Structural and electrical properties of sputtered indium-zinc oxide thin films

In this study, indium-zinc oxide (IZO) thin films have been prepared at a room temperature, 200 and 300 °C by radio frequency magnetron sputtering from a In₂O₃-12 wt.% ZnO sintered ceramic target, and their dependence of electrical and structural properties on the oxygen content in sputter gas, the substrate temperature and the post-heat treatment was investigated. X-ray diffraction measurements showed that amorphous IZO films were formed at room temperature (RT) regardless of oxygen content in sputter gas, and micro-crystalline and In₂O₃-oriented crystalline films were obtained at 200 and 300 °C, respectively. From the analysis on the electrical and the structural properties of annealed IZO films under Ar atmosphere at 200, 300, 400 and 500 °C, it was shown that oxygen content in sputter gas is a critical parameter that determines the local structure of amorphous IZO film, stability of amorphous phase as well as its eventual crystalline structure, which again decide the electrical properties of the IZO films. As-prepared amorphous IZO film deposited at RT gave specific resistivity as low as 4.48 × 10^− 4 Ω cm, and the highest mobility value amounting to 47 cm²/V s was obtained from amorphous IZO film which was deposited in 0.5% oxygen content in sputter gas and subsequently annealed at 400 °C in Ar atmosphere.     

A study of amorphous and crystalline phases in In2O3-10 wt.% ZnO thin films deposited by DC magnetron sputtering

We report on the processing, phase stability, and electronic transport properties of indium oxide (In₂O₃) doped with 10 wt.% zinc oxide (ZnO) deposited to a thickness of 100 nm using DC magnetron sputter deposition at room temperature and 350 °C. We compare the optimum oxygen content in the sputter gas for pure In₂O₃ and doped with (i) 10 wt.% ZnO and (ii) 9.8 wt.% SnO₂. Amorphous IZO films were annealed at 200 °C in air and N₂/H₂ and resistivity, Hall mobility, and carrier density along with molar volume change were monitored simultaneously as a function of time at temperature. We report that annealing the amorphous oxide in air at 200 °C does not lead to crystallization but does result in a 0.5% decrease in the amorphous phase molar volume and an associated drop in carrier density. Annealing in forming gas leads to an increase in carrier density and a small decrease in molar volume. We also report that when annealed in air at 500 °C, the amorphous IZO phase may crystallize either in the cubic bixbyite or in a recently observed rhombohedral phase.     

Temperature dependence of the microstructure and resistivity of indium zinc oxide films deposited by direct current magnetron reactive sputtering

Indium zinc oxide (IZO) films were deposited as a function of the deposition temperature using a sintered indium zinc oxide target (In₂O₃:ZnO = 90:10 wt.%) by direct current (DC) magnetron reactive sputtering method. The influence of the substrate temperature on the microstructure, surface roughness and electrical properties was studied. With increasing the temperature up to 200 °C, the characteristic properties of amorphous IZO films were improved and the specific resistivity was about 3.4 × 10^− 4 Ω cm. Change of structural properties according to the deposition temperature was also observed with X-ray diffraction patterns, transmission electron microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. IZO films deposited above 300 °C showed polycrystalline phases evolved on the amorphous IZO layer. Very flat surface roughness could be obtained at lower than 200 °C of the substrate temperature, while surface roughness of the films was increased due to the formation of grains over 300 °C. Consequently, high quality IZO films could be prepared by DC magnetron sputtering with O₂/Ar of 0.03 and deposition temperature in range of 150-200 °C; a specific resistivity of 3.4 × 10^− 4 Ω cm, and the values of peak to valley roughness and root-mean-square roughness are less than 4 nm and 0.5 nm, respectively.     

Study on In2O3-SnO2 transparent and conductive films prepared by d.c. sputtering using high density ceramic targets

The influence of SnO₂ concentration in the target on the film characteristics was studied in order to make the useful database for the device design when low discharge voltage sputtering method and a high density In₂O₃-SnO₂ ceramic targets were used. In the case of the films deposited on unheated substrate, X-ray diffraction profile showed amorphous structure. Minimum resistivity of 358 μΩ cm was obtained by In₂O₃ film with mobility of 40.1 cm² (V s)⁻¹ and carrier density of 4.35E+20 cm⁻³. With the increase of SnO₂ contents, resistivity of the films increased because of the decrease in both carrier density and mobility. Whereas, the films deposited on heated substrates showed polycrystalline structure. Resistivity was reduced, ranging from 5 to 20 wt.% SnO₂, and minimum resistivity of 136 μΩ cm was obtained at 15 wt.% with mobility of 40.5 cm² (V s)⁻¹ and carrier density of 1.13E+21 cm⁻³. Transmittance and reflectance of these films strongly depend on carrier density.     

Advantages of using amorphous indium zinc oxide films for window layer in Cu(In,Ga)Se2 solar cells

The advantages of using indium zinc oxide (IZO) films instead of conventional Ga-doped zinc oxide (ZnO:Ga) films for Cu(In,Ga)Se₂ (CIGS) solar cells are described. The electrical properties of IZO are independent of film thickness. IZO films have higher mobility (30-40 cm²/Vs) and lower resistivity (4-5 × 10^− 4 Ω cm) compared to ZnO:Ga films deposited without intentional heating, because the number of grain boundaries in amorphous IZO films is small. The properties of a CIGS solar cell using IZO at the window layer were better than those obtained using a conventional ZnO:Ga at the window layer; moreover, the properties tended to be independent of thickness. These results indicate that use of IZO as a transparent conducting oxide layer is expected to increase the efficiency of CIGS solar cells.     

Amorphous structure and electrical performance of low-temperature annealed amorphous indium zinc oxide transparent thin film transistors

The effect of low-temperature (200 °C) annealing on the threshold voltage, carrier density, and interface defect density of amorphous indium zinc oxide (a-IZO) thin film transistors (TFTs) is reported. Transmission electron microscopy and x-ray diffraction analysis show that the amorphous structure is retained after 1 h at 200 °C. The TFTs fabricated from as-deposited IZO operate in the depletion mode with on-off ratio of > 10⁶, sub-threshold slope (S) of ~ 1.5 V/decade, field effect mobility (μ_FE) of 18 ± 1.6 cm²/Vs, and threshold voltage (V_Th) of − 3 ± 0.7 V. Low-temperature annealing at 200 °C in air improves the on-current, decreases the sub-threshold slope (1.56 vs. 1.18 V/decade), and increases the field effect mobility (μ_FE) from 18.2 to 23.3 cm²/Vs but also results in a V_Th shift of − 15 ± 1.1 V. The carrier density in the channel of the as-deposited (4.3 × 10¹⁶ /cm³) and annealed at 200 °C (8.1 × 10¹⁷ /cm³) devices were estimated from test-TFT structures using the transmission line measurement methods to find channel resistivity at zero gate voltage and the TFT structures to estimate carrier mobility.     

Polycrystalline films of tungsten-doped indium oxide prepared by d.c. magnetron sputtering

Electrical and optical properties of polycrystalline films of W-doped indium oxide (IWO) were investigated. These films were deposited on glass substrate at 300 °C by d.c. magnetron sputtering using ceramic targets. The W-doping in the sputter-deposited indium oxide film effectively increased the carrier density and the mobility and decreased the resistivity. A minimum resistivity of 1.8 × 10^− 4 Ω cm was obtained at 3.3 at.% W-doping using the In₂O₃ ceramic targets containing 7.0 wt.% WO₃. The 2.2 at.% W-doped films obtained from the targets containing 5.0 wt.% WO₃, showed the high Hall mobility of 73 cm² V^− 1 s^− 1 and relatively low carrier density of 2.9 × 10²⁰ cm^− 3. Such properties resulted in novel characteristics of both low resistivity (3.0 × 10^− 4 Ω cm) and high transmittance in the near-infrared region.     

Structural, electrical and optical properties of zirconium-doped zinc oxide films prepared by radio frequency magnetron sputtering

Transparent and conducting zirconium-doped zinc oxide films have been prepared by radio frequency magnetron sputtering at room temperature. The ZrO₂ content in the target is varied from 0 to 10 wt.%. The films are polycrystalline with a hexagonal structure and a preferred orientation along the c axis. As the ZrO₂ content increases, the crystallinity and conductivity of the film are initially improved and then both show deterioration. Zr atoms mainly substitute Zn atoms when the ZrO₂ content are 3 and 5 wt.%, but tend to cluster into grain boundaries at higher contents. The lowest resistivity achieved is 2.07 × 10^− 3 Ω cm with the ZrO₂ content of 5 wt.% with a Hall mobility of 16 cm² V^− 1 s^− 1 and a carrier concentration of 1.95 × 10²⁰ cm^− 3. All the films present a high transmittance of above 90% in the visible range. The optical band gap depends on the carrier concentration, and the value is larger at higher carrier concentration.     

Improvement of bias stability of indium zinc oxide thin film transistors by the incorporation of hafnium fabricated by radio-frequency magnetron sputtering

We report on the fabrication and performance of amorphous oxide thin film transistors with indium zinc oxide (In₂O₃:ZnO = 1:1 mol%) and various ratios of hafnium-doped indium zinc oxide (IZO:HfO₂ = 2:0, 0.3, 0.7, and 1.1 mol%) deposited at the same deposition conditions for semiconductor channel layer. The carrier concentration (N_cp) of the HIZO films was further decreased from 7.08 × 10¹⁷ to 5.0 × 10¹⁶ cm^− 3. This indicates that Hf metal cations effectively suppress carrier generation due to the high electron negativity (1.3) of Hf. In addition, we compared bias instability of both devices after bias temperature stress (BTS) test under on-current state at V_DS of 10 V and I_DS of 3 μA at 60 °C for 420 min. It was found that the Hf metal cations could be effectively incorporated in the IZO thin films as a suppressor against both the oxygen deficiencies and the carrier generation in the ZnO-based system.     

Investigation on structural, electrical and optical properties of tungsten-doped tin oxide thin films

Tungsten-doped tin oxide (SnO₂:W) transparent conductive films were prepared on quartz substrates by pulsed plasma deposition method with a post-annealing. The structure, chemical states, electrical and optical properties of the films have been investigated with tungsten-doping content and annealing temperature. The lowest resistivity of 6.67 × 10^− 4 Ω cm was obtained, with carrier mobility of 65 cm² V^− 1 s^− 1 and carrier concentration of 1.44 × 10²⁰ cm^− 3 in 3 wt.% tungsten-doping films annealed at 800 °C in air. The average optical transmittance achieves 86% in the visible region, and approximately 85% in near-infrared region, with the optical band gap ranging from 4.05 eV to 4.22 eV.     

DC sputter deposition of amorphous indium-gallium-zinc-oxide (a-IGZO) films with H2O introduction

Amorphous indium-gallium-zinc-oxide (a-IGZO) films were deposited by dc magnetron sputtering with H₂O introduction and how the H₂O partial pressure (P_H2O) during the deposition affects the electrical properties of the films was investigated in detail. Resistivity of the a-IGZO films increased dramatically to over 2 × 10⁵ Ωcm with increasing P_H2O to 2.7 × 10^− 2 Pa while the hydrogen concentration in the films increased to 2.0 × 10²¹ cm^− 3. TFTs using a-IGZO channels deposited under P_H2O at 1.6-8.6 × 10^− 2 Pa exhibited a field-effect mobility of 1.4-3.0 cm²/Vs, subthreshold swing of 1.0-1.6 V/decade and on-off current ratio of 3.9 × 10⁷-1.0 × 10⁸.     

Deterioration and recovery in the resistivity of Al-doped ZnO films prepared by the plasma sputtering

A hot-cathode plasma sputtering technique was used for fabricating the highly transparent and conducting aluminum-doped zinc oxide (AZO) films on glass substrates from a disk-shaped AZO (Al₂O₃: 2 wt.%) target. Under particular conditions where the target voltage was V_T = −200 V and the plasma excitation pressure was P_S = 1.5 × 10⁻³ Torr, the lowest resistivity of 4.2 × 10⁻⁴ Ω cm was obtained at 400 nm, and this was associated with a carrier density of 8.7 × 10²⁰ cm⁻³ and a Hall mobility of 17 cm²/V s. From the annealing experiment of the AZO films in the oxygen and nitrogen gases of the atmospheric pressure it was revealed that both the oxygen vacancies and the grain boundaries in the polycrystalline AZO film played an important role in the electrical properties of the film.     

Transparent Ga and Zn co-doped In2O3 electrode prepared by co-sputtering of Ga:In2O3 and Zn:In2O3 targets at room temperature

This study examined the characteristics of Ga:In₂O₃ (IGO) co-sputtered Zn:In₂O₃ (IZO) films prepared by dual target direct current (DC) magnetron sputtering at room temperature in a pure Ar atmosphere for transparent electrodes in IGZO-based TFTs. Electrical, optical, structural and surface properties of Ga and Zn co-doped In₂O₃ (IGZO) electrodes were investigated as a function of IGO and IZO target DC power during the co-sputtering process. Unlike semiconducting InGaZnO₄ films, which were widely used as a channel layer in the oxide TFTs, the co-sputtered IGZO films showed a high transmittance (91.84%) and low resistivity (4.1 × 10^− 4 Ω cm) at optimized DC power of the IGO and IZO targets, due to low atomic percent of Ga and Zn elements. Furthermore, the IGO co-sputtered IZO films showed a very smooth and featureless surface and an amorphous structure regardless of the IGO and IZO DC power due to the room temperature sputtering process. This indicates that co-sputtered IGZO films are a promising S/D electrode in the IGZO-based TFTs due to their low resistivity, high transmittance and same elements with channel InGaZnO₄ layer.     

Uniformity of gallium doped zinc oxide thin film prepared by pulsed laser deposition

Recently, transparent conducting oxide thin films have attracted attention for the application to transparent conducting electrodes. In this work, we evaluated the uniformity of electrical, optical and structural properties for gallium doped zinc oxide thin films prepared on the 10 × 10 cm² silica glass substrate by pulsed laser deposition. The resistivity, carrier concentration, mobility, bonding state and atomic composition of the film were uniform along in-plane and depth direction over the 10 × 10 cm² area of the substrate. The film showed the average transmittance of 81-87%, resistivity of 1.4 × 10^− 3 Ω cm, carrier concentration of 9.7 × 10²⁰/cm³ and mobility of 5 cm²/Vs in spite of the amorphous X-ray diffraction pattern. The gradual thickness distribution was found, however, the potential for large-area and low temperature deposition of transparent conducting oxide thin film using pulsed laser deposition method was confirmed.     

Contribution to carrier densities of the oxygen vacancy in a low-resistivity tin-doped indium oxide film by the hot-cathode plasma sputtering method

In order to clarify the contribution to carrier density by oxygen vacancies in tin-doped indium oxide (ITO) films prepared on glass substrates by the hot-cathode plasma sputtering method, we have investigated the effect of annealing on the electrical properties of an ITO film with a resistivity of 1.0 × 10^− 4 Ω cm. A drastic decrease in carrier density from 2.0 × 10²¹ to 0.88 × 10²¹ cm^− 3 was found with gradual increase in the Hall mobility from 29 to 35 cm² V^− 1 s^− 1 for repeated annealing cycles, when the ITO film was exposed for one hour to 400 °C oxygen gas at atmospheric pressure. The results indicate that the contribution of oxygen vacancies to carrier density was ca. 1.12 × 10²¹ cm^− 3 for the ITO film with an overall carrier density of 2.0 × 10²¹ cm^− 3.     

Novel transparent conducting oxide: Anatase Ti1−xNbxO2

Single-crystalline Ti_1−xNb_xO₂ (x = 0.2) films of 40 nm thickness were deposited on SrTiO₃ (100) substrates by the pulsed laser deposition (PLD) technique. X-ray diffraction measurement confirmed epitaxial growth of anatase (001) film. The resistivity of Ti_1−xNb_xO₂ films with x ≥ 0.03 is 2-3 × 10^− 4 Ω cm at room temperature. The carrier density of Ti_1−xNb_xO₂, which is almost proportional to the Nb concentration, can be controlled in a range of 1 × 10¹⁹ to 2 × 10²¹ cm^− 3. Optical measurements revealed that internal transmittance in the visible and near-infrared region for films with x = 0.03 was more than 97%. These results demonstrate that the presently developed anatase Ti_1−xNb_xO₂ is one of the promising candidates for the practical TCOs.     

Chemical vapor deposition of phase-rich WC thin films on silicon and carbon substrates

Chemical vapor deposition was used to deposit tungsten carbide from a mixture of WCl₆, H₂ and C₃H₈ at 750-1050 °C on silicon and carbon substrates. The phase composition of the films was correlated with substrate temperature, substrate position in the reactor, and total flow rates. X-ray diffraction and X-ray photoelectron spectroscopy were employed to investigate the surface and bulk properties of the thin films. Thick, adherent films of phase-rich hexagonal WC were deposited using 1.3 × 10³ Pa total pressure, 1050 °C substrate temperature, and reactant flow rates of H₂/C₃H₈/Ar/WCl₆ = 1.8 × 10^− 2/3.6 × 10^− 3/8.9 × 10^− 4/1.8 × 10^− 4 mol/min, where Ar is the carrier gas. The surface composition was oxygen and carbon rich as compared with the bulk.     

Enhanced conductivity of pulsed laser deposited n-InGaZn6O9 films and its rectifying characteristics with p-SiC

Wide band gap InGaZn₆O₉ films of thickness ~ 350 nm were deposited on sapphire (0001) at room temperature by using the pulsed laser deposition technique. The transparent films showed the optical transmission of > 80% with the room temperature Hall mobility of ~ 10 cm²/V s and conductivity of 4 × 10² S/cm at a carrier density > 10²⁰ cm^− 3. The electrical properties as a function of deposition temperatures revealed that the conductivity and mobility almost retained up to the deposition temperature of 200 °C. The films annealed in different atmospheres suggested oxygen vacancy plays an important role in determining the electrical conductivity of the compound. Room temperature grown heterostructure of n-InGaZn₆O₉/p-SiC showed a good rectifying behavior with a leakage current density of less than 10^− 9 A/cm², current rectifying ratio of 10⁵ with a forward turn on voltage ~ 3 V, and a breakdown voltage greater than 32 V.     

Room temperature ferromagnetic multilayer thin film based on indium oxide and iron oxide for transparent spintronic applications

Pulsed laser deposition technique is used for fabrication of multilayer thin film of indium oxide (In₂O₃) and iron oxide (Fe₃O₄). X-ray diffraction study shows that In₂O₃ film is highly oriented along (222) direction. The optical band gap of the multilayer is observed to be 3.65 eV. The film shows n-type behavior with resistivity, carrier concentration, and mobility of 5.59 × 10⁻⁴ Ω.cm, 2.33 × 10²⁰ cm⁻³, and 48 cm ²v⁻¹ s⁻¹ respectively. Magnetic measurement shows that the film is ferromagnetic at room temperature. Hysteresis measurements at 5 K after field cooling show a shift and broadening of the hysteresis loop, which is due to exchange bias coupling.     

Transparent conducting ZnO thin films deposited by vacuum arc plasma evaporation

A high rate deposition of co-doped ZnO:Ga,F and ZnO-In₂O₃ multicomponent oxide thin films on large area substrates has been attained by a vacuum arc plasma evaporation method using oxide fragments as a low-cost source material. Highly transparent and conductive ZnO:Ga,F and ZnO-In₂O₃ thin films were prepared on low temperature substrates at a deposition rate of approximately 375 nm/min with a cathode plasma power of 10 kW. A resistivity of 4.5×10⁻⁴ Ω cm was obtained in ZnO:Ga,F films deposited at 100 °C using ZnO fragments co-doped with 1 wt.% ZnF₂ and 1 wt.% Ga₂O₃ as the source material. In addition, the stability in acid solution of ZnO films was improved by co-doping. It was found that the Zn/(In+Zn) atomic ratio in the deposited ZnO-In₂O₃ thin films was approximately the same as that in the fragments used. The ZnO-In₂O₃ thin films with a Zn/(In+Zn) atomic ratio of approximately 10-30 at.% deposited on substrates at 100 °C exhibited an amorphous and smooth surface as well as a low resistivity of 3-4×10⁻⁴ Ω cm.