Screening of Functional Small Molecules via Modified Machine Learning Strategy toward Efficient All-Inorganic Perovskite Solar Cells.

Organic small molecules are proven to be capable of passivating the bulk/interfacial defects in inorganic perovskite solar cells. Considering the burdensome situation to screen the functional small molecules, we employ a modified machine learning (ML) strategy to guide screening suitable small molecules toward efficient solar cells through three modified ML algorithms to construct the prediction model: (i) random forest algorithm (RF), (ii) support vector machine algorithm (SVR), and (iii) XGBoost. Among them, the XGBoost algorithm displays a better overall predictive performance, whereby the R2 index reaches 0.939. Accordingly, eight small molecules are selected to modify the interface of perovskite films, and both the theoretical and experimental results certify that the difluorobenzylamine with additional fluorine atoms has a better interface modification effect among the small molecules containing functional groups, e.g., the benzene ring and amino group. The high accuracy of the modified machine learning model enables us to simplify the small-molecule screening process and form an important step for ongoing developments in perovskite solar cells and other optoelectronic devices.

In-Situ Self-Assembly Dipole Shielding Layer Toward Efficient and Stable Inorganic Perovskite Solar Cells.

Despite CsPbI2.75Br0.25 inorganic perovskites exhibit high potential for single-junction and/or tandem solar cells, unexpected non-radiative recombination, and mismatched interfacial band alignment within the inorganic perovskite solar cells (PSCs) disadvantageously affect their photovoltaic performance. Rational design of the dipole shielding layer (DSL) is vital to realize a win-win situation for the defect passivation and band alignment. Herein, A-site dipole molecules, that is, neopentylamine and 2-methylbutylamine, are employed for in-situ self-assembly of a thus-far unreported DSL at the interface between 3D perovskite and hole transport layer. The as-prepared DSL demonstrates a 2D RP phase perovskite and the lattice-matching structurally-stable DSL@3D perovskite enables to alleviate the unexpected surface defects and suppress the spontaneous non-radiative recombination by means of effectively tuning the surface work function via regulating the dipole moment length and Van der Waals gap. Accordingly, the top dipole-modified inorganic PSCs exhibit a champion power conversion efficiency (PSC) as high as 19.77% and a fill factor over 83%. Equally importantly, the corresponding solar cells demonstrate a remarkable enhanced stability, maintaining 90% of its initial efficiency for more than 1200 h without encapsulation under a 20% ± 5% relative humidity.

Emerging lead-free all inorganic perovskite single crystals K7Bi3X16 (X = Cl, Br) toward photodetector application.

Lead-free inorganic perovskites have attracted intensive attention in the field of photodetectors owing to their high stability, non-toxicity, and remarkable photoelectric characteristics. Herein, we designed and developed a series of thus-far unreported lead-free all inorganic perovskite single crystals, K7Bi3X16 (X = Cl, Br). In particular, we resorted to cooling crystallization and intercalated K+ to inorganic Bi-Br and Bi-Cl frameworks as inorganic A-site cations, obtaining zero-dimensional (0D) K7Bi3X16 (X = Cl, Br) perovskite single crystals, which display suitable bandgaps, excellent electron mobility and low trap-state density, as analysed by experimental characterization and density functional theory (DFT) calculations. Accordingly, the vertical structure K7Bi3Br16 photodetector can achieve a fast ON/OFF switch under the irradiation of 395 nm light. When the light intensity is 5 mW cm-2 and the voltage is 3 V, the responsivity is calculated to be 0.052 mA W-1. The above characteristics make K7Bi3Br16 a promising material for fabricating ultraviolet photodetectors.

Accurate Dimension Prediction for Low-Dimensional Organic-Inorganic Halide Perovskites via a Self-Established Machine Learning Strategy.

Low-dimensional perovskites (LDPs) have enormous potential for the development of advanced optoelectronic devices and tackling the stability issue for the commercial application of perovskites. However, quantified structural dimensionality prediction for LDPs is still an intractable issue. Herein, we develop a self-established machine learning (ML)-assisted approach to predict the dimensionality of LDPs based on 195 reported amines that are classified as two-dimensional, one-dimensional, and zero-dimensional. The optimal K-nearest neighbor model allows us to realize an accuracy rate of 92.3% for the test data set containing 39 reported amines. Two features, i.e., ATSC1pe and SlogP_VSA2, associated with polarity and electrostatic potential on the van der Waals surface of an organic spacer, are identified from >1800 descriptors as key controlling factors determining the structure dimensionality. This work develops a typical paradigm for the application of a multiple-classification strategy of ML with an extremely high accuracy rate, which would thereby motivate the development of new types of LDPs.

Temperature Dependent Hydrogen Bond Toward High Emission in an Emerging Indium-Based Perovskite.

Low-dimensional organic-inorganic hybrid perovskites (OIHPs) with broadband emission attract immense scientific interest due to their potential application for the next generation of solid-state lighting. However, due to low exciton utilization, organic cations generally adjust structure rather than contribute the band edge to affect optical properties. Based on this, OIHPs are usually allowed to obtain a low photoluminescence quantum yield (PLQY). Herein, a good charge transfer carrier (p-phenylenediamine, PPDA) as organic cation is rationally employed and a novel indium-based perovskite is synthesized. By coupling with H2 O molecules, a strong interaction between organic and inorganic components is realized by hydrogen bonding, which has good transportability and greatly improves the exciton utilization. The regions of hydrogen bonding show high electron mobility, combined with the induced recombination center, improving the progress of charge relaxation. As a result, the regulation of hydrogen bond strength based on the microstructure optimization directly determines the optical emission intensity, realizing nearly 100% PLQY. Further, the polyhydrogen bond structure makes each component a stronger interaction, showing high stability in polar, organic, and acidic solvent, as well as long-term storing, which represents one of the highest overall performances for lighting in OIHPs.

Octahedral Distortion Co-Regulation via Dual Strategies toward Luminescence Enhancement for the MA4InBr7 Perovskite Single Crystal.

A series of novel perovskite single crystals are innovatively grown. Aiming to enhance the luminescence performance, octahedral distortion co-regulation via dual strategies for the as-prepared perovskite single crystals is performed. The distortion of the octahedral structure strengthens the electron-phonon coupling and electron localization, resulting in a more stable self-trapped state, which thereby increases the potential for radiative recombination, accompanied by the self-trapped exciton emission. Accordingly, the luminescence spectra of the as-prepared MA4In0.975Sb0.025Br7 single crystal can cover the 450-800 nm range, and the photoluminescence quantum yield is up to 81.25%.

Electron Delocalization and Structure Coupling Promoted π-Conjugated Charge Transport in a Novel [Ga-Tpy2]PbI5 Perovskite-like Single Crystal.

Multidimensional perovskite techniques are of intense research interest since they are proved to be advantageous to enhance the perovskite stability. Thereinto, the structure engineering strategy has been widely used to regulate the low dimensional (LD) perovskite structures and obtain expected optoelectronic properties. In this work, we intercalate a thus far unreported metallic coordination compound [Ga-Tpy2]3+ (Tpy: 2,2';6',2″-terpyridine) to the inorganic Pb-I building block as the A-site organic group, and the zero dimensional (0D) [Ga-Tpy2]PbI5 perovskite-like single crystal is obtained. This material displays suitable band edge levels, which enable its potential application as light absorber in solar cells. The DFT calculations manifest delocalized charge distribution on Tpy ligands that can facilitate electron transport, which is attributed to the formation of a double hybrid coordinate bond, i.e., σ bonds and π bonds, between Ga3+ ions and Tpy ligands. These coordinate bonds make metallic complexes promising molecules to regulate structure-associated optoelectronic performances of the LD perovskites.

Architecturing 1D-2D-3D Multidimensional Coupled CsPbI2 Br Perovskites toward Highly Effective and Stable Solar Cells.

Despite the rapid development of CsPbIx Br3- x (0 ≤ x ≤ 3) inorganic perovskite solar cells, associated with their superior thermal stability, their low moisture stability limits their commercial deployment. In this study, 1D-2D-3D multidimensional coupled perovskites are prepared by means of an in situ self-integration approach. This pioneering method allows incorporating thus far unreported 1D-Tpy2 Pb3 I6 and 2D-TpyPb3 I6 (Tpy; terpyridine) perovskites. Heterojunction perovskites demonstrate superior stability against water in comparison with control 3D CsPbI2 Br, which is related to the hydrophobicity of low-dimension (LD) perovskites. Remarkably, the spontaneous involvement of LD perovskites can adjust/reconstruct the interfacial structure. This modification allows releasing the residual strain, establishing effective charge transfer channels that increase the carrier transport ability. Accordingly, 1D-2D-3D hybrid CsPbI2 Br perovskite solar cells demonstrate a stabilized power conversion efficiency as high as 16.1%, which represents a very significant improvement, by a factor of 43%, with respect to control 3D CsPbI2 Br perovskite solar cell. Equally importantly, the multidimensional coupled perovskite solar cells exhibit extraordinary stability, well above 1000 h in ambient atmosphere.

Terpyridine-derived perovskite single crystals with tunable structures and electronic dimensionality.

Dimensionality engineering has proved to be a reliable strategy for addressing the issue of perovskite stability. In this study, a series of previously unreported low-dimensional organic-inorganic hybrid perovskite single crystals were designed and grown by following a simple hydrothermal approach involving solution processing. The as-prepared terpyridine-derived perovskite single crystals displayed tunable structures and electronic dimensionality, which was closely associated with the crystal growth conditions. The performed DFT calculations suggested that the fluctuating conduction band edge demonstrates obvious charge delocalization associated with the π-conjugation effect, a feature promoting efficient charge transport by means of coupling structural dimensionality and electronic dimensionality. This study has provided new ideas for the design of new materials to be used in fields involving photovoltaic devices.

Engineered Electronic Structure and Carrier Dynamics in Emerging Cs2AgxNa1-xFeCl6 Perovskite Single Crystals.

Lead-free double perovskites have attracted noteworthy attention due to their compositional flexibility and electronic diversity. In this study, we hydrothermally grow a new class of Cs2AgxNa1-xFeCl6 (0 ≤ x ≤ 1) perovskite single crystals with high thermal stability. The substitution of B-site cation allows to regulate the crystallographic and band structure, which gives rise to enlarged band absorbance close to the near-infrared region (∼800 nm) via composition engineering. Ultrafast transient absorption spectroscopy (TAS) certifies that the decay time of excited-state absorption is 5.02 and 2450 ps in the case of Cs2NaFeCl6 and Cs2AgFeCl6, respectively. The corresponding charge carrier diffusion length accordingly enhances from 3.7 to 311 nm by means of increasing Ag dopant concentration. Structurally, the primitive cell shrinks due to the partial replacement of [NaCl6]5- octahedra by [AgCl6]5- octahedra. It is proved theoretically as well as experimentally that the introduction of Ag species can effectively enhance the electron mobility (from 1.06 to 15.3 cm2 V-1 s-1) by ∼15 times through realizing stronger orbital coupling of the conductive ions, which enables such a novel double perovskite to be a potential candidate for the optoelectronic and photovoltaic applications.

Controllable Cs xFA1- xPbI3 Single-Crystal Morphology via Rationally Regulating the Diffusion and Collision of Micelles toward High-Performance Photon Detectors.

Cs xFA1- xPbI3 single crystals are expected to provide more excitement in optoelectronic applications, including photodetector, laser, light-emitting diode, etc. Herein, we aim to gain an in-depth understanding of the growth mechanisms of perovskite single crystal with various morphologies in view of microscopic dynamics by the combination of component, structure, and solvent engineering. A sequence of Cs xFA1- xPbI3 (0 ≤ x ≤ 0.14) perovskite single crystals with a dodecahedron morphology and tunable aspect ratio can be obtained by means of a solution-processed uniform-cooling approach. The optimized Cs0.1FA0.9PbI3 single crystals prepared in γ-butyrolactone mixed with dimethyl sulfoxide are theoretically and experimentally demonstrated to have superior performances, e.g., extremely higher long-term stability, lower trap density, and higher mobility. The broadband absorption, i.e., 300-910 nm, enables its application in near-infrared detection (880 nm), and the corresponding detector demonstrates higher responsivity at different light intensities and a fast photocurrent response (τ1 = 11 µs, τ2 = 10 µs). Equally important, we also explore the application of optimized Cs0.1FA0.9PbI3 single crystals with a tunable aspect ratio in an X-ray detector and the extremely high sensitivity (2772.1 µC Gyair-1 cm-2 under a bias of 150 V) demonstrates their good potential for radiation detection.

All-Inorganic CsPbI2Br Perovskite Solar Cells with High Efficiency Exceeding 13.

All-inorganic perovskite solar cells provide a promising solution to tackle the thermal instability problem of organic-inorganic perovskite solar cells (PSCs). Herein, we designed an all-inorganic perovskite solar cell with novel structure (FTO/NiO x/CsPbI2Br/ZnO@C60/Ag), in which ZnO@C60 bilayer was utilized as the electron-transporting layers that demonstrated high carrier extraction efficiency and low leakage loss. Consequently, the as-fabricated all-inorganic CsPbI2Br perovskite solar cell yielded a power conversion efficiency (PCE) as high as 13.3% with a Voc of 1.14 V, Jsc of 15.2 mA·cm-2, and FF of 0.77. The corresponding stabilized power output (SPO) of the device was demonstrated to be ∼12% and remarkably stable within 1000 s. Importantly, the obtained all-inorganic PSCs without encapsulation exhibited only 20% PCE loss with thermal treatment at 85 °C for 360 h, which largely outperformed the organic-species-containing PSCs. The present study demonstrates potential in overcoming the intractable issue concerning the thermal instability of perovskite solar cells.

Efficiency enhancement of Cu2ZnSnS4 solar cells via surface treatment engineering.

Pure-sulphide Cu2ZnSnS4 (CZTS) thin film solar cells were prepared by a low-cost, non-toxic and high-throughput method based on the thermal decomposition and reaction of sol-gel precursor solution, followed by a high temperature sulfurization process in sulphur atmosphere, which usually gave rise to the unexpected Cu-poor and Zn-rich phase after sulfurization. In order to remove the formation of detrimental secondary phases, e.g. ZnS, a novel method with hydrochloric acid solution treatment to the CZTS absorber layer surface was employed. By using this method, a competitive power conversion efficiency as high as 4.73% was obtained, which is a factor of 4.8 of that of the control CZTS solar cell without surface treatment. This presents a customized process for CZTS photovoltaic technologies that is more environmentally friendly and considerably less toxic than the widely used KCN etching approach.

C60 additive-assisted crystallization in CH3NH3Pb0.75Sn0.25I3 perovskite solar cells with high stability and efficiency.

The development of hybrid tin (Sn)-lead (Pb) perovskite solar cells likely tackles the toxic problem with the power conversion efficiency (PCE) exceeding 17%. However, the stability problems, e.g. hysteresis effect, degeneration and oxidation, appear to be the bottleneck that limit its further development. Here, we innovatively introduced C60 at the grain boundaries throughout the CH3NH3Pb0.75Sn0.25I3 (MAPb0.75Sn0.25I3) thin film, playing a role not only in in situ passivating the interfaces and reducing the pinholes of perovskite thin films, but also in preventing the penetration of moisture and oxygen from ambient atmosphere. Electrochemical impedance spectroscopy (EIS) illustrated that the recombination lifetime of both the bulk and surface of MAPb0.75Sn0.25I3 thin films was increased by additive incorporation of C60. Dark I-V results for the electron/hole-only devices showed that the charge trap-state density decreased with C60 additive incorporated into the hybrid Sn-Pb perovskite thin films. Importantly, the hybrid Sn-Pb perovskite solar cells modified with C60 additive were demonstrated to have superior stability and efficiency when exposed to the ambient environment without encapsulation.

Molecular Self-Assembly Fabrication and Carrier Dynamics of Stable and Efficient CH3 NH3 Pb(1-x) Snx I3 Perovskite Solar Cells.

The Sn-based perovskite solar cells (PSCs) provide the possibility of swapping the Pb element toward developing toxic-free PSCs. Here, we innovatively employed a molecular self-assembly approach to obtain a series CH3 NH3 Pb(1-x) Snx I3 (0≤x≤1) perovskite thin films with full coverage. The optimized planar CH3 NH3 Pb0.75 Sn0.25 I3 PSC with inverted structure was consequently realized with a maximum power conversion efficiency (PCE) over 14 %, which displayed a stabilized power output (SPO) over 12 % within 200 s at 0.6 V forward bias. Afterward, we investigated the factors that limited the efficiency improvement of hybrid Sn-Pb PSCs, and analyzed the possible reason of the hysteresis effect occurred even in the inverted structure cell. Particularly, the oxidation of hybrid Sn-Pb perovskite thin film was demonstrated to be the main reason that limited its further efficiency improvement. The imbalance of charge transport was intensified, which was associated with the increased hole defect-state density and decreased electron defect-state density after Sn was introduced. This study helps tackle the intractable issue regarding the toxic Pb in perovskite devices and is a step forward toward realizing lead-free PSCs with high stability and efficiency.

Highly Efficient Perovskite Solar Cells with Substantial Reduction of Lead Content.

Despite organometal halide perovskite solar cells have recently exhibited a significant leap in efficiency, the Sn-based perovskite solar cells still suffer from low efficiency. Here, a series homogeneous CH3NH3Pb(1-x)SnxI3 (0 ≤ x ≤ 1) perovskite thin films with full coverage were obtained via solvent engineering. In particular, the intermediate complexes of PbI2/(SnI2)∙(DMSO)x were proved to retard the crystallization of CH3NH3SnI3, thus allowing the realization of high quality Sn-introduced perovskite thin films. The external quantum efficiency (EQE) of as-prepared solar cells were demonstrated to extend a broad absorption minimum over 50% in the wavelength range from 350 to 950 nm accompanied by a noteworthy absorption onset up to 1050 nm. The CH3NH3Pb0.75Sn0.25I3 perovskite solar cells with inverted structure were consequently realized with maximum power conversion efficiency (PCE) of 14.12%.

High Performance of Perovskite Solar Cells via Catalytic Treatment in Two-Step Process: The Case of Solvent Engineering.

Currently, the potential mechanism of the solvent-assisted crystallization for mixed cations perovskite thin film (FAxMA1-xPbI3) prepared via two-step solution-process still remains obscure. Here, we clarified the molecular-competing-reacted process of NH2CH═NH2I (FAI) and CH3NH3I (MAI) with PbI2(DMSO)x complex in dimethyl sulfoxide (DMSO) and diethyl ether (DE) catalytic solvent system in the sequential two-step solution-process. The microscopic dynamics was characterized via the characterizations of in situ photoluminescence spectra. In addition, we found that the thermal stability of the perovskite films suffered from the residual solvent with high boiling point, for example, DMSO. The further DE treatment could promote the volatility process of DMSO and accelerate the crystallization process of perovskite films. The highest PCE over 19% with slight hysteresis effect was eventually obtained with a reproducible FA0.88MA0.12PbI3 solar cell, which displayed a constant power output within 100 s upon light soaking and stable PCE output within 30 d in the thermal stability test.

Solution-Processed One-Dimensional ZnO@CdS Heterojunction toward Efficient Cu2ZnSnS4 Solar Cell with Inverted Structure.

Kesterite Cu2ZnSnS4 (CZTS) semiconductor has been demonstrated to be a promising alternative absorber in thin film solar cell in virtue of its earth-abundant, non-toxic element, suitable optical and electrical properties. Herein, a low-cost and non-toxic method that based on the thermal decomposition and reaction of metal-thiourea-oxygen sol-gel complexes to synthesize CZTS thin film was developed. The low-dimensional ZnO@CdS heterojunction nano-arrays coupling with the as-prepared CZTS thin film were employed to fabricate a novel solar cell with inverted structure. The vertically aligned nanowires (NWs) allow facilitating the charge carrier collection/separation/transfer with large interface areas. By optimizing the parameters including the annealing temperature of CZTS absorber, the thickness of CdS buffer layer and the morphology of ZnO NWs, an open-circuit voltage (VOC) as high as 589 mV was obtained by such solar cell with inverted structure. The all-solution-processed technic allows the realization of CZTS solar cell with extremely low cost.

Controllable Grain Morphology of Perovskite Absorber Film by Molecular Self-Assembly toward Efficient Solar Cell Exceeding 17%.

The highly developed crystallization process with respect to perovskite thin films is favorable for efficient solar cells. Here, an innovative intermolecular self-assembly approach was employed to retard the crystallization of PbI2 in dimethylformamide (DMF) by additional solvent of dimethyl sulfoxide (DMSO), which was proved to be capable of coordinating with PbI2 by coordinate covalent bond. The obtained PbI2(DMSO)x (0 ≤ x ≤ 1.86) complexes tend to be closely packed by means of intermolecular self-assembly. Afterward, an intramolecular exchange of DMSO with CH3NH3I (MAI) enabled the complexes to deform their shape and finally to reorganize to be an ultraflat and dense thin film of CH3NH3PbI3. The controllable grain morphology of perovskite thin film allows obtaining a power conversion efficiency (PCE) above 17% and a stabilized power output above 16% within 240 s by controlling DMSO species in the complex-precursor system (CPS). The present study gives a reproductive and facile strategy toward high quality of perovskite thin films and efficient solar cells.

Hysteretic Behavior upon Light Soaking in Perovskite Solar Cells Prepared via Modified Vapor-Assisted Solution Process.

Recently, the organic-inorganic hybrid perovskite solar cells exhibit rapidly rising efficiencies, while anomalous hysteresis in perovskite solar cells remains unsolvable. Herein, a high-quality perovskite thin film is prepared by a modified vapor-assisted solution process, which is a simple but well-controllable method proven to be capable of producing a thin film with full surface coverage and grain size up to micrometers. The as-fabricated perovskite solar cell has efficiency as high as 10.2%. The hysteresis effects of both planar and mesoscopic TiO2-based perovskite solar cells have been comprehensively studied upon illumination. The results demonstrate that mesoporous-based perovskite cells combined with remarkable grain size are subject to alleviating the hysteresis effects in comparison to the planar cells. Likewise, mesoscopic TiO2-based perovskite cells perform independently of illumination and bias conditions prior to the measurements, whereas the planar cells display a reversible behavior of illumination and applied bias-dependent I-V curves. The present study would refer strip road for the stability study of the perovskite solar cells.