Lead-based halide perovskites (APbX3, where A = organic
or inorganic cation, X = Cl, Br, I) are suitable materials for many
optoelectronic devices due to their many attractive properties. However,
the concern of lead toxicity and the poor ambient and operational
stability of the organic cation group greatly limit their practical
utilization. Therefore, there has recently been great interest in
lead-free, environment-friendly all-inorganic halide perovskites (IHPs).
Sb and Sn are common species suggested to replace Pb for Pb-free IHPs.
However, the large difference in the melting points of the precursor
materials (e.g., CsBr and SbBr3 precursors for Cs3Sb2Br9) makes the chemical vapor deposition
(CVD) growth of high-quality Pb-free IHPs a very challenging task.
In this work, we developed a two-step CVD method to overcome this
challenge and successfully synthesized Pb-free Cs3Sb2Br9 perovskite microplates. Cs3Sb2Br9 microplates ∼25 μm in size with
the exciton absorption peak at ∼2.8 eV and a band gap of ∼2.85
eV were obtained. The microplates have a smooth hexagonal morphology
and show a large Stokes shift of ∼450 meV and exciton binding
energy of ∼200 meV. To demonstrate the applications of these
microplates in optoelectronics, simple photoconductive devices were
fabricated. These photodetectors exhibit a current on/off ratio of
2.36 × 102, a responsivity of 36.9 mA/W, and a detectivity
of 1.0 × 1010 Jones with a fast response of rise and
decay time of 61.5 and 24 ms, respectively, upon 450 nm photon irradiation.
Finally, the Cs3Sb2Br9 microplates
also show good stability in ambient air without encapsulation. These
results demonstrate that the 2-step CVD process is an effective approach
to synthesize high-quality all-inorganic lead-free Cs3Sb2Br9 perovskite microplates that have the potential
for future high-performance optoelectronic device applications.
Native defects in semiconductors play an important role in their optoelectronic properties. Nickel oxide (NiO) is one of the few wide-gap p-type oxide semiconductors and its conductivity is believed to be controlled primarily by Ni-vacancy acceptors. Herein, we present a systematic study comparing the optoelectronic properties of stoichiometric NiO, oxygen-rich NiO with Ni vacancies (NiO:VNi) and Ni-rich NiO with O vacancies (NiO:VO). The optical properties were obtained by spectroscopic ellipsometry while valence band spectra were probed by high-resolution X-ray photoelectron spectroscopy. The experimental results are directly compared to firstprinciples DFT + U calculations. Computational results confirm that gap states are present in both NiO systems with vacancies. Gap states in NiO:Vo are predominantly Ni 3d states while those in NiO:VNi are composed of both the Ni 3d and O 2p states. The absorption spectra for the NiO:VNi sample show significant defect-induced features below 3.0 eV compared to NiO and NiO:VO samples. The increase in sub-gap absorptions in the NiO:VNi can be attributed to gap states observed in the electronic density of states. The relation between native vacancy defects and electronic and optical properties of NiO are demonstrated, showing that at similar vacancy concentration, the optical constants of NiO:VNi deviate significantly from those of NiO:VO. Our experimental and computational results reveal that although VNi are an effective acceptors in NiO, they also degrade the visible transparency of the material. Hence, for transparent optoelectronic device applications, an optimization of native VNi defects with extrinsic doping is required to simultaneously enhance p-type conductivity and transparency.
SnO/[Formula: see text]-Ga2O3 vertical p–n diodes with planar geometry have been fabricated on c-plane Al2O3 and investigated by current–voltage measurements. The effects of the in-plane conduction through the Si-doped [Formula: see text]-Ga2O3 layer on the diode performance and their relevance have been evaluated. A significant series resistance is observed, which shows typical features of the variable range hopping transport observed in Si-doped [Formula: see text]-Ga2O3; this in-plane transport mechanism is probably induced by the columnar domain structure of this polymorph. The dependence of the series resistance on the geometry of the diode supports the interpretation. A simple equivalent model is presented to describe the experimental behavior of the diode, supported by preliminary impedance spectroscopy investigation.
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