Efficient perovskite solar cells via improved carrier management.

Metal halide perovskite solar cells (PSCs) are an emerging photovoltaic technology with the potential to disrupt the mature silicon solar cell market. Great improvements in device performance over the past few years, thanks to the development of fabrication protocols1-3, chemical compositions4,5 and phase stabilization methods6-10, have made PSCs one of the most efficient and low-cost solution-processable photovoltaic technologies. However, the light-harvesting performance of these devices is still limited by excessive charge carrier recombination. Despite much effort, the performance of the best-performing PSCs is capped by relatively low fill factors and high open-circuit voltage deficits (the radiative open-circuit voltage limit minus the high open-circuit voltage)11. Improvements in charge carrier management, which is closely tied to the fill factor and the open-circuit voltage, thus provide a path towards increasing the device performance of PSCs, and reaching their theoretical efficiency limit12. Here we report a holistic approach to improving the performance of PSCs through enhanced charge carrier management. First, we develop an electron transport layer with an ideal film coverage, thickness and composition by tuning the chemical bath deposition of tin dioxide (SnO2). Second, we decouple the passivation strategy between the bulk and the interface, leading to improved properties, while minimizing the bandgap penalty. In forward bias, our devices exhibit an electroluminescence external quantum efficiency of up to 17.2 per cent and an electroluminescence energy conversion efficiency of up to 21.6 per cent. As solar cells, they achieve a certified power conversion efficiency of 25.2 per cent, corresponding to 80.5 per cent of the thermodynamic limit of its bandgap.

Fabrication of Efficient Formamidinium Tin Iodide Perovskite Solar Cells through SnF2-Pyrazine Complex.

To fabricate efficient formamidinium tin iodide (FASnI3) perovskite solar cells (PSCs), it is essential to deposit uniform and dense perovskite layers and reduce Sn(4+) content. Here we used solvent-engineering and nonsolvent dripping process with SnF2 as an inhibitor of Sn(4+). However, excess SnF2 induces phase separation on the surface of the perovskite film. In this work, we report the homogeneous dispersion of SnF2 via the formation of the SnF2-pyrazine complex. Consequently, we fabricated FASnI3 PSCs with high reproducibility, achieving a high power conversion efficiency of 4.8%. Furthermore, the encapsulated device showed a stable performance for over 100 days, maintaining 98% of its initial efficiency.

Anionic ligand assisted synthesis of 3-D hollow TiO2 architecture with enhanced photoelectrochemical performance.

Hollow structured materials have shown great advantages for use in photoelectrochemical devices. However, their poor charge transport limits overall device performance. Here, we report a unique 3-D hollow architecture of TiO2 that greatly improves charge transport properties. We found that citric acid (CA) plays crucial roles in the formation of the 3-D hollow architecture. First, CA controls the hydrolysis rate of Ti ions and facilitates surface hydrolysis on templates during hydrothermal synthesis. Second, CA suppresses the growth of the carbon template at the initial reaction stage, resulting in the formation of comparatively small hollow fibers. More importantly, a prolonged hydrothermal reaction with CA enables a hollow sphere to grow into entangled hollow fibers via biomimetic swallowing growth. To demonstrate advantages of the 3-D hollow architecture for photoelectrochemical devices, we evaluated its photoelectrochemical performance, specifically the electrolyte diffusion and electron dynamics, by employing dye-sensitized solar cells as a model device. A systemic analysis reveals that the 3-D hollow architecture greatly improves both the electrolyte diffusion and electron transport compared to those of the nanoparticle and hollow sphere due to the elongated porous hollow morphology as well as the densely interconnected nanoparticles at the wall layer.

Rapid Surface Reconstruction of In2S3 Photoanode via Flame Treatment for Enhanced Photoelectrochemical Performance.

Surface reconstruction, reorganizing the surface atoms or structure, is a promising strategy to manipulate materials' electrical, electrochemical, and surface catalytic properties. Herein, a rapid surface reconstruction of indium sulfide (In2S3) is demonstrated via a high-temperature flame treatment to improve its charge collection properties. The flame process selectively transforms the In2S3 surface into a diffusionless In2O3 layer with high crystallinity. Additionally, it controllably generates bulk sulfur vacancies within a few seconds, leading to surface-reconstructed In2S3 (sr-In2S3). When using those sr-In2S3 as photoanode for photoelectrochemical water splitting devices, these dual functions of surface In2O3/bulk In2S3 reduce the charge recombination in the surface and bulk region, thus improving photocurrent density and stability. With optimized surface reconstruction, the sr-In2S3 photoanode demonstrates a significant photocurrent density of 8.5 mA cm-2 at 1.23 V versus a reversible hydrogen electrode (RHE), marking a 2.5-fold increase compared to pristine In2S3 (3.5 mA cm-2). More importantly, the sr-In2S3 photoanode exhibits an impressive photocurrent density of 7.3 mA cm-2 at 0.6 V versus RHE for iodide oxidation reaction. A practical and scalable surface reconstruction is also showcased via flame treatment. This work provides new insights for surface reconstruction engineering in sulfide-based semiconductors, making a breakthrough in developing efficient solar-fuel energy devices.

Surface modified TiO2 nanostructure with 3D urchin-like morphology for dye-sensitized solar cell application.

Three-dimensional (3D) urchin-like rutile TiO2 powders were synthesized by a mild hydrothermal method without any templates. An individual urchin-like TiO2 powder consists of self-assembled nanorods with a length of about 150 nm and width of about 10 nm. Additionally, the urchin-like TiO2 nanopowders were coated with an ultra-thin ZnO layer in order to modify the surface properties of the nanopowders, and the ZnO layer was confirmed by high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analysis. The ZnO-modified TiO2 was used as a photoelectrode of a dye-sensitized solar cell (DSSC) and the solar cell performances were investigated. In comparison with bare TiO2, ZnO-modified TiO2 improved the photovoltaic performances, i.e., energy conversion efficiency, open circuit voltage, and short circuit current were increased. The higher DSSC performance of ZnO-modified TiO2 was attributed to its higher dye loading and lower charge recombination rate.

Influence of niobium doping in hierarchically organized titania nanostructure on performance of dye-sensitized solar cells.

Niobium doped hierarchically organized TiO2 nanostructures composed of 20 nm size anatase nanocrystals were synthesized using pulsed laser deposition (PLD). The Nb doping concentration could be facilely controlled by adjusting the concentration of Nb in target materials. We could investigate the influence of Nb doping in the TiO2 photoelectrode on the cell performance of dye-sensitized solar cells (DSSCs) by the exclusion of morphological effects using the prepared Nb-doped TiO2 anostructures. We found no significant change in short circuit current density (Jsc) as a function of Nb doping concentration. However, open circuit voltage (Voc) and fill factor (FF) monotonously decrease with increasing Nb concentration. Dark current characteristics of the DSSCs reveal that the decrease in Voc and FF is attributed to the decrease in shunt resistance due to the increase in conductivity TiO2 by Nb doping. However, electrochemical impedance spectra (EIS) analysis at open circuit condition under illumination showed that the resistance at the TiO2/dye/electrolyte interface increases with Nb concentration, revealing that Nb doping suppress the charge recombination at the interface. In addition, electron life time obtained using characteristic frequency in Bode plot increases from 14 msec to 56 msec with increasing Nb concentration from 0 to 1.2 at%. This implies that the improved light harvesting can be achieved by increasing diffusion length through Nb-doping in the conventional TiO2 photoelectrode.

Achieving Long-Term Operational Stability of Perovskite Solar Cells with a Stabilized Efficiency Exceeding 20% after 1000 h.

Perovskite solar cells (PSCs) with mesoporous TiO2 (mp-TiO2) as the electron transport material attain power conversion efficiencies (PCEs) above 22%; however, their poor long-term stability is a critical issue that must be resolved for commercialization. Herein, it is demonstrated that the long-term operational stability of mp-TiO2 based PSCs with PCE over 20% is achieved by isolating devices from oxygen and humidity. This achievement attributes to systematic understanding of the critical role of oxygen in the degradation of PSCs. PSCs exhibit fast degradation under controlled oxygen atmosphere and illumination, which is accompanied by iodine migration into the hole transport material (HTM). A diffusion barrier at the HTM/perovskite interface or encapsulation on top of the devices improves the stability against oxygen under light soaking. Notably, a mp-TiO2 based PSC with a solid encapsulation retains 20% efficiency after 1000 h of 1 sun (AM1.5G including UV) illumination in ambient air.

Colloidally prepared La-doped BaSnO3 electrodes for efficient, photostable perovskite solar cells.

Perovskite solar cells (PSCs) exceeding a power conversion efficiency (PCE) of 20% have mainly been demonstrated by using mesoporous titanium dioxide (mp-TiO2) as an electron-transporting layer. However, TiO2 can reduce the stability of PSCs under illumination (including ultraviolet light). Lanthanum (La)-doped BaSnO3 (LBSO) perovskite would be an ideal replacement given its electron mobility and electronic structure, but LBSO cannot be synthesized as well-dispersible fine particles or crystallized below 500°C. We report a superoxide colloidal solution route for preparing a LBSO electrode under very mild conditions (below 300°C). The PSCs fabricated with LBSO and methylammonium lead iodide (MAPbI3) show a steady-state power conversion efficiency of 21.2%, versus 19.7% for a mp-TiO2 device. The LBSO-based PSCs could retain 93% of their initial performance after 1000 hours of full-Sun illumination.

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.

Improving the Carrier Lifetime of Tin Sulfide via Prediction and Mitigation of Harmful Point Defects.

Tin monosulfide (SnS) is an emerging thin-film absorber material for photovoltaics. An outstanding challenge is to improve carrier lifetimes to >1 ns, which should enable >10% device efficiencies. However, reported results to date have only demonstrated lifetimes at or below 100 ps. In this study, we employ defect modeling to identify the sulfur vacancy and defects from Fe, Co, and Mo as most recombination-active. We attempt to minimize these defects in crystalline samples through high-purity, sulfur-rich growth and experimentally improve lifetimes to >3 ns, thus achieving our 1 ns goal. This framework may prove effective for unlocking the lifetime potential in other emerging thin-film materials by rapidly identifying and mitigating lifetime-limiting point defects.

Tailoring of Electron-Collecting Oxide Nanoparticulate Layer for Flexible Perovskite Solar Cells.

Low-temperature-processed perovskite solar cells (PSCs), especially those fabricated on flexible substrates, exhibit device performance that is worse than that of high-temperature-processed PSCs. One of the main reasons for the inferior performance of low-temperature-processed PSCs is the loss of photogenerated electrons in the electron collection layer (ECL) or related interfaces, i.e., indium tin oxide/ECL and ECL/perovskite. Here, we report that tailoring of the energy level and electron transporting ability in oxide ECLs using Zn2SnO4 nanoparticles and quantum dots notably minimizes the loss of photogenerated electrons in the low-temperature-fabricated flexible PSC. The proposed ECL with methylammonium lead halide [MAPb(I0.9Br0.1)3] leads to fabrication of significantly improved flexible PSCs with steady-state power conversion efficiency of 16.0% under AM 1.5G illumination of 100 mW cm(-2) intensity. These results provide an effective method for fabricating high-performance, low-temperature solution-processed flexible PSCs.

Efficient CH3 NH3 PbI3 Perovskite Solar Cells Employing Nanostructured p-Type NiO Electrode Formed by a Pulsed Laser Deposition.

Highly transparent and nanostructured nickel oxide (NiO) films through pulsed laser deposition are introduced for efficient CH3 NH3 PbI3 perovskite solar cells. The (111)-oriented nanostructured NiO film plays a key role in extracting holes and preventing electron leakage as hole transporting material. The champion device exhibits a power conversion efficiency of 17.3% with a very high fill factor of 0.813.

High-performance flexible perovskite solar cells exploiting Zn2SnO4 prepared in solution below 100 °C.

Fabricating inorganic-organic hybrid perovskite solar cells (PSCs) on plastic substrates broadens their scope for implementation in real systems by imparting portability, conformability and allowing high-throughput production, which is necessary for lowering costs. Here we report a new route to prepare highly dispersed Zn2SnO4 (ZSO) nanoparticles at low-temperature (<100 °C) for the development of high-performance flexible PSCs. The introduction of the ZSO film significantly improves transmittance of flexible polyethylene naphthalate/indium-doped tin oxide (PEN/ITO)-coated substrate from ∼75 to ∼90% over the entire range of wavelengths. The best performing flexible PSC, based on the ZSO and CH3NH3PbI3 layer, exhibits steady-state power conversion efficiency (PCE) of 14.85% under AM 1.5G 100 mW·cm(-2) illumination. This renders ZSO a promising candidate as electron-conducting electrode for the highly efficient flexible PSC applications.

1-D structured flexible supercapacitor electrodes with prominent electronic/ionic transport capabilities.

A highly efficient 1-D flexible supercapacitor with a stainless steel mesh (SSM) substrate is demonstrated. Indium tin oxide (ITO) nanowires are prepared on the surface of the stainless steel fiber (SSF), and MnO2 shell layers are coated onto the ITO/SSM electrode by means of electrodeposition. The ITO NWs, which grow radially on the SSF, are single-crystalline and conductive enough for use as a current collector for MnO2-based supercapacitors. A flake-shaped, nanoporous, and uniform MnO2 shell layer with a thickness of ~130 nm and an average crystallite size of ~2 nm is obtained by electrodeposition at a constant voltage. The effect of the electrode geometry on the supercapacitor properties was investigated using electrochemical impedance spectroscopy, cyclic voltammetry, and a galvanostatic charge/discharge study. The electrodes with ITO NWs exhibit higher specific capacitance levels and good rate capability owing to the superior electronic/ionic transport capabilities resulting from the open pore structure. Moreover, the use of a porous mesh substrate (SSM) increases the specific capacitance to 667 F g(-1) at 5 mV s(-1). In addition, the electrode with ITO NWs and the SSM shows very stable cycle performance (no decrease in the specific capacitance after 5000 cycles).

Three-dimensional hierarchical Li4Ti5O12 nanoarchitecture by a simple hydrothermal method.

The spinel Li4Ti5O12 (LTO) is a promising candidate as a superior electrode material for energy storage devices due to the extremely small volume expansion/contraction during the charge/discharge processes of a battery. There are various synthetic approaches for the nanostructured LTO electrode: sol-gel, sonochemical, solution-combustion, hydrothermal methods, and others. Herein, three-dimensional (3D) high-density heterogeneous LTO architectures are fabricated by employing the TiO2 nanorods (NRs) branched SnO2 nanowire (NW) arrays as the template. The TiO2 NRs were effectively converted by the hydrothermal method into the LTO NRs that have a width of 40-nm and length of 100-nm, which induce branch/backbone structured LTO-SnO2 composites. Interestingly, the 3D LTO architectures exhibit unique geometrical shapes because the NRs are surrounded by small nanoparticles. We also discuss how the temperature and solvent affect the LTO nanostructure formation in detail. These results suggest that using a template can provide a new method for designing and synthesizing various classes of 3D architecturing synthesis.

Controlled interfacial electron dynamics in highly efficient Zn2 SnO4 -based dye-sensitized solar cells.

Among ternary oxides, Zn2 SnO4 (ZSO) is considered for dye-sensitized solar cells (DSSCs) because of its wide bandgap, high optical transmittance, and high electrical conductivity. However, ZSO-based DSSCs have a poor performance record owing largely to the absence of systematic efforts to enhance their performance. Herein, general strategies are proposed to improve the performance of ZSO-based DSSCs involving interfacial engineering/modification of the photoanode. A conformal ZSO thin film (blocking layer) deposited at the fluorine-doped tin oxide-electrolyte interface by pulsed laser deposition suppressed the back-electron transfer effectively while maintaining a high optical transmittance, which resulted in a 22 % improvement in the short-circuit photocurrent density. Surface modification of ZSO nanoparticles (NPs) resulted in an ultrathin ZnO shell layer, a 9 % improvement in the open-circuit voltage, and a 4 % improvement in the fill factor because of the reduced electron recombination at the ZSO NPs-electrolyte interface. The ZSO-based DSSCs exhibited a faster charge injection and electron transport than their TiO2 -based counterparts, and their superior properties were not inhibited by the ZnO shell layer, which indicates their feasibility for highly efficient DSSCs. Each interfacial engineering strategy could be applied to the ZSO-based DSSC independently to lead to an improved conversion efficiency of 6 %, a very high conversion efficiency for a non-TiO2 based DSSC.

BaSnO3 perovskite nanoparticles for high efficiency dye-sensitized solar cells.

The synthesis of highly crystalline perovskite BaSnO3 nanoparticles for use as photoanode materials in dye-sensitized solar cells (DSSCs) is reported, and the photovoltaic properties of DSSCs based on BaSnO3 nanoparticles (BaSnO3 cells) are demonstrated. The resulting DSSCs exhibit remarkably rapid charge collection and a DSSC fabricated with a BaSnO3 film thickness of 43 µm leads to a high energy conversion efficiency of 5.2 %, which is one of the highest reported for ternary oxide-based DSSCs. More importantly, the BaSnO3 cells show superior charge collection in nanoparticle films compared to TiO2 cells and could offer a breakthrough in the efficiencies of DSSCs.

Improved quantum efficiency of highly efficient perovskite BaSnO3-based dye-sensitized solar cells.

Ternary oxides are potential candidates as an electron-transporting material that can replace TiO2 in dye-sensitized solar cells (DSSCs), as their electronic/optical properties can be easily controlled by manipulating the composition and/or by doping. Here, we report a new highly efficient DSSC using perovskite BaSnO3 (BSO) nanoparticles. In addition, the effects of a TiCl4 treatment on the physical, chemical, and photovoltaic properties of the BSO-based DSSCs are investigated. The TiCl4 treatment was found to form an ultrathin TiO2 layer on the BSO surface, the thickness of which increases with the treatment time. The formation of the TiO2 shell layer improved the charge-collection efficiency by enhancing the charge transport and suppressing the charge recombination. It was also found that the TiCl4 treatment significantly reduces the amount of surface OH species, resulting in reduced dye adsorption and reduced light-harvesting efficiency. The trade-off effect between the charge-collection and light-harvesting efficiencies resulted in the highest quantum efficiency (i.e., short-circuit photocurrent density), leading to the highest conversion efficiency of 5.5% after a TiCl4 treatment of 3 min (cf. 4.5% for bare BSO). The conversion efficiency could be increased further to 6.2% by increasing the thickness of the BSO film, which is one of the highest efficiencies from non-TiO2-based DSSCs.

Anatase TiO2 nanorod-decoration for highly efficient photoenergy conversion.

In recent studies of inorganic materials for energy applications, surface modification processes have been shown to be among the most effective methods to enhance the performance of devices. Here, we demonstrate a facile nano-decoration method which is generally applicable to anatase TiO2 nanostructures, as well as a nano-decorated hierarchical TiO2 nanostructure which improves the energy conversion efficiency of a dye-sensitized solar cell (DSSC). Using a facile sol-gel method, 0-D, 1-D, and 2-D type anatase TiO2 nanostructures were decorated with 200 nm long anatase TiO2 nanorods to create various hierarchical nanostructures. A structural analysis reveals that the branched nanorod has a highly crystalline anatase phase with anisotropic growth in the [001] longitudinal direction. When one of the hierarchical structures, a chestnut bur-like nanostructure, was employed in a dye-sensitized solar cell as a scattering layer, offering increased dye-loading properties, preserving a sufficient level of light-scattering ability and preserving superior charge transport and recombination properties as well, the energy conversion efficiency of the cell improved by 19% (from 7.16% to 9.09%) compared to a cell with a 0-D TiO2 sphere as a scattering layer. This generally applicable anatase nanorod-decorating method offers potential applications in various energy-conversion applications, especially in DSSCs, quantum-dot solar cells, photoelectrochemical water-splitting devices, photocatalysis, and lithium ion batteries.

Synthesis and photovoltaic property of fine and uniform Zn2SnO4 nanoparticles.

Zn(2)SnO(4) nanoparticles (NPs) with a narrow size distribution were synthesized by a simple hydrothermal route by controlling the crystallization process. The average size of NPs was 8 nm, and this was attributed to the formation of a hydroxy carbonate compound as an intermediate phase, which was demonstrated by the structural and elemental analyses. The fine size and visible-transparency of the synthesized NPs enabled the fabrication of transparent films for efficient photoelectrochemical devices. In particular, we demonstrated dye-sensitized solar cells (DSSCs) employing these transparent Zn(2)SnO(4) photoelectrodes with a high energy conversion efficiency of 4.7%, which is mainly due to an improvement of light harvesting property.