Effect of Cr and V dopants on the chemical stability of AZO thin film

The effect of the dopants of Cr and V on the optoelectronic properties of AZO thin film by pulsed DC magnetron sputtering has been investigated. We also use HCl and KOH solutions to conduct the chemical stability of AZO:Cr:V thin film. The experimental results show that the optimum AZO optoelectronic properties without Cr and V doping obtain the resistivity of 9.87 × 10⁻⁴ Ω cm, optical transmittance of 84% and surface roughness rms value of 2.6 nm. The chemical stability of AZO will increase after Cr and V doping. Under the added V = 0.19 wt.%, Cr = 0.56 wt.%, AZO:Cr:V thin film showed 52% increased chemical stability and 128% decrease in surface roughness after etching (the resistivity was 3.62 × 10⁻³ Ω cm and optical transmittance 81%). From the experimental results, the higher resistivity obtained after KOH etching compared with after HCl etching. The reason is that the Zn/Al ratio will reduce after etching and cause the AZO film carrier density to reduce as well. However, the optical transmittance obtained after KOH etching will be higher than that after HCl etching. This is because that a better surface roughness after KOH etching obtained than after HCl etching.     

PECVD制备AZO（ZnO:Al）透明导电薄膜

采用PECVD（等离子体增强化学气相沉积）工艺在普通玻璃和Si基上制备出了方块电阻低至89 Ω,可见光透过率高达79%,对基体附着力强的多晶态的AZO（ZnO:Al）薄膜.采用PECVD法制备AZO薄膜是一种有益的尝试,AZO透明导电薄膜不仅具有与ITO（透明导电薄膜,如In₂O₃:Sn）可比拟的光电特性,而且价格低廉、无毒,在氢等离子体环境中更稳定,所获结果对实际工艺条件的选择具有一定借鉴作用和参考价值. 关键词： AZO（ZnO:Al） 等离子体增强化学气相沉积 透明导电薄膜     

Comparing study of subpicosecond and nanosecond wet etching of fused silica

The effectiveness of the laser induced backside wet etching (LIBWE) of fused silica produced by subpicosecond (600 fs) and nanosecond (30 ns) KrF excimer laser pulses (248 nm) was studied. Fused silica plates were the transparent targets, and naphthalene-methyl-methacrylate (c = 0.85, 1.71 M) and pyrene-acetone (c = 0.4 M) solutions were used as liquid absorbents. We did not observe etching using 600 fs laser pulses, in contrast with the experiments at 30 ns, where etched holes were found. The threshold fluences of the LIBWE at nanosecond pulses were found to be in the range of 360-450 mJ cm⁻² depending on the liquid absorbers and their concentrations. On the basis of the earlier results the LIBWE procedure can be explain by the thermal heating of the quartz target and the high-pressure bubble formation in the liquid. According to the theories, these bubbles hit and damage the fused silica surface. The pressure on the irradiated quartz can be derived from the snapshots of the originating and expanding bubbles recorded by fast photographic setup. We found that the bubble pressure at 460 mJ cm⁻² fluence value was independent of the pulse duration (600 fs and 30 ns) using pyrene-acetone solution, while using naphthalene-methyl-methacrylate solutions this pressure was 4, 5 times higher at 30 ns pulses than it was at 600 fs pulses. According to the earlier studies, this result refers to that the pressure should be sufficiently high to remove a thin layer from the quartz surface using pyrene-acetone solution. These facts show that the thermal and chemical phenomena in addition to the mechanical effects also play important role in the LIBWE procedure.     

掺钼ZnO透明导电薄膜的太赫兹电磁波传输性质

采用直流磁控反应溅射方法,通过调节氧分压在玻璃基底上制备了不同载流子浓度的掺Mo的ZnO（ZMO）透明导电薄膜.应用太赫兹电磁波时域光谱技术研究了ZMO导电膜的太赫兹电磁波透射性质及介电响应,得到了与频率相关的电导率、能量吸收和薄膜折射率,实验结果与经典Drude模型相符很好.ZMO导电膜的太赫兹电磁波脉冲透射性质表明,通过调节ZMO薄膜的载流子浓度,该导电膜可作为应用于衬底和光学器件等太赫兹电磁波频率范围的宽带抗反射涂层. 关键词： 太赫兹电磁波光谱 薄膜电导率 宽带抗反射 透明导电薄膜     

掺杂透明导电半导体薄膜的光电性能研究

掺杂氧化锌透明导电膜(AZO)是一种重要的光电子信息材料，其制备方法有真空蒸镀法、磁控溅射法，化学气相沉积和脉冲激光沉积法等。该文采用溶胶 凝胶（sol gel)工艺在普通玻璃基片上成功地制备出Al3+掺杂型ZnO透明导电薄膜。将这种薄膜在空气和真空中以不同的温度进行了退火处理，并对薄膜进行了XRD分析和光电性能研究。结果表明，所制备的薄膜为钎锌矿型结构，在c轴方向择优生长，真空退火有利于薄膜结晶状况的改善，并使薄膜的载流子浓度大幅度地增加而电阻率下降，并且真空退火对薄膜的透射率影响不大。     

射频溅射功率对AZO薄膜结构及光电特性和热稳定性的影响

采用射频磁控溅射法,在玻璃基片上制备了ZnO:Al(AZO)透明导电薄膜。用X射线衍射(XRD)仪、紫外-可见分光光度计、方块电阻测试仪和台阶仪对不同溅射功率下Al掺杂ZnO薄膜的结晶、光学、电学性能、沉积速率以及热稳定性进行了研究。研究结果表明:不同溅射功率下沉积的AZO薄膜具有六角纤锌矿结构,均呈c轴择优取向;(002)衍射峰强和薄膜的结晶度随溅射功率的提高逐渐增强;随溅射功率的提高,AZO薄膜的透射率有所下降,但在可见光(380～780nm)范围内平均透射率仍80%;薄膜的方块电阻随溅射功率的增加逐渐减小;功率为160～200W时,薄膜的热稳定性最好,升温前后方块电阻变化率为13%。     

湿法和溶脱法的亚微米ZnO:Al光栅制备

以激光干涉法得到的光刻胶图案为掩模,采用湿法刻蚀和溶脱-剥离法制备了具有良好减反射特性的亚微米掺铝氧化锌（ZnO:Al, AZO）光栅。表面形貌特征和反射光谱测试结果表明,湿法刻蚀较溶脱-剥离法得到的AZO光栅表面更为粗糙,两者均方根粗糙度分别为25.4,7.6 nm。在400～900 nm波段,两种方法制备的周期和高度相同的光栅,平均总反射率分别由AZO薄膜的12.5%下降到8.3%和10.2%。两者的平均镜面反射率分别为6.2%和6.6%,平均漫反射率分别为2.1%和3.6%。湿法刻蚀得到的表面较为粗糙AZO光栅的漫反射明显减弱,从而导致总的减反特性优于溶脱-剥离法得到的表面起伏相对较小的AZO光栅。     

The structural properties of Al doped ZnO films depending on the thickness and their effect on the electrical properties

In this study, the structural and electrical properties of AZO films with different film thickness deposited by r.f. magnetron sputtering were interpreted in relation with film growth process. The result shows that the grain size increases during film growth, which is accompanied by decrease of compressive stress, indicating the enhancement of crystallinity. The relationship between grain size and compressive stress follows the same tendency for the samples regardless of deposition temperature, which implies the strong dependencies between the grain size and the compressive stress. The XPS analysis shows that the defects such as chemisorbed oxygen and segregated Al₂O₃ cluster at grain boundary are reduced with increase of film thickness or deposition temperature, leading to increase of carrier concentration and mobility. The mobility increase is accompanied by grain size increase and compressive stress reduction, indicating the influences of grain boundary and crystallinity on the mobility.     

Optical and electrical properties of aluminum zinc oxide (AZO) nanostructured thin film deposited on polycarbonate substrate

Transparent polymer materials, due to their unique properties, such as light weight, optical transparency, and electrical and mechanical properties, have become very attractive as a replacement for inorganic glass substrates in a wide range of optoelectronic applications. In this research, aluminum zinc oxide nanostructured thin film was deposited on polycarbonate polymer substrates using a magnetron sputtering technique. The structure, morphology, and surface composition of the thin film were investigated by X-ray diffraction and field emission scanning electron microscopy. The optical and electrical properties of the thin film were investigated by UV–VIS-NIR spectrophotometer, ellipsometer, and four point probe method. The X-ray diffraction pattern showed that the aluminum zinc oxide thin film had a polycrystalline structure. The optical and electrical results indicated that the refractive index, band gap, and sheet resistance of the aluminum zinc oxide thin film were 1.8, 3.2 eV, and 265 Ω/sq, respectively.     

Preparation and infrared emissivity of ZnO: Al (AZO) thin films

ZnO:Al(AZO) thin films with different Al-doped concentration were developed under different temperature. The effects of the temperature and Al-doped concentration on the infrared emissivity were investigated. Results show that the crystalline phase of the AZO films is hexagonal wurtzite which is the same as that of the un-doped ZnO film. The crystalline size become larger and the particle shapes become more regular with the increase of temperature, which lead to the increase of resistivity and the decreases of the infrared emissivity.     

Effect of crystallinity of ZnO buffer layer on the properties of epitaxial (ZnO:Al)/(ZnO:Ga) bi-layer films deposited on c-sapphire substrate

Bi-layer ZnO films with 2 wt.% Al (AZO; ZnO:Al) and 4 wt.% Ga-doped (GZO; ZnO:Ga) were deposited on the ZnO buffered and annealed ZnO buffered c(0 0 0 1)-sapphire(Al₂O₃) substrates respectively by Pulsed Laser Deposition (PLD). The effect of crystallinity of ZnO buffer layer on the crystallinity and electrical properties of the AZO/GZO bi-layer thin films was investigated. It was seen that the crystallinity of ZnO buffer layer had a great influence on the orientation and defect density of AZO/GZO bi-layer thin films from X-ray Diffraction (XRD) peaks and High Resolution Transmission Electron Microscopy (HRTEM) images. In a word, it was found in the films that more preferred c-axis orientation texture and reduction of the defects such as stacking faults and dislocations, with increasing of the crystallinity of ZnO buffer layer.     

Mechanical reliability of transparent conducting IZTO film electrodes for flexible panel displays

The mechanical reliability of transparent In-Zn-Sn-O (IZTO) films grown using pulsed DC magnetron sputtering with a single oxide alloyed ceramic target on a transparent polyimide (PI) substrate at room temperature is investigated. All IZTO films deposited at room temperature have an amorphous structure. However, their optical and electrical properties change depending on the oxygen partial pressure applied during depositing process. At an oxygen partial pressure of 3%, the films exhibit a resistivity of 8.3 × 10⁻⁴ Ω cm and an optical transmittance of 86%. Outer bending tests show that the critical bending radius decreases from 10 mm to 7.5 mm when the oxygen partial pressure increases from 1% to 3%. In the inner bending test, the critical bending radius is independent of oxygen partial pressure at 3.5 mm, indicating excellent film flexibility. In the dynamic fatigue test, the electrical resistance of the films reduces by less than 1% for more than 2000 bending cycles. These results suggest that IZTO films have excellent mechanical durability and flexibility in comparison to ITO films.     

Highly conductive and transparent laser ablated nanostructured Al: ZnO thin films

Al doped ZnO thin films are prepared by pulsed laser deposition on quartz substrate at substrate temperature 873 K under a background oxygen pressure of 0.02 mbar. The films are systematically analyzed using X-ray diffraction, atomic force microscopy, micro-Raman spectroscopy, UV-vis spectroscopy, photoluminescence spectroscopy, z-scan and temperature-dependent electrical resistivity measurements in the temperature range 70-300 K. XRD patterns show that all the films are well crystallized with hexagonal wurtzite structure with preferred orientation along (0 0 2) plane. Particle size calculations based on XRD analysis show that all the films are nanocrystalline in nature with the size of the quantum dots ranging from 8 to 17 nm. The presence of high frequency E₂ mode and longitudinal optical A₁ (LO) modes in the Raman spectra suggest a hexagonal wurtzite structure for the films. AFM analysis reveals the agglomerated growth mode in the doped films and it reduces the nucleation barrier of ZnO by Al doping. The 1% Al doped ZnO film presents high transmittance of ∼75% in the visible and near infrared region and low dc electrical resistivity of 5.94 × 10⁻⁶ Ω m. PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. Nonlinear optical measurements using the z-scan technique shows optical limiting behavior for the 5% Al doped ZnO film.     

Growth of transparent conducting nano-structured In doped ZnO thin films by pulsed DC magnetron sputtering

Transparent conducting nano-structured In doped zinc oxide (IZO) thin films are deposited on corning 7059 glass substrates by bipolar pulsed DC magnetron sputtering with variation of pulsed frequency and substrate temperature. Highly c-axis oriented IZO thin films were grown in perpendicular to the substrate on the 30 kHz and 500 °C. The IZO films exhibited surface roughness of 3.6 nm similar to the commercial ITO and n-type semiconducting properties with electrical resistivity (carrier mobility) of about 5 × 10⁻³ Ω cm (14 cm²/V s). The optical characterization showed high transmittance of over 85% in the UV-vis region and exhibited the absorption edge of near 350 nm. In micro-Raman spectra, the origin of two additional modes is attributed to the host lattice defect due to the addition of In dopant. These results suggest that the IZO film can possibly be applied to make transparent conducting electrodes for flat panel displays.     

Aluminum thin film enhanced IR nanosecond laser-induced frontside etching of transparent materials

Laser processing of glass is of significant commercial interest for microfabrication of precision optical engineering devices. In this work, a laser ablation enhancement mechanism for microstructuring of glass materials is presented. The method consists of depositing a thin film of aluminum on the front surface of the glass material to be etched. The laser beam modifies the glass material by being incident on this front-side. The influence of ablation fluence in the nanosecond regime, in combination with the deposition of the aluminum layer of various thicknesses, is investigated by determining the ablation threshold for different glass materials including soda-lime, borosilicate, fused silica and sapphire. Experiments are performed using single laser pulse per shot in an air environment. The best enhancement in terms of threshold fluence reduction is obtained for a 16 nm thick aluminum layer where a reduction of two orders of magnitude in the ablation threshold fluence is observed for all the glass samples investigated in this work.     

Influence of the deposition pressure on the properties of transparent conducting zirconium-doped zinc oxide films prepared by RF magnetron sputtering

Transparent and conducting zirconium-doped zinc oxide films with high transparency and relatively low resistivity have been successfully prepared by RF magnetron sputtering at room temperature. The deposition pressure was varied from 0.6 to 2.5 Pa. A transformation from a relatively compact structure to individual grains was observed with the increase of deposition pressure. As the deposition pressure increases, the resistivity increases sharply due to both, the decrease of hall mobility and carrier concentration. The lowest resistivity achieved was 2.07 × 10⁻³ Ω cm at a deposition pressure of 0.6 Pa with a hall mobility of 16 cm² V⁻¹ s⁻¹ and a carrier concentration of 1.95 × 10²⁰ cm⁻³. The films are polycrystalline with a hexagonal structure and a preferred orientation along the c-axis. All the films present a high transmittance of above 90% in the visible range. The optical band gap decreases from 3.35 to 3.20 eV as the deposition pressure increases from 0.6 to 2.5 Pa.     

湿法刻蚀对Si基片孔点阵及ZnO外延薄膜周期形貌的影响

利用射频等离子体辅助分子束外延法,在刻有周期性孔点阵结构的Si衬底上生长了ZnO二维周期结构薄膜,系统研究了湿法化学刻蚀对孔形点阵Si(100),Si(111)基片表面形貌的影响,以及两种初底上ZnO外延薄膜的结晶质量与周期形貌的差异.X射线衍射及扫描电子显微测试结果表明：Si (111)衬底上生长出的ZnO二维周期结构薄膜具有较好的结晶质量与较好的周期性表面形貌.该研究结果为二维周期结构的制备提供了一种新颖的方法. 关键词： ZnO 分子束外延 Si 湿法刻蚀     

Influence of Zr_(50)Cu_(50) thin film metallic glass as buffer layer on the structural and optoelectrical properties of AZO films

Aluminum-doped ZnO(AZO) thin films with thin film metallic glass of Zr(50)Cu(50) as buffer are prepared on glass substrates by the pulsed laser deposition. The influence of buffer thickness and substrate temperature on structural, optical, and electrical properties of AZO thin film are investigated. Increasing the thickness of buffer layer and substrate temperature can both promote the transformation of AZO from amorphous to crystalline structure, while they show(100)and(002) unique preferential orientations, respectively. After inserting Zr(50)Cu(50) layer between the glass substrate and AZO film, the sheet resistance and visible transmittance decrease, but the infrared transmittance increases. With substrate temperature increasing from 25℃ to 520℃, the sheet resistance of AZO(100 nm)/Zr(50)Cu(50)(4 nm) film first increases and then decreases, and the infrared transmittance is improved. The AZO(100 nm)/Zr(50)Cu(50)(4 nm) film deposited at a substrate temperature of 360℃ exhibits a low sheet resistance of 26.7 ?/, high transmittance of 82.1% in the visible light region, 81.6% in near-infrared region, and low surface roughness of 0.85 nm, which are useful properties for their potential applications in tandem solar cell and infrared technology.     

Temperature dependence of optical absorption for the visible region in transparent conducting oxides

We study theoretically the temperature dependence of the optical-absorption coefficient, for the visible region, in thin films of transparent conducting oxides by using the well-known Varshni approach relative to optical band-gap energy. Zero absorption is considered and an approximate formula for the coefficient of visible absorption is derived when photon energy is near the band-gap energy, that is, when absorption is negligible.     

Synthesis of P-type transparent conducting silver:indium oxide (AIO) thin films by reactive electron beam evaporation technique

Present paper reports the synthesis, electrical and optical properties of p-type conducting and transparent silver indium oxide (AIO) thin films prepared on glass substrates by reactive electron beam evaporation technique at three substrate temperatures (50, 200 and 250 °C) and at five evaporation rates (0.05 to 16.0 nm/s). The source material is pure powders of Ag₂O:In₂O₃=50:50 mol%. The AIO films are amorphous. The films, though not corresponding to Delafossite crystal structure, exhibit p-type conductivity, when prepared at an evaporation rate of 0.05 nm/s at all the three substrate temperatures. With increasing filament current, it is observed that (i) the electrical resistivity decreases and (ii) the refractive index of the films (at 632.8 nm, and is in the range: 1.219-1.211) decreases. The work function (effective Fermi level) has been measured on these samples by Kelvin Probe method. The results are explained on the basis of partial ionic charge and localization of covalent bonds in the AIO thin films.