Centimetre-scale perovskite solar cells with fill factors of more than 86 per cent.

Owing to rapid development in their efficiency1 and stability2, perovskite solar cells are at the forefront of emerging photovoltaic technologies. State-of-the-art cells exhibit voltage losses3-8 approaching the theoretical minimum and near-unity internal quantum efficiency9-13, but conversion efficiencies are limited by the fill factor (<83%, below the Shockley-Queisser limit of approximately 90%). This limitation results from non-ideal charge transport between the perovskite absorber and the cell's electrodes5,8,13-16. Reducing the electrical series resistance of charge transport layers is therefore crucial for improving efficiency. Here we introduce a reverse-doping process to fabricate nitrogen-doped titanium oxide electron transport layers with outstanding charge transport performance. By incorporating this charge transport material into perovskite solar cells, we demonstrate 1-cm2 cells with fill factors of >86%, and an average fill factor of 85.3%. We also report a certified steady-state efficiency of 22.6% for a 1-cm2 cell (23.33% ± 0.58% from a reverse current-voltage scan).

In Situ Formation of Mixed-Dimensional Surface Passivation Layers in Perovskite Solar Cells with Dual-Isomer Alkylammonium Cations.

Dimensional engineering of perovskite solar cells has attracted significant research attention recently because of the potential to improve both device performance and stability. Here, a novel 2D passivation scheme for 3D perovskite solar cells is demonstrated using a mixed cation composition of 2D perovskite based on two different isomers of butylammonium iodide. The dual-cation 2D perovskite outperforms its single cation 2D counterparts in surface passivation quality, resulting in devices with an impressive open-circuit voltage of 1.21 V for a perovskite composition with an optical bandgap of ≈1.6 eV, and a champion efficiency of 23.27%. Using a combination of surface elemental analysis and valence electron spectra decomposition, it is shown that an in situ interaction between the 2D perovskite precursor and the 3D active layer results in surface intermixing of 3D and 2D perovskite phases, providing an effective combination of defect passivation and enhanced charge transfer, despite the semi-insulating nature of the 2D perovskite phase. The demonstration of the synergistic interaction of multiple organic spacer cations in a 2D passivation layer offers new opportunities for further enhancement of device performance with mixed dimensional perovskite solar cells.

Light-activated inorganic CsPbBr2I perovskite for room-temperature self-powered chemical sensing.

Halide perovskite materials are excellent light harvesters that have generated enormous interest for photovoltaic technology and an increasing number of other optoelectronic applications. Very recently, their use for miniaturized chemical sensors has shown a promising room-temperature response. Here, we present some insights on the use of CsPbBr2I (CPBI) perovskites for self-powered room-temperature sensing of several environmentally and medically relevant compounds demonstrating rapid detection of down to concentrations of 1 ppm. Notably, the photocurrent of these self-powered CPBI-based devices increases under exposure to both reducing (e.g. acetone, propane) and oxidizing (e.g. NO2, O2) gas molecules and decreases rapidly upon reverting to an inert atmosphere. In situ photoluminescence (PL) analysis of the CPBI during exposure to oxidizing molecules reveals a strongly increased PL intensity and longer lifetime indicating a prevalent role of CPBI trap states in the sensing mechanism. These findings provide new insights for the engineering of perovskite-based materials for their future chemical sensing applications.

Superior Self-Powered Room-Temperature Chemical Sensing with Light-Activated Inorganic Halides Perovskites.

Hybrid halide perovskite is one of the promising light absorber and is intensively investigated for many optoelectronic applications. Here, the first prototype of a self-powered inorganic halides perovskite for chemical gas sensing at room temperature under visible-light irradiation is presented. These devices consist of porous network of CsPbBr3 (CPB) and can generate an open-circuit voltage of 0.87 V under visible-light irradiation, which can be used to detect various concentrations of O2 and parts per million concentrations of medically relevant volatile organic compounds such as acetone and ethanol with very quick response and recovery time. It is observed that O2 gas can passivate the surface trap sites in CPB and the ambipolar charge transport in the perovskite layer results in a distinct sensing mechanism compared with established semiconductors with symmetric electrical response to both oxidizing and reducing gases. The platform of CPB-based gas sensor provides new insights for the emerging area of wearable sensors for personalized and preventive medicine.

Hysteresis phenomena in perovskite solar cells: the many and varied effects of ionic accumulation.

The issue of hysteresis in perovskite solar cells has now been convincingly linked to the presence of mobile ions within the perovskite layer. Here we test the limits of the ionic theory by attempting to account for a number of exotic characterization results using a detailed numerical device model that incorporates ionic charge accumulation at the perovskite interfaces. Our experimental observations include a temporary enhancement in open-circuit voltage following prolonged periods of negative bias, dramatically S-shaped current-voltage sweeps, decreased current extraction following positive biasing or "inverted hysteresis", and non-monotonic transient behaviours in the dark and the light. Each one of these phenomena can be reproduced and ultimately explained by our models, providing further evidence for the ionic theory of hysteresis as well as valuable physical insight into the factors that coincide to bring these phenomena about. In particular we find that both interfacial recombination and carrier injection from the selective contacts are heavily affected by ionic accumulation, and are essential to explaining the non-monotonic voltage transients and S-shaped J-V curves. Inverted hysteresis is attributed to the occurrence of "positive" ionic accumulation, which may also be responsible for enhancing the stabilized open-circuit voltage in some perovskite cells.

Flame-made ultra-porous TiO2 layers for perovskite solar cells.

We report methyl ammonium lead iodide (MAPbI3) solar cells with an ultra-porous TiO2 electron transport layer fabricated using sequential flame aerosol and atomic layer depositions of porous and compact TiO2 layers. Flame aerosol pyrolysis allows rapid deposition of nanostructured and ultra-porous TiO2 layers that could be easily scaled-up for high-throughput low-cost industrial solar cell production. An efficiency of 13.7% was achieved with a flame-made nanostructured and ultra-porous TiO2 electrode that was coated with a compact 2 nm TiO2 layer. This demonstrates that MAPbI3 solar cells with a flame-made porous TiO2 layer can have a comparable efficiency to that of the control MAPbI3 solar cell with the well-established spin-coated porous TiO2 layer. The combination of flame aerosol and atomic layer deposition provides precise control of the TiO2 porosity. Notably, the porosity of the as-deposited flame-made TiO2 layers was 97% which was then fine-tuned down to 87%, 56% and 35% by varying the thickness of the subsequent compact TiO2 coating step. The effects of the decrease in porosity on the device performance are discussed. It is also shown that MAPbI3 easily infiltrates into the flame-made porous TiO2 nanostructure thanks to their high porosity and large pore size.

Photoluminescence study of time- and spatial-dependent light induced trap de-activation in CH3NH3PbI3 perovskite films.

Organometal halide perovskite-based solar cells have rapidly achieved high efficiency in recent years. However, many fundamental recombination mechanisms underlying the excellent performance are still not well understood. Here we apply confocal photoluminescence microscopy to investigate the time and spatial characteristics of light-induced trap de-activation in CH3NH3PbI3 perovskite films. Trap de-activation is characterized by a dramatic increase in PL emission during continuous laser illumination accompanied by a lateral expansion of the PL enhancement far beyond the laser spot. These observations are attributed to an oxygen-assisted trap de-activation process associated with carrier diffusion. To model this effect, we add a trap de-activation term to the standard semiconductor carrier recombination and diffusion models. With this approach we are able to reproduce the observed temporal and spatial dependence of laser induced PL enhancement using realistic physical parameters. Furthermore, we experimentally investigate the role of trap diffusion in this process, and demonstrate that the trap de-activation is not permanent, with the traps appearing again once the illumination is turned off. This study provides new insights into recombination and trap dynamics in perovskite films that could offer a better understanding of perovskite solar cell performance.

Light trapping efficiency comparison of Si solar cell textures using spectral photoluminescence.

The band-to-band absorption enhancement due to various types of light trapping structures is studied experimentally with photoluminescence (PL) on monocrystalline silicon wafers. Four basic light trapping structures are examined: reactive ion etched texture (RIE), metal-assisted etched texture (MET), random pyramid texture (RAN) and plasmonic Ag nanoparticles with a diffusive reflector (Ag/DR). We also compare two novel combined structures of front side RIE/rear side RAN and front side RIE/rear side Ag/DR. The use of photoluminescence allows us to measure the absorption due to band-to-band transitions only, and excludes parasitic absorption from free carriers and other sources. The measured absorptance spectra are used to calculate the maximum generation current for each structure, and the light trapping efficiency is compared to a recently-proposed figure of merit. The results show that by combining RIE with RAN and Ag/DR, we can fabricate two structures with excellent light trapping efficiencies of 55% and 52% respectively, which is well above previously reported values for similar wafer thicknesses. A comparison of the measured band-band absorption and the EQE of back-contact silicon solar cells demonstrates that PL extracted absorption provides a very good indication of long wavelength performance for high efficiency silicon solar cells.

Three-dimensional nanotub submicrometer diffraction gratings for solar cells.

Diffraction gratings are a promising approach for reducing reflection and achieving light-trapping in solar cells. Using square lattices as a base structure, we investigate a novel bi-periodic nanotub three-dimensional grating structure and compare it with established textured structures for thin-film and wafer applications. For wafer application, simulations show that optimal AR coated nanotubs demonstrated solar weighted reflectance (SWR) of 2% compared to AR coated square pyramids with values 1.9%. Nanotubs also show SWR below 8% for polar angles to 60°. Simulated short-circuit current thin-film cells with nanotubs using smaller dimensions show higher yields (3-6 mA/cm2 average) compared to square pyramids. For periods greater than 700 nm at aspect ratios of 0.7 and greater, nanotubs have reduced current attributed to the increased planar surface area of the nanotub base, and evident in increased SWR. A simple nanoimprint lithography process was employed in experiments to define a square array of circular holes, utilizing a polydimethylsiloxane (PDMS) stamp applied onto a sol-gel imprint resist. The underlying silicon was then wet etched to produce the nanotub textures of 200 nm height and 513 nm period. AR coated nanotub wafers were produced via plasma enhanced chemical vapor deposition (PECVD), with an experimental and theoretical SWR of 6.4% and 5.4%, respectively.

Enhanced light trapping in solar cells using snow globe coating.

A novel method, snow globe coating, is found to show significant enhancement of the short circuit current JSC (35%) when applied as a scattering back reflector for polycrystalline silicon thin-film solar cells. The coating is formed from high refractive index titania particles without containing binder and gives close to 100% reflectance for wavelengths above 400 nm. Snow globe coating is a physicochemical coating method executable in pH neutral media. The mild conditions of this process make this method applicable to many different types of solar cells.

Light trapping with plasmonic particles: beyond the dipole model.

Disk-shaped metal nanoparticles on high-index substrates can support resonant surface plasmon polariton (SPP) modes at the interface between the particle and the substrate. We demonstrate that this new conceptual model of nanoparticle scattering allows clear predictive abilities, beyond the dipole model. As would be expected from the nature of the mode, the SPP resonance is very sensitive to the area in contact with the substrate, and insensitive to particle height. We can employ this new understanding to minimise mode out-coupling and Ohmic losses in the particles. Taking into account optical losses due to parasitic absorption and outcoupling of scattered light, we estimate that an optimal array of nanoparticles on a 2 µm Si substrate can provide up to 71% of the enhancement in absorption achievable with an ideal Lambertian rear-reflector. This result compares to an estimate of 67% for conventional pyramid-type light trapping schemes.

Nanoscale localized contacts for high fill factors in polymer-passivated perovskite solar cells.

Polymer passivation layers can improve the open-circuit voltage of perovskite solar cells when inserted at the perovskite-charge transport layer interfaces. Unfortunately, many such layers are poor conductors, leading to a trade-off between passivation quality (voltage) and series resistance (fill factor, FF). Here, we introduce a nanopatterned electron transport layer that overcomes this trade-off by modifying the spatial distribution of the passivation layer to form nanoscale localized charge transport pathways through an otherwise passivated interface, thereby providing both effective passivation and excellent charge extraction. By combining the nanopatterned electron transport layer with a dopant-free hole transport layer, we achieved a certified power conversion efficiency of 21.6% for a 1-square-centimeter cell with FF of 0.839, and demonstrate an encapsulated cell that retains ~91.7% of its initial efficiency after 1000 hours of damp heat exposure.

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.

In situ recombination junction between p-Si and TiO2 enables high-efficiency monolithic perovskite/Si tandem cells.

Increasing the power conversion efficiency of silicon (Si) photovoltaics is a key enabler for continued reductions in the cost of solar electricity. Here, we describe a two-terminal perovskite/Si tandem design that increases the Si cell's output in the simplest possible manner: by placing a perovskite cell directly on top of the Si bottom cell. The advantageous omission of a conventional interlayer eliminates both optical losses and processing steps and is enabled by the low contact resistivity attainable between n-type TiO2 and Si, established here using atomic layer deposition. We fabricated proof-of-concept perovskite/Si tandems on both homojunction and passivating contact heterojunction Si cells to demonstrate the broad applicability of the interlayer-free concept. Stabilized efficiencies of 22.9 and 24.1% were obtained for the homojunction and passivating contact heterojunction tandems, respectively, which could be readily improved by reducing optical losses elsewhere in the device. This work highlights the potential of emerging perovskite photovoltaics to enable low-cost, high-efficiency tandem devices through straightforward integration with commercially relevant Si solar cells.

Improved Reproducibility for Perovskite Solar Cells with 1 cm2 Active Area by a Modified Two-Step Process.

With rapid progress in recent years, organohalide perovskite solar cells (PSC) are promising candidates for a new generation of highly efficient thin-film photovoltaic technologies, for which up-scaling is an essential step toward commercialization. In this work, we propose a modified two-step method to deposit the CH3NH3PbI3 (MAPbI3) perovskite film that improves the uniformity, photovoltaic performance, and repeatability of large-area perovskite solar cells. This method is based on the commonly used two-step method, with one additional process involving treating the perovskite film with concentrated methylammonium iodide (MAI) solution. This additional treatment is proved to be helpful for tailoring the residual PbI2 level to an optimal range that is favorable for both optical absorption and inhibition of recombination. Scanning electron microscopy and photoluminescence image analysis further reveal that, compared to the standard two-step and one-step methods, this method is very robust for achieving uniform and pinhole-free large-area films. This is validated by the photovoltaic performance of the prototype devices with an active area of 1 cm2, where we achieved the champion efficiency of ∼14.5% and an average efficiency of ∼13.5%, with excellent reproducibility.

Inverted Hysteresis in CH3NH3PbI3 Solar Cells: Role of Stoichiometry and Band Alignment.

J-V hysteresis in perovskite solar cells is known to be strongly dependent on many factors ranging from the cell structure to the preparation methods. Here we uncover one likely reason for such sensitivity by linking the stoichiometry in pure CH3NH3PbI3 (MAPbI3) perovskite cells with the character of their hysteresis behavior through the influence of internal band offsets. We present evidence indicating that in some cells the ion accumulation occurring at large forward biases causes a temporary and localized increase in recombination at the MAPbI3/TiO2 interface, leading to inverted hysteresis at fast scan rates. Numerical semiconductor models including ion accumulation are used to propose and analyze two possible origins for these localized recombination losses: one based on band bending and the other on an accumulation of ionic charge in the perovskite bulk.

Ultralow Absorption Coefficient and Temperature Dependence of Radiative Recombination of CH3NH3PbI3 Perovskite from Photoluminescence.

Spectrally resolved photoluminescence is used to measure the band-to-band absorption coefficient α(BB)(ℏω) of organic-inorganic hybrid perovskite methylammonium lead iodide (CH3NH3PbI3) films from 675 to 1400 nm. Unlike other methods used to extract the absorption coefficient, photoluminescence is only affected by band-to-band absorption and is capable of detecting absorption events at very low energy levels. Absorption coefficients as low as 10⁻¹4 cm⁻¹ are detected at room temperature for long wavelengths, which is 14 orders of magnitude lower than reported values at shorter wavelengths. The temperature dependence of α(BB)(ℏω) is calculated from the photoluminescence spectra of CH3NH3PbI3 in the temperature range 80-360 K. Based on the temperature-dependent α(BB)(ℏω), the product of the radiative recombination coefficient and square of the intrinsic carrier density, B(T) × n(i)², is also obtained.

Nanostructures in photovoltaics.

The world has recently been waking up to the urgent need to move away from fossil fuels and towards a low-carbon economy. To achieve this, we need a way of producing electricity that is efficient, widely applicable and cheap. At the same time, there has recently been an appreciation of the tremendous scope for making entirely new types of devices, and even seeing new physics, by structuring matter at the nanoscale. Furthermore, the occurrence of self-assembly in nature suggests that a range of types of nanoscale structures could be made simply and cheaply. The application of nanostructures to photovoltaics combines a field of almost limitless possibilities with a problem of vital urgency. In this paper, some of the newer ideas emerging from this trend are described, along with how they challenge our ideas on what a solar cell looks like. We are at the beginning of a time of radically rethinking the design of the solar cell, which may lead to the exploitation of completely new physical ideas in achieving a sustainable energy future.