HF sputtered indium oxide films doped with tin

Indium-tin-oxide films (ITO films) sputtered in Ar-atmosphere with and without addition of oxygen reveal an irreversible increase in conductivity during annealing in vacuum. This annealing process increases drastically the density of free electrons, while the Hall mobility changes only slightly. Below the annealing temperature the temperature dependence of the conductivity is reversible. In films with low density of free electrons, which behave like non-degenerated semiconductors, two activation energies for the mobility could be found. The irreversible changes, observed during annealing in the vacuum, are explained by diffusion of oxygen from the interior of the film to the surface, followed by desorption of the oxygen from the surface into the vacuum. The excess oxygen in the non-stoichiometric films plays the role of electron traps. The irreversible effects during annealing in the vacuum are partly reversible in the long run. If the annealed films are exposed to oxygen or air their conductivity decreases because of diffusion of oxygen from the surface into the film.     

Ellipsometry investigation of the effects of annealing temperature on the optical properties of indium tin oxide thin films studied by Drude-Lorentz model

Float glass substrates covered by high quality ITO thin films (Balzers) were subjected for an hour to single thermal treatments at different temperature between 100 °C and 600 °C. In order to study the electric and optical properties of both annealed and not annealed ITO-covered float glasses, ellipsometry, spectrophotometry, impedance analysis, and X-ray measurements were performed. Moreover, variable angle spectroscopic ellipsometry provides relevant information on the electronic and optical properties of the samples. ITO film is modeled as a dense lower layer and a surface roughness layer. The estimated optical density for ITO and the optical density of the surface roughness ITO layer increases with the annealing temperature. In the near-IR range, the extinction coefficient decreases while the maximum of the absorption in the near UV range shift towards low photon energy as the annealing temperature increases. Spectrophotometry was used to estimate the optical band-gap energy of the samples. The thermal annealing changes strongly the structural and optical properties of ITO thin films, because during the thermal processes, the ITO thin film absorbs oxygen from air. This oxygen absorption decreases the oxygen vacancies therefore the defect densities in the crystalline structure of the ITO thin films also decrease, as confirmed both by ellipsometry and X-ray measurements.     

Effects of laser irradiation energy density on the properties of pulsed laser deposited ITO thin films

The properties of indium tin oxide (ITO) thin films, deposited at room temperature by simultaneous pulsed laser deposition (PLD), and laser irradiation of the substrate are reported. The films were fabricated from different Sn-doped In₂O₃ pellets at an oxygen pressure of 10 mTorr. During growth, a laser beam with an energy density of 0, 40 or 70 mJ/cm² was directed at the middle part of the substrate, covering an area of ∼1 cm². The non-irradiated (0 mJ/cm²) films were amorphous; films irradiated with 40 mJ/cm² exhibited microcrystalline phases; and polycrystalline ITO films with a strong 〈111〉> preferred orientation was obtained for a laser irradiation density of 70 mJ/cm². The resistivity, carrier density, and Hall mobility of the ITO films were strongly dependent on the Sn doping concentration and the laser irradiation energy density. The smallest resistivity of ∼1×10^-4 Ω cm was achieved for a 5 wt % Sn doped ITO films grown with a substrate irradiation energy density of 70 mJ/cm². The carrier mobility diminished with increasing Sn doping concentration. Theoretical models show that the decrease in mobility with increasing Sn concentration is due to the scattering of electrons in the films by ionized centers. PACS 81.15.Fg; 73.61.-r; 73.50.-h     

Wavelet–fractal approach to surface characterization of nanocrystalline ITO thin films

In this study, indium tin oxide (ITO) thin films were prepared by electron beam deposition method on glass substrates at room temperature (RT). Surface morphology characterization of ITO thin films, before and after annealing at 500 °C, were investigated by analyzing the surface profile of atomic force microscopy (AFM) images using wavelet transform formalism. The wavelet coefficients related to the thin film surface profiles have been calculated, and then roughness exponent (α) of the films has been estimated using the scalegram method. The results reveal that the surface profiles of the films before and after annealing process have self-affine nature.     

非晶InGaZnO薄膜成分配比对透明性和迁移率的影响

利用固相反应法制备了富铟含量在不同成分配比下的高质量InGaZnO陶瓷靶材,采用脉冲激光沉积法,在基片温度为20℃、氧压为1Pa条件下,在石英玻璃衬底上生长了非晶InGaZnO薄膜,并对薄膜进行X射线衍射、透射吸收光谱、拉曼光谱与霍尔效应测试。通过对InGaZnO薄膜的测试表征,在较低温度条件下,铟含量较高的薄膜样品保持了非晶结构、可见光的高透明性和高电子迁移率,InGaZnO薄膜有望应用于电子器件。     

Chemical and structural analysis of low-temperature excimer-laser annealing in indium-tin oxide sol-gel films

We investigated the influence of excimer-laser annealing (ELA) on the electrical, chemical, and structural properties of indium–tin oxide (ITO) films prepared by a solution process. The ITO film was prepared by the sol-gel method and annealed by excimer-laser pulses with an energy density up to 240?mJ/cm². Hall measurements showed that the ELA substantially enhanced the electrical properties of the ITO films, including their resistivity, carrier density, and mobility, as increasing the laser energy density. In-depth x-ray photoelectron spectroscopy analysis of the chemical states in the film surface showed that the ELA reduced carbon species and promoted both an oxidation and crystallization. These changes were consistent with results of x-ray diffraction and transmission electron microscopy measurements, where expansions in the microcrystal growth were observed for higher laser energy density. We comprehensively understand that the chemical rearrangement and concomitant crystallization are the main factors for achieving the electrical properties during the ELA. These results suggest the potential of the ELA-treated sol-gel films for providing high-quality ITO films at low temperatures toward the flexible device applications.     

Development of conductive transparent indium tin oxide (ITO) thin films deposited by direct current (DC) magnetron sputtering for photon-STM applications

Highly conductive and transparent indium tin oxide (ITO) thin films, each with a thickness of 100 nm, were deposited on glass and Si(100) by direct current (DC) magnetron sputtering under an argon (Ar) atmosphere using an ITO target composed of 95% indium oxide and 5% tin oxide for photon-STM use. X-ray diffraction, STM observations, resistivity and transmission measurements were carried out to study the formation of the films at substrate temperatures between 40 and 400 °C and the effects of thermal annealing in air between 200 and 400 °C for between1 and 5 h. The film properties were highly dependent on deposition conditions and on post-deposition film treatment. The films deposited under an Ar atmosphere pressure of ∼1.7×10^-3 Torr by DC power sputtering (100 W) at substrate temperatures between 40 and 400 °C exhibited resistivities in the range 3.0–5.7×10^-5 Ω m and transmissions in the range 71–79%. After deposition and annealing in air at 300 °C for 1 h, the films showed resistivities in the range 2.9–4.0×10^-5 Ω m and transmissions in the range 78–81%. Resistivity and transmission measurements showed that in order to improve conductive and transparent properties, 2 h annealing in air at 300 °C was necessary. X-ray diffraction data supported the experimental measurements of resistivity and transmission on the studies of annealing time. The surface roughness and film uniformity improve with increasing substrate temperature. STM observations found the ITO films deposited at a substrate temperature of 325 °C, and up to 400 °C, had domains with crystalline structures. After deposition and annealing in air at 300 °C for 1 h the films still exhibited similar domains. However, after deposition at substrate temperatures from 40 °C to 300 °C, and annealing in air at 300 °C for 1 h, the films were shown to be amorphous. More importantly, the STM studies found that the ITO film surfaces were most likely to break after deposition at a substrate temperature of 325 °C and annealing in air at 300 °C for 2 or 3 h. Such findings give some inspiration to us in interpreting the effects of annealing on the improvement of conductive and transparent properties and on the transition of phases. In addition, correlations between the conductive/transparent properties and the phase transition, the annealing time and the phase transition, and the conductive/transparent properties and the annealing time have been investigated. Received: 10 July 2000 / Accepted: 27 October 2000 / Published online: 9 February 2001     

Characterization of gallium-doped CdS thin films grown by chemical bath deposition

Ga-doped CdS thin films, with different [Ga]/[Cd] ratios, were grown using chemical bath deposition. The effect of Ga-doping on optical properties and bandgap of CdS films is investigated. Resistivity, carrier density, and mobility of doped films were acquired using Hall effect measurements. Crystal structure as well as crystal quality and phase transition were determined using X-ray diffraction (XRD) and Micro-Raman spectroscopy. Film morphology was studied using scanning electron microscopy, while film chemistry and binding states were studied using X-ray photoelectron spectroscopy (XPS). A minimum bandgap of 2.26 eV was obtained at [Ga]/[Cd] ratio of 1.7 × 10⁻². XRD studies showed Ga³⁺ ions entering the lattice substitutionally at low concentration, and interstitially at high concentration. Phase transition, due to annealing, as well as induced lattice defects, due to doping, were detected by Micro-Raman spectroscopy. The highest carrier density and lowest resistivity were obtained at [Ga]/[Cd] ratio of 3.4 × 10⁻². XPS measurements detect an increase in sulfur deficiency in doped films.     

Stable p-ZnO thin films by oxygen control using reverse spray dynamics

Semiconducting ZnO thin films were deposited on glass substrates by a modified CVD method using reverse spray of the precursor solutions. The films were characterized by X-ray diffraction (XRD) and Hall effect measurements at room temperature. The results of XRD analysis revealed polycrystalline nature of the grown films with different crystallographic orientations. The type of conductivity and the carrier concentration as determined from Hall effect measurements were dependent on the deposition temperature and annealing conditions. Oxygen control at 220 °C produced p-ZnO film with high hole mobility (193 cm²/V s). The electrical conductivity was correlated to the stoichiometry of the grown films.     

Investigation of diffusion and crystallization processes in thin ITO films by temperature and time resolved grazing incidence X-ray diffractometry

Oxygen diffusion into metallic In/Sn films and crystallite growth of thin indium tin oxide (ITO) films were investigated by in situ high temperature grazing incidence X-ray diffractometry (HT-GIXRD) at temperatures ranging from 100 to 300 °C. The investigated films were deposited by dc magnetron sputtering from a metallic target at different oxygen flows and bias voltages. The deposition process influences not only the film properties but also the film reactions during the post-deposition annealing process.

The ITO formation is determined by two processes: the diffusion of oxygen into the metallic grains and a fast crystallization process. Kinetic parameters for both processes were derived. A model was developed which allows the determination of the diffusion coefficient D from the time dependence of the integral intensity of the ITO X-ray reflection. Diffusion coefficients as well as the activation energies are influenced by the bias voltage but not by the oxygen flow.

According to the Johnson–Mehl–Avrami theory, the crystallization can be described as a two-dimensional process.     

Highly transparent and conductive indium tin oxide thin films for solar cells grown by reactive thermal evaporation at low temperature

Transparent conductive tin-doped indium oxide (In₂O₃:Sn, ITO) thin films with various Sn-doping concentrations have been prepared using the low cost reactive thermal evaporation (RTE) technique at a low growth temperature of ~160 °C. The structural characteristics, optical and electrical properties of the ITO thin films were investigated. These polycrystalline ITO films exhibited preferential orientation along (222) plane and possessed low resistivities ranging from 3.51 to 5.71 × 10^?4 Ω cm. The decreased mobility was attributed to the scattering by ionized and neutral impurities at high doping concentrations. The optimized ITO thin film deposited with 6.0 wt% Sn-doping concentration exhibited a high average transparency of 87 % in the wavelength range of 380–900 nm and a low resistivity of 3.74 × 10^?4 Ω cm with a high Hall mobility of 47 cm² V^?1s^?1. A hydrogenated amorphous silicon and silicon–germanium (a-Si:H/a-SiGe:H) double-junction solar cell fabricated with the RTE-grown ITO electrodes presented a conversion efficiency of 10.51 %.     

Indium tin oxide thin films by bias magnetron rf sputtering for heterojunction solar cells application

In this investigation ITO thin films were prepared by bias magnetron rf sputtering technique at substrate temperature of 180 °C and low substrate-target distance for future a-Si:H/c-Si heterojunction (HJ) solar cells application. Microstructure, surface morphology, electrical and optical properties of these films were characterized and analyzed. The effects of ion bombardments on growing ITO films are well discussed. XRD analysis revealed a change in preferential orientation of polycrystalline structure from (2 2 2) to (4 0 0) plane with the increase of negative bias voltage. Textured surface were observed on AFM graphs of samples prepared at high negative bias. Hall measurements showed that the carrier density and Hall mobility of these ITO films are sensitive to the bias voltage applied. We attributed these effects to the sensitivity of energy of Ar⁺ ions bombarding on growing films to the applied bias voltage in our experiments. At last the figure of merit was calculated to evaluate the quality of ITO thin films, the results of which show that sample prepared at bias voltage of −75 V is good to be used in HJ cells application.     

The effect of electro-annealing on the electrical properties of ITO film on colorless polyimide substrate

The effect of different annealing methods on the sheet resistance of indium tin oxide (ITO) on polyimide (PI) substrate has been investigated. ITO thin films were prepared by RF magnetron sputtering in pure Ar gas and electro-annealing, this was carried out in the flow of an electric current at several temperatures between 100 and 180 °C in air. Electro- and thermal annealing were compared in order to confirm differences between the electrical, optical and microstructural properties of the ITO thin films. As electro-annealing induced the predominant growth of crystallites of ITO thin films along (4 0 0) plane, the sheet resistance of ITO films that were electro-annealed for 2 mA at 180 °C considerably decreased from 50 to 28 Ω/cm².     

Pulsed laser deposition of ZnO grown on glass substrates for realizing high-performance thin-film transistors

We report characterization of ZnO thin-film transistors (TFTs) on glass substrates fabricated by pulsed laser deposition (PLD). ZnO films were characterized by X-ray diffraction (XRD), atomic force microscopy and Hall effect measurements. The XRD results showed high c-axis-oriented ZnO(0002) diffraction corresponding to the wurtzite phase. Moreover, the crystallization and the electrical properties of ZnO thin films grown at room temperature are controllable by PLD growth conditions such as oxygen gas pressure. The ZnO films are very smooth, with a root-mean-square roughness of 1 nm. From the Hall effect measurements, we have succeeded in fabricating ZnO films on glass substrates with an electron mobility of 21.7 cm²/V s. By using the ZnO thin film grown by two-step PLD and a HfO₂ high-k gate insulator, a transconductance of 24.1 mS/mm, a drain current on/off ratio of 4.4×10⁶ and a subthreshold gate swing of 0.26 V/decade were obtained for the ZnO TFT.     

Electron scattering mechanisms in indium-tin-oxide thin films prepared at the various process conditions

The carrier concentrations and mobilities of indium-tin-oxide (ITO) thin films by DC magnetron sputtering at the various process conditions were measured by means of the Hall technique. The relationship between the carrier concentration and mobility showed two distinct features: (i) roughly up to the carrier concentration of 9.0 × 10²⁰/cm³, both the carrier concentration and mobility increased together; (ii) above the carrier concentration of 9.0 × 10²⁰/cm³, the carrier mobility decreased as the carrier concentration further increased. The distinct behavior of the carrier concentration and mobility was due to the transition of the dominant electron scattering mechanism. ITO thin film with a low degree of crystallinity was governed by the grain boundary scattering. However, the ionized impurity scattering was dominant in ITO thin film with a high carrier concentration over 9.0 × 10²⁰/cm³. The overall characterizations related to the carrier concentration and mobility were also performed using X-ray diffractometer, UV-vis-NIR spectrometer, scanning electron microscope, atomic force microscope.     

生长条件对脉冲激光沉积制备ZnO：Al薄膜光电性能的影响

本文研究了脉冲激光沉积(PLD)生长过程中, 铝掺量、氧压及衬底温度等实验参数对ZnO:Al(AZO)薄膜生长的影响, 并利用扫描电子显微镜、原子力显微镜、X射线衍射、霍尔效应、光透射光谱等实验手段对其透明导电性能进行了探讨. 变温霍尔效应和光透射测量表明, 当靶材中铝掺量大于0.5 wt%时, 所制备AZO薄膜中铝施主在80 K时已完全电离, 因Bernstein-Moss (BM) 效应其带隙变大, 均为重掺杂简并半导体. 进一步系统研究了氧压和衬底温度对AZO薄膜透明导电性能的影响, 实验发现当氧压为1 Pa, 衬底温度为200 ℃时, AZO 导电性能最好, 其霍尔迁移率为28.8 cm²/V·s, 薄膜电阻率最小可达2.7×10^-4 Ω·cm, 且在可见光范围内光透过率超过了85%. 氧压和温度的增加, 都会导致薄膜电阻率变大. 关键词： 脉冲激光沉积法 ZnO：Al薄膜 透光性 导电性     

Deposition and characterization of sputtered ZnO films

Zinc oxide thin films were deposited by radio frequency magnetron sputtering at room temperature using a metallic zinc target in a gas mixture of argon and oxygen. Plasma power, oxygen /argon gas ratio, gas pressure, and substrate temperature were varied, and an experimental design method was used to optimize these deposition parameters by considering their interdependence. Crystalline structures and film stresses were examined. Post-deposition rapid thermal annealing was also carried out to observe its effects on the film properties. Statistical analysis was then used to find the optimal sputtering conditions. Results indicated that plasma power and gas pressure have the largest effects on film crystallization and stress and that postdeposition annealing can be used to improve the quality of the film properties.     

Electrical, structural, and optical properties of ITO thin films prepared at room temperature by pulsed laser deposition

Indium tin oxide (ITO) thin films were prepared by pulsed laser deposition (PLD) on glass substrate at room temperature. Structural, optical, and electrical properties of these films were analyzed in order to investigate its dependence on oxygen pressure, and rapid thermal annealing (RTA) temperature. High quality ITO films with a low resistivity of 3.3 × 10⁻⁴ Ω cm and a transparency above 90% were able to be formed at an oxygen pressure of 2.0 Pa and an RTA temperature of 400 °C. A four-point probe method, X-ray diffraction (XRD), atomic force microscopy (AFM), and UV-NIR grating spectrometer are used to investigate the properties of ITO films.     

Morphology and photoluminescence study of electrodeposited ZnO films

ZnO films on ITO substrates and Au coated ITO substrates were fabricated by using electrodeposition technique. We carried out the experiments by adjusting the concentration of solution, potential, substrate, and temperature. The effect of temperature on the growth of the film has been examined. SEM images have shown that there are several kinds of grown competitions for the deposition of ZnO films, but three kinds of them are dominant. One is the discrete hexagonal column structure, the other is the pentagonal structure, and the third one is of well-oriented hexagonal columns with well-aligned structure. The explanation on the grown competition is discussed. ZnO hexagonal column structures with well-aligned and well-perpendicular to the surface were successfully obtained on Au/ITO substrate in aqueous solvent of electrolyte. Clearly the main columns in the film were obtained by increasing the temperature. Its photoluminescence (PL) study at low temperature exhibited the optical properties as wurtzite ZnO and indicated the existence of macrocrystalline ZnO. A better quality of ZnO columnar structures after annealing was demonstrated from PL analysis and discussion on the existence of 370 nm, 384 nm and 639 nm in the emission bands before and after annealing.     

Effect of process parameters on surface morphology and characterization of PE-ALD SnO2 thin films for gas sensing

Tin dioxide (SnO₂) thin films were deposited by plasma enhanced-atomic layer deposition (PE-ALD) on Si(1 0 0) substrate using dibutyl tin diacetate (DBTA) ((CH₃CO₂)₂Sn[(CH₂)₃-CH₃]₂) as precursor. The process parameters were optimized as a function of substrate temperature, source temperature and purging time. It is observed that the surface phenomenon of the thin films was changed with film thickness. Atomic force microscopy (AFM) images and X-ray diffraction (XRD) pattern were used to observe the texture and crystallanity of the films. The films deposited for 100, 200 and 400 cycles were characterized by XPS to determine the chemical bonding properties. XPS results reveal that the surface dominant oxygen species for 100, 200 and 400 cycles deposited films are O₂⁻, O⁻ and O²⁻, respectively. The 200 cycles film has exhibited highest concentration of oxygen (O⁻) species before and after annealing. Conductivity studies revel that this film has best adsorption strength to the oxygen ions forming on the surface. The sensor with 200 cycles SnO₂ thin film has shown highest sensitivity to CO gas than other films. A correlation between the characteristics of Sn3d_5/2 and O1s XPS spectra before and after annealing and the electrical behavior of the SnO₂ thin films is established.