Development of an automated ultrasonic spray pyrolysis system and the growth of Cu2ZnSnS4 thin films

An automated ultrasonic spray pyrolysis system is fabricated for the growth of thin films. The system is equipped with x-y movement and enables film deposition in different patterns and spray rates. Cu-2(Zn,Sn)S-4 (CZTS) films are deposited using this setup. The substrate temperature (T-s) is varied from 240 to 490 degrees C. Kesterite CZTS phase is observed in all the films together with binary phases. The films prepared at T-s <340 degrees C showed SnxSy phase and those at T-s >340 degrees C showed Cu2S phase. Sulfur incorporation is maximum (40%) at 440 degrees C and the films showed better morphology. The Cu and S concentrations are varied to remove binary phases. Depth wise elemental analysis confirmed the existence of single phase CZTS. p-Type CZTS films of resistivity in the range of 10(2)-10(3) Omega cm are obtained. (C) 2015 Elsevier B.V. All rights reserved.

Thickness And Component Distributions Of Yttrium-Titanium Alloy Films In Electron-Beam Physical Vapor Deposition

Thickness and component distributions of large-area thin films are an issue of international concern in the field of material processing. The present work employs experiments and direct simulation Monte Carlo (DSMC) method to investigate three-dimensional low-density, non-equilibrium jets of yttrium and titanium vapor atoms in an electron-beams physical vapor deposition (EBPVD) system furnished with two or three electron-beams, and obtains their deposition thickness and component distributions onto 4-inch and 6-inch mono-crystal silicon wafers. The DSMC results are found in excellent agreement with our measurements, such as evaporation rates of yttrium and titanium measured in-situ by quartz crystal resonators, deposited film thickness distribution measured by Rutherford backscattering spectrometer (RBS) and surface profilometer and deposited film molar ratio distribution measured by RBS and inductively coupled plasma atomic emission spectrometer (ICP-AES). This can be taken as an indication that a combination of DSMC method with elaborate measurements may be satisfactory for predicting and designing accurately the transport process of EBPVD at the atomic level.

A thin liquid film and its effects in an atomic force microscopy measurement

Recently, it has been observed that a liquid film spreading on a sample surface will significantly distort atomic force microscopy (AFM) measurements. In order to elaborate on the effect, we establish an equation governing the deformation of liquid film under its interaction with the AFM tip and substrate. A key issue is the critical liquid bump height y(0c) at which the liquid film jumps to contact the AFM tip. It is found that there are three distinct regimes in the variation of y(0c) with film thickness H, depending on Hamaker constants of tip, sample and liquid. Noticeably, there is a characteristic thickness H* physically defining what a thin film is; namely, once the film thickness H is the same order as H* , the effect of film thickness should be taken into account. The value of H* is dependent on Hamaker constants and liquid surface tension as well as tip radius.

Oxidative chemisorption of SO_2 on γ - Al_2O_3 and deposition of H_2-permselective SiO_2 films

The interaction of SO_2 with γ - Al_2O_3 and the deposition of H_2 permselective SiO_2 films have been investigated. The adsorption and oxidative adsorption of SO_2 on γ - Al_2O_3 have been examined at temperatures 500-700°C by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). At temperatures above 500°C most of SO_2 adsorbed on the strong sites on alumina. The adsorbed SO_2 species was characterized by an IR band at 1065 cm^(-1). The equilibrium coverage and initial rate of adsorption decreased with temperature suggesting a two-step adsorption. When γ - Al_2O_3 was contacted with a mixture of SO_2 and O_2, adsorption of SO_2 and oxidation of the adsorbed SO_2 to a surface sulfate characterized by broad IR bands at 1070 cm^(-1), 1390 cm^(-1) took place. The results of a series of TGA experiments under different atmospheres strongly suggest that surface SO_2 and surface sulfate involve the same active sites such that SO_2 adsorption is inhibited by already formed sulfate. The results also indicate a broad range of site strengths.

The desorption of adsorbed SO_2 and the reductive desorption of oxidatively adsorbed SO_2 have been investigated by microreactor experiments and thermogravimetric analysis (TGA). Temperature programmed reduction (TPR) of adsorbed SO_2 showed that SO_2 was desorbed without significant reaction with H_2 when H_2 concentration was low while considerable reaction occurred when 100% H_2 was used. SO_2 adsorbed on the strong sites on alumina was reduced to sulfur and H_2S. The isothermal reduction experiments of oxidatively adsorbed SO_2 reveal that the rate of reduction is very slow below 550°C even with 100% H_2. The reduction product is mainly composed of SO_2. TPR experiments of oxidatively adsorbed SO_2 showed that H_2S arose from a sulfate strongly chemisorbed on the surface.

Films of amorphous SiO_2 were deposited within the walls of porous Vycor tubes by SiH_4 oxidation in an opposing reactants geometry : SiH_4 was passed inside the tube while O_2 was passed outside the tube. The two reactants diffused opposite to each other and reacted within a narrow front inside the tube wall to form a thin SiO_2 film. Once the pores were plugged the reactants could not reach each other and the reaction stopped. At 450°C and 0.1 and 0.33 atm of SiH_4 and O_2, the reaction was complete within 15 minutes. The thickness of the SiO_2 film was estimated to be about 0.1 µm. Measurements of H_2 and N_2 permeation rates showed that the SiO_2 film was highly selective to H_2 permeation. The H_2:N_2 flux at 450°C varied between 2000-3000.

Thin SiO_2 films were heat treated in different gas mixtures to determine their stability in functioning as high-temperature hydrogen-permselective membranes. The films were heat-treated at 450-700°C in dry N_2, dry O_2, N_2-H_2O, and O_2-H_2O mixtures. The permeation rates of H_2 and N_2 changed depending on the original conditions of film formation as well as on the heat treatment. Heating in dry N_2 slowly reduced the permeation rates of both H_2 and N_2. Heating in a N_2-H_2O atmosphere led to a steeper decline of H_2 permeability. But the permeation rate of N_2 increased or decreased according to whether the film deposition had been carried out in the absence or presence of H_2O vapor, respectively. Thermal treatment in O_2 caused rapid decline of the permeation rates of H_2 and N_2 in films that were deposited under dry conditions. The decline was moderate in films deposited under wet conditions.

Nonlinear response and optical limiting in SrBi2Ta2O9 thin films

SrBi2Ta2O9 (SBT) thin films on quartz substrates were prepared by use of the pulsed-laser deposition technique. The nonlinear refractive indices, n(2), Of the SBT films were measured by use of z-scan techniques with picosecond pulses. Large negative nonlinear refractive indices of 3.84 and 3.58 cm(2)/GW were obtained for the wavelengths 532 nm and 1.064 mum, respectively. The two-photon absorption coefficient was determined to be 7.3 cm/GW for 532 nm. The limiting behavior of SBT thin film on a quartz substrate was investigated in an f/5 defocusing geometry by use of 38-ps-duration, 532-nm, 1.064-mum. laser excitation. (C) 2001 Optical Society of America.

MOCVD growth and properties of ZnO thin films on LiNbO3 substrates

ZnO thin films were grown on (0001)LiNbO3 substrates by the MOCVD technique. The substrate temperatures during growth were changed from 400 to 600 degrees C. The X-ray diffraction (XRD) pattern of the ZnO film showed a strong [002] reflection peak, and the peak intensity was dependent on substrate temperature. The ZnO columnar grains were highly oriented along the (002) direction when the film processing temperature was 600 degrees C. The optical transmission and PL results also indicated that highest crystalline quality of the ZnO films could be obtained at elevated temperatures. (c) 2005 Elsevier B.V. All rights reserved.

Effect of microstructure of TiO2 thin films on optical band gap energy

TiO2 coatings are prepared on fused silica with conventional electron beam evaporation deposition. After annealed at different temperatures for four hours, the spectra and XRD patterns of TiO2 thin film are obtained. XRD patterns reveal that only anatase phase can be observed in TiO2 coatings regardless of the different annealing temperatures, and with the increasing annealing temperature, the grain size gradually increases. The relationship between the energy gap and microstructure of anatase is determined and discussed. The quantum confinement effect is observed that with the increasing grain size of TiO2 thin film, the band gap energy shifts from 3.4 eV to 3.21 eV. Moreover, other possible influence of the TiO2 thin-film microstructure, such as surface roughness and thin film absorption, on band gap energy is also expected.

Influence of annealing temperature on structure, optical loss and laser-induced damage threshold of TiO2 thin films

TiO2 thin films are prepared on fused silica with conventional electron beam evaporation deposition. After annealed at different temperatures for 4h, the spectra and XRD patterns of the TiO2 thin film are obtained. Weak absorption of coatings is measured by the surface thermal lensing technique, and laser-induced damage threshold (LIDT) is determined. It is found that with the increasing annealing temperature, the transmittance of TiO2 films decreases. Especially when coatings are annealed at high temperature over 1173K, the optical loss is very serious. Weak absorption detection indicates that the absorption of coatings decreases firstly and then increases, and the absorption and defects play major roles in the LIDT of TiO2 thin films.

Working pressure dependence of properties of Al2O3 thin films prepared by electron beam evaporation

The effects of working pressure on properties of Al2O3 thin films are investigated. Transmittance of the Al2O3 thin film is measured by a Lambda 900 spectrometer. Laser-induced damage threshold (LIDT) is measured by a Nd:YAG laser at 355nm with a pulse width of 7ns. Microdefects were observed under a Nomarski microscope. The samples are characterized by optical properties and defect, as well as LIDT under the 355 nm Nd: YAG laser radiation. It is found that the working pressure has fundamental effect on the LIDT. It is the absorption rather than the microdefect that plays an important role on the LID T of Al2O3 thin film.

Optical properties and microstructure of Ta2O5 biaxial film

This study investigates the optical properties and microstructure of Ta2O5 film deposited with the glancing angle deposition technique. The tilted nanocolumn microstructure, examined with scanning electron microscopy, induces the optical anisotropy of thin film. The optical properties of thin film are characterized with an inverse synthesis method. Based on the Cauchy model, the dispersion equations of optical constants of film are determined from the transmittance spectra measured at normal and oblique incidence over 400-800 nm. The starting values derived with an envelope method quicken the optimization process greatly. The dispersion of the principal indices N-1, N-2, and N-3 and the thickness d of thin film are presented statistically. A good agreement between the measured optical properties and theoretical calculation is obtained, which validates the model established for thin film produced by glancing angle deposition. (C) 2008 Optical Society of America

Diameter and wall number control of carbon nanotubes by chemical vapor deposition

We analyze the relationship between the average wall number (N) and the diameter (d) for carbon nanotubes (CNTs) grown by chemical vapour deposition. It is found that N depends linearly on d for diameters in the range of 2.5-10 nm, while single wall nanotubes predominate for diameters under about 2.1 nm. The linear relationship is found to depend somewhat on the growth conditions. It is also verified that the mean diameter depends on the diameter of the originating catalyst nanoparticle, and thus on the initial catalyst thickness where a thin film catalyst is used. This simplifies the characterisation of CNTs by electron microscopy. We also find a linear relationship between nanotube diameter and initial catalyst film thickness. © 2013 AIP Publishing LLC.

Promoting strain relaxation of Si0.72Ge0.28 film on Si (100) substrate by inserting a low-temperature Ge islands layer in UHVCVD

A flat, fully strain-relaxed Si0.72Ge0.28 thin film was grown on Si (1 0 0) substrate with a combination of thin low-temperature (LT) Ge and LT-Si0.72Ge0.28 buffer layers by ultrahigh vacuum chemical vapor deposition. The strain relaxation ratio in the Si0.72Ge0.28 film was enhanced up to 99% with the assistance of three-dimensional Ge islands and point defects introduced in the layers, which furthermore facilitated an ultra-low threading dislocation density of 5 x 10(4) cm (2) for the top SiGe film. More interestingly, no cross-hatch pattern was observed on the SiGe surface and the surface root-mean-square roughness was less than 2 nm. The temperature for the growth of LT-Ge layer was optimized to be 300 degrees C. (C) 2008 Elsevier B.V. All rights reserved.

The effects of substrate temperature on the structure and properties of ZnO films prepared by pulsed laser deposition

ZnO thin films were prepared by pulsed laser deposition (PLD) on glass substrates with growth temperature from room temperature (RT) to 500 degrees C. The effects of substrate temperature on the structural and optical properties of ZnO films have been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission spectra, and RT photoluminescence (PL) measurements. The results showed that crystalline and (0 0 2)-oriented ZnO films were obtained at all substrate temperatures. As the substrate temperature increased from RT to 500 degrees C, the ratio of grain size in height direction to that in the lateral direction gradually decreased. The same grain size in two directions was obtained at 200 degrees C, and the size was smallest in all samples, which may result in maximum E, and E-0 of the films. UV emission was observed only in the films grown at 200 degrees C, which is probably because the stoichiometry of ZnO films was improved at a suitable substrate temperature. It was suggested that the UV emission might be related to the stoichiometry in the ZnO film rather than the grain size of the thin film. (c) 2007 Elsevier Ltd. All rights reserved.

Kinetically controlled InN nucleation on GaN templates by metalorganic chemical vapour deposition

This paper presents a study on the nucleation and initial growth kinetics of InN on GaN, especially their dependence on metalorganic chemical vapour deposition conditions. It is found that the density and size of separated InN nano-scale islands can be adjusted and well controlled by changing the V/III ratio and growth temperature. InN nuclei density increases for several orders of magnitude with decreasing growth temperature between 525 and 375 degrees C. At lower growth temperatures, InN thin films take the form of small and closely packed islands with diameters less than 100 nm, whereas at elevated temperatures the InN islands grow larger and become well separated, approaching an equilibrium hexagonal shape due to enhanced surface diffusion of adatoms. The temperature dependence of InN island density gives two activation energies of InN nucleation behaviour, which is attributed to two different kinetic processes related to In adatom surface diffusion and desorption, respectively.