Quantum barriers engineering toward radiative and stable perovskite photovoltaic devices.

Efficient photovoltaic devices must be efficient light emitters to reach the thermodynamic efficiency limit. Here, we present a promising prospect of perovskite photovoltaics as bright emitters by harnessing the significant benefits of photon recycling, which can be practically achieved by suppressing interfacial quenching. We have achieved radiative and stable perovskite photovoltaic devices by the design of a multiple quantum well structure with long (∼3 nm) organic spacers with oleylammonium molecules at perovskite top interfaces. Our L-site exchange process (L: barrier molecule cation) enables the formation of stable interfacial structures with moderate conductivity despite the thick barriers. Compared to popular short (∼1 nm) Ls, our approach results in enhanced radiation efficiency through the recursive process of photon recycling. This leads to the realization of radiative perovskite photovoltaics with both high photovoltaic efficiency (in-lab 26.0%, certified to 25.2%) and electroluminescence quantum efficiency (19.7 % at peak, 17.8% at 1-sun equivalent condition). Furthermore, the stable crystallinity of oleylammonium-based quantum wells enables our devices to maintain high efficiencies for over 1000 h of operation and >2 years of storage.

Redox-mediated changes in the release dynamics of lead (Pb) and bacterial community composition in a biochar amended soil contaminated with metal halide perovskite solar panel waste.

This study explored the redox-mediated changes in a lead (Pb) contaminated soil (900 mg/kg) due to the addition of solar cell powder (SC) and investigated the impact of biochar derived from soft wood pellet (SWP) and oil seed rape straw (OSR) (5% w/w) on Pb immobilization using an automated biogeochemical microcosm system. The redox potential (Eh) of the untreated (control; SC) and biochar treated soils (SC + SWP and SC + OSR) ranged from -151 mV to +493 mV. In SC, the dissolved Pb concentrations were higher under oxic (up to 2.29 mg L-1) conditions than reducing (0.13 mg L-1) conditions. The addition of SWP and OSR to soil immobilized Pb, decreased dissolved concentration, which could be possibly due to the increase of pH, co-precipitation of Pb with FeMn (hydro)oxides and pyromorphite, and complexation with biochar surface functional groups. The ability and efficiency of OSR for Pb immobilization were higher than SWP, owing to the higher pH and density of surface functional groups of OSR than SWP. Biochar enhanced the relative abundance of Proteobacteria irrespective of Eh changes, while the relative abundance of Bacteroidota increased under oxidizing conditions. Overall, we found that both OSR and SWP immobilized Pb in solar panel waste contaminated soil under both oxidizing and reducing redox conditions which may mitigate the potential risk of Pb contamination.

Defect Engineering of Metal Halide Perovskite Nanocrystals via Spontaneous Diffusion of Ag Nanocrystals.

Perovskite nanocrystals (NCs) have emerged as a promising building block for the fabrication of optic-/optoelectronic-/electronic devices owing to their superior characteristics, such as high absorption coefficient, rapid ion mobilities, and tunable energy levels. However, their low structural stability and poor surface passivation have restricted their application to next-generation devices. Herein, a drug delivery system (DDS)-inspired post-treatment strategy is reported for improving their structural stability by doping of Ag into CsPbBr3 (CPB) perovskite NCs; delivery to damaged sites can promote their structural recovery slowly and uniformly, averting the permanent loss of their intrinsic characteristics. Ag NCs are designed through surface-chemistry tuning and structural engineering to enable their circulation in CPB NC dispersions, followed by their delivery to the CPB NC surface, defect-site recovery, and defect prevention. The perovskite-structure healing process through the DDS-type process (with Ag NCs as the drug) is analyzed by a combination of theoretical calculations (with density functional theory) and experimental analyses. The proposed DDS-inspired healing strategy significantly enhances the optical properties and stability of perovskite NCs, enabling the fabrication of white light-emitting diodes.

Environmental impact of metal halide perovskite solar cells and potential mitigation strategies: A critical review.

Metal halide perovskite solar cells (PSCs) have gained extensive attention in the field of solar photovoltaic technology over the past few years. Despite being a remarkable alternative to fossil fuels, solar cells may have detrimental effects on the environment and human health owing to the use of toxic materials during manufacturing. Although modern metal-halide-based PSCs are stable and have encapsulation to prevent the release of potentially toxic materials into the environment, their destruction due to strong winds, hail, snow, landslides, fires, or waste disposal can result in the exposure of these materials to the environment. This may lead to the contamination of soil and groundwater, and uptake of potentially toxic elements by plants, subsequently affecting humans and other living organisms via food chain contamination. Despite worldwide concern, the environmental and ecotoxicological impacts of metal-halide-based PSCs have not been comprehensively surveyed. This review summarizes and critically evaluates the current status of metal-halide-based PSC production and its impact on environmental sustainability, food security, and human health. Furthermore, safe handling and disposal methods for the waste generated from metal-halide-based PSCs are proposed, with a focus on recycling and reuse. Although some studies have suggested that the amount of lead released from metal halide PSCs is far below the maximum permissible levels in most soils, a clear conclusion cannot be reached until real contamination scenarios are assessed under field conditions. Precautions must be taken to minimize environmental contamination throughout the lifecycle of PSCs until nontoxic and similarly performing alternative solar photovoltaic products are developed.

Efficient vertical charge transport in polycrystalline halide perovskites revealed by four-dimensional tracking of charge carriers.

Fast diffusion of charge carriers is crucial for efficient charge collection in perovskite solar cells. While lateral transient photoluminescence microscopies have been popularly used to characterize charge diffusion in perovskites, there exists a discrepancy between low diffusion coefficients measured and near-unity charge collection efficiencies achieved in practical solar cells. Here, we reveal hidden microscopic dynamics in halide perovskites through four-dimensional (directions x, y and z and time t) tracking of charge carriers by characterizing out-of-plane diffusion of charge carriers. By combining this approach with confocal microscopy, we discover a strong local heterogeneity of vertical charge diffusivities in a three-dimensional perovskite film, arising from the difference between intragrain and intergrain diffusion. We visualize that most charge carriers are efficiently transported through the direct intragrain pathways or via indirect detours through nearby areas with fast diffusion. The observed anisotropy and heterogeneity of charge carrier diffusion in perovskites rationalize their high performance as shown in real devices. Our work also foresees that further control of polycrystal growth will enable solar cells with micrometres-thick perovskites to achieve both long optical path length and efficient charge collection simultaneously.

High-Performance Cold Cathode X-ray Tubes Using a Carbon Nanotube Field Electron Emitter.

A cold cathode X-ray tube was fabricated using a carbon nanotube (CNT) field electron emitter made by a free-standing CNT film which is composed of a highly packed CNT network. A lot of CNT bundles with a sharp tip are vertically aligned at the edge of the thin CNT film with a length of 10 mm and a thickness of 7 µm. The cold cathode X-ray tube using the CNT field emitter presents an extremely high tube current density of 152 A/cm2 (corresponding to tube current of 106.4 mA), the electron beam transmittance of 95.2% and a small focal spot size (FSS) of 0.5 mm. In addition, the cold cathode X-ray tube also shows stable lifetime during 100 000 shots. High emission current density of the cold cathode X-ray tube is mainly attributed to a lot of electron emission sites at an edge of the CNT film. The small FSS is caused by an ensemble of the CNT field electron emitter made by a free-standing thin CNT film and the optimized curve-shape elliptical focusing lens. Based on obtained results, the cold cathode X-ray tube can be widely used for various X-ray applications such as medical diagnosis systems and security check systems in the future.

Suppressing Halide Segregation in Wide-Band-Gap Mixed-Halide Perovskite Layers through Post-Hot Pressing.

Mixed-halide perovskites (MHPs) have attracted attention as suitable wide-band-gap candidate materials for tandem applications owing to their facile band-gap tuning. However, when smaller bromide ions are incorporated into iodides to tune the band gap, photoinduced halide segregation occurs, which leads to voltage deficit and photoinstability. Here, we propose an original post-hot pressing (PHP) treatment that suppresses halide segregation in MHPs with a band gap of 2.0 eV. The PHP treatment reconstructs open-structured grain boundaries (GBs) as compact GBs through constrained grain growth in the in-plane direction, resulting in the inhibition of defect-mediated ion migration in GBs. The PHP-treated wide-band-gap (2.0 eV) MHP solar cells showed a high efficiency of over 11%, achieving an open-circuit voltage (Voc) of 1.35 V and improving the maintenance of the initial efficiency under the working condition at AM 1.5G. The results reveal that the management of GBs is necessary to secure the stability of wide-band-gap MHP devices in terms of halide segregation.

Effects of photon recycling and scattering in high-performance perovskite solar cells.

Efficient external radiation is essential for solar cells to achieve high power conversion efficiency (PCE). The classical limit of 1/2n2 (n, refractive index) for electroluminescence quantum efficiency (ELQE) has recently been approached by perovskite solar cells (PSCs). Photon recycling (PR) and light scattering can provide an opportunity to surpass this limit. We investigate the role of PR and scattering in practical device operation using a radiative PSC with an ELQE (13.7% at 1 sun) that significantly surpasses the classical limit (7.4%). We experimentally analyze the contributions of PR and scattering to this strong radiation. A novel optical model reveals an increase of 39 mV in the voltage of our PSC. This analysis can provide design principles for future PSCs to approach the Shockley-Queisser efficiency limit.

Microstructural Evaluation of Phase Instability in Large Bandgap Metal Halide Perovskites.

The optoelectronic performance of organic-inorganic halide perovskite (OIHP)-based devices has been improved in recent years. Particularly, solar cells fabricated using mixed-cations and mixed-halides have outperformed their single-cation and single-halide counterparts. Yet, a systematic evaluation of the microstructural behavior of mixed perovskites is missing despite their known composition-dependent photoinstability. Here, we explore microstructural inhomogeneity in (FAPbI3)x(MAPbBr3)1-x using advanced scanning probe microscopy techniques. Contact potential difference (CPD) maps measured by Kelvin probe force microscopy show an increased fraction of grains exhibiting a low CPD with flat topography as MAPbBr3 concentration is increased. The higher portion of low CPD contributes to asymmetric CPD distribution curves. Chemical analysis reveals these grains being rich in MA, Pb, and I. The composition-dependent phase segregation upon illumination, reflected on the emergence of a low-energy peak emission in the original photoluminescence spectra, arises from the formation of such grains with flat topology. Bias-dependent piezo-response force microscopy measurements, in these grains, further confirm vigorous ion migration and cause a hysteretic piezo-response. Our results, therefore, provide insights into the microstructural evaluation of phase segregation and ion migration in OIHPs pointing toward process optimization as a mean to further enhance their optoelectronic performance.

Simultaneous Enhanced Efficiency and Stability of Perovskite Solar Cells Using Adhesive Fluorinated Polymer Interfacial Material.

For enhancing the performance and long-term stability of perovskite solar cell (PSC) devices, interfacial engineering between the perovskite and hole-transporting material (HTM) is important. We developed a fluorinated conjugated polymer PFPT3 and used it as an interfacial layer between the perovskite and HTM layers in normal-type PSCs. Interaction of perovskite and PFPT3 via Pb-F bonding effectively induces an interfacial dipole moment, which resulted in energy-level bending; this was favorable for charge transfer and hole extraction at the interface. The PSC device achieved an increased efficiency of 22.00% with an open-circuit voltage of 1.13 V, short-circuit current density of 24.34 mA/cm2, and fill factor of 0.80 from a reverse scan and showed an averaged power conversion efficiency of 21.59%, which was averaged from forward and reverse scans. Furthermore, the device with PFPT3 showed much improved stability under an 85% RH condition because hydrophobic PFPT3 reduced water permeation into the perovskite layer, and more importantly, the enhanced contact adhesion at the PFPT3-mediated perovskite/HTM interface suppressed surface delamination and retarded water intrusion. The fluorinated conjugated polymeric interfacial material is effective for improving not only the efficiency but also the stability of the PSC devices.

Recent Progress in Metal Halide Perovskite-Based Tandem Solar Cells.

Metal halide perovskite (MHP)-based tandem solar cells are a promising candidate for use in cost-effective and high-performance solar cells that can compete with fossil fuels. To understand the research trends for MHP-based tandem solar cells, a general introduction to single-junction and multiple-junction MHP solar cells and the configuration of tandem devices is provided, along with an overview of the recent progress regarding various MHP-based tandem cells, including MHP/crystalline silicon, MHP/CuInGaS, MHP/organic photovoltaic, MHP/quantum dot, and all-perovskite tandem cell. Future research directions for MHP-based tandem solar cells are also discussed.

Carrier-resolved photo-Hall effect.

The fundamental parameters of majority and minority charge carriers-including their type, density and mobility-govern the performance of semiconductor devices yet can be difficult to measure. Although the Hall measurement technique is currently the standard for extracting the properties of majority carriers, those of minority carriers have typically only been accessible through the application of separate techniques. Here we demonstrate an extension to the classic Hall measurement-a carrier-resolved photo-Hall technique-that enables us to simultaneously obtain the mobility and concentration of both majority and minority carriers, as well as the recombination lifetime, diffusion length and recombination coefficient. This is enabled by advances in a.c.-field Hall measurement using a rotating parallel dipole line system and an equation, ΔµH = d(σ2H)/dσ, which relates the hole-electron Hall mobility difference (ΔµH), the conductivity (σ) and the Hall coefficient (H). We apply this technique to various solar absorbers-including high-performance lead-iodide-based perovskites-and demonstrate simultaneous access to majority and minority carrier parameters and map the results against varying light intensities. This information, which is buried within the photo-Hall measurement1,2, had remained inaccessible since the original discovery of the Hall effect in 18793. The simultaneous measurement of majority and minority carriers should have broad applications, including in photovoltaics and other optoelectronic devices.

Band Alignment Engineering between Planar SnO2 and Halide Perovskites via Two-Step Annealing.

Managing defects in SnO2 is critical for improving the power conversion efficiency (PCE) of halide perovskite-based solar cells. However, typically reported SnO2-based perovskite solar cells have inherent defects in the SnO2 layer, which lead to a lower PCE and hysteresis. Here, we report that a dual-coating approach for SnO2 with different annealing temperatures can simultaneously form a SnO2 layer with high crystallinity and uniform surface coverage. Along with these enhanced physical properties, the dual-coated SnO2 layer shows favorable band alignment with a mixed halide perovskite. After careful optimization of the dual-coating method, the average PCE of the perovskite solar cell based on the dual-coated SnO2 layer increases from 18.07 to 19.23% with a best-performing cell of 20.03%. Note that a facile two-step coating and annealing method can open new avenues to develop SnO2-based perovskite solar cells with stabilized and improved photovoltaic performances.

Single-Solution Bar-Coated Halide Perovskite Films via Mediating Crystallization for Scalable Solar Cell Fabrication.

The development of a scalable fabrication technology for halide perovskite solar cells (HPSCs) is an important challenge to realize their commercialization. In particular, continuous solution-coating processes are needed to produce scalable large-area HPSCs. Herein, we report a single-solution bar-coating process that introduces an intermediate phase stage for large-area CH3NH3PbI3 films with full coverage and smooth morphology using N-cyclohexyl-2-pyrrolidone (CHP) as a mediator. In contrast to the conventional double-solution coating methods that use antisolvent treatments, the preformed uniform intermediate phase in the single-solution bar-coating process enables the formation of highly uniform perovskite films with a 10 cm × 10 cm area even without antisolvent treatment. The HPSCs fabricated using the resultant single-solution bar-coated perovskite films exhibit superior photovoltaic performance, narrower distribution, and smaller loss with a larger active area than devices fabricated using single-solution spin-coated perovskite films.

Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene).

Perovskite solar cells typically comprise electron- and hole-transport materials deposited on each side of a perovskite active layer. So far, only two organic hole-transport materials have led to state-of-the-art performance in these solar cells1: poly(triarylamine) (PTAA)2-5 and 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD)6,7. However, these materials have several drawbacks in terms of commercialization, including high cost8, the need for hygroscopic dopants that trigger degradation of the perovskite layer9 and limitations in their deposition processes10. Poly(3-hexylthiophene) (P3HT) is an alternative hole-transport material with excellent optoelectronic properties11-13, low cost8,14 and ease of fabrication15-18, but so far the efficiencies of perovskite solar cells using P3HT have reached only around 16 per cent19. Here we propose a device architecture for highly efficient perovskite solar cells that use P3HT as a hole-transport material without any dopants. A thin layer of wide-bandgap halide perovskite is formed on top of the narrow-bandgap light-absorbing layer by an in situ reaction of n-hexyl trimethyl ammonium bromide on the perovskite surface. Our device has a certified power conversion efficiency of 22.7 per cent with hysteresis of ±0.51 per cent; exhibits good stability at 85 per cent relative humidity without encapsulation; and upon encapsulation demonstrates long-term operational stability for 1,370 hours under 1-Sun illumination at room temperature, maintaining 95 per cent of the initial efficiency. We extend our platform to large-area modules (24.97 square centimetres)-which are fabricated using a scalable bar-coating method for the deposition of P3HT-and achieve a power conversion efficiency of 16.0 per cent. Realizing the potential of P3HT as a hole-transport material by using a wide-bandgap halide could be a valuable direction for perovskite solar-cell research.

Simultaneous Ligand Exchange Fabrication of Flexible Perovskite Solar Cells using Newly Synthesized Uniform Tin Oxide Quantum Dots.

Halide perovskite solar cells (HPSCs) have a significant potential for future photovoltaic systems because of a high power conversion efficiency (PCE) exceeding 23% using solution processing methods. A low-temperature processed oxide layer is a challenging issue for large-scale manufacture of flexible and low-cost HPSCs. Here, we propose a simple reverse micelle-water injection method for highly dispersed ligand-capped ultrafine SnO2 quantum dots (QD). Interestingly, we observed that the ligands, which help in the formation of a uniform SnO2 QD thin film, spontaneously exchange for halide through a perovskite solution, and finally we form a suitable SnO2 QD-halide junction for high-performance HPSCs. The flexible HPSC with the SnO2 QD-halide junction formed via the ligand exchange exhibits a high PCE of 17.7% using a flexible substrate. It also shows an excellent flexibility, where the initial PCE is maintained within 92% after 1000 bending cycles with a bending radius of 18 mm.

Highly Durable and Flexible Transparent Electrode for Flexible Optoelectronic Applications.

A highly-durable, highly-flexible transparent electrode (FTE) is developed by applying a composite made of a thin metal grid and a doped conducting polymer onto a colorless polyimide-coated NOA63 substrate. The proposed FTE exhibits a transparency of 90.7% at 550 nm including the substrate and a sheet resistance of 30.3 Ω/sq and can withstand both moderately high-temperature annealing (∼180 °C) and acidic solution (70 °C, pH 0.3) processes without performance degradation. The fabricated FTE yielded good mechanical stability under 10 000 cycles of bending deformations at a bending radius less than 1 mm without degradation of electrical conductivity. The high durability of the proposed FTE allows for the fabrication of flexible energy harvesting devices requiring harsh conditions, such as highly flexible perovskite solar cells (FPSCs) with a steady-state power conversion efficiency (PCE) of 12.7%. Notably, 93% of the original PCE is maintained after 2000 bending cycles at an extremely small bending radius of 1.5 mm. The FPSCs installed on curved surfaces of commercial devices drive them under various environments. The applicability of the proposed FTE is further confirmed via the fabrication of a flexible perovskite light-emitting diode. The proposed FTE demonstrates great potential for applications in the field of flexible optoelectronic devices.

Iodide management in formamidinium-lead-halide-based perovskite layers for efficient solar cells.

The formation of a dense and uniform thin layer on the substrates is crucial for the fabrication of high-performance perovskite solar cells (PSCs) containing formamidinium with multiple cations and mixed halide anions. The concentration of defect states, which reduce a cell's performance by decreasing the open-circuit voltage and short-circuit current density, needs to be as low as possible. We show that the introduction of additional iodide ions into the organic cation solution, which are used to form the perovskite layers through an intramolecular exchanging process, decreases the concentration of deep-level defects. The defect-engineered thin perovskite layers enable the fabrication of PSCs with a certified power conversion efficiency of 22.1% in small cells and 19.7% in 1-square-centimeter cells.

Indolo[3,2-b]indole-based crystalline hole-transporting material for highly efficient perovskite solar cells.

We have designed and synthesized fluorinated indolo[3,2-b]indole (IDID) derivatives as crystalline hole-transporting materials (HTM) for perovskite solar cells. The fluorinated IDID backbone enables a tight molecular arrangement stacked by strong π-π interactions, leading to a higher hole mobility than that of the current HTM standard, p,p-spiro-OMeTAD, with a spherical shape and amorphous morphology. Moreover, the photoluminescence quenching in a perovskite/HTM film is more effective at the interface of the perovskite with IDIDF as compared to that of p,p-spiro-OMeTAD. As a consequence, the device fabricated using IDIDF shows superior photovoltaic properties compared to that using p,p-spiro-OMeTAD, exhibiting an optimal performance of 19%. Thus, this remarkable result demonstrates IDID core-based materials as a new class of HTMs for highly efficient perovskite solar cells.