Structural study of TiO2 thin films by micro-Raman spectroscopy

The Raman spectroscopy method was used for structural characterization of TiO₂ thin films prepared by atomic layer deposition (ALD) and pulsed laser deposition (PLD) on fused silica and single-crystal silicon and sapphire substrates. Using ALD, anatase thin films were grown on silica and silicon substrates at temperatures 125–425 °C. At higher deposition temperatures, mixed anatase and rutile phases grew on these substrates. Post-growth annealing resulted in anatase-to-rutile phase transitions at 750 °C in the case of pure anatase films. The films that contained chlorine residues and were amorphous in their as-grown stage transformed into anatase phase at 400 °C and retained this phase even after annealing at 900 °C. On single crystal sapphire substrates, phase-pure rutile films were obtained by ALD at 425 °C and higher temperatures without additional annealing. Thin films that predominantly contained brookite phase were grown by PLD on silica substrates using rutile as a starting material.     

XRD study on the effect of the deposition condition on pulsed laser deposition of ZnO films

Using a pulsed laser deposition (PLD) process on a ZnO target in an oxygen atmosphere, thin films of this material have been deposited on Si(111) substrates. An Nd: YAG pulsed laser with a wavelength of 1064 nm was used as the laser source. The influences of the deposition temperature, laser energy, annealing temperature and focus lens position on the crystallinity of ZnO films were analyzed by X-ray diffraction. The results show that the ZnO thin films obtained at the deposition temperature of 400°C and the laser energy of 250 mJ have the best crystalline quality in our experimental conditions. The ZnO thin films fabricated at substrate temperature 400°C were annealed at the temperatures from 400°C to 800°C in an atmosphere of N₂. The results show that crystalline quality has been improved by annealing, the optimum temperature being 600°C. The position of the focusing lens has a strong influence on pulsed laser deposition of the ZnO thin films and the optimum position is 59.5 cm from the target surface for optics with a focal length of 70 cm.      

Pulsed laser deposition of Co and growth of CoSi2 on Si(111)

Monolayers of Co were prepared by pulsed laser deposition (PLD) and thermal deposition (TD) on Si(111) substrates. The surface structure and morphology were studied as a function of annealing temperature with scanning tunneling microscopy and low-energy electron diffraction (LEED). Comparing PLD to TD in the monolayer regime, we find surface phases with lower Co content in the top layer for annealing temperatures below 500 °C, indicating an implantation of Co into the Si substrate. The implanted Co leads to an increased intermixing of Co and Si and a higher density of nucleation centers for Co multilayers produced by PLD compared to TD. Multilayer PLD films therefore show an improved film quality, which is detected by an increased intensity of the LEED reflectivity. PACS 68.37.Ef; 61.14.Hg; 68.55.-a     

碳化硅薄膜脉冲激光晶化特性研究

采用XeCl准分子激光对非晶碳化硅(a-SiC)薄膜的脉冲激光晶化特性进行了研究.通过原子力显微镜（AFM）和Raman光谱技术对退火前后薄膜样品的形貌、结构及物相特性进行了分析.结果表明，选用合适的激光能量采用激光退火技术能够实现a-SiC薄膜的纳米晶化.退火薄膜中的纳米颗粒大小随着激光能量密度的增加而增大；Raman谱分析结果显示了退火后的薄膜的晶态结构特性并给出了伴随退火过程存在的物相分凝现象.根据以上结果并结合激光退火特性，对a-SiC的脉冲激光晶化机理进行了讨论. 关键词： 激光退火 晶化 碳化硅     

Pulsed laser deposition of tantalum pentoxide film

We report thin tantalum pentoxide (Ta₂O₅) films grown on quartz and silicon substrates by the pulsed laser deposition (PLD) technique employing a Nd:YAG laser (wavelength 5=532 nm) in various O₂ gas environments. The effect of oxygen pressure, substrate temperature, and annealing under UV irradiation using a 172-nm excimer lamp on the properties of the grown films has been studied. The optical properties determined by UV spectrophotometry were also found to be a sensitive function of oxygen pressure in the chamber. At an O₂ pressure of 0.2 mbar and deposition temperatures between 400 and 500 °C, the refractive index of the films was around 2.18 which is very close to the bulk Ta₂O₅ value of 2.2, and an optical transmittance around 90% in the visible region of the spectrum was obtained. X-ray diffraction measurements showed that the as-deposited films were amorphous at temperatures below 500 °C and possessed an orthorhombic (#-Ta₂O₅) crystal structure at temperatures above 600 °C. The most significant result of the present study was that oxygen pressure could be used to control the composition and modulate optical band gap of the films. It was also found that UV annealing can significantly improve the optical and electrical properties of the films deposited at low oxygen pressures (<0.1 mbar).     

The effect of nitrogen pressure on the two-step method deposition of GaN films

GaN thin films were deposited on sapphire (0001) substrates at different nitrogen pressures by pulsed laser deposition (PLD) of GaN target in nitrogen atmosphere. Good single crystal GaN thin films were obtained after annealing at 1000 °C for 15 min in a NH₃ atmosphere. An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as the laser source. The influence of nitrogen pressure on the thickness, crystallinity and surface morphology of GaN films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM) and Raman spectroscopy. The results show that at low nitrogen pressure, the surface diffusion of adatoms can be influenced by the collisions between the nitrogen gas molecules and the activated atoms, which can influence the kinetic energy of the activated atoms. However, at high nitrogen pressure, the kinetic energy of adatoms is decided by the annealing temperature. In our experimental conditions, the GaN thin films deposited at 0.75 and 7.5 Pa have a high surface morphology and crystalline quality. PACS 71.55.Eq; 74.62.Fj     

Optical properties of PMN–PT thin films prepared using pulsed laser deposition

(1 ? x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ (PMN–PT) thin films have been deposited on quartz substrates using pulsed laser deposition (PLD). Crystalline microstructure of the deposited PMN–PT thin films has been investigated with X-ray diffraction (XRD). Optical transmission spectroscopy and Raman spectroscopy are used to characterize optical properties of the deposited PMN–PT thin films. The results show that the PMN–PT thin films of perovskite structure have been formed, and the crystalline and optical properties of the PMN–PT thin films can be improved as increasing the annealing temperature to 750 °C, but further increasing the annealing temperature to 950 °C may lead to a degradation of the crystallinity and the optical properties of the PMN–PT thin films. In addition, a weak second harmonic intensity (SHG) has been observed for the PMN–PT thin film formed at the optimum annealing temperature of 750 °C according to Maker fringe method. All these suggest that the annealing temperature has significant effect on the structural and optical properties of the PMN–PT thin films.     

Fabrication of ZnO thin films by femtosecond pulsed laser deposition

The growth of ZnO thin films on sapphire substrate using the femtosecond PLD technique is reported. The effect of substrate temperature and oxygen pressure on the structural properties of the films was studied. Highly c-axis oriented ZnO films can be grown on sapphire substrates under vacuum conditions using the femtosecond PLD process. There is an optimum substrate temperature for the pulsed laser deposition of ZnO film that enhances the thermodynamic stability and allows the formation of well-crystallized thin films. The crystal quality of the films can be further improved by increasing the deposition time and introducing oxygen during the pulsed laser deposition process.     

The comparison between CdS thin films grown on Si(111) substrate and quartz substrate by femtosecond pulsed laser deposition

Two kinds of cadmium sulfate (CdS) thin films have been grown at 600 °C onto Si(111) and quartz substrates using femtosecond pulsed laser deposition (PLD). The influence of substrates on the structural and optical properties of the CdS thin films grown by femtosecond pulsed laser deposition have been studied. The CdS thin films were characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), photoluminescence (PL) and Raman spectroscopy. Although CdS thin films deposited both on Si(111) and quartz substrates were polycrystalline and hexagonal as shown by the XRD , SEM and AFM results, the crystalline quality and optical properties were found to be different. The size of the grains for the CdS thin film grown on Si(111) substrate were observed to be larger than that of the CdS thin film grown on quartz substrate, and there is more microcrystalline perpendicularity of c-axis for the film deposited on the quartz substrate than that for the films deposited on the Si substrate. In addition, in the PL spectra, the excitonic peak is more intense and resolved for CdS film deposited on quartz than that for the CdS film deposited on Si(111) substrate. The LO and TO Raman peaks in the CdS films grown on Si(111) substrate and quartz substrate are different, which is due to higher stress and bigger grain size in the CdS film grown on Si(111) substrate, than that of the CdS film grown on the amorphous quartz substrate. All this suggests that the substrates have a significant effect on the structural and optical properties of thin CdS films. PACS 81.15.Fg; 81.05.Ea; 78.20.-e; 78.67.-n; 42.62.-b     

Critical role of laser wavelength on carbon films grown by PLD of graphite

The structure of thin films deposited by pulsed laser ablation (PLD) is strongly dependent on experimental conditions, like laser wavelength and fluence, substrate temperature and pressure. Depending on these parameters we obtained various kinds of carbon materials varying from dense, mainly tetrahedral amorphous carbon (ta-C), to less compact vertically oriented graphene nano-particles. Thin carbon films were grown by PLD on n-Si 〈100〉 substrates, at temperatures ranging from RT to 800°C, from a rotating graphite target operating in vacuum. The laser ablation of the graphite target was performed by a UV pulsed ArF excimer laser (λ=193 nm) and a pulsed Nd:YAG laser, operating in the near IR (λ=1064 nm). The film structure and texturing, characterised by X-ray diffraction analysis, performed at grazing incidence (GI-XRD), and the film density, evaluated by X-ray reflectivity measurements, are strongly affected both by laser wavelength and fluence and by substrate temperature. Micro-Raman and GI-XRD analysis established the progressive formation of aromatic clusters and cluster condensation into vertically oriented nano-sized graphene structures as a direct function of increasing laser wavelength and deposition temperature. The film density, negatively affected by substrate temperature and laser wavelength and fluence, in turn, results in a porous bulk configuration and a high macroscopic surface roughness as shown by SEM characterisation. These structural property modifications induce a relevant variation also on the emission properties of carbon nano-structures, as evidenced by field emission measurements. This work is dedicated to our friend Giorgio who passed away 20th August.     

Adjusting chemical bonding of hard amorphous CSixNy thin films by N*-plasma-assisted pulsed laser deposition

Hard amorphous carbon silicon nitride thin films have been grown by pulsed laser deposition (PLD) of various carbon silicon nitride targets by using an additional nitrogen RF plasma source on [100] oriented silicon substrates at room temperature. The influence of the number of laser shots per target site on the growth rate and film surface morphology was studied. Up to about 30 at. % nitrogen and up to 20 at. % silicon were found in the films by Rutherford backscattering spectroscopy (RBS) and X-ray photoelectron spectroscopy (XPS). The XPS of the films showed a clear correlation of binding energy to the variation of PLD parameters. The films show a universal hardness value up to 23 GPa (reference value for silicon substrate 14 GPa) in dependence on target composition and PLD parameters. The results emphasise the possibility of variation of chemical bonding and corresponding properties, such as nanohardness, of amorphous CSi_xN_y thin films by the plasma-assisted PLD process.     

Effect of temperature on pulsed laser deposition of HgCdTe films

HgCdTe thin films have been deposited on Si(1 1 1) substrates at different substrate temperatures by pulsed laser deposition (PLD). An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the substrate temperature on the crystalline quality, surface morphology and composition of HgCdTe thin films were characterized by X-ray diffraction (XRD), selected area electron diffraction (SAED), atomic force microscopy (AFM) and energy dispersive X-ray spectroscopy (EDS). The results show that in our experimental conditions, the HgCdTe thin films deposited at 200 °C have the best quality. When the substrate temperature is over 250 °C, the HgCdTe film becomes thermodynamically unstable and the quality of the film is degraded.     

Effect of process parameters and post-deposition annealing on the microwave dielectric and optical properties of pulsed laser deposited Bi<Subscript>1.5</Subscript>Zn<Subscript>1.0</Subscript>Nb<Subscript>1.5</Subscript>O<Subscript>7</Subscript> thin films

Bismuth Zinc niobate (Bi_1.5Zn_1.0Nb_1.5O₇) thin films were deposited by pulsed laser deposition (PLD) method on fused silica substrates at different oxygen pressures. The structural, microwave dielectric and optical properties of these thin films were systematically studied for both the as-deposited and the annealed films at 600°C. The as-deposited films were all amorphous in nature but crystallized on annealing at 600°C in air. The surface morphology as studied by atomic force microscopy (AFM) reveals ultra-fine grains in the case of as-deposited thin films and cluster grain morphology on annealing. The as-deposited films exhibit refractive index in the range of 2.36–2.53 (at a wavelength of 750 nm) with an optical absorption edge value of 3.30–3.52 eV and a maximum dielectric constant of 11 at 12.15 GHz. On annealing the films at 600°C they crystallize to the cubic pyrochlore structure accompanied by an increase in band gap, refractive index and microwave dielectric constant.     

Low-temperature growth of epitaxial ZnO films on (001) sapphire by ultraviolet- assisted pulsed laser deposition

ZnO thin films have been grown on thin Si₃N₄ membranes and (001) sapphire substrates by an ultraviolet-assisted pulsed laser deposition (UVPLD) technique. The microstructure of the films grown on Si₃N₄ membranes, investigated by transmission electron microscopy, showed that crystalline and textured films can be grown by UVPLD at a substrate temperature of only 100 °C. For deposition temperatures higher than 400 °C, ZnO films grown on sapphire substrates were found to be epitaxial by Rutherford backscattering (RBS) and X-ray diffraction measurements. The minimum yield of channeling RBS spectra recorded from films deposited at 550 °C was around 2% and the FWHM of the rocking curve for the (002) diffraction peak was 0.17°; these values are similar to those recorded from ZnO layers grown by conventional PLD at 750 °C.     

Pulsed laser deposition and its current research status in preparing hydroxyapatite thin films

Pulsed laser deposition (PLD) is a conceptually and experimentally simple yet highly versatile tool for thin films and multi-layer film research. The mechanisms, advantages and disadvantages of pulsed laser deposition were reviewed. The process and some methods to resolve the drawbacks of PLD were discussed. Pulsed laser deposition of hydroxyapatite thin films was reviewed. Simple adjustment of PLD parameters can deposit hydroxyapatite in situ in crystalline form, amorphous films or HA with other calcium phosphate phases. Compared with plasma sprayed HA coatings the pulsed laser deposition HA thin films have higher coating/substrate adhesion and have minor undesirable phases under optimal conditions. Finally, we suggested some new researches should be done.     

Laser ablation of La0.9Sr0.1Ga0·8Mg0.2O2.85 — plume and film characterization

Thin films of La_0.9Sr_0.1Ga_0·8Mg_0.2O_2.85 (LSGMO), an electrolyte material for the solid oxide fuel cells (SOFC), have been prepared by pulsed laser deposition method. Preparation of thin films under high vacuum gives amorphous films, which on annealing at 730 °C in air give stochiometric thin films. Highly oriented, polycrystalline and amorphous films of LSGMO are obtained on SrTiO₃ (001), sapphire (0001) and quartz substrates, respectively. The ionic conductivity value for the film deposited on sapphire substrate is an order of magnitude larger than for the film deposited on SrTiO₃. The plume composition is analyzed by a mass spectrometer. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Structural and optical properties of YSZ thin films grown by PLD technique

We report on the structural and optical properties of yttria stabilized zirconia (YSZ) thin films grown by pulsed laser deposition (PLD) technique and in situ crystallized at different substrate temperatures (T_s = 400 °C, 500 °C and 600 °C). Yttria-stabilized zirconia target of ∼1 in. diameter (∼95% density) was fabricated by solid state reaction method for thin film deposition by PLD. The YSZ thin films were grown on an optically polished quartz substrates and the deposition time was 30 min for all the films. XRD analysis shows cubic crystalline phase of YSZ films with preferred orientation along 〈1 1 1〉. The surface roughness was determined by AFM for the films deposited at different substrate temperatures. The nano-sized surface roughness is found to increase with the increase of deposition temperatures. For the optical analysis, a UV-vis-NIR spectrophotometer was used and the optical band gap of ∼5.7 eV was calculated from transmittance curves.     

生长温度对Ga掺杂ZnO薄膜光电性能的影响

在不同衬底温度(室温~750 ℃)条件下,采用脉冲激光沉积(PLD)方法在石英玻璃和单晶硅(111)衬底上制备了Ga掺杂ZnO(GZO)薄膜。结果显示:衬底温度的变化导致衬底表面吸附原子扩散速率和脱附速率的不同,从而导致合成薄膜结晶质量的差异,衬底温度450 ℃时制备的GZO薄膜具有最好的结晶特性;GZO薄膜中载流子浓度随衬底温度升高而单调减小的现象与GZO薄膜中的本征缺陷密切相关,晶界散射强度的变化导致迁移率出现先增大后减小的趋势,衬底温度450 ℃时制备的GZO薄膜具有最小的电阻率~0.02 Ω·cm;随着衬底温度的升高,薄膜载流子浓度的单调减小导致了薄膜光学带隙变窄,所有合成样品的平均可见光透过率均达到85%以上。采用PLD方法制备GZO薄膜,衬底温度的改变可以对薄膜的光电性能起到调制作用。     

Studies on highly resistive ZnO thin films grown by DC-discharge-assisted pulsed laser deposition

It was found that by changing the substrate temperature from room temperature to ～850 °C, ZnO thin films with widely varying resistivity values could be grown on sapphire substrates using DC-discharge-assisted pulsed laser deposition (PLD) in oxygen ambient. The resistivity of the film grown at room temperature was too high to measure using our existing setup. However, as the growth temperature was increased from 550 °C to 750 °C, the resistivity first decreased slowly from ～14.0 to 4.4 Ω?m and then dropped suddenly to get saturated at ～2.0×10^?3 Ω?m as the growth temperature was further increased. In contrast to these, when there was no DC-discharge, the variation of resistivity for ZnO thin films grown by PLD was marginal up to the substrate temperature of ～850 °C. The reason for these observations was found to be the combined effects of reduction in donor defect densities like oxygen vacancies and zinc interstitials, introduction of acceptor type defects like interstitial oxygen and zinc vacancies, and the resultant poor carrier mobility at lower growth temperatures. At higher growth temperatures (800 °C and above), the appearance of oxygen vacancies and increase in mobility due to better crystalline quality were found to be responsible for reducing the resistivity. The PL of these films had significant emission in the green and red regions of the spectrum due to the aforesaid defect related transitions. Such highly resistive and luminescent films might be suited for applications such as resistive RAM, UV-photo detector, TFT, piezoelectric, transparent phosphor, and broadband LED applications.     

Pulsed laser deposition of PrFe4Sb12 thin films

Results from a growth and characterization study of PrFe₄Sb₁₂ thin films synthesized by pulsed laser deposition (PLD) are reported. Films were grown under a variety of conditions where substrate temperature, annealing schedule, and laser power were optimized to produce single phase material. Various substrates were used for film growth. X-ray diffraction data indicate that the films are primarily single phase with very small amounts of antimony inclusions. The high quality of the films is reflected in electrical resistivity vs temperature data which are consistent with previous results for bulk polycrystalline and single crystal specimens. PACS 71.27.+a; 73.50.-h; 81.15.Fg; 68.55.JK