Antiferromagnetism and p‐type conductivity of nonstoichiometric nickel oxide thin films

Plasma‐enhanced atomic layer deposition was used to grow non‐stoichiometric nickel oxide thin films with low impurity content, high crystalline quality, and p‐type conductivity. Despite the non‐stoichiometry, the films retained the antiferromagnetic property of NiO

Assessing the Impact of Defects on Lead-Free Perovskite-Inspired Photovoltaics via Photoinduced Current Transient Spectroscopy

Funder: Collaborative Innovation Center of Suzhou Nano Science & TechnologyFunder: Priority Academic Program Development of Jiangsu Higher Education Institutions; Id: http://dx.doi.org/10.13039/501100012246Funder: 111 Project; Id: http://dx.doi.org/10.13039/501100013314Funder: Joint International Research Laboratory of Carbon‐Based Functional Materials and DevicesThe formidable rise of lead-halide perovskite photovoltaics has energized the search for lead-free perovskite-inspired materials (PIMs) with related optoelectronic properties but free from toxicity limitations. The photovoltaic performance of PIMs closely depends on their defect tolerance. However, a comprehensive experimental characterization of their defect-level parameters—concentration, energy depth, and capture cross-section—has not been pursued to date, hindering the rational development of defect-tolerant PIMs. While mainstream, capacitance-based techniques for defect-level characterization have sparked controversy in lead-halide perovskite research, their use on PIMs is also problematic due to their typical near-intrinsic character. This study demonstrates on four representative PIMs (Cs3Sb2I9, Rb3Sb2I9, BiOI, and AgBiI4) for which Photoinduced Current Transient Spectroscopy (PICTS) offers a facile, widely applicable route to the defect-level characterization of PIMs embedded within solar cells. Going beyond the ambiguities of the current discussion of defect tolerance, a methodology is also presented to quantitatively assess the defect tolerance of PIMs in photovoltaics based on their experimental defect-level parameters. Finally, PICTS applied to PIM photovoltaics is revealed to be ultimately sensitive to defect-level concentrations <1 ppb. Therefore, this study provides a versatile platform for the defect-level characterization of PIMs and related absorbers, which can catalyze the development of green, high-performance photovoltaics.Royal Academy of Engineerin

Strongly Enhanced Photovoltaic Performance and Defect Physics of Air-Stable Bismuth Oxyiodide (BiOI)

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|NiO$_x$|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.R.L.Z.H. thanks Magdalene College, Cambridge. L.C.L. and J.L.M.-D. thank the EPRSC Centre for Doctoral Training: New and Sustainable Photovoltaics, and the Cambridge Winton Programme for the Physics of Sustainability for funding. T.N.H. thanks the Cambridge Graphene Centre, funded by the EPSRC. K.H.L.Z. was supported by the Herschel Smith fellowship. The U.S.-based theory and synthesis portions of this work were supported primarily as part of the Center for Next Generation Materials by Design (CNGMD), an Energy Frontier Research Center funded by the DOE Office of Science, Basic Energy Sciences under Contract No. DE-AC36-08GO28308. The MIT-based characterization portion of this work was supported primarily through a TOTAL SA research grant funded through MITei, as well as a SusChem grant funded by the National Science Foundation (No. CBET-1605495). The TCSPC work was supported as part of the Center for Excitonics, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award No. DE-SC0001088 (MIT). The computations were performed using resources sponsored by the Department of Energy’s Office of Energy Efficiency and Renewable Energy and located at the NREL. The authors also acknowledge the MRSEC Shared Experimental Facilities at MIT, supported by the National Science Foundation (No. DMF-08019762)

Lead-Free Perovskite-Inspired Absorbers for Indoor Photovoltaics

With the exponential rise in the market value and number of devices part of the Internet of Things (IoT), the demand for indoor photovoltaics (IPV) to power autonomous devices is predicted to rapidly increase. Lead-free perov skite-inspired materials (PIMs) have recently attracted significant attention in photovoltaics research, due to the similarity of their electronic structure to high-performance lead-halide perovskites, but without the same toxicity limitations. However, the capability of PIMs for indoor light harvesting has not yet been considered. Herein, two exemplar PIMs, BiOI and CsSbClxI-x are examined. It is shown that while their bandgaps are too wide for single-junction solar cells, they are close to the optimum for indoor light harvesting. As a result, while BiOI and CsSbClxI-x devices are only circa %-ecient under -sun illumination, their eciencies increase to –% under indoor illumination. These eciencies are within the range of reported values for hydrogenated amorphous silicon, i.e., the industry standard for IPV. It is demonstrated that such performance levels are already sucient for millimeter-scale PIM devices to power thin-film-transistor circuits. Intensity-dependent and optical loss analyses show that future improvements in eciency are possible. Furthermore, calculations of the optically limited eciency of these and other low-toxicity PIMs reveal their considerable potential for IPV, thus encouraging future eorts for their exploration for powering IoT devic

Controlling the preferred orientation of layered BiOI solar absorbers

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.EPSRC Royal Academy of Engineering Downing College Isaac Newton Trust Bill Wellan

Lead‐Free Perovskite‐Inspired Absorbers for Indoor Photovoltaics

With the exponential rise in the market value and number of devices part of the Internet of Things (IoT), the demand for indoor photovoltaics (IPV) to power autonomous devices is predicted to rapidly increase. Lead-free perov skite-inspired materials (PIMs) have recently attracted significant attention in photovoltaics research, due to the similarity of their electronic structure to high-performance lead-halide perovskites, but without the same toxicity limitations. However, the capability of PIMs for indoor light harvesting has not yet been considered. Herein, two exemplar PIMs, BiOI and CsSbClxI-x are examined. It is shown that while their bandgaps are too wide for single-junction solar cells, they are close to the optimum for indoor light harvesting. As a result, while BiOI and CsSbClxI-x devices are only circa %-ecient under -sun illumination, their eciencies increase to –% under indoor illumination. These eciencies are within the range of reported values for hydrogenated amorphous silicon, i.e., the industry standard for IPV. It is demonstrated that such performance levels are already sucient for millimeter-scale PIM devices to power thin-film-transistor circuits. Intensity-dependent and optical loss analyses show that future improvements in eciency are possible. Furthermore, calculations of the optically limited eciency of these and other low-toxicity PIMs reveal their considerable potential for IPV, thus encouraging future eorts for their exploration for powering IoT devic

Atomic layer deposited μ;-Ga<inf>2</inf>O<inf>3</inf> solar-blind photodetectors

Low temperature atomic layer deposition was used to deposit α-Ga2O3 films, which were subsequently annealed at various temperatures and atmospheres. The α-Ga2O3 phase is stable up to 400 oC, which is also the temperature that yields the most intense and sharpest reflection by X-ray diffraction. Upon annealing at 450 oC and above, the material gradually turns into the more thermodynamically stable ε or β phase. The suitability of the materials for solar-blind photodetector applications has been demonstrated with the best responsivity achieved being 1.2 A/W under 240 nm illumination and 10 V bias, for the sample annealed at 400 oC in argon. It is worth noting however that the device performance strongly depends on the annealing conditions, with the device annealed in forming gas behaving poorly. Given that the tested devices have similar microstructure, the discrepancies in device performance are attributed to hydrogen impurities

Atomic layer deposited alpha-Ga2O3 solar-blind photodetectors

Low temperature atomic layer deposition was used to deposit α-Ga2O3 films, which were subsequently annealed at various temperatures and atmospheres. The α-Ga2O3 phase is stable up to 400 °C, which is also the temperature that yields the most intense and sharpest reflection by x-ray diffraction. Upon annealing at 450 °C and above, the material gradually turns into the more thermodynamically stable ε or β phase. The suitability of the materials for solar-blind photodetector applications has been demonstrated with the best responsivity achieved being 1.2 A W−1 under 240 nm illumination and 10 V bias, for the sample annealed at 400 °C in argon. It is worth noting however that the device performance strongly depends on the annealing conditions, with the device annealed in forming gas behaving poorly. Given that the tested devices have similar microstructure, the discrepancies in device performance are attributed to hydrogen impurities

Electron Beam Sterilization of Poly(Methyl Methacrylate)—Physicochemical and Biological Aspects

Electron beam (E-beam) irradiation is an attractive and efficient method for sterilizing clinically implantable medical devices made of natural and/or synthetic materials such as poly(methyl methacrylate) (PMMA). As ionizing irradiation can affect the physicochemical properties of PMMA, understanding the consequences of E-beam sterilization on the intrinsic properties of PMMA is vital for clinical implementation. A detailed assessment of the chemical, optical, mechanical, morphological, and biological properties of medical-grade PMMA after E-beam sterilization at 25 and 50 kiloGray (kGy) is reported. Fourier transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry studies indicate that E-beam irradiation has minimal effect on the chemical properties of the PMMA at these doses. While 25 kGy irradiation does not alter the mechanical and optical properties of the PMMA, 50 kGy reduces the flexural strength and transparency by 10% and 2%, respectively. Atomic force microscopy demonstrates that E-beam irradiation reduces the surface roughness of PMMA in a dose dependent manner. Live-Dead, AlamarBlue, immunocytochemistry, and complement activation studies show that E-beam irradiation up to 50 kGy has no adverse effect on the biocompatibility of the PMMA. These findings suggest that E-beam irradiation at 25 kGy may be a safe and efficient alternative for PMMA sterilization

Role of ALD Al2O3 surface passivation on the performance of p-type Cu2O thin film transistors

High-performance p-type oxide thin film transistors (TFTs) have great potential for many semiconductor applications. However, these devices typically suffer from low hole mobility and high off-state currents. We fabricated p-type TFTs with a phase-pure polycrystalline Cu2O semiconductor channel grown by atomic layer deposition (ALD). The TFT switching characteristics were improved by applying a thin ALD Al2O3 passivation layer on the Cu2O channel, followed by vacuum annealing at 300 C. Detailed characterisation by TEM-EDX and XPS shows that the surface of Cu2O is reduced following Al2O3 deposition and indicates the formation of 1-2 nm thick CuAlO2 interfacial layer. This, together with field-effect passivation caused by the high negative fixed charge of the ALD Al2O3, leads to an improvement in the TFT performance by reducing the density of deep trap states as well as by reducing the accumulation of electrons in the semiconducting layer in the device off-state