Effect of inserting a buffer layer on the characteristics of transparent conducting impurity-doped ZnO thin films prepared by dc magnetron sputtering

In transparent conducting impurity-doped ZnO thin films prepared on glass substrates by a dc magnetron sputtering (dc-MS) deposition, the obtainable lowest resistivity and the spatial resistivity distribution on the substrate surface were improved by a newly developed MS deposition method. The decrease of obtainable lowest resistivity as well as the improvement of spatial resistivity distribution on the substrate surface in Al- or Ga-doped ZnO (AZO or GZO) thin films were successfully achieved by inserting a very thin buffer layer, prepared using the same MS apparatus with the same target, between the thin film and the glass substrate. The deposition of the buffer layer required a more strongly oxidized target surface than possible to attain during a conventional dc-MS deposition. The optimal thickness of the buffer layer was found to be about 10 nm for both GZO and AZO thin films. The resistivity decrease is mainly attributed to an increase of Hall mobility rather than carrier concentration, resulting from an improvement of crystallinity coming from insertion of the buffer layer. Resistivities of 3 × 10^− 4 and 4 × 10^− 4Ω cm were obtained in 100 nm-thick-GZO and AZO thin films, respectively, incorporating a 10 nm-thick-buffer layer prepared at a substrate temperature around 200 °C.     

Deposition and characterization of c-axis oriented aluminum nitride films by radio frequency magnetron sputtering without external substrate heating

Aluminum nitride (AlN) films were deposited on a variety of substrates (glass, Si, oxidized Si, Al-SiO₂-Si, Cr-SiO₂-Si, and Au-Cr-SiO₂-Si) by radio frequency (RF) magnetron sputtering using an AlN target. The films were deposited without external substrate heating. The effect of RF power, ambient gas (Ar and Ar-N₂) and sputtering pressure on deposition rate and crystallinity were investigated. The structure and morphology of the films were studied by X-ray diffraction, scanning electron microscopy and atomic force microscopy techniques. These investigations revealed that the AlN films prepared in mixed gas ambient (Ar-N₂) were highly c-axis oriented with moderate surface roughness on all the substrate. A strong IR absorption band was observed around 670 cm^− 1 which confirms the presence of Al-N bond in the film. The dc resistivity of the films was measured to be in the range of 10¹¹ to 10¹² Ω-cm at moderate electric fields. The application of these films in piezoelectric based micro-electro-mechanical systems is discussed.     

Power and pressure effects upon magnetron sputtered aluminum doped ZnO films properties

In this work, polycrystalline aluminum doped zinc oxide (ZnO:Al) films with c-axis (002) orientation have been grown on glass and silicon substrates by RF (radio frequency) magnetron sputtering technique, at room temperature. A systematic study of the effect of sputtering deposition parameters (i.e. RF power and argon gas pressure) on the structural, optical and electrical properties of the films was carried out. We observed that, with increasing RF power the growth rate increased, while it decreased with increasing gas pressure. As mentioned above, the films were polycrystalline in nature with a strong preferred (002) orientation. The intrinsic compressive stress was found to decrease with both increasing RF power and gas pressure, and near stress-free film was obtained at 200 W RF power and 2 × 10^− 1 Pa gas pressure. The obtained ZnO:Al films, not only have an average transmittance greater than 90% in the visible region, but also have an optical band gap between 3.33 and 3.47 eV depending on the sputtering parameters. Moreover, a low value of the electrical resistivity (~ 1.25 × 10^− 3 Ω cm) was obtained for the film deposited at 200 W and 2 × 10^− 3 mbar.     

溅射功率对ZnO：Si透明导电薄膜性能的影响

采用直流磁控溅射法在室温玻璃基片上制备出了掺硅氧化锌（ZnO：Si）透明导电薄膜,研究了溅射功率对ZnO：Si薄膜结构、形貌、光学及电学性能的影响,实验结果表明,溅射功率对ZnO：Si薄膜的生长速率、结晶质量及电学性能有很大影响,而对其光学性能影响不大。实验制备的ZnO：LSi薄膜为六方纤锌矿结构的多晶薄膜,且具有垂直于基片方向的c轴择优取向。当溅射功率从45W增加到105W时,薄膜的晶化程度提高、晶粒尺寸增大,薄膜的电阻率减小;当溅射功率为105W时,薄膜的电阻率达到最小值3．83~104n·cm,其可见光透过率为94．41％。实验制备的ZnO：Si薄膜可以用作薄膜太阳能电池和液晶显示器的透明电极。     

Study on the doping effect of Li-doped ZnO film

Zinc oxide (ZnO) is an excellent piezoelectric material with simple composition. ZnO film is applied to the piezoelectric devices because it has high resistivity and highly oriented direction at c-axis. Structural and electrical properties in ZnO films are influenced by deposition conditions. Lithium-doped ZnO (LZO) films were deposited by RF magnetron sputtering method using Li-doped ZnO ceramic target with various ratios (0 to 10 wt.% LiCl dopant). LZO films revealed high resistivity of above 10⁷ Ω cm with smooth surface when they were deposited with 4% LiCl-doped ZnO target under room temperature. However, their c-axis orientation was worse than the c-axis orientation of pure ZnO films. We have also studied on structural, optical and electrical properties of the ZnO films by XRD, AFM, SEM, XPS, and 4-point probe analyses. We concluded that LZO films were deposited with 4 wt.% LiCl-doped ZnO target and were apposite for piezoelectrical application.     

氢化及沉积温度对掺铝ZnO透明导电薄膜性能影响

采用射频磁控溅射方法在玻璃衬底上制备了掺铝ZnO透明导电薄膜(AZO)。为了降低AZO薄膜的电阻率, 采用在溅射气氛中通入一定比例H₂的方法对AZO薄膜进行氢化处理, 并研究了溅射气氛中H₂含量及衬底温度对AZO薄膜氢化效果的影响。结果表明: 在低温条件下, 氢化处理能有效降低AZO薄膜的电阻率; 在衬底温度为100℃的低温条件下, 通过调节溅射气氛中H₂的比例, 制备了电阻率为6.0×10^-4 Ω·cm的高质量氢化AZO薄膜, 该电阻值低于同等条件下未氢化AZO薄膜电阻值的1/3; 但随着衬底温度的升高, 氢化处理对薄膜电学性能的改善效果逐渐减弱。     

The effects of impurity and temperature for transparent conducting oxide properties of Al:ZnO deposited by dc magnetron sputtering

Aluminum-doped zinc oxide films (ZnO:Al) were deposited on Si wafers and glass substrates by dc magnetron sputtering from a ZnO target mixed with 2 wt% Al₂O₃ for photovoltaic films. The effect of base pressure, additional oxygen, and substrate temperature were studied in detail. By dc magnetron sputtering at room temperature, the resistivity and the average transmittance in visible range was 2.3 × 10⁻³ Ω cm and 77.3%, respectively. And these were improved up to 3.3 × 10⁻⁴ Ω cm and 86% at the substrate temperature of 400 °C by high deposition rate and low impurity ambient. The mobility and the carrier concentration were improved by the increased preferred orientation of (002) plane and grain size of film with increasing deposition temperature. This advanced AZO film with good resistivity and transmittance can be expected as the front TCO of thin film solar cells.     

Novel properties of AZO film sputtered in Ar+H2 ambient at high temperature

AZO (ZnO:Al) transparent conductive thin film was prepared by RF magnetron sputtering with a AZO (98 wt% ZnO 2 wt% Al₂O₃) ceramic target in the same Ar+H₂ ambient at different substrate temperatures ranging from 100 to 300 °C. The minimum resistivity of AZO films was 7.9×10⁻⁴ Ω cm at the substrate temperature of 200 °C. The average transmission in the visible rang was more than 90%. Scanning electron microscopy and XRD analyses showed that the surface morphology of the AZO samples altered with the increasing of the substrate temperature. AZO film prepared at 200 °C in the pure Ar ambient was also made as comparison about the resistivity, carrier concentration and the average crystallite size. The resistivity became about 3 times higher. The carrier concentration became lower and the average crystallite size was smaller.     

Effect of Ga Doping Concentration on Electrical and Optical Properties of Nano-ZnO:Ga Transparent Conductive Films

Transparent conductive nano ZnO thin films with different Ga doping concentrations (1, 3, 5, 7 at.%) were prepared on glass substrate by RF magnetron sputtering. The influence of Ga doping concentration on the structural, electrical and optical properties of ZnO:Ga films was investigated by XRD, SEM, Hall measurement and optical-transmission spectroscopy. It shows that the nano ZnO:Ga films are dense and flat, and have polycrystalline structure with preferential (002) and weak (101) orientation. The grain sizes, carrier concentration and Hall mobility changes non-linearly with the increase of Ga-content. The lowest resistivity of 1.44×10⁻³ Ωcm appears at 3 at.% Ga doping concentration. The average transmittance of the films is about 80∼90% in the visible range. The optical band gap obtained for these films is larger than for pure ZnO (∼3.37 eV).     

High density plasma treatment of polyimide substrate to improve structural and electrical properties of Ga-doped ZnO films

We investigated the effects of a high density O₂ plasma treatment on the structural and electrical properties of sputter-deposited GZO films. The GZO films were deposited on polyimide substrate without substrate heating by RF magnetron sputtering from a ZnO target mixed with 5 wt.% Ga₂O₃. Prior to the GZO film growth, we treated a polyimide substrate with highly dense inductively coupled oxygen plasma. The optical transmittance of the GZO film, about 80%, was maintained regardless of the plasma pre-treatment. However, the resistivity of the film was strongly influenced by the plasma pre-treatment. The resistivity of the GZO film decreased from 1.02 × 10^− 2 Ω cm without an O₂ plasma pre-treatment to 1.89 × 10^− 3 Ω cm with an O₂ plasma pre-treatment.     

Effects of sputtering power and pressure on properties of ZnO:Ga thin films prepared by oblique-angle deposition

The effects of power and pressure on radiofrequency (RF) diode sputtering in oblique-angle (80°) deposition arrangement are presented. Oblique-angle sputtering of ZnO:Ga (GZO) thin films resulted in a tilted columnar crystalline structure and inclination of the c-axis by an angle of approximately 9° with respect to the substrate. This improved their structural, electrical and optical properties in comparison with films deposited perpendicularly to the substrate. GZO films sputtered by an RF power of 600 W at room temperature of the substrate in Ar pressure 1.3 Pa showed strong crystalline (002) texture, lowest electrical resistivity 3.4 × 10^− 3 Ωcm, highest electron mobility 10 cm² V^− 1 s^− 1, high electron concentration 1.8 × 10²⁰ cm^− 3 and good optical transparency up to 88%. The small inclination angle of the film structure is caused by the high kinetic energy of sputtered species and additional energetic particle bombardment causes random surface diffusion, which is suppressing the shadow effect produced by oblique-angle sputtering.     

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.     

Deposition of Al-doped ZnO films on polyethylene naphthalate substrate with radio frequency magnetron sputtering

100 nm Al-doped ZnO (AZO) thin films were deposited on polyethylene naphthalate (PEN) substrates with radio frequency magnetron sputtering using 2 wt.% Al-doped ZnO target at various deposition conditions including sputtering power, target to substrate distance, working pressure and substrate temperature. When the sputtering power, target to substrate distance and working pressure were decreased, the resistivity was decreased due to the improvement of crystallinity with larger grain size. As the substrate temperature was increased from 25 to 120 °C, AZO films showed lower electrical resistivity and better optical transmittance due to the significant improvement of the crystallinity. 2 wt.% Al-doped ZnO films deposited on glass and PEN substrates at sputtering power of 25 W, target to substrate distance of 6.8 cm, working pressure of 0.4 Pa and substrate temperature of 120 °C showed the lowest resistivity (5.12 × 10^− 3 Ω cm on PEN substrate, 3.85 × 10^− 3 Ω cm on glass substrate) and high average transmittance (> 90% in both substrates). AZO films deposited on PEN substrate showed similar electrical and optical properties like AZO films deposited on glass substrates.     

Structural and electrical properties of Al doped ZnO thin films deposited at room temperature on poly(vinilidene fluoride) substrates

Transparent, conducting, Al-doped ZnO films have been deposited, by dc and pulsed dc magnetron sputtering, on glass and electroactive polymer (poly(vinylidene fluoride)–PVDF) substrates. Samples have been prepared at room temperature varying the argon sputtering pressure, after optimizing other processing conditions. All ZnO:Al films are polycrystalline and preferentially oriented along the [002] axis. Electrical resistivity around 3.3 × 10^− 3 Ω cm and optical transmittance of ~ 85% at 550 nm have been obtained for AZOY films deposited on glass, while a resistivity of 1.7 × 10^− 2 Ω cm and transmittance of ~ 70% at 550 nm have been attained in similar coatings on PVDF. One of the main parameters affecting film resistivity seems to be the roughness of the substrate.     

Properties of RF magnetron sputtered indium tin oxide thin films on externally unheated glass substrate

Indium tin oxide (ITO) thin films were deposited by radio frequency (RF) magnetron sputtering onto glass substrates. The transparent and conducting ITO thin films were obtained on externally unheated glass substrate, without any post-heat treatment, and by varying the deposition process parameters such as the working pressure and the RF Power. The effect of the variation of the above deposition parameters on the structural, surface morphology, electrical, and optical properties of the thin films have been studied. A minimum resistivity of 2.36 × 10⁻⁴ Ω cm and 80% transmittance with a figure of merit 37.2 × 10⁻³ Ω⁻¹ is achieved for the thin films grown on externally unheated substrate with 75 W RF power and 0.5 mTorr working pressure.     

直流磁控溅射法制备掺钛氧化锌透明导电薄膜

采用直流磁控溅射法在室温水冷玻璃衬底上制备出高质量的掺钛氧化锌(ZnO:Ti)透明导电薄膜,研究了溅射功率对ZnO:Ti薄膜结构、形貌和光电性能的影响,结果表明,溅射功率对ZnO:Ti薄膜的结构和电阻率有显著影响.XRD表明,ZnO:Ti薄膜为六角纤锌矿结构的多晶薄膜,且具有c轴择优取向.当溅射功率为130W时,实验制备的ZnO:Ti薄膜的电阻率具有最小值9.67×10~(-5)Ω·cm.实验制备的ZnO:Ti薄膜具有良好的附着性能,可见光区平均透过率超过91%.ZnO:Ti薄膜可以用作薄膜太阳能电池和液晶显示器的透明电极.     

Nematic liquid crystal alignment on the ion beam-exposed ZnO film

This paper investigates the nematic liquid crystal (NLC) alignment on ion beam-exposed zinc oxide (ZnO) films. The ZnO films are deposited by a radio frequency magnetron sputtering. During the deposition of ZnO film, we supplied sufficient oxygen gas for high resistivity and transmittance. The deposited films show a high transmittance of over 90% and high resistivity of over 10¹⁰ Ω cm. The ZnO films show a high deposition rate of 26.7 Å/min. Images obtained via scanning electron microscopy of the ZnO film surfaces, before and after the ion beam exposure, show that groove patterns are formed being to be parallel to the ion beam exposure direction. LC cells are fabricated with the ion beam-exposed ZnO films. The NLC molecules align parallel to the ion beam exposure direction. The electro-optic and response characteristics of fabricated cells show the possibility of application to liquid crystal displays.     

ZnO thin films prepared by atomic layer deposition and rf sputtering as an active layer for thin film transistor

Recently, the application of ZnO thin films as an active channel layer of transparent thin film transistor (TFT) has become of great interest. In this study, we deposited ZnO thin films by atomic layer deposition (ALD) from diethyl Zn (DEZ) as a metal precursor and water as a reactant at growth temperatures between 100 and 250 °C. At typical growth conditions, pure ZnO thin films were obtained without any detectable carbon contamination. For comparison of key film properties including microstructure and chemical and electrical properties, ZnO films were also prepared by rf sputtering at room temperature. The microstructure analyses by X-ray diffraction have shown that both of the ALD and sputtered ZnO thin films have (002) preferred orientation. At low growth temperature T_s ≤ 125 °C, ALD ZnO films have high resistivity (> 10 Ω cm) with small mobility (< 3 cm²/V s), while the ones prepared at higher temperature have lower resistivity (< 0.02 Ω cm) with higher mobility (> 15 cm²/V s). Meanwhile, sputtered ZnO films have much higher resistivity than ALD ZnO at most of the growth conditions studied. Based upon the experimental results, the electrical properties of ZnO thin films depending on the growth conditions for application as an active channel layer of TFT were discussed focusing on the comparisons between ALD and sputtering.     

Structural and optical properties of Ti-doped ZnO thin films prepared by the cathodic vacuum arc technique with different annealing processes

Highly transparent Ti-doped ZnO thin films were prepared on glass substrates at a deposition rate of approximately 33 nm/min using the cathodic vacuum arc technique with a Zn target power of 550 W and a Ti target power of 750 W, respectively. X-ray diffraction measurements have shown that the Ti-doped ZnO thin film with a vacuum post-annealing condition is c-axis oriented but an amorphous phase at the other post-annealing atmosphere and as-deposited condition. Transmittance measurements show that the best optical quality of the Ti-doped ZnO thin films occurred at a post-annealing atmosphere of N₂/H₂ mixed gases. Additionally, the optical transmittance of all films has been found more than 85% in a range of 500-700 nm. The lowest electrical resistivity was 3.48 × 10⁻³ Ω cm, obtained on as-deposited films. However, the post-annealing condition greatly increased the resistivity.     

Effect of Thickness on the Properties of Ga-doped Nano-ZnO Thin Films Prepared by RF Magnetron Sputtering

Nano transparent conductive oxide (TCO) Ga-doped ZnO (GZO) thin films with thickness from 260 nm to 620 nm were prepared on glass substrates by RF magnetron sputtering from a powder target with 3 at.% Ga₂O₃. The substrate temperature was kept at 300 °C. The effect of thickness on the structural, electrical, and optical properties of GZO thin films was investigated. It shows that the nano-GZO films are dense and flat, and have polycrystalline structure with preferentially in the (002) orientation. With the increase of thickness, the crystallinity and the grain sizes of the films are improved, meanwhile the carrier concentration increases and the lowest resistivity of 3.685×10⁻³ Ω cm occurs in the 620 nm thick GZO film. The average optical transmittance of all the films is over 80% in the visible range. Decreasing the thickness, the optical transmission of the films increase, and the absorption edge shifts to shorter wavelength, which means the optical band gap is broadened.