Search

Material synthesis is one of the most important aspects in humankinds' endeavor to discover and create new materials for energy applications. One strategy to tailor materials with desired functions in a rational way is by knowing how functions relate to structure, synthetic variables, arrangement of atoms and molecules, and how functions evolve during synthesis. In order to accelerate materials synthesis, discovery, and optimization by 10 times it is the right time now to integrate computational tools, synthesis, and characterization. One particular barrier to realizing this concept is the understanding of when and how phases form in real time during synthesis, which is challenging to asses by existing theoretical frameworks. In addition, transient or metastable phases with positive free energy above the lowest‐free energy ground state can be revealed by such real time (in situ) measurements. Metastable materials are ubiquitous in condensed matter and can show superior properties compared to their equilibrium form. This essay discusses the value of emerging multimodal in situ characterizations exemplified on hybrid halide perovskites. Finally, the ways in which the implementation of in situ measurements can advance the materials science synthesis field as well as their role to enable close‐loop feedback control and autonomous synthesis are discussed. [ABSTRACT FROM AUTHOR]

Halide perovskites have emerged as materials for high‐performance optoelectronic devices. Often, progress made to date in terms of higher efficiency and stability is based on increasing material complexity, i.e., formation of multicomponent halide perovskites with multiple cations and anions. In this review article, the use of in situ optical methods, namely, photoluminescence (PL) and UV‐vis, that provide access to the relevant time and length scales to ascertain chemistry–property relationships by monitoring evolving properties is discussed. Additionally, because halide perovskites are electron/ion conductors and prone to solid‐state ion transport under various external stimuli, application of these optical methods in the context of ionic movement is described to reveal mechanistic insights. Finally, examples of using in situ PL and UV‐vis to study degradation and phase transitions are reviewed to demonstrate the wealth of information that can be obtained regarding many different aspects of ongoing research activities in the field of halide perovskites. [ABSTRACT FROM AUTHOR]

Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH2)2CsPb-halide (FACsPb-) and CH3NH3Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials. However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells. [ABSTRACT FROM AUTHOR]

The thin-film vapor-liquid-solid (TF-VLS) growth technique presents a promising route for high quality, scalable, and cost-effective InP thin films for optoelectronic devices. Toward this goal, careful optimization of material properties and device performance is of utmost interest. Here, we show that exposure of polycrystalline Zn-doped TF-VLS InP to a hydrogen plasma (in the following referred to as hydrogenation) results in improved optoelectronic quality as well as lateral optoelectronic uniformity. A combination of low temperature photoluminescence and transient photocurrent spectroscopy was used to analyze the energy position and relative density of defect states before and after hydrogenation. Notably, hydrogenation reduces the relative intragap defect density by 1 order of magnitude. As a metric to monitor lateral optoelectronic uniformity of polycrystalline TF-VLS InP, photoluminescence and electron beam induced current mapping reveal homogenization of the grain versus grain boundary upon hydrogenation. At the device level, we measured more than 260 TF-VLS InP solar cells before and after hydrogenation to verify the improved optoelectronic properties. Hydrogenation increased the average open-circuit voltage (VOC) of individual TF-VLS InP solar cells by up to 130 mV and reduced the variance in VOC for the analyzed devices. [ABSTRACT FROM AUTHOR]

Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH3NH3PbI3-xBrx perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamic range. The internal luminescence quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ Eg ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells. [ABSTRACT FROM AUTHOR]

Cu2ZnSnS4 (CZTS) layers are deposited by a direct solution coating of metal salts dissolved in dimethyl sulfoxide (DMSO) and thiourea as sulphur source. An intentional Sn-rich precursor is used and the influence of reactive and inert atmosphere on the layer morphology is investigated during high temperature sintering. Larger grain growth is observed when annealing the precursor in inert N2 atmosphere as compared to reactive sulphur atmosphere. An initial Sn-rich precursor composition with Zn/Sn < 1 promotes the grain growth while Sn leaves the sample during crystallization ending up with a final Zn-rich (Zn/Sn > 1) layer composition. [ABSTRACT FROM AUTHOR]

Cu2ZnSn(S,Se)4thin layers processed fromsolution-deposited earth-abundant precursors emerge as absorber materialsfor low-cost thin film solar cells. A frequently observed drawbackof the chemical solution processingpoor crystallinity of thechalcogenide absorbercan be overcome by employing a sodium-containingreactive agent. We demonstrate a massive improvement in grain growthin the presence of sodium. It enhances the surface chemisorption ofselenium molecules and can promote the formation of liquid Na2Sexphases during reactive annealingof the precursor. The sodium is also incorporated into the semiconductorabsorber and significantly modifies its electronic properties. Byadjusting the sodium precursor quantity, it is possible to tune dopinglevels and gradients to maximize the collection of photogeneratedcarriers in thin film Cu2ZnSn(S,Se)4solar cells.The presented approach can be extended to other solution-processedmetal chalcogenides to enhance their structural and electronic properties,which are critical for applications such as thin film solar cellsand transistors. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) have been investigated recently in perovskite photovoltaics owing to their potential to boost optoelectronic performance and device stability. However, the impact of variations in the MOF side chain on perovskite characteristics and the mechanism of MOF/perovskite film formation remains unclear. In this study, three nanoscale thiol‐functionalized UiO‐66‐type Zr‐based MOFs (UiO‐66‐(SH)2, UiO‐66‐MSA, and UiO‐66‐DMSA) are systematically employed and examined in perovskite solar cells (PSCs). Among these MOFs, UiO‐66‐(SH)2, with its rigid organic ligands, exhibited a strong interaction with perovskite materials with more efficient suppression of perovskite vacancy defects. More importantly, A detailed and in‐depth discussion is provided on the formation mechanism of UiO‐66‐(SH)2‐assisted perovskite film upon in situ GIWAXS performed during the annealing process. The incorporation of UiO‐66‐(SH)2 additives substantially facilitates the conversion of PbI2 into the perovskite phase, prolongs the duration of stage I, and induces a delayed phase transformation pathway. Consequently, the UiO‐66‐(SH)2‐assisted device demonstrates reduced defect density and superior optoelectronic properties with optimized power conversion efficiency of 24.09% and enhanced long‐term stability under ambient environment and continuous light illumination conditions. This study acts as a helpful design guide for desired MOF/perovskite structures, enabling further advancements in MOF/perovskite optoelectronic devices. [ABSTRACT FROM AUTHOR]

The introduction of chiral organic spacers in low‐dimensional metal‐halide perovskites triggers chiroptical activity, which is appealing for spintronic applications. However, a comprehensive understanding of structure formation and the ability to control phase purity in such materials have yet to be developed. Herein, the impact of processing conditions on the phase purity, microstructure, and chiroptical properties of chiral 2D perovskites is explored. The anisotropic emergence of a 1D perovskite inside the 2D matrix and its dependence on the organic cation chirality, solvent, and thermal annealing conditions are shown. By controlling these parameters, the in‐plane conductivity of the films is nearly doubled. Furthermore, it is demonstrated, for the first time, that solvent choice and the spatial configuration of the organic cation can have an impact on the residual lattice strain and the energetic disorder of the system. The fundamentals presented here can help to improve the film deposition methods for low‐dimensional chiral perovskites, offering strategies to control phase purity. [ABSTRACT FROM AUTHOR]

Simultaneously optimizing the processing parameters of functional thin films remains a challenge. The design and utilization of a fully automated platform called SPINBOT is presented for the engineering of solution‐processed functional thin films. The SPINBOT is capable of performing experiments with high sampling variability through the unsupervised processing of hundreds of substrates with exceptional experimental control. Through the iterative optimization process enabled by the Bayesian optimization (BO) algorithm, the SPINBOT explores an intricate parameter space, continuously improving the quality and reproducibility of the produced thin films. This machine learning (ML)‐guided reliable SPINBOT platform enables the acceleration of the optimization process of perovskite solar cells via a simple photoluminescence characterization of films. As a result, this study arrives at an optimal film that, when processed into a solar cell in an ambient atmosphere, immediately yields a champion power conversion efficiency (PCE) of 21.6% with satisfactory performance reproducibility. The unsealed devices retain 90% of their initial efficiency after 1100 h of continuous operation at 60–65 °C under metal‐halide lamps. It is anticipated that the integration of robotic platforms with the intelligent algorithm will facilitate the widespread adoption of effective autonomous experimentation to address the evolving needs and constraints within the materials science research community. [ABSTRACT FROM AUTHOR]

Wide‐bandgap perovskites are of paramount importance as the photoactive layer of the top cell in high‐efficiency tandem solar cells. Comparably high Br contents are required to widen the perovskite bandgap. However, the increase in Br content causes heterogeneous halide distribution and photoinstability. Here, the positive effect of the additive methylammonium chloride (MACl) on the optical and electronic properties of Br‐rich perovskite, deposited using N‐methyl‐2‐pyrrolidone (NMP) as co‐solvent and the gas quenching method, is investigated. Simultaneous in situ grazing‐incidence wide‐angle X‐ray scattering and photoluminescence spectroscopy are used to track the evolution of the structural and optoelectronic properties of the perovskites with different amounts of Br and MACl during the spin‐coating and thermal annealing steps. The formation mechanism is elucidated in the presence of MACl. It is observed that chloride ions inhibit the intermediate phases, favoring the formation of a perovskite phase with higher crystallinity. Nano X‐ray fluorescence mapping recognizes Br‐richer and poorer nanometric domains, whose average sizes reduce for samples with MACl. In conclusion, it is demonstrated that adding MACl affects the formation of wide‐bandgap perovskites via destabilization of the intermediate phases and acts on the homogenization of the halide distribution, leading to improved solar cell performances. [ABSTRACT FROM AUTHOR]

Using in situ photoluminescence measurements during the spin‐coating and annealing steps, this study probes the formation of 2D layers on 3D triple cation perovskite films comparing phenylethylammonium and 2‐thiophenemethylammonium iodide bulky cations. This study elucidates the formation mechanisms of the surface layers for both cases and reveals two regimes during 2D layer formation: a kinetic‐driven and a thermodynamic‐driven process. These driving forces result in different compositions of the 2D/3D interface for each treatment, namely, different ratios of pure 2D (n = 1) and quasi‐2D (n > 1) structures. This study shows that a higher ratio of quasi‐2D phases is more beneficial for device performance, as pure‐2D layers may hamper current extraction. Due to a more evenly distributed formation energy profile among 2D and quasi‐2D phases, highly concentrated 2‐thiophenemethylammonium iodide appears to be more suited for effective surface passivation than its phenylethylammonium analog. [ABSTRACT FROM AUTHOR]

The non-toxic and wide bandgap material TiO2 is explored as an n-type buffer layer on p-type Cu(In,Ga)Se2 (CIGS) absorber layer for thin film solar cells. The amorphous TiO2 thin film deposited by atomic layer deposition process at low temperatures shows conformal coverage on the CIGS absorber layer. Solar cells from non-vacuum deposited CIGS absorbers with TiO2 buffer layer result in a high short-circuit current density of 38.9 mA/cm2 as compared to 36.9 mA/cm2 measured in the reference cell with CdS buffer layer, without compromising open-circuit voltage. The significant photocurrent gain, mainly in the UV part of the spectrum, can be attributed to the low parasitic absorption loss in the ultrathin TiO2 layer (~10 nm) with a larger bandgap of 3.4 eV compared to 2.4 eV of the traditionally used CdS. Overall the solar cell conversion efficiency was improved from 9.5% to 9.9% by substituting the CdS by TiO2 on an active cell area of 10.5 mm2. Optimized TiO2/CIGS solar cells show excellent long-term stability. The results imply that TiO2 is a promising buffer layer material for CIGS solar cells, avoiding the toxic CdS buffer layer with added performance advantage. [ABSTRACT FROM AUTHOR]

NaTaO3 is a stable and wide bandgap n‐type semiconductor material with many different applications. Here, a flux‐mediated synthesis method is presented for NaTaO3 resulting in highly distinctive, substrate covering shapes via precursor chemistry variation at comparatively low temperatures. It is found that the microstructure of the resulting NaTaO3 films can be varied from nanocubes to smooth thin films. These shapes and surface chemistries can be correlated by employing density functional theory calculations and surface sensitive X‐ray photoemission spectroscopy. This study provides guidance on how to synthesize the material and tailor its shape and surface termination for different applications. Finally, as a proof of concept of one possible application, NaTaO3 is applied to perovskite solar cells as the electron transport layer, resulting in conversion efficiencies of >19%. This study provides a new strategy for designing ternary oxide thin films for renewable energy applications. [ABSTRACT FROM AUTHOR]

All‐inorganic perovskites have emerged as promising photovoltaic materials due to their superior thermal stability compared to their heat‐sensitive hybrid organic–inorganic counterparts. In particular, CsPbI2Br shows the highest potential for developing thermally‐stable perovskite solar cells (PSCs) among all‐inorganic compositions. However, controlling the crystallinity and morphology of all‐inorganic compositions is a significant challenge. Here, a simple, thermal gradient‐ and antisolvent‐free method is reported to control the crystallization of CsPbI2Br films. Optical in situ characterization is used to investigate the dynamic film formation during spin‐coating and annealing to understand and optimize the evolving film properties. This leads to high‐quality perovskite films with micrometer‐scale grain sizes with a noteworthy performance of 17% (≈16% stabilized), fill factor (FF) of 80.5%, and open‐circuit voltage (VOC) of 1.27 V. Moreover, excellent phase and thermal stability are demonstrated even after extreme thermal stressing at 300 °C. [ABSTRACT FROM AUTHOR]

The design and performance of solar cells based on InP grown by the nonepitaxial thin-film vapor-liquid-solid (TF-VLS) growth technique is investigated. The cell structure consists of a Mo back contact, p-InP absorber layer, n-TiO2 electron selective contact, and indium tin oxide transparent top electrode. An ex situ p-doping process for TF-VLS grown InP is introduced. Properties of the cells such as optoelectronic uniformity and electrical behavior of grain boundaries are examined. The power conversion efficiency of first generation cells reaches 12.1% under simulated 1 sun illumination with open-circuit voltage ( VOC) of 692 mV, short-circuit current ( JSC) of 26.9 mA cm−2, and fill factor (FF) of 65%. The FF of the cell is limited by the series resistances in the device, including the top contact, which can be mitigated in the future through device optimization. The highest measured VOC under 1 sun is 692 mV, which approaches the optically implied VOC of ≈795 mV extracted from the luminescence yield of p-InP. [ABSTRACT FROM AUTHOR]

Chirality is a desired property in functional semiconductors for optoelectronic, catalytic, and spintronic applications. Here, introducing enantiomerically‐pure 3‐aminobutyric acid (3‐ABA) into thin films of the 1D semiconductor dimethylammonium lead iodide (DMAPbI3) is found to result in strong circular dichroism (CD) in the optical absorption. X‐ray diffraction and grazing incidence small angle X‐ray scattering (GISAXS) are applied to gain molecular‐scale insights into the chirality transfer mechanism, which is attributed to a chiral surface modification of DMAPbI3 crystallites. This study demonstrates that the CD signal strength can be controlled by the amino‐acid content relative to the crystallite surface area. The CD intensity is tuned by the composition of the precursor solution and the spin‐coating time, thereby achieving anisotropy factors (gabs) as high as 1.75 × 10–2. Grazing incidence wide angle scattering reveals strong preferential ordering that can be suppressed via tailored synthesis conditions. Different contributions to the chiroptical properties are resolved by a detailed analysis of the CD signal utilizing an approach based on the Mueller matrix model. This report of a novel class of chiral hybrid semiconductors with precise control over their optical activity presents a promising approach for the design of circularly polarized light detectors and emitters. [ABSTRACT FROM AUTHOR]

The article focuses on wide-bandgap (WBG) mixed-halide perovskites as the front cell absorber are accomplishing perovskite-based tandem solar cells with over 29% power conversion efficiency. Topics include the large voltage deficits limit their ultimate performance, and the studies probe the fundamental mechanisms underlying the voltage deficits, which remain an unsolved challenge in the field.

In the article "Optimizing Perovskite Thin-Film Parameter Spaces with Machine Learning-Guided Robotic Platform for High-Performance Perovskite Solar Cells," Jiyun Zhang, Yicheng Zhao, Christoph J. Brabec, and their colleagues introduce the SPINBOT, an automated platform that uses machine learning to optimize solution-processed perovskite thin films. The platform efficiently explores various parameters to produce high-quality and reproducible films. The optimized film achieved an impressive 21.6% power conversion efficiency (PCE) in solar cells under ambient conditions, along with excellent long-term stability. [Extracted from the article]

The exploration of the synthetic space of halide perovskites hinges on an enormous number of parameters requiring time‐consuming experimentation to decouple and optimize. Here, the formation of the prototype material CH3NH3PbI3 (MAPbI3) is investigated at different time and length scales using multimodal in situ measurements to monitor the evolution of crystalline phases, morphology, and photoluminescence as a function of the lead precursors. Kinetically fast formation of crystalline precursor phases already during the spin‐coat deposition is observed using lead iodide (PbI2) or lead chloride (PbCl2) routes. These precursor phases most likely template final MAPbI3 film morphology. In particular, the emergence of the "needle‐like" structure is shown to appear before film annealing. In situ photoluminescence measurements suggest nanoscale nucleation followed by rapid nuclei densification and growth. Using this multimodal in situ approach, different formation pathways can be identified either via precursor phases in the PbI2 and PbCl2 routes or direct perovskite formation from molecular building blocks as observed in the lead acetate (PbAc2) route. Correlation of in situ results with photovoltaic device performance demonstrates the power of in situ multimodal techniques, paves the way to a fast screening of synthetic parameters, and ultimately leads to controlled synthetic procedures that yield high‐efficiency devices. [ABSTRACT FROM AUTHOR]

Low-resistance contact to lightly doped n-type crystalline silicon (c-Si) has long been recognized as technologically challenging due to the pervasive Fermi-level pinning effect. This has hindered the development of certain devices such as n-type c-Si solar cells made with partial rear contacts (PRC) directly to the lowly doped c-Si wafer. Here, a simple and robust process is demonstrated for achieving mΩ cm2 scale contact resistivities on lightly doped n-type c-Si via a lithium fluoride/aluminum contact. The realization of this low-resistance contact enables the fabrication of a first-of-its-kind high-efficiency n-type PRC solar cell. The electron contact of this cell is made to less than 1% of the rear surface area, reducing the impact of contact recombination and optical losses, permitting a power conversion efficiency of greater than 20% in the initial proof-of-concept stage. The implementation of the LiF x/Al contact mitigates the need for the costly high-temperature phosphorus diffusion, typically implemented in such a cell design to nullify the issue of Fermi level pinning at the electron contact. The timing of this demonstration is significant, given the ongoing transition from p-type to n-type c-Si solar cell architectures, together with the increased adoption of advanced PRC device structures within the c-Si photovoltaic industry. [ABSTRACT FROM AUTHOR]

Molybdenum disulfide (MoS2) has been widely examined as a catalyst containing no precious metals for the hydrogen evolution reaction (HER); however, these examinations have utilized synthesized MoS2 because the pristine MoS2 mineral is known to be a poor catalyst. The fundamental challenge with pristine MoS2 is the inert HER activity of the predominant (0001) basal surface plane. In order to achieve high HER performance with pristine MoS2, it is essential to activate the basal plane. Here, we report a general thermal process in which the basal plane is texturized to increase the density of HER-active edge sites. This texturization is achieved through a simple thermal annealing procedure in a hydrogen environment, removing sulfur from the MoS2 surface to form edge sites. As a result, the process generates high HER catalytic performance in pristine MoS2 across various morphologies such as the bulk mineral, films composed of micron-scale flakes, and even films of a commercially available spray of nanoflake MoS2. The lowest overpotential (η) observed for these samples was η = 170 mV to obtain 10 mA/cm² of HER current density. [ABSTRACT FROM AUTHOR]

Solution processing of inorganic thin films has become an important thrust in material research community because it offers low-cost and high-throughput deposition of various functional coatings and devices. Especially inorganic thin film solar cells - macroelectronic devices that rely on consecutive deposition of layers on large-area rigid and flexible substrates - could benefit from solution approaches in order to realize their low-cost nature. This article critically reviews existing deposition approaches of functional layers for chalcogenide solar cells with an extension to other thin film technologies. Only true solutions of readily available metal salts in appropriate solvents are considered without the need of pre-fabricated nanoparticles. By combining three promising approaches, an air-stable Cu(In,Ga)Se2 thin film solar cell with efficiency of 13.8% is demonstrated where all constituent layers (except the metal back contact) are processed from solutions. Notably, water is employed as the solvent in all steps, highlighting the potential for safe manufacturing with high utilization rates. [ABSTRACT FROM AUTHOR]