Optical properties of SrTiO<Subscript>3</Subscript> thin films by pulsed laser deposition

SrTiO₃ thin films were prepared on a fused-quartz substrate by pulsed laser deposition (PLD). Dense and homogeneous films with a thickness of 260 nm were prepared. Optical constants (refractive index n and extinction coefficient k) were determined from the transmittance spectra using the envelope method. The optical band gap energy of the films was found to be 3.58 eV, higher than the 3.22 eV for bulk SrTiO₃, attributable to the film stress exerted by the substrate. The dispersion relation of the refractive index vs. wavelength follows the single electronic oscillator model. The refractive index and the packing density for the PLD-prepared SrTiO₃ thin films are higher than those for the SrTiO₃ films prepared by physical vapor deposition, sol–gel and RF sputtering. Received: 18 March 2002 / Accepted: 7 October 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +86-25/359-5535, E-mail: mszhang@nju.edu.cn     

Influence of deposition conditions on the structural characteristics of sublimated CdTe thin films

In this paper the results obtained by X-ray diffraction studies on the structural characteristics of CdTe thin films deposited onto glass substrates by close-spaced sublimation technique are presented. Using different experimental arrangements and appropriate settings for growth parameters, the films with different polycrystalline structures were prepared. The geometry and the volume of the deposition chamber influence the size of film crystallites and also their preferential orientation. The role of deposition parameters such as the substrate temperature, the incidence angle, the film thickness, and the heat treatment in determination of the structural properties of the films are also investigated. Received: 26 November 1999 / Accepted: 7 January 2000 / Published online: 5 April 2000     

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.     

Synthesis of LECBD grown cluster assembled SeO2 thin films

Cluster assembled selenium oxide (SeO₂) thin films, as a function of oxygen flow pressure (OFP) have been synthesized by a low energy cluster beam deposition (LECBD) technique. The OFP dependent surface morphology leading to well separated nanoclusters (size ranging from 50 to 200 nm) and fractal features are confirmed from transmission electron microscopic (TEM) measurements. A diffusion limited aggregation (DLA) mediated fractal growth with dimension as 1.71 ± 0.01 has been observed for high OFP (60 mbar). Structural analysis by glancing angle X-ray diffraction (GXRD) and selected area diffraction (SAD) studies identify the presence of tetragonal phase SeO₂ in the deposit. Micro-Raman studies indicate the shifts in bending and stretching vibrational phonon modes in cluster assembled SeO₂ as compared to their bulk counter part due to the phonon confinement effect.     

Formation of the ferroelectric domains in epitaxial PbTiO3 thin films grown by metalorganic chemical vapor deposition

3 thin films have been prepared by metalorganic chemical vapor deposition under reduced pressure. The formation of ferroelectric domains in films grown on SrTiO₃ and LaAlO₃ substrates was investigated by synchrotron radiation and Rutherford backscattering spectroscopy. Single-domain (3000-Å thick) and multi-domain (4500-Å thick) PbTiO₃ films were produced on SrTiO₃. For multi-domain PbTiO₃ film, the c-domain presented epitaxial structure with its c-axis perpendicular to the substrate surface, while a-domains aligned four-fold symmetrically with c-domains by 2.79^° off the c-axis of c-domains. In the film, the measured lattice constants (a, b and c) of the a- and c-domains were different from each other, indicating that the films suffered a modulated strain during domain formation. In contrast, both the a and c domains of films on LaAlO₃ were alternatively aligned on substrate with the a-axis of the a-domain and the c-axis of c-domains perpendicular to the substrate surface. Two-dimensional distribution of these domains is proposed and the formation of these kinds of domains is discussed. The surface morphology and phase transition process of single and multi domain PbTiO₃ film on SrTiO₃ were studied by atomic force microscope (AFM) and high temperature X-ray diffraction, respectively. Received: 15 August 1996/Accepted: 21 January 1997     

Thickness influence on surface morphology and ozone sensing properties of nanostructured ZnO transparent thin films grown by PLD

Transparent zinc oxide (ZnO) thin films with a thickness from 10 to 200 nm were prepared by the PLD technique onto silicon and Corning glass substrates at 350 °C, using an Excimer Laser XeCl (308 nm). Surface investigations carried out by atomic force microscopy (AFM) and X-ray diffraction (XRD) revealed a strong influence of thickness on film surface topography. Film roughness (RMS), grain shape and dimensions correlate with film thickness. For the 200 nm thick film, the RMS shows a maximum (13.9 nm) due to the presence of hexagonal shaped nanorods on the surface. XRD measurements proved that the films grown by PLD are c-axis textured. It was demonstrated that the gas sensing characteristics of ZnO films are strongly influenced and may be enhanced significantly by the control of film deposition parameters and surface characteristics, i.e. thickness and RMS, grain shape and dimension.     

Optical and waveguiding properties of Nd:KGW films grown by pulsed laser deposition

 Nd: KGd(WO₄)₂ thin films were deposited by KrF laser ablation on MgO, YAP, YAG and Si substrates at temperatures up to 800 °C. Film crystallinity, morphology, stoichiometry (WDX, RBS and PIXE), excitation spectra, fluorescence, refractive index and waveguiding properties were studied in connection with deposition conditions. The best films were crystalline and exhibited losses of approximately 5 dB cm^-1 at a wavelength of 633 nm. Received: 8 January 2001 / Accepted: 7 November 2001 / Published online: 11 February 2002     

Optical properties of Al-doped ZnO thin films by ellipsometry

Al-doped ZnO thin films (AZO) were prepared on Si (1 0 0) substrates by using sub-molecule doping technique. The Al content was controlled by varying Al sputtering time. The as-prepared samples were annealed in vacuum chamber at 800 °C for 30 min. From the XRD observations, it is found that all films exhibit only the (0 0 2) peak, suggesting that they have c-axis preferred orientation. The average transmittance of the visible light is above 80%. Spectroscopic ellipsometry was used to extract the optical constants of the films. The absorption coefficient and the energy gap were then calculated. The results show that the absorption edge initially blue-shifts and then red-shifts with increase of Al content.     

Influence of annealing temperature on structural, optical and magnetic properties of Mn-doped ZnO thin films prepared by sol-gel method

Thin films of Zn_1−xMn_xO (x=0.01) diluted magnetic semiconductor were prepared on Si (1 0 0) substrates by the sol-gel method. The influence of annealing temperature on the structural, optical and magnetic properties was studied by X-ray diffraction (XRD), atom force microscopy (AFM), photoluminescence (PL) and SQUID magnetometer (MPMS, Quantum Design). The XRD spectrum shows that all the films are single crystalline with (0 0 2) preferential orientation along c-axis, indicating there are not any secondary phases. The atomic force microscopy images show the surfaces morphologies change greatly with an increase in annealing temperature. PL spectra reveal that the films marginally shift the near band-edge (NBE) position due to stress. The magnetic measurements of the films using SQUID clearly indicate the room temperature ferromagnetic behavior, and the Curie temperature of the samples is above room temperature. X-ray photoelectron spectroscopy (XPS) patterns suggest that Mn²⁺ ions were successfully incorporated into the lattice position of Zn²⁺ ions in ZnO host. It is also found that the post-annealing treatment can affect the ferromagnetic behavior of the films effectively.     

Microstructure and mechanical properties of CrN films fabricated by high power pulsed magnetron discharge plasma immersion ion implantation and deposition

CrN films with strong adhesion with the substrate have been fabricated on Ti6Al4V alloy using novel plasma immersion ion implantation and deposition (PIII&D) based on high power pulsed magnetron sputtering (HPPMS). A macro-particle free chromium plasma is generated by HPPMS while the samples are subjected to high voltage pulses to conduct PIII&D. The CrN coatings have a dense columnar structure and low surface roughness. The grains in the films have the face-center cubic (fcc) structure with the (2 0 0) preferred orientation. An excellent adhesion is achieved with a critical load up to 74.7 N. An implantation voltage of 18 kV yields a hardness of 18 GPa and better wear resistance and a low friction coefficient of 0.48 are achieved.     

Optical and structural parameters of the ZnO thin film grown by pulsed filtered cathodic vacuum arc deposition

Transparent conductive ZnO film was deposited on glass substrate by pulsed filtered cathodic vacuum arc deposition (PFCVAD). Optical parameters such as absorption coefficient α, the refractive index n, energy band gap E_g and dielectric constants have been determined using different methods. Kramers-Kronig and dispersion relations were employed to determine the complex refractive index and dielectric constants using reflection data in the ultraviolet-visible-near infrared regions. The spectra of the dielectric coefficient were used to calculate the energy band gap and the value was 3.24 eV. The experimental energy band gap was found to be 3.22 eV for 357 nm thick ZnO thin film. The envelope method was also used to calculate the refractive index and the data were consistent with K-K relation results. The structure of the film was analyzed with an x-ray diffractometer and the film was polycrystalline in nature with preferred (002) orientation.     

Dependence of film thickness on the structural and optical properties of ZnO thin films

ZnO thin films are prepared on glass substrates by pulsed filtered cathodic vacuum arc deposition (PFCVAD) at room temperature. Optical parameters such as optical transmittance, reflectance, band tail, dielectric coefficient, refractive index, energy band gap have been studied, discussed and correlated to the changes with film thickness. Kramers-Kronig and dispersion relations were employed to determine the complex refractive index and dielectric constants using reflection data in the ultraviolet-visible-near infrared regions. Films with optical transmittance above 90% in the visible range were prepared at pressure of 6.5 × 10⁻⁴ Torr. XRD analysis revealed that all films had a strong ZnO (0 0 2) peak, indicating c-axis orientation. The crystal grain size increased from 14.97 nm to 22.53 nm as the film thickness increased from 139 nm to 427 nm, however no significant change was observed in interplanar distance and crystal lattice constant. Optical energy gap decreased from 3.21 eV to 3.19 eV with increasing the thickness. The transmission in UV region decreased with the increase of film thickness. The refractive index, Urbach tail and real part of complex dielectric constant decreased as the film thickness increased. Oscillator energy of as-deposited films increased from 3.49 eV to 4.78 eV as the thickness increased.     

ZnO thin films on Si(1 1 1) grown by pulsed laser deposition from metallic Zn target

ZnO thin films with highly c-axis orientation have been fabricated on p-type Si(1 1 1) substrates at 400 °C by pulsed laser deposition (PLD) from a metallic Zn target with oxygen pressures between 0.1 and 0.7 mbar. Experimental results indicate that the films deposited at 0.3 and 0.5 mbar have better crystalline and optical quality and flatter surfaces than the films prepared at other pressures. The full width at half maximum (FWHM) of (0 0 0 2) diffraction peak decreases remarkably from 0.46 to 0.19° with increasing annealing temperature for the film prepared at 0.3 mbar. In photoluminescence (PL) spectra at room temperature, the annealed film at 700 °C exhibits a smaller ultraviolet (UV) peak FWHM of 108 meV than the as-grown film (119 meV). However, an enhanced deep-level emission is observed. Possible origins to above results are discussed.     

Study on the orientation of silver films by ion-beam assisted deposition

Low energy ion beam assisted deposition (IBAD) was employed to prepare Ag films on Mo/Si (100) substrate. It was found that Ag films deposited by sputtering method without ion beam bombardment were preferred (111) orientation. When the depositing film was simultaneously bombardment by Ar⁺ beam perpendicular to the film surface at ion/atom arrival ratio of 0.18, the prepared films exhibited weak (111) and (200) mixed orientations. When the direction of Ar⁺ beam was off-normal direction of the film surface, Ag films showed highly preferred (111) orientation. Monte Carlo method was used to calculate the sputtering yields of Ar⁺ ions at various incident and azimuth angles. The effects of channeling and surface free energy on the crystallographic orientation of Ag films were discussed.     

The structural and optical properties of ZnO/Si thin films by RTA treatments

ZnO/Si thin films were prepared by rf magnetron sputtering method and some of the samples were treated by rapid thermal annealing (RTA) process at different temperatures ranging from 400 to 800 °C. The effects of RTA treatment on the structural properties were studied by using X-ray diffraction and atomic force microscopy while optical properties were studied by the photoluminescence measurements. It is observed that the ZnO film annealed at 600 °C reveals the strongest UV emission intensity and narrowest full width at half maximum among the temperature ranges studied. The enhanced UV emission from the film annealed at 600 °C is attributed to the improved crystalline quality of ZnO film due to the effective relaxation of residual compressive stress and achieving maximum grain size.     

Post-annealing effect upon optical properties of electron beam evaporated molybdenum oxide thin films

Molybdenum oxide (MoO₃) thin films were deposited by electron beam evaporation. The chemical composition, microstructure, optical and electrical properties of MoO₃ thin films depend on the annealing temperature and ambient atmosphere. X-ray diffraction (XRD) shows that crystalline MoO₃ films can be obtained at various post-annealing temperatures from 200 to 500 °C in N₂ and O₂. X-ray photoelectron spectroscopy (XPS) results reveal that the O-1s emission peak was shifted slightly toward lower binding energies as the annealing temperature in N₂ was increased. The oxygen vacancies and conductivity of MoO₃ film increased with the annealing temperature. However, when the MoO₃ films were annealed in an atmosphere of O₂, the optical transmission, the O/Mo ratio and the photon energy increased with the annealing temperature. The results differ from those for films annealed in a N₂ atmosphere.     

Determination of optical properties in nanostructured thin films using the Swanepoel method

We present the methodological framework of the Swanepoel method for the spectrophotometric determination of optical properties in thin films using transmittance data. As an illustrative case study, we determined the refractive index, thickness, absorption index, and extinction coefficient of a nanostructured 3 mol% Y₂O₃-doped ZrO₂ (yttria stabilized zirconia, 3YSZ) thin film prepared by the sol-gel method and deposited by dipping onto a soda-lime glass substrate. In addition, using the absorption index obtained with the Swanepoel method, we calculated the optical band gap of the film. The refractive index was found to increase, then decrease, and finally stabilize with increasing wavelength of the radiation, while the absorption index and extinction coefficient decreased monotonically to zero. These trends are explained in terms of the location of the absorption bands. We also deduced that this 3YSZ thin film has a direct optical band gap of 4.6 eV. All these results compared well with those given in the literature for similar thin films. This suggests that the Swanepoel method has an important role to play in the optical characterization of ceramic thin films.     

Substrate and orientation influence on electrical properties of sputtered La-doped PZT thin films

Pb_1−2y/3La_yZr_xTi_1−xO₃ (PLZT) thin films have been prepared “in situ” by multi-target sputtering on Silicon, LaAlO₃ (LAO) and MgO substrates covered with a Pt bottom electrode. The purpose was to grow tetragonal PLZT films (Zr/Ti = 28/72 with different La contents) on these various substrates and to compare their electrical properties. To this aim, Pt was first deposited on the three different substrates to get (1 1 1)Pt/Si, (1 1 1)Pt/LAO and (2 0 0)Pt/MgO. Then PLZT was deposited in a same run on these three kinds of substrates and the influence of La contents and film orientation on electrical properties was investigated. The La content was varied from y = 0 to y = 32 in order to explore the phase transition between ferroelectric and paraelectric phases as a function of the substrate. For large amount of Lanthanum, relaxor behavior has been observed and studied.     

Morphology and photoluminescence properties of zinc oxide films grown by pulsed laser deposition

Zinc oxide films with different morphologies have been grown by pulsed laser deposition, varying substrate temperature and oxygen pressure. At low oxygen pressure and low substrate temperature continuous films with different roughness have been obtained, while at high substrate temperature a film with sparse hexagonal pyramids has been observed. Increasing the oxygen pressure the film became rougher and at 100 Pa a rod-array has been deposited. The columns of this rod-array grew along the wurtzite c-axis perpendicularly to the substrate surface as proved by X-ray diffraction measurements. Near to the sample borders the columns were slightly tilted towards the center of the sample. The possible growth mechanisms giving rise to the different morphologies have been discussed. Low-temperature photoluminescence measurements allowed to get information about the film quality, showing the variations of the excitonic peak and two defect bands (green and violet-blue) with the different deposition parameters.     

Properties of NiO thin films deposited by chemical spray pyrolysis using different precursor solutions

NiO thin films have been deposited by chemical spray pyrolysis using a perfume atomizer to grow the aerosol. The influence of the precursor, nickel chloride hexahydrate (NiCl₂·6H₂O), nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O), nickel hydroxide hexahydrate (Ni(OH)₂·6H₂O), nickel sulfate tetrahydrate (NiSO₄·4H₂O), on the thin films properties has been studied. In the experimental conditions used (substrate temperature 350 °C, precursor concentration 0.2-0.3 M, etc.), pure NiO thin films crystallized in the cubic phase can be achieved only with NiCl₂ and Ni(NO₃)₂ precursors. These films have been post-annealed at 425 °C for 3 h either in room atmosphere or under vacuum. If all the films are p-type, it is shown that the NiO films conductivity and optical transmittance depend on annealing process. The properties of the NiO thin films annealed under room atmosphere are not significantly modified, which is attributed to the fact that the temperature and the environment of this annealing is not very different from the experimental conditions during spray deposition. The annealing under vacuum is more efficient. This annealing being proceeded in a vacuum no better than 10⁻² Pa, it is supposed that the modifications of the NiO thin film properties, mainly the conductivity and optical transmission, are related to some interaction between residual oxygen and the films.