Thermodynamic Study of Formamidinium Lead Iodide (CH5N2PbI3) from 5 to 357 K.

In the present study, the molar heat capacity of solid formamidinium lead iodide (CH5N2PbI3) was measured over the temperature range from 5 to 357 K using a precise automated adiabatic calorimeter. In the above temperature interval, three distinct phase transitions were found in ranges from 49 to 56 K, from 110 to 178 K, and from 264 to 277 K. The standard thermodynamic functions of the studied perovskite, namely the heat capacity C°p(T), enthalpy [H0(T) - H0(0)], entropy S0(T), and [G°(T) - H°(0)]/T, were calculated for the temperature range from 0 to 345 K based on the experimental data. Herein, the results are discussed and compared with those available in the literature as measured by nonclassical methods.

Stabilizing lead halide perovskites with quaternary ammonium cations: the case of tetramethylammonium lead iodide.

Organoammonium lead halide perovskites, especially methylammonium lead iodide CH3NH3PbI3, are promising photovoltaic materials, but they are far from commercial applications due in particular to their thermal instability and moisture sensitivity. Here, we present a multitechnique study aimed at investigating the kinetic and thermodynamic stability of the simplest quaternary ammonium lead iodide, tetramethylammonium lead iodide N(CH3)4PbI3. The kinetics of thermal decomposition was studied by X-ray powder diffraction of samples treated in air at different temperatures combined with Rietveld quantitative phase analysis, and by the isoconversional analysis of differential thermal analysis measurements. Evidence for first order kinetics was obtained, with an activation energy of 280-290 kJ mol-1, suggesting that the breaking of the C-N bond is the rate determining step. The composition of the gas phase released under heating was investigated by Knudsen Effusion Mass Spectrometry, giving evidence for the occurrence of the process N(CH3)4PbI3(s) = PbI2(s) + N(CH3)3(g) + CH3I(g), consistent with the kinetic results. Decomposition pressures and thermodynamic properties were derived by Knudsen effusion mass loss experiments, obtaining values of 391.5 ± 2.0 kJ mol-1 and -577.4 ± 4.0 kJ mol-1 for the decomposition and formation enthalpies at 298 K, respectively. The reactivity towards water of N(CH3)4PbI3 was checked by XRD after total and prolonged immersion in water at room temperature. Overall, N(CH3)4PbI3 was found to be thermally much more stable than CH3NH3PbI3, both kinetically and thermodynamically, and much less prone to water-induced degradation, suggesting that the use of a quaternary ammonium cation may be an effective strategy in order to produce more stable materials.

In-vacuum thermolysis of ethane 1,2-diamineborane for the synthesis of ternary borocarbonitrides.

High-temperature (1000 °C) thermolytic decomposition of ethane 1,2-diamineborane (BH3NH2CH2CH2NH2BH3) deposited onto a Cu foil has been performed in an ultra-high-vacuum environment. A combined thermolytic, structural (x-ray diffraction), microscopic (scanning electron microscopy) and spectroscopic (Raman, x-ray photoemission spectroscopy) analysis, has identified a ternary borocarbonitride (BCN) compound as a result of the process. The obtained BCN compound is nanocrystalline, surrounded by crystallites of ammonium hydroxide borate hydrate. The ternary compound presents a 0.2:0.6:0.2 B:C:N composition in the bulk and 0.11:0.76:0.13 stoichiometry at the very surface, richer in C-C networks with respect to the bulk. Furthermore, the resulting BCN compound does not show oxidation at the surface due to the in-vacuum thermolysis of the single precursor.

4,4'-(Anthracene-9,10-diylbis(ethyne-2,1-diyl))bis(1-methyl-1-pyridinium) Lead Iodide C30H22N2Pb2I6: A Highly Luminescent, Chemically and Thermally Stable One-Dimensional Hybrid Iodoplumbate.

A new one-dimensional hybrid iodoplumbate, namely, 4,4'-(anthracene-9,10-diylbis(ethyne-2,1-diyl))bis(1-methyl-1-pyridinium) lead iodide C30H22N2Pb2I6 (AEPyPbI), is reported here for the first time with its complete characterization. The material exhibits remarkable thermal stability (up to 300 °C), and it is unreactive under ambient conditions toward water and atmospheric oxygen, due to the quaternary nature of the nitrogen atoms present in the organic cation. The cation exhibits strong visible fluorescence under ultraviolet (UV) irradiation, and when its iodide is combined with PbI2, it forms AEPyPb2I6, an efficient light-emitting material, with a photoluminescence emission intensity comparable to that of high-quality InP epilayers. The structure determination was obtained using three-dimensional electron diffraction, and the material was extensively studied by using a wide range of techniques, such as X-ray powder diffraction, diffuse reflectance UV-visible spectroscopy, thermogravimetry-differential thermal analysis, elemental analysis, Raman and infrared spectroscopies, and photoluminescence spectroscopy. The emissive properties of the material were correlated with its electronic structure by using state-of-the-art theoretical calculations. The complex, highly conjugated electronic structure of the cation interacts strongly with that of the Pb-I network, giving rise to the peculiar optoelectronic properties of AEPyPb2I6. The material, considering its relatively easy synthesis and stability, shows promise for light-emitting and photovoltaic devices. The use of highly conjugated quaternary ammonium cations may be useful for the development of new hybrid iodoplumbates and perovskites with optoelectronic properties tailored for specific applications.

Synthesis, Structure, and Characterization of 4,4'-(Anthracene-9,10-diylbis(ethyne-2,1-diyl))bis(1-methyl-1-pyridinium) Bismuth Iodide (C30H22N2)3Bi4I18, an Air, Water, and Thermally Stable 0D Hybrid Perovskite with High Photoluminescence Efficiency.

4,4'-(Anthracene-9,10-diylbis(ethyne-2,1-diyl))bis(1-methyl-1-pyridinium) bismuth iodide (C30H22N2)3Bi4I18 (AEPyBiI) was obtained as a black powder by a very simple route by mixing an acetone solution of BiI3 and an aqueous solution of C30H22N2I2. This novel perovskite is air and water stable and displays a remarkable thermal stability up to nearly 300 °C. The highly conjugated cation C30H22N2 2+ is hydrolytically stable, being nitrogen atoms quaternarized, and this accounts for the insensitivity of the perovskite toward water and atmospheric oxygen under ambient conditions. The cation in aqueous solution is highly fluorescent under UV irradiation (emitting yellow-orange light). AEPyBiI as well is intensely luminescent, its photoluminescence emission being more than 1 order of magnitude greater than that of high-quality InP epilayers. The crystal structure of AEPyBiI was determined using synchrotron radiation single-crystal X-ray diffraction. AEPyBiI was extensively characterized using a wide range of techniques, such as X-ray powder diffraction, diffuse reflectance UV-vis spectroscopy, Fourier transform infrared (FTIR) and Raman spectroscopies, thermogravimetry-differential thermal analysis (TG-DTA), elemental analysis, electrospray ionization mass spectroscopy (ESI-MS), and photoluminescence spectroscopy. AEPyBiI displays a zero-dimensional (0D) perovskite structure in which the inorganic part is constituted by binuclear units consisting of two face-sharing BiI6 octahedra (Bi2I9 3- units). The C30H22N2 2+ cations are stacked along the a-axis direction in a complex motif. Considering its noteworthy light-emitting properties coupled with an easy synthesis and environmental stability, and its composition that does not contain toxic lead or easily oxidable Sn(II), AEPyBiI is a promising candidate for environmentally friendly light-emitting devices.

Synthesis and characterization of multiwalled carbon nanotube/FeCo nanocomposites.

Multiwalled carbon nanotube/FeCo nanocomposites were produced by Catalytic Chemical Vapour Deposition using highly porous FeCo-SiO2 aerogels with different loadings and dimensions of FeCo nanoparticles as catalysts. Multiwalled carbon nanotubes with average number of walls depending on the size of the catalyst nanoparticles were obtained. Inside the nanotubes spherical or elliptical FeCo nanoparticles are retained, and the magnetic properties of the resulting nanocomposites were characterized in detail.

Thermodynamic and Kinetic Aspects of Formamidinium Lead Iodide Thermal Decomposition.

We report the results of a multi-technique study on the thermodynamics and kinetics of formamidinium lead iodide (FAPI) thermal decomposition. Thermodynamics was investigated by means of Knudsen effusion techniques. Kinetics was studied either by temperature-controlled powder X-ray diffraction or by two isoconversional treatments of differential scanning calorimetry data. FAPI appears to be much more thermally stable compared to methylammonium lead iodide, as predictable from the lower acidity of the formamidinium cation compared to methylammonium. The chemical processes responsible for its thermal degradation appear to be quite complex as highlighted by the composition of the gaseous phase evolved during the process. The apparent activation energy values of the decomposition obtained from X-ray diffraction (XRD) (112 ± 9 kJ/mol) and differential scanning calorimetry (DSC) measurements (205 ± 20 and 410 ± 20 kJ/mol, respectively, for the first and second decomposition steps identified by the deconvolution procedure) reflect the different steps of the process observed by the two techniques. The thermodynamic properties of the more important decomposition channels and the enthalpy of formation of FAPI were estimated by combining the results of Knudsen effusion measurements.

Two-Dimensional Restructuring of Cu2O Can Improve the Performance of Nanosized n-TiO2/p-Cu2O Photoelectrodes under UV-Visible Light.

p-Cu2O/n-TiO2 photoanodes were produced by electrodeposition of octahedral p-type Cu2O nanoparticles over n-type TiO2 nanotubes. The photoresponse of the composite p-n photoanodes was evaluated in photoelectrochemical cells operating at "zero-bias" conditions under either visible or UV-vis irradiation. In both operating conditions, the produced electrodes invariably followed the p-n-based photoanode operations but exhibited lower photoelectrochemical performance as compared to the bare n-TiO2 photoanode under UV-vis light. The reported experimental analysis evidenced that such decreased photoactivity is mainly induced by the scarce efficiency of the nanosized p-n interfaces upon irradiation. To overcome such limitation, a restructuring of the originally electrodeposited p-Cu2O was promoted, following a photoelectrochemical post-treatment strategy. p-Cu2O, restructured in a 2D leaf-like morphology, allowed reaching an improved photoelectrochemical performance for the p-n-based photoanode under UV-vis light. As compared to the bare n-TiO2 behavior, such improvement consisted of photoanodic currents up to three times larger. An analysis of the mechanisms driving the transition from compact (∼100 nm) octahedral p-Cu2O to wider (∼1 µm) 2D leaf-like structures was performed, which highlighted the pivotal role played by the irradiated n-TiO2 NTs.

Brightly Luminescent and Moisture Tolerant Phenyl Viologen Lead Iodide Perovskites for Light Emission Applications.

Lead halide perovskites are outstanding materials for optoelectronics, but they typically feature low stability against external agents. To overcome this drawback, LHPs based on quaternary ammonium cations, such as phenyl viologen lead iodide (PhVPI), were found to be promising candidates, being water-resistant and thermally stable. In this Letter, the optoelectronic properties of the PhVPI are investigated by a combined experimental-theoretical approach. Although the as-prepared material is photoluminescence-inactive, a short thermal (5 min @ 290 °C) or laser annealing turns PhVPI into a highly luminescent material, in the 600-1000 nm range. The PhVPI PL emission was characterized at different annealing conditions, and the structural evolution following thermal treatments was investigated by means of X-ray diffraction, Raman, and NMR spectroscopies. Besides this, the electronic structure and emission properties were investigated by density functional theory simulations. The intense optical emission and high stability make PhVPI an intriguing material for applications related to light-emitting devices.

A novel water-resistant and thermally stable black lead halide perovskite, phenyl viologen lead iodide C22H18N2(PbI3)2.

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.

Novel Hybrid Composites Based on PVA/SeTiO2 Nanoparticles and Natural Hydroxyapatite for Orthopedic Applications: Correlations between Structural, Morphological and Biocompatibility Properties.

The properties of poly(vinyl alcohol) (PVA)-based composites recommend this material as a good candidate for the replacement of damaged cartilage, subchondral bone, meniscus, humeral joint and other orthopedic applications. The manufacturing process can be manipulated to generate the desired biomechanical properties. However, the main shortcomings of PVA hydrogels are related to poor strength and bioactivity. To overcome this situation, reinforcing elements are added to the PVA matrix. The aim of our work was to develop and characterize a novel composition based on PVA reinforced with Se-doped TiO2 nanoparticles and natural hydroxyapatite (HA), for possible orthopedic applications. The PVA/Se-doped TiO2 composites with and without HA were structurally investigated by FTIR and XRD, in order to confirm the incorporation of the inorganic phase in the polymeric structure, and by SEM and XRF, to evidence the ultrastructural details and dispersion of nanoparticles in the PVA matrix. Both the mechanical and structural properties of the composites demonstrated a synergic reinforcing effect of HA and Se-doped TiO2 nanoparticles. Moreover, the tailorable properties of the composites were proved by the viability and differentiation potential of the bone marrow mesenchymal stem cells (BMMSC) to osteogenic, chondrogenic and adipogenic lineages. The novel hybrid PVA composites show suitable structural, mechanical and biological features to be considered as a promising biomaterial for articular cartilage and subchondral bone repair.

Experimental thermodynamics of high temperature transformations in single-walled carbon nanotube bundles.

The thermodynamic quantities associated to the transformation of carbon in single-walled carbon nanotube (SWCNT) bundles to carbon in graphite were determined from 750 to 1015 K by a CaF2 solid electrolyte galvanic cell: (-) Mo | Cr3C2,CrF2,C'' | CaF2s.c. | Cr3C2,CrF2,C' | Mo (+). The trend with temperature of the electromotive force of the cell was found to be greatly dependent on temperature and fully reversible with it. The standard enthalpy DeltaH(T)(o) and entropy DeltaS(T)(o) changes are 7.1, 6.0, and 60.2 kJ mol(-1) and 8.6, 14.7, and 72.8 J K(-1) mol(-1) at 778, 883, and 975 K, respectively. This most likely correlates with the different arrangements and shapes of tubes that deviate from the ideal triangular closed packed structure of the SWCNT bundles. The constraints to the thermal expansion of bundles in the electrode containing them generated high internal pressures that were responsible for deformations of tube shape and lattice. Stable bundle states were formed that interconvert as a function of temperature. Comparative analyses by low angle XRD, microRaman, and HR-TEM of SWCNT bundles before and after experiments support this scenario. The cohesion energy and associated entropy changes are also reported for such states. The formation enthalpy of unbundled SWCNTs was calculated equal to 9.5 +/- 0.4 kJ mol(-1).

Synthesis, physico-chemical characterization and structure of the elusive hydroxylammonium lead iodide perovskite NH3OHPbI3.

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 Brønsted 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.

Engineering Human-Scale Artificial Bone Grafts for Treating Critical-Size Bone Defects.

The manufacturing of artificial bone grafts can potentially circumvent the issues associated with current bone grafting treatments for critical-size bone defects caused by pathological disorders, trauma, or massive tumor ablation. In this study, we report on a potentially patient-specific fabrication process in which replicas of bone defects, in particular zygomatic and mandibular bones and phalanxes of a hand finger, were manufactured by laser stereolithography and used as templates for the creation of PDMS molds. Gas-in-water foams were cast in the molds, rapidly frozen, freeze-dried, and cross-linked. Since bone matrix consists essentially of collagen and hydroxyapatite, biomimetic scaffolds were fabricated using gelatin and hydroxyapatite in a ratio very similar to that found in bone. The obtained composite scaffolds were excellent replicas of the original bone defects models and presented both a superficial and internal porous texture adequate for cellular and blood vessels infiltration. In particular, scaffolds exhibited a porous texture consisting of pores and interconnects with average size of about 300 and 100 µm, respectively, and a porosity of 90%. In vitro culture tests using hMSCs demonstrated scaffold biocompatibility and capacity in inducing differentiation toward osteoblasts progenitors. In vivo cellularized implants showed bone matrix deposition and recruitment of blood vessels. Overall, the technique/materials combination used in this work led to the fabrication of promising mechanically stable, bioactive, and biocompatible composite scaffolds with well-defined architectures potentially valuable in the regeneration of patient-specific bone defects.

Thermodynamics and the Intrinsic Stability of Lead Halide Perovskites CH3NH3PbX3.

The role of thermodynamics in assessing the intrinsic instability of the CH3NH3PbX3 perovskites (X = Cl,Br,I) is outlined on the basis of the available experimental information. Possible decomposition/degradation pathways driven by the inherent instability of the material are considered. The decomposition to precursors CH3NH3X(s) and PbX2( s) is first analyzed, pointing out the importance of both the enthalpic and the entropic factor, the latter playing a stabilizing role making the stability higher than often asserted. For CH3NH3PbI3, the disagreement between the available calorimetric results makes the stability prediction uncertain. Subsequently, the gas-releasing decomposition paths are discussed, with emphasis on the discrepant results presently available, probably reflecting the predominance of thermodynamic or kinetic control. The competition between the formation of NH3(g) + CH3X(g), CH3NH2(g) + HX(g) or CH3NH3X(g) is analyzed, in comparison with the thermal decomposition of methylammonium halides. In view of the scarce and inconclusive thermodynamic studies to-date available, the need for further experimental data is emphasized.

Screen Printed Pb3O4 Films and Their Application to Photoresponsive and Photoelectrochemical Devices.

A new and simple procedure for the deposition of lead (II, IV) oxide films by screen printing was developed. In contrast to conventional electrochemical methods, films can be also deposited on non-conductive substrates without any specific dimensional restriction, being the only requirement the thermal stability of the substrate in air up to 500 °C to allow for the calcination of the screen printing paste and sintering of the film. In this study, films were exploited for the preparation of both photoresponsive devices and photoelectrochemical cell photoanodes. In both cases, screen printing was performed on FTO (Fluorine-Tin Oxide glass) substrates. The photoresponsive devices were tested with I-V curves in dark and under simulated solar light with different irradiation levels. Responses were evaluated at different voltage biases and under light pulses of different durations. Photoelectrochemical cells were tested by current density⁻voltage (J-V) curves under air mass (AM) 1.5 G illumination, incident photon-to-current efficiency (IPCE) measurements, and electrochemical impedance spectroscopy.

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

This corrects the article DOI: 10.1038/srep31896.

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

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.

Calcium phosphate and fluorinated calcium phosphate coatings on titanium deposited by Nd:YAG laser at a high fluence.

Calcium phosphate coatings are known to enhance long-term fixation, reliability and promote osteointegration of cementless titanium-based implant devices. This study was aimed at the pulsed laser deposition of calcium phosphate coatings onto titanium using hydroxyapatite and hydroxyapatite-fluorapatite targets. The deposition was carried out at the high laser beam fluence conditions, about 12 J/cm(2). The coatings were characterized with respect to their morphology, phase composition and hardness. X-ray energy dispersive analysis revealed the coatings retain their elemental composition, and fluoride content within the film is the same as in the initial target. However, unlike sintered targets, the deposited films contain no apatite-like phases. The hardness of the films, about 18 GPa, is surprisingly high compared to that of hydroxyapatite and hydroxyapatite-fluorapatite ceramic targets. The deposited coatings of 2.7-2.9 microm thickness have uniform and dense microstructure, containing the solidified droplets of the expulsed from the target phase. The uncommon structure and hardness of the films can be attributed to the melting and phase decomposition of the initial material in the laser plasma.