Influence of oxygen pressure of ZnO/glass substrate produced by pulsed filtered cathodic vacuum arc deposition

The effects of oxygen pressure on the structural and optical properties of high quality transparent conductive ZnO thin films were studied in detail. ZnO thin films were prepared by pulsed filtered cathodic vacuum arc deposition system under various oxygen pressures on glass substrate at room temperature. With increasing oxygen pressure, the structure and optical properties of films change. The structural and optical properties of the ZnO thin films were investigated using X-ray diffraction, transmittance spectrometry, refractive index, oscillator parameters, energy band gap and Urbach tail. The films show c-axis oriented (0 0 2) hexagonal wurtize crystal structure. It has been found that the grain size of ZnO thin films increases from 16.9 to 22.6 nm with the increase of oxygen pressure from 3.8×10⁻⁴ to 6.9×10⁻⁴ Torr and the crystallinity is enhanced. Average transmittance is about 90% in the visible region of the ZnO thin films. From optical transmittance spectra of ZnO films, the absorption edge shifts towards the taller wavelength with an increase in oxygen pressure. The energy band gap decreases from 3.31 to 3.20 eV with an increase in oxygen pressure. The packing density investigation shows in ZnO films high packing densities (above 0.78) can be obtained.     

氧分压对磁控溅射制备ZnO薄膜的结构及光学特性的影响

采用射频反应磁控溅射法在玻璃衬底上成功制备出具有c轴高择优取向的ZnO薄膜,利用X射线衍射及紫外-可见吸收和透射光谱研究了氧分压变化对ZnO薄膜的微观结构及光吸收特性的影响。结果表明,当工作气压恒定时,用射频反应磁控溅射制备的ZnO薄膜的生长行为主要取决于成膜空间中氧的密度,合适的氧分压能够提高ZnO薄膜的结晶质量;薄膜在可见光区的平均透过率达到90%以上,且随着氧分压的增大,薄膜的光学带隙发生了一定程度的变化。采用量子限域模型对薄膜的光学带隙作了相应的理论计算,计算结果与对样品吸收谱所作的拟合结果符合较好,二者的变化趋势完全一致,表明ZnO纳米晶粒较小时,薄膜光学带隙的变化与量子限域效应有很大关系。     

Spectroscopic ellipsometry modeling of ZnO thin films with various O2 partial pressures

ZnO films were deposited on thermally oxidized SiO₂/p-type Si (100) substrates and glass substrates by DC magnetron sputtering using a metal Zn target. Three types of samples were prepared with various O₂/(Ar + O₂) ratios (O₂ partial pressure) of 20%, 50%, and 80%. The properties of these ZnO thin films were investigated using X-ray diffraction (XRD), optical transmittance, atomic force microscopy (AFM), and spectroscopic ellipsometry in the spectral region of 1.7–3.1 eV. The structural and optical properties of ZnO thin films were affected by O₂ partial pressure. Relationships between crystallinity, the ZnO surface roughness layer, and the refractive index (n) were investigated with varying O₂ partial pressure. It was shown that the spectroscopic ellipsometry extracted parameters well represented the ZnO thin film characteristics for different O₂ partial pressures.     

The influence of oxygen on the optical properties of RF-sputtered zinc oxide thin films

In this article, we investigate the effects of oxygen partial pressure in the deposition chamber on the optical properties of zinc oxide (ZnO) thin films; in particular, we examine the variation of the refractive index with oxygen flux.ZnO thin films were deposited by radio-frequency (RF) magnetron sputtering and studied by means of X-ray diffraction (XRD) and spectroscopic ellipsometry (SE). We have found a preferential c-axis growth of ZnO films, with slightly variable deposition rates from 2.6 to 3.8 Å/s. Conversely, the refractive index exhibits, from ultraviolet (UV) to near infrared (IR), a considerable and almost linear variation when the oxygen flux value in the deposition chamber varies from 0 to 10 sccm.     

Effect of temperature on pulsed laser deposition of ZnO films

ZnO thin films have been deposited on Si(1 1 1) substrates at different substrate temperature by pulsed laser deposition (PLD) of ZnO target in oxygen atmosphere. An Nd:YAG pulsed laser with a wavelength of 1064 nm was used as laser source. The influences of the deposition temperature on the thickness, crystallinity, surface morphology and optical properties of ZnO films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), selected area electron diffraction (SAED), photoluminescence (PL) spectrum and infrared spectrum. The results show that in our experimental conditions, the ZnO thin films deposited at 400 °C have the best surface morphology and crystalline quality. And the PL spectrum with the strongest ultraviolet (UV) peak and blue peak is observed in this condition.     

工作气压对磁控溅射ZnO薄膜结晶特性及生长行为的影响

采用射频反应磁控溅射方法，在Si(001)基片上制备了具有高c轴择优取向的ZnO薄膜.利用原子力显微镜、X射线衍射、透射电子显微镜和透射光谱分析技术，对不同工作气压下合成的ZnO薄膜的表面形貌、微观结构和光学性能进行表征，研究了工作气压对ZnO薄膜的结晶性能以及生长行为的影响.研究结果显示：对于Ar/O₂流量比例接近1∶1的固定比值下，ZnO薄膜的生长行为主要取决于成膜空间中氧的密度，临界工作气压介于0.5—1.0 Pa之间.当工作气压小于临界值时，ZnO薄膜的成核密度较高，且随工作气压的变化明显，ZnO的生长行为受控于氧的密度，属于氧支配的薄膜生长；当工作气压大于临界值以后，ZnO薄膜的成核密度基本保持不变，Zn原子的数量决定薄膜的生长速率；在0.1—5.0 Pa的工作气压范围内，均可获得高度c轴取向的ZnO薄膜，但工作气压的变化改变着ZnO晶粒之间的界面特征和取向关系.随着工作气压的增加，ZnO晶粒之间的界面失配缺陷减少，但平面织构特征逐渐消失，三叉晶界的空洞逐渐扩大，薄膜的密度下降，折射率减小. 关键词： ZnO薄膜 磁控溅射 表面形貌 微观结构 光学性能     

Sol–gel derived zinc oxide films: Effect of deposition parameters on structure, microstructure and photoluminescence properties

ZnO films were prepared by sol–gel method and deposited onto glass substrates with spin coating system. XRD patterns and FESEM analysis were used to investigate the effect of deposition parameters such as spin speed and molar concentration on the crystallinity and surface morphology of the films. XRD patterns show that ZnO films are polycrystalline with type-wurtzite hexagonal structure. The film which is deposited at 4000 rpm and with 0.5 M sol has the best crystallinity. The FESEM micrographs showed that the surface morphology of the films was not significantly affected from the spin speed. FESEM micrographs showed that the crystallite sizes of 1000, 4000 and 5000 rpm are almost same. But 2000 and 3000 rpm have lower crystallite sizes than the others. Also, the amount of voids in the 1 M was found higher. The effect of spin speed and molar concentration on the optical properties of ZnO films was investigated by PL spectroscopy. The electrical properties of the ZnO films were investigated by using two probe methods in dark. The highest conductivity values were obtained for ZnO films prepared by 4000 spin speed and 0.5 M of concentration.     

基片温度对PLD制备ZnO薄膜光学常数的影响

光谱椭偏仪被用来研究用脉冲激光沉积方法在Si(100)基片上,温度分别为400,500,600,700 ℃制备的ZnO薄膜的特性。利用三层Cauchy散射模型拟合椭偏参数,计算了每个温度下制备的ZnO薄膜在400~800 nm波长范围内的折射率(n)和消光系数(k)。发现基片温度对光学常数有很大的影响。通过分析XRD表征的晶体结构和 AFM表征的薄膜表面形貌,发现折射率的变化归因于薄膜堆积密度的变化。为了获得具有较好的光学和薄膜质量的ZnO薄膜,相比与其他沉积温度600 ℃或许是最佳的沉积温度。     

氧分压对PLD制备ZnO薄膜结构和发光性质的影响

采用脉冲激光沉积(PLD)技术,在Si(100)衬底上制备出高度c轴取向的ZnO薄膜。通过X射线衍射(XRD)谱,扫描电镜(SEM)和室温光致发光(PL)光谱的测量,研究了生长气氛压强的改变对薄膜结构和光致发光的影响。实验结果表明,当氧压从10Pa升高到100Pa时ZnO(002)衍射峰的半峰全宽(FWHM)增大。可以认为这是由于较高的氧压下,到达衬底表面的离子动能减小。这样部分离子没有足够的能量迁移到生长较快的(002)面,c轴取向变差,导致(002)衍射峰的强度降低,半峰全宽增大。随着氧压增大,紫外发光强度增强。这可能是氧压变大,薄膜的化学配比升高,说明化学配比对UV发光的影响要大于薄膜微结构的影响。改变氧气压强对薄膜的表面形貌也有较大的影响。     

Effects of the oxygen partial pressure and annealing atmospheres on the microstructures and optical properties of Cu-doped ZnO films

Cu-doped zinc oxide (ZnO:Cu) films were deposited on p-Si (1 0 0) substrates at 200 °C under various oxygen partial pressures by using radio frequency reactive magnetron sputtering. The properties of the films were characterized by the X-ray diffraction spectroscopy (XRD), energy dispersive spectrometer, X-ray photoelectron spectroscopy (XPS) and fluorescence spectrophotometer with the emphasis on the evolution of microstructures, element composition, valence state of Cu, optical properties. The results indicated that the properties of ZnO:Cu films were significantly affected by oxygen partial pressures. XRD measurements revealed that the sample prepared at the ratio of O₂:Ar of 15:10 sccm had the best crystal quality among all ZnO:Cu films. XPS analysis results suggested that the valence of Cu in the ZnO films was a mixed state of +1 and +2, and the integrated intensity ratio of Cu²⁺ to Cu⁺ increased with the increment of oxygen partial pressure. The photoluminescence measurements at room temperature revealed a violet, two blue and a green emission. We considered that the origin of green emission came from various oxygen defects when the ZnO:Cu films grew in oxygen poor and enriched environment. Furthermore, the influence of annealing atmosphere on the microstructures and optical properties of ZnO:Cu films were discussed.     

The effect of UV irradiation on nanocrysatlline zinc oxide thin films related to gas sensing characteristics

The effect of ultraviolet (UV) light irradiation on the nanocrystalline ZnO thin films was investigated. The degree of crystallinity, electrical conductivity, optical properties and surface properties of ZnO thin films were measured as a function of UV irradiation time. It was found that the degree of crystallinity and electrical properties of ZnO films were affected by UV irradiation, however, no noticeable change in the surface morphology was observed. The gas sensing properties of as-deposited and UV irradiated films were also measured. It was observed that the gas sensing properties were affected by the UV irradiation. The irradiation time less than 5 min has improved the sensor while the irradiation time more than 5 min degraded the sensor characteristics for a UV power density of 2.45 W cm⁻².     

Regrowth of ZnO thin film with high surface flatness and enhanced optical properties on annealed buffer layers by rf sputtering deposition

We report a study on improving the surface flatness, optical properties, and crystallinity of ZnO thin films by rf sputtering deposition. ZnO thin films grown on sapphire substrate were first exposed to post-growth annealing, and then used to regrow high-quality ZnO thin films on top. Under the same deposition conditions, the regrown ZnO layers showed much improved crystallinity, surface flatness and enhanced optical properties. The effect of the annealed layer in improving the quality of the ZnO thin film is discussed in terms of characterization results from crystal orientation, surface morphology, and photoluminescence. It was clearly observed that, during the annealing process, the ZnO grains coalesced to form larger grains and smoother surfaces, with better crystallinity and fewer defects, which resulted in the much improved quality of the regrown ZnO thin films.     

Influences of oxygen partial pressure on structure and related properties of ZrO2 thin films prepared by electron beam evaporation deposition

ZrO₂ thin films were prepared by electron beam evaporation at different oxygen partial pressures. The influences of oxygen partial pressure on structure and related properties of ZrO₂ thin films were studied. Transmittance, thermal absorption, structure and residual stress of ZrO₂ thin films were measured by spectrophotometer, surface thermal lensing technique (STL), X-ray diffraction and optical interferometer, respectively. The results showed that the structure and related properties varied progressively with the increase of oxygen partial pressure. The refractive indices and the packing densities of the thin films decreased when the oxygen partial pressure increased. The tetragonal phase fraction in the thin films decreased gradually as oxygen partial pressure increased. The residual stress of film deposited at base pressure was high compressive stress, the value decreased with the increase of oxygen partial pressure, and the residual stress became tensile with the further increase of oxygen pressure, which was corresponding to the evolution of packing densities and variation of interplanar distances.     

Effect of O2 gas partial pressure on structures and dielectric characteristics of rf sputtered ZrO2 thin films

Amorphous and polycrystalline zirconium oxide thin films have been deposited by reactive rf magnetron sputtering in a mixed argon/oxygen or pure oxygen atmosphere with no intentional heating of the substrate. The films were characterized by high-resolution transmission electron microscopy (HR-TEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and capacitance versus voltage (C-V) measurements to investigate the variation of structure, surface morphology, thickness of SiO₂-like interfacial layer as well as dielectric characteristics with different oxygen partial pressures. The films deposited at low oxygen partial pressures (less than 15%) are amorphous and dense with a smooth surface. In contrast, the films prepared at an oxygen partial pressure higher than 73% are crystallized with the microstructure changing from the mixture of monoclinic and tetragonal phases to a single monoclinic structure. The film structural transition is believed to be consequences of decrease in the oxygen vacancy concentration in the film and of increase of the energetically neutral particles in the plasma due to an increased oxygen partial pressure. SE measurements showed that significant interfacial SiO₂ growth has taken place above approximately 51%. The best C-V results in terms of relative dielectric constant values are obtained for thin films prepared at an oxygen partial pressure of 15%.     

Deposition and properties of B-N codoped p-type ZnO thin films by RF magnetron sputtering

B-N codoped p-type ZnO thin films have been realized by radio frequency (rf) magnetron sputtering using a mixture of argon and oxygen as sputtering gas. Types of conduction and electrical properties in codoped ZnO films were found to be dependent on oxygen partial pressure ratios in the sputtering gas mixture. When oxygen partial pressure ratio was 70%, the codoped ZnO film showed p-type conduction and had the best electrical properties. Additionally, the p-ZnO/n-Si heterojunction showed a clear p-n diode characteristic. XRD results indicate that the B-N codoped ZnO film prepared in 70% oxygen partial pressure ratio has high crystal quality with (0 0 2) preferential orientation. Meanwhile, the B-N codoped ZnO film has high optical quality and displays the stronger near band edge (NBE) emission in the temperature-dependent photoluminescence spectrum, the acceptor energy level was estimated to be located at 125 meV above the valence band.     

纳米ZnO生长及性质分析

利用低压金属有机化学气相沉积(LP-MOCVD)技术,在表面含有ZnO颗粒作为催化剂的Si(111)衬底上制备了ZnO纳米柱阵列。采用X射线衍射(XRD)、喇曼光谱(Raman)、扫描电子显微镜(SEM)、光致发光(PL)谱分析了样品的晶体结构质量、表面性质和光学性质。结果表明,生长出来的纳米ZnO具有较好的c轴择优取向性。发现氧分压对ZnO纳米柱的生长有重要影响:当氧分压较低时,生长基于VLS机制;当氧分压较高时,生长基于VS机制;通过对N2O流量的控制可实现对ZnO纳米材料的可控生长。     

Temperature dependence of the optical band gap and electrical conductivity of sol-gel derived undoped and Li-doped ZnO films

Undoped and lithium (Li)-doped ZnO films were prepared by sol-gel method using spin coating technique. The effects of Li content on the crystallinity and morphological properties of ZnO films were assessed by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). XRD patterns of the films showed the hexagonal wurtzite type polycrystalline structure and that the incorporation of lithium leads to substantial changes in the structural characteristics of ZnO films. The SEM and AFM measurements showed that the surface morphology of the films was affected from the lithium incorporation. The wrinkle network was observed on the surface from both SEM and AFM results for undoped ZnO. The wrinkle structure disappeared with increasing Li content. The absorption spectra of the ZnO and 5% Li-doped ZnO (LZO5) films were carried out between 140 and 400 K temperatures. The optical band gap of ZnO and LZO5 films (calculated at various temperatures) showed a linear dependence on the temperature. The absolute zero value optical band gap and the rate of change of the band gap with temperature of the ZnO and LZO5 films were found to be 3.339 and 3.322 eV, and 2.95 × 10⁻⁴ and 1.60 × 10⁻⁴ eV/K, respectively. The transport mechanisms in the ZnO and LZO5 films have been investigated by analyzing of the temperature (80-300 K) dependence of the conductivity. The activation energies of the ZnO film increased with Li content.     

Transparent conductive ZnO:Ga films prepared by DC reactive magnetron sputtering at low temperature

Ga-doped ZnO (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. The structural, electrical, and optical properties of ZnO:Ga films were investigated in a wide temperature range from room temperature up to 400 °C. The crystallinity and surface morphology of the films are strongly dependent on the growth temperatures, which in turn exert an influence on the electrical and optical properties of the ZnO:Ga films. The film deposited at 350 °C exhibited the relatively well crystallinity and the lowest resistivity of 3.4 × 10⁻⁴ Ω cm. More importantly, the low-resistance and high-transmittance ZnO:Ga films were also obtained at a low temperature of 150 °C by changing the sputtering powers, having acceptable properties for application as transparent conductive electrodes in LCDs and solar cells.     

Synthesis and characterization of ZnO thin films by thermal evaporation

ZnO thin films have been successfully synthesized by thermal evaporation of pure zinc at 900 °C under the flow of different percentages of argon and oxygen gases. The films were characterized by X-ray diffraction (XRD), variable pressure scanning electron microscopy (VPSEM), energy dispersive X-ray spectroscopy (EDS) and UV–vis spectroscopy. The aim of this paper is to study the influence of the oxygen percentage on the structural and morphological properties of the ZnO films. VPSEM results show that very thick needle structures were produced at high oxygen percentages. EDS results revealed that only Zn and O are present in the sample, indicating a composition of pure ZnO. XRD results showed that the ZnO synthesized under different quantities of oxygen were crystalline with the hexagonal wurtzite structure. UV–vis spectroscopy results indicated that the optical band gap energies from the transmission spectrum are between 3.62 and 3.69 eV for ZnO thin films.     

Surface morphology of ZnO buffer layer and its effects on the growth of GaN films on Si substrates by magnetron sputtering

ZnO thin films were first prepared on Si(111) substrates using a radio frequency magnetron sputtering system. Then the as-grown ZnO films were annealed in oxygen ambient at temperatures of 700, 800, 900, and 1000°C , respectively. The morphologies of ZnO films were studied by an atom force microscope (AFM). Subsequently, GaN epilayers about 500 nm thick were deposited on the ZnO buffer layers. The GaN/ZnO films were annealed in NH₃ ambient at 900°C. The microstructure, morphology and optical properties of GaN films were studied by x-ray diffraction (XRD), AFM, scanning electron microscopy (SEM) and photoluminescence (PL). The results are shown, their properties having been investigated particularly as a function of the ZnO layers. For better growth of the GaN films, the optimal annealing temperature of the ZnO buffer layers was 900°C.