Low-Temperature Synthesized Nb-Doped TiO2 Electron Transport Layer Enabling High-Efficiency Perovskite Solar Cells by Band Alignment Tuning.

An Nb-doped TiO2 (Nb-TiO2) film comprising a double structure stacked with a bottom compact layer and top mesoporous layers was synthesized by treating a Ti precursor-coated substrate using a one-step low-temperature steam-annealing (SA) method. The SA-based Nb-TiO2 films possess high crystallinity and conductivity, and that allows better control over the conduction band (CB) of TiO2 for the electron transport layer (ETL) of the perovskite solar cells by the Nb doping level. Optimization of power conversion efficiency (PCE) for the Nb-TiO2-based ETL was combined with the CB level tuning of the mixed-halide perovskite by changing the Br/I ratio. This band offset management enabled to establish the most suitable energy levels between the ETL and the perovskites. This method was applied to reduce the band gap of perovskites to enhance the photocurrent density while maintaining a high open-circuit voltage. As a result, the optimal combination of 5 mol % Nb-TiO2 ETL and 10 mol % Br in the mixed-halide perovskite exhibited high photovoltaic performance for low-temperature device fabrication, achieving a high-yield PCE of 21.3%.

Proton Irradiation Tolerance of High-Efficiency Perovskite Absorbers for Space Applications.

Lead halide perovskite single layers with three grain sizes are subjected to proton-beam irradiation in order to assess the durability and radiation tolerance of perovskite solar cells (PSCs) against space radiation. Proton-beam irradiation is chosen because proton beams significantly affect solar cell performance in the space environment. We evaluate the effects of proton beams by focusing on the grain structure, crystal structure, and carrier lifetime of a perovskite single layer by using scanning electron microscopy, X-ray diffraction, photoluminescence (PL) spectra, and time-resolved PL (TRPL). The results show that proton irradiation does not significantly affect the grain structure and crystal structure of perovskite layer; the TRPL results show that the carrier lifetime inside the grain is constant up to a fluence of 1 × 1014 p+/cm2 and decreases significantly at a fluence of 1 × 1015 p+/cm2. Proton-beam radiation tolerance of the grain inside the perovskite layer is dominant in the radiation tolerance of PSCs.

Performance enhancement of AgBi2I7 solar cells by modulating a solvent-mediated adduct and tuning remnant BiI3 in one-step crystallization.

We modulated a solvent-mediated adduct for one-step crystallization of lead-free AgBi2I7 at a lower temperature (90 °C) and to obtain remnant BiI3 by controlling the nature of the substrate and precursor concentration. This eventually resulted in remarkable enhancement in the power conversion efficiency, reaching 2.12%, and the long-term stability of AgBi2I7 solar cells towards light, heat and humidity.

Tolerance of Perovskite Solar Cell to High-Energy Particle Irradiations in Space Environment.

Materials to be used in the space environment have to withstand extreme conditions, particularly with respect to cosmic particle irradiation. We report robust stability and high tolerance of organolead trihalide perovskite solar cells against high-fluence electron and proton beams. We found that methylammonium and formamidinium-based lead iodide perovskite solar cells composed of TiO2 and a conductive polymer, as electron and hole transport materials, can survive against accumulated dose levels up to 1016 and 1015particles/cm2 of electrons (1 MeV) and protons (50 KeV), respectively, which are known to completely destroy crystalline Si-, GaAS-, and InGaP/GaAs-based solar cells in spacecraft. These results justify the superior tolerance of perovskite photovoltaic materials to severe space radiations and their usefulness in satellite missions.

Spontaneous Synthesis of Highly Crystalline TiO2 Compact/Mesoporous Stacked Films by a Low-Temperature Steam-Annealing Method for Efficient Perovskite Solar Cells.

Highly crystalline TiO2 nanostructured films were synthesized by a simple steam treatment of a TiCl4 precursor film under a saturated water vapor atmosphere at 125 °C, here referred to as the steam-annealing method. In a single TiO2 film preparation step, a bilayer structure comprising a compact bottom layer and a mesoporous surface layer was formed. The mesoporous layer was occupied by bipyramidal nanoparticles, with a composite phase of anatase and brookite crystals. Despite the low-temperature treatment process, the crystallinity of the TiO2 film was high, comparable with that of the TiO2 film sintered at 500 °C. The compact double-layered TiO2 film was applied to perovskite solar cells (PSCs) as an electron-collecting layer. The PSC exhibited a maximum power conversion efficiency (PCE) of 18.9% with an open-circuit voltage ( VOC) of 1.15 V. The PCE and VOC were higher than those of PSCs using a TiO2 film formed by 500 °C sintering.

Vapor Annealing Controlled Crystal Growth and Photovoltaic Performance of Bismuth Triiodide Embedded in Mesostructured Configurations.

Low stability of organic-inorganic lead halide perovskite and toxicity of lead (Pb) still remain a concern. Therefore, there is a constant quest for alternative nontoxic and stable light-absorbing materials with promising optoelectronic properties. Herein, we report about nontoxic bismuth triiodide (BiI3) photovoltaic device prepared using TiO2 mesoporous film and spiro-OMeTAD as electron- and hole-transporting materials, respectively. Effect of annealing methods (e.g., thermal annealing (TA), solvent vapor annealing (SVA), and Petri dish covered recycled vapor annealing (PR-VA)) and different annealing temperatures (90, 120, 150, and 180 °C for PR-VA) on BiI3 film morphology have been investigated. As found in the study, grain size increased and film uniformity improved as temperature was raised from 90 to 150 °C. The photovoltaic devices based on BiI3 films processed at 150 °C with PR-VA treatment showed power conversion efficiency (PCE) of 0.5% with high reproducibility, which is, so far, the best PCE reported for BiI3 photovoltaic device employing organic hole-transporting material (HTM), owing to the increase in grain size and uniform morphology of BiI3 film. These devices showed stable performance even after 30 days of exposure to 50% relative humidity, and after 100 °C heat stress and 20 min light soaking test. More importantly, the study reveals many challenges and room (discussed in the details) for further development of the BiI3 photovoltaic devices.

Amorphous Metal Oxide Blocking Layers for Highly Efficient Low-Temperature Brookite TiO2-Based Perovskite Solar Cells.

A fully low-temperature-processed perovskite solar cell was fabricated with an ultrathin amorphous TiOx hole-blocking layer in combination with brookite TiO2 prepared at temperature <150 °C. Structured with TiOx/brookite TiO2 bilayer electron collector, the perovskite solar cells exhibit high efficiency up to 21.6% being supported by high open-circuit voltage and fill factor up to 1.18 V and 0.83, respectively. Compared to SnOx hole-blocking layer, TiOx has better electron band alignment with brookite TiO2 and hence, results in higher efficiency.

Lead-free perovskite solar cells using Sb and Bi-based A3B2X9 and A3BX6 crystals with normal and inverse cell structures.

Research of CH3NH3PbI3 perovskite solar cells had significant attention as the candidate of new future energy. Due to the toxicity, however, lead (Pb) free photon harvesting layer should be discovered to replace the present CH3NH3PbI3 perovskite. In place of lead, we have tried antimony (Sb) and bismuth (Bi) with organic and metal monovalent cations (CH3NH3+, Ag+ and Cu+). Therefore, in this work, lead-free photo-absorber layers of (CH3NH3)3Bi2I9, (CH3NH3)3Sb2I9, (CH3NH3)3SbBiI9, Ag3BiI6, Ag3BiI3(SCN)3 and Cu3BiI6 were processed by solution deposition way to be solar cells. About the structure of solar cells, we have compared the normal (n-i-p: TiO2-perovskite-spiro OMeTAD) and inverted (p-i-n: NiO-perovskite-PCBM) structures. The normal (n-i-p)-structured solar cells performed better conversion efficiencies, basically. But, these environmental friendly photon absorber layers showed the uneven surface morphology with a particular grow pattern depend on the substrate (TiO2 or NiO). We have considered that the unevenness of surface morphology can deteriorate the photovoltaic performance and can hinder future prospect of these lead-free photon harvesting layers. However, we found new interesting finding about the progress of devices by the interface of NiO/Sb3+ and TiO2/Cu3BiI6, which should be addressed in the future study.

Solar Water Splitting Utilizing a SiC Photocathode, a BiVO4 Photoanode, and a Perovskite Solar Cell.

We have successfully demonstrated solar water splitting using a newly fabricated photoelectrochemical system with a Pt-loaded SiC photocathode, a CoOx -loaded BiVO4 photoanode, and a perovskite solar cell. Detection of the evolved H2 and O2 with a 100 % Faradaic efficiency indicates that the observed photocurrent was used for water splitting. The solar-to-hydrogen (STH) efficiency was 0.55 % under no additional bias conditions.

Poly(4-Vinylpyridine)-Based Interfacial Passivation to Enhance Voltage and Moisture Stability of Lead Halide Perovskite Solar Cells.

It is well known that the surface trap states and electronic disorders in the solution-processed CH3 NH3 PbI3 perovskite film affect the solar cell performance significantly and moisture sensitivity of photoactive perovskite material limits its practical applications. Herein, we show the surface modification of a perovskite film with a solution-processable hydrophobic polymer (poly(4-vinylpyridine), PVP), which passivates the undercoordinated lead (Pb) atoms (on the surface of perovskite) by its pyridine Lewis base side chains and thereby eliminates surface-trap states and non-radiative recombination. Moreover, it acts as an electron barrier between the perovskite and hole-transport layer (HTL) to reduce interfacial charge recombination, which led to improvement in open-circuit voltage (Voc ) by 120 to 160 mV whereas the standard cell fabricated in same conditions showed Voc as low as 0.9 V owing to dominating interfacial recombination processes. Consequently, the power conversion efficiency (PCE) increased by 3 to 5 % in the polymer-modified devices (PCE=15 %) with Voc more than 1.05 V and hysteresis-less J-V curves. Advantageously, hydrophobicity of the polymer chain was found to protect the perovskite surface from moisture and improved stability of the non-encapsulated cells, which retained their device performance up to 30 days of exposure to open atmosphere (50 % humidity).

Solution-Processed Transparent Nickel-Mesh Counter Electrode with in-Situ Electrodeposited Platinum Nanoparticles for Full-Plastic Bifacial Dye-Sensitized Solar Cells.

A new type of embedded metal-mesh transparent electrode (EMTE) with in-situ electrodeposited catalytic platinum nanoparticles (PtNPs) is developed as a high-performance counter electrode (CE) for lightweight flexible bifacial dye-sensitized solar cells (DSSCs). The thick but narrow nickel micromesh fully embedded in a plastic film provides superior electrical conductivity, optical transmittance, and mechanical stability to the novel electrode. PtNPs decorated selectively on the nickel micromesh surface provide catalytic function with minimum material cost and without interfering with optical transparency. Facile and fully solution-processed fabrication of the novel CE is demonstrated with potential for scalable and cost-effective production. Using this PtNP-decorated nickel EMTE as the CE and titanium foil as the photoanode, unifacial flexible DSSCs are fabricated with a power conversion efficiency (PCE) of 6.91%. By replacing the titanium foil with a transparent ITO-PEN photoanode, full-plastic bifacial DSSCs are fabricated and tested, demonstrating a remarkable PCE of 4.87% under rear-side illumination, which approaches 85% of the 5.67% PCE under front-side illumination, among the highest ratio in published results. These promising results reveal the enormous potential of this hybrid transparent CE in scalable production and commercialization of low-cost and efficient flexible DSSCs.

Efficiency Enhancement of Hybrid Perovskite Solar Cells with MEH-PPV Hole-Transporting Layers.

In this study, hybrid perovskite solar cells are fabricated using poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and poly(3-hexylthiophene-2,5-diyl) (P3HT) as dopant-free hole-transporting materials (HTMs), and two solution processes (one- and two-step methods, respectively) for preparing methylammonium lead iodide perovskite. By optimizing the concentrations and solvents of MEH-PPV solutions, a power conversion efficiency of 9.65% with hysteresis-less performance is achieved, while the device with 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'spirobifluorene (Spiro-OMeTAD) doped with lithium salts and tert-butylpyridine (TBP) exhibits an efficiency of 13.38%. This result shows that non-doped MEH-PPV is a suitable, low-cost HTM for efficient polymer-based perovskite solar cells. The effect of different morphologies of methylammonium lead iodide perovskite on conversion efficiency is also investigated by incident photon-to-electron conversion efficiency (IPCE) curves and electrochemical impedance spectroscopy (EIS).

A SnOx-brookite TiO2 bilayer electron collector for hysteresis-less high efficiency plastic perovskite solar cells fabricated at low process temperature.

Thin plastic film-based CH3NH3PbI3-xClx perovskite solar cells were fabricated at low process temperature using a bilayer comprising an amorphous SnOx and mesoporous brookite TiO2 as electron collectors. Void-less high quality heterojunction structures achieve hysteresis-less photovoltaic performance with a power conversion efficiency as high as 13.4% and mechanical stability against cyclic bending.

Effect of Electron Transporting Layer on Bismuth-Based Lead-Free Perovskite (CH3NH3)3 Bi2I9 for Photovoltaic Applications.

Methylammonium iodo bismuthate ((CH3NH3)3Bi2I9) (MBI) perovskite is a promising alternative to rapidly progressing hybrid organic-inorganic lead perovskites because of its better stability and low toxicity compared to lead-based perovskites. Solution-processed perovskite fabricated by single-step spin-coating and subsequent heating produced polycrystalline films of hybrid perovskite (CH3NH3)3Bi2I9), whose morphology was influenced drastically by the nature of substrates. The optical measurements showed a strong absorption band around 500 nm. The devices made on anatase TiO2 mesoporous layer showed good performance with current density over 0.8 mA cm(-2) while the devices on brookite TiO2 layer and planar (free of porous layer) was inefficient. However, all the MBI devices were stable to ambient conditions for more than 10 weeks.

Emergence of Hysteresis and Transient Ferroelectric Response in Organo-Lead Halide Perovskite Solar Cells.

Although there has been rapid progress in the efficiency of perovskite-based solar cells, hysteresis in the current-voltage performance is not yet completely understood. Owing to its complex structure, it is not easy to attribute the hysteretic behavior to any one of different components, such as the bulk of the perovskite or different heterojunction interfaces. Among organo-lead halide perovskites, methylammonium lead iodide perovskite (CH3NH3PbI3) is known to have a ferroelectric property. The present investigation reveals a strong correlation between transient ferroelectric polarization of CH3NH3PbI3 induced by an external bias in the dark and hysteresis enhancement in photovoltaic characteristics. Our results demonstrate that the reverse bias poling (-0.3 to -1.1 V) of CH3NH3PbI3 photovoltaic layers prior to the photocurrent-voltage measurement generates stronger hysteresis whose extent changes significantly by the cell architecture. The phenomenon is interpreted as the effect of remanent polarization in the perovskite film on the photocurrent, which is most enhanced in planar perovskite structures without mesoporous scaffolds.

A Switchable High-Sensitivity Photodetecting and Photovoltaic Device with Perovskite Absorber.

Amplified photocurrent gain has been obtained by photodiodes of inorganic semiconductors such as GaAs and Si. The avalanche photodiode, developed for high-sensitivity photodetectors, requires an expensive vapor-phase epitaxy manufacture process and high driving voltage (50-150 V). Here, we show that a low-cost solution-processed device using a planar-structured ferroelectric organo-lead triiodide perovskite enables light detection in a large dynamic range of incident power (10(-7)-10(-1) W cm(-2)) by switching with small voltage (-0.9 to +0.5 V). The device achieves significantly high external quantum conversion efficiency (EQE) up to 2.4 × 10(5)% (gain value of 2400) under weak monochromatic light. On a single dual-functional device, incident small power (0.2-100 µW cm(-2)) and medium to large power (>0.1 mW cm(-2)) are captured by reverse bias and forward bias modes, respectively, with linear responsivity of current. For weak light detection, the device works with a high responsivity value up to 620 A W(-1).

Efficient perovskite solar cells fabricated using an aqueous lead nitrate precursor.

A novel, aqueous precursor system (Pb(NO3)2 + water) is developed to replace conventional (PbI2 + DMF) for fabricating methylammonium lead iodide (MAPbI3) perovskite solar cells (PSCs). When the morphology and surface coverage of the Pb(NO3)2 film was controlled during coating, a power conversion efficiency of 12.58% under standard conditions (AM1.5, 100 mW cm(-2)) was achieved for the PSC.

The Interface between FTO and the TiO2 Compact Layer Can Be One of the Origins to Hysteresis in Planar Heterojunction Perovskite Solar Cells.

Organometal halide perovskite solar cells have shown rapid rise in power conversion efficiency, and therefore, they have gained enormous attention in the past few years. However, hysteretic photovoltaic characteristics, found in these solid-state devices, have been a major problem. Although it is being proposed that the ferroelectric property of perovskite causes hysteresis in the device, we observed hysteresis in a device made of nonferroelectric PbI2 as a light absorber. This result evidently supports the fact that ferroelectric property cannot be the sole reason for hysteresis. The present study investigates the roles of some key interfaces in a planar heterojunction perovskite (CH3NH3PbI(3-x)Cl(x)) solar cell that can potentially cause hysteresis. The results confirm that the interface between fluorine doped tin oxide (FTO) substrate and the TiO2 compact layer has a definite contribution to hysteresis. Although this interface is one of the origins to hysteresis, we think that other interfaces, especially the interface of the TiO2 compact layer with perovskite, can also play major roles. Nevertheless, the results indicate that hysteresis in such devices can be reduced/eliminated by changing the interlayer between FTO and perovskite.