Through a process of photoelectrochemical (PEC) water splitting, we demonstrated an effective strategy for engineering the barrier height of a heterogeneous semiconductor interface by piezoelectric polarization, known as the piezotronic effect. A consistent enhancement or reduction of photocurrent was observed when tensile or compressive strains were applied to the ZnO anode, respectively. The photocurrent variation is attributed to a changed barrier height at the ZnO/ITO interface, which is a result of the remnant piezoelectric potential across the interface due to a nonideal free charge distribution in the ITO electrode. In our system, ∼1.5 mV barrier height change per 0.1% applied strain was identified, and 0.21% tensile strain yielded a ∼10% improvement of the maximum PEC efficiency. The remnant piezopotential is dictated by the screening length of the materials in contact with piezoelectric component. The difference between this time-independent remnant piezopotential effect and time-dependent piezoelectric effect is also studied in details.
Chemical
vapor deposition (CVD)-grown flakes of high-quality monolayers
of WS2 can be stabilized at elevated temperatures by encapsulation
with several layer hexagonal boron nitride (h-BN),
but to different degrees in the presence of ambient air, flowing N2, and flowing forming gas (95% N2, 5% H2). The best passivation of WS2 at elevated temperature
occurs for h-BN-covered samples with flowing N2 (after heating to 873 K), as judged by optical microscopy
and photoluminescence (PL) intensity after a heating/cooling cycle.
Stability is worse for uncovered samples, but best with flowing forming
gas. PL from trions, in addition to that from excitons, is seen for
covered WS2 only for forming gas, during cooling below
∼323 K; the trion has an estimated binding energy of ∼28
meV. It might occur because of doping level changes caused by charge
defect generation by H2 molecules diffusing between the h-BN and the SiO2/Si substrate. The decomposition
of uncovered WS2 flakes in air suggests a dissociation
and chemisorption energy barrier of O2 on the WS2 surface of ∼1.6 eV. Fitting the high-temperature PL intensities
in air gives a binding energy of a free exciton of ∼229 meV.
We improved the optical quality and stability of an exfoliated monolayer (ML) MoSe 2 and chemical vapor deposition (CVD)-grown WS 2 MLs by encapsulating and sealing them with both top and bottom few-layer h-BN, as tested by subsequent hightemperature annealing up to 873 K and photoluminescence (PL) measurements. These transition-metal dichalcogenide (TMD) MLs remained stable up to this maximum temperature, as seen visually. After the heating/cooling cycle, the integrated photoluminescence (PL) intensity at 300 K in the MoSe 2 ML was ∼4 times larger than that before heating and that from exciton and trion PL in the analogous WS 2 ML sample was ∼14 times and ∼2.5 times larger at 77 K and the exciton peak was ∼9.5 times larger at 300 K. This is attributed to the reduction of impurities, the lateral expulsion of contamination leading to clean and atomically flat surfaces, and the sealing provided by the h-BN layers that prevents the diffusion of molecules such as trace O 2 and H 2 O to the TMD ML. Stability and optical performance are much improved compared to that in earlier work using top h-BN only, in which the WS 2 ML PL intensity decreased even for an optimal gas environment. This complete encapsulation is particularly promising for CVD-grown TMD MLs because they have relatively more charge and other impurities than do exfoliated MLs. These results open a new route for improving the optical properties of TMD MLs and their performance and applications both at room and higher temperatures.
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