Nanocrystalline properties of chemically deposited (Cd0.95‐Pb0.05)S:CdCl2, Gd/Dy films

Results of SEM and XRD studies, optical absorption spectra and photoluminescence emission spectra are presented for the films of (Cd_0.95‐Pb_0.05)S:CdCl₂, Gd/Dy prepared by chemical bath deposition technique and using thiophenol and methanol as capping agents. The deposition of films is based on precipitation followed by condensation on the substrates. SEM studies show existence of irregular distribution of particles alongwith presence of rod/tube type structure. The XRD studies show diffraction lines of CdS, PbS and CdCl₂. Blue shift has been observed in absorption spectra showing quantum confinement. Particle sizes determined from XRD studies and absorption spectral studies are found to lie in the nano range. Photoluminescence emission spectra consist of emissions in blue and green‐yellow regions. The observed emissions are related to the combination of defect levels and levels due to rare earths. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photoconductivity and photoluminescence in chemically deposited (Cd‐Zn)S:CdCl2,Tb films

Results of SEM, EDX and XRD studies, Optical Absorption spectra, Photoconductivity (PC) rise and decay, PC excitation spectra and Photoluminescence (PL) emission spectra are presented for (Cd‐Zn)S:CdCl₂, Tb films prepared by chemical deposition method on glass substrates either at room temperature (RT) or at 60 °C in a water bath (WB). SEM studies show ball type structure which is related to layered growth. EDX measurements show excess of Cd in such preparations along with the presence of Tb. XRD studies show prominent diffraction lines of CdS and ZnS along with lines of CdCl₂ and impurity. The values of strain (ε), grain size (D), and dislocation density (δ) are evaluated from XRD studies and the nature of crystallinity of the films are discussed. Optical Absorption spectra also show the presence of Tb in the lattice corresponding to the transition ⁷F₆(4f⁸) → ⁵D₀(5d¹4f⁷) of Tb³⁺ ions. From results of optical absorption spectra, the band gaps are determined, whose values are quite similar to those obtained from PC excitation spectra. Sufficiently high photo current (I_pc) to dark current (I_dc) ratios with a maximum value of the order of 10⁶ are observed. This high photosensitisation is related to increase in mobility and lifetime of carriers due to photo excitation. PL emission spectra consist of peaks due to transitions in Tb levels. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation of PbS nano‐microcrystals with different morphologies and their optical properties

PbS nano‐microcrystals were prepared from Pb(OAc)₂·3H₂O and sulfur in a solution without any surfactant using the solvothermal process. Different morphologies, mainly including polyhedron microcrystals and sphere‐like assemblies, were characterized using a scanning electron microscope (SEM) and a transmission electron microscope (TEM). PbS nano‐microcrystals with cubic crystal structure were detected using X‐ray diffraction (XRD), electron diffraction (ED) and high resolution transmission electron micrograph (HRTEM) techniques. The optical properties were investigated by ultraviolet‐visible (UV‐vis) spectroscopy, and photoluminescence spectroscopy (PL). The UV‐vis absorption peaks of PbS exhibited a large blue‐shift and the PL spectra had a strong and broad emission bands centered at 408 nm. The crystal growth mechanism of PbS was also discussed.     

Growth and photoluminescence properties of CdS solid solution semiconductor

Photoluminescence (PL) emitted from Cd_1‐xZn_xS and CdS_1‐ySe_y solid solution semiconductor was significantly stronger than PL from the pure CdS and CdSe semiconductor. The samples were prepared using an improved Se‐S‐Na₂S flux route. Photoluminescence in Cd_1‐xZn_xS crystal was brightly yellow at the room temperature under VU radiation. The phase and composition of the solid solution was measured by the XRD and was confirmed by UV‐NIS spectrum as x of 0.3 and y of 0.2. The enhanced photoluminescence was presumably due to the introduction of extra defect (vacancies) by solid solution action and consequently the increasing of luminescence center concentration. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

CIS and CIGS nanomaterials prepared by solvothermal method and their spectral properties

Uniform CIS and CIGS nanomaterials were successfully synthesized by a simple amino‐based assisted solvothermal technique using PVP‐30 as the surfactant. The influence of surfactant, temperature and Ga amount on the structure, morphology, phase and spectral property was analyzed in detail. The results show that CIS and CIGS nanomaterials with 40∼70 nm in diameter can be gained at 200 °C for 24 h. PVP‐30 surfactant can greatly improve the dispersion characteristics of particles. XRD pattern shows that the “three peaks” obviously shift to bigger 2θ after gallium implantation because of lattice contraction. EDAX and Raman show that the final product is close to CuIn_0.7Ga_0.3Se₂. The possible reaction mechanism has also been explained in detail. UV‐vis‐NIR spectra show that the absorption peak and absorption edge of CIGS with 1.278 eV bandgap obviously shift to a lower energy compared to CIS with 1.051 eV bandgap, which shows the potential application in enhanced conversion efficiency.     

Effect of annealing and composition on crystal structure,surface morphology and optical absorption of chemically deposited Cd1‐xSnxS films

Cd_1‐xSn_xS thin films were successfully deposited on suitably cleaned glass substrate by chemical bath deposition method at 74 °C. Hydrated Stannous Chloride (SnCl₂.2H₂O) in aqueous solution was added to the CdS growing solution in different proportions. The experimental results indicate, a successful doping for lower concentration of Sn, saturation for intermediate doping levels, and a degradation of the doping process for higher concentration of Sn. Indirect (X‐ray diffraction) and Direct (Scanning electron microscopy) measurements were performed to characterize the growth and the nature of crystallinity of the different Cd_1‐xSn_xS films. The effect of annealing on the crystal structure and morphology of the deposited films has also been discussed. The X‐ray diffraction spectra show that the thin films are polycrystalline and have both cubic and hexagonal structure. The Interplanar spacing, lattice constant, grain size, strain, and dislocation density were calculated for as‐deposited and annealed films. The grain size was found to decrease from 5 nm to 0.89 nm with doping concentration of Sn. The grain size further decreased due to annealing at 400 °C. SEM studies show layered growth and long needle like structures along with some voids. After annealing the densification and smaller size of the particles was also observed. The optical absorption spectra show shifting of absorption peaks towards lower wavelength side (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photoluminescence and optical absorption in glassy AsxSe1−x

The photoluminescence and optical absorption spectra in glassy As_xSe_1−x with 0.08 ? x ? 0.40 are essentially independent of x. The PL spectra peak at approximately half the optical gap and the exponential slopes of the optical absorption edges are all approximately 75 meV. For x > 0.4, the PL peaks shift to higher energies, the widths of the PL spectra increase, and there is a strong component to the optical absorption well below the optical gap. Comparisons with ESR experiments in the As_xS_1−x system suggest the possibility of two PL peaks. The second PL peak and the optical absorption below the optical band gap for x > 0.4 are attributed to the presence of As-As bonds.     

Effect of rapid thermal annealing on Zn1‐xCdxO layers grown by radio‐frequency magnetron co‐sputtering

Zn_1‐xCd_xO layers were deposited on the sapphire substrate using the radio‐frequency magnetron co‐sputtering system. The grown Zn_1‐xCd_xO layers were carried out in the post‐annealing treatment for 1 min at the 800 °C oxygen‐ambient by the rapid thermal annealing (RTA) method. X‐ray diffraction (XRD) experiment shows that the Zn_1‐xCd_xO layers are changed from the single phase of the hexagonal structure at 0≤x ≤0.08 to the double phase of hexagonal‐and‐cubic structure at x =0.13. Thus, the maximum Cd‐composition ratio with the hexagonal structure was found out to be x =0.08. Also, the crystallinity of Zn_1‐xCd_xO layers at x =0.13 was remarkably improved by the RTA annealing treatment. This crystal quality improvement was thought to be associated with the relaxation of the compressive strain remaining in the Zn_1‐xCd_xO layers. Therefore, the results of XRD and transmittance lead that the crystal quality of the Zn_1‐xCd_xO layers forming the hexagonal ZnO phase is better than that forming the cubic CdO phase. Consequently, the reliable formation and the crystallinity of the Zn_1‐xCd_xO layers were achieved by using the RTA method of short‐time thermal‐annealing at the high temperature. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effects of CdCl2 treatment on properties of CdTe thin films grown by evaporation at low substrate temperatures

The structural, morphological and optical properties of vacuum‐evaporated CdTe thin films were investigated as a function of substrate temperature and post‐deposition annealing without and with CdCl₂/treatment at 400°C for 30 min. Diffraction patterns are almost the same exhibiting higher preferential orientation corresponding to (111) plane of the cubic phase. The intensity of the (111) peak increased with the CdCl₂/annealing treatment. The microstructure observed for all films following the CdCl₂/annealing treatment are granular, regardless of the as‐deposited microstructure. The grain sizes are increased after the CdCl₂/annealing treatment but now contain voids around the grain boundaries. The optical band gaps, E_g, were found to be 1.50, 1.50 and 1.48 eV for films deposited at 200 K and annealed without and with CdCl₂/treatment at 400°C for 30 min respectively. A progressive sharpening of the absorption edge upon heat treatment particularly for the CdCl₂/treated was observed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X‐ray Determination of Lattice Constants of CdXSn1‐XSe Mixed Crystal Systems

Cd_XSn_1‐XSe with x = 0, 0.25, 0.3, 0.5, 0.75 and 1 are synthesized by melt technique and are found to be polycrystalline in nature. The X‐ray powder diffraction data of polycrystalline Cd_XSn_1‐XSe with x = 0, 0.25, 0.3, 0.5, 0.75 and 1 are analysed at room temperature and reported. The XRD peaks are indexed using DICVOL91 and cell constants are refined using the software UNITCELL. The powder diffraction patterns, lattice parameters and other data describing these compounds are presented in this paper.     

Multimode phonon structure of Be‐containing II ‐ VI mixed crystals determined by IR spectroscopic ellipsometry

Spectroscopic ellipsometry in the infrared spectral range 250‐5000 cm^‐1 is used for analysis of the dielectric response of Zn_1‐x‐yBe_xMg_ySe and Zn_1‐x‐yBe_xMn_ySe crystals grown by a high‐pressure Bridgman method. Ellipsometric spectra display features in the spectral range 390‐500 cm^‐1 associated with BeSe‐type phonon modes. In the optical spectra of Zn_1‐x‐yBe_xMg_ySe crystals both BeSe‐type and MgSe‐type lattice absorption bands are detected. The MgSe‐like modes are located at approximately 300 cm^‐1. The complex dielectric functions can be reproduced using a model with two or three and one or two classical damped oscillators corresponding to the BeSe‐like and the MgSe‐like transverse‐optical phonon modes, respectively. The frequencies of longitudinal‐optical phonons have been derived from the dielectric loss functions. A red‐shift of the BeSe‐like phonons frequencies with a mean rate 0.42 cm^‐1 (0.50 cm^‐1) per mole percent of Mg (Mn) incorporated to the alloy has been found for examined concentration range x, y ≤ 0.25. A noticeable damping the intensities of BeSe‐type modes with increasing fraction of Mg and Mn dopant is observed in comparison to the strengths of BeSe‐type modes in Zn_1‐xBe_xSe crystals. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Cd2Ge2O6 nanowires grown by a simple hydrothermal route

Cd₂Ge₂O₆ nanowires have been synthesized by a simple hydrothermal route in the absence of any surfactants. The diameter and length of the Cd₂Ge₂O₆ nanowires with flat tips are 30‐300 nm and several dozens of micrometers, respectivley. X‐ray diffraction and high‐resolution transmission electron microscopy results show that the nanowires are composed of monoclinic Cd₂Ge₂O₆ phase. The growth condition dependence results show that the formation of the Cd₂Ge₂O₆ nanowires undergoes three morphological changes from spherical particles to nanorods, and finally to nanowires. The photoluminescence spectrum of the Cd₂Ge₂O₆ nanowires exhibits three fluorescence emission peaks centered at 422 nm, 490 nm and 528 nm showing the potential application for optical devices. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and optical properties of CuInS2 thin films prepared by sulfurization of electrodeposited Cu‐In layers

The chalcopyrite CuInS₂ thin film was fabricated at 500 °C for 2 h by sulfurization of Cu‐In layers (as precursors) that were sulfurized in a glass tube with pure sulfur powder. The structural, morphological, and optical properties of CuInS₂ thin films are characterized using X‐ray diffraction (XRD), field‐emission scanning electron microscope (FE‐SEM), and UV/Visible/NIR spectrophotometer. The study of UV/Visible/NIR absorption shows the band gap energy value of CuInS₂ thin films is 1.5 eV. The XRD pattern shows the film is pure CuInS₂; no other peaks, such as CuS or CuIn₅S₈ were observed. Furthermore, the surface of the CuInS₂ film is compact characterized by FE‐SEM, which also shows the disappearance of CuS on the surface at 500 °C.     

Optical properties of Al‐doped ZnO thin films deposited by two different sputtering methods

Aluminum‐doped zinc oxide (AZO) thin films were deposited on sapphire (002) and glass substrates by two different sputtering techniques radio frequency magnetron cosputtering of AZO and ZnO targets and sputtering of an AZO target. The dependence of the photoluminescence (PL) and transmittance properties of the AZO films deposited by cosputtering and sputtering on the AZO/ZnO target power ratio, R and the O₂/Ar flow ratio, r were investigated, respectively. Only a deep level emission peak appears in the PL spectra of cosputtered AZO films whereas both UV emission and deep level emission peaks are observed in the PL spectra of sputtered AZO films. The absorption edges in the transmittance spectra of the AZO films shift to the lower wavelength region as R and r increase. Also effects of crystallinity, surface roughness, PL on the transmittance of the AZO films were explained using the X‐ray diffraction (XRD), atomic force microscopy (AFM), and PL analysis results. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterization of Vacuum Evaporated Polycrystalline Cd0.96Zn0.04Te Thin Films by XRD,Raman Scattering and Spectroscopic Ellipsometry

Cd_0.96Zn_0.04Te thin films are deposited onto well cleaned glass substrates (Corning 7059) kept at room temperature by vacuum evaporation and the films are annealed at 423 K. Rutherford Backscattering Spectrometry and X‐ray diffraction techniques are used to determine the thickness, composition and crystalline structure and grain size of the films respectively. The films exhibited zinc blende structure with predominant (111) orientation. The surface morphology of the films is studied by Atomic Force Microscopy. The rms roughness of the as‐deposited films is 3.7 nm and on annealing the films at 423K, the rms roughness value decreases to 3.4 nm. The Raman spectra of the Cd_0.96Zn_0.04Te films are recorded at room temperature to study lattice vibrations and their interactions with other excitations. The intensity of the peak increases and the FWHM decreases on annealing the films. The pseudodielectric‐function spectra, ε(E) = ε₁(E) + i ε₂(E), of polycrystalline Cd_0.96Zn_0.04Te thin films in the 1.3 ‐ 5.5eV photon energy range at room temperature are measured by spectroscopic ellipsometry. The measured dielectric function spectra reveal distinct structures at energies of the E₁, E₁+Δ₁ and E₂ critical points are due to interband transitions.     

Grain boundary defects induced room temperature ferromagnetism in V doped ZnO thin films

Vanadium (V) doped ZnO thin films (Zn_1‐xV_x O, where x = 0, 0.05, 0.10) have been grown on sapphire substrates by RF magnetron sputtering to realize room temperature ferromagnetism (RTFM). The grown films have been subjected to X‐ray diffraction (XRD), resonant Raman scattering, photoluminescence (PL) and vibrating sample magnetometer (VSM) measurements to investigate their structural, optical and magnetic properties, respectively. The full width at half maximum of XRD and Raman scattering peaks increases with V ion concentration indicates that the V ions have been substituted on Zn²⁺ ions in the ZnO matrix. The increase in oxygen vacancies with V concentration is evidenced by PL measurements. Rutherford backscattering spectrometry analysis confirms the presence of the V ions in the films. The room temperature VSM measurements reveal the signature of ferromagnetism in V doped ZnO thin films. It has been observed that the grain boundary defects, i.e., oxygen vacancies play a crucial role in inducing RTFM in V doped ZnO films. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Controllable synthesis of novel In2O3 nanostructures and their field emission properties

Three kinds of novel indium oxide (In₂O₃) nanostructures, namely, nanorods, nanoflowers and nanowhiskers were synthesized on silicon substrate via a simple vapor‐phase transport method under atmospheric pressure. The In₂O₃nanostructures were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and energy‐dispersive X‐ray spectrometer (EDS) spectrum. The Raman spectra of these nanostructures showed four sharp scattering peaks centered at 308, 365, 522, and 628 cm^‐1, whose position and intensity were characteristic of standard Raman spectra for In₂O₃. The Room‐temperature photoluminescence (PL) spectra showed visible emissions centered around 576, 592, and 624 nm. Field emission measurements demonstrated that the nanoflowers possessed the best performance with a turn‐on field of 3.54 V/µm and a threshold field of 9.83 V/µm. And the field enhancement factors of these nanostructures are high enough for the application of field emission display devices. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural and optical properties of Zn(Mg,Cd)O alloy films grown by remote-plasma-enhanced MOCVD

We report the structural and optical properties of wurtzite-structure Zn(Mg,Cd)O ternary alloys. Wurtzite (0 0 0 1) Zn_1−xCd_xO and Mg_yZn_1−yO films were grown on (11–20) sapphire substrates using remote-plasma-enhanced metalorganic chemical vapor deposition. The large bowing parameters of Zn_1−xCd_xO and Mg_yZn_1−yO ternary alloys are 3.0 and 3.5, respectively, which reflects the large difference of each binary’s electronegativity. We have analyzed the broadening of photoluminescence (PL) in Zn(Mg,Cd)O alloys on alloy content by taking into account the statistical alloy fluctuation and the localization of the exciton, and have clarified that the localization of the exciton strongly affects to PL full-width at half-maximum (FWHM) in Zn(Mg,Cd)O alloys. The alloy broadenings in steady-state PL of Zn(Mg,Cd)O alloys are in good agreement with the calculated tendency by the theoretical model based on the statistical alloy fluctuation, while PL FWHM of Zn_1−xCd_xO is three times larger than the calculated results. Moreover, as another way to confirm alloy broadening, we also have done time-resolved PL measurements and derived the localized depth of the exciton in ZnO-based system, indicating a good agreement with the tendency of PL FWHM broadening.     

Synthesis by organic molten salt method and characterization of chalcopyrite AgInS2 nanorods

In this paper, chalcopyrite AgInS₂ nanorods were synthesized for the first time by a one‐step, ambient pressure, environment friendly organic molten salt (OMS) method at 200 °C. The as‐synthesized products were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), respectively. The XRD results reveal that the as‐synthesized products at 120–160 °C under ambient pressure contain AgIn₅S₈ which will decrease with the increase of growth temperature. A sample containing only the chalcopyrite AgInS₂ phase is successfully obtained at 200 °C. Furthermore, the elemental compositions are found to become increasingly stoichiometric with increasing temperature. UV‐Vis and photoluminescence (PL) spectra are utilized to investigate the optical properties of AgInS₂ nanorods. By testing on UV‐Vis spectra, it is concluded that the limiting wavelength of the AgInS₂ nanorods is 661 nm and the band gap is 1.88 eV. A broad red emission band peak centered at about 1.874 eV (662 nm) is clearly observed at room temperature, and the intensity of the emission increases with excitation wavelength. In addition, the photoluminescence quantum yield (PLQY) of the nanocrystals at the excitation wavelength of 250 nm was determined to be 13.2%. A possible growth mechanism of AgInS₂ nanorods was discussed. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis of radial‐like ZnO structure by hydrothermal method with ZnSO4·7H2O and Zn(CH3COO)2·2H2O as zinc sources

Radial‐like ZnO structures were prepared using zinc sulfate (ZnSO₄·7H₂O) and zinc acetate [Zn(CH₃COO)₂·2H₂O] as zinc sources by a facile template‐free hydrothermal method in this paper. Structural and optical properties of radial‐like ZnO structures are characterized by X‐ray diffraction (XRD), field emission scanning electron microscopy (FESEM), UV‐vis spectrophotometer and photoluminescence measurement (PL). It has been found that the distinct surface morphologies of radial‐like ZnO structures grown by different zinc sources. Slim radial‐like ZnO with a hexagonal wurtzite structure is grown by using ZnSO₄·7H₂O as zinc sources, whereas coarse radial‐like ZnO with zincite structure is achieved by zinc acetate. The UV‐vis absorption spectra of them both display an obvious and significant absorption in the ultraviolet region. The room temperature PL spectra of ZnO structures grown by two different zinc sources possess a common feature that consists of a strong ultraviolet (UV) peak and visible emission band.