10101-63-0Relevant articles and documents
Synthetic Variation and Structural Trends in Layered Two-Dimensional Alkylammonium Lead Halide Perovskites
Paritmongkol, Watcharaphol,Dahod, Nabeel S.,Stollmann, Alexia,Mao, Nannan,Settens, Charles,Zheng, Shao-Liang,Tisdale, William A.
, p. 5592 - 5607 (2019)
We report the cooling-induced crystallization of layered two-dimensional (2D) lead halide perovskites with controllable inorganic quantum-well thicknesses (n = 1, 2, 3, and 4), organic-spacer chain lengths (butyl-, pentyl-, and hexylammonium), A-site cations (methylammonium and formamidinium), and halide anions (iodide and bromide). Using single-crystal X-ray diffraction, we refined crystal structures for the iodide family as a function of these compositional parameters and across their temperature-dependent phase transitions. In general, lower-symmetry crystal structures, increasing extents of organic-spacer interdigitation, and increasing organic-spacer corrugation tilts are observed at low temperature. Moreover, greater structural distortions are observed in lead halide octahedra closest to the organic-spacer layer, and higher-n structures exhibit periodic variation in Pb-I bond lengths. These structural trends are used to explain corresponding temperature-dependent changes in the photoluminescence spectra. We also provide detailed guidance regarding the combination of synthetic parameters needed to achieve phase-pure crystals of each composition and discuss difficulties encountered when trying to synthesize particular members of the 2D perovskite family containing formamidinium or cesium as the A-site cation. These results provide a foundation for understanding structural trends in 2D lead halide perovskites and the effects these trends have on their thermal, electronic, and optical properties.
Imai, I.
, p. 81 - 86 (1961)
Chemical and Size Characterization of Layered Lead Iodide Quantum Dots via Optical Spectroscopy and Atomic Force Microscopy
Mu, R.,Tung, Y. S.,Ueda, A.,Henderson, D. O.
, p. 19927 - 19932 (1996)
Lead iodide (PbI2) clusters were synthesized from the chemical reaction of NaI (or KI) with Pb(NO3)2 in H2O, D2O, CH3OH, and C3H7OH solvents.The observation of absorption features between the 550 and 350 nm region obtained with an integrating sphere stron
Balarew, D.
, p. 51 - 57 (1934)
Role of Gravity in the Formation of Liesegang Patterns
Garcia-Ruiz, J. M.,Rondon, D.,Garcia-Romero, A.,Otalora, F.
, p. 8854 - 8860 (1996)
We report the results obtained in four different kinds of experiments designed to test the effect of gravity on the formation of Liesegang patterns.Both reacting solutions (KI and Pb(NO3)2) were gelled with agarose L.The position of the PbI2 precipitates was determined by image analysis, and the kinetic coefficients km = (Xn+1 - Xn)/Xn and kp = (Xn/A)1/n were obtained at different relative orientations of the gravitational field with respect to the direction of the advance of the precipitation front.We conclude that there is not an apparent influence of the gravitational forces on the kinetics of the pattern formation when it is obtained in gelled media at an agarose concentration of 1percent (w/v).When the experiments were performed with agarose at 0.5percent (w/v) or when one of the reacting solutions was ungelled, our tests show clearly the effect of gravity.
Tsobgny, B.,Videau, J. J.,Portier, J.,Tanguy, B.,Hagenmuller, P.
, p. 170 - 177 (1989)
A novel water-resistant and thermally stable black lead halide perovskite, phenyl viologen lead iodide C22H18N2(PbI3)2
Latini, Alessandro,Quaranta, Simone,Menchini, Francesca,Lisi, Nicola,Di Girolamo, Diego,Tarquini, Ombretta,Colapietro, Marcello,Barba, Luisa,Demitri, Nicola,Cassetta, Alberto
, p. 2616 - 2627 (2020)
A novel black organoammonium iodoplumbate semiconductor, namely phenyl viologen lead iodide C22H18N2(PbI3)2 (PhVPI), was successfully synthesized and characterized. This material showed physical and chemical properties suitable for photovoltaic applications. Indeed, low direct allowed band gap energy (Eg = 1.32 eV) and high thermal stability (up to at least 300 °C) compared to methylammonium lead iodide CH3NH3PbI3 (MAPI, Eg = 1.5 eV) render PhVPI potentially attractive for solar cell fabrication. The compound was extensively characterized by means of X-ray diffraction (performed on both powder and single crystals), UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS), UV-photoelectron spectroscopy (UPS), FT-IR spectroscopy, TG-DTA, and CHNS analysis. Reactivity towards water was monitored through X-ray powder diffraction carried out after prolonged immersion of the material in water at room temperature. Unlike its methyl ammonium counterpart, PhVPI proved to be unaffected by water exposure. The lack of reactivity towards water is to be attributed to the quaternary nature of the nitrogen atoms of the phenyl viologen units that prevents the formation of acid-base equilibria when in contact with water. On the other hand, PhVPI's thermal stability was evaluated by temperature-controlled powder XRD measurements following an hour-long isothermal treatment at 250 and 300 °C. In both cases no signs of decomposition could be detected. However, the compound melted incongruently at 332 °C producing, upon cooling, a mostly amorphous material. PhVPI was found to be slightly soluble in DMF (～5 mM) and highly soluble in DMSO. Nevertheless, its solubility in DMF can be dramatically increased by adding an equimolar amount of DMSO. Therefore, phenyl viologen lead iodide can be amenable for the fabrication of solar devices by spin coating as actually done for MAPI-based cells. The crystal structure, determined by means of single crystal X-ray diffraction using synchrotron radiation, turned out to be triclinic and consequently differs from the prototypal perovskite structure. In fact, it comprises infinite double chains of corner-sharing PbI6 octahedra along the a-axis direction with phenyl viologen cations positioned between the columns. Finally, the present determination of PhVPI's electronic band structure achieved through UPS and UV-Vis DRS is instrumental in using the material for solar cells.
Reentrant Structural and Optical Properties and Large Positive Thermal Expansion in Perovskite Formamidinium Lead Iodide
Fabini, Douglas H.,Stoumpos, Constantinos C.,Laurita, Geneva,Kaltzoglou, Andreas,Kontos, Athanassios G.,Falaras, Polycarpos,Kanatzidis, Mercouri G.,Seshadri, Ram
, p. 15392 - 15396 (2016)
The structure of the hybrid perovskite HC(NH2)2PbI3(formamidinium lead iodide) reflects competing interactions associated with molecular motion, hydrogen bonding tendencies, thermally activated soft octahedral rotations, and the propensity for the Pb2+lone pair to express its stereochemistry. High-resolution synchrotron X-ray powder diffraction reveals a continuous transition from the cubic α-phase (Pm3m, #221) to a tetragonal β-phase (P4/mbm, #127) at around 285 K, followed by a first-order transition to a tetragonal γ-phase (retaining P4/mbm, #127) at 140 K. An unusual reentrant pseudosymmetry in the β-to-γ phase transition is seen that is also reflected in the photoluminescence. Around room temperature, the coefficient of volumetric thermal expansion is among the largest for any extended crystalline solid.
High purity lead iodide for crystal growth and its characterization
Eckstein, J.,Erler, B.,Benz, K. W.
, p. 537 - 544 (1992)
High-purity lead iodide (PbI2) is prepared by precipitation of lead nitrate (Pb(NO3)) and potassium iodide (KI) solutions. Thoroughly dried PbI2 is then zone-refined. The main impurity causing strong adherence of the solidified melt to the glass ampoule wall is identified as lead hydroxyl iodate (Pb(OH)I). In order to decrease the OH- concentration and consequently the deviation from stoichiometry, molten PbI2 is treated with a gaseous mixture of methylene iodide (CH2I2) and iodoethane (C2H5I). The criterion for the efficiency of this scavenging process is the removal of the adhesive effect; thus, the solidified PbI2 ingot can move freely in the ampoule. A wet chemical analytic method for determining the deviations from stoichiometry is described.
Heintz, E. A.
, p. 64 - 68 (1961)
Hybrid Perovskites with Larger Organic Cations Reveal Autocatalytic Degradation Kinetics and Increased Stability under Light
Ellis, Christie L. C.,Javaid, Hamza,Smith, Emily C.,Venkataraman
, p. 12176 - 12186 (2020)
Hybrid organic-inorganic perovskites have shown incredible promise as active materials for photovoltaic devices, but their instability to light remains a significant roadblock in realizing these applications. Changing the organic cation has been shown to affect light-induced degradation. As a strategy for increasing the stability of these materials, we replaced varying percentages of methylammonium ion in the archetypical methylammonium lead iodide (MAPbI3) hybrid organic-inorganic perovskite with three significantly larger organic ammonium cations: imidazolium, dimethylammonium, and guanidinium. We were able to synthesize hybrid organic-inorganic perovskites with the same 3D perovskite structure as MAPbI3 with substitution of the larger ions as high as 20-30%. These substituted hybrid organic-inorganic perovskites retained similar optoelectronic properties. We discovered that the light-induced degradation in MAPbI3 and its substituted derivatives is autocatalytic, and we calculated rate coefficients for the degradation. All of the substituted hybrid organic-inorganic perovskites showed light-induced degradation slower than that of MAPbI3, up to a 62% decrease in degradation rate coefficient, at all substitution percentages up to 20%. This work provides evidence that a high percentage of a variety of large ammonium cations can be substituted into the hybrid organic-inorganic perovskite lattice without compromising its desirable optoelectronic properties. Insight into the autocatalytic mechanism of light-induced degradation will be valuable for designing additional strategies to improve the stability of hybrid organic-inorganic perovskites. We also offer insights into how factors other than size, such as hydrogen bonding, influence the stability of the materials. Overall, we have shown that substitution of methylammonium ion for the much larger imidazolium, dimethylammonium, and guanidinium cations in MAPbI3 is a valid strategy for creating stable hybrid organic-inorganic perovskite derivatives by slowing the rate of light-induced degradation.
Bolam, T. R.
, p. 463 - 470 (1928)
Denham, H. G.
, p. 29 - 41 (1917)
Inherent electrochemistry of layered post-transition metal halides: The unexpected effect of potential cycling of PbI2
Chua, Chun Kiang,Sofer, Zdenk,Lim, Chee Shan,Pumera, Martin
, p. 3073 - 3078 (2015)
The development of two-dimensional nanomaterials has expedited the growth of advanced technological applications. PbI2 is a layered inorganic solid with important and unique properties suitable for applications in the detection of electromagnetic radiation. While the optical and electrical properties of layered PbI2 have been generally established, its electrochemistry has remained largely unexplored. In this work, we examine the inherent electrochemistry of PbI2 in relation to its morphological and structural properties. A direct comparison between commercially available and solution-grown PbI2 showed high similarity in properties based on characterizations by X-ray photoelectron spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The respective layered PbI2 materials also exhibited similar inherent electrochemistry. Electrochemical potential cycling of PbI2 in phosphate buffer resulted in the dissolution of iodide ions from PbI2 to form complex lead-phosphate-chloride with the oxygen groups of the phosphate ions while retaining the hexagonal structure. In the cas of KCl solution, the formation of PbO2 was observed.
Hybrid Organic-Inorganic Coordination Complexes as Tunable Optical Response Materials
Travis, Will,Knapp, Caroline E.,Savory, Christopher N.,Ganose, Alex M.,Kafourou, Panagiota,Song, Xingchi,Sharif, Zainab,Cockcroft, Jeremy K.,Scanlon, David O.,Bronstein, Hugo,Palgrave, Robert G.
, p. 3393 - 3400 (2016)
Novel lead and bismuth dipyrido complexes have been synthesized and characterized by single-crystal X-ray diffraction, which shows their structures to be directed by highly oriented π-stacking of planar fully conjugated organic ligands. Optical band gaps are influenced by the identity of both the organic and inorganic component. Density functional theory calculations show optical excitation leads to exciton separation between inorganic and organic components. Using UV-vis, photoluminescence, and X-ray photoemission spectroscopies, we have determined the materials' frontier energy levels and show their suitability for photovoltaic device fabrication by use of electron- and hole-transport materials such as TiO2 and spiro-OMeTAD respectively. Such organic/inorganic hybrid materials promise greater electronic tunability than the inflexible methylammonium lead iodide structure through variation of both the metal and organic components.
Solvent-Mediated Crystallization of CH3NH3SnI3 Films for Heterojunction Depleted Perovskite Solar Cells
Hao, Feng,Stoumpos, Constantinos C.,Guo, Peijun,Zhou, Nanjia,Marks, Tobin J.,Chang, Robert P. H.,Kanatzidis, Mercouri G.
, p. 11445 - 11452 (2015)
Organo-lead halide perovskite solar cells have gained enormous significance and have now achieved power conversion efficiencies of ～20%. However, the potential toxicity of lead in these systems raises environmental concerns for widespread deployment. Here we investigate solvent effects on the crystallization of the lead-free methylammonium tin triiodide (CH3NH3SnI3) perovskite films in a solution growth process. Highly uniform, pinhole-free perovskite films are obtained from a dimethyl sulfoxide (DMSO) solution via a transitional SnI2·3DMSO intermediate phase. This high-quality perovskite film enables the realization of heterojunction depleted solar cells based on mesoporous TiO2 layer but in the absence of any hole-transporting material with an unprecedented photocurrent up to 21 mA cm-2. Charge extraction and transient photovoltage decay measurements reveal high carrier densities in the CH3NH3SnI3 perovskite device which are one order of magnitude larger than CH3NH3PbI3-based devices but with comparable recombination lifetimes in both devices. The relatively high background dark carrier density of the Sn-based perovskite is responsible for the lower photovoltaic efficiency in comparison to the Pb-based analogues. These results provide important progress toward achieving improved perovskite morphology control in realizing solution-processed highly efficient lead-free perovskite solar cells.
Reaction products of methylene iodide with tertiary arsines
Gigauri,Arabuli,Machaidze,Rusiya
, p. 240 - 243 (2005)
The reactions products of tertiary arsines with methylene iodide are (iodomethyl)trialkyl(aryl)-arsonium iodides. Treatment of the latter with lead(II) nitrate in aqueous ethanol solutions gives rise to an exchange reaction to form the corresponding nitra
Synthesis, Raman spectroscopy and dielectric properties of Ag:Mn co-doped nanostructured PbI2 for solid state radiation detectors
Yahia,Abutalib
, p. 215 - 221 (2017)
Microwave-assisted synthesis of pure and Ag: Mn co-doped PbI2 nanostructures have been reported for the first time. The structural and vibrational confirmations were carried out by X-ray diffraction and FT-Raman spectroscopic analysis. Furtherm
Stabilization of Organic-Inorganic Perovskite Layers by Partial Substitution of Iodide by Bromide in Methylammonium Lead Iodide
Ruess, Raffael,Benfer, Felix,B?cher, Felix,Stumpp, Martina,Schlettwein, Derck
, p. 1505 - 1511 (2016)
Thin films of the methylammonium lead halides CH3NH3Pb(I1-xBrx)3 are prepared on fluorine-doped tin oxide substrates and exposed to humid air in the dark and under illumination. To characterize the st
Ba2PO4I, Sr2PO4I, and Pb2PO4I - A new structure type and three of its representatives
Haberkorn, Robert,Bauer, Jessica,Kickelbick, Guido
, p. 3153 - 3158 (2014)
The compound Pb2PO4I was synthesized via a solid state reaction under inert conditions. None of the known structure types of other compounds of the type M2(P,V,As,Cr)O4(F,Cl,Br,I) provided a similar pattern. Structure solution was carried out by evaluation of an X-ray diffractogram of polycrystalline powder using the methods simulated annealing and difference Fourier. Pb2PO4I crystallizes in the/space group P21/c with the lattice parameters a = 9.0451(1) ?, b = 8.7593(1) ?, c = 8.5740(1) ?, and β = 111.128(1)° . The isotypic compounds Sr2PO4I and Ba2PO4I were synthesized, too. Their crystallographic structure was refined by Rietveld analysis. The structure of the three compounds is described and discussed.
Chatterji, A. C.,Bhagwan, H.
, p. 232 - 236 (1958)
Blachnik, R.,Stoeter, U.
, p. 293 - 296 (1989)
Insight on the optoelectronics and enhanced dielectric properties of strontium decorated PbI2 nanosheets for hot carrier solar cell applications
Mariappan, S. Muthu,Shkir, Mohd,Alshahrani,Elangovan,Algarni,AlFaify
, (2021)
Dielectric properties determine by electric field distributions play a decisive role in energy harvesting and storage applications. In this context, strontium decorated lead iodide nanosheets (Sr:PbI2) are prepared, and its vibrational and dielectric properties are studied. The bandgap changes are explained by Brustein-Moss effect and renormalization process. Raman spectral studies reveal that introducing Sr atoms into PbI2 lattice enhance the lifetime of LO phonon through bottleneck effect. Subsequently, the dielectric constant (ε′) values of 5 wt% Sr:PbI2 are increased 20% than pure PbI2. The results conclude that the vibrational properties of Sr decorated PbI2 nanosheets are much significant for hot carrier solar cell devices.
Deposition of lead iodide films on Rh(1 0 0) electrodes from colloidal solutions - The effect of an iodine adlayer
Yang, Chia-Huei,Yau, Shueh-Lin,Fan, Liang-Jen,Yang, Yaw-Wen
, p. 274 - 284 (2003)
The growth of PbI2 precipitates on single crystal substrates from colloidal solutions has been investigated with in air scanning tunneling microscopy and synchrotron-based X-ray photoelectron spectroscopy. The PbI2 growth on Rh(1 0 0) results in nano-clusters with lateral dimensions between 30 and 60 ?, consistent with earlier reports. However, the growth of PbI2 on a well-ordered iodinated Rh(1 0 0), denoted as (√2 × √2)R45°-I, leads to atomically smooth PbI2 films having a hexagonal symmetry with lattice constant identical to the bulk value of 4.5 ?. The heteroepitaxy is believed to be effected by the atomic iodine monolayer that helps to accommodate large lattice mismatch between PbI2 and Rh surface with short-range van der Waals interaction.
Synthesis, physico-chemical characterization and structure of the elusive hydroxylammonium lead iodide perovskite NH3OHPbI3
D'Annibale, Andrea,Panetta, Riccardo,Tarquini, Ombretta,Colapietro, Marcello,Quaranta, Simone,Cassetta, Alberto,Barba, Luisa,Chita, Giuseppe,Latini, Alessandro
, p. 5397 - 5407 (2019)
The synthesis of hydroxylammonium lead iodide NH3OHPbI3 was accomplished by means of the reaction between water solutions of HI and NH2OH with PbI2 in sulfolane in conjunction with either crystallization by CH2Cl2 vapor diffusion or sulfolane extraction with toluene. The appropriate choice of the solvent was found to be crucial in order to attain the desired material. The synthesized compound was extensively characterized by single crystal and powder X-ray diffraction, UV-Vis diffuse reflectance spectroscopy, FT-IR spectroscopy, 1H-NMR spectroscopy, TG-DTA-QMS EGA (Evolved Gas Analysis), ESI-MS, and CHNS analysis. NH3OHPbI3 is an extremely reactive, deliquescent solid that easily oxidizes in air releasing iodine. Furthermore, it is the first reported perovskite to melt (m.p. around 80 °C) before decomposing exothermally at 103 °C. Such a chemical behavior, together with its optical absorption properties (i.e. yellow-colored perovskite), renders this material totally unsuitable for photovoltaic applications. The deliquescence of the material is to be ascribed to the strong hydrophilicity of hydroxylammonium ion. On the other hand, the relatively high Br?nsted acidity of hydroxylammonium (pKa = 5.97) compared to other ammonium cations, promotes the reduction of atmospheric oxygen to water and the NH3OHPbI3 oxidation. The crystal structure, determined by single crystal X-ray diffraction with synchrotron radiation, is orthorhombic, but differs from the prototypal perovskite structure. Indeed it comprises infinite chains of face-sharing PbI6 octahedra along the c-axis direction with hydroxylammonium cations positioned between the columns, forming layers on the ac plane. The solvent intercalates easily between the layers. The crystal structure is apparently anomalous considering that the expected Goldschmidt's tolerance factor for the system (0.909) lies in the range of a stable prototypal perovskite structure. Therefore, the strong hydrogen bond forming tendency of hydroxylamine is likely to account for the apparent structural anomaly.
Pronounced effect of PbI2 nanoparticles doping on optoelectronic properties of PVA films for photo-electronic applications
Ashraf, I. M.,El-Zahhar, Adel A.,Idris, Abubakr M.,Zkria, Abdelrahman
, (2022/01/24)
Composite films of polyvinyl alcohol/lead iodide (PVA/PbI2) were prepared with different concentrations of PbI2 using low-cost casting process. The characteristics of the prepared films were analyzed by XRD and SEM. The XRD results s
