Blade-Coating of High Crystallinity Cesium-Formamidinium Perovskite Formulations.

Up-scalable coating processes need to be developed to manufacture efficient and stable perovskite-based solar modules. In this work, we combine two Lewis base additives (N,N'-dimethylpropyleneurea and thiourea) to fabricate high-quality Cs0.15FA0.85PbI3 perovskite films by blade-coating on large areas. Selected-area electron diffraction patterns reveal a minimization of stacking faults in the α-FAPbI3 phase for this specific cesium-formamidinium composition in both spin-coated and blade-coated perovskite films, demonstrating its scaling potential. The underlying mechanism of the crystallization process and the specific role of thiourea are characterized by Fourier transform infrared spectroscopy and in situ optical absorption, showing clear interaction between thiourea and perovskite precursors and halved film-formation activation energy (from 114 to 49 kJ/mol), which contribute to the obtained specific morphology with the formation of large domain sizes on a short time scale. The blade-coated perovskite solar cells demonstrate a maximum efficiency of approximately 16.9% on an aperture area of 1 cm2.

Alleviating nanostructural phase impurities enhances the optoelectronic properties, device performance and stability of cesium-formamidinium metal-halide perovskites.

The technique of alloying FA+ with Cs+ is often used to promote structural stabilization of the desirable α-FAPbI3 phase in halide perovskite devices. However, the precise mechanisms by which these alloying approaches improve the optoelectronic quality and enhance the stability have remained elusive. In this study, we advance that understanding by investigating the effect of cationic alloying in CsxFA1-xPbI3 perovskite thin-films and solar-cell devices. Selected-area electron diffraction patterns combined with microwave conductivity measurements reveal that fine Cs+ tuning (Cs0.15FA0.85PbI3) leads to a minimization of stacking faults and an increase in the photoconductivity of the perovskite films. Ultra-sensitive external quantum efficiency, kelvin-probe force microscopy and photoluminescence quantum yield measurements demonstrate similar Urbach energy values, comparable surface potential fluctuations and marginal impact on radiative emission yields, respectively, irrespective of Cs content. Despite this, these nanoscopic defects appear to have a detrimental impact on inter-grains'/domains' carrier transport, as evidenced by conductive-atomic force microscopy and corroborated by drastically reduced solar cell performance. Importantly, encapsulated Cs0.15FA0.85PbI3 devices show robust operational stability retaining 85% of the initial steady-state power conversion efficiency for 1400 hours under continuous 1 sun illumination at 35 °C, in open-circuit conditions. Our findings provide nuance to the famous defect tolerance of halide perovskites while providing solid evidence about the detrimental impact of these subtle structural imperfections on the long-term operational stability.

A Universal Perovskite/C60 Interface Modification via Atomic Layer Deposited Aluminum Oxide for Perovskite Solar Cells and Perovskite-Silicon Tandems.

The primary performance limitation in inverted perovskite-based solar cells is the interface between the fullerene-based electron transport layers and the perovskite. Atomic layer deposited thin aluminum oxide (AlOX) interlayers that reduce nonradiative recombination at the perovskite/C60 interface are developed, resulting in >60 millivolts improvement in open-circuit voltage and 1% absolute improvement in power conversion efficiency. Surface-sensitive characterizations indicate the presence of a thin, conformally deposited AlOx layer, functioning as a passivating contact. These interlayers work universally using different lead-halide-based absorbers with different compositions where the 1.55 electron volts bandgap single junction devices reach >23% power conversion efficiency. A reduction of metallic Pb0 is found and the compact layer prevents in- and egress of volatile species, synergistically improving the stability. AlOX-modified wide-bandgap perovskite absorbers as a top cell in a monolithic perovskite-silicon tandem enable a certified power conversion efficiency of 29.9% and open-circuit voltages above 1.92 volts for 1.17 square centimeters device area.

Rear textured p-type high temperature passivating contacts and their implementation in perovskite/silicon tandem cells.

Silicon solar cells based on high temperature passivating contacts are becoming mainstream in the photovoltaic industry. Here, we developed a high-quality boron-doped poly-silicon hole contact. When combined with a co-processed phosphorus-doped poly-silicon electron contact, high-voltage silicon bottom cells could be demonstrated and included in 28.25%-efficient perovskite/Si tandems. The active area was 4 cm2 active area and the front electrode was screen-printed.

Interface passivation for 31.25%-efficient perovskite/silicon tandem solar cells.

Silicon solar cells are approaching their theoretical efficiency limit of 29%. This limitation can be exceeded with advanced device architectures, where two or more solar cells are stacked to improve the harvesting of solar energy. In this work, we devise a tandem device with a perovskite layer conformally coated on a silicon bottom cell featuring micrometric pyramids-the industry standard-to improve its photocurrent. Using an additive in the processing sequence, we regulate the perovskite crystallization process and alleviate recombination losses occurring at the perovskite top surface interfacing the electron-selective contact [buckminsterfullerene (C60)]. We demonstrate a device with an active area of 1.17 square centimeters, reaching a certified power conversion efficiency of 31.25%.

Understanding and Mitigating the Degradation of Perovskite Solar Cells Based on a Nickel Oxide Hole Transport Material during Damp Heat Testing.

The development of stable materials, processable on a large area, is a prerequisite for perovskite industrialization. Beyond the perovskite absorber itself, this should also guide the development of all other layers in the solar cell. In this regard, the use of NiOx as a hole transport material (HTM) offers several advantages, as it can be deposited with high throughput on large areas and on flat or textured surfaces via sputtering, a well-established industrial method. However, NiOx may trigger the degradation of perovskite solar cells (PSCs) when exposed to environmental stressors. Already after 100 h of damp heat stressing, a strong fill factor (FF) loss appears in conjunction with a characteristic S-shaped J-V curve. By performing a wide range of analysis on cells and materials, completed by device simulation, the cause of the degradation is pinpointed and mitigation strategies are proposed. When NiOx is heated in an air-tight environment, its free charge carrier density drops, resulting in a band misalignment at the NiOx/perovskite interface and in the formation of a barrier impeding hole extraction. Adding an organic layer between the NiOx and the perovskite enables higher performances but not long-term thermal stability, for which reducing the NiOx thickness is necessary.

Revealing the Role of Tin Fluoride Additive in Narrow Bandgap Pb-Sn Perovskites for Highly Efficient Flexible All-Perovskite Tandem Cells.

Tin fluoride (SnF2) is an indispensable additive for high-efficiency Pb-Sn perovskite solar cells (PSCs). However, the spatial distribution of SnF2 in the perovskite absorber is seldom investigated while essential for a comprehensive understanding of the exact role of the SnF2 additive. Herein, we revealed the spatial distribution of the SnF2 additive and made structure-optoelectronic properties-flexible photovoltaic performance correlation. We observed the chemical transformation of SnF2 to a fluorinated oxy-phase on the Pb-Sn perovskite film surface due to its rapid oxidation. In addition, at the buried perovskite interface, we detected and visualized the accumulation of F- ions. We found that the photoluminescence quantum yield of Pb-Sn perovskite reached the highest value with 10 mol % SnF2 in the precursor solution. When integrating the optimized absorber in flexible devices, we obtained the flexible Pb-Sn perovskite narrow bandgap (1.24 eV) solar cells with an efficiency of 18.5% and demonstrated 23.1% efficient flexible four-terminal all-perovskite tandem cells.

Monolithic Perovskite-Silicon Tandem Solar Cells: From the Lab to Fab?

This review focuses on monolithic 2-terminal perovskite-silicon tandem solar cells and discusses key scientific and technological challenges to address in view of an industrial implementation of this technology. The authors start by examining the different crystalline silicon (c-Si) technologies suitable for pairing with perovskites, followed by reviewing recent developments in the field of monolithic 2-terminal perovskite-silicon tandems. Factors limiting the power conversion efficiency of these tandem devices are then evaluated, before discussing pathways to achieve an efficiency of >32%, a value that small-scale devices will likely need to achieve to make tandems competitive. Aspects related to the upscaling of these device active areas to industry-relevant ones are reviewed, followed by a short discussion on module integration aspects. The review then focuses on stability issues, likely the most challenging task that will eventually determine the economic viability of this technology. The final part of this review discusses alternative monolithic perovskite-silicon tandem designs. Finally, key areas of research that should be addressed to bring this technology from the lab to the fab are highlighted.

Multimodal Microscale Imaging of Textured Perovskite-Silicon Tandem Solar Cells.

Halide perovskite/crystalline silicon (c-Si) tandem solar cells promise power conversion efficiencies beyond the limits of single-junction cells. However, the local light-matter interactions of the perovskite material embedded in this pyramidal multijunction configuration, and the effect on device performance, are not well understood. Here, we characterize the microscale optoelectronic properties of the perovskite semiconductor deposited on different c-Si texturing schemes. We find a strong spatial and spectral dependence of the photoluminescence (PL) on the geometrical surface constructs, which dominates the underlying grain-to-grain PL variation found in halide perovskite films. The PL response is dependent upon the texturing design, with larger pyramids inducing distinct PL spectra for valleys and pyramids, an effect which is mitigated with small pyramids. Further, optimized quasi-Fermi level splittings and PL quantum efficiencies occur when the c-Si large pyramids have had a secondary smoothing etch. Our results suggest that a holistic optimization of the texturing is required to maximize light in- and out-coupling of both absorber layers and there is a fine balance between the optimal geometrical configuration and optoelectronic performance that will guide future device designs.

Nanoscale Study of the Hole-Selective Passivating Contacts with High Thermal Budget Using C-AFM Tomography.

We investigate hole-selective passivating contacts that consist of an interfacial layer of silicon oxide (SiOx) and a layer of boron-doped SiCx(p). The fabrication process of these contacts involves an annealing step at temperatures above 750 °C which crystallizes the initially amorphous layer and diffuses dopants across the interfacial oxide into the wafer to facilitate charge transport, but it can also disrupt the SiOx layer necessary for wafer-surface passivation. To investigate the transport mechanism of the charge carriers through the selective contact and its changes during the annealing process, we utilize various characterization methods, such as transmission electron microscopy, micro Raman spectroscopy, and conductive atomic force microscopy. Combining the latter with a sequential removal of material, we assemble a tomographic reconstruction of the crystallized layer that reveals the presence of preferential vertical transport channels.

Spectrally Selective Mid-Wave Infrared Detection Using Fabry-Pérot Cavity Enhanced Black Phosphorus 2D Photodiodes.

Thin two-dimensional (2D) material absorbers have the potential to reduce volume-dependent thermal noise in infrared detectors. However, any reduction in noise must be balanced against lower absorption from the thin layer, which necessitates advanced optical architectures. Such architectures can be particularly effective for applications that require detection only within a specific narrow wavelength range. This study presents a Fabry-Pérot cavity enhanced bP/MoS2 midwave infrared (MWIR) photodiode. This simple structure enables tunable narrow-band (down to 0.42 µm full width at half-maximum) photodetection in the 2-4 µm range by adjusting the thickness of the Fabry-Pérot cavity resonator. This is achieved while maintaining room-temperature performance metrics comparable to previously reported 2D MWIR detectors. Zero bias specific detectivity and responsivity values of up to 1.7 × 109 cm Hz1/2 W-1 and 0.11 A W-1 at λ = 3.0 µm are measured with a response time of less than 3 ns. These results introduce a promising family of 2D detectors with applications in MWIR spectroscopy.

Correlation of fluorescence microscopy, electron microscopy, and NanoSIMS stable isotope imaging on a single tissue section.

Correlative light and electron microscopy allows localization of specific molecules at the ultrastructural level in biological tissue but does not provide information about metabolic turnover or the distribution of labile molecules, such as micronutrients. We present a method to directly correlate (immuno)fluorescent microscopy, (immuno)TEM imaging and NanoSIMS isotopic mapping of the same tissue section, with nanometer-scale spatial precision. The process involves chemical fixation of the tissue, cryo sectioning, thawing, and air-drying under a thin film of polyvinyl alcohol. It permits to effectively retain labile compounds and strongly increases NanoSIMS sensitivity for 13C-enrichment. The method is illustrated here with correlated distribution maps of a carbonic anhydrase enzyme isotype, ß-tubulin proteins, and 13C- and 15N-labeled labile micronutrients (and their anabolic derivates) within the tissue of a reef-building symbiotic coral. This broadly applicable workflow expands the wealth of information that can be obtained from multi-modal, sub-cellular observation of biological tissue.

New Route for "Cold-Passivation" of Defects in Tin-Based Oxides.

Transparent conductive oxides (TCOs) are essential in technologies coupling light and electricity. For Sn-based TCOs, oxygen deficiencies and undercoordinated Sn atoms result in an extended density of states below the conduction band edge. Although shallow states provide free carriers necessary for electrical conductivity, deeper states inside the band gap are detrimental to transparency. In zinc tin oxide (ZTO), the overall optoelectronic properties can be improved by defect passivation via annealing at high temperatures. Yet, the high thermal budget associated with such treatment is incompatible with many applications. Here, we demonstrate an alternative, low-temperature passivation method, which relies on cosputtering Sn-based TCOs with silicon dioxide (SiO2). Using amorphous ZTO and amorphous/polycrystalline tin dioxide (SnO2) as representative cases, we demonstrate through optoelectronic characterization and density functional theory simulations that the SiO2 contribution is twofold. First, oxygen from SiO2 passivates the oxygen deficiencies that form deep defects in SnO2 and ZTO. Second, the ionization energy of the remaining deep defect centers is lowered by the presence of silicon atoms. Remarkably, we find that these ionized states do not contribute to sub-gap absorptance. This simple passivation scheme significantly improves the optical properties without affecting the electrical conductivity, hence overcoming the known transparency-conductivity trade-off in Sn-based TCOs.

Fully textured monolithic perovskite/silicon tandem solar cells with 25.2% power conversion efficiency.

Tandem devices combining perovskite and silicon solar cells are promising candidates to achieve power conversion efficiencies above 30% at reasonable costs. State-of-the-art monolithic two-terminal perovskite/silicon tandem devices have so far featured silicon bottom cells that are polished on their front side to be compatible with the perovskite fabrication process. This concession leads to higher potential production costs, higher reflection losses and non-ideal light trapping. To tackle this issue, we developed a top cell deposition process that achieves the conformal growth of multiple compounds with controlled optoelectronic properties directly on the micrometre-sized pyramids of textured monocrystalline silicon. Tandem devices featuring a silicon heterojunction cell and a nanocrystalline silicon recombination junction demonstrate a certified steady-state efficiency of 25.2%. Our optical design yields a current density of 19.5 mA cm-2 thanks to the silicon pyramidal texture and suggests a path for the realization of 30% monolithic perovskite/silicon tandem devices.

Tilt-less 3-D electron imaging and reconstruction of complex curvilinear structures.

The ability to obtain three-dimensional (3-D) information about morphologies of nanostructures elucidates many interesting properties of materials in both physical and biological sciences. Here we demonstrate a novel method in scanning transmission electron microscopy (STEM) that gives a fast and reliable assessment of the 3-D configuration of curvilinear nanostructures, all without needing to tilt the sample through an arc. Using one-dimensional crystalline defects known as dislocations as a prototypical example of a complex curvilinear object, we demonstrate their 3-D reconstruction two orders of magnitude faster than by standard tilt-arc TEM tomographic techniques, from data recorded by selecting different ray paths of the convergent STEM probe. Due to its speed and immunity to problems associated with a tilt arc, the tilt-less 3-D imaging offers important advantages for investigations of radiation-sensitive, polycrystalline, or magnetic materials. Further, by using a segmented detector, the total electron dose is reduced to a single STEM raster scan acquisition; our tilt-less approach will therefore open new avenues for real-time 3-D electron imaging of dynamic processes.

Silicon-Rich Silicon Carbide Hole-Selective Rear Contacts for Crystalline-Silicon-Based Solar Cells.

The use of passivating contacts compatible with typical homojunction thermal processes is one of the most promising approaches to realizing high-efficiency silicon solar cells. In this work, we investigate an alternative rear-passivating contact targeting facile implementation to industrial p-type solar cells. The contact structure consists of a chemically grown thin silicon oxide layer, which is capped with a boron-doped silicon-rich silicon carbide [SiCx(p)] layer and then annealed at 800-900 °C. Transmission electron microscopy reveals that the thin chemical oxide layer disappears upon thermal annealing up to 900 °C, leading to degraded surface passivation. We interpret this in terms of a chemical reaction between carbon atoms in the SiCx(p) layer and the adjacent chemical oxide layer. To prevent this reaction, an intrinsic silicon interlayer was introduced between the chemical oxide and the SiCx(p) layer. We show that this intrinsic silicon interlayer is beneficial for surface passivation. Optimized passivation is obtained with a 10-nm-thick intrinsic silicon interlayer, yielding an emitter saturation current density of 17 fA cm-2 on p-type wafers, which translates into an implied open-circuit voltage of 708 mV. The potential of the developed contact at the rear side is further investigated by realizing a proof-of-concept hybrid solar cell, featuring a heterojunction front-side contact made of intrinsic amorphous silicon and phosphorus-doped amorphous silicon. Even though the presented cells are limited by front-side reflection and front-side parasitic absorption, the obtained cell with a Voc of 694.7 mV, a FF of 79.1%, and an efficiency of 20.44% demonstrates the potential of the p+/p-wafer full-side-passivated rear-side scheme shown here.

In Situ TEM Analysis of Organic-Inorganic Metal-Halide Perovskite Solar Cells under Electrical Bias.

Changes in the nanostructure of methylammonium lead iodide (MAPbI3) perovskite solar cells are assessed as a function of current-voltage stimulus by biasing thin samples in situ in a transmission electron microscope. Various degradation pathways are identified both in situ and ex situ, predominantly at the positively biased MAPbI3 interface. Iodide migrates into the positively biased charge transport layer and also volatilizes along with organic species, which triggers the nucleation of PbI2 nanoparticles and voids and hence decreases the cell performance.

PbI2-HMPA Complex Pretreatment for Highly Reproducible and Efficient CH3NH3PbI3 Perovskite Solar Cells.

Interfacial engineering of the meso-TiO2 surface through a modified sequential deposition procedure involving a novel PbI2-HMPA complex pretreatment is conducted as a reproducible method for preparing MAPbI3 based perovskite solar cells providing the highest efficiencies yet reported with the polymer HTM layer. Grazing-incidence X-ray diffraction depth profiling confirms the formation of a perovskite film with a PbI2-rich region close to the electron transport layer (ETL) due to the strong interaction of HMPA with PbI2, which successfully retarded the dissolution of the PbI2 phase when depositing the perovskite layer on top. These results are further confirmed by energy-dispersive X-ray spectroscopy performed in a scanning transmission electron microscope, which reveals that the I/Pb ratio in samples treated with the complex is indeed reduced in the vicinity of the ETL contact when compared to samples without the treatment. The engineered interface leads to an average power conversion efficiency of 19.2% (reverse scan, standard deviation SD < 0.2) over 30 cells (best cell at 19.5% with high FF of 0.80).

Measurements of local chemistry and structure in Ni(O)-YSZ composites during reduction using energy-filtered environmental TEM.

Energy-filtered transmission electron microscopy images are acquired during the reduction of a NiO-YSZ composite in H2 up to 600 °C. Temperature-resolved quantitative information about both chemistry and structure is extracted with nm spatial resolution from the data, paving the way for the development of detailed reduction models.