Crystallization process and electro-optical properties of In2O3 and ITO thin films

Amorphous indium oxide (In₂O₃) and 10-wt% SnO₂ doped In₂O₃ (ITO) thin films were prepared by pulsed-laser deposition. These films were crystallized upon heating in vacuum at an effective heating rate of 0.00847 °C/s, while the evolution of the structure was observed by in situ X-ray diffraction measurements. Fast crystallization of the films is observed in the temperature ranges 165–210 °C and 185–230 °C for the In₂O₃ and ITO films, respectively. The crystallization kinetics is described by a reaction equation, with activation energies of 2.31 ± 0.06 eV and 2.41 eV and order of reactions of 0.75 ± 0.07 and 0.75 for the In₂O₃ and ITO films, respectively. The structures of the films observed here during heating are compared with those obtained upon film growth at different temperatures. The resistivity of the films depends on the evolution of the structure, the oxygen content and the activation of tin dopants in the films. A low resistivity of 5.5 × 10⁻⁴ Ω cm was obtained for the In₂O₃ and ITO films at room temperature, after annealing to 250 °C the resistivity of the ITO film reduces to 1.2 × 10⁻⁴ Ω cm.     

Structural and electrical properties of RuO2 thin films prepared by rf-magnetron sputtering and annealing at different temperatures

Conductive ruthenium oxide (RuO₂) thin films have been deposited at different substrate temperatures on various substrates by radio-frequency (rf) magnetron sputtering and were later annealed at different temperatures. The thickness of the films ranges from 50 to 700 nm. Films deposited at higher temperatures show larger grain size (about 140 nm) with (200) preferred orientation. Films deposited at lower substrate temperature have smaller grains (about 55 nm) with (110) preferred orientation. The electrical resistivity decreases slightly with increasing film thickness but is more influenced by the deposition and annealing temperature. Maximum resistivity is 861 μΩ cm, observed for films deposited at room temperature on glass substrates. Minimum resistivity is 40 μΩ cm observed for a thin film (50 nm) deposited at 540°C on a quartz substrate. Micro-Raman investigations indicate that strain-free well-crystallized thin films are deposited on oxidized Si substrates.     

Preparation of titanium-dioxide films by heating titanium/silicon-dioxide structures on silicon in oxygen

 When titanium/silicon-dioxide (Ti/SiO₂) structures prepared by depositing titanium (Ti) on thermally oxidized silicon in vacuum were heated to temperatures of 800–1000°C in flowing oxygen gas, silicon surfaces were covered with a mixture films containing preferentially (110)-oriented Ti0₂ instead of the SiO₂ films. The thickness of the mixture films could be determined by that of the deposited Ti films. Titanium silicide grew only in the region near between the grown mixture film and the silicon substrate. The dielectric constants of the grown mixture films increased exponentially with increasing oxidation temperature and increased slowly with increasing the Ti film thickness, while the breakdown field strength increased slowly with increasing oxidation temperature and increased exponentially with increasing the Ti film thickness. The oxide films prepared at 1000°C had dielectric constants of (15–25)ɛ_o resistivities of 10¹⁰–10¹¹ Ω cm, and breakdown field strengths of about 10⁶ V/cm. Received: 10 February 1998 / Accepted: 10 March 1998     

Grain growth of copper films prepared by chemical vapour deposition

Copper films having thickness 600 nm were prepared on TiN using chemical vapour deposition (CVD). The deposited films were annealed at various temperatures (350–550°C) in Ar and H₂(10%)-Ar ambients. The changes in the grain size of the films upon annealing were investigated. Annealing in an H₂(10%)-Ar ambient produced normal grain growth; annealing in an Ar ambient caused grain growth to stop at 550°C. The grain size followed a monomodal distribution and the mean size increased in proportion to the square root of the annealing time, indicating the curvature of the grain is the main driving force for grain growth. Upon annealing at 450°C for 30 min in an H₂(10%)-Ar ambient, the average grain size of the film increased from 122 nm to 219 nm, and the resistivity decreased from 2.35 μΩ cm to 2.12 μΩ cm at a film thickness of 600 nm. This revised version was published online in July 2006 with corrections to the Cover Date.     

The effect of post-annealing under CdCl<Subscript>2</Subscript> atmosphere on the properties of ITO thin films deposited by DC magnetron sputtering

Indium tin oxide (ITO) films deposited by DC magnetron sputtering were annealed under CdCl₂ atmosphere at different temperatures. The effects of CdCl₂ heat-treatment on the structural, electrical and optical properties of the films were investigated. The X-ray diffraction measurement proves the annealing results in a change of preferred orientation from (400) to (222). It is found the resistivity increases from 1.49 × 10⁻⁴ Ω cm of the as-deposited film to 6.82 × 10⁻⁴ Ω cm of the film annealed at 420 °C. The optical energy gap for the film varies from 3.97 to 3.89 eV. It is also found that the CdCl₂ heat-treatment results in narrowing the energy gap of ITO film.     

Effect of deposition conditions on the InP thin films prepared by spray pyrolysis method

InP thin films were prepared by spray pyrolysis technique using aqueous solutions of InCl₃ and Na₂HPO₄, which were atomized with compressed air as carrier gas. The InP thin films were obtained on glass substrates. Thin layers of InP have been grown at various substrate temperatures in the range of 450–525°C. The structural properties have been determined by using X-ray diffraction (XRD). The changes observed in the structural phases during the film formation in dependence of growth temperatures are reported and discussed. Optical properties, such as transmission and the band gap have been analyzed. An analysis of the deduced spectral absorption of the deposited films revealed an optical direct band gap energy of 1.34–1.52 eV for InP thin films. The InP films produced at a substrate temperature 500°C showed a low electrical resistivity of 8.12 × 10³ Ω cm, a carrier concentration of 11.2 × 10²¹ cm⁻³, and a carrier mobility of 51.55 cm²/Vs at room temperature.     

Structure and electrical properties of CuAlO<Subscript>2</Subscript> thin films derived by sol–gel processing

CuAlO₂ (CAO) thin films were prepared on quartz glass substrates by sol–gel spin-coating method. The effects of annealing temperatures, concentrations of sols and Al/Cu atomic ratios on structure, morphology and electrical properties have been investigated. It was found that CAO film with an Al/Cu atomic ratio of 0.8 approximately and the total metallic ion concentration of 0.7 M after heat treatment at 750 °C for 3 h in argon gas flow of 450 mL/min exhibited the lowest room temperature resistivity of 13.5 Ωcm.     

Influence of Li<Superscript>+</Superscript> dopants on the properties of the ZnO piezoelectric films

ZnO piezoelectric films with the preferred 002-orientation were prepared by sol-gel method. The annealing temperature was 600^∘C and the resistivity of the ZnO film was 1 × 10⁶ Ω ⋅ cm. Li₂CO₃ and LiCl were added respectively into ZnO precursor as source of Li⁺-ion. The molar ratio of [Li⁺]/[Zn^{2 +}] was 0.05. It is observed that the annealing temperature for forming preferred 002-orientation of ZnO films decreases from 660 to 550^∘ C after Li₂CO₃ being doped. When Li₂CO₃ and LiCl are doped, the resistivity of ZnO films increases to 10⁸Ω ⋅ cm and 10⁹Ω ⋅ cm, respectively, with an annealing temperature of 550^∘ C. When annealing temperature is 600^∘ C, the resistivity of the ZnO film with LiCl dopant increases to 10⁷Ω cm. The influence mechanism of the two dopants on the properties of the ZnO films is analyzed.     

Effect of substrate temperature on structural, optical and electrical properties of ZnO thin films deposited by pulsed laser deposition

ZnO thin films were grown by the pulse laser deposition (PLD) method using Si (100) substrates at various substrate temperatures. The influence of the substrate temperature on the structural, optical, and electrical properties of the ZnO thin films was investigated. All of the thin films showed c-axis growth perpendicular to the substrate surface. At a substrate temperature of 500 °C, the ZnO thin film showed the highest (002) peak with a full width at half maximum (FWHM) of 0.39°. The X-ray Photoelectron Spectroscopy (XPS) study showed that Zn was in excess irrespective of the substrate temperature and that the thin film had a nearly stoichiometrical composition at a substrate temperature of 500 °C. The photoluminescence (PL) investigation showed that the narrowest UV FWHM of 15.8 nm and the largest ratio of the UV peak to the deep-level peak of 32.9 were observed at 500 °C. Hall effect measurement systems provided information about the carrier concentration, mobility and resistivity. At a substrate temperature of 500 °C, the Hall mobility was the value of 37.4 cm²/Vs with carrier concentration of 1.36 × 10¹⁸ cm⁻³ and resistivity of 2.08 × 10⁻¹ Ω cm.     

Dependence of the electrical and optical properties of sputter-deposited ZnO:Ga films on the annealing temperature,time, and atmosphere

Effects of annealing process parameters such as annealing temperature, time, and atmosphere on the electrical resistivity and transmittance properties of Ga-doped ZnO (ZnO:Ga) thin films deposited on glass by rf magnetron sputtering were investigated. The electrical resistivity of a ZnO:Ga thin film is effectively decreased with increasing annealing temperature and time in a reducing atmosphere such as N₂ + 5%H₂. This is attributed to passivation of grain boundaries and zinc ions by hydrogen atoms resulting in increases in carrier concentration and mobility. Also the resistivity of 4.9 × 10⁻⁴Ω cm was obtained by annealing at 200°C for 15 h in the same atmosphere, which is not bad for a transparent conductor for solar cell applications. However, annealing at a temperature higher than 400°C is less effective. The lowest resistivity of 2.3 × 10⁻⁴Ω cm was obtained by annealing at 400°C for 1 h in an N₂ + 5%H₂ atmosphere. The optical transmittance of the ZnO:Ga film is improved by annealing regardless of the annealing atmosphere. Annealing in N₂ + 5%H₂ atmosphere widens the optical band gap, while annealing in an O₂ atmosphere makes the band gap narrower, which can be explained as a blue shift phenomenon.     

Ellipsometric studies of microscopic surface roughness of CdS thin films

Analysis of changes in surface roughness of CdS thin films with preparation temperature was carried out using variable angle spectroscopic ellipsometry (VASE). The films studied were prepared by spray pyrolysis technique, in the substrate temperature range 200–360°C. The VASE measurements were carried out in the visible region below the band gap (E _g=2·4eV) of CdS so as to reduce absorption by the film. The thickness of the films was in the range 500–600 nm. Bruggeman’s effective medium theory was used for analysis of the surface roughness of the film. The roughness of the film had a high value (∼ 65 nm) for films prepared at low temperature (200°C) and decreased with increase in substrate temperature. This reached minimum value (∼ 27 nm) in the temperature range 280–300°C. Thereafter roughness increased slowly with temperature. The growth rate of the films was calculated for different temperature ranges. It was found that the deposition rate decreases with the increase in substrate temperature and have an optimum value at 300°C. Above this temperature deposition rate decreased sharply. The scanning electron micrograph (SEM) of the film also showed that the film prepared at 280–300°C had very smooth surface texture.     

Characterization of rubrene polycrystalline thin film transistors fabricated using various heat-treatment conditions

We observed the crystal structure changes of rubrene (5,6,11,12-tetraphenylnaphthacene) polycrystal thin films on SiO₂/Si(100) substrates at various heat-treatment temperatures by X-ray diffraction, and a near-field microwave microprobe technique. An amorphous rubrene thin film was initially observed at heat-treatment temperature of 35 °C. After the treatment with in-situ vacuum post-annealing at 80 °C for 22 h, the rubrene thin film was transformed from the amorphous phase into a crystalline phase of orthorhombic structure. We could obtain a higher field effect mobility of 0.047 cm²/V·s and lower threshold voltage of − 4 V for the following heat-treatment process: pre-annealing at 80 °C, cooling at 40 °C, and post-annealing at 80 °C for 22 h.     

Synthesis,characterization and gas sensing performance of SnO<Subscript>2</Subscript> thin films prepared by spray pyrolysis

In this work, SnO₂ thin films were deposited onto alumina substrates at 350°C by spray pyrolysis technique. The films were studied after annealing in air at temperatures 550°C, 750°C and 950°C for 30 min. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical absorption spectroscopy technique. The grain size was observed to increase with the increase in annealing temperature. Absorbance spectra were taken to examine the optical properties and bandgap energy was observed to decrease with the increase in annealing temperature. These films were tested in various gases at different operating temperatures ranging from 50–450°C. The film showed maximum sensitivity to H ₂S gas. The H₂S sensing properties of the SnO₂ films were investigated with different annealing temperatures and H ₂S gas concentrations. It was found that the annealing temperature significantly affects the sensitivity of the SnO₂ to the H ₂S. The sensitivity was found to be maximum for the film annealed at temperature 950°C at an operating temperature of 100°C. The quick response and fast recovery are the main features of this film. The effect of annealing temperature on the optical, structural, morphological and gas sensing properties of the films were studied and discussed.     

Properties of Nb-doped ZnO transparent conductive thin films deposited by rf magnetron sputtering using a high quality ceramic target

Nb-doped ZnO films with (002) orientation have been grown on glass substrates by rf magnetron sputtering followed by vacuum annealing at 400°C for 3 h. The microstructures and surface figures of the Nbdoped ZnO films were investigated with X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. And its optical and electrical properties were measured at room temperature using a four-point probe technique and 756-type spectrophotometer, respectively. X-ray diffraction (XRD) revealed that the films are highly textured along the c axis and perpendicular to the surface of the substrate. After annealing at 400°C for 180 min under vacuum, transmittance of about 90% in visible region for Nb doped ZnO films was confirmed by the optical transmission spectra, and the low resistivity of 5·47 × 10⁻³ Ω·cm was obtained.     

Influence of the substrate temperature on the optical and electrical properties of Ga-doped ZnO thin films fabricated by pulsed laser deposition

Ga-doped (5 wt%) zinc oxide (GZO) thin films were fabricated on corning 1737 substrates at a fixed oxygen pressure of 200 mTorr at various substrate temperatures (100–300 °C) by using pulsed laser deposition (PLD) in order to investigate the microstructure, optical, and electrical properties of the GZO thin films. It was observed that all the thin films exhibit c-axis orientation and exhibit only a (002) diffraction peak. The GZO thin film, which was fabricated at 200 mTorr and 300 °C, showed the highest (002) orientation, and the full width at half maximum (FWHM) of the (002) diffraction peak was 0.38°. The position of the XRD peak shifted to a higher angle with increase in the substrate temperature. The optical transmittance in the visible region was greater than 85%. The Burstein-Moss effect, which causes a shift toward a high photon energy level, was observed. The electrical property indicated that the highest carrier concentration (2.33 × 10²¹ cm⁻³) and the lowest resistivity (3.72 × 10⁻⁴ Ωcm) were obtained in the GZO thin film fabricated at 200 mTorr and 300 °C.     

Structural characterization and frequency response of sol–gel derived Bi3/2MgNb3/2O7 thin films

The Bi_3/2MgNb_3/2O₇ (BMN) thin films were prepared via a modified sol–gel process on glass substrates at various post-annealing temperatures. The crystalline structure, morphology and frequency response have been investigated systematically. The X-ray diffraction results indicated that the BMN thin films had different orientations depending on post-annealing temperature. Thin films annealed above 650 °C presented well crystallized cubic pyrochlore structure with (222) orientation, and (400) preferentially oriented were observed when they were annealed below 600 °C. The surface morphology images of the BMN thin films revealed different grain size and grain size distribution, and the average grain size increased from 28.3 to 37.0 nm as the post-annealing temperature increasing. The low frequency dielectric properties of the BMN thin films were closely correlated with the (222) orientation, which was favorable to enhanced dielectric constant and tunability. The high-frequency optical measurements revealed an average transmittance (T _av ) varying between 76.6 and 82.2 % and band gap energy (E _g ) ranging from 3.40 to 3.44 as a function of the temperature and the crystallite size. Thin film annealed at 700 °C possessed the best crystallinity and highest (222) orientation, and showed the best electrical properties, with a dielectric constant of 105 at 1 MHz, dielectric tunability of 25.8 %, and an average optical transmittance of 82.2 % in the visible range (400–800 nm), making it promising for optical/electronic tunable devices applications.     

Studies on tin oxide films prepared by electron beam evaporation and spray pyrolysis methods

Transparent conducting tin oxide thin films have been prepared by electron beam evaporation and spray pyrolysis methods. Structural, optical and electrical properties were studied under different preparation conditions like substrate temperature, solution flow rate and rate of deposition. Resistivity of undoped evaporated films varied from 2.65 × 10⁻² ω-cm to 3.57 × 10⁻³ ω-cm in the temperature range 150–200°C. For undoped spray pyrolyzed films, the resistivity was observed to be in the range 1.2 × 10⁻¹ to 1.69 × 10⁻² ω-cm in the temperature range 250–370° C. Hall effect measurements indicated that the mobility as well as carrier concentration of evaporated films were greater than that of spray deposited films. The lowest resistivity for antimony doped tin oxide film was found to be 7.74 × 10⁻⁴ ω-cm, which was deposited at 350°C with 0.26 g of SbCl₃ and 4 g of SnCl₄ (SbCl₃/SnCl₄ = 0.065). Evaporated films were found to be amorphous in the temperature range up to 200°C, whereas spray pyrolyzed films prepared at substrate temperature of 300– 370°C were poly crystalline. The morphology of tin oxide films was studied using SEM.     

Preparation of highly transparent conductive Al-doped ZnO thin films and annealing effects on properties

Aluminum-doped ZnO (ZAO) thin films were deposited on fused quartz substrates by radio frequency sputtering in pure argon ambient at 450 °C. Effects of in situ annealing temperature and annealing atmosphere on microstructure, electrical and optical properties of ZAO films have been investigated. Results showed that as-grown film without annealing treatments attained lowest resistivity of 1.1 × 10⁻⁴Ω cm. And all films performed high average transmittance greater than 90% in visible region. X-Ray diffraction (XRD), photoluminescence (PL), X-ray photoelectron spectroscopy (XPS) were utilized to characterize the microstructure properties of films. XRD results indicated that as-grown film had higher crystalline quality and larger grain size than annealed films. Al atoms replaced Zn efficiently to provide electrons stable in all samples. PL spectra revealed that high annealing temperature and oxygen atmosphere would generate more Zn vacancy (V_Zn) and oxide antisite defect (O_Zn), respectively and composition content results from XPS provided supports to this.     

Growth and characterizations of dual ion beam sputtered CIGS thin films for photovoltaic applications

The growth of CIGS thin films on soda-lime glass substrates at different substrate temperatures by dual ion beam sputtering system in a single-step route from a single quaternary sputtering target with the composition of Cu (In_0.70 Ga_0.30) Se₂ was reported. The effects of the substrate temperature on structural, optical, morphological and electrical properties of CIGS films were investigated. Stoichiometry of one such film was investigated by X-ray photoelectron spectroscopy. All CIGS films had demonstrated a strong (112) orientation located at 2θ ~26.70^o, which indicated the chalcopyrite structure of films. The value of full-width at half-maximum of (112) peak was reduced from 0.58° to 0.19° and crystallite size was enlarged from 14.98 to 43.05 nm as growth temperature was increased from 100 to 400 °C. However, atomic force microscope results showed a smooth and uniform surface at lower growth temperature and the surface roughness was observed to increase with increasing growth temperature. Hall measurements exhibited the minimum film resistivity of 0.09 Ω cm with a hole concentration of 2.42 × 10¹⁸ cm^?3 and mobility of 28.60 cm² V^?1 s^?1 for CIGS film grown at 100 °C. Film absorption coefficient was found to enhance nominally from 1 × 10⁵ to 2.3 × 10⁵ cm^?1 with increasing growth temperature from 100 to 400 °C.     

Characterization of poly(vinylidene fluoride-trifluoroethylene) 50/50 copolymer films as a gate dielectric

Thin films of poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) 50/50 copolymer were prepared by spin coating on p-Si substrate. Thermal behavior of the film was observed by measuring the film thickness with ellipsometry as a function of the temperature and abrupt volume expansion was observed at 130–150 °C. Capacitance-voltage (C-V) and current-voltage (I-V) behavior of the aluminum/P(VDF-TrFE)/p-Si MIS (metal-insulator-semiconductor) structures were studied and dielectric constant of the P(VDF-TrFE) film was measured to be about 15.3 at optimum condition. No hysteresis was observed in the C-V curve for films as deposited and annealed (70–200 °C). Films annealed at temperatures higher than the volume expansion temperature showed substantial surface roughness due to the crystallization. Flat band voltage (V_FB) of the MIS structure with as deposited films was about −0.3 V and increased up to −2.0 V with annealing. This suggested that positive charges were generated in the film. Electronic properties of the annealed P(VDF-TrFE) film at above melting temperature were degraded substantially with larger shift in flat band voltage, low dielectric constant and low breakdown voltage. Organic thin film transistor with pentacene active layer and P(VDF-TrFE) as a gate dielectric layer showed a mobility of 0.31 cm²/V·s and threshold voltage of −0.45 V.