室温下射频磁控溅射制备ZnO:Al透明导电薄膜及其性能研究

采用射频磁控溅射技术,在室温下,以ZnO:Al2O3(2%Al2O3(质量比))为靶材,在石英玻璃基底上,采用不同工艺条件制备了ZnO:Al(AZO)薄膜。使用扫描电子显微镜观察了薄膜的表面形貌,X射线衍射分析了薄膜的结构,四探针测量仪得到薄膜的表面电阻,轮廓仪测量了薄膜厚度,并计算了电阻率,最后采用分光光度计测量了薄膜的透过率;研究了溅射功率、溅射气压与薄膜厚度对薄膜电阻率及透过率的影响。结果表明:所制备的AZO薄膜具有(002)择优取向,并且发现薄膜厚度对薄膜的光电性能有明显影响,溅射气压和溅射功率对薄膜电学性能有较大影响,但是对薄膜透过率影响不大。当功率为1kW、溅射气压0.052Pa、AZO薄膜厚度为250nm时,其电阻率为8.38×10-4Ω·cm,波长在550nm处透过率为89%,接近基底的本底透过率92%。当薄膜厚度为1125 nm时薄膜的电阻率降至最低(6.16×10-4Ω·cm)。     

Characteristics of Al-doped ZnO films grown by atomic layer deposition for silicon nanowire photovoltaic device

We report the structural, electrical, and optical characteristics of Al-doped ZnO (ZnO:Al) films deposited on glass by atomic layer deposition (ALD) with various Al2O3 film contents for use as transparent electrodes. Unlike films fabricated by a sputtering method, the diffraction peak position of the films deposited by ALD progressively moved to a higher angle with increasing Al2O3 film content. This indicates that Zn sites were effectively replaced by Al, due to layer-by-layer growth mechanism of ALD process which is based on alternate self-limiting surface chemical reactions. By adjusting the Al2O3 film content, a ZnO:Al film with low electrical resistivity (9.84 x 10(-4) Omega cm) was obtained at an Al2O3 film content of 3.17%, where the Al concentration, carrier mobility, optical transmittance, and bandgap energy were 2.8 wt%, 11.20 cm2 V(-1) s(-1), 94.23%, and 3.6 eV, respectively. Moreover, the estimated figure of merit value of our best sample was 8.2 m7Omega(-1). These results suggest that ZnO:Al films deposited by ALD could be useful for electronic devices in which especially require 3-dimensional conformal deposition of the transparent electrode and surface passivation.     

Fluorine-doped tin oxide films grown by pulsed direct current magnetron sputtering with an Sn target

Fluorine-doped tin oxide (FTO) films have been deposited by pulsed DC magnetron sputtering with an Sn target. Various ratios of CF4/O2 gas were injected to enhance the optical and electrical properties of the films. The extinction coefficient was lower than 1.5×10(-3) in the range from 400 to 800?nm when the CF4O2 ratio was 0.375. The resistivity of fluorine-doped SnO2 films (1.63×10(-3)?Ω?cm) deposited at 300?°C was 27.9 times smaller than that of undoped SnO2 (4.55×10(-2)?Ω?cm). Finally, an FTO film was consecutively deposited for protecting the oxidation of indium tin oxide films. The resistivity of the double-layered film was 2.68×10(-4)?Ω?cm, which increased by less than 39% at a 450?°C annealing temperature for 1?h in air.     

Optical properties of electrochemically deposited ZnO thin films on colloidal crystal film of SiO2 microspheres

The optical properties of electrochemically deposited ZnO thin films on colloidal crystal film of SiO2 microspheres structures were studied. Colloidal crystal film of SiO2 microspheres were self-assembled by evaporation using SiO2 in solution at a constant 0.1 wt%. ZnO in thin films was then electrochemically deposited on to colloidal crystal film of SiO2 microspheres. During electrochemical deposition, the content of Zn(NO3)2 x 6H2O in solution was 5 wt%, and the process's conditions were varied between of 2-4 V and 30-120 s at room temperature, with subsequent heat-treatment between 200 and 400 degrees C. A smooth surface and uniform thickness of 1.8 microm were obtained at 3 V for 90 s. The highest PL peak intensity was obtained in the ZnO thin film heat-treated at 400 degrees C. The double layered ZnO/SiO2 colloidal crystals showed clearly better emission properties than the SiO2/ZnO and ZnO structures.     

磁控溅射制备镁镓共掺氧化锌透明半导体薄膜及其性能研究

以MgO∶Ga_2O_3∶ZnO(2%∶2%∶96%,质量分数)陶瓷靶作为溅射源,采用磁控溅射技术在石英玻璃衬底上制备了镁镓共掺氧化锌(MGZO)透明半导体薄膜。采用XRD、SEM、霍尔效应仪和分光光度计对MGZO薄膜进行测试表征,研究了溅射压强对MGZO薄膜晶体结构、电学性质和光学性能的影响。结果表明:所有MGZO薄膜均为六角纤锌矿结构并具有(002)择优取向生长特性,溅射压强对薄膜晶体结构和光电性能有明显影响,但几乎不影响其直接光学能隙(3.41~3.44eV)。当溅射压强为3.5Pa时,MGZO薄膜的结晶质量最好、张应力最小(8.29×10-2 GPa)、电阻率最低(1.62×10-3Ω·cm)、可见光区平均透过率最高(87.8%)、品质因数最大(4.76×103Ω~(-1)·cm~(-1)),具有最好的光电综合性能。     

Atomic layer deposition of SiO2 thin films using tetrakis(ethylamino)silane and ozone

We examined the atomic layer deposition (ALD) of silicon dioxide thin films on a silicon wafer by alternating exposures to tetrakis(ethylamino)silane [Si(NHC2H5)4] and O3. The growth kinetics of silicon oxide films was examined at substrate temperatures ranging from 325 to 514 degrees C. The deposition was governed by a self-limiting surface reaction, and the growth rate at 478 degrees C was saturated at 0.17 nm/cycle for Si(NHC2H5)4 exposures of 2 x 10(6) L (1 L = 10(-6) Torr x s). The films deposited at 365-404 degrees C exhibited a higher deposition rate of 0.20-0.21 nm/cycle. However, they contained impurities, such as carbon and nitrogen, and showed poor film qualities. The concentration of impurities decreased with increasing substrate temperature. It was found that the films deposited in the high-temperature regime (478-514 degrees C) showed excellent physical and electrical properties equivalent to those of LPCVD films.     

介孔硅基WO3纳米颗粒薄膜室温气敏元件特性

采用双槽电化学腐蚀法在p＋单晶硅片表面制备介孔硅层（meso-PSlayer）,然后用对向靶磁控反应溅射法在介孔硅表面沉积WO3纳米颗粒薄膜,在干燥空气中于400℃下保温4h进行退火热处理,制备出介孔硅基WO3纳米颗粒薄膜（WO3-PS）室温气敏元件.利用扫描电子显微镜（SEM）分析介孔硅层及WO3-PS的表面形貌,通过X射线衍射（XRD）研究WO3的结晶状态,测试WO3-PS气敏元件在室温下对NO2、NH3的气敏性能,并探讨了WO3-PS气敏元件的工作机理.实验结果表明,在介孔硅表面沉积WO3纳米颗粒薄膜可使介孔硅的气敏性能显著提高,其中在室温下对10×10^-6NO2的灵敏度由5提高至56,大大提高了介孔硅的灵敏度,并降低了其响应/恢复时间,提高了对NO2的选择性.     

Effect of Ni7+ Ion Irradiation on Structure and Ammonia Sensing Properties of Thermally Oxidized Zinc and Indium Films

ZnO and In2O3 films were prepared by thermal oxidation of vacuum deposited zinc and indium films, respectively onto the glass substrate at 30 C. The fabricated films have been irradiated with 100-MeV Ni7+ ions at different fluences ranging from 5×1011 to 5×1013 ions/cm2. The structural and gas sensing properties of pristine and irradiated films have been discussed. X-ray diffraction (XRD) pattern of pristine and irradiated films reveal that the films are polycrystalline in nature and crystallinity increases after irradiation. In this study, highly porous In2O3 nanorods evolved when being irradiated at a fluence of 5×1013 ions/cm2 while ZnO film shows decrease in number of nanowires. The ammonia sensing performance of the Ni7+ irradiated In2O3 films shows an improvement as compared to its pristine counterpart.     

Optical and photoconductivity properties of ZnO thin films grown by pulsed filtered cathodic vacuum arc deposition

High quality transparent conductive ZnO thin films with various thicknesses were prepared by pulsed filtered cathodic vacuum arc deposition (PFCVAD) system on glass substrates at room temperature.The high quality of the ZnO thin films was verified by X-ray diffraction and optical measurements. XRD analysis revealed that all films had a strong ZnO (200) peak, indicating c-axis orientation. The ZnO thin films are very transparent (92%) in the near vis regions. For the ZnO thin films deposited at a pressure of 0.086 Pa (6.5 × 10⁻⁴ Torr) optical energy band gap decreased from 3.21 eV to 3.19 eV with increasing the thickness. Urbach tail energy also decreased as the film thickness increased.Spectral dependence of the photoconductivity was obtained from measurements of the samples deposited at various thicknesses. Photoconductivities were observed at energies lower than energy gap which indicates the existence of energy states in the forbidden gap. Photoconductivities of ZnO thin films increase with energy of the light and reach its maximum value at around 2.32 eV. Above this value surface recombination becomes dominant process and reduces the photocurrent. The photoconductivity increases with decreasing the film thickness.     

Preferential growth of ZnO thin films by the atomic layer deposition technique

Preferred orientation of ZnO thin films deposited by the atomic layer deposition (ALD) technique could be manipulated by deposition temperature. In this work, diethyl zinc (DEZn) and deionized water (H(2)O) were used as a zinc source and oxygen source, respectively. The results demonstrated that (10.0) dominant ZnO thin films were grown in the temperature range of 155-220?°C. The c-axis crystal growth of these films was greatly suppressed. Adhesion of anions (such as fragments of an ethyl group) on the (00.2) polar surface of the ZnO thin film was believed to be responsible for this suppression. In contrast, (00.2) dominant ZnO thin films were obtained between 220 and 300?°C. The preferred orientations of (10.0) and (00.2) of the ZnO thin films were examined by XRD texture analysis. The texture analysis results agreed well with the alignments of ZnO nanowires (NWs) which were grown from these ZnO thin films. In this case, the nanosized crystals of ZnO thin films acted as seeds for the growth of ZnO nanowires (NWs) by chemical vapor deposition (CVD) process. The highly (00.2) textured ZnO thin films deposited at high temperatures, such as 280?°C, contained polycrystals with the c?axis perpendicular to the substrate surface and provided a good template for the growth of vertically aligned ZnO NWs.     

The effect of sputtering gas pressure on structure and photocatalytic properties of nanostructured titanium oxide self-cleaning thin film

Titanium oxide thin films were deposited by DC reactive magnetron sputtering on ZnO (80 nm thickness)/soda-lime glass and SiO₂ substrates at different gas pressures. The post annealing on the deposited films was performed at 400 °C in air atmosphere. The results of X-ray diffraction (XRD) showed that the films had anatase phase after annealing at 400 °C. The structure and morphology of deposited layers were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface grain size and roughness of TiO₂ thin films after annealing were around 10-15 nm and 2-8 nm, respectively. The optical transmittance of the films was measured using ultraviolet-visible light (UV-vis) spectrophotometer and photocatalytic activities of the samples were evaluated by the degradation of Methylene Blue (MB) dye. Using ZnO thin film as buffer layer, the photocatalytic properties of TiO₂ films were improved.     

Al2O3 and TiO2 atomic layer deposition on copper for water corrosion resistance

Al(2)O(3) and TiO(2) atomic layer deposition (ALD) were employed to develop an ultrathin barrier film on copper to prevent water corrosion. The strategy was to utilize Al(2)O(3) ALD as a pinhole-free barrier and to protect the Al(2)O(3) ALD using TiO(2) ALD. An initial set of experiments was performed at 177 °C to establish that Al(2)O(3) ALD could nucleate on copper and produce a high-quality Al(2)O(3) film. In situ quartz crystal microbalance (QCM) measurements verified that Al(2)O(3) ALD nucleated and grew efficiently on copper-plated quartz crystals at 177 °C using trimethylaluminum (TMA) and water as the reactants. An electroplating technique also established that the Al(2)O(3) ALD films had a low defect density. A second set of experiments was performed for ALD at 120 °C to study the ability of ALD films to prevent copper corrosion. These experiments revealed that an Al(2)O(3) ALD film alone was insufficient to prevent copper corrosion because of the dissolution of the Al(2)O(3) film in water. Subsequently, TiO(2) ALD was explored on copper at 120 °C using TiCl(4) and water as the reactants. The resulting TiO(2) films also did not prevent the water corrosion of copper. Fortunately, Al(2)O(3) films with a TiO(2) capping layer were much more resilient to dissolution in water and prevented the water corrosion of copper. Optical microscopy images revealed that TiO(2) capping layers as thin as 200 ? on Al(2)O(3) adhesion layers could prevent copper corrosion in water at 90 °C for ~80 days. In contrast, the copper corroded almost immediately in water at 90 °C for Al(2)O(3) and ZnO films by themselves on copper. Ellipsometer measurements revealed that Al(2)O(3) films with a thickness of ~200 ? and ZnO films with a thickness of ~250 ? dissolved in water at 90 °C in ~10 days. In contrast, the ellipsometer measurements confirmed that the TiO(2) capping layers with thicknesses of ~200 ? on the Al(2)O(3) adhesion layers protected the copper for ~80 days in water at 90 °C. The TiO(2) ALD coatings were also hydrophilic and facilitated H(2)O wetting to copper wire mesh substrates.     

Natively textured surface aluminum-doped zinc oxide transparent conductive layers for thin film solar cells via pulsed direct-current reactive magnetron sputtering

Natively textured surface aluminum-doped zinc oxide (ZnO:Al) layers for thin film solar cells were directly deposited without any surface treatments via pulsed direct-current reactive magnetron sputtering on glass substrates. Such an in-situ texturing method for sputtered ZnO:Al thin films has the advantages of efficiently reducing production costs and dramatically saving time in photovoltaic industrial processing. High purity metallic Zn-Al (purity: 99.999%, Al 2.0 wt.%) target and oxygen (purity: 99.999%) were used as source materials. During the reactive sputtering process, the oxygen gas flow rate was controlled using plasma emission monitoring. The performance of the textured surface ZnO:Al transparent conductive oxides (TCOs) thin films can be modified by changing the number of deposition rounds (i.e. thin-film thicknesses). The initially milky ZnO:Al TCO thin films deposited at a substrate temperature of ~ 553 K exhibit rough crater-like surface morphology with high transparencies (T ~ 80-85% in visible range) and excellent electrical properties (ρ ~ 3.4 × 10^− 4 Ω cm). Finally, the textured-surface ZnO:Al TCO thin films were preliminarily applied in pin-type silicon thin film solar cells.     

A ZnO nanowire vacuum pressure sensor

In this study, we report the growth and characterization of lateral ZnO nanowires (NWs) on ZnO:Ga/glass templates. Using x-ray diffraction and micro-Raman spectroscopy, it was found that crystal quality of the as-grown ZnO NWs is good. It was also found that the average length and average diameter of the laterally grown ZnO NWs were 5?μm and 30?nm, respectively. A vacuum pressure sensor was then fabricated using a single NW bridging across two electrodes. By measuring the current-voltage characteristics of the samples at low pressure, we found that the currents were of 17, 34.28, 57.37 and 96.06?nA for the ZnO NW measured at 1 × 10(-3)?Torr, 1 × 10(-4)?Torr, 3 × 10(-5)?Torr and 5 × 10(-6)?Torr, respectively. These values suggest that the laterally grown ZnO NWs prepared in this study are potentially useful for vacuum pressure sensing.     

掺钼氧化锌透明导电薄膜光学性质研究

采用直流磁控反应溅射制备了掺钼氧化锌透明导电薄膜。研究了掺钼氧化锌薄膜的结构、表面形貌及其光学和电学性能。原子力显微镜扫描显示薄膜表面较为平整致密。制备出的掺钼氧化锌薄膜最低电阻率为9.4×10-4Ω.cm,相应载流子迁移率为27.3cm2V-1s-1,载流子浓度为3.1×1020cm-3。在可见光区域的平均透射率大于85%,折射率(550nm)为1.853,消光系数为7.0×10-3。通过调节氧分压可以调节薄膜载流子浓度,禁带宽度随载流子浓度的增加由3.37增大到3.8eV,薄膜的载流子有效质量m*为0.33倍的电子质量。     

The role of the Zn buffer layers in the structural and photoluminescence properties of ZnO films on Zn buffer layers deposited by RF magnetron sputtering

Highly c-axis oriented ZnO thin films were grown on Si (100) substrates with Zn buffer layers. Effects of the Zn buffer layer thickness on the structural and optical qualities of ZnO thin films were investigated for the ZnO films with the buffer layers 90, 110, and 130 nm thick using X-ray diffraction (XRD), photoluminescence (PL) and atomic force microscopy (AFM) analysis techniques. It was confirmed that the quality of a ZnO thin film deposited by RF magnetron sputtering was substantially improved by using a Zn buffer layer. The highest ZnO film quality was obtained with a Zn buffer layer 110 nm thick. The surface roughness of the ZnO thin film increases as the Zn buffer layer thickness increases.     

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.     

Effect of variable pressure on growth and photoluminescence of ZnO nanostructures

Thin films constituted of equiaxed and one dimensional nanostructures of ZnO via metal-catalyst-free vapor phase were grown using a simplistic thermal evaporation technique under two different pressure conditions approximately of the order of 10(-1) and 10(-3) torr, respectively. ZnO deposited at low vacuum (approximately 10(-1) torr) exhibited the formation of nanograins of variable size between 60 to 180 nm. In contrast the film grown at high vacuum (approximately 10(-3) torr) resulted the nanowired type morphology with a random networking, generally distributed with equiaxed grains of film microstructure. The diameter of maximum number of these nanowires lies between 45 to 65 nm. The films grown at low vacuum has shown almost equal composition of Zn and O while the film grown at high vacuum has shown lower content of O. The nanowires formed under limited O (high vacuum: approximately 10(-3) torr) signifies the role of O vacancies during growth. It has been postulated that presumably under high vacuum deposition, initially formed ZnO transforms to ZnOx (x < 1) through creation of O vacancies due to limited presence of O. Subsequently ZnOx acts as self-catalyst and heterogeneous nuclei are responsible for the formation of nanowired type morphology. The effect of different microstructures has been correlated and discussed to understand the photoluminescence characteristics obtained on these films.     

溅射法制备Mn-Zn铁氧体薄膜的磁性与微结构

以交替真空溅射的方法使用成分分别为MnFe2O4与ZnFe2O4的双靶制备了成分变化的系列Mn1-xZnxFe2O4铁氧体薄膜,衬底为Si(100)。薄膜的成分通过控制不同靶的溅射时间来进行调整。沉积态的薄膜呈非晶结构,在真空炉中以适当的温度对薄膜进行退火之后能够得到多晶Mn-Zn铁氧体薄膜。组成成分为Mn0.5Zn0.5Fe2O4的薄膜呈现了相对最高的饱和磁化强度。同时还研究了制备条件对薄膜结构与磁性的影响,如溅射氧分压,退火真空度,退火温度及薄膜厚度等等。制备的薄膜相对于块状材料具有较高的矫顽力,进而讨论了应力对薄膜矫顽力的影响。