Sculpting the Electronic Nano-Terrain on a Perovskite Film for Efficient Charge Transport.

Nanopatterned halide perovskites have emerged to improve the performance of optoelectronic devices by controlling the crystallographic and optical properties via morphological modification. However, the correlation between the photophysical property and morphology transformation in nanopatterned perovskite films remains elusive, which hinders the rational design of nanopatterned halide perovskites for optoelectronic devices. In this study, we employed nanoimprinting lithography on a perovskite film to exert a precise control over grain growth and manipulate electronic structures at the level of individual grains. Surface-selective fluorescence lifetime imaging microscopy (FLIM) analyzes the spatiotemporally disentangled geometrical variations in carrier recombination rate and band structure modulation according to different pattern morphologies. Consequently, the stereoscopic mechanism of confined grain growth was unveiled, highlighting the quantitative grain size-based parameters that are crucial for nanoscale material engineering. Notably, the pattern-induced reduction of effective charge mass enabled exclusive control over the subdiffusive carrier transport dynamics on perovskite surfaces, ultimately realizing the surface-selective perovskite photodetectors. The implications of this study are expected to provide valuable guidelines, inspiring innovative design protocols for advancing the next-generation optoelectronic technologies.

Unnatural Hygroscopic Property of Nicotinic Acid by Restructuring Molecular Density: Self-Healing Halide Perovskites.

An unnatural hygroscopic property of nonhygroscopic nicotinic acid (NA) is demonstrated by tuning the intermolecular distance. After addition of NA into methylammonium lead iodide, (MAPbI3) NA molecules are preferentially aligned on the interface of the three-dimensional (3D) MAPbI3 crystal structure by a hydrogen bond. This unique behavior allows NA to be used as a versatile additive to improve the water durability of MAPbI3. After exposure under a high humidity atmosphere (RH 100%, 35 °C), MAPbI3 films with NA exhibited self-healing phenomena against moisture while bare MAPbI3 rapidly lost its own intrinsic property. Density functional theory (DFT) calculations were conducted to reveal how H2O molecules can effectively be absorbed by NA according to its planar molecular density. Also, further optimization of photovoltaic device performances was carried out by investigating the relationship between NA concentration and additive alignment.

Band Alignment Engineering between Planar SnO2 and Halide Perovskites via Two-Step Annealing.

Managing defects in SnO2 is critical for improving the power conversion efficiency (PCE) of halide perovskite-based solar cells. However, typically reported SnO2-based perovskite solar cells have inherent defects in the SnO2 layer, which lead to a lower PCE and hysteresis. Here, we report that a dual-coating approach for SnO2 with different annealing temperatures can simultaneously form a SnO2 layer with high crystallinity and uniform surface coverage. Along with these enhanced physical properties, the dual-coated SnO2 layer shows favorable band alignment with a mixed halide perovskite. After careful optimization of the dual-coating method, the average PCE of the perovskite solar cell based on the dual-coated SnO2 layer increases from 18.07 to 19.23% with a best-performing cell of 20.03%. Note that a facile two-step coating and annealing method can open new avenues to develop SnO2-based perovskite solar cells with stabilized and improved photovoltaic performances.

Grain Boundary Healing of Organic-Inorganic Halide Perovskites for Moisture Stability.

Although organic-inorganic halide perovskite (OIHP)-based photovoltaics have high photoconversion efficiency (PCE), their poor humidity stability prevents commercialization. To overcome this critical hurdle, focusing on the grain boundary (GB) of OIHPs, which is the main humidity penetration channel, is crucial. Herein, pressure-induced crystallization of OIHP films prepared with controlled mold geometries is demonstrated as a GB-healing technique to obtain high moisture stability. When exposed to 85% RH at 30 °C, OIHP films fabricated by pressure-induced crystallization have enhanced moisture stability due to the enlarged OIHP grain size and low-angle GBs. The crystallographic and optical properties indicate the effect of applying pressure onto OIHP films in terms of moisture stability. The photovoltaic devices with pressure-induced crystallization exhibited dramatically stabilized performance and sustained over 0.95 normalized PCE after 200 h at 40% RH and 30 °C.

Methodologies toward Efficient and Stable Cesium Lead Halide Perovskite-Based Solar Cells.

In an attempt to replace thermally vulnerable organic perovskites, considerable research effort has recently been focused on the development of all-inorganic perovskites in the field of photovoltaics. The preceding studies demonstrated that cesium lead halide perovskites are promising candidates for thermally stable and efficient solar cell materials. Here, the recent progress in cesium lead halide perovskite-based solar cells is summarized. Whether organic cations are essential for the superiority of halide perovskites is controversial. However, more than 13% efficient solar cells have been successfully fabricated by employing cesium lead halide perovskites in a short amount of time. The state-of-the-art materials engineering techniques will help to achieve a remarkable photovoltaic performance comparable to that of organic perovskites. In addition, improved understanding of the intrinsic photophysical behaviors will provide new insights that will facilitate further improvements in solar cell applications.

Halide Perovskite Nanopillar Photodetector.

Numerous studies have reported the use of halide perovskites as highly functional light-harvesting materials. The development of optimized compositions and deposition approaches has led to impressive improvements; however, no noticeable breakthrough in performance has been observed for these materials recently. Here, a breakthrough that enables the fabrication of vertically grown halide perovskite (VGHP) nanopillar photodetectors via a nanoimprinting crystallization technique is demonstrated. We used engraved nanopatterned polymer stamps to form VGHP nanopillars during the pressurized crystallization of the softly baked gel state of a methylammonium lead iodide (CH3NH3PbI3, denoted MAPI) film. The VGHP films exhibit much lower defect density and higher conductivity, as supported by current-voltage characteristic measurements and conductive atomic force microscopy measurements. Ultimately, two-terminal lateral photodetectors based on the VGHP nanopillar films show a greatly enhanced photoresponse compared with flat film-based photodetectors. We expect that the deposition method presented here will help surpass the technical limits and contribute to further improvements in various halide-perovskite-based devices.

Improved Stability of Interfacial Energy-Level Alignment in Inverted Planar Perovskite Solar Cells.

Even though poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been commonly used as a hole extraction layer (HEL) for p-i-n perovskite solar cells (PSCs), the cells' photovoltaic performance deteriorates because of the low and unstable work functions (WFs) of PEDOT:PSS versus those of a perovskite layer. To overcome this drawback, we synthesized a copolymer (P(SS- co-TFPMA)) ionomer consisting of PSS and tetrafluoropropylmethacrylate (TFPMA) as an alternative to conventional PEDOT:PSS. The PEDOT:P(SS- co-TFPMA) copolymer solution and its film exhibited excellent homogeneity and high phase stability compared with a physical mixture of TFPMA with PEDOT:PSS solution. During spin coating, a self-organized conducting PEDOT:P(SS- co-TFPMA) HEL evolved and the topmost PEDOT:P(SS- co-TFPMA) film showed a hydrophobic surface with a higher WF compared to that of the pristine PEDOT:PSS film because of its chemically bonded electron-withdrawing fluorinated functional groups. Interestingly, the WF of the conventional PEDOT:PSS film dramatically deteriorated after being coated with a perovskite layer, whereas the PEDOT:P(SS- co-TFPMA) film represented a relatively small influence. Because of the superior energy-level alignment between the HEL and a perovskite layer even after the contact, the open-circuit voltage, short-circuit current, and fill factor of the inverted planar p-i-n PSCs (IP-PSCs) with PEDOT:P(SS- co-TFPMA) were improved from 0.92 to 0.98 V, 18.96 to 19.66 mA/cm2, and 78.96 to 82.43%, respectively, resulting in a 15% improvement in the power conversion efficiency vs that of IP-PSCs with conventional PEDOT:PSS. Moreover, the IP-PSCs with PEDOT:P(SS- co-TFPMA) layer showed not only improved photovoltaic performance but also enhanced device stability due to hydrophobic surface of PEDOT:P(SS- co-TFPMA) film.