Monolithic FAPbBr3 photoanode for photoelectrochemical water oxidation with low onset-potential and enhanced stability.

Despite considerable research efforts on photoelectrochemical water splitting over the past decades, practical application faces challenges by the absence of efficient, stable, and scalable photoelectrodes. Herein, we report a metal-halide perovskite-based photoanode for photoelectrochemical water oxidation. With a planar structure using mesoporous carbon as a hole-conducting layer, the precious metal-free FAPbBr3 photovoltaic device achieves 9.2% solar-to-electrical power conversion efficiency and 1.4 V open-circuit voltage. The photovoltaic architecture successfully applies to build a monolithic photoanode with the FAPbBr3 absorber, carbon/graphite conductive protection layers, and NiFe catalyst layers for water oxidation. The photoanode delivers ultralow onset potential below 0 V versus the reversible hydrogen electrode and high applied bias photon-to-current efficiency of 8.5%. Stable operation exceeding 100 h under solar illumination by applying ultraviolet-filter protection. The photothermal investigation verifies the performance boost in perovskite photoanode by photothermal effect. This study is significant in guiding the development of photovoltaic material-based photoelectrodes for solar fuel applications.

Can photoluminescence quenching be a predictor for perovskite solar cell efficiencies?

Bromide-based perovskites have large bandgaps, making them attractive for tandem solar cells developed to overcome the Shockley-Queisser limit. A perovskite solar cell architecture employs transporting layers to improve charge extraction and transport. Due to the wide variety of materials and preparation methods, it is critical to devise fast screening methods to rank transporting layers. Herein, we evaluate perovskite fluorescence quenching followed by time- and energy-resolved photoluminescence (TER-PL) and analyse the intensity dependence as a potential method to qualify charge-transporting layers rapidly. The capability of the technique was evaluated with TiO2/FAPbBr3 and SnO2/FAPbBr3, the most commonly used electron transporting layers, which were prepared using standard protocols to make best-performing devices. The results revealed that TiO2 is the most effective quencher due to the higher density of states in the conduction band, consistent with Marcus-Gerischer's theory. However, record-performance devices use SnO2 as the electron transport layer. This shows that the relationship between photoluminescence quenching and device performance is not bidirectional. Therefore, additional measurements like conductivity are also needed to provide reliable feedback for device performance.

The Complex Degradation Mechanism of Copper Electrodes on Lead Halide Perovskites.

Lead halide perovskite solar cells have reached power conversion efficiencies during the past few years that rival those of crystalline silicon solar cells, and there is a concentrated effort to commercialize them. The use of gold electrodes, the current standard, is prohibitively costly for commercial application. Copper is a promising low-cost electrode material that has shown good stability in perovskite solar cells with selective contacts. Furthermore, it has the potential to be self-passivating through the formation of CuI, a copper salt which is also used as a hole selective material. Based on these opportunities, we investigated the interface reactions between lead halide perovskites and copper in this work. Specifically, copper was deposited on the perovskite surface, and the reactions were followed in detail using synchrotron-based and in-house photoelectron spectroscopy. The results show a rich interfacial chemistry with reactions starting upon deposition and, with the exposure to oxygen and moisture, progress over many weeks, resulting in significant degradation of both the copper and the perovskite. The degradation results not only in the formation of CuI, as expected, but also in the formation of two previously unreported degradation products. The hope is that a deeper understanding of these processes will aid in the design of corrosion-resistant copper-based electrodes.

Enhancing the efficiency and stability of perovskite solar cells based on moisture-resistant dopant free hole transport materials by using a 2D-BA2PbI4 interfacial layer.

In this work, the photovoltaic performance and stability of perovskite solar cells (PSCs) based on a dopant-free hole transport layer (HTL) are efficiently improved by inserting a two-dimensional (2D) interfacial layer. The benzyl ammonium lead iodide (BA2PbI4) 2D perovskite is used as an interfacial layer between the 3D CH3NH3PbI3 perovskite and two moisture-resistant dopant-free HTLs including poly[[2,3-bis(3-octyloxyphenyl)-5,8-quinoxalinediyl]-2,5-thiophenediyl] (TQ1) and poly(3-hexylthiophene) (P3HT). TQ1 with a facile synthesis procedure has a higher moisture resistivity compared to P3HT which can improve the stability of PSCs. The 2D BA2PbI4 perovskite with a less-volatile bulkier organic cation efficiently passivates the defects at the perovskite/HTL interface, leading to 11.95% and 15.04% efficiency for the modified TQ1 and P3HT based cells, respectively. For a better understanding, the structural, optical, and electrical properties of PSCs comprising P3HT and TQ1 HTLs with and without interface modification are studied. The interface modified PSCs show slower open-circuit voltage decay and longer carrier lifetimes compared to unmodified cells. In addition, impedance spectroscopy reveals lower charge transport resistance and higher recombination resistance for the modified devices, which could be associated with the modification of the interface between the 3D CH3NH3PbI3 perovskite and HTL caused by the 2D interfacial layer. Also after aging under ambient conditions for about 800 hours, the modified PCSs retain more than 80% of their initial PCEs. These results give us the hope of achieving simpler, cheaper, and more stable PSCs with dopant-free HTLs through 2D interfacial layers, which have great potential for commercialization.

Mixed-Halide Double Perovskite Cs2 AgBiX6 (X=Br, I) with Tunable Optical Properties via Anion Exchange.

Lead-free double perovskites, A2 M+ M'3+ X6 , are considered as promising alternatives to lead-halide perovskites, in optoelectronics applications. Although iodide (I) and bromide (Br) mixing is a versatile tool for bandgap tuning in lead perovskites, similar mixed I/Br double perovskite films have not been reported in double perovskites, which may be due to the large activation energy for ion migration. In this work, mixed Br/I double perovskites were realized utilizing an anion exchange method starting from Cs2 AgBiBr6 solid thin-films with large grain-size. The optical and structural properties were studied experimentally and theoretically. Importantly, the halide exchange mechanism was investigated. Hydroiodic acid was the key factor to facilitate the halide exchange reaction, through a dissolution-recrystallization process. In addition, the common organic iodide salts could successfully perform halide-exchange while retaining high mixed-halide phase stability and strong light absorption capability.

Perovskite and quantum dot tandem solar cells with interlayer modification for improved optical semitransparency and stability.

In this work, four-terminal (4T) tandem solar cells were fabricated by using a methylammonium lead iodide (MAPbI3) perovskite solar cell (PSC) as the front-cell and a lead sulfide (PbS) colloidal quantum dot solar cell (CQDSC) as the back-cell. Different modifications of the tandem interlayer, at the interface between the sub-cells, were tested in order to improve the infrared transparency of the perovskite sub-cell and consequently increase the utilization of infrared (IR) light by the tandem system. This included the incorporation of a semi-transparent thin gold electrode (Au) on the MAPbI3 solar cell, followed by adding a molybdenum(vi) oxide (MoO3) layer or a surlyn layer. These interlayer modifications resulted in an increase of the IR transmittance to the back cell and improved the optical stability, compared to that in the reference devices. This investigation shows the importance of the interlayer, connecting the PSC with a strong absorption in the visible region and the CQDSC with a strong infrared absorption to obtain efficient next-generation tandem photovoltaics (PVs).

SnO x Atomic Layer Deposition on Bare Perovskite-An Investigation of Initial Growth Dynamics, Interface Chemistry, and Solar Cell Performance.

High-end organic-inorganic lead halide perovskite semitransparent p-i-n solar cells for tandem applications use a phenyl-C61-butyric acid methyl ester (PCBM)/atomic layer deposition (ALD)-SnO x electron transport layer stack. Omitting the PCBM would be preferred for manufacturing, but has in previous studies on (FA,MA)Pb(Br,I)3 and (Cs,FA)Pb(Br,I)3 and in this study on Cs0.05FA0.79MA0.16PbBr0.51I2.49 (perovskite) led to poor solar cell performance because of a bias-dependent light-generated current. A direct ALD-SnO x exposure was therefore suggested to form a nonideal perovskite/SnO x interface that acts as a transport barrier for the light-generated current. To further investigate the interface formation during the initial ALD SnO x growth on the perovskite, the mass dynamics of monitor crystals coated by partial p-i-n solar cell stacks were recorded in situ prior to and during the ALD using a quartz crystal microbalance. Two major finds were made. A mass loss was observed prior to ALD for growth temperatures above 60 °C, suggesting the decomposition of the perovskite. In addition, a mostly irreversible mass gain was observed during the first exposure to the Sn precursor tetrakis(dimethylamino)tin(IV) that is independent of growth temperature and that disrupts the mass gain of the following 20-50 ALD cycles. The chemical environments of the buried interface were analyzed by soft and hard X-ray photoelectron spectroscopy for a sample with 50 ALD cycles of SnO x on the perovskite. Although measurements on the perovskite bulk below and the SnO x film above did not show chemical changes, additional chemical states for Pb, Br, and N as well as a decrease in the amount of I were observed in the interfacial region. From the analysis, these states and not the heating of the perovskite were concluded to be the cause of the barrier. This strongly suggests that the detrimental effects can be avoided by controlling the interfacial design.

PbS Colloidal Quantum Dot Inks for Infrared Solar Cells.

Infrared PbS colloidal quantum dot (CQD)-based materials receive significant attention because of its unique properties. The PbS CQD ink that originates from ligand exchange of CQDs is highly potential for efficient and stable infrared CQD solar cells (CQDSCs) using low-temperature solution-phase processing. In this review, we present a comprehensive overview of CQD inks for the development of efficient infrared solar cells, which can effectively harvest the photons from the infrared wavelength region of the solar spectrum, including the importance of infrared absorbers for solar cells, the unique properties of CQDs, ligand-exchange determined CQD inks, and related photovoltaic performance of CQDSCs. Finally, we present a brief conclusion, and the possible challenges and opportunities of the CQD inks are discussed in-depth to further develop highly efficient and stable infrared solar cells.

Large-Grained All-Inorganic Bismuth-Based Perovskites with Narrow Band Gap via Lewis Acid-Base Adduct Approach.

Bismuth halide perovskites have recently been considered a potential alternative to lead halide analogues due to their low toxicity and high stability. However, the layered flake structure and wide band gap limit their applications in perovskite solar cells (PSCs). We herein show that large-grained all-inorganic bismuth-based perovskites with a narrow band gap can be obtained from a Lewis acid-base adduct reaction under ambient conditions. Thiourea (CH4N2S) is utilized as a Lewis base to interact with BiI3, confirmed with infrared (IR) spectra. The strong coordination between thiourea and the Bi3+ center could slow down the perovskite crystallization and promote the preferred orientation of the perovskite crystals with a hexagonal phase. The morphology of the perovskite films varies dramatically with an increase of molar ratio of BiI3 and thiourea in the precursor. The perovskites derived from a BiI3/thiourea ratio of 1:2 display extrathick grains, higher surface coverage, extended light absorption, higher crystallinity, and similar air stability compared to the pristine sample. The power conversion efficiency (PCE) of the thiourea-induced bismuth perovskite solar cells is significantly enhanced due to the higher surface coverage and the broader absorption of the perovskite film.

Dual Passivation of CsPbI3 Perovskite Nanocrystals with Amino Acid Ligands for Efficient Quantum Dot Solar Cells.

Inorganic CsPbI3 perovskite quantum dot (PQD) receives increasing attention for the application in the new generation solar cells, but the defects on the surface of PQDs significantly affect the photovoltaic performance and stability of solar cells. Herein, the amino acids are used as dual-passivation ligands to passivate the surface defects of CsPbI3 PQDs using a facile single-step ligand exchange strategy. The PQD surface properties are investigated in depth by combining experimental studies and theoretical calculation approaches. The PQD solid films with amino acids as dual-passivation ligands on the PQD surface are thoroughly characterized using extensive techniques, which reveal that the glycine ligand can significantly improve defect passivation of PQDs and therefore diminish charge carrier recombination in the PQD solid. The power conversion efficiency (PCE) of the glycine-based PQD solar cell (PQDSC) is improved by 16.9% compared with that of the traditional PQDSC fabricated with Pb(NO3 )2 treating the PQD surface, owning to improved charge carrier extraction. Theoretical calculations are carried out to comprehensively understand the thermodynamic feasibility and favorable charge density distribution on the PQD surface with a dual-passivation ligand.

Degradation Mechanism of Silver Metal Deposited on Lead Halide Perovskites.

Lead halide perovskite solar cells have significantly increased in both efficiency and stability over the last decade. An important aspect of their long-term stability is the reaction between the perovskite and other materials in the solar cell. This includes the contact materials and their degradation if they can potentially come into contact through, e.g., pinholes or material diffusion and migration. Here, we explore the interactions of silver contacts with lead halide perovskites of different compositions by using a model system where thermally evaporated silver was deposited directly on the surface of the perovskites. Using X-ray photoelectron spectroscopy with support from scanning electron microscopy, X-ray diffraction, and UV-visible absorption spectroscopy, we studied the film formation and degradation of silver on perovskites with different compositions. The deposited silver does not form a continuous silver film but instead tends to form particles on a bare perovskite surface. These particles are initially metallic in character but degrade into AgI and AgBr over time. The degradation and migration appear unaffected by the replacement of methylammonium with cesium but are significantly slowed down by the complete replacement of iodide with bromide. The direct contact between silver and the perovskite also significantly accelerates the degradation of the perovskite, with a significant loss of organic cations and the possible formation of PbO, and, at the same time, changed the surface morphology of the iodide-rich perovskite interface. Our results further indicate that an important degradation pathway occurred through gas-phase perovskite degradation products. This highlights the importance of control over the interface materials and the use of completely hermetical barrier layers for the long-term stability and therefore the commercial viability of silver electrodes.

A method for studying pico to microsecond time-resolved core-level spectroscopy used to investigate electron dynamics in quantum dots.

Time-resolved photoelectron spectroscopy can give insights into carrier dynamics and offers the possibility of element and site-specific information through the measurements of core levels. In this paper, we demonstrate that this method can access electrons dynamics in PbS quantum dots over a wide time window spanning from pico- to microseconds in a single experiment carried out at the synchrotron facility BESSY II. The method is sensitive to small changes in core level positions. Fast measurements at low pump fluences are enabled by the use of a pump laser at a lower repetition frequency than the repetition frequency of the X-ray pulses used to probe the core level electrons: Through the use of a time-resolved spectrometer, time-dependent analysis of data from all synchrotron pulses is possible. Furthermore, by picosecond control of the pump laser arrival at the sample relative to the X-ray pulses, a time-resolution limited only by the length of the X-ray pulses is achieved. Using this method, we studied the charge dynamics in thin film samples of PbS quantum dots on n-type MgZnO substrates through time-resolved measurements of the Pb 5d core level. We found a time-resolved core level shift, which we could assign to electron injection and charge accumulation at the MgZnO/PbS quantum dots interface. This assignment was confirmed through the measurement of PbS films with different thicknesses. Our results therefore give insight into the magnitude of the photovoltage generated specifically at the MgZnO/PbS interface and into the timescale of charge transport and electron injection, as well as into the timescale of charge recombination at this interface. It is a unique feature of our method that the timescale of both these processes can be accessed in a single experiment and investigated for a specific interface.

Cesium Bismuth Iodide Solar Cells from Systematic Molar Ratio Variation of CsI and BiI3.

Metal halide compounds with photovoltaic properties prepared from solution have received increased attention for utilization in solar cells. In this work, low-toxicity cesium bismuth iodides are synthesized from solution, and their photovoltaic and optical properties as well as electronic and crystal structures are investigated. The X-ray diffraction patterns reveal that a CsI/BiI3 precursor ratio of 1.5:1 can convert pure rhombohedral BiI3 to pure hexagonal Cs3Bi2I9, but any ratio intermediate of this stoichiometry and pure BiI3 yields a mixture containing the two crystalline phases Cs3Bi2I9 and BiI3, with their relative fraction depending on the CsI/BiI3 ratio. Solar cells from the series of compounds are characterized, showing the highest efficiency for the compounds with a mixture of the two structures. The energies of the valence band edge were estimated using hard and soft X-ray photoelectron spectroscopy for more bulk and surface electronic properties, respectively. On the basis of these measurements, together with UV-vis-near-IR spectrophotometry, measuring the band gap, and Kelvin probe measurements for estimating the work function, an approximate energy diagram has been compiled clarifying the relationship between the positions of the valence and conduction band edges and the Fermi level.

Experimental and Theoretical Investigation of the Function of 4- tert-Butyl Pyridine for Interface Energy Level Adjustment in Efficient Solid-State Dye-Sensitized Solar Cells.

4- tert-Butylpyridine ( t-BP) is commonly used in solid state dye-sensitized solar cells (ssDSSCs) to increase the photovoltaic performance. In this report, the mechanism how t-BP functions as a favorable additive is investigated comprehensively. ssDSSCs were prepared with different concentrations of t-BP, and a clear increase in efficiency was observed up to a maximum concentration and for higher concentrations the efficiency thereafter decreases. The energy level alignment in the complete devices was measured using hard X-ray photoelectron spectroscopy (HAXPES). The results show that the energy levels of titanium dioxide are shifted further away from the energy levels of spiro-OMeTAD as the t-BP concentration is increased. This explains the higher photovoltage obtained in the devices with higher t-BP concentration. In addition, the electron lifetime was measured for the devices and the electron lifetime was increased when adding t-BP, which can be explained by the recombination blocking effect at the surface of TiO2. The results from the HAXPES measurements agree with those obtained from density functional theory calculations and give an understanding of the mechanism for the improvement, which is an important step for the future development of solar cells including t-BP.

The Effect of Dopant-Free Hole-Transport Polymers on Charge Generation and Recombination in Cesium-Bismuth-Iodide Solar Cells.

The photovoltaic characteristics of CsBi3 I10 -based solar cells with three dopant-free hole-conducting polymers are investigated. The effect on charge generation and charge recombination in the solar cells using the different polymers is studied and the results indicate that the choice of polymer strongly affects the device properties. Interestingly, for the solar cell with poly[[2,3-bis(3-octyloxyphenyl)-5,8-quinoxalinediyl]-2,5-thiophenediyl] (TQ1), the photon-to-current conversion spectrum is highly improved in the red wavelength region, suggesting that the polymer also contributes to the photocurrent generation in this case. This report provides a new direction for further optimization of Bi-halide solar cells by using dopant-free hole-transporting polymers and shows that the energy levels and the interaction between the Bi-halide and the conducting polymers are very important for solar cell performance.

Al2 O3 Underlayer Prepared by Atomic Layer Deposition for Efficient Perovskite Solar Cells.

Perovskite solar cells, as an emergent technology for solar energy conversion, have attracted much attention in the solar cell community by demonstrating impressive enhancement in power conversion efficiencies. However, the high temperature and manually processed TiO2 underlayer prepared by spray pyrolysis significantly limit the large-scale application and device reproducibility of perovskite solar cells. In this study, lowtemperature atomic layer deposition (ALD) is used to prepare a compact Al2 O3 underlayer for perovskite solar cells. The thickness of the Al2 O3 layer can be controlled well by adjusting the deposition cycles during the ALD process. An optimal Al2 O3 layer effectively blocks electron recombination at the perovskite/fluorine-doped tin oxide interface and sufficiently transports electrons through tunneling. Perovskite solar cells fabricated with an Al2 O3 layer demonstrated a highest efficiency of 16.2 % for the sample with 50 ALD cycles (ca. 5 nm), which is a significant improvement over underlayer-free PSCs, which have a maximum efficiency of 11.0 %. Detailed characterization confirms that the thickness of the Al2 O3 underlayer significantly influences the charge transfer resistance and electron recombination processes in the devices. Furthermore, this work shows the feasibility of using a high band-gap semiconductor such as Al2 O3 as the underlayer in perovskite solar cells and opens up pathways to use ALD Al2 O3 underlayers for flexible solar cells.

Highly Efficient Flexible Quantum Dot Solar Cells with Improved Electron Extraction Using MgZnO Nanocrystals.

Colloidal quantum dot (CQD) solar cells have high potential for realizing an efficient and lightweight energy supply for flexible or wearable electronic devices. To achieve highly efficient and flexible CQD solar cells, the electron transport layer (ETL), extracting electrons from the CQD solid layer, needs to be processed at a low-temperature and should also suppress interfacial recombination. Herein, a highly stable MgZnO nanocrystal (MZO-NC) layer is reported for efficient flexible PbS CQD solar cells. Solar cells fabricated with MZO-NC ETL give a high power conversion efficiency (PCE) of 10.4% and 9.4%, on glass and flexible plastic substrates, respectively. The reported flexible CQD solar cell has the record efficiency to date of flexible CQD solar cells. Detailed theoretical simulations and extensive characterizations reveal that the MZO-NCs significantly enhance charge extraction from CQD solids and diminish the charge accumulation at the ETL/CQD interface, suppressing charge interfacial recombination. These important results suggest that the low-temperature processed MZO-NCs are very promising for use in efficient flexible solar cells or other flexible optoelectronic devices.

High Photon-to-Current Conversion in Solar Cells Based on Light-Absorbing Silver Bismuth Iodide.

Here, a lead-free silver bismuth iodide (AgI/BiI3 ) with a crystal structure with space group R3‾ m is investigated for use in solar cells. Devices based on the silver bismuth iodide deposited from solution on top of TiO2 and the conducting polymer poly(3-hexylthiophene-2,5-diyl) (P3HT) as a hole-transport layer are prepared and the photovoltaic performance is very promising with a power conversion efficiency over 2 %, which is higher than the performance of previously reported bismuth-halide materials for solar cells. Photocurrent generation is observed between 350 and 700 nm, and the maximum external quantum efficiency is around 45 %. The results are compared to solar cells based on the previously reported material AgBi2 I7 , and we observe a clearly higher performance for the devices with the new silver and bismuth iodides composition and different crystal structure. The X-ray diffraction spectrum of the most efficient silver bismuth iodide material shows a hexagonal crystal structure with space group R3‾ m, and from the light absorption spectrum we obtain an indirect band gap energy of 1.62 eV and a direct band gap energy of 1.85 eV. This report shows the possibility for finding new structures of metal-halides efficient in solar cells and points out new directions for further exploration of lead-free metal-halide solar cells.

Photoinduced Stark Effects and Mechanism of Ion Displacement in Perovskite Solar Cell Materials.

Organometallic halide perovskites (OMHPs) have recently emerged as a promising class of materials in photovoltaic technology. Here, we present an in-depth investigation of the physics in these systems by measuring the photoinduced absorption (PIA) in OMHPs as a function of materials composition, excitation wavelength, and modulation frequency. We report a photoinduced Stark effect that depends on the excitation wavelength and on the dipole strength of the monovalent cations in the A position of the ABX3 perovskite. The results presented are corroborated by density functional theory calculations and provide fundamental information about the photoinduced local electric field change under blue and red excitation as well as insights into the mechanism of light-induced ion displacement in OMHPs. For optimized perovskite solar cell devices beyond 19% efficiency, we show that excess thermalization energy of blue photons plays a role in overcoming the activation energy for ion diffusion.

High Temperature-Stable Perovskite Solar Cell Based on Low-Cost Carbon Nanotube Hole Contact.

Mixed ion perovskite solar cells (PSC) are manufactured with a metal-free hole contact based on press-transferred single-walled carbon nanotube (SWCNT) film infiltrated with 2,2,7,-7-tetrakis(N,N-di-p-methoxyphenylamine)-9,90-spirobifluorene (Spiro-OMeTAD). By means of maximum power point tracking, their stabilities are compared with those of standard PSCs employing spin-coated Spiro-OMeTAD and a thermally evaporated Au back contact, under full 1 sun illumination, at 60 °C, and in a N2 atmosphere. During the 140 h experiment, the solar cells with the Au electrode experience a dramatic, irreversible efficiency loss, rendering them effectively nonoperational, whereas the SWCNT-contacted devices show only a small linear efficiency loss with an extrapolated lifetime of 580 h.