Characterization of oxide thin films using optical techniques

Thin films of oxide materials are playing a growing role as critical elements in optoelectronic devices and nanoscale devices. In this work, thin films of some typical oxides such as WO₃, Ga₂O₃ and SrTiO₃ were investigated. We present measurements of those films, using various optical techniques like photoconductivity transients over a wide time range and photo-Hall measurements. Analysis of the photo-Hall and photoconductivity data permits the determination of the contribution to the photoconductivity made by the carrier mobility and concentration. A model for dispersive carrier transport was proposed to explain the relaxation of the photoconductivity in oxide thin films. In addition, photoluminescence characterization was used to study microstructures and energy band in oxide thin films. The broad emission from oxide host, consisting of several band peaks, was likely due to a recombination process with several possible paths. The dependence of the luminescent intensity on the annealing atmosphere was associated with the presence of oxygen vacancies. It is suggested that our optical analysis efforts have improved the understanding of oxide thin films, and this should lead to the necessary advancements in a variety of devices.     

Optical characterization of thin thermal oxide films on copper by ellipsometry

A complete optical characterization in the visible region of thin copper oxide films has been performed by ellipsometry. Copper oxide films of various thicknesses were grown on thick copper films by low temperature thermal oxidation at 125 °C in air for different time intervals. The thickness and optical constants of the copper oxide films were determined in the visible region by ellipsometric measurements. It was found that a linear time law is valid for the oxide growth in air at 125 °C. The spectral behaviour of the optical constants and the value of the band gap in the oxide films determined by ellipsometry in this study are in agreement with the behaviour of those of Cu₂O, which have been obtained elsewhere through reflectance and transmittance methods. The band gap of copper oxide, determined from the spectral behaviour of the absorption coefficient was about 2 eV, which is the generally accepted value for Cu₂O. It was therefore concluded that the oxide composition of the surface film grown on copper is in the form of Cu₂O (cuprous oxide). It was also shown that the reflectance spectra of the copper oxide–copper structures exhibit behaviour expected from a single layer antireflection coating of Cu₂O on Cu. Received: 19 July 2001 / Accepted: 27 July 2001 / Published online: 17 October 2001     

Structural characterization and optical properties of ZnSe thin films

Zinc selenide (ZnSe) thin films (d = 0.11-0.93 μm) were deposited onto glass substrates by the quasi-closed volume technique under vacuum. Their structural characteristics were studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). The experiments showed that the films are polycrystalline and have a zinc blende (cubic) structure. The film crystallites are preferentially oriented with the (1 1 1) planes parallel to the substrate surface. AFM images showed that the films have a grain like surface morphology. The average roughness, R_a = 3.3-6.4 nm, and the root mean square roughness, R_rms = 5.4-11.9 nm, were calculated and found to depend on the film thickness and post-deposition heat treatment.The spectral dependence of the absorption coefficient was determined from transmission spectra, in the range 300-1400 nm.The values of optical bandgap were calculated from the absorption spectra, E_g = 2.6-2.7 eV.The effect of the deposition conditions and post-deposition heat treatment on the structural and optical characteristics was investigated.     

Size dependence of non-linear optical properties of SiO2 thin films containing InP nanocrystals

SiO₂ composite thin films containing InP nanocrystals were fabricated by radio-frequency magnetron co-sputtering technique. The microstructure of the composite thin films was characterized by X-ray diffraction and Raman spectrum. The optical absorption band edges exhibit marked blueshift with respect to bulk InP due to strong quantum confinement effect. Non-linear optical absorption and non-linear optical refraction were studied by a Z-scan technique using a single Gaussian beam of a He-Ne laser (632.8 nm). We observed the saturation absorption and two-photon absorption in the composite films. An enhanced third-order non-linear optical absorption coefficient and non-linear optical refractive index were achieved in the composite films. The nonlinear optical properties of the films display the dependence on InP nanocrystals size. Received: 27 June 2000 / Accepted: 27 June 2000 / Published online: 13 September 2000     

Ellipsometry study of thin metallic films under constraint by the size effect

Received: 9 July 1997/Accepted: 17 October 1997     

Controlled synthesis and relationship between luminescent properties and shape/crystal structure of Zn2SiO4:MN phosphor

Mn-doped Zn₂SiO₄ phosphors with different morphology and crystal structure, which show different luminescence and photoluminescence intensity, were synthesized via a low-temperature hydrothermal route without further calcining treatment. As-synthesized zinc silicate nanostructures show green or yellow luminescence depending on their different crystal structure obtained under different preparation conditions. The yellow peak occurring at 575 nm comes from the β-phase zinc silicate, while the green peak centering at 525 nm results from the usual α-phase zinc silicate. From photoluminescence spectra, it is found that Zn₂SiO₄ nanorods have higher photoluminescence intensity than Zn₂SiO₄ nanoparticles. It can be ascribed to reduced surface-damaged region and high crystallinity of nanorods.     

Transport of microscopic objects using asymmetric transverse optical gradient force

We report an efficient technique based on an optical tweezers setup for optically controlled transport of microscopic objects. The technique makes use of an elliptically profiled trap beam that has an asymmetric intensity distribution about the center of its long axis. Microscopic objects pulled into the trap from the side having the larger intensity gradient become accelerated along the major axis of the focus and are ejected from the lower-stiffness end. The speed of transport is determined by the laser-beam power and the degree of asymmetry in the intensity profile. The approach could be used to simultaneously trap and transport hundreds of particles, varying in sizes from sub-micrometer to a few micrometers. Further, transport of red blood cells using this method is demonstrated.     

The characterization of plasma-polymerized C60 thin films

Plasma-polymerized C₆₀ thin films were investigated in the form of a field effect transistor (FET) structure. In the FET device, the C₆₀ polymer acts as a p-type semiconductor, whereas C₆₀ is an n-type semiconductor. Its conduction mechanism can be described as due to variable range hopping. As a sensing device, the C₆₀ polymer can behave as a gas sensor for electrophoric gases and can also be operated as a photo-sensing device in air. Received: 21 April 2001 / Accepted: 23 July 2001 / Published online: 2 October 2001     

Synthesis and luminescent properties of two Schiff-base boron complexes

Schiff bases N,N′-o-phenylenebis (salicylideneimine) (H₂L¹), N,N′-p-phenylenebis (salicylideneimine) (H₂L²) and their corresponding boron complexes (BF₂)₂L¹, (BF₂)₂L² were synthesized, respectively. The two boron complexes have been characterized by ¹H NMR, mass spectrometry and elemental analysis, while the luminescent properties of them were investigated with UV-VIS spectroscopy and photoluminescence spectroscopy. Then the three-layer devices [ITO/NPB (60 nm)/(BF₂)₂L¹ (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device I) and [ITO/NPB (60 nm)/(BF₂)₂L² (50 nm)/Alq3 (20 nm)/LiF (1 nm)/Al (200 nm)] (device II) were fabricated by vacuum deposition. These two devices both exhibited blue green emission at 500 nm, but showed different luminances and efficiencies.     

Chemical bath-deposited ZnS thin films: Preparation and characterization

Chemical bath deposition of ZnS thin films from NH₃/SC(NH₂)₂/ZnSO₄ solutions has been studied. The effect of various process parameters on the growth and the film quality are presented. The influence on the growth rate of solution composition and the structural, optical properties of the ZnS thin films deposited by this method have been studied. The XRF analysis confirmed that volume of oxygen of the as-deposited film is very high. The XRD analysis of as-deposited films shows that the films are cubic ZnS structure. The XRD analysis of annealed films shows the annealed films are cubic ZnS and ZnO mixture structure. Those results confirmed that the as-deposited films have amorphous Zn(OH)₂. SEM studies of the ZnS thin films grown on various growth phases show that ZnS film formed in the none-film phase is discontinuous. ZnS film formed in quasi-linear phase shows a compact and a granular structure with the grain size about 100 nm. There are adsorbed particles on films formed in the saturation phase. Transmission measurement shows that an optical transmittance is about 90% when the wavelength over 500 nm. The band gap (E_g) value of the deposited film is about 3.51 eV.     

Structural and optical properties of thin films porous amorphous silicon carbide formed by Ag-assisted photochemical etching

In this work, we present the formation of porous layers on hydrogenated amorphous SiC (a-SiC: H) by Ag-assisted photochemical etching using HF/K₂S₂O₈ solution under UV illumination at 254 nm wavelength. The amorphous films a-SiC: H were elaborated by d.c. magnetron sputtering using a hot pressed polycrystalline 6H-SiC target. Because of the high resistivity of the SiC layer, around 1.6 MΩ cm and in order to facilitate the chemical etching, a thin metallic film of high purity silver (Ag) has been deposited under vacuum onto the thin a-SiC: H layer. The etched surface was characterized by scanning electron microscopy, secondary ion mass spectroscopy, infrared spectroscopy and photoluminescence. The results show that the morphology of etched a-SiC: H surface evolves with etching time. For an etching time of 20 min the surface presents a hemispherical crater, indicating that the porous SiC layer is perforated. Photoluminescence characterization of etched a-SiC: H samples for 20 min shows a high and an intense blue PL, whereas it has been shown that the PL decreases for higher etching time. Finally, a dissolution mechanism of the silicon carbide in 1HF/1K₂S₂O₈ solution has been proposed.     

Cathodoluminescence from nanocrystalline silicon films and porous silicon

Received: 4 May 1998 / Accepted: 30 October 1998     

Voltage-controlled electroluminescence from SiO2 films containing Ge nanocrystals and its mechanism

Luminescent SiO₂ films containing Ge nanocrystals are fabricated by using Ge ion implantation, and metal–oxide–semiconductor structures employing these films as the active layers show yellow electroluminescence (EL) under both forward and reverse biases. The EL spectra are strongly dependent on the applied voltage, but slightly on the mean size of Ge nanocrystals. When the forward bias increases towards 30 V, the EL spectral peak shifts from 590 nm to 485 nm. It is assumed that the EL originates from the recombination of injected electrons and holes in Ge nanocrystals near the Si/SiO₂ interface, or through luminescent centers in the SiO₂ matrix near the SiO₂/metal interface. The mismatch of the injection amounts between holes and electrons results in the low EL efficiency. Received: 28 February 2000 / Accepted: 28 March 2000 / Published online: 5 July 2000     

The analysis of thermoluminescent glow peaks of copper doped ZnS thin films after β-irradiation

In the given study, the thermoluminescence (TL) properties of copper (Cu)-doped ZnS thin films were investigated after β-irradiation at room temperature (RT). It was observed that the glow curve of this material has two broad TL peaks, in which one of them was centered at about 110 °C and the other at about 170 °C for a heating rate of 1 °C s⁻¹ in the temperature range from RT to 350 °C. The additive dose (AD), T_m(E_a)−T_stop, repeated initial rise (RIR), variable heating rate (VHR) and computerized glow curve deconvolution (CGCD) methods were used to analyze its glow curves. These methods indicated that the glow curve of this material is the superposition of a number of first- and general-order glow peaks, or at least due to the distribution of traps. The dose responses and fading process of both peaks were also examined, and it was observed that the dose responses of both peaks have similar pattern. First they follow a good linearity with different slopes and then saturate at approximately same dose level (2 kGy). The low-temperature broad peak nearly disappeared after 1 week storage in the dark at RT. On the other hand, the intensity of the high-temperature broad peak was approximately reduced to 50% of its original value. The TL emission spectrum of this material has two main emission bands, namely, the blue and green bands. The first glow peak emits predominantly in blue region, whereas the second glow peak in the green region.     

Optical and non-linear optical properties of vanadium oxide phthalocyanine films

The optical and non-linear optical properties of peripheral-substituted vanadium oxide phthalocyanine (VOPc) film and substituted VOPc/polymer composite film were investigated using stationary and transient spectroscopy techniques. The absorption Q band of the VOPc/polymer composite film shows a red shift relative to that of the peripheral-substituted VOPc film, revealing the monomeric characteristics of VOPc molecules. Effective quenching of PL emission was observed for the VOPc/polymer composite film and could be assigned to the efficient VOPc–polymer interaction. From pump-probe and optical Kerr effect (OKE) measurements, two decay components were obtained by fitting the transients for both VOPc films. The fast component, in a femtosecond time domain, originates from the electron–phonon interaction, and the difference in their slow decay is an indication of an efficient ISC process in the VOPc/polymer composite film. The third-order non-linear optical susceptibilities of these films were determined to be in the order of 10^-11 esu. Received: 25 October 2001 / Revised version: 8 January 2002 / Published online: 7 February 2002     

Investigation of charge carrier mobility in 5,6,11,12-tetraphenylnapthacene (rubrene) and coumarin 6 doped Alq3 films

The doping effect on charge carrier mobility in tris (8-hydroxyquinolinato) aluminum (Alq₃) was studied by time-of-flight (TOF) measurements. The polar dopant, coumarin 6 (C-6) and extensive π conjugated dopant, 5,6,11,12-tetraphenylnaphthacene (rubrene) were used for this study. The co-doped of rubrene (Rb) with C-6 into Alq₃ improved the carrier mobility compared to the single doped Alq₃:C-6 film. The carrier mobility in single doped Alq₃:C-6 film did not follow the linear relationship of Poole-Frenkel (PF) model with applied electric field. The mobility was in agreement with the PF model at two different ranges of electric fields (F) separated by a critical field . The mobility in co-doped Alq₃:(Rb:C-6) film followed the linear relationship with the PF model. The energetic disorder was found as ∼0.32 eV in co-doped films. It was ∼0.55 and ∼0.27 eV before and after the critical field in Alq₃:C-6 film. The values of positional disorders in co-doped films were estimated as ∼1.8 and it was ∼2 in Alq₃:C-6 film at . The organic light emitting diode performance of the co-doped film was improved compared to single doped film. The luminescence efficiency was improved tremendously to ∼6  Cd/A in co-doped device at 45 mA/cm² current compared to Alq₃:C-6 film device of ∼1  Cd/A.     

Crystallographic and luminescent characterizations of blue-emitting BaAl2S4 : Eu electroluminescent thin films

We characterized the crystallization and luminescence of blue-emitting BaAl₂S₄ : Eu electroluminescent thin films, prepared using switching electron-beam evaporation with two targets. From the photoluminescence intensity and decay profile of the activated Eu²⁺ ions in the BaAl₂S₄ : Eu, we found that the optimum annealing conditions for preparing highly luminescent thin films are a temperature of around 900°C and an annealing time of 2 min. We analyzed the crystalline properties using cross-sectional transmission electron microscope images. Evaluation of the cathodoluminescence spectra in the cross-sections showed that the BaAl₂S₄ : Eu emitting layer was luminously inhomogeneous on the depth of the layer and that the main luminescent area was near the surface of the emitting layer. We discuss here the relationship between the crystalline and luminescent properties.     

Influence of substrate temperature on electrical and optical properties of p-type semitransparent conductive nickel oxide thin films deposited by radio frequency sputtering

Nickel oxide thin films were deposited on fused silica and Si(1 0 0) substrates at different substrate temperatures ranging from room temperature to 400 °C using radio frequency reactive magnetron sputtering from a Ni metal target in a mixture of O₂ and Ar. With the increase of substrate temperature, nickel oxide films deposited on the Si substrates exhibit transition from amorphous to poly-crystalline structures with different preferred orientations of NiO(2 0 0) and (1 1 1). The films deposited at higher temperature exhibit higher Ni²⁺/Ni³⁺ ratio. With substrate temperature increasing from room temperature to 400 °C, the electrical resistivities of nickel oxide films increase from (2.8 ± 0.1) × 10⁻² to (8.7 ± 0.1) Ω cm, and the optical band-gap energies increase from 3.65 to 3.88 eV. A p-nickel oxide/n-zinc oxide heterojunction was fabricated to confirm the p-type conduction of nickel oxide thin film, which exhibited a steadily rectifying behavior.     

Reversible and athermal photo-vitrification of As50Se50 thin films deposited onto silicon wafer and glass substrates

Photo-vitrification of As₅₀Se₅₀ thin films deposited onto silicon wafer and glass substrates has been studied using X-ray diffraction, far-infrared, and differential infrared spectroscopies. The optical study of this photo-amorphization effect has been carried out by two different methods enabling the determination of the average thickness and refractive index of a wedge-shaped thin film. The refractive-index behaviour of the as-evaporated, crystallized, and photo-vitrified As₅₀Se₅₀ films is analyzed within the single-oscillator approach. The optical-absorption edge is described using the non-direct transition model, and the optical energy gap is calculated. In the course of the vitrification of an As₅₀Se₅₀ thin film deposited on a silicon substrate the photo-oxidation of the film has been additionally detected and arsenic trioxide micro-crystals were formed on the surface of the film. Such oxidation has not been observed with As₅₀Se₅₀ films deposited on glass substrates, which demonstrates that the photo-vitrification phenomenon depends also on the type of substrate. Finally, it is concluded from the optical study that a reversible photo-darkening effect accompanies the photo-induced vitrification phenomenon. Received: 3 August 1998 / Accepted: 13 January 1999 / Published online: 7 April 1999     

On thickness dependence of electrical and optical properties of Te thin films

Received: 1 July 1997/Accepted: 6 August 1997