Carrier dynamics in highly excited TlInS2: evidence of 2D electron-hole charge separation at parallel layers.

We report a comprehensive study of the time-resolved photoluminescence (PL), carrier recombination, and carrier diffusion under diverse laser pulse excitation in TlInS2. The 2D-layered crystals were grown by the Bridgman method without or with the presence of a small amount of erbium in the melt. The investigation exposes large differences in two crystal types, although, a linear nonradiative lifetime and carrier diffusivity attain close values under high excitation with no contribution of the Auger recombination and the absence of the band gap narrowing effect. Moreover, at high pulse power, we detect imprinted transient grating fringes which are attributed to a new crystal phase formed by 2D electron-hole charge separation on local layers. The versatile model of the spontaneously polarized 2D-crystal has been developed to explain the observed features and ergodicity of charge dynamic processes. The model embraces the planar stacking fault (PSF) which edge provides a distortion and act as sink of strong recombination. The reduced occurrence of the PSFs in the erbium doped TlInS2 is the main attribute which determines the enhancement of PL by a factor of 50 and improves carrier diffusion along 2D-layers. The simulation permits evaluation of the PSF sizes of about 0.7 µm. The presented results allow improving 2D-crystal growth technology for novel sensor devices with separated excess charges.

The effect of atmospheric doping on pressure-dependent Raman scattering in supported graphene.

Atmospheric doping of supported graphene was investigated by Raman scattering under different pressures. Various Raman spectra parameters were found to depend on the pressure and the substrate material. The results are interpreted in terms of atmospheric adsorption leading to a change in graphene charge carrier density and the effect of the substrate on the electronic and phonon properties of graphene. It was found that adsorption of molecules from the atmosphere onto graphene doped with nitrogen (electron doping) compensates for the electron charge. Furthermore, the atmosphere-induced doping drastically decreases the spatial heterogeneity of charge carriers in graphene doped with nitrogen, while the opposite effect was observed for undoped samples. The results of this study should be taken into account for the development of sensors and nanoelectronic devices based on graphene.

Nitrogen-doped twisted graphene grown on copper by atmospheric pressure CVD from a decane precursor.

We present Raman studies of graphene films grown on copper foil by atmospheric pressure CVD with n-decane as a precursor, a mixture of nitrogen and hydrogen as the carrier gas, under different hydrogen flow rates. A novel approach for the processing of the Raman spectroscopy data was employed. It was found that in particular cases, the various parameters of the Raman spectra can be assigned to fractions of the films with different thicknesses. In particular, such quantities as the full width at half maximum of the 2D peak and the position of the 2D graphene band were successfully applied for the elaborated approach. Both the G- and 2D-band positions of single layer fractions were blue-shifted, which could be associated with the nitrogen doping of studied films. The XPS study revealed the characteristics of incorporated nitrogen, which was found to have a binding energy around 402 eV. Moreover, based on the statistical analysis of spectral parameters and the observation of a G-resonance, the twisted nature of the double-layer fraction of graphene grown with a lower hydrogen feeding rate was demonstrated. The impact of the varied hydrogen flow rate on the structural properties of graphene and the nitrogen concentration is also discussed.

Influence of wide band gap oxide substrates on the photoelectrochemical properties and structural disorder of CdS nanoparticles grown by the successive ionic layer adsorption and reaction (SILAR) method.

The photoelectrochemical properties of nanoheterostructures based on the wide band gap oxide substrates (ZnO, TiO2, In2O3) and CdS nanoparticles deposited by the successive ionic layer adsorption and reaction (SILAR) method have been studied as a function of the CdS deposition cycle number (N). The incident photon-to-current conversion efficiency (IPCE) passes through a maximum with the increase of N, which is ascribed to the competition between the increase in optical absorption and photocarrier recombination. The maximal IPCE values for the In2O3/CdS and ZnO/CdS heterostructures are attained at N ≈ 20, whereas for TiO2/CdS, the appropriate N value is an order of magnitude higher. The photocurrent and Raman spectroscopy studies of CdS nanoparticles revealed the occurrence of the quantum confinement effect, demonstrating the most rapid weakening with the increase of N in ZnO/CdS heterostructures. The structural disorder of CdS nanoparticles was characterized by the Urbach energy (E U), spectral width of the CdS longitudinal optical (LO) phonon band and the relative intensity of the surface optical (SO) phonon band in the Raman spectra. Maximal values of E U (100-120 meV) correspond to СdS nanoparticles on a In2O3 surface, correlating with the fact that the CdS LO band spectral width and intensity ratio for the CdS SO and LO bands are maximal for In2O3/CdS films. A notable variation in the degree of disorder of CdS nanoparticles is observed only in the initial stages of CdS growth (several tens of deposition cycles), indicating the preservation of the nanocrystalline state of CdS over a wide range of SILAR cycles.

Photoelectrochemical and Raman characterization of In2O3 mesoporous films sensitized by CdS nanoparticles.

The method of successive ion layer adsorption and reaction was applied for the deposition of CdS nanoparticles onto a mesoporous In2O3 substrate. The filling of the nanopores in In2O3 films with CdS particles mainly occurs during the first 30 cycles of the SILAR deposition. The surface modification of In2O3 with CdS nanoparticles leads to the spectral sensitization of photoelectrochemical processes that manifests itself in a red shift of the long-wavelength edge in the photocurrent spectrum by 100-150 nm. Quantum-confinement effects lead to an increase of the bandgap from 2.49 to 2.68 eV when decreasing the number of SILAR cycles from 30 to 10. The spectral shift and the widening of the Raman line belonging to CdS evidences the lattice stress on the CdS/In2O3 interfaces and confirms the formation of a close contact between the nanoparticles.