Silicon-rich silicon oxide thin films have been prepared by thermal evaporation of silicon monoxide in vacuum. The SiOx film composition (1.1⩽ x ⩽1.7) has been controlled by varying the deposition rate and residual pressure in the chamber. Long time stability of all films has been ensured by a postdeposition annealing at 523 K for 30 min in Ar atmosphere. Some films were further annealed at 973 K and some others at 1303 K. Raman scattering measurements have implied the formation of amorphous silicon nanoparticles in films annealed at 973 K and Si nanocrystals in films annealed at 1303 K. The latter conclusion is strongly supported by high resolution electron microscopy studies which show a high density of Si nanocrystals in these films. Photoluminescence has been observed from both amorphous and crystalline nanoparticles and interpreted in terms of band-to-band recombination in the nanoparticles having average size greater than 2.5 nm and carrier recombination through defect states in smaller nanoparticles.
The transport properties of nonequilibrium (photoexcited) charge carriers in sonochemically synthesized threedimensional (3D) assemblies of AgBiS 2 quantum dots (QDs) deposited as thin films were studied. To characterize the photoconduction of quantum-confined nanocrystals close packed in thin film form, both stationary and time-resolved experiments were performed. Besides by interband electronic transitions in the bulklike part of the nanocrystals, the photoresponse of nanocrystalline films was found to be also affected to a greater extent by the crystal boundary barrier height modulation upon illumination. The surface and bulk recombination velocities were found to be comparable. Good agreement was obtained between the band gap energy determined by analysis of the photoconductivity data measured by the constant field and the constant photocurrent method (∼1.18 eV). This value is in agreement with the optical spectroscopy data. It is higher than the optical band gap of a bulk specimen of this semiconductor, due to 3D confinement effects on the charge carrier motions within individual QDs. The nonequilibrium conductivity was found to relax exponentially with a time constant of 1.67 ms, which corresponds to average lifetime of minority charge carriers (holes).
Superlattices of a-SiO x /nc-CdSe and thin composite films of SiO x doped with CdSe nanocrystals have been investigated. The CdSe nanocrystals size in both kinds of samples was determined by x-ray diffraction and HREM measurements. A significant difference has been found in the size values determined by both methods, which has been ascribed to appreciable nanocrystal lattice deformations. Subband absorption, room-temperature photoluminescence and thermally stimulated currents have been measured. It has been observed that in the superlattices the absorption in the tail region increases as sublayer thickness decreases. A new photoluminescence band has also appeared in the superlattices having thinnest (2.5 nm) CdSe sublayers. Two new maximums at about 220 K and 240 K, not existing in the CdSe single layers studied, have been found in thermally stimulated current spectra of the composite films. Both maximums are less expressed in the superlattices. The described results have been connected with a size-induced increase in the concentration of interface defect states in CdSe nanocrystals. It has been estimated that these defects are disposed at about 0.35 eV above the highest occupied molecular orbit in CdSe.
Nanoparticles of CdSe embedded in amorphous SiO x , GeS 2 and polycrystalline ZnSe thin films have been produced by sequential physical vapour deposition of CdSe and one of the matrix materials. High-resolution electron microscopy has been used to prove the formation of CdSe nanoparticles. Particles with nearly spherical shape were observed whose spatial distribution follows the surface morphology of the 'matrix' films. The mechanism of nanoparticle formation on a rough surface has been discussed. It has been found that annealing of SiO x -CdSe films at 973 K leads to the formation of isolated CdSe nanoparticles homogeneously distributed in the matrix. Quantum-size increase in the optical band gap of CdSe nanoparticles has been observed in all matrices used. r
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