Thermal degradation of CH3NH3PbI3 perovskite into NH3 and CH3I gases observed by coupled thermogravimetry–mass spectrometry analysis

Juárez-Pérez, Emilio J.; Hawash, Zafer; Raga, Sonia R.; Ono, Luis K.; Qi, Yabing

doi:10.1039/c6ee02016j

Cited by 684 publications

(631 citation statements)

References 21 publications

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“…Juarez-Perez et al reported the chemical decomposition of MAPbI 3 using thermogravimetric analysis and differential thermal analysis, and found that decomposition to CH 3 I, NH 3 , and PbI 2 started at 294 °C. [160] These studies imply that the surface of the MAPbI 3 film decomposed to PbI 2 , CH 3 I, and NH 3 after being heated at >100 °C, and only PbI 2 remained on the surface after CH 3 I and NH 3 evaporated. Decomposition of CH 3 NH 3 + is more likely to happen during the rapid formation of MAPbI 3 from precursor materials.…”

Section: Thermally Induced Chemical Decompositionmentioning

confidence: 99%

Low‐Dimensional Perovskites: From Synthesis to Stability in Perovskite Solar Cells

Yusoff

Nazeeruddin

2017

Advanced Energy Materials

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ruthenium molecular dye, wide absorption range, direct and tunable bandgaps, superior charge carrier mobility, and long carrier diffusion length. [6,[43][44][45] Although it has been synthesized for over 100 years, Mitzi et al. were the first to investigate the electrical properties of tin-based perovskite in 1994, [46] which was later used in numerous devices, including field effect transistors (FETs) and LEDs. [47][48][49] The attention toward metal halide perovskites sparked yet again in 2009, [42] and they were later named one of the most promising emerging technologies in 2016. In brief, metal halide perovskites can be divided into two types based on their crystal structure motif: (i) 3D-structured perovskite (AMX 3 ) and (ii) 2D-structured perovskite (A 2 MX 4 ). The structure of the perovskite could either be 2D or 3D, while the dimensions of the perovskite probably belong to 0D-3D. The term "perovskite" implies to the general class of materials derived from an elemental composition of AMX 3 and demonstrates the crystal structure of perovskite crystal CaTiO 3 , where the divalent metal M resides at the body center and surrounded by six X-anions located at the face centers in an octahedral cluster. The MX 6 in the octahedral cluster may form an extended 3D structure by all-corner-connected type with A-cation sitting at the center. It could also form a 2D perovskite when the 3D perovskite network is cut into one-layer-thick slices along the 〈100〉 direction and separates them apart. In principle, 2D perovskite is the easiest to synthesize because of its natural layered structure, which is held together by weak van der Waals forces. Dou et al. reported the large-scale synthesis of the monolayer (C 4 H 9 NH 3 ) 2 -PbBr 4 by a chemical method. [50] Along the same lines, several groups have prepared and characterized nanomaterials composed of various forms of perovskites. [51][52][53] Also, our group has recently successfully prepared a low-dimensional mixed 2D/3D perovskite using the protonated salt of amino valeric acid iodide (AVAI) as an organic precursor mixed with PbI 2 , in which a yellowish film was containing needle-like crystallite formed. [54] In this topical review, we present the latest advances in the synthesis of low-dimensional perovskites and the growth mechanism to develop a strategy to achieve best performing devices. Later, we focus the instability and a cost-effective solution to circumvent this problem, which is vital for the eventual deployment of perovskite solar cells to consumers market. We present an analysis of the origins for instability in perovskite solar cells, and present a summary of the main achievements and possible future developments of these low-dimensional perovskite. [2,55] Perovskite solar cells have been heralded as one of the most promising emerging technologies in 2016 because of the very high power conversion efficiency of 22% and the low cost of generating electricity compared to even fossil fuels. These are formed with various dimensionalities and can be fully mani...

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Section: Thermally Induced Chemical Decompositionmentioning

confidence: 99%

Low‐Dimensional Perovskites: From Synthesis to Stability in Perovskite Solar Cells

Yusoff

Nazeeruddin

2017

Advanced Energy Materials

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“…These results indicate that the tetragonal phase was transformed into the cubic phase during heat stress application, and the onset temperature of thermal degradation was estimated at 100 °C. The cubic phase of MAPbI 3 perovskite started to decompose while going through the intermediate phase, leaving only PbI 2 once CH 3 I and NH 3 evaporated 38 . In addition to the rapid thermal degradation that took place when the sample was heated for a short time at 100 °C, long-term application (1 h) of heat stress also led to thermal decomposition at lower temperature of 80 °C (Fig.…”

Section: Resultsmentioning

confidence: 99%

“…Juarez-Perez et al . reported the thermal decomposition of MAPbI 3 through thermogravimetric analysis and differential thermal analysis (TG-DTA) coupled with quadrupole mass spectrometry (MS), and reported that MAPbI 3 started to decompose to CH 3 I, NH 3 and PbI 2 at 294 °C 38 . These results indicate that the surface of the MAPbI 3 film decomposed to PbI 2 , CH 3 I, and NH 3 after being heated at >100 °C, and only PbI 2 remained on the surface after CH 3 I and NH 3 evaporated.…”

Section: Resultsmentioning

confidence: 99%

Investigation of Thermally Induced Degradation in CH3NH3PbI3 Perovskite Solar Cells using In-situ Synchrotron Radiation Analysis

Kim¹,

Min²,

Noh³

et al. 2017

Sci Rep

203

111

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In this study, we employ a combination of various in-situ surface analysis techniques to investigate the thermally induced degradation processes in MAPbI3 perovskite solar cells (PeSCs) as a function of temperature under air-free conditions (no moisture and oxygen). Through a comprehensive approach that combines in-situ grazing-incidence wide-angle X-ray diffraction (GIWAXD) and high-resolution X-ray photoelectron spectroscopy (HR-XPS) measurements, we confirm that the surface structure of MAPbI3 perovskite film changes to an intermediate phase and decomposes to CH3I, NH3, and PbI2 after both a short (20 min) exposure to heat stress at 100 °C and a long exposure (>1 hour) at 80 °C. Moreover, we observe clearly the changes in the orientation of CH3NH3 + organic cations with respect to the substrate in the intermediate phase, which might be linked directly to the thermal degradation processes in MAPbI3 perovskites. These results provide important progress towards improved understanding of the thermal degradation mechanisms in perovskite materials and will facilitate improvements in the design and fabrication of perovskite solar cells with better thermal stability.

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“…While Sample E contains 16.8% Cs + in bulk and 52.8% Cs + at the film surface. Although it has been reported that 15% Cs + in Cs 0.15 FA 0.85 PbI 3 PSC is thermally stable, [33] such a high Cs + ratio at perovskite surface can lead to obvious phase Inset of (b) shows the enlarged spectra by five times, which is assigned to Pb 0 impurity. Ratios between g) Pb 2+ to I − and h) Cs + to I − calculated from XPS, UV-vis, XRD, and PL.…”

Section: Stability Of the Mixed Cs X Fa 1−x Pbi 3 Perovskite Solar Cementioning

confidence: 99%

“…[24] For example, the most widely investigated methylammonium (CH 3 NH 3 + or MA) lead iodide (MAPbI 3 ) is reported to undergo a phase transition at 54-57 °C [30,31] and degrade at temperature over 85 °C, [32] suggesting its poor thermal stability. [33] Among other perovskite materials, formamidinium (NH 2 CHNH 2 + or FA) lead iodide (FAPbI 3 ) possesses better thermal stability compared to MAPbI 3 and relatively high device performance among various types of perovskites. [34] However, an obvious drawback is its phase stability in the perovskite structure.…”

Section: Introductionmentioning

confidence: 99%

Combination of Hybrid CVD and Cation Exchange for Upscaling Cs‐Substituted Mixed Cation Perovskite Solar Cells with High Efficiency and Stability

Jiang

Leyden

Qiu

et al. 2017

Adv Funct Materials

Self Cite

174

178

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Mixed cation hybrid perovskites such as Cs [16][17][18] and adjusting the composition of perovskite films, [19][20][21][22] research efforts are also urgently needed to increase the scalability of research findings obtained in research labs and make this technology amenable for industry. There are two main challenges we are still facing.(I) The first is the stability challenge. At present stability of PSCs is still poorer than inorganic semiconductor based solar cells, foe example, crystalline silicon solar cells and thin film copper indium gallium selenide (CIGS) solar cells. [10,[23][24][25] To overcome the instability issue, external protections (e.g., perovskite surface functionalization, [26] utilization of chemically inert electron transport materials, hole transport materials and top electrode, deposition of additional protection layer, etc.) have been attempted. [27][28][29] Stability of the perovskite layer itself is Large-Area Perovskite Solar Modules

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Thermal degradation of CH₃NH₃PbI₃ perovskite into NH₃ and CH₃I gases observed by coupled thermogravimetry–mass spectrometry analysis

Abstract: Thermal gravimetric and differential thermal analysis (TG-DTA) coupled with quadrupole mass spectrometry (MS) and first principles calculations were employed to elucidate the chemical nature of released gases during the thermal decomposition of CH3NH3PbI3.

Cited by 684 publications

References 21 publications

Low‐Dimensional Perovskites: From Synthesis to Stability in Perovskite Solar Cells

Low‐Dimensional Perovskites: From Synthesis to Stability in Perovskite Solar Cells

Investigation of Thermally Induced Degradation in CH3NH3PbI3 Perovskite Solar Cells using In-situ Synchrotron Radiation Analysis

Combination of Hybrid CVD and Cation Exchange for Upscaling Cs‐Substituted Mixed Cation Perovskite Solar Cells with High Efficiency and Stability

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