InN/XS2 (X = Zr, Hf) vdW heterojunctions: promising Z-scheme systems with high hydrogen evolution activity for photocatalytic water splitting.

Z-scheme van der Waals heterojunctions are very attractive photocatalysts attributed to their excellent reduction and oxidation abilities. In this paper, we designed InN/XS2 (X = Zr, Hf) heterojunctions and explored their electronic structure properties, photocatalytic performance, and light absorption systematically using first-principles calculations. We found that the valence-band maximum (VBM) and conduction-band minimum (CBM) of the InN/XS2 (X = Zr, Hf) heterojunctions are contributed by InN and XS2, respectively. Photo-generated carriers transferring along the Z-path can accelerate the recombination of interlayer electron-hole pairs. Therefore, the photogenerated electrons in the CBM of the InN layer can be maintained making the hydrogen evolution reaction occur continuously, while photogenerated holes in the VBM of the Ti2CO2 layer make the oxygen evolution reaction occur continuously. The band edge positions of heterojunctions can straddle the required water redox potentials, while pristine InN and XS2 (X = Zr, Hf) can only be used for photocatalytic hydrogen evolution or oxygen evolution, respectively. Furthermore, the HER barriers can be tuned by transition metal doping. With Cr doping, the hydrogen evolution reaction (HER) barriers decrease to -0.12 for InN/ZrS2 and -0.05 eV for InN/HfS2, very close to the optimal value (0 eV). In addition, the optical absorption coefficient is as high as 105 cm-1 in the visible and ultraviolet regions. Therefore, the InN/XS2 (X = Zr, Hf) heterojunctions are expected to be excellent photocatalysts for water splitting.

Interfacial contact barrier and charge carrier transport of MoS2/metal(001) heterostructures.

The rapid rise of two-dimensional (2D) materials has aroused increasing interest in the fields of microelectronics and optoelectronics; various types of 2D van der Waals heterostructures (vdWHs), especially those based on MoS2, have been widely investigated in theory and experiment. However, the interfacial properties of MoS2 and the uncommon crystal surface of traditional three-dimensional (3D) metals are yet to be explored. In this paper, we studied heterostructures composed of MoS2 and metal(001) slabs, based on the first-principles calculations, and we uncovered that MoS2/Au(001) and MoS2/Ag(001) vdWHs reveal Schottky contacts, and MoS2/Cu(001) belongs to Ohmic contact and possesses ultrahigh electron tunneling probability at the equilibrium distance. Thus, the MoS2/Cu(001) heterostructure exhibits the best contact performance. Further investigations demonstrate that external longitudinal strain can modulate interfacial contact to engineer the Schottky-Ohmic contact transition and regulate interfacial charge transport. We believe that it is a general strategy to exploit longitudinal strain to improve interfacial contact performance to design and fabricate a multifunctional MoS2-based electronic device.

The unique photoelectronic properties of the two-dimensional Janus MoSSe/WSSe superlattice: a first-principles study.

Designing photocatalysts with suitable band alignment and considerable carrier mobility is extremely important. Here, by means of first-principles calculation, we systematically investigated the structural, photoelectronic, and carrier mobility behavior of the two-dimensional Janus MoSSe/WSSe superlattice. The results show that both armchair-type (AN-SL) and zigzag-type (ZN-SL) superlattices are relatively stable with negative Ef values in the range of -2.35 to -1.16 eV. Band gap and band edge position calculations demonstrate that these superlattices are completely suitable for water splitting by visible light. Particularly, the interface contact of the superlattice can be spontaneously changed from type-I to type-II when N > 4, facilitating separation of photogenerated carriers. Furthermore, the hole carrier mobility (µh) in AN-SL can be effectively regulated from 1200 to 2200 cm2 V-1 s-1, much larger than that of the isolated components. Interestingly, the disparity of hole/electron carrier mobility is remarkably large with an approximately 20-fold difference, showing the potential in prohibiting the recombination of photogenerated carriers. This unique behavior is further illustrated by the relaxation times of carriers, where the lifetime of hole carriers is about 7 times larger than that of electron carriers. These findings suggest that forming a Janus superlattice is a promising approach for regulating the photoelectronic properties of semiconductors, providing a promising way to design high efficiency photocatalysts.

First-principles study on photovoltaic properties of 2D Cs2PbI4-black phosphorus heterojunctions.

Both 2D perovskite Cs2PbI4 and phosphorus are significant optoelectronic semiconductor materials, the optical-electrical characters between both contact interfaces are interesting topics. In present work, we demonstrate comparative investigation of optoelectronic properties for two kinds of electrical contact interfaces. i.e. Pb-I and Cs-I interfaces with black phosphorus contacts. The carrier transport, charge transferring and optical properties for both cases are investigated by using first principle calculation. Both contact interfaces exhibit type II band alignment with direct band gap. Charge carrier migration from Cs-I interface to black phosphorus is more strong than that of Pb-I interface by considering differential charge density and bader charge between distinct electrical contact interfaces. Besides, electron-hole effective masses of heterojunctions for both cases along different direction are investigated. Optical absorption coefficients of both cases are compared with those of free-standing Cs2PbI4 and black phosphorus in the visible spectrum. We systematically compared advantages and disadvantages of two kinds of contact interfaces for photovoltaic application, and the results reveal interfacial engineering of 2D heterojunction plays a important role in tuning optoelectronic properties.

Elastic properties and intrinsic strength of two-dimensional InSe flakes.

The mechanical properties of two-dimensional (2D) materials are critical for their applications in functional devices as well as for strain engineering. Here, we report the Young's modulus and breaking strength of multilayered InSe, an emerging 2D semiconductor of the layered group III chalcogenide. Few-layer InSe flaks were exfoliated from bulk InSe crystal onto Si/SiO2 substrate with micro-fabricated holes, and indentation tests were carried out using an atomic force microscopy probe. In combination with both continuum analysis and finite element simulation, we measured the Young's modulus of multilayer 2D InSe (>5 L) to be 101.37 ± 17.93 GPa, much higher than its bulk counterpart, while its breaking strength is determined to be 8.68 GPa, approaching the theoretical limit of 10.1 GPa. Density functional theory calculations were also carried out to explain the insensitivity of Young's modulus to the layer count. It is found that 2D InSe is softer than most 2D materials, and exhibits breaking strength higher than that of carbon fiber, yet remaining more compliant, making it ideal for flexible electronics applications. The reliability of our method is also validated by measurement of graphene.

[Influence of nitrogen doping on electron structure and optical properties of amorphous carbon thin films].

Nitrogen doped amorphous carbon (a-C : N) thin films were prepared by DC magnetron sputtering. The films were investigated by AES, UV-Vis and ellipsometer. A parameter 'D' defined as the distance between the maximum of positive going excursion and the minimum of negative going excursion was calculated in the derivative AES spectra. The values of 'D' were used to calculate the percentage of sp2 hybrid bonds. The optical transmission and the optical band gap of the films were characterized by an UV-Vis spectrophotometer. The results showed that the optical band gap decreased and then increased with the increase of N2 gas source. The transmission and refractive index changed in reverse order. It was demonstrated that the thin film with low percentage of nitrogen was beneficial to the formation of sp3 hybrid bonds and caused the optical band gap of the thin film to increase. As a result, the thin film should be prepared under low percentage of nitrogen pressure to ensure that it possesses fine optical properties.