Bismuth‐based compounds have recently gained increasing attention as potentially nontoxic and defect‐tolerant solar absorbers. However, many of the new materials recently investigated show limited photovoltaic performance. Herein, one such compound is explored in detail through theory and experiment: bismuth oxyiodide (BiOI). BiOI thin films are grown by chemical vapor transport and found to maintain the same tetragonal phase in ambient air for at least 197 d. The computations suggest BiOI to be tolerant to antisite and vacancy defects. All‐inorganic solar cells (ITO|NiOx|BiOI|ZnO|Al) with negligible hysteresis and up to 80% external quantum efficiency under select monochromatic excitation are demonstrated. The short‐circuit current densities and power conversion efficiencies under AM 1.5G illumination are nearly double those of previously reported BiOI solar cells, as well as other bismuth halide and chalcohalide photovoltaics recently explored by many groups. Through a detailed loss analysis using optical characterization, photoemission spectroscopy, and device modeling, direction for future improvements in efficiency is provided. This work demonstrates that BiOI, previously considered to be a poor photocatalyst, is promising for photovoltaics.
sources at 1000 lux had an irradiance of 340 and 320 µW cm −2 , respectively. The accuracy of the light meter and power meter is the primary determinant of the uncertainty in the measured PCE values, which amounts to approximately ±6-7%, as can be determined from a straightforward uncertainty analysis based on the device testing conditions and the specifications of the power and light meters. Consequently, the PCE values are reported herein with 1 decimal place.
Perovskite nanoplatelets (NPls) hold promise for light-emitting applications, having achieved photoluminescence quantum efficiencies approaching unity in the blue wavelength range, where other metal-halide perovskites have typically been ineffective. However, the external quantum efficiencies (EQEs) of blue-emitting NPl light-emitting diodes (LEDs) have reached only 0.12%. In this work, we show that NPl LEDs are primarily limited by a poor electronic interface between the emitter and hole injector. We show that the NPls have remarkably deep ionization potentials (≥6.5 eV), leading to large barriers for hole injection, as well as substantial nonradiative decay at the NPl/hole-injector interface. We find that an effective way to reduce these nonradiative losses is by using poly(triarylamine) interlayers, which lead to an increase in the EQE of the blue (464 nm emission wavelength) and sky-blue (489 nm emission wavelength) LEDs to 0.3% and 0.55%, respectively. Our work also identifies the key challenges for further efficiency increases.
Bismuth-based compounds have recently gained interest as solar absorbers with the potential to have low toxicity, be efficient in devices, and be processable using facile methods. We review recent theoretical and experimental investigations into bismuth-based compounds, which shape our understanding of their photovoltaic potential, with particular focus on their defect-tolerance. We also review the processing methods that have been used to control the structural and optoelectronic properties of single crystals and thin films. Additionally, we discuss the key factors limiting their device performance, as well as the future steps needed to ultimately realize these new materials for commercial applications.
Bismuth oxyiodide has anisotropic transport properties, and optimal device performance requires control over its preferred orientation. We find that this preferred orientation can be finely tuned through the precursor and substrate temperatures.
Nickel oxide (NiOx), a p‐type oxide semiconductor, has gained significant attention due to its versatile and tunable properties. It has become one of the critical materials in wide range of electronics applications, including resistive switching random access memory devices and highly sensitive and selective sensor applications. In addition, the wide band gap and high work function, coupled with the low electron affinity, have made NiOx widely used in emerging optoelectronics and p‐n heterojunctions. The properties of NiOx thin films depend strongly on the deposition method and conditions. Efficient implementation of NiOx in next‐generation devices will require controllable growth and processing methods that can tailor the morphological and electronic properties of the material, but which are also compatible with flexible substrates. In this review, we link together the fundamental properties of NiOx with the chemical processing methods that have been developed to grow the material as thin films, and with its application in electronic devices. We focus solely on thin films, rather than NiOx incorporated with one‐dimensional or two‐dimensional materials. This review starts by discussing how the p‐type nature of NiOx arises and how its stoichiometry affects its electronic and magnetic properties. We discuss the chemical deposition techniques for growing NiOx thin films, including chemical vapor deposition, atomic layer deposition, and a selection of solution processing approaches, and present examples of recent progress made in the implementation of NiOx thin films in devices, both on rigid and flexible substrates. Furthermore, we discuss the remaining challenges and limitations in the deposition of device‐quality NiOx thin films with chemical growth methods.
In the search for nontoxic alternatives to lead-halide perovskites, bismuth oxyiodide (BiOI) has emerged as a promising contender. BiOI is air-stable for over three months, demonstrates promising early-stage photovoltaic performance and, importantly, is predicted from calculations to tolerate vacancy and antisite defects. Here, whether BiOI tolerates point defects is experimentally investigated. BiOI thin films are annealed at a low temperature of 100 °C under vacuum (25 Pa absolute pressure). There is a relative reduction in the surface atomic fraction of iodine by over 40%, reduction in the surface bismuth fraction by over 5%, and an increase in the surface oxygen fraction by over 45%. Unexpectedly, the Bi 4f 7/2 core level position, Fermi level position, and valence band density of states of BiOI are not significantly changed. Further, the charge-carrier lifetime, photoluminescence intensity, and the performance of the vacuum-annealed BiOI films in solar cells remain unchanged. The results show BiOI to be electronically and optoelectronically robust to percent-level changes in surface composition. However, from photoinduced current transient spectroscopy measurements, it is found that the as-grown BiOI films have deep traps located ≈0.3 and 0.6 eV from the band edge. These traps limit the charge-carrier lifetimes of BiOI, and future improvements in the performance of BiOI photovoltaics will need to focus on identifying their origin. Nevertheless, these deep traps are three to four orders of magnitude less concentrated than the surface point defects induced through vacuum annealing. The charge-carrier lifetimes of the BiOI films are also orders of magnitude longer than if these surface defects were recombination active. This work therefore shows BiOI to be robust against processing conditions that lead to percent-level iodine-, bismuth-, and oxygen-related surface defects. This will simplify and reduce the cost of fabricating BiOI-based electronic devices, and stands in contrast to the defect-sensitivity of traditional covalent semiconductors.
Perovskite solar cells (PSCs) with transparent electrodes can be integrated with existing solar panels in tandem configurations to increase the power conversion efficiency. A critical layer in semi-transparent PSCs is the inorganic buffer layer, which protects the PSC against damage when the transparent electrode is sputtered on top. The development of n-i-p structured semi-transparent PSCs has been hampered by the lack of suitable p-type buffer layers. In this work we develop a ptype CuO x buffer layer, which can be grown uniformly over the perovskite device without damaging the perovskite or organic hole transport layers. The CuO x layer has high hole mobility (4.3 ± 2 cm 2 V -1 s -1 ), high transmittance (>95%), and a suitable ionization potential for hole extraction (5.3 ± 0.2 eV). Semi-transparent PSCs with efficiencies up to 16.7% are achieved using the CuO x buffer layer. Our work demonstrates a new approach to integrate n-i-p structured PSCs into tandem configurations, as well as enable the development of other devices that need high quality, protective p-type layers.
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