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.

Ultrathin ALD Aluminum Oxide Thin Films Suppress the Thermal Shrinkage of Battery Separator Membranes.

Thermal runaway is a major safety concern in the applications of Li-ion batteries, especially in the electric vehicle (EV) market. A key component to mitigate this risk is the separator membrane, a porous polymer film that prevents physical contact between the electrodes. Traditional polyolefin-based separators display significant thermal shrinkage (TS) above 100 °C, which increases the risk of battery failure; hence, suppressing the TS up to 180 °C is critical to enhancing the cell's safety. In this article, we deposited thin-film coatings (less than 10 nm) of aluminum oxide by atomic layer deposition (ALD) on three different types of separator membranes. The deposition conditions and the plasma pretreatment were optimized to decrease the number of ALD cycles necessary to suppress TS without hindering the battery performance for all of the studied separators. A dependency on the separator composition and porosity was found. After 100 ALD cycles, the thermal shrinkage of a 15 µm thick polyethylene membrane with 50% porosity was measured to be below 1% at 180 °C, with ionic conductivity >1 mS/cm. Full battery cycling with NMC532 cathodes demonstrates no hindrance to the battery's rate capability or the capacity retention rate compared to that of bare membranes during the first 100 cycles. These results display the potential of separators functionalized by ALD to enhance battery safety and improve battery performance without increasing the separator thickness and hence preserving excellent volumetric energy.

In Situ Reflectometry and Diffraction Investigation of the Multiscale Structure of p-Type Polysilicon Passivating Contacts for c-Si Solar Cells.

The integration of passivating contacts based on a highly doped polycrystalline silicon (poly-Si) layer on top of a thin silicon oxide (SiOx) layer has been identified as the next step to further increase the conversion efficiency of current mainstream crystalline silicon (c-Si) solar cells. However, the interrelation between the final properties of poly-Si/SiOx contacts and their fabrication process has not yet been fully unraveled, which is mostly due to the challenge of characterizing thin-film stacks with features in the nanometric range. Here, we apply in situ X-ray reflectometry and diffraction to investigate the multiscale (1 Å-100 nm) structural evolution of poly-Si contacts during annealing up to 900 °C. This allows us to quantify the densification and thinning of the poly-Si layer during annealing as well as to monitor the disruption of the thin SiOx layer at high temperature >800 °C. Moreover, results obtained on a broader range of thermal profiles, including firing with dwell times of a few seconds, emphasize the impact of high thermal budgets on poly-Si contacts' final properties and thus the importance of ensuring a good control of such high-temperature processes when fabricating c-Si solar cells integrating such passivating contacts. Overall, this study demonstrates the robustness of combining different X-ray elastic scattering techniques (here XRR and GIXRD), which present the unique advantage of being rapid, nondestructive, and applicable on a large sample area, to unravel the multiscale structural evolution of poly-Si contacts in situ during high-temperature processes.

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.

Routing of Electric Vehicles With Intermediary Charging Stations: A Reinforcement Learning Approach.

In the past few years, the importance of electric mobility has increased in response to growing concerns about climate change. However, limited cruising range and sparse charging infrastructure could restrain a massive deployment of electric vehicles (EVs). To mitigate the problem, the need for optimal route planning algorithms emerged. In this paper, we propose a mathematical formulation of the EV-specific routing problem in a graph-theoretical context, which incorporates the ability of EVs to recuperate energy. Furthermore, we consider a possibility to recharge on the way using intermediary charging stations. As a possible solution method, we present an off-policy model-free reinforcement learning approach that aims to generate energy feasible paths for EV from source to target. The algorithm was implemented and tested on a case study of a road network in Switzerland. The training procedure requires low computing and memory demands and is suitable for online applications. The results achieved demonstrate the algorithm's capability to take recharging decisions and produce desired energy feasible paths.

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.

Light Management: A Key Concept in High-Efficiency Perovskite/Silicon Tandem Photovoltaics.

The remarkable recent progress in perovskite photovoltaics affords a novel opportunity to advance the power conversion efficiency of market-dominating crystalline silicon (c-Si) solar cells. A severe limiting factor in the development of perovskite/c-Si tandems to date has been their inferior light-harvesting ability compared to single-junction c-Si solar cells, but recent innovations have made impressive headway on this front. Here, we provide a quantitative perspective on future steps to advance perovskite/c-Si tandem photovoltaics from a light-management point of view, addressing key challenges and available strategies relevant to both the 2-terminal and 4-terminal perovskite/c-Si tandem architectures. In particular, we discuss the challenge of achieving low optical reflection in 2-terminal cells, optical shortcomings in state-of-the-art devices, the impact of transparent electrode performance, and a variety of factors which influence the optimal bandgap for perovskite top-cells. Focused attention in each of these areas will be required to make the most of the tandem opportunity.

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.

Field Performance versus Standard Test Condition Efficiency of Tandem Solar Cells and the Singular Case of Perovskites/Silicon Devices.

Multijunction cells may offer a cost-effective route to boost the efficiency of industrial photovoltaics. For any technology to be deployed in the field, its performance under actual operating conditions is extremely important. In this perspective, we evaluate the impact of spectrum, light intensity, and module temperature variations on the efficiency of tandem devices with crystalline silicon bottom cells with a particular focus on perovskite top cells. We consider devices with different efficiencies and calculate their energy yields using field data from Denver. We find that annual losses due to differences between operating conditions and standard test conditions are similar for single-junction and four-terminal tandem devices. The additional loss for the two-terminal tandem configuration caused by current mismatch reduces its performance ratio by only 1.7% when an optimal top cell bandgap is used. Additionally, the unusual bandgap temperature dependence of perovskites is shown to have a positive, compensating effect on current mismatch.

Direct Imaging of Dopant Distribution in Polycrystalline ZnO Films.

Two fundamental requirements of transparent conductive oxides are high conductivity and low optical absorptance, properties strongly dependent on the free-carrier concentration of the film. The free-carrier concentration is usually tuned by the addition of dopant atoms; which are commonly assumed to be uniformly distributed in the films or partially segregated at grain boundaries. Here, the combination of secondary ion mass spectroscopy at the nanometric scale (NanoSIMS) and Kelvin probe force microscopy (KPFM) allows direct imaging of boron-dopant distribution in polycrystalline zinc oxide (ZnO) films. This work demonstrates that the boron atoms have a bimodal spatial distribution within each grain of the ZnO films. NanoSIMS analysis shows that boron atoms are preferentially incorporated into one of the two sides of each ZnO grain. KPFM measurements confirm that boron atoms are electrically active, locally increasing the free-carrier concentration in the film. The proposed cause of this nonuniform dopant distribution is the different sticking coefficient of Zn adatoms on the two distinct surface terminations of the ZnO grains. The higher sticking coefficient of Zn on the c+ surface restricts the boron incorporation on this side of the grains, resulting in preferential boron incorporation on the c- side and causing the bimodal distribution.

Photocurrent Spectroscopy of Perovskite Layers and Solar Cells: A Sensitive Probe of Material Degradation.

Optical absorptance spectroscopy of polycrystalline CH3NH3PbI3 films usually indicates the presence of a PbI2 phase, either as a preparation residue or due to film degradation, but gives no insight on how this may affect electrical properties. Here, we apply photocurrent spectroscopy to both perovskite solar cells and coplanar-contacted layers at various stages of degradation. In both cases, we find that the presence of a PbI2 phase restricts charge-carrier transport, suggesting that PbI2 encapsulates CH3NH3PbI3 grains. We also find that PbI2 injects holes into the CH3NH3PbI3 grains, increasing the apparent photosensitivity of PbI2. This phenomenon, known as modulation doping, is absent in the photocurrent spectra of solar cells, where holes and electrons have to be collected in pairs. This interpretation provides insights into the photogeneration and carrier transport in dual-phase perovskites.

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.

Probing Photocurrent Nonuniformities in the Subcells of Monolithic Perovskite/Silicon Tandem Solar Cells.

Perovskite/silicon tandem solar cells with high power conversion efficiencies have the potential to become a commercially viable photovoltaic option in the near future. However, device design and optimization is challenging because conventional characterization methods do not give clear feedback on the localized chemical and physical factors that limit performance within individual subcells, especially when stability and degradation is a concern. In this study, we use light beam induced current (LBIC) to probe photocurrent collection nonuniformities in the individual subcells of perovskite/silicon tandems. The choices of lasers and light biasing conditions allow efficiency-limiting effects relating to processing defects, optical interference within the individual cells, and the evolution of water-induced device degradation to be spatially resolved. The results reveal several types of microscopic defects and demonstrate that eliminating these and managing the optical properties within the multilayer structures will be important for future optimization of perovskite/silicon tandem solar cells.

Profilometry of thin films on rough substrates by Raman spectroscopy.

Thin, light-absorbing films attenuate the Raman signal of underlying substrates. In this article, we exploit this phenomenon to develop a contactless thickness profiling method for thin films deposited on rough substrates. We demonstrate this technique by probing profiles of thin amorphous silicon stripes deposited on rough crystalline silicon surfaces, which is a structure exploited in high-efficiency silicon heterojunction solar cells. Our spatially-resolved Raman measurements enable the thickness mapping of amorphous silicon over the whole active area of test solar cells with very high precision; the thickness detection limit is well below 1 nm and the spatial resolution is down to 500 nm, limited only by the optical resolution. We also discuss the wider applicability of this technique for the characterization of thin layers prepared on Raman/photoluminescence-active substrates, as well as its use for single-layer counting in multilayer 2D materials such as graphene, MoS2 and WS2.