An official website of the United States government
Abstract The performance of large‐area perovskite solar cells (PSCs) has been assessed for typical compositions, such as methylammonium lead iodide (MAPbI3), using a blade coater, slot‐die coater, solution shearing, ink‐jet printing, and thermal evaporation. However, the fabrication of large‐area all‐inorganic perovskite films is not well developed. This study develops, for the first time, an eco‐friendly solvent engineered all‐inorganic perovskite ink of dimethyl sulfoxide (DMSO) as a main solvent with the addition of acetonitrile (ACN), 2‐methoxyethanol (2‐ME), or a mixture of ACN and 2‐ME to fabricate large‐area CsPbI2.77Br0.23films with slot‐die coater at low temperatures (40–50 °C). The perovskite phase, morphology, defect density, and optoelectrical properties of prepared with different solvent ratios are thoroughly examined and they are correlated with their respective colloidal size distribution and solar cell performance. The optimized slot‐die‐coated CsPbI2.77Br0.23perovskite film, which is prepared from the eco‐friendly binary solvents dimethyl sulfoxide:acetonitrile (0.8:0.2 v/v), demonstrates an impressive power conversion efficiency (PCE) of 19.05%. Moreover, the device maintains ≈91% of its original PCE after 1 month at 20% relative humidity in the dark. It is believed that this study will accelerate the reliable manufacturing of perovskite devices.
more »
« less
Soft Lattice and Defect Covalency Rationalize Tolerance of β‐CsPbI 3 Perovskite Solar Cells to Native Defects
Abstract Although all‐inorganic metal halide perovskites (MHPs) have shown tremendous improvement, they are still inferior to the hybrid organic–inorganic MHPs in efficiency. Recently, a conceptually new β‐CsPbI3perovskite reached 18.4 % efficiency combined with good thermodynamic stability at ambient conditions. We use ab initio non‐adiabatic molecular dynamics to show that native point defects in β‐CsPbI3are generally benign for nonradiative charge recombination, regardless of whether they introduce shallow or deep trap states. These results indicate that MHPs do not follow the simple models used to explain defect‐mediated charge recombination in the conventional semiconductors. The strong tolerance is due to the softness of the perovskite lattice, which permits separation of electrons and holes upon defect formation, and only allows carriers to couple to the low‐frequency vibrations. Both factors decrease notably the non‐adiabatic coupling and slow down the dissipation of energy to heat.
more »
« less
- Award ID(s):
- 1809085
- PAR ID:
- 10135472
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie International Edition
- Volume:
- 59
- Issue:
- 16
- ISSN:
- 1433-7851
- Page Range / eLocation ID:
- p. 6435-6441
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract All‐inorganic CsPbI3quantum dots (QDs) have shown great potential in photovoltaic applications. However, their performance has been limited by defects and phase stability. Herein, an anion/cation synergy strategy to improve the structural stability of CsPbI3QDs and reduce the pivotal iodine vacancy (VI) defect states is proposed. The Zn‐doped CsPbI3(Zn:CsPbI3) QDs have been successfully synthesized employing ZnI2as the dopant to provide Zn2+and extra I−. Theoretical calculations and experimental results demonstrate that the Zn:CsPbI3QDs show better thermodynamic stability and higher photoluminescence quantum yield (PLQY) compared to the pristine CsPbI3QDs. The doping of Zn in CsPbI3QDs increases the formation energy and Goldschmidt tolerance factor, thereby improving the thermodynamic stability. The additional I−helps to reduce theVIdefects during the synthesis of CsPbI3QDs, resulting in the higher PLQY. More importantly, the synergistic effect of Zn2+and I−in CsPbI3QDs can prevent the iodine loss during the fabrication of CsPbI3QD film, inhibiting the formation of newVIdefect states in the construction of solar cells. Consequently, the anion/cation synergy strategy affords the CsPbI3quantum dot solar cells (QDSC) a power conversion efficiency over 16%, which is among the best efficiencies for perovskite QDSCs.more » « less
-
Abstract Dimethylammonium lead iodide (DMAPbIx) has the potential to address the phase stability issue of inorganic perovskite solar cells (PSCs). In this study, the crystallinity, phase structure, defect states, and crystal growth habits of DMAPbIxare controlled by adjusting thexvalue during synthesis, where N,N‐dimethylacetamide (DMAC) is used as the solvent to regulate perovskite film growth. Furthermore, large‐area CsPbI2.85Br0.15perovskite films with preferred oriented growth are achieved using the optimizedxvalue in DMAPbIxthrough the slot‐die coating method. The inorganic PSCs, with a n‐i‐p structure and the active area of 0.04 cm2, achieve a champion power conversion efficiency (PCE) of 19.82%, with an open‐circuit voltage (Voc) of 1.16 V based on perovskite films formed by slot‐die coating. This work provides important insights into the DMAPbIx‐based method for fabricating high‐quality inorganic perovskite films, and paves the way for large‐area inorganic PSCs fabrication for practical applications.more » « less
-
Abstract All‐inorganic lead halide perovskite nanocrystals (NCs) have great optoelectronic properties with promising applications in light‐emitting diodes (LEDs), lasers, photodetectors, solar cells, and photocatalysis. However, the intrinsic toxicity of Pb and instability of the NCs impede their broad applications. Shell‐coating is an effective method for enhanced environmental stability while reducing toxicity by choosing non‐toxic shell materials such as metal oxides, polymers, silica, etc. However, multiple perovskite NCs can be encapsulated within the shell material and a uniform epitaxial‐type shell growth of well‐isolated NCs is still challenging. In this work, lead‐free vacancy‐ordered double perovskite Cs2SnX6(X = Cl, Br, and I) shells are epitaxially grown on the surface of CsPbX3NCs by a hot‐injection method. The effectiveness of the non‐toxic double perovskite shell protection is demonstrated by the enhanced environmental and phase stability against UV illumination and water. In addition, the photoluminescence quantum yields (PL QYs) increase for the CsPbCl3and CsPbBr3NCs after shelling because of the type I band alignment of the core/shell materials, while enhanced charge transport properties obtained from CsPbI3/Cs2SnI6core/shell NCs are due to the efficient charge separation in the type II core/shell band alignment.more » « less
-
Abstract Tailoring the doping of semiconductors in heterojunction solar cells shows tremendous success in enhancing the performance of many types of inorganic solar cells, while it is found challenging in perovskite solar cells because of the difficulty in doping perovskites in a controllable way. Here, a small molecule of 4,4′,4″,4″′‐(pyrazine‐2,3,5,6‐tetrayl) tetrakis (N,N‐bis(4‐methoxyphenyl) aniline) (PT‐TPA) which can effectively p‐dope the surface of FAxMA1−xPbI3(FA: HC(NH2)2; MA: CH3NH3) perovskite films is reported. The intermolecular charge transfer property of PT‐TPA forms a stabilized resonance structure to accept electrons from perovskites. The doping effect increases perovskite dark conductivity and carrier concentration by up to 4737 times. Computation shows that electrons in the first two layers of octahedral cages in perovskites are transferred to PT‐TPA. After applying PT‐TPA into perovskite solar cells, the doping‐induced band bending in perovskite effectively facilitates hole extraction to hole transport layer and expels electrons toward cathode side, which reduces the charge recombination there. The optimized devices demonstrate an increased photovoltage from 1.12 to 1.17 V and an efficiency of 23.4% from photocurrent scanning with a stabilized efficiency of 22.9%. The findings demonstrate that molecular doping is an effective route to control the interfacial charge recombination in perovskite solar cells which is in complimentary to broadly applied defect passivation techniques.more » « less
