead halide perovskites have been widely used as absorbers on mesoporous TiO2 films as well as thin films in planar heterojunction solar cells, yielding very high photovoltaic conversion efficiencies. Both the addition of chloride and sequential deposition methods were successfully employed to enhance the photovoltaic performance. Here, both approaches are combined in a sequential method by spincoating PbCl2 + PbI2 on a mesoporous TiO2 film followed by the perovskite transformation. The role of Cl in determining the optical, electrical, structural and morphological properties is correlated with the photovoltaic performance. The highest photovoltaic efficiency of 14.15% with the Voc, FF and Jsc being 1.09 V, 0.65 and 19.91 mA cm-2 respectively was achieved with 10 mol% of PbCl2 addition due to an increase of the film conductivity induced by a better perovskite morphology. This is linked to an improvement of the hysteresis and reproducibility of the solar cells.Organic-inorganic lead halide perovskites have been widely used as absorbers on mesoporous TiO2 films as well as thin films in planar heterojunction solar cells, yielding very high photovoltaic conversion efficiencies. Both the addition of chloride and sequential deposition methods were successfully employed to enhance the photovoltaic performance. Here, both approaches are combined in a sequential method by spincoating PbCl2 + PbI2 on a mesoporous TiO2 film followed by the perovskite transformation. The role of Cl in determining the optical, electrical, structural and morphological properties is correlated with the photovoltaic performance. The highest photovoltaic efficiency of 14.15% with the Voc, FF and Jsc being 1.09 V, 0.65 and 19.91 mA cm-2 respectively was achieved with 10 mol% of PbCl2 addition due to an increase of the film conductivity induced by a better perovskite morphology. This is linked to an improvement of the hysteresis and reproducibility of the solar cells. Electronic

  7. Single Cesium Lead Halide Perovskite Nanocrystals at Low Temperature: Fast Single-Photon Emission, Reduced Blinking, and Exciton Fine Structure

    PubMed Central

    2016-01-01

    Metal-halide semiconductors with perovskite crystal structure are attractive due to their facile solution processability, and have recently been harnessed very successfully for high-efficiency photovoltaics and bright light sources. Here, we show that at low temperature single colloidal cesium lead halide (CsPbX3, where X = Cl/Br) nanocrystals exhibit stable, narrow-band emission with suppressed blinking and small spectral diffusion. Photon antibunching demonstrates unambiguously nonclassical single-photon emission with radiative decay on the order of 250 ps, representing a significant acceleration compared to other common quantum emitters. High-resolution spectroscopy provides insight into the complex nature of the emission process such as the fine structure and charged exciton dynamics. PMID:26771336

  8. All-inorganic cesium lead halide perovskite nanocrystals for photodetector applications.

    PubMed

    Ramasamy, Parthiban; Lim, Da-Hye; Kim, Bumjin; Lee, Seung-Ho; Lee, Min-Sang; Lee, Jong-Soo

    2016-02-01

    Herein, we describe simple, fast and reproducible halide ion exchange reactions in CsPbX3 (X = Cl, Br, I) nanocrystals (NCs) at room temperature. Through the simple adjustment of the halide ion concentration, the photoluminescence of these NCs can be tuned over the entire visible region (425-655 nm). Photodetector devices based on entirely inorganic CsPbI3 NCs are demonstrated for the first time. The photodetectors exhibited a good on/off photocurrent ratio of 10(5). PMID:26688424

  9. Spectral and Dynamical Properties of Single Excitons, Biexcitons, and Trions in Cesium-Lead-Halide Perovskite Quantum Dots.

    PubMed

    Makarov, Nikolay S; Guo, Shaojun; Isaienko, Oleksandr; Liu, Wenyong; Robel, István; Klimov, Victor I

    2016-04-13

    Organic-inorganic lead-halide perovskites have been the subject of recent intense interest due to their unusually strong photovoltaic performance. A new addition to the perovskite family is all-inorganic Cs-Pb-halide perovskite nanocrystals, or quantum dots, fabricated via a moderate-temperature colloidal synthesis. While being only recently introduced to the research community, these nanomaterials have already shown promise for a range of applications from color-converting phosphors and light-emitting diodes to lasers, and even room-temperature single-photon sources. Knowledge of the optical properties of perovskite quantum dots still remains vastly incomplete. Here we apply various time-resolved spectroscopic techniques to conduct a comprehensive study of spectral and dynamical characteristics of single- and multiexciton states in CsPbX3 nanocrystals with X being either Br, I, or their mixture. Specifically, we measure exciton radiative lifetimes, absorption cross-sections, and derive the degeneracies of the band-edge electron and hole states. We also characterize the rates of intraband cooling and nonradiative Auger recombination and evaluate the strength of exciton-exciton coupling. The overall conclusion of this work is that spectroscopic properties of Cs-Pb-halide quantum dots are largely similar to those of quantum dots of more traditional semiconductors such as CdSe and PbSe. At the same time, we observe some distinctions including, for example, an appreciable effect of the halide identity on radiative lifetimes, considerably shorter biexciton Auger lifetimes, and apparent deviation of their size dependence from the "universal volume scaling" previously observed for many traditional nanocrystal systems. The high efficiency of Auger decay in perovskite quantum dots is detrimental to their prospective applications in light-emitting devices and lasers. This points toward the need for the development of approaches for effective suppression of Auger

  10. Lead Halide Perovskite Photovoltaic as a Model p-i-n Diode.

    PubMed

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

    2016-02-16

    The lead halide perovskite photovoltaic cells, especially the iodide compound CH3NH3PbI3 family, exhibited enormous progress in the energy conversion efficiency in the past few years. Although the first attempt to use the perovskite was as a sensitizer in a dye-sensitized solar cell, it has been recognized at the early stage of the development that the working of the perovskite photovoltaics is akin to that of the inorganic thin film solar cells. In fact, theoretically perovskite is always treated as an ordinary direct band gap semiconductor and hence the perovskite photovoltaics as a p-i-n diode. Despite this recognition, research effort along this line of thought is still in pieces and incomplete. Different measurements have been applied to different types of devices (different not only in the materials but also in the cell structures), making it difficult to have a coherent picture. To make the situation worse, the perovskite photovoltaics have been plagued by the irreproducible optoelectronic properties, most notably the sweep direction dependent current-voltage relationship, the hysteresis problem. Under such circumstances, it is naturally very difficult to analyze the data. Therefore, we set out to make hysteresis-free samples and apply time-tested models and numerical tools developed in the field of inorganic semiconductors. A series of electrical measurements have been performed on one type of CH3NH3PbI3 photovoltaic cells, in which a special attention was paid to ensure that their electronic reproducibility was better than the fitting error in the numerical analysis. The data can be quantitatively explained in terms of the established models of inorganic semiconductors: current/voltage relationship can be very well described by a two-diode model, while impedance spectroscopy revealed the presence of a thick intrinsic layer with the help of a numerical solver, SCAPS, developed for thin film solar cell analysis. These results point to that CH3NH3PbI3 is an

  11. Charge-Carrier Dynamics and Mobilities in Formamidinium Lead Mixed-Halide Perovskites.

    PubMed

    Rehman, Waqaas; Milot, Rebecca L; Eperon, Giles E; Wehrenfennig, Christian; Boland, Jessica L; Snaith, Henry J; Johnston, Michael B; Herz, Laura M

    2015-12-22

    The mixed-halide perovskite FAPb(Bry I1-y )3 is attractive for color-tunable and tandem solar cells. Bimolecular and Auger charge-carrier recombination rate constants strongly correlate with the Br content, y, suggesting a link with electronic structure. FAPbBr3 and FAPbI3 exhibit charge-carrier mobilities of 14 and 27 cm(2) V(-1) s(-1) and diffusion lengths exceeding 1 μm, while mobilities across the mixed Br/I system depend on crystalline phase disorder. PMID:26402226

  12. A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells.

    PubMed

    McMeekin, David P; Sadoughi, Golnaz; Rehman, Waqaas; Eperon, Giles E; Saliba, Michael; Hörantner, Maximilian T; Haghighirad, Amir; Sakai, Nobuya; Korte, Lars; Rech, Bernd; Johnston, Michael B; Herz, Laura M; Snaith, Henry J

    2016-01-01

    Metal halide perovskite photovoltaic cells could potentially boost the efficiency of commercial silicon photovoltaic modules from ∼20 toward 30% when used in tandem architectures. An optimum perovskite cell optical band gap of ~1.75 electron volts (eV) can be achieved by varying halide composition, but to date, such materials have had poor photostability and thermal stability. Here we present a highly crystalline and compositionally photostable material, [HC(NH2)2](0.83)Cs(0.17)Pb(I(0.6)Br(0.4))3, with an optical band gap of ~1.74 eV, and we fabricated perovskite cells that reached open-circuit voltages of 1.2 volts and power conversion efficiency of over 17% on small areas and 14.7% on 0.715 cm(2) cells. By combining these perovskite cells with a 19%-efficient silicon cell, we demonstrated the feasibility of achieving >25%-efficient four-terminal tandem cells. PMID:26744401

  13. Spectral and dynamical properties of single excitons, biexcitons, and trions in cesium-lead-halide perovskite quantum dots

    DOE PAGESBeta

    Makarov, Nikolay Sergeevich; Guo, Shaojun; Isaienko, Oleksandr; Liu, Wenyong; Robel, Istvan; Klimov, Victor Ivanovich

    2016-02-16

    Organic–inorganic lead-halide perovskites have been the subject of recent intense interest due to their unusually strong photovoltaic performance. A new addition to the perovskite family is all-inorganic Cs–Pb-halide perovskite nanocrystals, or quantum dots, fabricated via a moderate-temperature colloidal synthesis. While being only recently introduced to the research community, these nanomaterials have already shown promise for a range of applications from color-converting phosphors and light-emitting diodes to lasers, and even room-temperature single-photon sources. Knowledge of the optical properties of perovskite quantum dots still remains vastly incomplete. Here we apply various time-resolved spectroscopic techniques to conduct a comprehensive study of spectral andmore » dynamical characteristics of single- and multiexciton states in CsPbX3 nanocrystals with X being either Br, I, or their mixture. Specifically, we measure exciton radiative lifetimes, absorption cross-sections, and derive the degeneracies of the band-edge electron and hole states. We also characterize the rates of intraband cooling and nonradiative Auger recombination and evaluate the strength of exciton–exciton coupling. The overall conclusion of this work is that spectroscopic properties of Cs–Pb-halide quantum dots are largely similar to those of quantum dots of more traditional semiconductors such as CdSe and PbSe. At the same time, we observe some distinctions including, for example, an appreciable effect of the halide identity on radiative lifetimes, considerably shorter biexciton Auger lifetimes, and apparent deviation of their size dependence from the “universal volume scaling” previously observed for many traditional nanocrystal systems. The high efficiency of Auger decay in perovskite quantum dots is detrimental to their prospective applications in light-emitting devices and lasers. Furthermore, this points toward the need for the development of approaches for effective

  14. Role of Microstructure in the Electron-Hole Interaction of Hybrid Lead-Halide Perovskites

    PubMed Central

    Frost, Jarvist M.; Barker, Alex J.; De Bastiani, Michele; Gandini, Marina; Marras, Sergio; Lanzani, Guglielmo; Walsh, Aron; Petrozza, Annamaria

    2015-01-01

    Solar cells based on hybrid inorganic-organic halide perovskites have demonstrated high power conversion efficiencies in a range of architectures. The existence and stability of bound electron-hole pairs in these materials, and their role in the exceptional performance of optoelectronic devices, remains a controversial issue. Here we demonstrate, through a combination of optical spectroscopy and multiscale modeling as a function of the degree of polycrystallinity and temperature, that the electron-hole interaction is sensitive to the microstructure of the material. The long-range order is disrupted by polycrystalline disorder and the variations in electrostatic potential found for smaller crystals suppress exciton formation, while larger crystals of the same composition demonstrate an unambiguous excitonic state. We conclude that fabrication procedures and morphology strongly influence perovskite behaviour, with both free carrier and excitonic regimes possible, with strong implications for optoelectronic devices. PMID:26442125

  15. Hot-carrier cooling and photoinduced refractive index changes in organic-inorganic lead halide perovskites.

    PubMed

    Price, Michael B; Butkus, Justinas; Jellicoe, Tom C; Sadhanala, Aditya; Briane, Anouk; Halpert, Jonathan E; Broch, Katharina; Hodgkiss, Justin M; Friend, Richard H; Deschler, Felix

    2015-01-01

    Metal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ∼ 1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a 'phonon bottleneck' substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon-impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance. PMID:26404048

  16. Hot-carrier cooling and photoinduced refractive index changes in organic-inorganic lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Price, Michael B.; Butkus, Justinas; Jellicoe, Tom C.; Sadhanala, Aditya; Briane, Anouk; Halpert, Jonathan E.; Broch, Katharina; Hodgkiss, Justin M.; Friend, Richard H.; Deschler, Felix

    2015-09-01

    Metal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ~1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a `phonon bottleneck' substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon-impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance.

  17. Hot-carrier cooling and photoinduced refractive index changes in organic–inorganic lead halide perovskites

    PubMed Central

    Price, Michael B.; Butkus, Justinas; Jellicoe, Tom C.; Sadhanala, Aditya; Briane, Anouk; Halpert, Jonathan E.; Broch, Katharina; Hodgkiss, Justin M.; Friend, Richard H.; Deschler, Felix

    2015-01-01

    Metal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ∼1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a ‘phonon bottleneck' substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon–impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance. PMID:26404048

  18. Third-order nonlinear optical properties of methylammonium lead halide perovskite films

    SciTech Connect

    Johnson, Justin C.; Li, Zhen; Ndione, Paul F.; Zhu, Kai

    2016-01-01

    We report third-order nonlinear coefficient values and decay time kinetics vs. halide composition (CH3NH3PbBr3 and CH3NH3PbBr2I), temperature, and excitation wavelength. The maximum values of the third-order nonlinear susceptibility X(3) (-1.6 x 10-6 esu) are similar to or larger than many common third-order materials. The source of the nonlinearity is shown to be primarily excitonic in the tribromide film by virtue of its strong enhancement near the exciton resonance. Nonresonant excitation reduces the nonlinearity significantly, as does increasing the temperature. Substitution of one I for one Br also reduces the nonlinearity by at least one order of magnitude, presumably due to the lack of strong exciton resonance in the substituted form. The thin films are stable, highly homogenous (lacking significant light scattering), and simple and inexpensive to fabricate, making them potentially useful in a variety of optoelectronic applications in which wavelength selectivity is important.

  19. 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

  20. Charge carrier recombination channels in the low-temperature phase of organic-inorganic lead halide perovskite thin films

    NASA Astrophysics Data System (ADS)

    Wehrenfennig, Christian; Liu, Mingzhen; Snaith, Henry J.; Johnston, Michael B.; Herz, Laura M.

    2014-08-01

    The optoelectronic properties of the mixed hybrid lead halide perovskite CH3NH3PbI3-xClx have been subject to numerous recent studies related to its extraordinary capabilities as an absorber material in thin film solar cells. While the greatest part of the current research concentrates on the behavior of the perovskite at room temperature, the observed influence of phonon-coupling and excitonic effects on charge carrier dynamics suggests that low-temperature phenomena can give valuable additional insights into the underlying physics. Here, we present a temperature-dependent study of optical absorption and photoluminescence (PL) emission of vapor-deposited CH3NH3PbI3-xClx exploring the nature of recombination channels in the room- and the low-temperature phase of the material. On cooling, we identify an up-shift of the absorption onset by about 0.1 eV at about 100 K, which is likely to correspond to the known tetragonal-to-orthorhombic transition of the pure halide CH3NH3PbI3. With further decreasing temperature, a second PL emission peak emerges in addition to the peak from the room-temperature phase. The transition on heating is found to occur at about 140 K, i.e., revealing significant hysteresis in the system. While PL decay lifetimes are found to be independent of temperature above the transition, significantly accelerated recombination is observed in the low-temperature phase. Our data suggest that small inclusions of domains adopting the room-temperature phase are responsible for this behavior rather than a spontaneous increase in the intrinsic rate constants. These observations show that even sparse lower-energy sites can have a strong impact on material performance, acting as charge recombination centres that may detrimentally affect photovoltaic performance but that may also prove useful for optoelectronic applications such as lasing by enhancing population inversion.

  1. Diode-Pumped Organo-Lead Halide Perovskite Lasing in a Metal-Clad Distributed Feedback Resonator.

    PubMed

    Jia, Yufei; Kerner, Ross A; Grede, Alex J; Brigeman, Alyssa N; Rand, Barry P; Giebink, Noel C

    2016-07-13

    Organic-inorganic lead halide perovskite semiconductors have recently reignited the prospect of a tunable, solution-processed diode laser, which has the potential to impact a wide range of optoelectronic applications. Here, we demonstrate a metal-clad, second-order distributed feedback methylammonium lead iodide perovskite laser that marks a significant step toward this goal. Optically pumping this device with an InGaN diode laser at low temperature, we achieve lasing above a threshold pump intensity of 5 kW/cm(2) for durations up to ∼25 ns at repetition rates exceeding 2 MHz. We show that the lasing duration is not limited by thermal runaway and propose instead that lasing ceases under continuous pumping due to a photoinduced structural change in the perovskite that reduces the gain on a submicrosecond time scale. Our results indicate that the architecture demonstrated here could provide the foundation for electrically pumped lasing with a threshold current density Jth < 5 kA/cm(2) under sub-20 ns pulsed drive. PMID:27331618

  2. Generalized colloidal synthesis of high-quality, two-dimensional cesium lead halide perovskite nanosheets and their applications in photodetectors

    NASA Astrophysics Data System (ADS)

    Lv, Longfei; Xu, Yibing; Fang, Hehai; Luo, Wenjin; Xu, Fangjie; Liu, Limin; Wang, Biwei; Zhang, Xianfeng; Yang, Dong; Hu, Weida; Dong, Angang

    2016-07-01

    All-inorganic cesium lead halide perovskite (CsPbX3, X = Cl, Br, and I) nanocrystals (NCs) are emerging as an important class of semiconductor materials with superior photophysical properties and wide potential applications in optoelectronic devices. So far, only a few studies have been conducted to control the shape and geometry of CsPbX3 NCs. Here we report a general approach to directly synthesize two-dimensional (2D) CsPbX3 perovskite and mixed perovskite nanosheets with uniform and ultrathin thicknesses down to a few monolayers. The key to the high-yield synthesis of perovskite nanosheets is the development of a new Cs-oleate precursor. The as-synthesized CsPbX3 nanosheets exhibit bright photoluminescence with broad wavelength tunability by composition modulation. The excellent optoelectronic properties of CsPbX3 nanosheets combined with their unique 2D geometry and large lateral dimensions make them ideal building blocks for building functional devices. To demonstrate their potential applications in optoelectronics, photodetectors based on CsPbBr3 nanosheets are fabricated, which exhibit high on/off ratios with a fast response time.All-inorganic cesium lead halide perovskite (CsPbX3, X = Cl, Br, and I) nanocrystals (NCs) are emerging as an important class of semiconductor materials with superior photophysical properties and wide potential applications in optoelectronic devices. So far, only a few studies have been conducted to control the shape and geometry of CsPbX3 NCs. Here we report a general approach to directly synthesize two-dimensional (2D) CsPbX3 perovskite and mixed perovskite nanosheets with uniform and ultrathin thicknesses down to a few monolayers. The key to the high-yield synthesis of perovskite nanosheets is the development of a new Cs-oleate precursor. The as-synthesized CsPbX3 nanosheets exhibit bright photoluminescence with broad wavelength tunability by composition modulation. The excellent optoelectronic properties of CsPbX3 nanosheets

  3. Filtrates and Residues. Recycling Lead(II) Halides from Solubility Experiments.

    ERIC Educational Resources Information Center

    Scaife, Charles W. J.; Hall, Chadlee D.

    1990-01-01

    Presented is an experiment in which students recover almost 90 percent of the original lead chloride thus saving on costs of chemicals and disposal. Included are experimental procedures and a discussion of typical results. (CW)

  4. Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut

    PubMed Central

    2015-01-01

    Metal halides perovskites, such as hybrid organic–inorganic CH3NH3PbI3, are newcomer optoelectronic materials that have attracted enormous attention as solution-deposited absorbing layers in solar cells with power conversion efficiencies reaching 20%. Herein we demonstrate a new avenue for halide perovskites by designing highly luminescent perovskite-based colloidal quantum dot materials. We have synthesized monodisperse colloidal nanocubes (4–15 nm edge lengths) of fully inorganic cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I or mixed halide systems Cl/Br and Br/I) using inexpensive commercial precursors. Through compositional modulations and quantum size-effects, the bandgap energies and emission spectra are readily tunable over the entire visible spectral region of 410–700 nm. The photoluminescence of CsPbX3 nanocrystals is characterized by narrow emission line-widths of 12–42 nm, wide color gamut covering up to 140% of the NTSC color standard, high quantum yields of up to 90%, and radiative lifetimes in the range of 1–29 ns. The compelling combination of enhanced optical properties and chemical robustness makes CsPbX3 nanocrystals appealing for optoelectronic applications, particularly for blue and green spectral regions (410–530 nm), where typical metal chalcogenide-based quantum dots suffer from photodegradation. PMID:25633588

  5. Generalized colloidal synthesis of high-quality, two-dimensional cesium lead halide perovskite nanosheets and their applications in photodetectors.

    PubMed

    Lv, Longfei; Xu, Yibing; Fang, Hehai; Luo, Wenjin; Xu, Fangjie; Liu, Limin; Wang, Biwei; Zhang, Xianfeng; Yang, Dong; Hu, Weida; Dong, Angang

    2016-07-14

    All-inorganic cesium lead halide perovskite (CsPbX3, X = Cl, Br, and I) nanocrystals (NCs) are emerging as an important class of semiconductor materials with superior photophysical properties and wide potential applications in optoelectronic devices. So far, only a few studies have been conducted to control the shape and geometry of CsPbX3 NCs. Here we report a general approach to directly synthesize two-dimensional (2D) CsPbX3 perovskite and mixed perovskite nanosheets with uniform and ultrathin thicknesses down to a few monolayers. The key to the high-yield synthesis of perovskite nanosheets is the development of a new Cs-oleate precursor. The as-synthesized CsPbX3 nanosheets exhibit bright photoluminescence with broad wavelength tunability by composition modulation. The excellent optoelectronic properties of CsPbX3 nanosheets combined with their unique 2D geometry and large lateral dimensions make them ideal building blocks for building functional devices. To demonstrate their potential applications in optoelectronics, photodetectors based on CsPbBr3 nanosheets are fabricated, which exhibit high on/off ratios with a fast response time. PMID:27378539

  6. Spectral dependence of direct and trap-mediated recombination processes in lead halide perovskites using time resolved microwave conductivity.

    PubMed

    Guse, Joanna A; Soufiani, Arman M; Jiang, Liangcong; Kim, Jincheol; Cheng, Yi-Bing; Schmidt, Timothy W; Ho-Baillie, Anita; McCamey, Dane R

    2016-04-28

    Elucidating the decay mechanisms of photoexcited charge carriers is key to improving the efficiency of solar cells based on organo-lead halide perovskites. Here we investigate the spectral dependence (via above-, inter- and sub-bandgap optical excitations) of direct and trap-mediated decay processes in CH3NH3PbI3 using time resolved microwave conductivity (TRMC). We find that the total end-of-pulse mobility is excitation wavelength dependent - the mobility is maximized (172 cm(2) V(-1) s(-1)) when charge carriers are excited by near bandgap light (780 nm) in the low charge carrier density regime (10(9) photons per cm(2)), and is lower for above- and sub-bandgap excitations. Direct recombination is found to occur on the 100-400 ns timescale across excitation wavelengths near and above the bandgap, whereas indirect recombination processes displayed distinct behaviour following above- and sub-bandgap excitations, suggesting the influence of different trap distributions on recombination dynamics. PMID:27067120

  7. Harnessing Defect-Tolerance at the Nanoscale: Highly Luminescent Lead Halide Perovskite Nanocrystals in Mesoporous Silica Matrixes.

    PubMed

    Dirin, Dmitry N; Protesescu, Loredana; Trummer, David; Kochetygov, Ilia V; Yakunin, Sergii; Krumeich, Frank; Stadie, Nicholas P; Kovalenko, Maksym V

    2016-09-14

    Colloidal lead halide perovskite nanocrystals (NCs) have recently emerged as a novel class of bright emitters with pure colors spanning the entire visible spectral range. Contrary to conventional quantum dots, such as CdSe and InP NCs, perovskite NCs feature unusual, defect-tolerant photophysics. Specifically, surface dangling bonds and intrinsic point defects such as vacancies do not form midgap states, known to trap carriers and thereby quench photoluminescence (PL). Accordingly, perovskite NCs need not be electronically surface-passivated (with, for instance, ligands and wider-gap materials) and do not noticeably suffer from photo-oxidation. Novel opportunities for their preparation therefore can be envisaged. Herein, we show that the infiltration of perovskite precursor solutions into the pores of mesoporous silica, followed by drying, leads to the template-assisted formation of perovskite NCs. The most striking outcome of this simple methodology is very bright PL with quantum efficiencies exceeding 50%. This facile strategy can be applied to a large variety of perovskite compounds, hybrid and fully inorganic, with the general formula APbX3, where A is cesium (Cs), methylammonium (MA), or formamidinium (FA), and X is Cl, Br, I or a mixture thereof. The luminescent properties of the resulting templated NCs can be tuned by both quantum size effects as well as composition. Also exhibiting intrinsic haze due to scattering within the composite, such materials may find applications as replacements for conventional phosphors in liquid-crystal television display technologies and in related luminescence down-conversion-based devices. PMID:27550860

  8. The effect of moisture on the structures and properties of lead halide perovskites: a first-principles theoretical investigation.

    PubMed

    Zhang, Lei; Ju, Ming-Gang; Liang, WanZhen

    2016-08-17

    With efficiencies exceeding 20% and low production costs, lead halide perovskite solar cells (PSCs) have become potential candidates for future commercial applications. However, there are serious concerns about their long-term stability and environmental friendliness, heavily related to their commercial viability. Herein, we present a theoretical investigation based on the ab initio molecular dynamics (AIMD) simulations and the first-principles density functional theory (DFT) calculations to investigate the effects of sunlight and moisture on the structures and properties of MAPbI3 perovskites. AIMD simulations have been performed to simulate the impact of a few water molecules on the structures of MAPbI3 surfaces terminated in three different ways. The evolution of geometric and electronic structures as well as the absorption spectra has been shown. It is found that the PbI2-terminated surface is the most stable while both the MAI-terminated and PbI2-defective surfaces undergo structural reconstruction, leading to the formation of hydrated compounds in a humid environment. The moisture-induced weakening of photoabsorption is closely related to the formation of hydrated species, and the hydrated crystals MAPbI3·H2O and MA4PbI6·2H2O scarcely absorb the visible light. The electronic excitation in the bare and water-absorbed MAPbI3 nanoparticles tends to weaken Pb-I bonds, especially those around water molecules, and the maximal decrease of photoexcitation-induced bond order can reach up to 20% in the excited state in which the water molecules are involved in the electronic excitation, indicating the accelerated decomposition of perovskites in the presence of sunlight and moisture. This work is valuable for understanding the mechanism of chemical or photochemical instability of MAPbI3 perovskites in the presence of moisture. PMID:27499005

  9. Lead-free solid-state organic-inorganic halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Hao, Feng; Stoumpos, Constantinos C.; Cao, Duyen Hanh; Chang, Robert P. H.; Kanatzidis, Mercouri G.

    2014-06-01

    Lead-free solution-processed solid-state photovoltaic devices based on methylammonium tin iodide (CH3NH3SnI3) perovskite semiconductor as the light harvester are reported. Featuring an optical bandgap of 1.3 eV, the CH3NH3SnI3 perovskite material can be incorporated into devices with the organic hole-transport layer spiro-OMeTAD and show an absorption onset at 950 nm, which is significantly redshifted compared with the benchmark CH3NH3PbI3 counterpart (1.55 eV). Bandgap engineering was implemented by chemical substitution in the form of CH3NH3SnI3-xBrx solid solutions, which can be controllably tuned to cover much of the visible spectrum, thus enabling the realization of lead-free solar cells with an initial power conversion efficiency of 5.73% under simulated full sunlight. Further efficiency enhancements are expected following optimization and a better fundamental understanding of the internal electron dynamics and corresponding interfacial engineering. The reported CH3NH3SnI3-xBrx perovskite solar cells represent a step towards the realization of low-cost, environmentally friendly solid-state solar cells.

  10. Optical characterizations of the surface states in hybrid lead-halide perovskites.

    PubMed

    Kong, Weiguang; Ding, Tao; Bi, Gang; Wu, Huizhen

    2016-05-14

    Methylammonium lead-iodide (CH3NH3PbI3, hereafter referred to as MAPbI3) perovskite has emerged as a dazzling nova in the solar cell realm. To date, the surface physics of these materials is still puzzling, but in this work, we demonstrate that the optical dynamics in MAPbI3 is primarily determined by the surface states. Pb dangling bonds on the surface of MAPbI3 introduce shallow electronic states. The carrier localization effect for these electronic states is rather weak as the lifetimes of the carriers on the iodine-poor surface are comparative to those in the interior region of MAPbI3. In contrast, rich-iodine on the surface of MAPbI3 induces deep trap centers for the carriers, which are detrimental to long carrier diffusion lengths. It is further proved that the surface passivation, which surprisingly prolongs the carrier diffusion lengths, mainly works on the rich-iodine on the surface rather than the Pb dangling bonds. This better understanding of the surface physics could provide essential information for improving the performance of photoelectronic devices based on MAPbI3 perovskites. PMID:27093894

  11. Detection of X-ray photons by solution-processed lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Yakunin, Sergii; Sytnyk, Mykhailo; Kriegner, Dominik; Shrestha, Shreetu; Richter, Moses; Matt, Gebhard J.; Azimi, Hamed; Brabec, Christoph J.; Stangl, Julian; Kovalenko, Maksym V.; Heiss, Wolfgang

    2015-07-01

    The evolution of real-time medical diagnostic tools such as angiography and computer tomography from radiography based on photographic plates was enabled by the development of integrated solid-state X-ray photon detectors made from conventional solid-state semiconductors. Recently, for optoelectronic devices operating in the visible and near-infrared spectral regions, solution-processed organic and inorganic semiconductors have also attracted a great deal of attention. Here, we demonstrate a possibility to use such inexpensive semiconductors for the sensitive detection of X-ray photons by direct photon-to-current conversion. In particular, methylammonium lead iodide perovskite (CH3NH3PbI3) offers a compelling combination of fast photoresponse and a high absorption cross-section for X-rays, owing to the heavy Pb and I atoms. Solution-processed photodiodes as well as photoconductors are presented, exhibiting high values of X-ray sensitivity (up to 25 μC mGyair-1 cm-3) and responsivity (1.9 × 104 carriers/photon), which are commensurate with those obtained by the current solid-state technology.

  12. Exciton Binding energies and effective masses in Organo-lead Tri-Halide Perovskites

    NASA Astrophysics Data System (ADS)

    Portugall, Oliver; Miyata, Atsuhiko; Mitioglu, Anatol; Plochocka, Paulina; Wang, Jacob Tse-Wei; Stranks, Samuel; Snaith, Henry; Nicholas, Robin; Lncmi Toulouse Team; Oxford University Team

    2015-03-01

    Solid-state perovskite-based solar cells have made a dramatic impact on emerging PV research with efficiencies of over 17% already achieved. However, to date the basic electronic properties of the perovskites such as the electron and hole effective masses and the exciton binding energy are not well known. We have measured both for methyl ammonium lead tri-iodide using magneto absorption in very high magnetic fields up to 150T showing that the exciton binding energy at low temperatures is only 16 meV, a value three times smaller than previously thought and sufficiently small to completely transform the way in which the devices must operate. Landau level spectroscopy shows that the reduced effective mass of 0.104 me is also smaller than previously thought. In addition by using a fast pulse 150T magnet we measure the band structure change due to the structural phase transition that occurs in this system at around 160K. We also observe Landau levels in the high temperature phase as used for device production, which has a very similar effective mass and the analysis suggests an exciton binding energy which is even smaller than in the low temperature phase.

  13. Broad Wavelength Tunable Robust Lasing from Single-Crystal Nanowires of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I).

    PubMed

    Fu, Yongping; Zhu, Haiming; Stoumpos, Constantinos C; Ding, Qi; Wang, Jue; Kanatzidis, Mercouri G; Zhu, Xiaoyang; Jin, Song

    2016-08-23

    Lead halide perovskite nanowires (NWs) are emerging as a class of inexpensive semiconductors with broad bandgap tunability for optoelectronics, such as tunable NW lasers. Despite exciting progress, the current organic-inorganic hybrid perovskite NW lasers suffer from limited tunable wavelength range and poor material stability. Herein, we report facile solution growth of single-crystal NWs of inorganic perovskite CsPbX3 (X = Br, Cl) and their alloys [CsPb(Br,Cl)3] and a low-temperature vapor-phase halide exchange method to convert CsPbBr3 NWs into perovskite phase CsPb(Br,I)3 alloys and metastable CsPbI3 with well-preserved perovskite crystal lattice and NW morphology. These single crystalline NWs with smooth end facets and subwavelength dimensions are ideal Fabry-Perot cavities for NW lasers. Optically pumped tunable lasing across the entire visible spectrum (420-710 nm) is demonstrated at room temperature from these NWs with low lasing thresholds and high-quality factors. Such highly efficient lasing similar to what can be achieved with organic-inorganic hybrid perovskites indicates that organic cation is not essential for light emission application from these lead halide perovskite materials. Furthermore, the CsPbBr3 NW lasers show stable lasing emission with no measurable degradation after at least 8 h or 7.2 × 10(9) laser shots under continuous illumination, which are substantially more robust than their organic-inorganic counterparts. The Cs-based perovskites offer a stable material platform for tunable NW lasers and other nanoscale optoelectronic devices. PMID:27437566

  14. Study on influence of growth conditions on position and shape of crystal/melt interface of alkali lead halide crystals at Bridgman growth

    NASA Astrophysics Data System (ADS)

    Král, Robert

    2012-12-01

    Suitable conditions for growth of high quality single crystals of ternary alkali lead halides prepared by a Bridgman method were explored using direct observation of a crystal/melt interface when pulling an ampoule out of a furnace, deliberated striations' induction and measurement of a temperature field in the filled ampoule in the vertical Bridgman arrangement, as model compounds lead chloride and ternary rubidium lead bromide were used. By direct observation only position of the crystal/melt interface was markedly determined, while by induced striations both the position and the shape of the interface were visualized but their contrast had to be intensified by adding admixtures. Performed temperature measurements in the filled ampoule brought both a view of temperature field in the 3D radial symmetry and basic data for comparison of a real temperature field with those obtained by projected modeling.

  15. Fast Anion-Exchange in Highly Luminescent Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I)

    PubMed Central

    2015-01-01

    Postsynthetic chemical transformations of colloidal nanocrystals, such as ion-exchange reactions, provide an avenue to compositional fine-tuning or to otherwise inaccessible materials and morphologies. While cation-exchange is facile and commonplace, anion-exchange reactions have not received substantial deployment. Here we report fast, low-temperature, deliberately partial, or complete anion-exchange in highly luminescent semiconductor nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, I). By adjusting the halide ratios in the colloidal nanocrystal solution, the bright photoluminescence can be tuned over the entire visible spectral region (410–700 nm) while maintaining high quantum yields of 20–80% and narrow emission line widths of 10–40 nm (from blue to red). Furthermore, fast internanocrystal anion-exchange is demonstrated, leading to uniform CsPb(Cl/Br)3 or CsPb(Br/I)3 compositions simply by mixing CsPbCl3, CsPbBr3, and CsPbI3 nanocrystals in appropriate ratios. PMID:26207728

  16. Fast Anion-Exchange in Highly Luminescent Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I).

    PubMed

    Nedelcu, Georgian; Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I; Grotevent, Matthias J; Kovalenko, Maksym V

    2015-08-12

    Postsynthetic chemical transformations of colloidal nanocrystals, such as ion-exchange reactions, provide an avenue to compositional fine-tuning or to otherwise inaccessible materials and morphologies. While cation-exchange is facile and commonplace, anion-exchange reactions have not received substantial deployment. Here we report fast, low-temperature, deliberately partial, or complete anion-exchange in highly luminescent semiconductor nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, I). By adjusting the halide ratios in the colloidal nanocrystal solution, the bright photoluminescence can be tuned over the entire visible spectral region (410-700 nm) while maintaining high quantum yields of 20-80% and narrow emission line widths of 10-40 nm (from blue to red). Furthermore, fast internanocrystal anion-exchange is demonstrated, leading to uniform CsPb(Cl/Br)3 or CsPb(Br/I)3 compositions simply by mixing CsPbCl3, CsPbBr3, and CsPbI3 nanocrystals in appropriate ratios. PMID:26207728

  17. Enhancing the Brightness of Cesium Lead Halide Perovskite Nanocrystal Based Green Light-Emitting Devices through the Interface Engineering with Perfluorinated Ionomer.

    PubMed

    Zhang, Xiaoyu; Lin, Hong; Huang, He; Reckmeier, Claas; Zhang, Yu; Choy, Wallace C H; Rogach, Andrey L

    2016-02-10

    High photoluminescence quantum yield, easily tuned emission colors, and high color purity of perovskite nanocrystals make this class of material attractive for light source or display applications. Here, green light-emitting devices (LEDs) were fabricated using inorganic cesium lead halide perovskite nanocrystals as emitters. By introducing a thin film of perfluorinated ionomer (PFI) sandwiched between the hole transporting layer and perovskite emissive layer, the device hole injection efficiency has been significantly enhanced. At the same time, PFI layer suppressed charging of the perovskite nanocrystal emitters thus preserving their superior emissive properties, which led to the three-fold increase in peak brightness reaching 1377 cd m(-2). The full width at half-maximum of the symmetric emission peak with color coordinates of (0.09, 0.76) was 18 nm, the narrowest value among perovskite based green LEDs. PMID:26745020

  18. Crystal growth and near infrared optical properties of Pr 3+ doped lead halide materials for resonantly pumped eye safe laser applications

    NASA Astrophysics Data System (ADS)

    Jones, Ivy Krystal

    In this dissertation the material development and optical spectroscopy of Pr3+ activated low phonon energy halide crystals is presented for possible applications in resonantly pumped eye-safe solid-state laser gain media. In the last twenty years, the developments in fiber and diode lasers have enabled highly efficient resonant pumping of Pr3+ doped crystals for possible lasing in the 1.6--1.7 microm region. In this work, the results of the purification, crystal growth, and near-infrared (NIR) spectroscopic characterization of Pr3+ doped lead (II) chloride, PbCl2 and lead (II) bromide, PbBr2 are presented. The investigated PbCl2 and PbBr2 crystals are non-hygroscopic with maximum phonon energies between ~180--200 cm-1, which enable efficient emission in the NIR spectral region (~ 1.6 microm) from the 3F3/3F4 → 3H4 transition of Pr3+ ions. The commercial available starting materials were purchased as ultra dry, high purity (~ 99.999 %) beads and purified through a combination of zone-refinement and halogenation. The crystal growth of Pr3+ doped PbCl 2 and PbBr2 was performed via vertical Bridgman technique using a two-zone furnace. The resulting Pr3+ doped PbCl 2 and PbBr2 crystals exhibited characteristic IR absorption bands in the 1.5--1.7 microm region (3H4 → 3F3/3F4), which allow for resonant pumping using commercial diode lasers. A broad IR emission band centered at ~1.6 microm was observed under ~1445 nm diode laser excitation from both Pr3+ doped halides. This dissertation presents comparative spectroscopic results for Pr 3+:PbCl2 and Pr3+:PbBr2 including NIR absorption and emission studies, lifetime measurements, modelling of radiative and non-radiative decay rates, determination of transition cross-section, and the net effective gain cross sections.

  19. Optical properties and structural phase transitions of lead-halide based inorganic-organic 3D and 2D perovskite semiconductors under high pressure

    NASA Astrophysics Data System (ADS)

    Matsuishi, K.; Ishihara, T.; Onari, S.; Chang, Y. H.; Park, C. H.

    2004-11-01

    Optical absorption, photoluminescence and Raman scattering of lead-halide based inorganic-organic perovskite semiconductors were measured under quasi-hydrostatic pressure at room temperature. For the 3D perovskite semiconductor, (CH3NH3)PbBr3, the free exciton photoluminescence band exhibits red-shifts with pressure, and jumps to a higher energy by 0.07 eV at 0.8 GPa, which is associated with a phase transition from a cubic to an orthorhombic structure confirmed by Raman scattering. Above the phase transition pressure, the exciton band shows blue-shifts with further increasing pressure, and eventually disappears above 4.7 GPa. The results are compared with those for the 2D perovskite semiconductor, (C4H9NH3)2PbI4. First principles pseudopotential calculations were performed to investigate changes in octahedral distortion and electronic band structures with pressure. The calculations have explained the origins of the intriguing changes in the electronic states with pressure in view of bonding characters between atomic orbitals in octahedra.

  20. Homogeneous Emission Line Broadening in the Organo Lead Halide Perovskite CH3NH3PbI3-xClx.

    PubMed

    Wehrenfennig, Christian; Liu, Mingzhen; Snaith, Henry J; Johnston, Michael B; Herz, Laura M

    2014-04-17

    The organic-inorganic hybrid perovskites methylammonium lead iodide (CH3NH3PbI3) and the partially chlorine-substituted mixed halide CH3NH3PbI3-xClx emit strong and broad photoluminescence (PL) around their band gap energy of ∼1.6 eV. However, the nature of the radiative decay channels behind the observed emission and, in particular, the spectral broadening mechanisms are still unclear. Here we investigate these processes for high-quality vapor-deposited films of CH3NH3PbI3-xClx using time- and excitation-energy dependent photoluminescence spectroscopy. We show that the PL spectrum is homogenously broadened with a line width of 103 meV most likely as a consequence of phonon coupling effects. Further analysis reveals that defects or trap states play a minor role in radiative decay channels. In terms of possible lasing applications, the emission spectrum of the perovskite is sufficiently broad to have potential for amplification of light pulses below 100 fs pulse duration. PMID:26269971

  1. Dipole-Promoted and Size-Dependent Cooperativity between Pyridyl-Containing Triazolophanes and Halides Leads to Persistent Sandwich Complexes with Iodide

    SciTech Connect

    Li, Yongjun; Pink, M.; Karty, J.A.; Flood, A.H.

    2009-01-06

    Triazolophanes that incorporate pyridyl subunits in place of phenylenes show a heightened propensity to form 2:1 sandwich complexes with halides. Persistent iodide-based sandwiches are observed. Binding constants confirm that the inward-facing electron pairs on the pyridyls destabilize the 1:1 complexes with halides. The {sup 1}H NMR spectra verify that the sandwich complexes have two {pi}-stacked triazolophanes rotated to allow registration between opposite dipoles on the pyridyls (directed inward) and triazoles (directed outward). These dipolar interactions cooperate to lower the pyridyl-based repulsions, therefore, increasing K{sub 2}. Modest cooperative effects are observed for the snugly fitting F{sup -}, Cl{sup -}, and Br{sup -} halides while the too-large I{sup -} shows highly positive cooperativity.

  2. The Silver Halides

    ERIC Educational Resources Information Center

    Sahyun, M. R. V.

    1977-01-01

    Illustrates the type of fractional bonding for solid silver halides. Treats the silver halides as electron excess compounds, and develops a model of a localized bonding unit that may be iterated in three dimensions to describe the bulk phase. (MLH)

  3. Effect of metal cation replacement on the electronic structure of metalorganic halide perovskites: Replacement of lead with alkaline-earth metals

    NASA Astrophysics Data System (ADS)

    Pazoki, Meysam; Jacobsson, T. Jesper; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

    2016-04-01

    Organic and inorganic lead halogen perovskites, and in particular, C H3N H3Pb I3 , have during the last years emerged as a class of highly efficient solar cell materials. Herein we introduce metalorganic halogen perovskite materials for energy-relevant applications based on alkaline-earth metals. Based on the classical notion of Goldschmidt's rules and quantum mechanical considerations, the three alkaline-earth metals, Ca, Sr, and Ba, are shown to be able to exchange lead in the perovskite structure. The three alkaline-earth perovskites, C H3N H3Ca I3,C H3N H3Sr I3 , and C H3N H3Ba I3 , as well as the reference compound, C H3N H3Pb I3 , are in this paper investigated with density functional theory (DFT) calculations, which predict these compounds to exist as stable perovskite materials, and their electronic properties are explored. A detailed analysis of the projected molecular orbital density of states and electronic band structure from DFT calculations were used for interpretation of the band-gap variations in these materials and for estimation of the effective masses of the electrons and holes. Neglecting spin-orbit effects, the band gap of MACa I3,MASr I3 , and MABa I3 were estimated to be 2.95, 3.6, and 3.3 eV, respectively, showing the relative change expected for metal cation exchange. The shifts in the conduction band (CB) edges for the alkaline-earth perovskites were quantified using scalar relativistic DFT calculations and tight-binding analysis, and were compared to the situation in the more extensively studied lead halide perovskite, C H3N H3Pb I3 , where the change in the work function of the metal is the single most important factor in tuning the CB edge and band gap. The results show that alkaline-earth-based organometallic perovskites will not work as an efficient light absorber in photovoltaic applications but instead could be applicable as charge-selective contact materials. The rather high CB edge and the wide band gap together with the large

  4. Influence of PbCl2 content in PbI2 solution of DMF on the absorption, crystal phase, morphology of lead halide thin films and photovoltaic performance in planar perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Wang, Mao; Shi, Chengwu; Zhang, Jincheng; Wu, Ni; Ying, Chao

    2015-11-01

    In this paper, the influence of PbCl2 content in PbI2 solution of DMF on the absorption, crystal phase and morphology of lead halide thin films was systematically investigated and the photovoltaic performance of the corresponding planar perovskite solar cells was evaluated. The result revealed that the various thickness lead halide thin film with the small sheet-like, porous morphology and low crystallinity can be produced by adding PbCl2 powder into PbI2 solution of DMF as a precursor solution. The planar perovskite solar cell based on the 300-nm-thick CH3NH3PbI3-xClx thin film by the precursor solution with the mixture of 0.80 M PbI2 and 0.20 M PbCl2 exhibited the optimum photoelectric conversion efficiency of 10.12% along with an open-circuit voltage of 0.93 V, a short-circuit photocurrent density of 15.70 mA cm-2 and a fill factor of 0.69.

  5. Hydrogen Halides on Jupiter and Saturn

    NASA Astrophysics Data System (ADS)

    Showman, Adam P.

    2001-07-01

    The quest to detect gaseous HCl, HBr, and HF in the atmospheres of Jupiter and Saturn has led to a tentative detection of 1 ppb HCl near Saturn's cloud deck. The detection is puzzling because, while these hydrogen halides may be present several scale heights below the clouds, they are expected to react with ammonia to form solid ammonium halide salts in the upper troposphere. I show that the loss timescale for condensation of gaseous hydrogen halides onto particles is ˜10 3-10 5 s for realistic cloud densities and particle sizes, which is much less than the ˜10 8 s residence time of upper tropospheric air. The hydrogen halides can only survive transport up to the cloud layer if less than 1 in 10 6 of their collisions with particle surfaces leads to condensation, which is unlikely. Even in the absence of foreign particles, homogeneous nucleation would probably prevent supersaturations in excess of a few hundred, which is ˜10 20-10 40 times too low to explain the observation. These calculations therefore suggest that hydrogen halides cannot exist at part-per-billion levels in the upper troposphere. The interplanetary source of halogens is also too low to produce detectable quantities of hydrogen halides except perhaps at pressures less than 1 mbar. A possible detection of chlorine by the Galileo probe at pressures exceeding 9 bars on Jupiter may be consistent with the equilibrium abundance of gaseous HCl or NH 4Cl.

  6. High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties.

    PubMed

    Jaffe, Adam; Lin, Yu; Beavers, Christine M; Voss, Johannes; Mao, Wendy L; Karunadasa, Hemamala I

    2016-04-27

    We report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX3 (MA = CH3NH3 (+), X = Br(-) or I(-)) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites' precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaque black with compression. Indeed, electronic conductivity measurements of (MA)PbI3 obtained within a diamond-anvil cell show that the material's resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(Br x I1-x )3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain the low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors. PMID:27163050

  7. High-Pressure Single-Crystal Structures of 3D Lead-Halide Hybrid Perovskites and Pressure Effects on their Electronic and Optical Properties

    PubMed Central

    2016-01-01

    We report the first high-pressure single-crystal structures of hybrid perovskites. The crystalline semiconductors (MA)PbX3 (MA = CH3NH3+, X = Br– or I–) afford us the rare opportunity of understanding how compression modulates their structures and thereby their optoelectronic properties. Using atomic coordinates obtained from high-pressure single-crystal X-ray diffraction we track the perovskites’ precise structural evolution upon compression. These structural changes correlate well with pressure-dependent single-crystal photoluminescence (PL) spectra and high-pressure bandgaps derived from density functional theory. We further observe dramatic piezochromism where the solids become lighter in color and then transition to opaque black with compression. Indeed, electronic conductivity measurements of (MA)PbI3 obtained within a diamond-anvil cell show that the material’s resistivity decreases by 3 orders of magnitude between 0 and 51 GPa. The activation energy for conduction at 51 GPa is only 13.2(3) meV, suggesting that the perovskite is approaching a metallic state. Furthermore, the pressure response of mixed-halide perovskites shows new luminescent states that emerge at elevated pressures. We recently reported that the perovskites (MA)Pb(BrxI1–x)3 (0.2 < x < 1) reversibly form light-induced trap states, which pin their PL to a low energy. This may explain the low voltages obtained from solar cells employing these absorbers. Our high-pressure PL data indicate that compression can mitigate this PL redshift and may afford higher steady-state voltages from these absorbers. These studies show that pressure can significantly alter the transport and thermodynamic properties of these technologically important semiconductors. PMID:27163050

  8. Prediction of (207)Pb NMR parameters for the solid ionic lead(II) halides using the relativistic ZORA-DFT formalism: Comparison with the lead-containing molecular systems.

    PubMed

    Dmitrenko, O; Bai, Shi; Dybowski, C

    2008-10-01

    Density functional calculations of (207)Pb NMR shielding in PbX(2) (X=F, Br, Cl and I) anionic fragments suggest that in solid PbX(2), the observed variation of chemical shift with halide is dominated by the paramagnetic contribution to the chemical shielding, with a lesser effect by the spin-orbit contribution. The calculations include relativistic effects at the level of the zero-order regular approximation (ZORA). The present observation contrasts with previous calculations for the molecular system, PbX(4), in which the spin-orbit contribution has been shown to be the major factor in the variation of the NMR chemical shift. PMID:18829270

  9. Band Gaps of the Lead-Free Halide Double Perovskites Cs2BiAgCl6 and Cs2BiAgBr6 from Theory and Experiment.

    PubMed

    Filip, Marina R; Hillman, Samuel; Haghighirad, Amir Abbas; Snaith, Henry J; Giustino, Feliciano

    2016-07-01

    The recent discovery of lead-free halide double perovskites with band gaps in the visible represents an important step forward in the design of environmentally friendly perovskite solar cells. Within this new family of semiconductors, Cs2BiAgCl6 and Cs2BiAgBr6 are stable compounds crystallizing in the elpasolite structure. Following the recent computational discovery and experimental synthesis of these compounds, a detailed investigation of their electronic properties is warranted in order to establish their potential as optoelectronic materials. In this work, we perform many-body perturbation theory calculations and obtain high accuracy band gaps for both compounds. In addition, we report on the synthesis of Cs2BiAgBr6 single crystals, which are stable in ambient conditions. From our complementary theoretical and experimental analysis, we are able to assign the indirect character of the band gaps and obtain both experimental and theoretical band gaps of these novel semiconductors that are in close agreement. PMID:27322413

  10. Impact of the organic halide salt on final perovskite composition for photovoltaic applications

    SciTech Connect

    Moore, David T.; Sai, Hiroaki; Wee Tan, Kwan; Estroff, Lara A.; Wiesner, Ulrich

    2014-08-01

    The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material. Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt's anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films.

  11. Room temperature synthesis of ultra-small, near-unity single-sized lead halide perovskite quantum dots with wide color emission tunability, high color purity and high brightness

    NASA Astrophysics Data System (ADS)

    Peng, Lucheng; Geng, Jing; Ai, Lisha; Zhang, Ying; Xie, Renguo; Yang, Wensheng

    2016-08-01

    Phosphor with extremely narrow emission line widths, high brightness, and wide color emission tunability in visible regions is required for display and lighting applications, yet none has been reported in the literature so far. In the present study, single-sized lead halide perovskite (APbX 3; A = CH3NH3 and Cs; X = Cl, Br, and I) nanocrystalline (NC) phosphors were achieved for the first time in a one-pot reaction at room temperature (25 °C). The size-dependent samples, which included four families of CsPbBr3 NCs and exhibited sharp excitonic absorption peaks and pure band gap emission, were directly obtained by simply varying the concentration of ligands. The continuity of the optical spectrum can be successively tuned over the entire UV–visible spectral region (360–610 nm) by preparing CsPbCl3, CsPbI3, and CsPb(Y/Br)3 (Y = Cl and I) NCs with the use of CsPbBr3 NCs as templates by anion exchange while maintaining the size of NCs and high quantum yields of up to 80%. Notably, an emission line width of 10–24 nm, which is completely consistent with that of their single particles, indicates the formation of single-sized NCs. The versatility of the synthetic strategy was validated by extending it to the synthesis of single-sized CH3NH3PbX 3 NCs by simply replacing the cesium precursor by the CH3NH3 X precursor.

  12. Room temperature synthesis of ultra-small, near-unity single-sized lead halide perovskite quantum dots with wide color emission tunability, high color purity and high brightness.

    PubMed

    Peng, Lucheng; Geng, Jing; Ai, Lisha; Zhang, Ying; Xie, Renguo; Yang, Wensheng

    2016-08-19

    Phosphor with extremely narrow emission line widths, high brightness, and wide color emission tunability in visible regions is required for display and lighting applications, yet none has been reported in the literature so far. In the present study, single-sized lead halide perovskite (APbX 3; A = CH3NH3 and Cs; X = Cl, Br, and I) nanocrystalline (NC) phosphors were achieved for the first time in a one-pot reaction at room temperature (25 °C). The size-dependent samples, which included four families of CsPbBr3 NCs and exhibited sharp excitonic absorption peaks and pure band gap emission, were directly obtained by simply varying the concentration of ligands. The continuity of the optical spectrum can be successively tuned over the entire UV-visible spectral region (360-610 nm) by preparing CsPbCl3, CsPbI3, and CsPb(Y/Br)3 (Y = Cl and I) NCs with the use of CsPbBr3 NCs as templates by anion exchange while maintaining the size of NCs and high quantum yields of up to 80%. Notably, an emission line width of 10-24 nm, which is completely consistent with that of their single particles, indicates the formation of single-sized NCs. The versatility of the synthetic strategy was validated by extending it to the synthesis of single-sized CH3NH3PbX 3 NCs by simply replacing the cesium precursor by the CH3NH3 X precursor. PMID:27383631

  13. Lead

    MedlinePlus

    ... Lead Share Facebook Twitter Google+ Pinterest Contact Us Lead Poisoning is Preventable If your home was built before ... of the RRP rule. Read more . Learn about Lead Poisoning Prevention Week . Report Uncertified Contractors and Environmental Violations ...

  14. PREPARATION OF HALIDES OF PLUTONIUM

    DOEpatents

    Garner, C.S.; Johns, I.B.

    1958-09-01

    A dry chemical method is described for preparing plutonium halides, which consists in contacting plutonyl nitrate with dry gaseous HCl or HF at an elevated temperature. The addition to the reaction gas of a small quantity of an oxidizing gas or a reducing gas will cause formation of the tetra- or tri-halide of plutonium as desired.

  15. Methods and Mechanisms for Cross-Electrophile Coupling of Csp(2) Halides with Alkyl Electrophiles.

    PubMed

    Weix, Daniel J

    2015-06-16

    Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C-H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of generally cross-selective reactions of aryl halides and acyl halides with alkyl halides, the mechanistic studies that illuminated the underlying principles of these reactions, and the use of these fundamental principles in the rational design of new cross-electrophile coupling reactions. Although the coupling of two different electrophiles under reducing conditions often leads primarily to symmetric dimers, the subtle differences in reactivity of aryl halides and alkyl halides with nickel catalysts allowed for generally cross-selective coupling reactions. These conditions could also be extended to the coupling of acyl halides with alkyl halides. These reactions are exceptionally functional group tolerant and can be assembled on the benchtop. A combination of stoichiometric and catalytic studies on the mechanism of these reactions revealed an unusual radical-chain mechanism and suggests that selectivity arises from (1) the preference of nickel(0) for oxidative addition to aryl halides and acyl halides over alkyl halides and (2) the greater propensity of alkyl halides to form free radicals. Bipyridine-ligated arylnickel intermediates react with alkyl radicals to efficiently form, after reductive elimination, new C-C bonds. Finally, the resulting nickel(I) species is proposed to regenerate an alkyl radical to carry the chain. Examples of new reactions designed using these principles include carbonylative coupling of aryl halides with alkyl halides to form ketones, arylation of epoxides to form β-aryl alcohols, and coupling of benzyl sulfonate esters with aryl halides to form

  16. Methods and Mechanisms for Cross-Electrophile Coupling of Csp2 Halides with Alkyl Electrophiles

    PubMed Central

    2016-01-01

    Conspectus Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C–H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of generally cross-selective reactions of aryl halides and acyl halides with alkyl halides, the mechanistic studies that illuminated the underlying principles of these reactions, and the use of these fundamental principles in the rational design of new cross-electrophile coupling reactions. Although the coupling of two different electrophiles under reducing conditions often leads primarily to symmetric dimers, the subtle differences in reactivity of aryl halides and alkyl halides with nickel catalysts allowed for generally cross-selective coupling reactions. These conditions could also be extended to the coupling of acyl halides with alkyl halides. These reactions are exceptionally functional group tolerant and can be assembled on the benchtop. A combination of stoichiometric and catalytic studies on the mechanism of these reactions revealed an unusual radical-chain mechanism and suggests that selectivity arises from (1) the preference of nickel(0) for oxidative addition to aryl halides and acyl halides over alkyl halides and (2) the greater propensity of alkyl halides to form free radicals. Bipyridine-ligated arylnickel intermediates react with alkyl radicals to efficiently form, after reductive elimination, new C–C bonds. Finally, the resulting nickel(I) species is proposed to regenerate an alkyl radical to carry the chain. Examples of new reactions designed using these principles include carbonylative coupling of aryl halides with alkyl halides to form ketones, arylation of epoxides to form β-aryl alcohols, and coupling of benzyl sulfonate esters with aryl

  17. Adsorption on Alkali Halides.

    NASA Astrophysics Data System (ADS)

    Urzua Duran, Gilberto Antonio

    1995-01-01

    Using a variety of interionic potentials, I have computed the configurations of adsorbed alkali halides monomers on the (001) surface of selected alkali halides crystals. In the majority of cases studied it is found that the monomer adsorbs perpendicular to the surface with the cation sitting nearly on top of the surface anion. In about ten percent of the cases though the monomer adsorbs tilted from the vertical. In these cases the ion that is closer to the surface can be the cation or the anion. The effect of polarization forces is found to be important. In order to discuss the effects of surface retaxation with adsorbates, I have evaluated the surface relaxation of the alkali halide crystals, using a shell model for the interionic forces. It is found that surface relaxation and rumpling are generally small, especially when the van der Waals forces are included. A theory of the effect of substrate vibrations on the binding of an adsorbed atom is developed. At T = 0 the binding energy is D_0-E, where D_0 is the surface well depth (classical binding energy) and E is the quantum correction. For several simple models, it is found that E is surprisingly model-independent. We compare D _0-E with the binding energies to a rigid substrate, D_0-E_{rs}, and to a vibrationally averaged substrate, D _0-E_{va}. We prove that E_{va}>=q E>=q E_ {rs} and that similar relations hold at finite temperature for the free energy of binding. In most cases E_{rs} is better than E_{va} as an approximation to E.

  18. Halide laser glasses

    SciTech Connect

    Weber, M.J.

    1982-01-14

    Energy storage and energy extraction are of prime importance for efficient laser action and are affected by the line strengths and linewidths of optical transitions, excited-state lifetimes, nonradiative decay processes, spectroscopic inhomogeneities, nonlinear refractive index, and damage threshold. These properties are all host dependent. To illustrate this, the spectroscopic properties of Nd/sup 3 +/ have been measured in numerous oxide, oxyhalide, and halide glasses. A table summarizes the reported ranges of stimulated emission cross sections, peak wavelengths, linewidths, and radiative lifetimes associated with the /sup 4/F/sub 3/2/ ..-->.. /sup 4/I/sub 11/2/ lasing transition.

  19. Lead

    MedlinePlus

    ... obvious symptoms, it frequently goes unrecognized. CDC’s Childhood Lead Poisoning Prevention Program is committed to the Healthy People ... Lead Levels Information for Parents Tips for preventing lead poisoning About Us Overview of CDC’s Childhood Lead Poisoning ...

  20. Heat capacity of molten halides.

    PubMed

    Redkin, Alexander A; Zaikov, Yurii P; Korzun, Iraida V; Reznitskikh, Olga G; Yaroslavtseva, Tatiana V; Kumkov, Sergey I

    2015-01-15

    The heat capacities of molten salts are very important for their practical use. Experimental investigation of this property is challenging because of the high temperatures involved and the corrosive nature of these materials. It is preferable to combine experimental investigations with empirical relationships, which allows for the evaluation of the heat capacity of molten salt mixtures. The isobaric molar heat capacities of all molten alkali and alkaline-earth halides were found to be constant for each group of salts. The value depends on the number of atoms in the salt, and the molar heat capacity per atom is constant for all molten halide salts with the exception of the lithium halides. The molar heat capacities of molten halides do not change when the anions are changed. PMID:25530462

  1. METHOD OF PREPARING METAL HALIDES

    DOEpatents

    Hendrickson, A.V.

    1958-11-18

    The conversion of plutonium halides from plutonium peroxide can be done by washing the peroxide with hydrogen peroxide, drying the peroxide, passing a dry gaseous hydrohalide over the surface of the peroxide at a temperature of about lOO icient laborato C until the reaction rate has stabillzed, and then ralsing the reaction temperature to between 400 and 600 icient laborato C until the conversion to plutonium halide is substantially complete.

  2. 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

  3. How specific halide adsorption varies hydrophobic interactions.

    PubMed

    Stock, Philipp; Müller, Melanie; Utzig, Thomas; Valtiner, Markus

    2016-03-01

    Hydrophobic interactions (HI) are driven by the water structure around hydrophobes in aqueous electrolytes. How water structures at hydrophobic interfaces and how this influences the HI was subject to numerous studies. However, the effect of specific ion adsorption on HI and hydrophobic interfaces remains largely unexplored or controversial. Here, the authors utilized atomic force microscopy force spectroscopy at well-defined nanoscopic hydrophobic interfaces to experimentally address how specific ion adsorption of halide ions as well as NH4 (+), Cs(+), and Na(+) cations alters interaction forces across hydrophobic interfaces. Our data demonstrate that iodide adsorption at hydrophobic interfaces profoundly varies the hydrophobic interaction potential. A long-range and strong hydration repulsion at distances D > 3 nm, is followed by an instability which could be explained by a subsequent rapid ejection of adsorbed iodides from approaching hydrophobic interfaces. In addition, the authors find only a weakly pronounced influence of bromide, and as expected no influence of chloride. Also, all tested cations do not have any significant influence on HI. Complementary, x-ray photoelectron spectroscopy and quartz-crystal-microbalance with dissipation monitoring showed a clear adsorption of large halide ions (Br(-)/I(-)) onto hydrophobic self-assembled monolayers (SAMs). Interestingly, iodide can even lead to a full disintegration of SAMs due to specific and strong interactions of iodide with gold. Our data suggest that hydrophobic surfaces are not intrinsically charged negatively by hydroxide adsorption, as it was generally believed. Hydrophobic surfaces rather interact strongly with negatively charged large halide ions, leading to a surface charging and significant variation of interaction forces. PMID:26753786

  4. Actinide halide complexes

    DOEpatents

    Avens, L.R.; Zwick, B.D.; Sattelberger, A.P.; Clark, D.L.; Watkin, J.G.

    1992-11-24

    A compound is described of the formula MX[sub n]L[sub m] wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands. A compound of the formula MX[sub n] wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds are described including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant.

  5. Actinide halide complexes

    DOEpatents

    Avens, Larry R.; Zwick, Bill D.; Sattelberger, Alfred P.; Clark, David L.; Watkin, John G.

    1992-01-01

    A compound of the formula MX.sub.n L.sub.m wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands, a compound of the formula MX.sub.n wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant, are provided.

  6. Halide-Substituted Electronic Properties of Organometal Halide Perovskite Films: Direct and Inverse Photoemission Studies.

    PubMed

    Li, Chi; Wei, Jian; Sato, Mikio; Koike, Harunobu; Xie, Zhong-Zhi; Li, Yan-Qing; Kanai, Kaname; Kera, Satoshi; Ueno, Nobuo; Tang, Jian-Xin

    2016-05-11

    Solution-processed perovskite solar cells are attracting increasing interest due to their potential in next-generation hybrid photovoltaic devices. Despite the morphological control over the perovskite films, quantitative information on electronic structures and interface energetics is of paramount importance to the optimal photovoltaic performance. Here, direct and inverse photoemission spectroscopies are used to determine the electronic structures and chemical compositions of various methylammonium lead halide perovskite films (MAPbX3, X = Cl, Br, and I), revealing the strong influence of halide substitution on the electronic properties of perovskite films. Precise control over halide compositions in MAPbX3 films causes the manipulation of the electronic properties, with a qualitatively blue shift along the I → Br → Cl series and showing the increase in ionization potentials from 5.96 to 7.04 eV and the change of transport band gaps in the range from 1.70 to 3.09 eV. The resulting light absorption of MAPbX3 films can cover the entire visible region from 420 to 800 nm. The results presented here provide a quantitative guide for the analysis of perovskite-based solar cell performance and the selection of optimal carrier-extraction materials for photogenerated electrons and holes. PMID:27101940

  7. Radiochemical synthesis of pure anhydrous metal halides

    NASA Technical Reports Server (NTRS)

    Philipp, W. H.; Marsik, S. J.; May, C. E.

    1973-01-01

    Method uses radiation chemistry as practical tool for inorganic preparations and in particular deposition of metals by irradiation of their aqueous metal salt solutions with high energy electrons. Higher valence metal halide is dissolved in organic liquid and exposed to high energy electrons. This causes metal halide to be reduced to a lower valence metal halide.

  8. Preparation of cerium halide solvate complexes

    DOEpatents

    Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

    2013-08-06

    Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

  9. Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution.

    PubMed

    Doane, Tennyson L; Ryan, Kayla L; Pathade, Laxmikant; Cruz, Kevin J; Zang, Huidong; Cotlet, Mircea; Maye, Mathew M

    2016-06-28

    The ability of cesium lead halide (CsPbX3; X = Cl(-), Br(-), I(-)) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. The exchange of CsPbI3 with Cl(-) or Br(-) causes a significant blue-shift in absorption and photoluminescence, whereas reacting I(-) with CsPbBr3 causes a red-shift of similar magnitudes. With the high local halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. The merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites. PMID:27149396

  10. CO2 electrochemical reduction via adsorbed halide anions

    NASA Astrophysics Data System (ADS)

    Ogura, Kotaro; Salazar-Villalpando, Maria D.

    2011-01-01

    The electrochemical reduction of CO2 was studied utilizing halide ions as electrolytes, specifically, aqueous solutions of KCl, KBr, KI. Electrochemical experiments were carried out in a laboratory-made, divided H-type cell. The working electrode was a copper mesh, while the counter and reference electrodes were a Pt wire and an Ag/AgCl electrode, respectively. The results of our work suggest a reaction mechanism for the electrochemical reduction of CO2 where the presence of Cu-X as the catalytic layer facilitates the electron transfer from the electrode to CO2. Electron-transfer to CO2 may occur via the X- ad(Br-, Cl-, I-)-C bond, which is formed by the electron flow from the specifically adsorbed halide anion to the vacant orbital of CO2. The stronger the adsorption of the halide anion to the electrode, the more strongly CO2 is restrained, resulting in higher CO2 reduction current. Furthermore, it is suggested that specifically adsorbed halide anions could suppress the adsorption of protons; leading to a higher hydrogen overvoltage. These effects may synergistically mitigate the over potential necessary for CO2 reduction, and thus increase the rate of electrochemical CO2 reduction.

  11. Development of Halide and Oxy-Halides for Isotopic Separations

    SciTech Connect

    Leigh R. Martin; Aaron T. Johnson; Jana Pfeiffer; Martha R. Finck

    2014-10-01

    The goal of this project was to synthesize a volatile form of Np for introduction into mass spectrometers at INL. Volatile solids of the 5f elements are typically those of the halides (e.g. UF6), however fluorine is highly corrosive to the sensitive internal components of the mass separator, and the other volatile halides exist as several different stable isotopes in nature. However, iodide is both mono-isotopic and volatile, and as such presents an avenue for creation of a form of Np suitable for introduction into the mass separator. To accomplish this goal, the technical work in the project sought to establish a novel synthetic route for the conversion NpO2+ (dissolved in nitric acid) to NpI3 and NpI4.

  12. Passive particle dosimetry. [silver halide crystal growth

    NASA Technical Reports Server (NTRS)

    Childs, C. B.

    1977-01-01

    Present methods of dosimetry are reviewed with emphasis on the processes using silver chloride crystals for ionizing particle dosimetry. Differences between the ability of various crystals to record ionizing particle paths are directly related to impurities in the range of a few ppm (parts per million). To understand the roles of these impurities in the process, a method for consistent production of high purity silver chloride, and silver bromide was developed which yields silver halides with detectable impurity content less than 1 ppm. This high purity silver chloride was used in growing crystals with controlled doping. Crystals were grown by both the Czochalski method and the Bridgman method, and the Bridgman grown crystals were used for the experiments discussed. The distribution coefficients of ten divalent cations were determined for the Bridgman crystals. The best dosimeters were made with silver chloride crystals containing 5 to 10 ppm of lead; other impurities tested did not produce proper dosimeters.

  13. TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

    DOEpatents

    Fried, S.

    1951-03-20

    Halides of transuranic elements are prepared by contacting with aluminum and a halogen, or with an aluminum halide, a transuranic metal oxide, oxyhalide, halide, or mixture thereof at an elevated temperature.

  14. 40 CFR 721.4095 - Quaternary ammonium alkyltherpropyl trialkylamine halides.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... trialkylamine halides. 721.4095 Section 721.4095 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4095 Quaternary ammonium alkyltherpropyl trialkylamine halides. (a... generically as quaternary ammonium alkyltherpropyl trialkylamine halides (PMNs...

  15. Cohesive Energy-Lattice Constant and Bulk Modulus-Lattice Constant Relationships: Alkali Halides, Ag Halides, Tl Halides

    NASA Technical Reports Server (NTRS)

    Schlosser, Herbert

    1992-01-01

    In this note we present two expressions relating the cohesive energy, E(sub coh), and the zero pressure isothermal bulk modulus, B(sub 0), of the alkali halides. Ag halides and TI halides, with the nearest neighbor distances, d(sub nn). First, we show that the product E(sub coh)d(sub 0) within families of halide crystals with common crystal structure is to a good approximation constant, with maximum rms deviation of plus or minus 2%. Secondly, we demonstrate that within families of halide crystals with a common cation and common crystal structure the product B(sub 0)d(sup 3.5)(sub nn) is a good approximation constant, with maximum rms deviation of plus or minus 1.36%.

  16. Multiple-Wavelength Metal/Halide Laser

    NASA Technical Reports Server (NTRS)

    Nerheim, N. M.

    1984-01-01

    Single device produces multiple lasing lines. Laser capable of producing many lasing lines has several reservoirs of halide lasant mixed with chlorides of copper, manganese and iron. Convection-control technique possible to rapidly change from one metal halide to another at maximum energy.

  17. Hygroscopicity Evaluation of Halide Scintillators

    SciTech Connect

    Zhuravleva, M; Stand, L; Wei, H; Hobbs, C. L.; Boatner, Lynn A; Ramey, Joanne Oxendine; Burger, Arnold; Rowe, E; Bhattacharya, P.; Tupitsyn, E; Melcher, Charles L

    2014-01-01

    A collaborative study of relative hygroscopicity of anhydrous halide scintillators grown at various laboratories is presented. We have developed a technique to evaluate moisture sensitivity of both raw materials and grown crystals, in which the moisture absorption rate is measured using a gravimetric analysis. Degradation of the scintillation performance was investigated by recording gamma-ray spectra and monitoring the photopeak position, count rate and energy resolution. The accompanying physical degradation of the samples exposed to ambient atmosphere was photographically recorded as well. The results were compared with ben

  18. 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. PMID:27336412

  19. Shallow halogen vacancies in halide optoelectronic materials

    DOE PAGESBeta

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VHmore » is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.« less

  20. Shallow halogen vacancies in halide optoelectronic materials

    NASA Astrophysics Data System (ADS)

    Shi, Hongliang; Du, Mao-Hua

    2014-11-01

    Halogen vacancies (VH ) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., C H3N H3Pb I3 and TlBr. Both C H3N H3Pb I3 and TlBr have been found to have shallow VH , in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., C H3N H3Pb I3 , C H3N H3Sn I3 (photovoltaic materials), TlBr, and CsPbB r3 (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of n s2 ions both play important roles in creating shallow VH in halides such as C H3N H3Pb I3 , C H3N H3Sn I3 , and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH , such as those with large cation-cation distances and low anion coordination numbers and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH . The results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  1. Cross-Electrophile Coupling of Vinyl Halides with Alkyl Halides.

    PubMed

    Johnson, Keywan A; Biswas, Soumik; Weix, Daniel J

    2016-05-23

    An improved method for the reductive coupling of aryl and vinyl bromides with alkyl halides that gave high yields for a variety of substrates at room temperature with a low (2.5 to 0.5 mol %) catalyst loading is presented. Under the optimized conditions, difficult substrates, such as unhindered alkenyl bromides, can be coupled to give the desired olefins with minimal diene formation and good stereoretention. These improved conditions also worked well for aryl bromides. For example, a gram-scale reaction was demonstrated with 0.5 mol % catalyst loading, whereas reactions at 10 mol % catalyst loading completed in as little as 20 minutes. Finally, a low-cost single-component pre-catalyst, (bpy)NiI2 (bpy=2,2'-bipyridine) that is both air- and moisture-stable over a period of months was introduced. PMID:27017436

  2. 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

  3. Quantum Size Effect in Organometal Halide Perovskite Nanoplatelets.

    PubMed

    Sichert, Jasmina A; Tong, Yu; Mutz, Niklas; Vollmer, Mathias; Fischer, Stefan; Milowska, Karolina Z; García Cortadella, Ramon; Nickel, Bert; Cardenas-Daw, Carlos; Stolarczyk, Jacek K; Urban, Alexander S; Feldmann, Jochen

    2015-10-14

    Organometal halide perovskites have recently emerged displaying a huge potential for not only photovoltaic, but also light emitting applications. Exploiting the optical properties of specifically tailored perovskite nanocrystals could greatly enhance the efficiency and functionality of applications based on this material. In this study, we investigate the quantum size effect in colloidal organometal halide perovskite nanoplatelets. By tuning the ratio of the organic cations used, we can control the thickness and consequently the photoluminescence emission of the platelets. Quantum mechanical calculations match well with the experimental values. We find that not only do the properties of the perovskite, but also those of the organic ligands play an important role. Stacking of nanoplatelets leads to the formation of minibands, further shifting the bandgap energies. In addition, we find a large exciton binding energy of up to several hundreds of meV for nanoplatelets thinner than three unit cells, partially counteracting the blueshift induced by quantum confinement. Understanding of the quantum size effects in perovskite nanoplatelets and the ability to tune them provide an additional method with which to manipulate the optical properties of organometal halide perovskites. PMID:26327242

  4. Environmental controls over methyl halide emissions from rice paddies

    NASA Astrophysics Data System (ADS)

    Redeker, K. R.; Cicerone, R. J.

    2004-03-01

    This paper examines primary controlling factors that affect methyl halide emissions from rice paddy ecosystems. Observations of four cultivars under multiple growth conditions during studies in commercial fields and the University of California, Irvine, greenhouse lead to the conclusion that daily emissions of methyl halides are primarily determined by the growth stage of the rice plant, with the exception that methyl chloride emissions show no clear seasonal pattern. Methyl chloride emissions appear to be more from the paddy water and/or soil as opposed to the plants; however, in soils with high chloride content, these emissions appear to peak during the reproductive phase. Strong secondary influences include air temperature, soil halide concentration, and soil pore water saturation. The cultivars studied had statistically separate seasonally integrated emissions. Irradiant light and aboveground biomass appear to have little effect on emissions. Emissions of methyl chloride, methyl bromide, and methyl iodide are estimated to be 3.5, 2.3, and 48 mg/m2/yr, or 5.3, 3.5, and 72 Gg/yr, from rice paddies globally.

  5. Environmental Effects on the Photophysics of Organic–Inorganic Halide Perovskites

    PubMed Central

    2015-01-01

    The photophysical properties of films of organic–inorganic lead halide perovskites under different ambient conditions are herein reported. We demonstrate that their luminescent properties are determined by the interplay between photoinduced activation and darkening processes, which strongly depend on the atmosphere surrounding the samples. We have isolated oxygen and moisture as the key elements in each process, activation and darkening, both of which involve the interaction with photogenerated carriers. These findings show that environmental factors play a key role in the performance of lead halide perovskites as efficient luminescent materials. PMID:26266592

  6. Toxicity of organometal halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Babayigit, Aslihan; Ethirajan, Anitha; Muller, Marc; Conings, Bert

    2016-03-01

    In the last few years, the advent of metal halide perovskite solar cells has revolutionized the prospects of next-generation photovoltaics. As this technology is maturing at an exceptional rate, research on its environmental impact is becoming increasingly relevant.

  7. Oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Rohrmann, Charles A.; Fullam, Harold T.

    1985-01-01

    A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

  8. Abiotic Formation of Methyl Halides in the Terrestrial Environment

    NASA Astrophysics Data System (ADS)

    Keppler, F.

    2011-12-01

    Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will

  9. Effects of halide ions on photodegradation of sulfonamide antibiotics: Formation of halogenated intermediates.

    PubMed

    Li, Yingjie; Qiao, Xianliang; Zhang, Ya-Nan; Zhou, Chengzhi; Xie, Huaijun; Chen, Jingwen

    2016-10-01

    The occurrence of sulfonamide antibiotics (SAs) in estuarine waters urges insights into their environmental fate for ecological risk assessment. Although many studies focused on the photochemical behavior of SAs, yet the effects of halide ions relevant to estuarine and marine environments on their photodegradation have been poorly understood. Here, we investigated the effects of halide ions on the photodegradation of SAs with sulfapyridine, sulfamethazine, and sulfamethoxazole as representative compounds. Results showed that halide ions did not significantly impact the photodegradation of sulfapyridine and sulfamethoxazole, while they significantly promoted the photodegradation of sulfamethazine. Further experiments found that ionic strength applied with NaClO4 significantly enhanced the photodegradation of the SAs, which was attributed to the decreased quenching rate constant of the triplet-excited SAs ((3)SA(∗)). Compared with ionic strength, specific Cl(-) effects retarded the photodegradation of the SAs. Our study found that triplet-excited sulfamethazine can oxidize halide ions to produce halogen radicals, subsequently leading to the halogenation of sulfamethazine, which was confirmed by the identification of both chlorinated and brominated intermediates. These results indicate that halide ions play an important role in the photochemical behavior of some SAs in estuarine waters and seawater. The occurrence of halogenation for certain organic pollutants can be predicted by comparing the oxidation potentials of triplet-excited contaminants with those of halogen radicals. Our findings are helpful in understanding the photochemical behavior and assessing the ecological risks of SAs and other organic pollutants in estuarine and marine environment. PMID:27393965

  10. Alkali Metal Halide Salts as Interface Additives to Fabricate Hysteresis-Free Hybrid Perovskite-Based Photovoltaic Devices.

    PubMed

    Wang, Lili; Moghe, Dhanashree; Hafezian, Soroush; Chen, Pei; Young, Margaret; Elinski, Mark; Martinu, Ludvik; Kéna-Cohen, Stéphane; Lunt, Richard R

    2016-09-01

    A new method was developed for doping and fabricating hysteresis-free hybrid perovskite-based photovoltaic devices by using alkali metal halide salts as interface layer additives. Such salt layers introduced at the perovskite interface can provide excessive halide ions to fill vacancies formed during the deposition and annealing process. A range of solution-processed halide salts were investigated. The highest performance of methylammonium lead mixed-halide perovskite device was achieved with a NaI interlayer and showed a power conversion efficiency of 12.6% and a hysteresis of less than 2%. This represents a 90% improvement compared to control devices without this salt layer. Through depth-resolved mass spectrometry, optical modeling, and photoluminescence spectroscopy, this enhancement is attributed to the reduction of iodide vacancies, passivation of grain boundaries, and improved hole extraction. Our approach ultimately provides an alternative and facile route to high-performance and hysteresis-free perovskite solar cells. PMID:27532662

  11. Iron-Catalyzed Acylation of Polyfunctionalized Aryl- and Benzylzinc Halides with Acid Chlorides.

    PubMed

    Benischke, Andreas D; Leroux, Marcel; Knoll, Irina; Knochel, Paul

    2016-08-01

    FeCl2 (5 mol %) catalyzes a smooth and convenient acylation of functionalized arylzinc halides at 50 °C (2-4 h) and benzylic zinc chlorides at 25 °C (0.5-4 h) with a variety of acid chlorides leading to polyfunctionalized diaryl and aryl heteroaryl ketones. PMID:27457108

  12. Purcell effect in an organic-inorganic halide perovskite semiconductor microcavity system

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Cao, Runan; Da, Peimei; Wang, Yafeng; Hu, Tao; Wu, Lin; Lu, Jian; Shen, Xuechu; Xu, Fei; Zheng, Gengfeng; Chen, Zhanghai

    2016-01-01

    Organic-inorganic halide perovskite semiconductors with the attractive physics properties, including strong photoluminescence (PL), huge oscillator strengths, and low nonradiative recombination losses, are ideal candidates for studying the light-matter interaction in nanostructures. Here, we demonstrate the coupling of the exciton state and the cavity mode in the lead halide perovskite microcavity system at room temperature. The Purcell effect in the coupling system is clearly observed by using angle-resolved photoluminescence spectra. Kinetic analysis based on time-resolved PL reveals that the spontaneous emission rate of the halide perovskite semiconductor is significantly enhanced at resonance of the exciton energy and the cavity mode. Our results provide the way for developing electrically driven organic polariton lasers, optical devices, and on-chip coherent quantum light sources.

  13. Dimming of metal halide lamps

    NASA Technical Reports Server (NTRS)

    Schurer, Kees

    1994-01-01

    We ran some tests on the effect of dimming of metal halide (MH) lamps upon the stability and the spectral quality of the light output. Lamps used were a new Philips lamp HPI-T 250W, a similar Philips lamp with a few thousand burning hours and a new Osram lamp HQI-T 250W/D. The ballast was a BBC type DJ 250/2KS, the starter a BAS TORGI type MZN 250 SE and the dimmer an Elstrom Control System type ERHQ-T 250. Power was derived from a Philips stabilizer, type PE 1602. Lamp output was monitored with a PAR meter. Spectra were taken at 100% and at 50% output as measured with the PAR meter. Lamps were allowed to stabilize at any setting for 30 minutes before measurements were made. Lamp manufacturers advise against dimming for fear of poor stability and intolerable changes of the spectrum. However, none of the lamps showed a decrease in stability, no flicker or wandering of the discharge, and the changes of the spectrum were not negligible, but certainly not dramatic. Lamps of either manufacture retain their white color, relative peak heights of spectral lines did shift, but no gaps in the spectrum occurred. Spectra taken at 50% with 30 minutes intervals coincided. Differences between the new and the older Philips lamp were noticeable, but not really significant.

  14. The Remarkable Reactivity of Aryl Halides with Nucleophiles

    ERIC Educational Resources Information Center

    Bunnett, Joseph F.

    1974-01-01

    Discusses the reactivity of aryl halides with nucleophilic or basic reagents, including nucleophilic attacks on carbon, hydrogen, halogen, and arynes. Suggestions are made concerning revisions of the sections on aryl halide chemistry courses and the corresponding chapters in textbooks. (CC)

  15. Shallow halogen vacancies in halide optoelectronic materials

    SciTech Connect

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  16. Lead zirconate titanate ceramics

    SciTech Connect

    Walker, B.E. Jr.

    1986-12-02

    This patent describes a lead zirconate titanate (PZT) piezoelectric ceramic composition which, based on total composition weight, consists essentially of a solid solution of lead zirconate and lead titanate in a PbZrO/sub 3/:PbTiO/sub 3/ ratio from about 0.505:0.495 to about 0.54:0.46; a halide salt selected from the group consisting of fluorides and chlorides of alkali metal and alkaline earth elements and mixtures thereof except for francium and radium in an amount from about 0.5 to 2 weight percent; and an oxide selected from the group consisting of magnesium, barium, scandium, aluminum, lanthanum, praesodynium, neodymium, samarium, and mixtures thereof in an amount from about 0.5 to about 6 weight percent, the relative amount of oxide being from about 1 to about 4 times that of the halide.

  17. 40 CFR 721.575 - Substituted alkyl halide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl halide. 721.575... Substances § 721.575 Substituted alkyl halide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted alkyl halide (PMN P-83-1222)...

  18. Method for recovering hydrocarbons from molten metal halides

    DOEpatents

    Pell, Melvyn B.

    1979-01-01

    In a process for hydrocracking heavy carbonaceous materials by contacting such carbonaceous materials with hydrogen in the presence of a molten metal halide catalyst to produce hydrocarbons having lower molecular weights and thereafter recovering the hydrocarbons so produced from the molten metal halide, an improvement comprising injecting into the spent molten metal halide, a liquid low-boiling hydrocarbon stream is disclosed.

  19. Recent advances in technetium halide chemistry.

    PubMed

    Poineau, Frederic; Johnstone, Erik V; Czerwinski, Kenneth R; Sattelberger, Alfred P

    2014-02-18

    Transition metal binary halides are fundamental compounds, and the study of their structure, bonding, and other properties gives chemists a better understanding of physicochemical trends across the periodic table. One transition metal whose halide chemistry is underdeveloped is technetium, the lightest radioelement. For half a century, the halide chemistry of technetium has been defined by three compounds: TcF6, TcF5, and TcCl4. The absence of Tc binary bromides and iodides in the literature was surprising considering the existence of such compounds for all of the elements surrounding technetium. The common synthetic routes that scientists use to obtain binary halides of the neighboring elements, such as sealed tube reactions between elements and flowing gas reactions between a molecular complex and HX gas (X = Cl, Br, or I), had not been reported for technetium. In this Account, we discuss how we used these routes to revisit the halide chemistry of technetium. We report seven new phases: TcBr4, TcBr3, α/β-TcCl3, α/β-TcCl2, and TcI3. Technetium tetrachloride and tetrabromide are isostructural to PtX4 (X = Cl or Br) and consist of infinite chains of edge-sharing TcX6 octahedra. Trivalent technetium halides are isostructural to ruthenium and molybdenum (β-TcCl3, TcBr3, and TcI3) and to rhenium (α-TcCl3). Technetium tribromide and triiodide exhibit the TiI3 structure-type and consist of infinite chains of face-sharing TcX6 (X = Br or I) octahedra. Concerning the trichlorides, β-TcCl3 crystallizes with the AlCl3 structure-type and consists of infinite layers of edge-sharing TcCl6 octahedra, while α-TcCl3 consists of infinite layers of Tc3Cl9 units. Both phases of technetium dichloride exhibit new structure-types that consist of infinite chains of [Tc2Cl8] units. For the technetium binary halides, we studied the metal-metal interaction by theoretical methods and magnetic measurements. The change of the electronic configuration of the metal atom from d(3) (Tc

  20. A lead-halide perovskite molecular ferroelectric semiconductor

    PubMed Central

    Liao, Wei-Qiang; Zhang, Yi; Hu, Chun-Li; Mao, Jiang-Gao; Ye, Heng-Yun; Li, Peng-Fei; Huang, Songping D.; Xiong, Ren-Gen

    2015-01-01

    Inorganic semiconductor ferroelectrics such as BiFeO3 have shown great potential in photovoltaic and other applications. Currently, semiconducting properties and the corresponding application in optoelectronic devices of hybrid organo-plumbate or stannate are a hot topic of academic research; more and more of such hybrids have been synthesized. Structurally, these hybrids are suitable for exploration of ferroelectricity. Therefore, the design of molecular ferroelectric semiconductors based on these hybrids provides a possibility to obtain new or high-performance semiconductor ferroelectrics. Here we investigated Pb-layered perovskites, and found the layer perovskite (benzylammonium)2PbCl4 is ferroelectric with semiconducting behaviours. It has a larger ferroelectric spontaneous polarization Ps=13 μC cm−2 and a higher Curie temperature Tc=438 K with a band gap of 3.65 eV. This finding throws light on the new properties of the hybrid organo-plumbate or stannate compounds and provides a new way to develop new semiconductor ferroelectrics. PMID:26021758

  1. 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.

  2. Interfacial Degradation of Planar Lead Halide Perovskite Solar Cells.

    PubMed

    Guerrero, Antonio; You, Jingbi; Aranda, Clara; Kang, Yong Soo; Garcia-Belmonte, Germà; Zhou, Huanping; Bisquert, Juan; Yang, Yang

    2016-01-26

    The stability of perovskite solar cells is one of the major challenges for this technology to reach commercialization, with water believed to be the major degradation source. In this work, a range of devices containing different cathode metal contacts in the configuration ITO/PEDOT:PSS/MAPbI3/PCBM/Metal are fully electrically characterized before and after degradation caused by steady illumination during 4 h that induces a dramatic reduction in power conversion efficiency from values of 12 to 1.8%. We show that a decrease in performance and generation of the S-shape is associated with chemical degradation of the metal contact. Alternatively, use of Cr2O3/Cr as the contact enhances the stability, but modification of the energetic profile during steady illumination takes place, significantly reducing the performance. Several techniques including capacitance-voltage, X-ray diffraction, and optical absorption results suggest that the properties of the bulk perovskite layer are little affected in the device degradation process. Capacitance-voltage and impedance spectroscopy results show that the electrical properties of the cathode contact are being modified by generation of a dipole at the cathode that causes a large shift of the flat-band potential that modifies the interfacial energy barrier and impedes efficient extraction of electrons. Ionic movement in the perovskite layer changes the energy profile close to the contacts, modifying the energy level stabilization at the cathode. These results provide insights into the degradation mechanisms of perovskite solar cells and highlight the importance to further study the use of protecting layers to avoid the chemical reactivity of the perovskite with the external contacts. PMID:26679510

  3. Structure and Chemistry in Halide Lead-Tellurite Glasses

    SciTech Connect

    McCloy, John S.; Riley, Brian J.; Lipton, Andrew S.; Windisch, Charles F.; Washton, Nancy M.; Olszta, Matthew J.; Rodriguez, Carmen P.

    2013-02-11

    A series of TeO2-PbO glasses were fabricated with increasing fractions of mixed alkali, alkaline earth, and lanthanide chlorides. The glass and crystal structure was studied with Raman spectroscopy, nuclear magnetic resonance (NMR), X-ray diffraction, and electron microscopy. As the chloride fraction increased, the medium-range order in the glass decreased up to a critical point (~14 mass% of mixed chlorides), above which the glasses became phase-separated. Resulting phases are a TeO2/PbO-rich phase and a crystalline phase rich in alkali chlorides. The 125Te NMR indicates, contrary to previous studies, that Te site distribution did not change with increased concentrations of M+, M2+, and M3+ cations, but rather is controlled by the Te/Pb molar ratio. The 207Pb NMR shows that two Pb species exist and their relative concentration changes nearly linearly with addition of the mixed chlorides, indicating that the additives to the TeO2-PbO glass are accommodated by changing the Pb species. The 23Na and 35Cl NMR indicate that Na and Cl are distributed in the single-phase glass phase up to the critical point, and at higher concentrations partition to crystalline phases. Transmission electron microscopy shows that the sample at the critical point contains ~10 nm seed nuclei that increase in size and concentration with exposure to the electron beam.

  4. A lead-halide perovskite molecular ferroelectric semiconductor.

    PubMed

    Liao, Wei-Qiang; Zhang, Yi; Hu, Chun-Li; Mao, Jiang-Gao; Ye, Heng-Yun; Li, Peng-Fei; Huang, Songping D; Xiong, Ren-Gen

    2015-01-01

    Inorganic semiconductor ferroelectrics such as BiFeO3 have shown great potential in photovoltaic and other applications. Currently, semiconducting properties and the corresponding application in optoelectronic devices of hybrid organo-plumbate or stannate are a hot topic of academic research; more and more of such hybrids have been synthesized. Structurally, these hybrids are suitable for exploration of ferroelectricity. Therefore, the design of molecular ferroelectric semiconductors based on these hybrids provides a possibility to obtain new or high-performance semiconductor ferroelectrics. Here we investigated Pb-layered perovskites, and found the layer perovskite (benzylammonium)2PbCl4 is ferroelectric with semiconducting behaviours. It has a larger ferroelectric spontaneous polarization Ps=13 μC cm(-2) and a higher Curie temperature Tc=438 K with a band gap of 3.65 eV. This finding throws light on the new properties of the hybrid organo-plumbate or stannate compounds and provides a new way to develop new semiconductor ferroelectrics. PMID:26021758

  5. Vibration-Resistant Support for Halide Lamps

    NASA Technical Reports Server (NTRS)

    Kiss, J.

    1987-01-01

    Lamp envelope protected against breakage. Old and new mounts for halide arc lamp sealed in housing with parabolic refector and quartz window. New version supports lamp with compliant garters instead of rigid brazed joint at top and dimensionally unstable finger stock at bottom.

  6. Molecular compressibility of some halides in alcohols

    NASA Technical Reports Server (NTRS)

    Serban, C.; Auslaender, D.

    1974-01-01

    After measuring ultrasonic velocity and density, the molecular compressibility values from Wada's formula were calculated, for alkali metal halide solutions in methyl, ethyl, butyl, and glycol alcohol. The temperature and concentration dependence were studied, finding deviations due to the hydrogen bonds of the solvent.

  7. The Additive Coloration of Alkali Halides

    ERIC Educational Resources Information Center

    Jirgal, G. H.; and others

    1969-01-01

    Describes the construction and use of an inexpensive, vacuum furnace designed to produce F-centers in alkali halide crystals by additive coloration. The method described avoids corrosion or contamination during the coloration process. Examination of the resultant crystals is discussed and several experiments using additively colored crystals are…

  8. Ionic alkali halide XUV laser feasibility study

    SciTech Connect

    Yang, T.T.; Gylys, V.T.; Bower, R.D.; Harris, D.G.; Blauer, J.A.; Turner, C.E.; Hindy, R.N.

    1989-11-10

    The objective of this work is to assess the feasibility of a select set of ionic alkali halide XUV laser concepts by obtaining the relevant kinetic and spectroscopic parameters required for a proof-of-principle and conceptual design. The proposed lasers operate in the 80--200 nm spectral region and do not require input from outside radiation sources for their operation. Frequency up-conversion and frequency mixing techniques and therefore not considered in the work to be described. An experimental and theoretical study of a new type of laser operating in the extreme ultraviolet wavelength region has been conducted. The lasing species are singly ionized alkali halide molecules such as Rb{sup 2+}F{sub {minus}}, Rb{sup 2+}Br{sup {minus}} and Cs{sup 2+}F{sup {minus}}. These species are similar in electronic structure to the rare gas halide excimers, such as XeF and Krf, except that the ionic molecules emit at wavelengths of 80--200 nm, much shorter than the conventional rare-gas halide excimer laser. The radiative lifetime of these molecules are typically near 1 ns, which is about an order of magnitude shorter than that for rare-gas halide systems. The values of the cross section for stimulated emission are on the order of 1 {times} 10{sup {minus}16}cm{sup 2}. Because of the fundamental similarity to existing UV lasers, these systems show promise as a high power, efficient XUV lasers. 55 refs., 50 figs., 5 tabs.

  9. Transport of Soil Halides through Rice Paddies: A Viable Mechanism for Rapid Dispersion of the Soil Halide Reservoir

    NASA Astrophysics Data System (ADS)

    Redeker, K. R.; Manley, S.; Wang, N.; Cicerone, R.

    2002-05-01

    On short time scales (1-10 years) soil halide concentrations have been assumed to be primarily driven by leaching and deposition processes. Recent results however, have shown that terrestrial plants volatilize soil halides in the form of methyl halides. Emissions of methyl chloride, methyl bromide and methyl iodide represent major pathways for delivery of inorganic halogen radicals to the atmosphere. Inorganic halogen radicals destroy ozone in the stratosphere and modify the oxidative capacity of the lower atmosphere. We have previously shown that rice paddies emit methyl halides and that emissions depend on growth stage of the rice plant as well as field water management. We show here that rice grown in a greenhouse at UCI is capable of volatilizing and/or storing up to 30%, 5%, and 10% of the available chloride, bromide and iodide within the top meter of soil. The percent of plant tissue halide volatilized as methyl halide over the course of the season is calculated to be 0.05%, 0.25% and 85.0% for chloride, bromide and iodide. We compare our greenhouse soil halide concentrations to other commercial rice fields around the world and estimate the e-folding time for soil halides within each region. We suggest that rice agriculture is the driving removal mechanism for halides within rice paddies and that terrestrial plants play a larger role in global cycling of halides than previously estimated.

  10. Flame inhibition by hydrogen halides - Some spectroscopic measurements

    NASA Technical Reports Server (NTRS)

    Lerner, N. R.; Cagliostro, D. E.

    1973-01-01

    The far-ultraviolet absorption spectrum of an air-propane diffusion flame inhibited with hydrogen halides has been studied. Plots of the absorption of light by hydrogen halides as a function of position in the flame and also as a function of the amount of hydrogen halide added to the flame have been obtained. The hydrogen halides are shown to be more stable on the fuel side of the reaction zone than they are on the air side. Thermal diffusion is seen to be important in determining the concentration distribution of the heavier hydrogen halides in diffusion flames. The relationship between the concentration distribution of the hydrogen halides in the flame and the flame inhibition mechanism is discussed.

  11. 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

  12. Recent progress and challenges of organometal halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Yang, Liyan; Barrows, Alexander T.; Lidzey, David G.; Wang, Tao

    2016-02-01

    We review recent progress in the development of organometal halide perovskite solar cells. We discuss different compounds used to construct perovskite photoactive layers, as well as the optoelectronic properties of this system. The factors that affect the morphology of the perovskite active layer are explored, e.g. material composition, film deposition methods, casting solvent and various post-treatments. Different strategies are reviewed that have recently emerged to prepare high performing perovskite films, creating polycrystalline films having either large or small grain size. Devices that are constructed using meso-superstructured and planar architectures are summarized and the impact of the fabrication process on operational efficiency is discussed. Finally, important research challenges (hysteresis, thermal and moisture instability, mechanical flexibility, as well as the development of lead-free materials) in the development of perovskite solar cells are outlined and their potential solutions are discussed.

  13. Large Magnetoresistance Effects in Novel Layered Rare Earth Halides

    NASA Astrophysics Data System (ADS)

    Kremer, R. K.; Ryazanov, M.; Simon, A.

    We give a survey of the structures, electric, magnetic and magnetoresistance properties of the two novel low dimensional rare-earth halide systems, GdI2 and GdIHy (2/3 < y ≤ 1). The large magnetoresistance e.ect observed for GdI2 can be understood on the basis of a conventional spin disorder scattering mechanism, however, strongly magni.ed by the structural anisotropy and the special topology of the Fermi surface. Bound magnetic polarons are formed in GdIHy leading to a metal insulator transition below ~ 30 K. The mobility of the magnetic polarons can be e.ectively modi.ed by external magnetic .fields resulting in the large experimentally found magnetoresistance.

  14. Lanthanide-halide based humidity indicators

    DOEpatents

    Beitz, James V.; Williams, Clayton W.

    2008-01-01

    The present invention discloses a lanthanide-halide based humidity indicator and method of producing such indicator. The color of the present invention indicates the humidity of an atmosphere to which it is exposed. For example, impregnating an adsorbent support such as silica gel with an aqueous solution of the europium-containing reagent solution described herein, and dehydrating the support to dryness forms a substance with a yellow color. When this substance is exposed to a humid atmosphere the water vapor from the air is adsorbed into the coating on the pore surface of the silica gel. As the water content of the coating increases, the visual color of the coated silica gel changes from yellow to white. The color change is due to the water combining with the lanthanide-halide complex on the pores of the gel.

  15. EVALUATION OF METHODS FOR THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER AND WASTE

    EPA Science Inventory

    Various methods for the determination of total organic halides (TOX) in groundwater and in waste oil samples have been evaluated. Of three inorganic halide species generation approaches and three inorganic halide determinative techniques evaluated for groundwater analyses, one co...

  16. Interpulse kinetics in copper and copper halide lasers

    NASA Technical Reports Server (NTRS)

    Harstad, K. G.

    1983-01-01

    The various rate processes that govern the interpulse relaxation in metal vapor and metal halide vapor lasers are considered. Computer calculations indicate that the rapid metastable levels relaxation observed in copper and copper halide laser experiments requires the existence of a relatively small resonance in the cross section for metastable excitation or deexcitation near threshold. The accurate calculation of interpulse relaxation requires knowledge of rate constants presently not well known; this is especially so for metal halide lasers.

  17. Process and composition for drying of gaseous hydrogen halides

    DOEpatents

    Tom, Glenn M.; Brown, Duncan W.

    1989-08-01

    A process for drying a gaseous hydrogen halide of the formula HX, wherein X is selected from the group consisting of bromine, chlorine, fluorine, and iodine, to remove water impurity therefrom, comprising: contacting the water impurity-containing gaseous hydrogen halide with a scavenger including a support having associated therewith one or more members of the group consisting of: (a) an active scavenging moiety selected from one or more members of the group consisting of: (i) metal halide compounds dispersed in the support, of the formula MX.sub.y ; and (ii) metal halide pendant functional groups of the formula -MX.sub.y-1 covalently bonded to the support, wherein M is a y-valent metal, and y is an integer whose value is from 1 to 3; (b) corresponding partially or fully alkylated compounds and/or pendant functional groups, of the metal halide compounds and/or pendant functional groups of (a); wherein the alkylated compounds and/or pendant functional groups, when present, are reactive with the gaseous hydrogen halide to form the corresponding halide compounds and/or pendant functional groups of (a); and M being selected such that the heat of formation, .DELTA.H.sub.f of its hydrated halide, MX.sub.y.(H.sub.2 O).sub.n, is governed by the relationship: .DELTA.H.sub.f .gtoreq.n.times.10.1 kilocalories/mole of such hydrated halide compound wherein n is the number of water molecules bound to the metal halide in the metal halide hydrate. Also disclosed is an appertaining scavenger composition and a contacting apparatus wherein the scavenger is deployed in a bed for contacting with the water impurity-containing gaseous hydrogen halide.

  18. Lanthanide doped strontium-barium cesium halide scintillators

    SciTech Connect

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

  19. NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning

    NASA Astrophysics Data System (ADS)

    Shmyreva, Anna A.; Safdari, Majid; Furó, István; Dvinskikh, Sergey V.

    2016-06-01

    Orders of magnitude decrease of 207Pb and 199Hg NMR longitudinal relaxation times T1 upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX2 (Me = Pb, Hg and X = Cl, Br, I). In lead(ii) halides, the most dramatic decrease of T1 relative to that in a static sample is in PbI2, while it is smaller but still significant in PbBr2, and not detectable in PbCl2. The effect is magnetic-field dependent but independent of the spinning speed in the range 200-15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.

  20. NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning.

    PubMed

    Shmyreva, Anna A; Safdari, Majid; Furó, István; Dvinskikh, Sergey V

    2016-06-14

    Orders of magnitude decrease of (207)Pb and (199)Hg NMR longitudinal relaxation times T1 upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX2 (Me = Pb, Hg and X = Cl, Br, I). In lead(ii) halides, the most dramatic decrease of T1 relative to that in a static sample is in PbI2, while it is smaller but still significant in PbBr2, and not detectable in PbCl2. The effect is magnetic-field dependent but independent of the spinning speed in the range 200-15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time. PMID:27306000

  1. Mechanism and Selectivity in Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Halides with Alkyl Halides

    PubMed Central

    Biswas, Soumik; Weix, Daniel J.

    2013-01-01

    The direct cross-coupling of two different electrophiles, such as an aryl halide with an alkyl halide, offers many advantages over conventional cross-coupling methods that require a carbon nucleophile. Despite its promise as a versatile synthetic strategy, a limited understanding of the mechanism and origin of cross selectivity has hindered progress in reaction development and design. Herein, we shed light on the mechanism for the nickel-catalyzed cross-electrophile coupling of aryl halides with alkyl halides and demonstrate that the selectivity arises from an unusual catalytic cycle that combines both polar and radical steps to form the new C-C bond. PMID:23952217

  2. Controlling Metal-Halide Vapor Density in Lasers

    NASA Technical Reports Server (NTRS)

    Pivirotto, T. J.

    1984-01-01

    Streams of buffer gas convect and dilute metal-halide vapor. Technique uses flow of buffer gas through reservoir, which contains heated metal halide, to convect vapors into discharge tube. Second stream of buffer gas dilutes vapor. Final vapor density in laser tube controlled and changed by adjusting either one or both of buffer gas flow rates.

  3. [Emissions of methyl halides from coastal salt marshes: A review].

    PubMed

    Xie, Wen-xia; Zhao, Quan-sheng; Cui, Yu-qian; Du, Hui-na; Ye, Si-yuan

    2015-11-01

    Methyl halides are the major carrier of halogens in the atmosphere, and they play an important role in tropospheric and stratospheric ozone depletion. Meanwhile, methyl halides can act as greenhouse gases in the atmosphere, and they are also environmentally significant because of their toxicity. Coastal salt marshes, the important intertidal ecosystems at the land-ocean interface, have been considered to be a large potential natural source of methyl halides. In this paper, the research status of the natural source or sink of methyl halides, the mechanisms of their emission from coastal salt marshes and affecting factors were summarized. In view of this, the following research fields need to be strengthened in the future: 1) Long time-scale and large region-range researches about the emission of methyl halides and the evaluation of their source and sink function, 2) Accurate quantification of contribution rates of different plant species and various biological types to fluxes of methyl halides, 3) Further researches on effects of the tidal fluctuation process and flooding duration on methyl halides emission, 4) Effects of the global change and human activities on methyl halides emission. PMID:26915215

  4. Seed-mediated growth of palladium nanocrystals: the effect of pseudo-halide thiocyanate ions.

    PubMed

    Zhang, Ling; Niu, Wenxin; Xu, Guobao

    2011-02-01

    In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed. PMID:21170425

  5. Raman spectra of hydroxide-halide melts

    NASA Astrophysics Data System (ADS)

    Zakiriyanova, I. D.; Khokhlov, V. A.

    2012-08-01

    The Raman spectra of molten binary mixtures based on sodium hydroxide and containing (mol %) 35 NaCl, 30 NaBr, and 30 NaI have been recorded at various temperatures. An increase in the vibrational frequency and the force constant of the O-H bond is detected under isothermal conditions upon a variation of the anionic composition of a melt in the series I → Br → Cl. Based on the experimental data, the viscosity of the hydroxide-halide melts is estimated.

  6. Ultraviolet absorption spectra of mercuric halides.

    NASA Technical Reports Server (NTRS)

    Templet, P.; Mcdonald, J. R.; Mcglynn, S. P.; Kendrow, C. H.; Roebber, J. L.; Weiss, K.

    1972-01-01

    The gas phase transitions of the mercuric halides were observed in the UV region by operating at temperatures above 400 K and at vapor pressures on the order of 0.5 mm. Spectral features exhibited by the chloride, bromide, and iodide of mercury correlate energetically with bands previously designated as intermolecular charge transfer transitions. The solution spectra of mercuric iodide and deep color of the crystals (if not due to some solid state interactions) indicate that this molecule may also have longer wavelength transitions.

  7. Seed-mediated growth of palladium nanocrystals: The effect of pseudo-halide thiocyanate ions

    NASA Astrophysics Data System (ADS)

    Zhang, Ling; Niu, Wenxin; Xu, Guobao

    2011-02-01

    In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed.In synthesis in a solution phase, adsorbates such as halides can interact selectively with different metal crystal facets and affect the final morphology of nanocrystals. Pseudo-halide thiocyanate ions (SCN-) can also adsorb on the metal surface, but they have never been used for the synthesis of shape-controlled colloidal metal nanocrystals. In this study, we first investigated the effect of SCN- on the morphology of palladium nanocrystals through a seed-mediated growth method. The presence of 1 µM SCN- in the growth solutions could lead to the formation of palladium polyhedra: truncated rhombic dodecahedra enclosed by twelve {110}, eight {111} and six {100} facets. The products were nanocubes enclosed with six {100} facets if cetyltrimethylammonium bromide (CTAB) was the only capping agent. Meanwhile, the mechanism of the effect of SCN- on the morphology of Pd nanocrystals is discussed. Electronic supplementary information (ESI) available: Additional SEM, TEM and XRD data. See DOI: 10.1039/c0nr00622j

  8. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  9. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 3 2014-01-01 2014-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  10. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  11. 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

  12. Methyl halide production associated with kelp

    NASA Technical Reports Server (NTRS)

    Dastoor, Minoo N.; Manley, Steven L.

    1985-01-01

    Methyl halides (MeX) are important trace constituents of the atmosphere because they, mostly MeCl, have a major impact on the atmospheric ozone layer. Also, MeCl may account for 5 pct. of the total Cl budget and MeI may have a central role in the biogeochemical cycling of iodine. High MeI concentrations were found in seawater from kelp beds and it has been suggested that MeI is produced by kelps and that MeI and MeBr along with numerous other halocarbons were released by non-kelp marine macroalgae. The objective was to determine if kelps (and other seaweeds) are sources of MeX and to assess their contribution to the estimated global source strength (EGSS) of MeX. Although the production of MeX appears to be associated with kelp, microbes involved with kelp degradation also produce MeX. Microbial MeX production may be of global significance. The microbial MeX production potential, assuming annual kelp production equals kelp degradation and 100 pct. conversion of kelp halides to MeX, is approx. 2 x the EGSS. This is not achieved but indicates that microbial production of MeX may be of global significance.

  13. 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.

  14. Double-Diffusive Convection During Growth of Halides and Selenides

    NASA Technical Reports Server (NTRS)

    Singh, N. B.; Su, Ching-Hua; Duval, Walter M. B.

    2015-01-01

    Heavy metal halides and selenides have unique properties which make them excellent materials for chemical, biological and radiological sensors. Recently it has been shown that selenohalides are even better materials than halides or selenides for gamma-ray detection. These materials also meet the strong needs of a wide band imaging technology to cover ultra-violet (UV), midwave infrared wavelength (MWIR) to very long wavelength infrared (VLWIR) region for hyperspectral imager components such as etalon filters and acousto-optic tunable filters (AO). In fact AOTF based imagers based on these materials have some superiority than imagers based on liquid crystals, FTIR, Fabry-Perot, grating, etalon, electro-optic modulation, piezoelectric and several other concepts. For example, broadband spectral and imagers have problems of processing large amount of information during real-time observation. Acousto-Optic Tunable Filter (AOTF) imagers are being developed to fill the need of reducing processing time of data, low cost operation and key to achieving the goal of covering long-wave infrared (LWIR). At the present time spectral imaging systems are based on the use of diffraction gratings are typically used in a pushbroom or whiskbroom mode. They are mostly used in systems and acquire large amounts of hyperspectral data that is processed off-line later. In contrast, acousto-optic tunable filter spectral imagers require very little image processing, providing new strategies for object recognition and tracking. They are ideally suited for tactical situations requiring immediate real-time image processing. But the performance of these imagers depends on the quality and homogeneity of acousto-optic materials. In addition for many systems requirements are so demanding that crystals up to sizes of 10 cm length are desired. We have studied several selenides and halide crystals for laser and AO imagers for MWIR and LWIR wavelength regions. We have grown and fabricated crystals of

  15. Interface Engineering in Metal Halides Perovskites: From molecules to devices

    NASA Astrophysics Data System (ADS)

    Petrozza, Annamaria

    In this talk 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 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 emission properties of the semiconductor looking both at polycrystalline thin films and single crystals. 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 microstructure of the hybrid crystals and not only on its chemical composition. This leads to the possibility of band gap engineering and the consequent control of the elementary photo-excitation dynamics that determine the perovskites' performances in different optoelectronic devices. Finally, the role of interface engineering, the effect of ion migration, and interface doping on charge extraction will be elucidated to provide a guideline for the design of hysteresis free solar cells. 1)G. Grancini & AR Srimath Kandada et al., Nature Photonics, 9 (10), 695-701, 2015 2) C. Tao et al,'' Energy Environ. Sci.,8, 2365-2370, 2015

  16. Detection of halide ions with AlGaN /GaN high electron mobility transistors

    NASA Astrophysics Data System (ADS)

    Kang, B. S.; Ren, F.; Kang, M. C.; Lofton, C.; Tan, Weihong; Pearton, S. J.; Dabiran, A.; Osinsky, A.; Chow, P. P.

    2005-04-01

    AlGaN /GaN high electron mobility transistors (HEMTs) both with and without a Au gate are found to exhibit significant changes in channel conductance upon exposing the gate region to various halide ions. The polar nature of the halide ions leads to a change of surface charge in the gate region on the HEMT, producing a change in the surface potential at the semiconductor/liquid interface. HEMTs with a Au-gate electrode not only doubled the sensitivity of changing the channel conductance as compared to gateless HEMT, but also showed the opposite conductance behavior. When anions adsorbed on the Au, they produced a counter charge for electrovalence. These anions drag some counter ions from the bulk solution or create an image positive charge on the metal for the required neutrality. The gateless HEMTs can be used as sensors for a range of chemicals through appropriate modification with covalently bonded halide functional groups on the Au surface. This creates many possibilities to functionalize the surface for a wide range of integrated biological, chemical, and fluid monitoring sensors.

  17. First-principles study of γ-ray detector materials in perovskite halides

    NASA Astrophysics Data System (ADS)

    Im, Jino; Jin, Hosub; Stoumpos, Constantinos; Chung, Duck; Liu, Zhifu; Peters, John; Wessels, Bruce; Kanatzidis, Mercouri; Freeman, Arthur

    2013-03-01

    In an effort to search for good γ-ray detector materials, perovskite halide compounds containing heavy elements were investigated. Despite the three-dimensional network of the corner shared octahedra and the extended nature of the outermost shell, its strong ionic character leads to a large band gap, which is one of the essential criteria for γ-ray detector materials. Thus, considering high density and high atomic number, these pervoskite halides are possible candidate for γ-ray detector materials. We performed first-principles calculations to investigate electronic structures and thermodynamic properties of intrinsic defects in the selected perovskite halide, CsPbBr3. The screened-exchange local density approximation scheme was employed to correct the underestimation of the band gap in the LDA method. As a result, the calculated band gap of CsPbBr3 is found to be suitable for γ-ray detection. Furthermore, defect formation energy calculations allow us to predict thermodynamic and electronic properties of possible intrinsic defects, which affect detector efficiency and energy resolution. Supported by the office of Nonproliferation and Verification R &D under Contract No. DE-AC02-06CH11357

  18. Enhancing stability of octahedral PtNi nanoparticles for oxygen reduction reaction by halide treatment

    NASA Astrophysics Data System (ADS)

    Choi, Juhyuk; Lee, Youhan; Kim, Jihan; Lee, Hyunjoo

    2016-03-01

    Because a reduction in the amount of Pt catalysts is essential for the commercialization of fuel cells, various approaches have been tested to maximize the mass activity of Pt-based catalysts. Among these, the most successful results so far were obtained using shaped PtNi alloy nanoparticles, preferably with PtNi(111) facets. However, these nanoparticles typically suffer from much lower activity after the durability tests due to the leaching out of the surface Ni during the oxygen reduction reaction (ORR), which leads to the disappearance of the activity-enhancing effect caused by electronic structure modification. Here, we showed that halide treatment of the octahedral PtNi nanoparticles could significantly enhance their durability. Halides are adsorbed on surface Ni more strongly than on surface Pt, and the surface halides are found to preserve the surface Ni that induces the ORR activity enhancement. Especially, Br can preserve the surface Ni effectively. Durability testing by repeating cyclic voltammetry 10,000 times in the 0.6-1.1 V range showed that the mass activity decreased by 52.6% for the as-prepared PtNi octahedral nanoparticles, whereas the mass activity decreased by only 15.0% for the Br-treated PtNi nanoparticles. The simple treatment significantly enhanced the long-term stability of the highly active PtNi alloy nano-octahedra.

  19. Alkali metal and alkali earth metal gadolinium halide scintillators

    DOEpatents

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  20. Vibrational Spectroscopy of Sodium Halide and Hydrogen Halide Aqueous Solutions: Application to Atmospheric Aerosol Chemistry

    NASA Astrophysics Data System (ADS)

    Levering, L. M.; Liu, D.; Allen, H. C.

    2003-12-01

    Heterogeneous reactions on the surfaces of atmospheric aerosols play an important role in atmospheric chemistry. These reactions are capable of converting alkyl and hydrogen halides (common constituents of marine boundary aerosols) into active halogen compounds. Fundamental questions still remain concerning surface species and reaction mechanisms pertaining to marine boundary aerosols. The first step in beginning to understand these heterogeneous reactions is to determine how ions in solution affect the structure of water at the interface. Vibrational sum frequency generation spectroscopy is used to examine the air-liquid interface of sodium halide and hydrogen halide (i.e. strong acid) solutions. In addition, comparison of the bulk water structure to that of the interface is accomplished using Raman spectroscopy. The hydrogen-bonding environment at the surface of NaCl is found to be similar to that of the air-water interface. In contrast, the interfacial water structure of NaBr, HCl, and HBr solutions is significantly altered from that of neat water. In the bulk, NaCl, NaBr, HCl, and HBr solutions disturb the hydrogen-bonding network of neat water. A comparison between the corresponding salts and acids show that the salts produce greater disorder (i.e. less coupling of the water symmetric stretching modes) in the bulk water structure.

  1. 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

  2. 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.

  3. Highly Tunable Colloidal Perovskite Nanoplatelets through Variable Cation, Metal, and Halide Composition.

    PubMed

    Weidman, Mark C; Seitz, Michael; Stranks, Samuel D; Tisdale, William A

    2016-08-23

    Colloidal perovskite nanoplatelets are a promising class of semiconductor nanomaterials-exhibiting bright luminescence, tunable and spectrally narrow absorption and emission features, strongly confined excitonic states, and facile colloidal synthesis. Here, we demonstrate the high degree of spectral tunability achievable through variation of the cation, metal, and halide composition as well as nanoplatelet thickness. We synthesize nanoplatelets of the form L2[ABX3]n-1BX4, where L is an organic ligand (octylammonium, butylammonium), A is a monovalent metal or organic molecular cation (cesium, methylammonium, formamidinium), B is a divalent metal cation (lead, tin), X is a halide anion (chloride, bromide, iodide), and n-1 is the number of unit cells in thickness. We show that variation of n, B, and X leads to large changes in the absorption and emission energy, while variation of the A cation leads to only subtle changes but can significantly impact the nanoplatelet stability and photoluminescence quantum yield (with values over 20%). Furthermore, mixed halide nanoplatelets exhibit continuous spectral tunability over a 1.5 eV spectral range, from 2.2 to 3.7 eV. The nanoplatelets have relatively large lateral dimensions (100 nm to 1 μm), which promote self-assembly into stacked superlattice structures-the periodicity of which can be adjusted based on the nanoplatelet surface ligand length. These results demonstrate the versatility of colloidal perovskite nanoplatelets as a material platform, with tunability extending from the deep-UV, across the visible, into the near-IR. In particular, the tin-containing nanoplatelets represent a significant addition to the small but increasingly important family of lead- and cadmium-free colloidal semiconductors. PMID:27471862

  4. 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. PMID:27315525

  5. Effects of isoelectronic and halide surfactants on compound semiconductors

    NASA Astrophysics Data System (ADS)

    Howard, Alexander David

    Isoelectronic surfactants Sb, Bi, and N, have proven to increase the doping efficiency of Zn while concurrently reducing the unintentional impurities C, Si, and S in GaP. Additionally, surfactant Sb and N have demonstrated that altering the incorporation efficiency in GaP is also possible with a surfactant surface coverage of less than one. Halide surfactants Br and Cl were shown to systematically destroy ordering in GaInP. Furthermore, a distinct correlation between increasing surfactant Br or Cl in the vapor and surface roughness was evident. This work is presented in three main sections. First, surfactants Sb and Bi, from the pyrolysis of TMSb and TMBi, were examined to determine the effect on Zn doping in GaP. The data demonstrate that the incorporation of Zn can be increased by an order of magnitude in GaP to a value of approximately 1020 cm-3, the highest value reported to date. Additionally, these same surfactants lead to significant decreases in carbon contamination during growth. At high growth temperatures, the reduction can be as large as 100 x in GaP. Second, the role of steps versus the singular surface between steps was studied by using a surfactant fractional surface coverage of less than one. When surfactant Sb was used, the Zn concentration was increased and C was reduced. However, there was no discernable change in incorporation efficiency over the entire range of surfactant Sb studied. Interestingly, surfactant N showed a linear increase in the Zn doping the with amount of surfactant present during growth resulting in an increase of 2 x at the highest flow rate used. Third, halide surfactants Br and Cl, carbon-tetrabromide and carbon-tetrachloride, were studied for their effects on ordering in GaInP. Bromine systematically decreased the amount of CuPt ordering observed by photoluminescence and transmission electron microscopy. Both surfactants Br and Cl were shown to significantly increase the surface roughness, which is postulated to be the

  6. Layered structures of organic/inorganic hybrid halide perovskites

    NASA Astrophysics Data System (ADS)

    Huan, Tran Doan; Tuoc, Vu Ngoc; Minh, Nguyen Viet

    2016-03-01

    Organic-inorganic hybrid halide perovskites, in which the A cations of an ABX3 perovskite are replaced by organic cations, may be used for photovoltaic and solar thermoelectric applications. In this contribution, we systematically study three lead-free hybrid perovskites, i.e., methylammonium tin iodide CH3NH3SnI3 , ammonium tin iodide NH4SnI3 , and formamidnium tin iodide HC (NH2)2SnI3 by first-principles calculations. We find that in addition to the commonly known motif in which the corner-shared SnI6 octahedra form a three-dimensional network, these materials may also favor a two-dimensional (layered) motif formed by alternating layers of the SnI6 octahedra and the organic cations. These two motifs are nearly equal in free energy and are separated by low barriers. These layered structures features many flat electronic bands near the band edges, making their electronic structures significantly different from those of the structural phases composed of three-dimension networks of SnI6 octahedra. Furthermore, because the electronic structures of HC (NH2)2SnI3 are found to be rather similar to those of CH3NH3SnI3 , formamidnium tin iodide may also be promising for the applications of methylammonium tin iodide.

  7. Imaging of hydrogen halides photochemistry on argon and ice nanoparticles

    NASA Astrophysics Data System (ADS)

    Poterya, V.; Lengyel, J.; Pysanenko, A.; Svrčková, P.; Fárník, M.

    2014-08-01

    The photodissociation dynamics of HX (X = Cl, Br) molecules deposited on large ArN and (H2O)N, bar{N}≈ 102-103, clusters is investigated at 193 nm using velocity map imaging of H and Cl photofragments. In addition, time-of-flight mass spectrometry after electron ionization complemented by pickup cross section measurements provide information about the composition and structure of the clusters. The hydrogen halides coagulate efficiently to generate smaller (HX)n clusters on ArN upon multiple pickup conditions. This implies a high mobility of HX molecules on argon. On the other hand, the molecules remain isolated on (H2O)N. The photodissociation on ArN leads to strong H-fragment caging manifested by the fragment intensity peaking sharply at zero kinetic energy. Some of the Cl-fragments from HCl photodissociation on ArN are also caged, while some of the fragments escape the cluster directly without losing their kinetic energy. The images of H-fragments from HX on (H2O)N also exhibit a strong central intensity, however, with a different kinetic energy distribution which originates from different processes: the HX acidic dissociation followed by H3O neutral hydronium radical formation after the UV excitation, and the slow H-fragments stem from subsequent decay of the H3O. The corresponding Cl-cofragment from the photoexcitation of the HCl.(H2O)N is trapped in the ice nanoparticle.

  8. Tallgrass Prairie as a Source and Sink of Methyl Halides

    NASA Astrophysics Data System (ADS)

    Abel, T.; Rhew, R. C.; Mazeas, O.; Atwood, A.; King, A. J.; Ma, L.; Whelan, M.

    2007-12-01

    Temperate grasslands are believed to be a globally significant sink for methyl bromide (CH3Br) and perhaps methyl chloride (CH3Cl), compounds which lead to stratospheric ozone destruction. Fluxes of these compounds were measured at Konza Prairie, a tallgrass prairie in the Flint Hills of Kansas, during June 2006 and August 2007. A stable isotope tracer technique was used to distinguish between simultaneous production and oxidation processes, allowing the first gross flux measurements of CH3Cl and CH3Br from a tallgrass prairie. Observed gross uptake rates of CH3Cl and CH3Br were similar to what we previously observed from the shortgrass steppe in Colorado and annual grasslands in California, but much lower than reported fluxes from a grassland in northeastern North America. A water manipulation experiment was performed both under controlled laboratory conditions, as well as in the field, demonstrating that uptake rates of both CH3Cl and CH3Br were strongly affected by soil moisture. On the production side, new sources of methyl halides were identified in association with certain plant species. Fluxes of these halogenated trace gases were compared to environmental variables, such as air temperature and volumetric water content. Net fluxes of methyl iodide (CH3I), carbon tetrachloride (CCl4), and other halogenated volatile organic compounds (HVOCs), were also measured.

  9. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    SciTech Connect

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

    2014-12-08

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10{sup 25}/m{sup 3}. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

  10. Density functional studies on hydrogen-bonded clusters of hydrogen halides and the interaction on halide anions

    NASA Astrophysics Data System (ADS)

    Nirmala, V.; Kolandaivel, P.

    Density functional theory (DFT) calculations have been performed to study the structures and stability of X-·(HX)n=2-5 clusters where X = F, Cl, Br at B3LYP/6-311++G** level of theory. The presence of halide ions in these clusters disintegrates the hydrogen halide clusters. All the hydrogen halides are then hydrogen bonded to the centrally placed halide ions, thereby forming multiple hydrogen bonds. The interaction energies have been corrected for the basis set superposition error (BSSE) using Boy's counterpoise correction method. Evidence for the destruction of hydrogen bonds in hydrogen halide clusters due to the presence of halide ions is further obtained from topological analysis and natural bond orbital analysis. The chemical hardness and chemical potential have been calculated for all the anion clusters. The above analysis reveals that hydrogen bonding in these systems is not an essentially electrostatic interaction. The nature of the stabilization interactions operative in these multiple hydrogen-bonded clusters has been explained in terms of many-body contribution to interaction energies. From these studies, an attempt has been made to understand the nature of the molecular properties resulting from different electronegativities of the halogens.

  11. Self-regulation mechanism for charged point defects in hybrid halide perovskites

    DOE PAGESBeta

    Walsh, Aron; Scanlon, David O.; Chen, Shiyou; Gong, X. G.; Wei, Su -Huai

    2014-12-11

    Hybrid halide perovskites such as methylammonium lead iodide (CH3NH3PbI3) exhibit unusually low free-carrier concentrations despite being processed at low-temperatures from solution. We demonstrate, through quantum mechanical calculations, that an origin of this phenomenon is a prevalence of ionic over electronic disorder in stoichiometric materials. Schottky defect formation provides a mechanism to self-regulate the concentration of charge carriers through ionic compensation of charged point defects. The equilibrium charged vacancy concentration is predicted to exceed 0.4 % at room temperature. Furthermore, this behavior, which goes against established defect conventions for inorganic semiconductors, has implications for photovoltaic performance.

  12. [Cu(NHC)]-Catalyzed C-H Allylation and Alkenylation of both Electron-Deficient and Electron-Rich (Hetero)arenes with Allyl Halides.

    PubMed

    Xie, Weilong; Chang, Sukbok

    2016-01-26

    New reactivity of a [Cu(NHC)] (NHC=N-heterocyclic carbene) catalyst is disclosed for the efficient C-H allylation of polyfluoroarenes using allyl halides in benzene at room temperature. The same catalyst system also promotes an isomerization-induced alkenylation of initially the generated allyl arenes when the reaction is run in tetrahydrofuran. Significantly, not only electron-deficient but also electron-rich (hetero)arenes undergo this double-bond migration process, thus leading to alkenylated products. The present system features mild reaction conditions, broad scope with respect to the arene substrates and allyl halide reactants, good functional-group tolerance, and high stereoselectivity. PMID:26695120

  13. Photoinduced electron transfer double fragmentation. An oxygen-mediated radical chain process in the cofragmentation of aminopinacol donors with organic halides

    SciTech Connect

    Chen, L.; Farahat, M.S.; Gan, H.; Whitten, D.G.; Farid, S. |

    1995-06-14

    We reprot an investigation in which excited states of amino pinacols 1-3 are reacted with the halides CCl{sub 4}, benzyl bromide, and p-cyanobenzyl bromide. Interesting results from this study include the finding that low-to-moderate quantum efficiencies for reaction are observed when the reactions are carried out under degassed conditions, indicating that the halide radical anions must survive long enough within the initial ion pair formed in the quenching step to undergo considerable return electron transfer. More strikingly we find that for certain pinacol-halide combinations reaction in aerared solutions leads to much higher efficiencies, which can be attributed to a chain reaction involving oxygen capture of a primary radical product. 25 refs., 1 fig., 1 tab.

  14. Ultrabroad Photoluminescence and Electroluminescence at New Wavelengths from Doped Organometal Halide Perovskites.

    PubMed

    Zhou, Yang; Yong, Zi-Jun; Zhang, Kai-Cheng; Liu, Bo-Mei; Wang, Zhao-Wei; Hou, Jing-Shan; Fang, Yong-Zheng; Zhou, Yi; Sun, Hong-Tao; Song, Bo

    2016-07-21

    Doping of semiconductors by introducing foreign atoms enables their widespread applications in microelectronics and optoelectronics. We show that this strategy can be applied to direct bandgap lead-halide perovskites, leading to the realization of ultrawide photoluminescence (PL) at new wavelengths enabled by doping bismuth (Bi) into lead-halide perovskites. Structural and photophysical characterization reveals that the PL stems from one class of Bi doping-induced optically active center, which is attributed to distorted [PbI6] units coupled with spatially localized bipolarons. Additionally, we find that compositional engineering of these semiconductors can be employed as an additional way to rationally tune the PL properties of doped perovskites. Finally, we accomplished the electroluminescence at cryogenic temperatures by using this system as an emissive layer, marking the first electrically driven devices using Bi-doped photonic materials. Our results suggest that low-cost, earth-abundant, solution-processable Bi-doped perovskite semiconductors could be promising candidate materials for developing optical sources operating at new wavelengths. PMID:27377481

  15. A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovoltaic Applications.

    PubMed

    Slavney, Adam H; Hu, Te; Lindenberg, Aaron M; Karunadasa, Hemamala I

    2016-02-24

    Despite the remarkable rise in efficiencies of solar cells containing the lead-halide perovskite absorbers RPbX3 (R = organic cation; X = Br(-) or I(-)), the toxicity of lead remains a concern for the large-scale implementation of this technology. This has spurred the search for lead-free materials with similar optoelectronic properties. Here, we use the double-perovskite structure to incorporate nontoxic Bi(3+) into the perovskite lattice in Cs2AgBiBr6 (1). The solid shows a long room-temperature fundamental photoluminescence (PL) lifetime of ca. 660 ns, which is very encouraging for photovoltaic applications. Comparison between single-crystal and powder PL decay curves of 1 suggests inherently high defect tolerance. The material has an indirect bandgap of 1.95 eV, suited for a tandem solar cell. Furthermore, 1 is significantly more heat and moisture stable compared to (MA)PbI3. The extremely promising optical and physical properties of 1 shown here motivate further exploration of both inorganic and hybrid halide double perovskites for photovoltaics and other optoelectronics. PMID:26853379

  16. 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

  17. Color silver halide hologram production and mastering

    NASA Astrophysics Data System (ADS)

    Bjelkhagen, Hans I.; Huang, Qiang

    1997-04-01

    Color reflection holograms recorded with the Denisyuk geometry have been demonstrated by the recently formed HOLOS Corporation in New Hampshire. The Slavich red-green-blue (RGB) sensitized ultra-high resolution silver halide emulsion was used for the hologram recording. The employed laser wavelengths were 647 nm, 532 nm, and 476 nm, generated by an argon ion, a frequency doubled Nd:YAG, and a krypton ion laser, respectively. A beam combination mechanism with dichroic filters enabled a simultaneous RGB exposure, which made the color balance and overall exposure energy easy to control as well as simplifying the recording procedure. HOLOS has been producing limited edition color holograms in various sizes from 4' X 5' to 12' X 16'. A 30 foot long optical table and high power lasers will enable HOLOS to record color holograms up to the size of one meter square in the near future. Various approaches have been investigated in generating color hologram masters which have sufficiently high diffraction efficiency to contact copy the color images onto photopolymer materials. A specially designed test object including the 1931 CIE chromaticity diagram, a rainbow ribbon cable, pure yellow dots, and a cloisonne elephant was used for color recording experiments. In addition, the Macbeth Color Checker chart was used. Both colorimetric evaluation and scattering noise measurements were performed using the PR-650 Photo Research SpectraScan SpectraCalorimeter.

  18. Vitrification of IFR and MSBR halide salt reprocessing wastes

    SciTech Connect

    Siemer, D.D.

    2013-07-01

    Both of the genuinely sustainable (breeder) nuclear fuel cycles (IFR - Integral Fast Reactor - and MSBR - Molten Salt Breeder Reactor -) studied by the USA's national laboratories would generate high level reprocessing waste (HLRW) streams consisting of a relatively small amount ( about 4 mole %) of fission product halide (chloride or fluoride) salts in a matrix comprised primarily (about 95 mole %) of non radioactive alkali metal halide salts. Because leach resistant glasses cannot accommodate much of any of the halides, most of the treatment scenarios previously envisioned for such HLRW have assumed a monolithic waste form comprised of a synthetic analog of an insoluble crystalline halide mineral. In practice, this translates to making a 'substituted' sodalite ('Ceramic Waste Form') of the IFR's chloride salt-based wastes and fluoroapatite of the MSBR's fluoride salt-based wastes. This paper discusses my experimental studies of an alternative waste management scenario for both fuel cycles that would separate/recycle the waste's halide and immobilize everything else in iron phosphate (Fe-P) glass. It will describe both how the work was done and what its results indicate about how a treatment process for both of those wastes should be implemented (fluoride and chloride behave differently). In either case, this scenario's primary advantages include much higher waste loadings, much lower overall cost, and the generation of a product (glass) that is more consistent with current waste management practices. (author)

  19. Genetic Control of Methyl Halide Production in Arabidopsis

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Ostergaard, L.; Saltzman, E. S.; Yanofsky, M. F.

    2003-12-01

    Methyl chloride and methyl bromide are the primary carriers of natural chlorine and bromine to the stratosphere where they catalyze the destruction of ozone, whereas methyl iodide influences aerosol formation and ozone loss in the troposphere. Methyl bromide is also an agricultural fumigant whose use is scheduled to be phased out by international agreement. Despite the economic and environmental importance of these methyl halides, their natural sources and biological production mechanisms are poorly understood. Currently identified sources include oceans, biomass burning, industrial and agricultural use, fuel combustion, salt marshes, wetlands, rice paddies, certain terrestrial plants and fungi, and abiotic processes. We demonstrate that the model plant Arabidopsis thaliana produces and emits methyl halides and that the enzyme primarily responsible for the production is encoded by the HARMLESS TO OZONE LAYER (HOL) gene located on chromosome II. In mutant plants that have a disruption of the HOL gene, methyl halide production is largely eliminated. A phylogenetic analysis using the HOL gene suggests that the ability to produce methyl halides is widespread among vascular plants. This approach provides a genetic basis for understanding and predicting patterns of methyl halide production by plants.

  20. Process for oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Lyke, Stephen E.

    1992-01-01

    An improved process for generating an elemental halogen selected from chlorine, bromine or iodine, from a corresponding hydrogen halide by absorbing a molten salt mixture, which includes sulfur, alkali metals and oxygen with a sulfur to metal molar ratio between 0.9 and 1.1 and includes a dissolved oxygen compound capable of reacting with hydrogen halide to produce elemental halogen, into a porous, relatively inert substrate to produce a substrate-supported salt mixture. Thereafter, the substrate-supported salt mixture is contacted (stage 1) with a hydrogen halide while maintaining the substrate-supported salt mixture during the contacting at an elevated temperature sufficient to sustain a reaction between the oxygen compound and the hydrogen halide to produce a gaseous elemental halogen product. This is followed by purging the substrate-supported salt mixture with steam (stage 2) thereby recovering any unreacted hydrogen halide and additional elemental halogen for recycle to stage 1. The dissolved oxygen compound is regenerated in a high temperature (stage 3) and an optical intermediate temperature stage (stage 4) by contacting the substrate-supported salt mixture with a gas containing oxygen whereby the dissolved oxygen compound in the substrate-supported salt mixture is regenerated by being oxidized to a higher valence state.

  1. 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

  2. Regeneration of zinc halide catalyst used in the hydrocracking of polynuclear hydrocarbons

    DOEpatents

    Gorin, Everett

    1978-01-01

    Improved recovery of spent molten zinc halide hydro-cracking catalyst is achieved in the oxidative vapor phase regeneration thereof by selective treatment of the zinc oxide carried over by the effluent vapors from the regeneration zone with hydrogen halide gas under conditions favoring the reaction of the zinc oxide with the hydrogen halide, whereby regenerated zinc halide is recovered in a solids-free state with little loss of zinc values.

  3. High Biomass Specific Methyl Halide Production Rates of Selected Coastal Marsh Plants and its Relationship to Halide Content

    NASA Astrophysics Data System (ADS)

    Manley, S. L.; Wang, N.; Cicerone, R. J.

    2002-12-01

    Salt tolerant coastal marsh plants (halophytes) have previously been shown to be globally significant producers of methyl chloride (MeCl) and methyl bromide (MeBr). While halophytes are known for their high salt content, there are few reports of their halide content. Our studies have attempted to quantify biomass specific methyl halide (MeX) production from these plants and relate it to tissue halide levels. MeCl, MeBr and MeI production rates and tissue chloride, bromide and iodide concentrations from selected coastal marsh plants were measured for nearly a year. Certain halophyte species (i.e. Batis and Frankenia) have very high summer biomass specific production rates for MeX (e.g. Frankenia: 1 ug MeCl /gfwt/hr; 80 ng MeBr/gfwt/hr; 8 ng MeI/gfwt/hr). These rates of MeCl and MeBr production are much higher than those from other coastal marsh plants or seaweeds. Plant halide levels remain high throughout the year, while MeX production peaks at a high level in mid summer falling to low winter rates. This implies a linkage to plant growth. Higher levels of chloride and bromide were seen in the fleshy marsh plants such as Batis (saltwort, approximately 20 percent dry wt chloride, 0.4 percent dry wt bromide) and Salicornia (pickleweed) than in the others such as Frankenia (alkali heath) approx 7 percent dry wt chloride, 0.1 percent dry wt bromide) or Spartina (cordgrass). No such trend was seen for iodide, which ranged from 4 - 10 ppm. Calculations show the daily halide losses from MeX production are far less than the variability in tissue halide content. MeX production removes a small fraction of the total tissue halide from these plants suggesting that MeX production is not a mechanism used by these species to control internal halide levels. Saltwort cell-free extracts incubated with bromide or iodide in the presence of S-adenosyl-L-methionine (SAM) produced the corresponding MeX. MeBr production was inhibited by caffeic acid the substrate of lignin-specific O

  4. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 3 2010-01-01 2010-01-01 false Definitions concerning metal halide lamp ballasts and... FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide lamp ballasts and fixtures. Ballast efficiency means, in the case of...

  5. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  6. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  7. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  8. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  9. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  10. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  11. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 3 2011-01-01 2011-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  12. Extended Photo-Conversion Spectrum in Low-Toxic Bismuth Halide Perovskite Solar Cells.

    PubMed

    Johansson, Malin B; Zhu, Huimin; Johansson, Erik M J

    2016-09-01

    Lead-based perovskites show very promising properties for use in solar cells; however, the toxicity of lead is a potential inhibitor for large-scale application of these solar cells. Here, a low-toxic bismuth halide, CsBi3I10, is synthesized from solution and the optical properties and crystal structure are compared with previously reported Cs3Bi2I9 perovskite, and the photovoltaic properties are also investigated. The XRD pattern suggests that the CsBi3I10 film has a layered structure with a different dominating crystal growth direction than the Cs3Bi2I9 perovskite. A band gap of 1.77 eV is obtained for the CsBi3I10 film, which is smaller than the band gap of Cs3Bi2I9 at 2.03 eV, and an extended visible light absorption spectrum is therefore obtained. The solar cell device with CsBi3I10 shows a photocurrent up to 700 nm, and this work shows therefore the possibility for increased light absorption and higher photocurrents in solar cells based on bismuth halide perovskites. PMID:27538852

  13. Metal-halide mixtures for latent heat energy storage

    NASA Technical Reports Server (NTRS)

    Chen, K.; Manvi, R.

    1981-01-01

    Alkali metal and alkali halide mixtures are identified which may be suitable for thermal energy storage at temperatures above 600 C. The use of metal-halides is appropriate because of their tendency to form two immiscible melts with a density difference, which reduces scale formation and solidification on heat transfer surfaces. Also, the accumulation of phase change material along the melt interface is avoided by the self-dispersing characteristic of some metal-halides, in particular Sr-SrCl2, Ba-BaCl2, and Ba-BaBr2 mixtures. Further advantages lie in their high thermal conductivities, ability to cope with thermal shock, corrosion inhibition, and possibly higher energy densities.

  14. A study of the influence of halide adsorption on a reconstructed Au(111) electrode by second harmonic generation

    NASA Astrophysics Data System (ADS)

    Friedrich, A.; Shannon, C.; Pettinger, B.

    1991-07-01

    Optical second harmonic generation (SHG) rotational anisotropy measurements were employed to study the influence of specifically adsorbed anions on the reconstructed Au(111)-(1 × 23) surface. Azimuthal rotation of the gold electrode at different potentials yields for the unreconstructed Au(111)-(1 × 1) surface the well-known three-fold symmetry pattern, while for the reconstructed Au(111)-(1 × 23) an additional one-fold symmetry pattern is observed, which leads to an assignment of Cs-symmetry for this surface. Due to the observation of this symmetry change Cs → C3v it is possible to monitor in situ the reversible transition between Au(111)-(1 × 23) and Au(111)-(1 × 1). While in perclorate solution the phase transition occurs over a wide potential region, in halide containing solution the same phase transition is restricted to the sharp potential region typical for the halide adsorption.

  15. Blue-Green Color Tunable Solution Processable Organolead Chloride-Bromide Mixed Halide Perovskites for Optoelectronic Applications.

    PubMed

    Sadhanala, Aditya; Ahmad, Shahab; Zhao, Baodan; Giesbrecht, Nadja; Pearce, Phoebe M; Deschler, Felix; Hoye, Robert L Z; Gödel, Karl C; Bein, Thomas; Docampo, Pablo; Dutton, Siân E; De Volder, Michael F L; Friend, Richard H

    2015-09-01

    Solution-processed organo-lead halide perovskites are produced with sharp, color-pure electroluminescence that can be tuned from blue to green region of visible spectrum (425-570 nm). This was accomplished by controlling the halide composition of CH3NH3Pb(BrxCl1-x)3 [0 ≤ x ≤ 1] perovskites. The bandgap and lattice parameters change monotonically with composition. The films possess remarkably sharp band edges and a clean bandgap, with a single optically active phase. These chloride-bromide perovskites can potentially be used in optoelectronic devices like solar cells and light emitting diodes (LEDs). Here we demonstrate high color-purity, tunable LEDs with narrow emission full width at half maxima (FWHM) and low turn on voltages using thin-films of these perovskite materials, including a blue CH3NH3PbCl3 perovskite LED with a narrow emission FWHM of 5 nm. PMID:26236949

  16. Blue-Green Color Tunable Solution Processable Organolead Chloride–Bromide Mixed Halide Perovskites for Optoelectronic Applications

    PubMed Central

    2015-01-01

    Solution-processed organo-lead halide perovskites are produced with sharp, color-pure electroluminescence that can be tuned from blue to green region of visible spectrum (425–570 nm). This was accomplished by controlling the halide composition of CH3NH3Pb(BrxCl1–x)3 [0 ≤ x ≤ 1] perovskites. The bandgap and lattice parameters change monotonically with composition. The films possess remarkably sharp band edges and a clean bandgap, with a single optically active phase. These chloride–bromide perovskites can potentially be used in optoelectronic devices like solar cells and light emitting diodes (LEDs). Here we demonstrate high color-purity, tunable LEDs with narrow emission full width at half maxima (FWHM) and low turn on voltages using thin-films of these perovskite materials, including a blue CH3NH3PbCl3 perovskite LED with a narrow emission FWHM of 5 nm. PMID:26236949

  17. Imaging of hydrogen halides photochemistry on argon and ice nanoparticles.

    PubMed

    Poterya, V; Lengyel, J; Pysanenko, A; Svrčková, P; Fárník, M

    2014-08-21

    The photodissociation dynamics of HX (X = Cl, Br) molecules deposited on large ArN and (H2O)N, N̄ ≈ 10(2)-10(3), clusters is investigated at 193 nm using velocity map imaging of H and Cl photofragments. In addition, time-of-flight mass spectrometry after electron ionization complemented by pickup cross section measurements provide information about the composition and structure of the clusters. The hydrogen halides coagulate efficiently to generate smaller (HX)n clusters on ArN upon multiple pickup conditions. This implies a high mobility of HX molecules on argon. On the other hand, the molecules remain isolated on (H2O)N. The photodissociation on ArN leads to strong H-fragment caging manifested by the fragment intensity peaking sharply at zero kinetic energy. Some of the Cl-fragments from HCl photodissociation on ArN are also caged, while some of the fragments escape the cluster directly without losing their kinetic energy. The images of H-fragments from HX on (H2O)N also exhibit a strong central intensity, however, with a different kinetic energy distribution which originates from different processes: the HX acidic dissociation followed by H3O neutral hydronium radical formation after the UV excitation, and the slow H-fragments stem from subsequent decay of the H3O. The corresponding Cl-cofragment from the photoexcitation of the HCl·(H2O)N is trapped in the ice nanoparticle. PMID:25149788

  18. Novel semiconductor radiation detector based on mercurous halides

    NASA Astrophysics Data System (ADS)

    Chen, Henry; Kim, Joo-Soo; Amarasinghe, Proyanthi; Palosz, Withold; Jin, Feng; Trivedi, Sudhir; Burger, Arnold; Marsh, Jarrod C.; Litz, Marc S.; Wiejewarnasuriya, Priyalal S.; Gupta, Neelam; Jensen, Janet; Jensen, James

    2015-08-01

    The three most important desirable features in the search for room temperature semiconductor detector (RTSD) candidate as an alternative material to current commercially off-the-shelf (COTS) material for gamma and/or thermal neutron detection are: low cost, high performance and long term stability. This is especially important for pager form application in homeland security. Despite years of research, no RTSD candidate so far can satisfy the above 3 features simultaneously. In this work, we show that mercurous halide materials Hg2X2 (X= I, Cl, Br) is a new class of innovative compound semiconductors that is capable of delivering breakthrough advances to COTS radiation detector materials. These materials are much easier to grow thicker and larger volume crystals. They can detect gamma and potentially neutron radiation making it possible to detect two types of radiation with just one crystal material. The materials have wider bandgaps (compared to COTS) meaning higher resistivity and lower leakage current, making this new technology more compatible with available microelectronics. The materials also have higher atomic number and density leading to higher stopping power and better detector sensitivity/efficiency. They are not hazardous so there are no environmental and health concerns during manufacturing and are more stable making them more practical for commercial deployment. Focus will be on Hg2I2. Material characterization and detector performance will be presented and discussed. Initial results show that an energy resolution better than 2% @ 59.6 keV gamma from Am-241 and near 1% @ 662 keV from Cs-137 source can be achieved at room temperature.

  19. Imaging of hydrogen halides photochemistry on argon and ice nanoparticles

    SciTech Connect

    Poterya, V. Lengyel, J.; Pysanenko, A.; Svrčková, P.; Fárník, M.

    2014-08-21

    The photodissociation dynamics of HX (X = Cl, Br) molecules deposited on large Ar{sub N} and (H{sub 2}O){sub N}, N{sup ¯}≈ 10{sup 2}–10{sup 3}, clusters is investigated at 193 nm using velocity map imaging of H and Cl photofragments. In addition, time-of-flight mass spectrometry after electron ionization complemented by pickup cross section measurements provide information about the composition and structure of the clusters. The hydrogen halides coagulate efficiently to generate smaller (HX){sub n} clusters on Ar{sub N} upon multiple pickup conditions. This implies a high mobility of HX molecules on argon. On the other hand, the molecules remain isolated on (H{sub 2}O){sub N}. The photodissociation on Ar{sub N} leads to strong H-fragment caging manifested by the fragment intensity peaking sharply at zero kinetic energy. Some of the Cl-fragments from HCl photodissociation on Ar{sub N} are also caged, while some of the fragments escape the cluster directly without losing their kinetic energy. The images of H-fragments from HX on (H{sub 2}O){sub N} also exhibit a strong central intensity, however, with a different kinetic energy distribution which originates from different processes: the HX acidic dissociation followed by H{sub 3}O neutral hydronium radical formation after the UV excitation, and the slow H-fragments stem from subsequent decay of the H{sub 3}O. The corresponding Cl-cofragment from the photoexcitation of the HCl·(H{sub 2}O){sub N} is trapped in the ice nanoparticle.

  20. Metallaphotoredox-catalysed sp(3)-sp(3) cross-coupling of carboxylic acids with alkyl halides.

    PubMed

    Johnston, Craig P; Smith, Russell T; Allmendinger, Simon; MacMillan, David W C

    2016-08-18

    In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp(3)-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp(2)-hybridized species, the development of methods for sp(3)-sp(3) bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp(3)-sp(3) bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp(3)-sp(3) coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp(3)-sp(3) bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox

  1. Boron and aluminum halides under pressure - polymerization and chemical transformations

    NASA Astrophysics Data System (ADS)

    Yao, Yansun

    2013-06-01

    High-pressure phase transitions of boron and aluminum halides have been theoretically studied. At low pressure, crystals of the familiar monomers (BX3) and dimers (Al2X6) are the structures of choice. While the higher oligomers as well as three dimensional infinite polymers are unstable at ambient pressure, they are stabilized by application of external pressure, taking advantage of the extra orbitals made accessible by the increased coordination. Several new crystal structures of boron and aluminum halides have been predicted at high pressures. Calculated x-ray diffraction patterns and Raman spectra of these phases are in good agreement with available experimental data.

  2. Applications of Raman scattering spectroscopy to halide glasses

    NASA Astrophysics Data System (ADS)

    Bendow, B.; Banerjee, P. K.; Drexhage, M. G.

    1983-04-01

    Polarized Raman scattering spectroscopy is a useful tool for investigating fundamental vibrational properties, structure and bonding, origins of IR edge absorption, and dispersion of the IR refractive index. In this paper, the application of Raman spectroscopy to halide glasses and, in particular, heavy metal fluoride glasses, is described. The spectra of the latter differ substantially from those of simple oxide, halide or chalcogenide glasses and, moreover, display a wide range of vibrational characteristics, depending on composition. In combination with infrared spectroscopy, useful guidelines can be developed for tailoring glass compositions for specific applications.

  3. Thermodynamic reactivity, growth and characterization of mercurous halide crystals

    NASA Technical Reports Server (NTRS)

    Singh, N. B.; Gottlieb, M.; Henningsen, T.; Hopkins, R. H.; Mazelsky, R.; Singh, M.; Glicksman, M. E.; Paradies, C.

    1992-01-01

    Thermodynamic calculations were carried out for the Hg-X-O system (X = Cl, Br, I) to identify the potential sources of contamination and relative stability of oxides and oxy-halide phases. The effect of excess mercury vapor pressure on the optical quality of mercurous halide crystal was studied by growing several mercurous chloride crystals from mercury-rich composition. The optical quality of crystals was examined by birefringence interferometry and laser scattering studies. Crystals grown in slightly mercury-rich composition showed improved optical quality relative to stoichiometric crystals.

  4. Thallous halide materials for use in cryogenic applications

    NASA Technical Reports Server (NTRS)

    Lawless, William N. (Inventor)

    1981-01-01

    Thallous halides, either alone or in combination with other ceramic materials, are used in cryogenic applications such as heat exchange material for the regenerator section of a closed-cycle cryogenic refrigeration section, as stabilizing coatings for superconducting wires, and as dielectric insulating materials. The thallous halides possess unusually large specific heats at low temperatures, have large thermal conductivities, are nonmagnetic, and are nonconductors of electricity. They can be formed into a variety of shapes such as spheres, bars, rods, or the like and can be coated onto substrates.

  5. Transformation of Sintered CsPbBr3 Nanocrystals to Cubic CsPbI3 and Gradient CsPbBrxI3-x through Halide Exchange.

    PubMed

    Hoffman, Jacob B; Schleper, A Lennart; Kamat, Prashant V

    2016-07-13

    All-inorganic cesium lead halide (CsPbX3, X = Br(-), I(-)) perovskites could potentially provide comparable photovoltaic performance with enhanced stability compared to organic-inorganic lead halide species. However, small-bandgap cubic CsPbI3 has been difficult to study due to challenges forming CsPbI3 in the cubic phase. Here, a low-temperature procedure to form cubic CsPbI3 has been developed through a halide exchange reaction using films of sintered CsPbBr3 nanocrystals. The reaction was found to be strongly dependent upon temperature, featuring an Arrhenius relationship. Additionally, film thickness played a significant role in determining internal film structure at intermediate reaction times. Thin films (50 nm) showed only a small distribution of CsPbBrxI3-x species, while thicker films (350 nm) exhibited much broader distributions. Furthermore, internal film structure was ordered, featuring a compositional gradient within film. Transient absorption spectroscopy showed the influence of halide exchange on the excited state of the material. In thicker films, charge carriers were rapidly transferred to iodide-rich regions near the film surface within the first several picoseconds after excitation. This ultrafast vectorial charge-transfer process illustrates the potential of utilizing compositional gradients to direct charge flow in perovskite-based photovoltaics. PMID:27322132

  6. Structural Characterization of Methanol Substituted Lanthanum Halides

    PubMed Central

    Boyle, Timothy J.; Ottley, Leigh Anna M.; Alam, Todd M.; Rodriguez, Mark A.; Yang, Pin; Mcintyre, Sarah K.

    2010-01-01

    The first study into the alcohol solvation of lanthanum halide [LaX3] derivatives as a means to lower the processing temperature for the production of the LaBr3 scintillators was undertaken using methanol (MeOH). Initially the de-hydration of {[La(µ-Br)(H2O)7](Br)2}2 (1) was investigated through the simple room temperature dissolution of 1 in MeOH. The mixed solvate monomeric [La(H2O)7(MeOH)2](Br)3 (2) compound was isolated where the La metal center retains its original 9-coordination through the binding of two additional MeOH solvents but necessitates the transfer of the innersphere Br to the outersphere. In an attempt to in situ dry the reaction mixture of 1 in MeOH over CaH2, crystals of [Ca(MeOH)6](Br)2 (3) were isolated. Compound 1 dissolved in MeOH at reflux temperatures led to the isolation of an unusual arrangement identified as the salt derivative {[LaBr2.75•5.25(MeOH)]+0.25 [LaBr3.25•4.75(MeOH)]−0.25} (4). The fully substituted species was ultimately isolated through the dissolution of dried LaBr3 in MeOH forming the 8-coordinated [LaBr3(MeOH)5] (5) complex. It was determined that the concentration of the crystallization solution directed the structure isolated (4 concentrated; 5 dilute) The other LaX3 derivatives were isolated as [(MeOH)4(Cl)2La(µ-Cl)]2 (6) and [La(MeOH)9](I)3•MeOH (7). Beryllium Dome XRD analysis indicated that the bulk material for 5 appear to have multiple solvated species, 6 is consistent with the single crystal, and 7 was too broad to elucidate structural aspects. Multinuclear NMR (139La) indicated that these compounds do not retain their structure in MeOD. TGA/DTA data revealed that the de-solvation temperatures of the MeOH derivatives 4 – 6 were slightly higher in comparison to their hydrated counterparts. PMID:20514349

  7. Exploring the Electronic Band Structure of Organometal Halide Perovskite via Photoluminescence Anisotropy of Individual Nanocrystals.

    PubMed

    Täuber, Daniela; Dobrovolsky, Alexander; Camacho, Rafael; Scheblykin, Ivan G

    2016-08-10

    Understanding electronic processes in organometal halide perovskites, flourishing photovoltaic, and emitting materials requires unraveling the origin of their electronic transitions. Light polarization studies can provide important information regarding transition dipole moment orientations. Investigating individual methylammonium lead triiodide perovskite nanocrystals enabled us to detect the polarization of photoluminescence intensity and photoluminescence excitation, hidden in bulk samples by ensemble averaging. Polarization properties of the crystals were correlated with their photoluminescence spectra and electron microscopy images. We propose that distortion of PbI6 octahedra leads to peculiarities of the electronic band structure close to the band-edge. Namely, the lowest band transition possesses a transition dipole moment along the apical Pb-I-Pb bond resulting in polarized photoluminescence. Excitation of photoluminescence above the bandgap is unpolarized because it involves molecular orbitals delocalized both in the apical and equatorial directions of the perovskite octahedron. Trap-assisted emission at 77 K, rather surprisingly, was polarized similar to the bandgap emission. PMID:27462927

  8. Electro-optic contribution to Raman scattering from alkali halides

    SciTech Connect

    Mahan, G.D.; Subbaswamy, K.R.

    1986-06-15

    The electro-optic contributions to second-order Raman scattering and field-induced first-order scattering from alkali halides are calculated explicitly in terms of the ionic hyperpolarizability coefficients. The relevant local-field corrections are evaluated. Illustrative numerical results are presented.

  9. Methyl halide emission estimates from domestic biomass burning in Africa

    NASA Astrophysics Data System (ADS)

    Mead, M. I.; Khan, M. A. H.; White, I. R.; Nickless, G.; Shallcross, D. E.

    Inventories of methyl halide emissions from domestic burning of biomass in Africa, from 1950 to the present day and projected to 2030, have been constructed. By combining emission factors from Andreae and Merlet [2001. Emission of trace gases and aerosols from biomass burning. Global Biogeochemical Cycles 15, 955-966], the biomass burning estimates from Yevich and Logan [2003. An assessment of biofuel use and burning of agricultural waste in the developing world. Global Biogeochemical Cycles 17(4), 1095, doi:10.1029/2002GB001952] and the population data from the UN population division, the emission of methyl halides from domestic biomass usage in Africa has been estimated. Data from this study suggest that methyl halide emissions from domestic biomass burning have increased by a factor of 4-5 from 1950 to 2005 and based on the expected population growth could double over the next 25 years. This estimated change has a non-negligible impact on the atmospheric budgets of methyl halides.

  10. Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

    ERIC Educational Resources Information Center

    Cruz-Ramirez de Arellano, Daniel

    2013-01-01

    Organic chemistry is an essential subject for many undergraduate students completing degrees in science, engineering, and pre-professional programs. However, students often struggle with the concepts and skills required to successfully solve organic chemistry exercises. Since alkyl halides are traditionally the first functional group that is…

  11. On the Boiling Points of the Alkyl Halides.

    ERIC Educational Resources Information Center

    Correia, John

    1988-01-01

    Discusses the variety of explanations in organic chemistry textbooks of a physical property of organic compounds. Focuses on those concepts explaining attractive forces between molecules. Concludes that induction interactions play a major role in alkyl halides and other polar organic molecules and should be given wider exposure in chemistry texts.…

  12. 40 CFR 721.10698 - Polyfluorinated alkyl halide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polyfluorinated alkyl halide (generic). 721.10698 Section 721.10698 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances §...

  13. Kinetic Studies of the Solvolysis of Two Organic Halides

    ERIC Educational Resources Information Center

    Duncan, J. A.; Pasto, D. J.

    1975-01-01

    Describes an undergraduate organic chemistry laboratory experiment which utilizes the solvolysis of organic halides to demonstrate first and second order reaction kinetics. The experiment also investigates the effect of a change of solvent polarity on reaction rate, common-ion and noncommon-ion salt effects, and the activation parameters of a…

  14. Method for calcining nuclear waste solutions containing zirconium and halides

    DOEpatents

    Newby, Billie J.

    1979-01-01

    A reduction in the quantity of gelatinous solids which are formed in aqueous zirconium-fluoride nuclear reprocessing waste solutions by calcium nitrate added to suppress halide volatility during calcination of the solution while further suppressing chloride volatility is achieved by increasing the aluminum to fluoride mole ratio in the waste solution prior to adding the calcium nitrate.

  15. Semiempirical and DFT Investigations of the Dissociation of Alkyl Halides

    ERIC Educational Resources Information Center

    Waas, Jack R.

    2006-01-01

    Enthalpy changes corresponding to the gas phase heats of dissociation of 12 organic halides were calculated using two semiempirical methods, the Hartree-Fock method, and two DFT methods. These calculated values were compared to experimental values where possible. All five methods agreed generally with the expected empirically known trends in the…

  16. Dielectric relaxation of alkyl chains in graphite oxide and n-alkylammonium halides

    NASA Astrophysics Data System (ADS)

    Ai, Xiaoqian; Tian, Yuchen; Gu, Min; Yu, Ji; Tang, Tong B.

    2016-05-01

    The dynamic of n-alkylammonium halides and n-alkylammonium cations (n = 12, 14, 16, 18) intercalated in graphite oxide (GO) have been investigated with complex impedance spectroscopy. X-ray diffraction, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, elemental analysis and thermogravimetry served to characterize the materials. The intercalated alkylammonium cations distributes as monolayers (when n = 12, 14 or 16) or bilayers (when n = 18), with their long axis parallel to GO layers, and with cations of headgroups bonded ionically to C-O- groups of GO; backbones of the confined molecules remain free. All halides and intercalation compounds suffer dielectric loss at low temperature. Arrhenius plots of the thermal dependence of the loss peaks, which are asymmetric, produce apparent activation energies that rise with increasing n. Ngai's correlated-state model helps to correct for effects of dipole-dipole interaction, leading to virtually identical values for actual activation energy of 110 meV ± 5%; the values are also almost the same as the barrier energy for internal rotation in the alkyl macromolecule. We conclude that the relaxation of the alkylammonium cations arises not from C3 reorientation of the CH3 at its headgroup, but from small-angle wobbling around its major axis, an intrinsic motion.

  17. Ab initio modeling of the optical properties in organometallic halide perovskites for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Neukirch, Amanda; Nei, Wanyi; Pedesseau, Laurent; Even, Jacky; Katan, Claudine; Mohite, Aditya; Tretiak, Segrei

    2015-03-01

    The need for an inexpensive, clean, and plentiful source of energy has generated large amounts of research in an assortment of solution processed organic and hybrid organic-inorganic solar cells. A relative newcomer to the field of solution processed photovoltaics is the lead halide perovskite solar cell. In the past 5 years, the efficiencies of devices made from this material have increased from 3.5% to nearly 20%. Despite the rapid development of organic-inorganic perovskite solar cells, a thorough understanding of the fundamental photophysical processes driving the high performance of these devices is not well understood. I am using state-of-the-art ab initio computational techniques in order to characterize the properties at the interface of perovskite devices in order to aide in materials design and device engineering. I will present an in-depth analysis of the electronic and optical properties of bulk and surface states of pure and mixed halide systems. The high-level static quantum mechanical calculations, including spin-orbit-coupling and the many body GW approach, identify the key electronic states involved in photoinduced dynamics. This knowledge provides important information on how the optical properties change with variations to the system. Supported by the DOE, the LANL LDRD program XW11, and CNLS.

  18. Calcium manganate: A promising candidate as buffer layer for hybrid halide perovskite photovoltaic-thermoelectric systems

    SciTech Connect

    Zhao, Pengjun; Wang, Hongguang; Kong, Wenwen; Xu, Jinbao Wang, Lei; Ren, Wei; Bian, Liang; Chang, Aimin

    2014-11-21

    We have systematically studied the feasibility of CaMnO{sub 3} thin film, an n-type perovskite, to be utilized as the buffer layer for hybrid halide perovskite photovoltaic-thermoelectric device. Locations of the conduction band and the valence band, spontaneous polarization performance, and optical properties were investigated. Results indicate the energy band of CaMnO{sub 3} can match up well with that of CH{sub 3}NH{sub 3}PbI{sub 3} on separating electron-hole pairs. In addition, the consistent polarization angle helps enlarge the open circuit voltage of the composite system. Besides, CaMnO{sub 3} film shows large absorption coefficient and low extinction coefficient under visible irradiation, demonstrating high carrier concentration, which is beneficial to the current density. More importantly, benign thermoelectric properties enable CaMnO{sub 3} film to assimilate phonon vibration from CH{sub 3}NH3PbI{sub 3}. All the above features lead to a bright future of CaMnO{sub 3} film, which can be a promising candidate as a buffer layer for hybrid halide perovskite photovoltaic-thermoelectric systems.

  19. Superconducting lead particles produced by chemical techniques

    SciTech Connect

    Fariss, T.L.; Nixon, W.E.; Bucelot, T.J.; Deaver, B.S. Jr.; Mitchell, J.W.

    1982-09-01

    The superconductivity of extremely small lead particles has been studied as a function of size, surface condition, and connectivity using chemical techniques to produce particles of well-controlled size and shape suspended in insulating media. Approximately monodisperse suspensions of equiaxed, rod, and lath-shaped particles of lead halides and other lead compounds suspended in gelatin, polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, methyl cellulose, and hydroxyethyl cellulose have been produced. These particles have been reduced to pseudomorphs of lead in the liquid phase or the suspensions have been coated on substrates and dried before reduction. Reducing solutions containing aminoiminomethanesulfinic acid are effective with particles of lead halides, lead phosphate, lead sulfate, and lead tartrate. Suspensions of smaller discrete lead particles have also been produced by direct reduction of solutions of soluble lead salts containing suitable polymers, chelating, and stabilizing agents. Dispersions with mean particle dimensions between 3 nm and 5 ..mu..m, and a narrow size-frequency distribution, have been produced. The superconductivity of the particles has been characterized by measurements of the magnetization as a function of temperature and magnetic field. The larger particles have a transition temperature of 7.2 K, the same as bulk lead; however, for particles of characteristic dimensions less than 20 nm, the transition temperature is lower by approx.0.1 K.

  20. Crystal structure of the novel haloalkane dehalogenase DatA from Agrobacterium tumefaciens C58 reveals a special halide-stabilizing pair and enantioselectivity mechanism.

    PubMed

    Guan, Lijun; Yabuki, Hideya; Okai, Masahiko; Ohtsuka, Jun; Tanokura, Masaru

    2014-10-01

    A novel haloalkane dehalogenase DatA from Agrobacterium tumefaciens C58 belongs to the HLD-II subfamily and hydrolyzes brominated and iodinated compounds, leading to the generation of the corresponding alcohol, a halide ion, and a proton. Because DatA possesses a unique Asn-Tyr pair instead of the Asn-Trp pair conserved among the subfamily members, which was proposed to keep the released halide ion stable, the structural basis for its reaction mechanism should be elucidated. Here, we determined the crystal structures of DatA and its Y109W mutant at 1.70 and 1.95 Å, respectively, and confirmed the location of the active site by using its novel competitive inhibitor. The structural information from these two crystal structures and the docking simulation suggested that (i) the replacement of the Asn-Tyr pair with the Asn-Trp pair increases the binding affinity for some halogenated compounds, such as 1,3-dibromopropane, mainly due to the electrostatic interaction between Trp109 and halogenated compounds and the change of substrate-binding mode caused by the interaction and (ii) the primary halide-stabilizing residue is only Asn43 in the wild-type DatA, while Tyr109 is a secondary halide-stabilizing residue. Furthermore, docking simulation using the crystal structures of DatA indicated that its enantioselectivity is determined by the large and small spaces around the halogen-binding site. PMID:24770384

  1. Matrix isolation infrared spectra of hydrogen halide and halogen complexes with nitrosyl halides

    NASA Technical Reports Server (NTRS)

    Allamandola, Louis J.; Lucas, Donald; Pimentel, George C.

    1982-01-01

    Matrix isolation infrared spectra of nitrosyl halide (XNO) complexes with HX and X2 (X = Cl, Br) are presented. The relative frequency shifts of the HX mode are modest (ClNO H-Cl, delta-nu/nu = -0.045; BrNO H-Br, delta-nu/nu = -0.026), indicating weak hydrogen bonds 1-3 kcal/mol. These shifts are accompanied by significant shifts to higher frequencies in the XN-O stretching mode (CIN-O HCl, delta-nu/nu = +0.016; BrN-O HBr, delta-nu/nu = +0.011). Similar shifts were observed for the XN-O X2 complexes (ClN-O Cl2, delta-nu/nu = +0.009; BrN-O-Br2, delta-nu/nu = +0.013). In all four complexes, the X-NO stretching mode relative shift is opposite in sign and about 1.6 times that of the NO stretching mode. These four complexes are considered to be similar in structure and charge distribution. The XN-O frequency shift suggests that complex formation is accompanied by charge withdrawal from the NO bond ranging from about .04 to .07 electron charges. The HX and X2 molecules act as electron acceptors, drawing electrons out of the antibonding orbital of NO and strengthening the XN-O bond. The implications of the pattern of vibrational shifts concerning the structure of the complexes are discussed.

  2. Spectroscopic effects of disorder and vibrational localization in mixed-halide metal-halide chain solids

    SciTech Connect

    Love, S.P.; Scott, B.; Worl, L.A.; Huckett, S.C.; Saxena, A.; Huang, X.Z.; Bishop, A.R.; Swanson, B.I.

    1993-02-01

    Resonance Raman techniques, together with lattice-dynamics and Peierls-Hubbard modelling, are used to explore the electronic and vibrational dynamics of the quasi-one-dimensional metal-halogen chain solids [Pt(en){sub 2}][R(en){sub 2}X{sub 2}](ClO{sub 4}){sub 4}, (en = C{sub 2}H{sub 8}N{sub 2} and X=Cl, Br), abbreviated ``PLX.`` The mixed-halide materials PtCl{sub 1-x}Br{sub x} and PtCl{sub 1-x}I{sub x} consist of long mixed chains with heterojunctions between segments of the two constituent materials. Thus, in addition to providing mesoscale modulation of the chain electronic states, they serve as prototypes for elucidating the properties to be expected for macroscopic heterojunctions of these highly nonlinear materials. Once a detailed understanding of the various local vibrational modes occurring in these disordered solids is developed, the electronic structure of the chain segments and junctions can be probed by tuning the Raman excitation through their various electronic resonances.

  3. Valence and Conduction Band Densities of States of Metal Halide Perovskites: A Combined Experimental-Theoretical Study.

    PubMed

    Endres, James; Egger, David A; Kulbak, Michael; Kerner, Ross A; Zhao, Lianfeng; Silver, Scott H; Hodes, Gary; Rand, Barry P; Cahen, David; Kronik, Leeor; Kahn, Antoine

    2016-07-21

    We report valence and conduction band densities of states measured via ultraviolet and inverse photoemission spectroscopies on three metal halide perovskites, specifically methylammonium lead iodide and bromide and cesium lead bromide (MAPbI3, MAPbBr3, CsPbBr3), grown at two different institutions on different substrates. These are compared with theoretical densities of states (DOS) calculated via density functional theory. The qualitative agreement achieved between experiment and theory leads to the identification of valence and conduction band spectral features, and allows a precise determination of the position of the band edges, ionization energy and electron affinity of the materials. The comparison reveals an unusually low DOS at the valence band maximum (VBM) of these compounds, which confirms and generalizes previous predictions of strong band dispersion and low DOS at the MAPbI3 VBM. This low DOS calls for special attention when using electron spectroscopy to determine the frontier electronic states of lead halide perovskites. PMID:27364125

  4. Valence and Conduction Band Densities of States of Metal Halide Perovskites: A Combined Experimental–Theoretical Study

    PubMed Central

    2016-01-01

    We report valence and conduction band densities of states measured via ultraviolet and inverse photoemission spectroscopies on three metal halide perovskites, specifically methylammonium lead iodide and bromide and cesium lead bromide (MAPbI3, MAPbBr3, CsPbBr3), grown at two different institutions on different substrates. These are compared with theoretical densities of states (DOS) calculated via density functional theory. The qualitative agreement achieved between experiment and theory leads to the identification of valence and conduction band spectral features, and allows a precise determination of the position of the band edges, ionization energy and electron affinity of the materials. The comparison reveals an unusually low DOS at the valence band maximum (VBM) of these compounds, which confirms and generalizes previous predictions of strong band dispersion and low DOS at the MAPbI3 VBM. This low DOS calls for special attention when using electron spectroscopy to determine the frontier electronic states of lead halide perovskites. PMID:27364125

  5. Electrolytic systems and methods for making metal halides and refining metals

    SciTech Connect

    Holland, Justin M.; Cecala, David M.

    2015-05-26

    Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

  6. A Photoferroelectric Perovskite-Type Organometallic Halide with Exceptional Anisotropy of Bulk Photovoltaic Effects.

    PubMed

    Sun, Zhihua; Liu, Xitao; Khan, Tariq; Ji, Chengmin; Asghar, Muhammad Adnan; Zhao, Sangen; Li, Lina; Hong, Maochun; Luo, Junhua

    2016-05-23

    Perovskite-type ferroelectrics composed of organometallic halides are emerging as a promising alternative to conventional photovoltaic devices because of their unique photovoltaic effects (PVEs). A new layered perovskite-type photoferroelectric, bis(cyclohexylaminium) tetrabromo lead (1), is presented. The material exhibits an exceptional anisotropy of bulk PVEs. Upon photoexcitation, superior photovoltaic behaviors are created along its inorganic layers, which are composed of corner-sharing PbBr6 octahedra. Semiconducting activity with remarkable photoconductivity is achieved in the vertical direction, showing sizeable on/off current ratios (>10(4) ), which compete with the most active photovoltaic material CH3 NH3 PbI3 . In 1 the temperature-dependence of photovoltage coincides fairly well with that of polarization, confirming the dominant role of ferroelectricity in such highly anisotropic PVEs. This finding sheds light on bulk PVEs in ferroelectric materials, and promotes their application in optoelectronic devices. PMID:27088882

  7. Radiative properties of ceramic metal-halide high intensity discharge lamps containing additives in argon plasma

    NASA Astrophysics Data System (ADS)

    Cressault, Yann; Teulet, Philippe; Zissis, Georges

    2016-07-01

    The lighting represents a consumption of about 19% of the world electricity production. We are thus searching new effective and environment-friendlier light sources. The ceramic metal-halide high intensity lamps (C-MHL) are one of the options for illuminating very high area. The new C-MHL lamps contain additives species that reduce mercury inside and lead to a richer spectrum in specific spectral intervals, a better colour temperature or colour rendering index. This work is particularly focused on the power radiated by these lamps, estimated using the net emission coefficient, and depending on several additives (calcium, sodium, tungsten, dysprosium, and thallium or strontium iodides). The results show the strong influence of the additives on the power radiated despite of their small quantity in the mixtures and the increase of visible radiation portion in presence of dysprosium.

  8. Ion Segregation and Deliquescence of Alkali Halide Nanocrystals on SiO2

    NASA Astrophysics Data System (ADS)

    Arima, Kenta; Jiang, Peng; Lin, Deng-Sung; Verdaguer, Albert; Salmeron, Miquel

    2009-08-01

    The adsorption of water on alkali halide (KBr, KCl, KF, NaCl) nanocrystals on SiO2 and their deliquescence was investigated as a function of relative humidity (RH) from 8% to near saturation by scanning polarization force microscopy. At low humidity, water adsorption solvates ions at the surface of the crystals and increases their mobility. This results in a large increase in the dielectric constant, which is manifested in an increase in the electrostatic force and in an increase in the apparent height of the nanocrystals. Above 58% RH, the diffusion of ions leads to Ostwald ripening, where larger nanocrystals grow at the expense of the smaller ones. At the deliquescence point, droplets were formed. For KBr, KCl, and NaCl, the droplets exhibit a negative surface potential relative to the surrounding region, which is indicative of the preferential segregation of anions to the air/solution interface.

  9. Charge Transfer Dynamics between Carbon Nanotubes and Hybrid Organic Metal Halide Perovskite Films.

    PubMed

    Schulz, Philip; Dowgiallo, Anne-Marie; Yang, Mengjin; Zhu, Kai; Blackburn, Jeffrey L; Berry, Joseph J

    2016-02-01

    In spite of the rapid rise of metal organic halide perovskites for next-generation solar cells, little quantitative information on the electronic structure of interfaces of these materials is available. The present study characterizes the electronic structure of interfaces between semiconducting single walled carbon nanotube (SWCNT) contacts and a prototypical methylammonium lead iodide (MAPbI3) absorber layer. Using photoemission spectroscopy we provide quantitative values for the energy levels at the interface and observe the formation of an interfacial dipole between SWCNTs and perovskite. This process can be ascribed to electron donation from the MAPbI3 to the adjacent SWCNT making the nanotube film n-type at the interface and inducing band bending throughout the SWCNT layer. We then use transient absorbance spectroscopy to correlate this electronic alignment with rapid and efficient photoexcited charge transfer. The results indicate that SWCNT transport and contact layers facilitate rapid charge extraction and suggest avenues for enhancing device performance. PMID:26757105

  10. Metal-halide perovskites for photovoltaic and light-emitting devices.

    PubMed

    Stranks, Samuel D; Snaith, Henry J

    2015-05-01

    Metal-halide perovskites are crystalline materials originally developed out of scientific curiosity. Unexpectedly, solar cells incorporating these perovskites are rapidly emerging as serious contenders to rival the leading photovoltaic technologies. Power conversion efficiencies have jumped from 3% to over 20% in just four years of academic research. Here, we review the rapid progress in perovskite solar cells, as well as their promising use in light-emitting devices. In particular, we describe the broad tunability and fabrication methods of these materials, the current understanding of the operation of state-of-the-art solar cells and we highlight the properties that have delivered light-emitting diodes and lasers. We discuss key thermal and operational stability challenges facing perovskites, and give an outlook of future research avenues that might bring perovskite technology to commercialization. PMID:25947963