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At least 1,495 records · Page 83

Conductive and Stable Magnesium Oxide Electron-Selective Contacts for Efficient Silicon Solar Cells

A high Schottky barrier (>0.65 eV) for electrons is typically found on lightly doped n–type crystalline (c–Si) wafers for a variety of contact metals. This behavior is commonly attributed to the Fermi–level pinning effect and has hindered the development of n–type c–Si solar cells, while its p–type counterparts have been commercialized for several decades, typically utilizing aluminium alloys in full–area, and more recently, partial–area rear contact configurations. Here the authors demonstrate a highly conductive and thermally stable electrode composed of a magnesium oxide/aluminium (MgOx/Al) contact, achieving moderately low resistivity Ohmic contacts on lightly doped n–type c–Si. The electrode, functionalized with nanoscale MgO x films, significantly enhances the performance of n–type c–Si solar cells to a power conversion efficiency of 20%, advancing n–type c–Si solar cells with full–area dopant–free rear contacts to a point of competitiveness with the standard p–type architecture. Here, the low thermal budget of the cathode formation, its dopant–free nature, and the simplicity of the device structure enabled by the MgO x /Al contact open up new possibilities in designing and fabricating low–cost optoelectronic devices, including solar cells, thin film transistors, or light emitting diodes.

36 MATERIALS SCIENCE↗

Effect of Precursor Solution Aging on the Crystallinity and Photovoltaic Performance of Perovskite Solar Cells

Perovskite materials due to their exceptional photophysical properties are beginning to dominate the field of thin‐film optoelectronic devices. However, one of the primary challenges is the processing‐dependent variability in the properties, thus making it imperative to understand the origin of such variations. Here, it is discovered that the precursor solution aging time before it is cast into a thin film, is a subtle but a very important factor that dramatically affects the overall thin‐film formation and crystallinity and therein factors such as grain growth, phase purity, surface uniformity, trap state density, and overall solar cell performance. It is shown that progressive aging of the precursor promotes efficient formation of larger seeds after the fast nucleation of a large density of small seeds. The hot‐casting method then leads to the growth of large grains in uniform thin‐films with excellent crystallinity validated using scanning microscopy images and X‐ray diffraction patterns. The high‐quality films cast from aged solution is ideal for thin‐film photovoltaic device fabrication with reduced shunt current and good charge transport. This observation is a significant step toward achieving highly crystalline thin‐films with reliability in device performance and establishes the subtle but dramatic effect of solution aging before fabricating perovskite thin‐films.

Tsai, Hsinhan↗

Effect of Cation Composition on the Mechanical Stability of Perovskite Solar Cells

Photoactive perovskite semiconductors are highly tunable, with numerous inorganic and organic cations readily incorporated to modify optoelectronic properties. However, despite the importance of device reliability and long service lifetimes, the effects of various cations on the mechanical properties of perovskites are largely overlooked. In this study, the cohesion energy of perovskites containing various cation combinations of methylammonium, formamidinium, cesium, butylammonium, and 5–aminovaleric acid is reported. A trade–off is observed between the mechanical integrity and the efficiency of perovskite devices. High efficiency devices exhibit decreased cohesion, which is attributed to reduced grain sizes with the inclusion of additional cations and PbI 2 additives. Microindentation hardness testing is performed to estimate the fracture toughness of single–crystal perovskite, and the results indicated perovskites are inherently fragile, even in the absence of grain boundaries and defects. As a result, the devices found to have the highest fracture energies are perovskites infiltrated into a porous TiO 2 /ZrO 2 /C triple layer, which provide extrinsic reinforcement and shielding for enhanced mechanical and chemical stability.

14 SOLAR ENERGY↗

The Impact of Device Polarity on the Performance of Polymer–Fullerene Solar Cells

Abstract Diketopyrrolopyrrole (DPP)‐conjugated polymers are a versatile class of semiconductors for application in organic solar cells because of their tunable optoelectronic properties. A record power conversion efficiency (PCE) of 9.4% was recently achieved for DPP polymers, but further improvements are required to reach true efficiency limits. Using five DPP polymers with different chemical structures and molecular weights, the device performance of polymer:fullerene solar cells is systematically optimized by considering device polarity, morphology, and light absorption. The polymer solubility is found to have a significant effect on the optimal device polarity. Soluble polymers show a 10–25% increase in PCE in inverted device configurations, while the device performance is independent of device polarity for less soluble DPP derivatives. The difference seems related to the polymer to fullerene weight ratio at the ZnO interface in inverted devices, which is higher for more soluble DPP polymers. Optimization of the nature of the cosolvent to narrow the fibril width of polymers in the blends toward the exciton diffusion length enhances charge generation. Additionally, the use of a retroreflective foil increases absorption of light. Combined, the effects afford a PCE of 9.6%, among the highest for DPP‐based polymer solar cells.

Li, Mengmeng↗

Temperature and Humidity Stable Alkali/Alkaline-Earth Metal Carbonates as Electron Heterocontacts for Silicon Photovoltaics

Nanometer scale interfacial layers between the metal cathode and the n-type semiconductor play a critical role in enhancing the transport of charge carriers in and out of optoelectronic devices. In this research, a range of nanoscale alkali and alkaline earth metal carbonates (i.e., potassium, rubidium, caesium, calcium, strontium, and barium) are shown to function effectively as electron heterocontacts to lightly doped n-type crystalline silicon (c-Si), which is particularly challenging to contact with common metals. These carbonate interlayers are shown to enhance the performance of n-type c-Si proof-of-concept solar cells up to a power conversion efficiency of ≈19%. Furthermore, these devices are thermally stable up to 350 °C and both the caesium and barium carbonates pass a standard 1000 h damp heat test, with >95% of their initial performance maintained. The temperature and humidity stable electron heterocontacts based on alkali and alkaline earth metal carbonates show a high potential for industrial feasibility and longevity for deployment in the field.

36 MATERIALS SCIENCE↗

Rapid Aqueous Spray Fabrication of Robust NiO x : A Simple and Scalable Platform for Efficient Perovskite Solar Cells

Organometal halide perovskites have powerful intrinsic potential to drive next-generation solar technology, but their insufficient thermomechanical reliability and unproven large-area manufacturability limit competition with incumbent silicon photovoltaics. This work addresses these limitations by leveraging large-area processing and robust inorganic hole transport layers (HTLs). Inverted perovskite solar cells utilizing NiO x HTLs deposited by rapid aqueous spray-coating that outperform spin-coated NiO x and lead to a 5× improvement in the fracture energy (Gc), a primary metric of thermomechanical stability, are presented. Additionally, the morphology, chemical composition, and optoelectronic properties of the NiO x films are characterized to understand and optimize compatibility with an archetypal double cation perovskite, Cs .17 FA .83 Pb(Br .17 I .83 ) 3 . Perovskite solar cells with sprayed NiO x show higher photovoltaic performance, exhibiting up to 82% fill factor and 17.7% power conversion efficiency (PCE)—the highest PCE reported for inverted cell with scalable charge transport layers—as well as excellent stability under full illumination and after 4000 h aging in inert conditions at room temperature. By utilizing open-air techniques and aqueous precursors, this combination of robust materials and low-cost processing provides a platform for scaling perovskite modules with long-term reliability.

36 MATERIALS SCIENCE↗

Enhanced Nucleation of Atomic Layer Deposited Contacts Improves Operational Stability of Perovskite Solar Cells in Air

Metal-halide perovskites show promise as highly efficient solar cells, light-emitting diodes, and other optoelectronic devices. Ensuring long-term stability is now a major priority. In this study, an ultrathin (2 nm) layer of polyethylenimine ethoxylated (PEIE) is used to functionalize the surface of C 60 for the subsequent deposition of atomic layer deposition (ALD) SnO 2 , a commonly used electron contact bilayer for p-i-n devices. The enhanced nucleation results in a more continuous initial ALD SnO 2 layer that exhibits superior barrier properties, protecting Cs 0.25 FA 0.75 Pb(Br 0.20 | 0.80 ) 3 films upon direct exposure to high temperatures (200 degrees C) and water. This surface modification with PEIE translates to more stable solar cells under aggressive testing conditions in air at 60 degrees C under illumination. This type of 'built-in' barrier layer mitigates degradation pathways not addressed by external encapsulation, such as internal halide or metal diffusion, while maintaining high device efficiency up to 18.5%. This nucleation strategy is also extended to ALD VOx films, demonstrating its potential to be broadly applied to other metal oxide contacts and device architectures.

14 SOLAR ENERGY↗

Critical Role of Polymer Aggregation and Miscibility in Nonfullerene‐Based Organic Photovoltaics

Abstract Understanding the correlation between polymer aggregation, miscibility, and device performance is important to establish a set of chemistry design rules for donor polymers with nonfullerene acceptors (NFAs). Employing a donor polymer with strong temperature‐dependent aggregation, namely PffBT4T‐2OD [poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐ alt ‐(3,3″′‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2″′‐quaterthiophen‐5,5‐diyl)], also known as PCE‐11 as a base polymer, five copolymer derivatives having a different thiophene linker composition are blended with the common NFA O‐IDTBR to investigate their photovoltaic performance. While the donor polymers have similar optoelectronic properties, it is found that the device power conversion efficiency changes drastically from 1.8% to 8.7% as a function of thiophene content in the donor polymer. Results of structural characterization show that polymer aggregation and miscibility with O‐IDTBR are a strong function of the chemical composition, leading to different donor–acceptor blend morphology. Polymers having a strong tendency to aggregate are found to undergo fast aggregation prior to liquid–liquid phase separation and have a higher miscibility with NFA. These properties result in smaller mixed donor–acceptor domains, stronger PL quenching, and more efficient exciton dissociation in the resulting cells. This work indicates the importance of both polymer aggregation and donor–acceptor interaction on the formation of bulk heterojunctions in polymer:NFA blends.

Yi, Xueping↗

First-Principles Simulation of Carrier Recombination Mechanisms in Halide Perovskites

In recent years, there have been remarkable developments in halide perovskites, which are used in highly efficient optoelectronic devices and exhibit intriguing materials physics. Detailed knowledge of carrier recombination mechanisms is essential for understanding their excellent performance and to further increase their efficiency. Obtaining such knowledge is challenging however, and different studies have reached divergent conclusions in some cases. This progress report outlines the critical developments in understanding the carrier recombination mechanisms in halide perovskites from a computational perspective. The primary focus is radiative and Auger recombination, since they have not been systematically assessed and discussed before, and a number of important issues have been actively debated. This comprehensive discussion of the carrier recombination mechanisms is aimed at establishing physically justified insights that can form the basis for better materials and devices design.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Electron-Beam-Related Studies of Halide Perovskites: Challenges and Opportunities

Electron beam microscopy and related characterization techniques play an important role in revealing the microstructural, morphological, physical, and chemical information of halide perovskites and their impact on associated optoelectronic devices. However, electron beam irradiation usually causes damage to these beam-sensitive materials, negatively impacting their device performance, and complicating this interpretation. Here, the electron microscopy and spectroscopy techniques are reviewed that are crucial for the understanding of the crystallization and microstructure of halide perovskites. In addition, special attention is paid to assessing and mitigating the electron beam-induced damage caused by these techniques. Since the halide perovskites are fragile, a protocol involving delicate control of both electron beam dose and dose rate, coupled with careful data analysis, is key to enable the acquisition of reliable structural and compositional information such as atomic-resolution images, chemical elemental mapping and electron diffraction patterns. Limiting the electron beam dose is critical parameter enabling the characterization of various halide perovskites. Novel methods to unveil the mechanisms of device operation, including charge carrier generation, diffusion, and extraction are presented in scanning electron microscopy studies combined with electron-beam-induced current and cathodoluminescence mapping. Future opportunities for electron-beam-related characterizations of halide perovskites are also discussed.

36 MATERIALS SCIENCE↗

Elucidating the Role of a Tetrafluoroborate-Based Ionic Liquid at the n-Type Oxide/Perovskite Interface

Halide perovskites are currently one of the most heavily researched emerging photovoltaic materials. Despite achieving remarkable power conversion efficiencies, perovskite solar cells have not yet achieved their full potential, with the interfaces between the perovskite and the charge-selective layers being where most recombination losses occur. In this study, a fluorinated ionic liquid (IL) is employed to modify the perovskite/SnO 2 interface. Using Kelvin probe and photoelectron spectroscopy measurements, it is shown that depositing the perovskite onto an IL-treated substrate results in the crystallization of a perovskite film which has a more n-type character, evidenced by a decrease of the work function and a shift of the Fermi level toward the conduction band. Photoluminescence spectroscopy and time-resolved microwave conductivity are used to investigate the optoelectronic properties of the perovskite grown on neat and IL-modified surfaces and it is found that the modified substrate yields a perovskite film which exhibits an order of magnitude lower trap density than the control. When incorporated into solar cells, we report this interface modification results in a reduction in the current-voltage hysteresis and an improvement in device performance, with the best performing devices achieving steady-state PCEs exceeding 20%.

14 SOLAR ENERGY↗

CsI-Antisolvent Adduct Formation in All-Inorganic Metal Halide Perovskites

The excellent optoelectronic properties shown by hybrid organic/inorganic metal halide perovskites are all predicated on precisely controlling the exact nucleation and crystallization dynamics that occur during film formation. In general, high-performance thin films are obtained by a method commonly called solvent engineering (or antisolvent quench) processing. The solvent engineering method removes excess solvent, but importantly leaves behind solvent that forms chemical adducts with the lead-halide precursor salts. These adduct-based precursor phases control nucleation and the growth of the polycrystalline domains. There has not yet been a comprehensive study comparing the various antisolvents used in different perovskite compositions containing cesium. In addition, there have been no reports of solvent engineering for high efficiency in all-inorganic perovskites such as CsPbI 3 . In this work, inorganic perovskite composition CsPbI 3 is specifically targeted and unique adducts formed between CsI and precursor solvents and antisolvents are found that have not been observed for other A-site cation salts. These CsI adducts control nucleation more so than the PbI 2 -dimethyl sulfoxide (DMSO) adduct and demonstrate how the A-site plays a significant role in crystallization. The use of methyl acetate (MeOAc) in this solvent engineering approach dictates crystallization through the formation of a CsI-MeOAc adduct and results in solar cells with a power conversion efficiency of 14.4%.

14 SOLAR ENERGY↗

Optical Absorption-Based In Situ Characterization of Halide Perovskites

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. In conclusion, 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.

36 MATERIALS SCIENCE↗

Retarded Charge-Carrier Recombination in Photoelectrochemical Cells from Plasmon-Induced Resonance Energy Transfer

N-type metal oxides such as hematite (α-Fe 2 O 3 ) and bismuth vanadate (BiVO 4 ) are promising candidate materials for efficient photoelectrochemical water splitting; however, their short minority carrier diffusion length and restricted carrier lifetime result in undesired rapid charge recombination. In this paper, a 2D arranged globular Au nanosphere (NS) monolayer array with a highly ordered hexagonal hole pattern (hereafter, Au array) is introduced onto the surface of photoanodes comprised of metal oxide films via a facile drying and transfer-printing process. Through plasmon-induced resonance energy transfer, the Au array provides a strong electromagnetic field in the near-surface area of the metal oxide film. The near-field coupling interaction and amplification of the electromagnetic field suppress the charge recombination with long-lived photogenerated holes and simultaneously enhance the light harvesting and charge transfer efficiencies. Consequently, an over 3.3-fold higher photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) is achieved for the Au array/α-Fe 2 O 3 . Furthermore, the high versatility of this transfer printing of Au arrays is demonstrated by introducing it on the molybdenum-doped BiVO 4 film, resulting in 1.5-fold higher photocurrent density at 1.23 V versus RHE. The tailored metal film design can provide a potential strategy for the versatile application in various light-mediated energy conversion and optoelectronic devices.

2D pattern array↗

Microstructure of Methylammonium Lead iodide Perovskite Thin Films: A Comprehensive Study of the Strain and Texture

Controlling the microstructure of hybrid halide perovskite thin films is essential for optimizing their performance in optoelectronic devices. It is well established that the strain state of the perovskite layer affects its stability. Likewise, the orientation of the perovskite lattice is a determining parameter as these materials have shown pronounced anisotropies in their physical and mechanical properties. In this work, the authors focus on the understanding of the mechanisms that govern the strain and texture observed in MAPbI 3 thin films deposited on various oxide substrates. A thorough study of the evolution of the strain of the perovskite layer upon cooling down to room temperature from the crystallization temperature (100 °C) shows an essentially relaxed behavior of the perovskite layers. This result contradicts the commonly accepted hypothesis according to which MAPbI 3 layers synthesized above ambient temperature are strained due to the large mismatch in the thermal expansion coefficients of the perovskite and its substrate. The texture in MAPbI 3 layers is investigated by means of synchrotron full-field diffraction X-ray microscopy. This technique allows the direct observation of the [hh0] and [00l]-oriented domains at the origin of the observed textures, demonstrating both their twin and ferroelastic nature. The stability of the different domain orientations is investigated by DFT calculations, illustrating the determining role of the chemical environment at the film-substrate interface. PbI 2- terminated surfaces are found to favor the [hh0] orientations while for MAI-terminated ones, both [hh0] and [00l] domains are equally stabilized. The different results constitute an important step of clarification and understanding from the perspective of controlling the microstructure of perovskite layers.

36 MATERIALS SCIENCE↗

Direct Characterization of Type-I Band Alignment in 2D Ruddlesden–Popper Perovskites

2D Ruddlesden–Popper halide perovskites have attracted considerable attention due to their desirable optoelectronic properties, high chemical and structural tunability, and improved environmental stability. However, the understanding of their structure–properties relationships is still limited. In particular, the energy level positions and band alignments at interfaces involving these materials, which are important features to control in the context of any applications, are still under debate. Here, the electronic structure of high-purity films of BA 2 MA n-1 Pb n I 3n+1 for n = 1–5 (where BA stands for butylammonium and MA for methylammonium) is investigated, using optical absorption, ultraviolet, and inverse photoemission spectroscopies, and density functional theory calculations. Further, this study determines the ionization energy and electron affinity of each compound and demonstrates a type-I band alignment for the BA 2 MA n-1 Pb n I 3n+1 series. This study further describes the evolution of the exciton binding energy as a function of the thickness of the inorganic layers.

2D Ruddlesden–Popper perovskites↗

Understanding the Role of Cesium on Chemical Complexity in Methylammonium-Free Metal Halide Perovskites

Mixed cesium- and formamidinium-based metal halide perovskites (MHPs) are emerging as ideal photovoltaic materials due to their promising performance and improved stability. While theoretical predictions suggest that a larger composition ratio of Cs (≈30%) aids the formation of a pure photoactive α-phase, high photovoltaic performances can only be realized in MHPs with moderate Cs ratios. In fact, elemental mixing in a solution can result in chemical complexities with non-equilibrium phases, causing chemical inhomogeneities localized in the MHPs that are not traceable with global device-level measurements. Thus, the chemical origin of the complexities and understanding of their effect on stability and functionality remain elusive. Herein, through spatially resolved analyses, the fate of local chemical structures, particularly the evolution pathway of non-equilibrium phases and the resulting local inhomogeneities in MHPs is comprehensively explored. It is illustrated that Cs-rich MHPs have substantial local inhomogeneities at the initial crystallization step, which do not fully convert to the α-phase and thereby compromise the optoelectronic performance of the materials. These fundamental observations allow the authors to draw a complete chemical landscape of MHPs including nanoscale chemical mechanisms, providing indispensable insights into the realization of a functional materials platform.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

How to GIWAXS: Grazing Incidence Wide Angle X‐Ray Scattering Applied to Metal Halide Perovskite Thin Films

Abstract The frequency of reports utilizing synchrotron‐based grazing incident wide angle X‐ray scattering (GIWAXS) to study metal halide perovskite thin films has exploded recently, as this technique has proven invaluable for understanding several structure‐property relationships that fundamentally limit optoelectronic performance. The GIWAXS geometry and temporal resolution are also inherently compatible with in situ and operando setups (including ISOS protocols), and a relatively large halide perovskite research community has deployed GIWAXS to unravel important kinetic and dynamic features in these materials. Considering its rising popularity, the aim here is to accelerate the required learning curve for new experimentalists by clearly detailing the underlying analytical concepts which can be leveraged to maximize GIWAXS studies of polycrystalline thin films and devices. Motivated by the vast range of measurement conditions offered, together with the wide variety of compositions and structural motifs available (i.e., from single‐crystal and polycrystalline systems, to quantum dots and layered superlatices), a comprehensive framework for conducting effective GIWAXS experiments is outlined for different purposes. It is anticipated that providing a clear perspective for this topic will help elevate the quality of future GIWAXS studies—which have become routine—and provide the impetus required to develop novel GIWAXS approaches to resolve unsettled scientific questions.

36 MATERIALS SCIENCE↗