Interfacial Charge Recombination Research Articles

Boosting Charge Utilization in Self-Powered Photodetector for Real-Time High-Throughput Ultraviolet Communication.

Ultraviolet (UV) communication is a cutting-edge technology in communication battlefields, and self-powered photodetectors as their optical receivers hold great potential. However, suboptimal charge utilization has largely limited the further performance enhancement of self-powered photodetectors for high-throughput communication application. Herein, a self-powered Ti3 C2 Tx -hybrid poly(3,4 ethylenedioxythiophene):poly-styrene sulfonate (PEDOT:PSS)/ZnO (TPZ) photodetector is designed, which aims to boost charge utilization for desirable applications. The device takes advantage of photothermal effect to intensify pyro-photoelectric effect as well as the increased conductivity of the PEDOT:PSS, which significantly facilitated charge separation, accelerated charge transport, and suppressed interface charge recombination. Consequently, the self-powered TPZ photodetector exhibits superior comprehensive performance with high responsivity of 12.3mA W-1 and fast response time of 62.2 µs, together with outstanding reversible and stable cyclic operation. Furthermore, the TPZ photodetector has been successfully applied in an integrated UV communication system as the self-powered optical receiver capable of real-time high-throughput information transmission with ASCII code under 9600 baud rate. This work provides the design insight of highly performing self-powered photodetectors to achieve high-efficiency optical communication in the future.

Roles of Cobalt-Coordinated Polymeric Perylene Diimide in Hematite Photoanodes for Improved Water Oxidation.

Interfacial charge recombination is a permanent issue that impedes the photon energy utilization in photoelectrochemical (PEC) water splitting. Herein, a conjugated polymer, urea linked perylene diimide polymer (PDI), is introduced to the designation of hematite-based composite photoanodes. On account of its unique molecule structure with abundant electronegative atoms, the O and N atoms with lone electron pairs can bond with Fe atoms at the surface of Zr4+ doped α-Fe2 O3 (Zr:Fe2 O3 ) and thus establish charge transfer channels for expediting hole separation and migration. Meanwhile, PDI molecules can passivate the surface states in Zr:Fe2 O3 , which is in favor of suppressing carrier recombination. Particularly, Co2+ is used to coordinate with PDI (Co-PDI) to accelerate hole extraction as well as utilization, and the as-obtained Co-PDI form type-II heterojunction with Zr:Fe2 O3 . Such a photoanode configuration takes advantage of the unique molecule structure of PDI, and the target Co-PDI/Zr:Fe2 O3 photoanodes eventually attain a photocurrent density of 2.17mAcm-2 , which is inspirational for unearthing the potential use of conjugative molecules in PEC fields.

Targeted passivation and optimized interfacial carrier dynamics improving the efficiency and stability of hole transport layer-free narrow-bandgap perovskite solar cells

Narrow-bandgap mixed Sn-Pb perovskite solar cells (PSCs) have showcased great potential to approach the Shockley-Queisser limit. Nevertheless, the practical application and long-term deployment of mixed Sn-Pb PSCs are still largely impeded by the rapid oxidation of Sn2+ ions and under-optimized carrier transport layer (CTL)/perovskite interfaces that would inevitably incur serious interfacial charge recombination and device performance degradation. Herein, we successfully removed the hole transport layer (HTL) by incorporating a small amount of organic phosphonic acid molecules into perovskites, which could preferably interact with Sn2+ ions (relative to Pb2+ analogues) at the grain boundaries (GBs) throughout the perovskite film thickness via coordination bonding, thus effectively retarding the oxidation of Sn2+, passivating the defects and suppressing the non-radiative recombination. Targeted modification effectively reinforced built-in potential by ∼100 mV, and favorably induced energy level cascade, thus accelerating spatial charge separation and facilitating the hole extraction from perovskite layer to underlying conductive electrodes even in the absence of HTL. Consequently, enhanced power conversion efficiencies up to 20.21% have been achieved, which is the record efficiency for the HTL-free mixed Sn-Pb PSCs, accompanied by a decent photovoltage of 0.87 V and improved long-term stability over 2400 h.

Constructing graded heterojunctions for rigid and flexible inverted photovoltaics under outdoor and indoor illumination

All inorganic perovskites (AIPs) have been widely used as an absorber for outdoor photovoltaics due to their high resistance toward thermal/light stress. Recently, CsPbI2Br with a wide bandgap of 1.93 eV has been considered optimal for indoor photovoltaics due to the higher efficiency limit than others. However, more often, inverted AIP devices suffer from serious charge recombination and inefficient carrier extraction, hence presenting unsatisfactory performance. In this work, solution-processable Bi2WO6 nanosheets (Nano-BWO) are prepared and deposited at the CsPbI2Br/PC61BM interface to form graded heterojunctions. A combined experimental and computational study reveals significant electron transfer from AIP to Nano-BWO and PC61BM due to their appropriate band structure offsets, leading to remarkably enhanced electron extraction in inverted devices. In addition, due to the defects passivation effect of Nano-BWO, the interfacial charge recombination is considerably reduced; meanwhile the electronic conductivity of the AIP absorber is remarkably enhanced. The resulting photovoltaics deliver a champion efficiency of 15.71% or 30.43% under one-sun (AM 1.5G) or white light emitting diode (WLED, 1000 lux) illumination. Furthermore, flexible devices with Nano-BWO achieve a high efficiency up to 13.74% (one-sun) or 24.50% (WLED). This work thus provides the first case of inverted AIP devices promising for indoor applications.

Engineering BiVO4 and Oxygen Evolution Cocatalyst Interfaces with Rapid Hole Extraction for Photoelectrochemical Water Splitting

Tailoring the oxygen evolution cocatalyst (OEC)/BiVO4 interfaces with a hole transfer layer (HTL) is expected to suppress the interfacial charge recombination, thus achieving highly efficient photoelectrochemical (PEC) water splitting. Herein, Co3O4 nanoparticles are inserted between the NiOOH OEC and BiVO4 as an HTL for the design of NiOOH/Co3O4/BiVO4 photoanodes. A champion photoanode achieves a photocurrent density of 6.4 mA cm–2 at 1.23 V versus the reversible hydrogen electrode (RHE) under AM 1.5 G illumination (100 mW cm–2). Stable PEC water splitting is realized for up to 90 h. Being highly dispersed at the surfaces of BiVO4, the p-type Co3O4 nanoparticles form p–n junctions with BiVO4, thus providing an extra driving force for the extraction of the photogenerated holes from BiVO4 to the NiOOH OEC, which efficiently suppresses charge recombination at the BiVO4/NiOOH interfaces and accelerates the surface water oxidation kinetics. A charge separation efficiency of 95.6% and a surface charge transfer efficiency of 97.7% are achieved at 1.23 V vs RHE. The strategy is applicable to other OEC (e.g., MnOx and FeOOH)/BiVO4 photoanodes. This work may inspire the rational design of high-performance photoanodes for feasible solar energy conversion.

Improving the Electron Transport Performance of TiO2 Film by Regulating TiCl4 Post-Treatment for High-Efficiency Carbon-Based Perovskite Solar Cells.

Titanium oxide (TiO2 ) has been widely used as an electron transport layer (ETL) in perovskite solar cells (PSCs). Typically, TiCl4 post-treatment is indispensable for modifying the surfaces of TiO2 ETL to improve the electron transport performance. However, it is challenging to produce the preferred anatase phase-dominated TiO2 by the TiCl4 post-treatment due to the higher thermodynamic stability of the rutile phase. In this work, a mild continuous pH control strategy for effectively regulating the hydrolysis process of TiCl4 post-treatment is proposed. As the weak organic base, urea has been demonstrated can maintain a moderate pH decrease during the hydrolysis process of TiCl4 while keeping the hydrolysis process relatively mild due to the ultra-weak alkalinity. The improved pH environment is beneficial for the formation of anatase TiO2 . Consequently, a uniform anatase-dominated TiO2 surface layer is formed on the mesoporous TiO2 , resulting in reduced defect density and superior band energy level. The interfacial charge recombination is effectively suppressed, and the charge extraction efficiency is improved simultaneously in the fabricated solar cells. The efficiency of the fabricated carbon electrode-based PSCs (C-PSCs) is improved from 16.63% to 18.08%, which is the highest for C-PSCs based on wide-bandgap perovskites.

Multifunctional Resonance Bridge-Mediated Dynamic Modulation of Perovskite Films For Enhanced Intrinsic Stability of Photovoltaics.

The improving intrinsic stability, determining the life span of devices, is a challenging task in the industrialization of inverted perovskite solar cells. The most important prerequisite for boosting intrinsic stability is high-quality perovskite films deposition. Here, a molecule, N-(2-pyridyl)pivalamide (NPP) is utilized, as a multifunctional resonance bridge between poly(triarylamine) (PTAA) and perovskite film to regulate the perovskite film quality and promote hole extraction for enhancing the device intrinsic stability. The pyridine groups in NPP couple with the phenyl groups in PTAA through π-π stacking to improve hole extraction capacities and minimize interfacial charge recombination, and the resonance linkages (NCO) in NPP dynamically modulate the perovskite buried defects through strong PbO bonds based on the fast self-adaptive tautomerization between resonance forms (NCO and N+ CO- ). Because of the combined effect of the reduction defect density and improved energy level in the perovskite buried interfaces as well as the optimized crystal orientation in perovskite film enabled by the NPP substrate, the devices based on NPP-grown perovskite films show an efficiency approaching 20% with negligible hysteresis. More impressively, the unencapsulated device displays start-of-the-art intrinsic photostability, operating under continuous 1-sun illumination for 2373 h at 65°C without loss of PCE.

Electro- and Photoinduced Interfacial Charge Transfers in Nanocrystalline Mesoporous TiO2 and TiO2/Iron Porphyrin Sensitized Films under CO2 Reduction Catalysis.

Electro- and photochemical CO2 reduction (CO2R) is the quintessence of modern-day sustainable research. We report our studies on the electro- and photoinduced interfacial charge transfer occurring in a nanocrystalline mesoporous TiO2 film and two TiO2/iron porphyrin hybrid films (meso-aryl- and β-pyrrole-substituted porphyrins, respectively) under CO2R conditions. We used transient absorption spectroscopy (TAS) to demonstrate that, under 355 nm laser excitation and an applied voltage bias (0 to -0.8 V vs Ag/AgCl), the TiO2 film exhibited a diminution in the transient absorption (at -0.5 V by 35%), as well as a reduction of the lifetime of the photogenerated electrons (at -0.5 V by 50%) when the experiments were conducted under a CO2 atmosphere changing from inert N2. The TiO2/iron porphyrin films showed faster charge recombination kinetics, featuring 100-fold faster transient signal decays than that of the TiO2 film. The electro-, photo-, and photoelectrochemical CO2R performance of the TiO2 and TiO2/iron porphyrin films are evaluated within the bias range of -0.5 to -1.8 V vs Ag/AgCl. The bare TiO2 film produced CO and CH4 as well as H2, depending on the applied voltage bias. In contrast, the TiO2/iron porphyrin films showed the exclusive formation of CO (100% selectivity) under identical conditions. During the CO2R, a gain in the overpotential values is obtained under light irradiation conditions. This finding was indicative of a direct transfer of the photogenerated electrons from the film to absorbed CO2 molecules and an observed decrease in the decay of the TAS signals. In the TiO2/iron porphyrin films, we identified the interfacial charge recombination processes between the oxidized iron porphyrin and the electrons of the TiO2 conduction band. These competitive processes are considered to be responsible for the diminution of direct charge transfer between the film and the adsorbed CO2 molecules, explaining the moderate performances of the hybrid films for the CO2R.

PbS Quantum Dots-Decorated BiVO4 Photoanodes for Highly Efficient Photoelectrochemical Hydrogen Production.

While metal oxides such as TiO2, Fe2O3, WO3, and BiVO4 have been previously studied for their potential as photoanodes in photoelectrochemical (PEC) hydrogen production, their relatively wide band-gap limits their photocurrent, making them unsuitable for the efficient utilization of incident visible light. To overcome this limitation, we propose a new approach for highly efficient PEC hydrogen production based on a novel photoanode composed of BiVO4/PbS quantum dots (QDs). Crystallized monoclinic BiVO4 films were prepared via a typical electrodeposition process, followed by the deposition of PbS QDs using a successive ionic layer adsorption and reaction (SILAR) method to form a p-n heterojunction. This is the first time that narrow band-gap QDs were applied to sensitize a BiVO4 photoelectrode. The PbS QDs were uniformly coated on the surface of nanoporous BiVO4, and their optical band-gap was reduced by increasing the number of SILAR cycles. However, this did not affect the crystal structure and optical properties of the BiVO4. By decorating the surface of BiVO4 with PbS QDs, the photocurrent was increased from 2.92 to 4.88 mA/cm2 (at 1.23 VRHE) for PEC hydrogen production, resulting from the enhanced light-harvesting capability arising from the narrow band-gap of the PbS QDs. Moreover, the introduction of a ZnS overlayer on the BiVO4/PbS QDs further improved the photocurrent to 5.19 mA/cm2, attributed to the reduction in interfacial charge recombination.

Cerium oxide nanoparticle as interfacial modifier for efficient and UV-stable perovskite solar cells

Ultraviolet (UV) illumination can induce the generation of defects at the interface of perovskite and commonly used electron transport materials (ETMs, such as TiO2 and SnO2) in perovskite solar cells (PSCs). This further increase the interfacial charge recombination and accelerate the decomposition of perovskite film, resulting in the attenuation of device efficiency and stability. Here, a cerium oxide (CeOx) nanoparticle with an average size of 18.66 nm is proposed as a novel mesoporous material to modify the interface of ETM and perovskite. The CeOx mesoporous layer with higher electron mobility and more suitable band energy level facilitates charge transfer from perovskite layer. As expected, the mesoporous CeOx based PSCs exhibits an improved power conversion efficiency up to 23.15% (22.57% for control device). More importantly, the mesoporous CeOx layer (about 70 nm) can realize the effective absorption of UV light, to efficiently improve the UV light stability of PSCs and the overall stability of the devices. The unencapsulated devices with mesoporous CeOx maintained almost 90% of initial efficiency after 850 h under UV illumination. This work provides a new approach to fabricate the efficient and UV stable PSCs by introducing the mesoporous CeOx layer.

Constructing a Surface Multi-cationic Heterojunction for CsPbI1.5Br1.5 Perovskite Solar Cells with Efficiency beyond 14%

All-inorganic CsPbI1.5Br1.5 perovskite solar cells are considered as top cell candidates for tandem cells as a result of their excellent thermal stability and photoelectric performance. However, their power conversion efficiencies (PCEs) are still low and far below the theoretical limit mainly as a result of the severe non-radiative recombination and optical loss. Herein, we introduce an versatile method to construct a surface multi-cationic heterojunction to achieve an efficient and stable CsPbI1.5Br1.5 perovskite solar cell. By precisely controlling the content of FA+ and MA+ on PbBr2-rich perovskite films, a high-quality heterojunction layer is formed to help effectively passivate the surface defects and reduce the optical loss of the CsPbI1.5Br1.5 perovskite. In addition, the incorporation of a heterojunction layer can also improve energy-level alignment and reduce interfacial charge recombination loss. As a result, the champion device with the incorporation of SMH exhibits a PCE of 14.11%, which presents the highest reported efficiency for inorganic CsPbI1.5Br1.5 solar cells thus far while retaining 85% of the initial efficiency after 1000 h of storage without encapsulation.

Key role of residual lead iodide in two-step processed perovskite layer for high performance perovskite solar cells

The delicate control of the crystallization behavior of the perovskite layer is critical for achieving high power conversion efficiency (PCE) and longer-term stability of perovskite solar cells (PSCs). Residual lead iodide (PbI2) was usually evitable in the two-step processed perovskite film due to incomplete reaction; however, its exact effects on the perovskite layer and resulting PSCs were not well elucidated so far. Here, the lead halide perovskite films were grown by the two-step process, where the residual PbI2 can be fine controlled by the concentration of organic salt solution. Results indicated that the properties of the perovskite layer may be varied greatly depending on the amount of residual PbI2, and a series of beneficial effects for PSCs can be achieved via suitable management of residue PbI2, i.e., prolonged carrier diffusion capacity, reduced defect density, inhibited ion migration, and interfacial charge recombination. Accordingly, an impressive PCE of 22.4% was achieved from the PSCs with optimized PbI2. Furthermore, the PSCs also displayed fairly good operational stability and retained 68% of its initial PCE after 400 h (at continuous irradiation under 1-sun illumination). This work may inspire solutions for further enhancing the performance of PSCs via fine controlled residual PbI2 in the perovskite layer.

New insights into the alkoxy effects on auxiliary adsorption and inhibiting charge recombination in dye-sensitized solar cells with high open circuit voltage: a theoretical investigation.

Although introducing an alkoxy group is one of the most popular methods to suppress the interfacial charge recombination process of dye-sensitized solar cells, understanding of its effects is still limited and a microscopic picture of the alkoxy effects is lacking. Two ullazine dyes with distinct alkoxy chains at the donor part are used to investigate the effects of the alkoxy group on the adsorption, dye aggregation and charge recombination process in our study. Different from the usual assumption, we find that alkoxy chains can not only play a shielding role, but can also assist dye adsorption and inhibit the charge recombination process more effectively by covering the TiO2 surface. We also find that the existence of alkyl chains can well inhibit the aggregation of dyes and reduce intermolecular electron transfer. Furthermore, an important structural feature at the interface, the Ti-O interaction between the oxygen atom of the alkoxy group and the Ti atom of the surface is also found to contribute substantially to the interface stability. New insights into the effects of the alkoxy group on auxiliary adsorption and inhibiting charge recombination through reducing the recombination sites pave the way for rational design of sensitizers with high performance.

AuNRs attached TiO2 NPs modified by cobalt-imidazolate frameworks as exceptional materials to improve the energy conversion efficiency of dye-sensitized solar cells.

This work reports a significant improvement in both the open-circuit voltage (VOC) and current density (J) of dye-sensitized solar cells (DSSCs) using gold nanorod-modified TiO2 nanoparticles (TiO2/AuNRs) together with a cobalt-imidazolate framework (ZIF-67) as an efficient photoanode. It was demonstrated that adding ZIF-67 (8 wt%) to TiO2 NPs increased the VOC by 160 mV and J by 2.5 times. This observation was described based on the significant increase in the amount of adsorbed dye in the presence of highly porous ZIF-67, which boosts the photoanode's light harvesting. Modifying TiO2 NPs with AuNRs also caused a remarkable enhancement in J (∼ 2.8 times), which can be explained via electron transfer between the TiO2 conduction band and AuNRs. It can result in a more efficient inhibiting effect on the interfacial charge recombination processes in TiO2/AuNRs/ZIF-67 because of the formation of a Schottky barrier at the interface between TiO2 and Au. These effects were confirmed by the reduction in the photoluminescence intensity of TiO2 in the presence of AuNRs. More reduction in the photoluminescence intensity was observed when ZIF-67 was added. The prepared photoanode showed an outstanding improvement in the overall efficiency of the DSSC (η) to 8.38% compared to the bare TiO2-based photoanode (1.83%). The notable improvement in the TiO2/AuNRs/ZIF-67 performance confirmed its practicality for high-efficiency DSSCs.

Enhancing the Efficiency of Perovskite Solar Cells by Bidirectional Modification of the Perovskite and Electron Transport Layer.

In perovskite solar cells (PSCs), the numerous defects present on the surface of the SnO2 electron transport layer (ETL) and the bottom of the perovskite film limit their power conversion efficiency (PCE) and stability. In view of this, a bidirectional modification strategy is designed using formamidine acetate (FAAc) to passivate the defects on the SnO2 ETL surface and bottom of the perovskite simultaneously. FA+ cations act on the harmful hydroxyl groups on the SnO2 ETL surface, whereas Ac- anions act on the iodine vacancy defect at the bottom of the perovskite. Because the interface defect is well passivated by FAAc, the interfacial charge recombination is restrained. This results in a significant increase in the filling factor of the PSC to ∼0.83 and the consequent increase in PCE to 23.05%, which considerably improves the stability. Bidirectional modification technology is an effective strategy for improving the PCE and stability of PSCs.

A Molecularly Tailored Photosensitizer with an Efficiency of 13.2% for Dye-Sensitized Solar Cells.

Photosensitizers yielding superior photocurrents are crucial for copper-electrolyte-based highly efficient dye-sensitized solar cells (DSCs). Herein, two molecularly tailored organic sensitizers are presented, coded ZS4 and ZS5, through judiciously employing dithieno[3,2-b:2″,3″-d]pyrrole (DTP) as the π-linker and hexyloxy-substituted diphenylquinoxaline (HPQ) or naphthalene-fused-quinoxaline (NFQ) as the auxiliary electron-accepting unit, respectively. Endowed with the HPQ acceptor, ZS4 shows more efficient electron injection and charge collection based on substantially reduced interfacial charge recombination as compared to ZS5. As a result, ZS4-based DSCs achieve a power conversion efficiency (PCE) of 13.2% under standard AM1.5G sunlight, with a high short-circuit photocurrent density (Jsc ) of 16.3mAcm-2 , an open-circuit voltage (Voc ) of 1.05V and a fill factor (FF) of 77.1%. Remarkably, DSCs sensitized with ZS4 exhibit an outstanding stability, retaining 95% of their initial PCE under continuous light soaking for 1000h. It is believed thatthis is a new record efficiency reported so far for copper-electrolyte-based DSCs using a single sensitizer. The work highlights the importance of developing molecularly tailored photosensitizers for highly efficient DSCs with copper electrolyte.

D 6 h Symmetric Radical Donor–Acceptor Nanographene Modulated Interfacial Carrier Transfer for High-Performance Perovskite Solar Cells

<i>D</i> ^{6 <i>h</i>} Symmetric Radical Donor–Acceptor Nanographene Modulated Interfacial Carrier Transfer for High-Performance Perovskite Solar Cells

TiO2/CdS/CdSe quantum dots co-sensitized solar cell with the staggered-gap (type-II) heterojunctions for the enhanced photovoltaic performance

The effect of co-sensitization and ZnS passivation on the photovoltaic performance of CdS quantum dot sensitized solar cells (QDSSCs) were investigated. The deposition of CdS, CdSe quantum dots (QD) and ZnS passivation on TiO2 photoanode was carried out by successive ionic layer adsorption and reaction (SILAR) method. CdS/CdSe co-sensitization developed two staggered type-II heterojunctions at TiO2/CdS and CdS/CdSe interfaces and resulted a cascade energy band structure. This suitable band alignment facilitated the double charge transfer mechanism at each heterojunction and transported the electrons easily into the photoanode. The narrow bandgap sensitizers CdS and CdSe significantly improved the potential utilization of solar spectrum with more charge carrier generation. ZnS passivation on QD surface suppressed electrode/electrolyte interfacial charge recombination and facilitated more electron injection from QDs into TiO2 photoanode. The EDAX elemental mapping results inferred that CdS, CdSe and ZnS have efficiently covered the TiO2 surface. TiO2/CdS and CdS/CdSe interfaces and the amorphous nature of ZnS could be verified with HRTEM images. Hence, the co-sensitization and surface passivation played a significant role to enhance the PCE of CdS QDSSC from 1.9% to 4.05%.

Effect of ZrS2 load single/dual-atom catalysts on the hydrogen evolution reaction: A first-principles study.

The hydrogen evolution effect of ZrS2 carrier loaded with transition metal single-atom (SA) was explored by first-principles method. ZrS2 was constructed with transition metal single-atom and dual-atom. The structure-activity relationship of supported single-atom catalysts was described by electronic properties and hydrogen evolution kinetics. The results show that the ZrS2 carrier-loaded atomic-level catalysts are more likely to occur in acidic environments, where the Mo SA load has a higher hydrogen precipitation capacity than the Pt SA. In the case of dual-atom adsorption, most of the hydrogen reduction processes are higher than that of single atom loading, which indicates that the outer orbital hybridization is more likely to lead to the interfacial charge recombination of the catalyst. Thereinto, Ni/Pt @ZrS2 has the lowest Gibbs free energy (0.08 eV), and the synergistic effect of transition metals induces the deviation of the center of the d-band from the Fermi level and improves the dissociation ability of H ions. The design provides a new catalytic model for the HER and provides some ideas for understanding the two-site catalysis.

Chemical Bath Deposition of NiOx‐NiSO4 Heterostructured Hole Transport Layer for Perovskite Solar Cells

Herein, the scalable chemical bath deposited NiOx‐NiSO4 heterostructured films are reported as the efficient hole transport layers (HTLs) in perovskite solar cells. The NiOx‐NiSO4 films show excellent hole extraction ability and reduce interfacial charge recombination in solar cell devices. By using NiOx‐NiSO4 HTLs, a high power conversion efficiency of 20.55% is obtained, which is about 12.23% greater than that of the pure NiOx transport layer. This study provides a simple solution‐processing route toward the large‐area production and fabrication of full inorganic transport layers for perovskite photovoltaics.