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.     

Electrical and optical properties of amorphous indium zinc oxide films

Valence electron control and electron transport mechanisms on the amorphous indium zinc oxide (IZO) films were investigated. The amorphous IZO films were deposited by dc magnetron sputtering using an oxide ceramic IZO target (89.3 wt.% In₂O₃ and 10.7 wt.% ZnO). N-type impurity dopings, such as Sn, Al or F, could not lead to the increase in carrier density in the IZO. Whereas, H₂ introduction into the IZO deposition process was confirmed to be effective to increase carrier density. By 30% H₂ introduction into the deposition process, carrier density increased from 3.08 × 10²⁰ to 7.65 × 10²⁰ cm^− 3, which must be originated in generations of oxygen vacancies or interstitial Zn²⁺ ions. Decrease in the transmittance in the near infrared region and increase in the optical band gap were observed with the H₂ introduction, which corresponded to the increase in carrier density. The lowest resistivity of 3.39 × 10^− 4 Ω cm was obtained by 10% H₂ introduction without substrate heating during the deposition.     

In2O3 films prepared by thermal oxidation of amorphous InSe thin films

In₂O₃ thin films were prepared by the thermal oxidation of amorphous InSe films in air atmosphere. The structure, morphology and composition of the thermal annealed products were characterized by X-ray diffraction (XRD), scanning electron microscopy and energy-dispersive spectroscopy, respectively. The XRD patterns indicate that the as-deposited InSe films were amorphous and they fully transformed into polycrystalline In₂O₃ films with a cubic crystal structure in the preferential (222) orientation at a temperature around 600 °C. The optical energy gap of 3.66 eV was determined at room temperature by transmittance and reflectance measurements using UV-vis-NIR spectroscopy. A preliminary characterization shows that these films have a promising response towards NO₂ gas at a working temperature around 180 °C.     

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.     

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.     

Synthesis and photocatalytic activity of cobalt oxide doped ZnFe2O4-Fe2O3-ZnO mixed oxides

Novel cobalt oxide doped ZnFe₂O₄-Fe₂O₃-ZnO mixed oxides with the Zn/Fe molar ratio of 1/2 were synthesized with a citric acid complex method. The effects of cobalt oxide and calcination temperature on phase composition and photocatalytic activity of the mixed oxides were investigated. X-ray diffraction (XRD) analysis revealed that there were mainly ZnFe₂O₄, α-Fe₂O₃, amorphous ZnO and Fe₂O₃ in the 6 mol% cobalt oxide doped products calcined at 500 °C. 5-10 mol% cobalt oxide doping could significantly enhance the formation of ZnFe₂O₄ and altered the phase composition of the mixed oxides. Experimental results showed that cobalt oxide doping could remarkably improve the photocatalytic activity of the mixed oxides for phenol degradation. The 6 mol% cobalt oxide doped mixed oxides calcined at 500 °C exhibited better photocatalytic activity as compared with other samples.     

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.     

Annealing effects of In2O3 thin films on electrical properties and application in thin film transistors

Considering practical applications in electronic devices, we studied the growth of In₂O₃ thin films on amorphous glasses by magnetron sputtering at room temperature and annealing effect on the structural and electrical properties. The vacuum annealed In₂O₃ thin films display a grain size enlargement and preferential orientation. Electrical characterization shows that the vacuum annealed In₂O₃ thin films exhibit a significant enhancement of both electron density and mobility, while air ambient annealing leads to a remarkable drop. The mechanism of the electrical characteristic changes in In₂O₃ thin films by annealing is explored by using different scattering mechanisms. Finally, a thin film transistor device using vacuum annealed In₂O₃ nano-meter thin films as active channel material is demonstrated.     

Characterization of copper oxide thin films deposited by the thermal evaporation of cuprous oxide (Cu2O)

Thin films of copper oxide were deposited by thermal evaporation of cuprous oxide (Cu₂O) powder. The substrates were either unheated or heated to a temperature of 300 °C. The films were also annealed in air at a temperature of 500 °C for 3 h. The films were characterized by X-ray photoelectron spectroscopy, X-ray diffraction and UV-visible spectrophotometry. The effects of the substrate temperature and post-deposition annealing on the chemical, structural and optical properties of the films were investigated. As-deposited films on unheated substrates consisted of mixed cupric oxide (CuO) and Cu₂O phases, with a higher concentration of the Cu₂O phase. However, the films deposited on heated substrates and the annealed films were predominantly of the CuO phase.     

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.     

H2S sensing properties of La-doped nanocrystalline In2O3

The nanocrystalline powders of pure and La³⁺-doped In₂O₃ with cubic structure were prepared by a simple hydrothermal decomposition route. The structure and crystal phase of the powders were characterized by X-ray diffraction (XRD) and microstructure by transmission electron microscopy (TEM). All the compositions exhibited a single phase, suggesting a formation of solid solution in the concentration of doping investigated. Gas-sensing properties of the sensor elements were tested by mixing a gas in air at static state, as a function of concentration of dopant, operating temperature and concentrations of the test gases. The pure In₂O₃ exhibited high response towards H₂S gas at an operating temperature 150 °C. Doping of In₂O₃ with La³⁺ increases its response towards H₂S and La³⁺ (5.0 wt.% La₂O₃)-doped In₂O₃ showed the maximum response at 125 °C. The selectivity of the sensor elements for H₂S against different reducing gases was studied. The results on response and recovery time were also discussed.     

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.     

Opto-electronic properties of sputter-deposited Cu2O films treated with rapid thermal annealing

Cu₂O thin films were first deposited using magnetron sputtering at 200 °C. The samples produced were then annealed by a rapid thermal annealing (RTA) system at 550 °C in a protective atmosphere with or without the addition of oxygen. After annealing, various Cu₂O and CuO films were formed. These films were characterized, as a function of oxygen concentration in RTA, using UV-VIS photometer, four-point probe, and Hall measurement system. The results show that these Cu₂O thin films annealed at 550 °C with more than 1.2% oxygen added in the protective argon atmosphere would transform into the CuO phase. Apparently, the results of RTA are sensitive to the amount of oxygen added in the protective atmosphere. The resistivity of these Cu₂O thin films decreases with the increase in the oxygen amount in the annealing atmosphere, most likely due to the increase in carrier mobility. In addition, Cu₂O/ZnO (doped with AlSc) junctions were produced at 200 °C and annealed. The rectifying effect of P-N junction disappeared after annealing, probably due to the damage of p-n interface, which directly causes current leakage at the junction.     

Electronic structural analysis of transparent In2O3-ZnO films by hard X-ray photoelectron spectroscopy

The electronic structural analysis of the conductive transparent films was carried out using bulk sensitive hard X-ray photoelectron spectroscopy (HAXPES). The In₂O₃-ZnO film has amorphous structure before and after annealed, and the conduction band spectrum around Fermi level showed the similar spectra with that of as-deposited amorphous In₂O₃ film. In these amorphous films, the conduction band minimum locates at the deeper level than the crystalline In₂O₃ film. The electronic state which comes from randomness of amorphous structure possibly exists around this level or below. These electrons are expected to act as scattering center. We concluded that the electron mobility depends on the density of this electronic state.     

Low indium content In–Zn–O system towards transparent conductive films: structure,properties and comparison with AZO and GZO

In this work, low content indium doped zinc oxide (IZO) thin films were deposited on glass substrates by RF magnetron sputtering using IZO ceramic targets with the In₂O₃ doping content of 2, 6, and 10 wt%, respectively. The influences of In₂O₃ doping content and substrate temperature on the structure and morphology, electrical and optical properties, and environmental stability of IZO thin films were investigated. It was found that the 6 wt% doped IZO thin film deposited at 150?°C exhibited the best crystal quality and the lowest resistivity of 9.87?×?10^?4 Ω cm. The corresponding Hall mobility and carrier densities were 9.20 cm² V^?1 s^?1 and 6.90?×?10²⁰ cm^?3, respectively. Compared with 2 wt% Al₂O₃ doped ZnO and 5 wt% Ga₂O₃ doped ZnO thin films, IZO thin film with the In₂O₃ doping content of 6 wt% featured the lowest surface roughness of 1.3 nm. It also showed the smallest degradation with the sheet resistance increased only about 4.4% at a temperature of 121?°C, a relative humidity of 97% for 30 h. IZO thin film with 6 wt% In₂O₃ doping also showed the smallest deterioration with the sheet resistance increased only about 2.8 times after heating at 500?°C for 30 min in air. The results suggested that low indium content doped ZnO thin films might meet practical requirement in environmental stability needed optoelectronic devices.     

Growth studies and characterization of In2S3 films prepared by hydrothermal method and their conversion to In2O3 films

For the first time, In₂S₃ films composed of nano-/microflakes were fabricated on fluorine-doped tin oxide (FTO) substrate using a simple and effective hydrothermal method. The structure, composition and morphology were examined by X-ray diffraction, energy-dispersive X-ray spectroscopy and field emission scanning electron microscopy. It was found that the reaction time, reaction temperature and the molar ratio of the reactants play key roles in controlling the final morphologies. The possible growth mechanism for the formation of In₂S₃ thin films was proposed. And the optical and photoelectrochemical properties were also investigated. In addition, In₂O₃ films were obtained by annealing the In₂S₃ precursor films in air at 500 °C.     

Characterization and optoelectronic properties of sol-gel-derived CuFeO2 thin films

In this study, CuFeO₂ thin films were deposited onto quartz substrates using a sol-gel and a two-step annealing process. The sol-gel-derived films were annealed at 500 °C for 1 h in air and then annealed at 600 to 800 °C for 2 h in N₂. X-ray diffraction patterns showed that the annealed sol-gel-derived films were CuO and CuFe₂O₄ phases in air annealing. When the films were annealed at 600 °C in N₂, an additional CuFeO₂ phase was detected. As the annealing temperature increased above 650 °C in N₂, a single CuFeO₂ phase was obtained. The binding energies of Cu-2p_3/2, Fe-2p_3/2, and O-1s were 932.5 ± 0.1 eV, 710.3 ± 0.2 eV and 530.0 ± 0.1 eV for CuFeO₂ thin films. The chemical composition of CuFeO₂ thin films was close to its stoichiometry, which was determined by X-ray photoelectron spectroscopy. Thermodynamic calculations can explain the formation of the CuFeO₂ phase in this study. The optical bandgap of the CuFeO₂ thin films was 3.05 eV, which is invariant with the annealing temperature in N₂. The p-type characteristics of CuFeO₂ thin films were confirmed by positive Hall coefficients and Seebeck coefficients. The electrical conductivities of CuFeO₂ thin films were 0.28 S cm^− 1 and 0.36 S cm^− 1 during annealing at 650 °C and 700 °C, respectively, in N₂. The corresponding carrier concentrations were 1.2 × 10¹⁸ cm^− 3 (650 °C) and 5.3 × 10¹⁸ cm^− 3 (700 °C). The activation energies for hole conduction were 140 meV (650 °C) and 110 meV (700 °C). These results demonstrate that sol-gel processing is a feasible preparation method for delafossite CuFeO₂ thin films.     

Influence of Ga2O3 addition on transparent conductive oxide films of In2O3-ZnO

Influence of incorporation of Ga in amorphous In-Zn-O transparent conductive oxide films was investigated as a function of Zn/(Zn + In). For In-Zn-O films with no Ga₂O₃, the range of Zn/(Zn + In) ratio where the amorphous phase appears became narrow at a substrate temperature of 250 °C. With increasing Ga₂O₃ quantity, amorphous films were obtained even at a high substrate temperature of 250 °C in a wider range of Zn/(Zn + In) than that of In-Zn-O films with no Ga₂O₃. This means that the trend of crystallization at higher substrate temperature was disturbed with additional Ga incorporation. For the film deposited from ZnO:Ga (Ga₂O₃: 4.5-7.5 wt%) and In₂O₃ targets, we obtained a resistivity of 2.8 × 10⁻⁴ Ω cm, nearly the same value as that for an In-Zn-O film with no Ga₂O₃. The addition of more than 7.5 wt% Ga₂O₃ induced a widening of the optical band gap.     

A gradual annealing of amorphous sputtered indium tin oxide: Crystalline structure and electrical characteristics

Thin films of amorphous indium tin oxide were deposited by soft sputtering. The film was gradually annealed in air at temperatures from 110 °C to 150 °C. Its structural and electrical properties were monitored in order to get a better understanding of the annealing process. Firstly, carrier density decreases by oxygen intake. Crystallization speeds up at 150 °C, with a 2.5 D growth of crystallites. The preferred orientations come from sputtering induced seeds. Then, the carrier density increases again due to tin activation. Meanwhile, the carrier mobility is more damaged by the low temperature annealing in air than by a standard annealing in a reducing atmosphere. Thus, tin oxide segregation is suspected at grain boundaries.     

Microstructure and electrical properties of Al2O3-ZrO2 composite films for gate dielectric applications

Al₂O₃-ZrO₂ composite films were fabricated on Si by ultrahigh vacuum electron-beam coevaporation. The crystallization temperature, surface morphology, structural characteristics and electrical properties of the annealed films are investigated. Our results indicate that the amorphous and mixed structure is maintained up to an annealing temperature of 900 °C, which is much higher than that of pure ZrO₂ film, and the interfacial oxide layer thickness does not increase after annealing at 900 °C. However, a portion of the Al₂O₃-ZrO₂ film becomes polycrystalline after 1000 °C annealing and interfacial broadening is observed. Possible explanations are given to explain our observations. A dielectric constant of 20.1 is calculated from the 900 °C-annealed ZrO₂-Al₂O₃ film based on high-frequency capacitance-voltage measurements. This dielectric characteristic shows an equivalent oxide thickness (EOT) as low as 1.94 nm. An extremely low leakage current density of ∼2×10⁻⁷ A/cm² at a gate voltage of 1 V and low interface state density are also observed in the dielectric film.