Stabilizing Perovskite Structures by Tuning Tolerance Factor: Formation of Formamidinium and Cesium Lead Iodide Solid-State Alloys

Li, Zhen; Yang, Mengjin; Park, Ji-Sang; Wei, Su‐Huai; Berry, Joseph J.; Zhu, Kai

doi:10.1021/acs.chemmater.5b04107

Cited by 1,654 publications

(1,514 citation statements)

References 37 publications

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“…[20] This indicates that the introduction of Cs cation into the perovskite precursor solution not only induces the gradual formation of the black perovskite phase by bringing the perovskite system into a new equilibrium state or by suppressing of the hexagonal yellow phase of perovskite but also stabilizes the perovskite phase as well as induces highly uniform perovskite grains. [21] The balanced performance of p-and n-channel PFETs as well as the fact that both transistors strictly behave as normally off transistors at zero gate voltage enables the construction of CMOS like inverters. The circuit consists of two PFETs, with a triple cation as the active layer.…”

Section: Doi: 101002/adma201602940mentioning

confidence: 99%

Ambipolar Triple Cation Perovskite Field Effect Transistors and Inverters

et al. 2016

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and inverters exhibit the best performance among perovskite PFETs. The present work demonstrates that triple cation perovskite can provide the ambipolar PFETs and complementary metal-oxide-semiconductor (CMOS)-like circuits for next generation, large-area microelectronics with low manufacturing cost.The PFETs with bottom contacts and a top gate were constructed by spin coating the triple cation precursor solution in anhydrous dimethylformamide:dimethylsulfoxide (DMF:DMSO) 4:1 (v:v) on the substrates (Figure 1a). The perovskite solution was deposited in two steps at 1000 and 6000 rpm for 10 and 30 s, respectively. Solvent treatment was conducted during the second step, where 100 µL chlorobenzene was poured on the spinning substrate followed by annealing at 100 °C for 1 h. Triple cation PFETs with various Cs amounts were fabricated, and their respective transfer and output characteristics are compared in Figures S1-S6 (Supporting Information). Figures S1-S6 (Supporting Information) illustrate transfer curves of the ambipolar triple cation PFETs, and I DS 1/2 versus V DS plot as a function of Cs cation. As Cs increased from 0% to 10%, the mobility increased monotonically from 1.95 × 10 −2 to 1.25 cm 2 V −1 s −1 for holes and from 4.81 × 10 −2 to 4.11 × 10 −2 cm 2 V −1 s −1 for electrons (Table S1, Supporting Information). However, no significant change in the charge-carrier mobilities was observed when Cs is higher than 15%. Figure 1b,c demonstrates the transfer characteristics for the p-and n-channel PFETs (Cs = 15%), respectively, with poly(methyl methacrylate) (PMMA) as a gate dielectric, in which ambipolar charge-transport characteristics were observed. Figure 1d,e represents the typical output characteristics with good current modulation. PMMA was selected since it can be processed at low temperature, soluble in a solvent orthogonal to triple cation, and contains negligible OH groups that could trap electrons. When V DS is low, the potential for the hole and electron injection cannot exceed the threshold voltage simultaneously. As a result, only one carrier can be accumulated, and the devices work in the unipolar model. Under these conditions, the transistors exhibit a very high I ON /I OFF ratio, typically higher than 10 4 at a high gate voltage (V GS = 130 V). The charge-carrier mobilities were determined using the drain current (I DS ) in the saturation region; Table S1 (Supporting Information) summarizes the maximum and average p-and n-channel mobilities. The maximum µ h and µ e mobilities are calculated to be 2.1 and 2.5 cm 2 V −1 s −1 , respectively. To the best of our knowledge, this is the highest carrier mobility for the perovskite PFETs. [17] The incorporation of Cs cation (Cs = 0%-30%) has notable effect on the performance of ambipolar triple cation PFETs.We have exposed freshly prepared PFETs to ambient air and monitored the p-and n-channel performance as a function of Organolead halide perovskites (ABX 3 where A is organic or inorganic cation, B is metal cation, and X is halogen anion) have signi...

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Section: Doi: 101002/adma201602940mentioning

confidence: 99%

Ambipolar Triple Cation Perovskite Field Effect Transistors and Inverters

et al. 2016

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“…3,37,38 Experimentally, it has been demonstrated that mixing a small amount of inorganic cations such as Cs + with methylammonium (CH 3 NH 3 + , i.e., MA + )/formamidinium (CH 3 (NH 2 ) 2 + , i.e., FA + ) at the A site significantly increases the stabilities of perovskite films. 2,[39][40][41] Contrast to the organicinorganic hybrid perovskites, purely inorganic CsPbX VII 3 perovskites exhibit excellent thermal stability. 3,38 Secondly, because the upper group-IVA elements such as Sn and Ge at the M IV site tend to be oxidized from divalent Sn 2+ /Ge 2+ to tetravalent Sn 4+ /Ge 4+ , 32,[42][43][44] and thus cause the instability issue, current halide perovskite based solar cells with high PCEs exclusively contain the toxic element -Pb.…”

Section: Introductionmentioning

confidence: 99%

Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation

et al. 2017

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Hybrid organic-inorganic halide perovskites with the prototype material of CH 3 NH 3 PbI 3 have recently attracted intense interest as low-cost and high-performance photovoltaic absorbers. Despite the high power conversion efficiency exceeding 20% achieved by their solar cells, two key issues -the poor device stabilities associated with their intrinsic material instability and the toxicity due to water soluble Pb 2+ -need to be resolved before large-scale commercialization. Here, we address these issues by exploiting the strategy of cation-transmutation to design stable inorganic Pb-free halide perovskites for solar cells. The idea is to convert two divalent Pb 2+ ions into one monovalent M + and one trivalent M 3+ ions, forming a rich class of quaternary halides in double-perovskite structure. We find through first-principles calculations this class of materials have good phase stability against decomposition and wide-range tunable optoelectronic properties. With photovoltaic-functionality-directed materials screening, we identify eleven optimal materials with intrinsic thermodynamic stability, suitable band gaps, small carrier effective masses, and low excitons binding energies as promising candidates to replace Pb-based photovoltaic absorbers in perovskite solar cells. The chemical trends of phase stabilities and electronic properties are also established for this class of materials, offering useful guidance for the development of perovskite solar cells fabricated with them.

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“…), solution deposition is a simple and low-cost way to fabricate high efficiency PSCs. [5][6][21][22][23][24][25][26][27][28][29][30][31] Several researches have been reported in obtaining high quality perovskite films based on growth engineering, solvent engineering and so on. In 2016, M. Dar and his coworkers studied the impact of chloride on the conversion of lead halide into CH3NH3PbI3.…”

Section: Introductionmentioning

confidence: 99%

Stitching triple cation perovskite by a mixed anti-solvent process for high performance perovskite solar cells

et al. 2017

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With the rapid development of organic-inorganic lead halide perovskite photovoltaics, increasingly more attentions are paid to explore the growth mechanism and precisely control the quality of perovskite films. In this study, we propose a "stitching effect" to fabricate high quality perovskite films by using chlorobenzene (CB) as an anti-solvent and isopropyl alcohol (IPA) as an additive into this anti-solvent. Because of the existence of IPA, CB can be efficiently released from the gaps of perovskite precursors and the perovskite film formation can be slightly modified in a controlled manner. More homogeneous surface morphology and larger grain size of perovskite films were achieved via this process. The reduced grain boundaries ensure low surface defect density and good carrier transport in the perovskite layer. Meanwhile, we also performed the Fourier transform infrared (FTIR) spectroscopy to investigate the film growth mechanism of unannealed and annealed perovskite films. Solar cells fabricated by using the "stitching effect" exhibited a best efficiency of 19.2%. Our results show that solvent and solvent additives dramatically influenced the formation and crystallization processes for perovskite materials due to their different coordination and extraction capabilities. This method presents a new path towards controlling the growth and morphology of perovskite films.

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Stabilizing Perovskite Structures by Tuning Tolerance Factor: Formation of Formamidinium and Cesium Lead Iodide Solid-State Alloys

Cited by 1,654 publications

References 37 publications

Ambipolar Triple Cation Perovskite Field Effect Transistors and Inverters

Ambipolar Triple Cation Perovskite Field Effect Transistors and Inverters

Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation

Stitching triple cation perovskite by a mixed anti-solvent process for high performance perovskite solar cells

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