Mixed Sn–Ge Perovskite for Enhanced Perovskite Solar Cell Performance in Air

Lead-based perovskite solar cells have gained ground in recent years, showing efficiency as high as 20%, which is on par with that of silicon solar cells. However, the toxicity of lead makes it a nonideal candidate for use in solar cells. Alternatively, tin-based perovskites have been proposed because of their nontoxic nature and abundance. Unfortunately, these solar cells suffer from low efficiency and stability. Here, we propose a new type of perovskite material based on mixed tin and germanium. The material showed a band gap around 1.4–1.5 eV as measured from photoacoustic spectroscopy, which is ideal from the perspective of solar cells. In a solar cell device with inverted planar structure, pure tin perovskite solar cell showed a moderate efficiency of 3.31%. With 5% doping of germanium into the perovskite, the efficiency improved up to 4.48% (6.90% after 72 h) when measured in air without encapsulation

Slow hot carrier cooling in cesium lead iodide perovskites

Lead halide perovskites are attracting a great deal of interest for optoelectronic applications such as solar cells, LEDs, and lasers because of their unique properties. In solar cells, heat dissipation by hot carriers results in a major energy loss channel responsible for the Shockley–Queisser efficiency limit. Hot carrier solar cells offer the possibility to overcome this limit and achieve energy conversion efficiency as high as 66% by extracting hot carriers. Therefore, fundamental studies on hot carrier relaxation dynamics in lead halide perovskites are important. Here, we elucidated the hot carrier cooling dynamics in all-inorganic cesium lead iodide (CsPbI3) perovskite using transient absorption spectroscopy. We observe that the hot carrier cooling rate in CsPbI3 decreases as the fluence of the pump light increases and the cooling is as slow as a few 10 ps when the photoexcited carrier density is 7 × 1018 cm−3, which is attributed to phonon bottleneck for high photoexcited carrier densities. Our findings suggest that CsPbI3 has a potential for hot carrier solar cell applications

Investigation of Interfacial Charge Transfer in Solution Processed Cs2SnI6 Thin Films

Cesium tin halide based perovskite Cs2SnI6 has been subjected to in-depth investigations owing to its potentiality toward the realization of environment benign Pb free and stable solar cells. In spite of the fact that Cs2SnI6 has been successfully utilized as an efficient hole transport material owing to its p-type semiconducting nature, however, the nature of the majority carrier is still under debate. Therefore, intrinsic properties of Cs2SnI6 have been investigated in detail to explore its potentiality as light absorber along with facile electron and hole transport. A high absorption coefficient (5 × 104 cm–1) at 700 nm indicates the penetration depth of 700 nm light to be 0.2 μm, which is comparable to conventional Pb based solar cells. Preparation of pure and CsI impurity free dense thin films with controllable thicknesses of Cs2SnI6 by the solution processable method has been reported to be difficult owing to its poor solubility. An amicable solution to circumvent such problems of Cs2SnI6 has been provided utilizing spray-coating in combination with spin-coating. The presence of two emission peaks at 710 and 885 nm in the prepared Cs2SnI6 thin films indicated coexistence of quantum dot and bulk parts which were further supported by transmission electron microscopy (TEM) investigations. Time-resolved photoluminescence (PL) and transient absorption spectroscopy (TAS) were employed to investigate the excitation carrier lifetime, which revealed fast decay kinetics in the picoseconds (ps) to nanoseconds (ns) time domains. Time-resolved microwave photoconductivity decay (MPCD) measurement provided the mobile charge carrier lifetime exceeding 300 ns, which was also in agreement with the nanosecond transient absorption spectroscopy (ns-TAS) indicating slow charge decay lasting up to 20 μs. TA assisted interfacial charge transfer investigations utilizing Cs2SnI6 in combination with n-type PCBM and p-type P3HT exhibited both intrinsic electron and hole transport

Solution‐Processed Air‐Stable Copper Bismuth Iodide for Photovoltaics

Bismuth‐based solar cells have been under intensive interest as an efficient non‐toxic absorber in photovoltaics. Within this new family of semiconductors, we herein report a new, long‐term stable copper bismuth iodide (CuBiI4). A solutionprocessed method under air atmosphere is used to prepare the material. The adopted HI‐assisted dimethylacetamide (DMA) co‐solvent can completely dissolve CuI and BiI3 powders with high concentration compared with other organic solvents. Moreover, the high vapor pressure of tributyl phosphate, selected for the solvent vapor annealing (SVA), enables complete low‐temperature (≤70°C) film preparation, resulting in a stable, uniform, dense CuBiI4 film. The average grain size increases with the precursor concentration, greatly improving the photoluminescence lifetime and hall mobility; a carrier lifetime of 3.03 ns as well as an appreciable hall mobility of 110 cm2V−1s−1 were obtained. XRD illustrates that the crystal structure is cubic (space group Fd3m) and favored in the [111] direction. Moreover, the photovoltaic performance of CuBiI4 was also investigated. A wide bandgap (2.67 eV) solar cell with 0.82% power conversion efficiency is presented, which exhibits excellent long‐term stability over 1008 h under ambient conditions. This air‐stable material may give an application in future tandem solar cells as a stable short‐wavelength light absorber

Ultrafast Electron Injection from Photoexcited Perovskite CsPbI3 QDs into TiO2 Nanoparticles with Injection Efficiency near 99%

Photoexcited electron injection dynamics from CsPbI3 quantum dots (QDs) to wide gap metal oxides are studied by transient absorption spectroscopy. Experimental results show under a low excitation intensity that ∼99% of the photoexcited electrons in CsPbI3 QDs can be injected into TiO2 with a size-dependent rate ranging from 1.30 × 1010 to 2.10 × 1010 s–1, which is also ∼2.5 times faster than that in the case of ZnO. A demonstration QD-sensitized solar cell based on a CsPbI3/TiO2 electrode is fabricated that delivers a power conversion efficiency of 5%

Highly Luminescent Phase-Stable CsPbI3 Perovskite Quantum Dots Achieving Near 100% Absolute Photoluminescence Quantum Yield

Perovskite quantum dots (QDs) as a new type of colloidal nanocrystals have gained significant attention for both fundamental research and commercial applications owing to their appealing optoelectronic properties and excellent chemical processability. For their wide range of potential applications, synthesizing colloidal QDs with high crystal quality is of crucial importance. However, like most common QD systems such as CdSe and PbS, those reported perovskite QDs still suffer from a certain density of trapping defects, giving rise to detrimental nonradiative recombination centers and thus quenching luminescence. In this paper, we show that a high room-temperature photoluminescence quantum yield of up to 100% can be obtained in CsPbI3 perovskite QDs, signifying the achievement of almost complete elimination of the trapping defects. This is realized with our improved synthetic protocol that involves introducing organolead compound trioctylphosphine–PbI2 (TOP–PbI2) as the reactive precursor, which also leads to a significantly improved stability for the resulting CsPbI3 QD solutions. Ultrafast kinetic analysis with time-resolved transient absorption spectroscopy evidence the negligible electron or hole-trapping pathways in our QDs, which explains such a high quantum efficiency. We expect the successful synthesis of the “ideal” perovskite QDs will exert profound influence on their applications to both QD-based light-harvesting and -emitting devices

Colloidal Synthesis of Air-Stable Alloyed CsSn1–xPbxI3 Perovskite Nanocrystals for Use in Solar Cells

Organic–inorganic hybrid perovskite solar cells have demonstrated unprecedented high power conversion efficiencies in the past few years. Now, the universal instability of the perovskites has become the main barrier for this kind of solar cells to realize commercialization. This situation can be even worse for those tin-based perovskites, especially for CsSnI3, because upon exposure to ambient atmosphere the desired black orthorhombic phase CsSnI3 would promptly lose single crystallinity and degrade to the inactive yellow phase, followed by irreversible oxidation into metallic Cs2SnI6. By alloying CsSnI3 with CsPbI3, we herein report the synthesis of alloyed perovskite quantum dot (QD), CsSn1–xPbxI3, which not only can be phase-stable for months in purified colloidal solution but also remains intact even directly exposed to ambient air, far superior to both of its parent CsSnI3 and CsPbI3 QDs. Ultrafast transient absorption spectroscopy studies reveal that the photoexcited electrons in the alloyed QDs can be injected into TiO2 nanocrystals at a fast rate of 1.12 × 1011 s–1, which enables a high photocurrent generation in solar cells

Solar cells using bulk crystals of rare metal-free compound semiconductor ZnSnP₂

We report on current density–voltage (J–V) characteristics of solar cells using bulk crystals of ZnSnP₂ obtained by solution growth, where Sn was used as a solvent. The minority carrier lifetimes of fast and slow components in bulk crystals of ZnSnP₂ were 0.442 and 37.8 ns, respectively, which were obtained by analysis using double exponential function in time‐resolved photoluminescence (TRPL) under the excitation power of 5.05 mW with the beam area of 0.5 mm². The lifetime is close to that of CIGS, which is as high as to achieve the conversion efficiency of over 16%. TRPL also revealed that the recombination at the surface was dominant since the intensity of fast component was much larger than that of slow component. The well‐known structure Al/Al‐doped ZnO/ZnO/CdS/ZnSnP₂/Mo was adopted for solar cells. The short‐circuit current density and the open‐circuit voltage are 1.99 mA cm⁻² and 0.172 V, respectively. The wavelength at the absorption edge in external quantum efficiency is consistent with the bandgap of ZnSnP₂. However, the conversion efficiency is 0.087%. The J–V curve suggests that the reduction of series resistance is required because it is higher than the value expected from the resistivity of bulk ZnSnP₂. The improvement of conduction band offset is also necessary considering from our previous works