Dependence of film thickness on the structural and optical properties of ZnO thin films

ZnO thin films are prepared on glass substrates by pulsed filtered cathodic vacuum arc deposition (PFCVAD) at room temperature. Optical parameters such as optical transmittance, reflectance, band tail, dielectric coefficient, refractive index, energy band gap have been studied, discussed and correlated to the changes with film thickness. Kramers-Kronig and dispersion relations were employed to determine the complex refractive index and dielectric constants using reflection data in the ultraviolet-visible-near infrared regions. Films with optical transmittance above 90% in the visible range were prepared at pressure of 6.5 × 10⁻⁴ Torr. XRD analysis revealed that all films had a strong ZnO (0 0 2) peak, indicating c-axis orientation. The crystal grain size increased from 14.97 nm to 22.53 nm as the film thickness increased from 139 nm to 427 nm, however no significant change was observed in interplanar distance and crystal lattice constant. Optical energy gap decreased from 3.21 eV to 3.19 eV with increasing the thickness. The transmission in UV region decreased with the increase of film thickness. The refractive index, Urbach tail and real part of complex dielectric constant decreased as the film thickness increased. Oscillator energy of as-deposited films increased from 3.49 eV to 4.78 eV as the thickness increased.     

Oxidation temperature dependent optical properties of bismuth oxide thin films: Effect of vapour chopping and air exposure

The optical properties of vapour chopped and nonchopped bismuth oxide thin films of two thicknesses 1500 Å and 2000 Å have been studied. The films were prepared by thermal oxidation in air; of vacuum evaporated vapour chopped and nonchopped bismuth thin films. As revealed by XRD studies, multiphase and polycrystalline bismuth oxide thin films were obtained. The refractive index was found to increase with the thickness and exposure to air for 40 days. The vapour chopped films showed higher refractive index, band gap and lower grain size than those of nonchopped films. The films showed high transmittance in the visible spectrum. The ageing effect on the vapour chopped films was found low.     

Determination of optical properties in nanostructured thin films using the Swanepoel method

We present the methodological framework of the Swanepoel method for the spectrophotometric determination of optical properties in thin films using transmittance data. As an illustrative case study, we determined the refractive index, thickness, absorption index, and extinction coefficient of a nanostructured 3 mol% Y₂O₃-doped ZrO₂ (yttria stabilized zirconia, 3YSZ) thin film prepared by the sol-gel method and deposited by dipping onto a soda-lime glass substrate. In addition, using the absorption index obtained with the Swanepoel method, we calculated the optical band gap of the film. The refractive index was found to increase, then decrease, and finally stabilize with increasing wavelength of the radiation, while the absorption index and extinction coefficient decreased monotonically to zero. These trends are explained in terms of the location of the absorption bands. We also deduced that this 3YSZ thin film has a direct optical band gap of 4.6 eV. All these results compared well with those given in the literature for similar thin films. This suggests that the Swanepoel method has an important role to play in the optical characterization of ceramic thin films.     

ZnO薄膜的光学性质研究

采用直流反应磁控溅射方法在玻璃基底上成功地淀积ｃ轴取向性好的ＺｎＯ薄膜。经过优化计算，获得并分析了不同氧分压下制备的ＺｎＯ薄膜的折射率ｎ和消光系数ｋ的数值；同时得到了吸收光学带隙Ｅｏｐｔ，用能带模型解释了Ｅｏｐｔ的变化规律。     

The effects of post-thermal annealing on the optical parameters of indium-doped ZnO thin films

Indium-doped ZnO thin films are deposited on quartz glass slides by RF magnetron sputtering at ambient temper- ature. The as-deposited films are annealed at different temperatures from 400 C to 800 C in air for 1 h. Transmittance spectra are used to determine the optical parameters and the thicknesses of the films before and after annealing using a nonlinear programming method, and the effects of the annealing temperatures on the optical parameters and the thickness are investigated. The optical band gap is determined from the absorption coefficient. The calculated results show that the film thickness and optical parameters both increase first and then decrease with increasing annealing temperature from 400 C to 800 C. The band gap of the as-deposited ZnO:In thin film is 3.28 eV, and it decreases to 3.17 eV after annealing at 400 C. Then the band gap increases from 3.17 eV to 3.23 eV with increasing annealing temperature from 400 C to 800 C.     

Calculation of optical constant of amorphous germanium arsenoselenide wedge-shaped thin films from their shrunk transmittance and reflectance spectra

The optical transmittance spectrum is influenced by inhomogeneities in germanium arsenoselenide thin films. The non-uniformity of thickness, found under the present deposition conditions, gives rise to a clear shrinking of the interference fringes of the transmittance spectrum at normal incidence. Inaccuracies and even serious errors occur if the refractive index and film thickness are calculated from such a shrunken transmittance spectrum, under the unrealistic assumption that the film is uniform. The analytical expressions proposed by Swanepoel [J. Phys. E. Sci. Instrum. 17 (1984) 896] enabled derivation of the refractive index and film thickness of a wedge-shaped thin film from its shrunk transmittance spectrum. This method was applied in this study making it possible to derive the refractive index and average thickness to an accuracy better than 1%. Dispersion of the refractive index is discussed in terms of the single-oscillator Wemple–DiDomenico model [Phys. Rev. B 3 (1971) 1338]. The absorption coefficient and, thus the extinction coefficient, can be calculated from transmittance and reflectance spectra in the strong absorption region. The optical energy gap is derived from Tauc's extrapolation [Amorphous and Liquid Semiconductor (Plenum Press, New York, 1974)]. The relationship between the optical gap and chemical composition in the Ge _x As_{30– x} Se₇₀ (with 0 ≤ x ≤ 30) amorphous system is discussed in terms of the chemical bond approach and cohesive energy.     

Influence of thickness and crystalline structure on thermal and optical properties of ZnO thin films

Measurements of the temperature dependence of refractive index of ZnO thin films and thermal diffusivity using photothermal deflection technique are presented. Thin film thickness and surface homogeneity were found to be the effective parameters on optical and thermal properties of the thin films. High refractive index gradient with temperature was found for films of a nonuniform distribution and gathered in clusters, and a high predicted value for thermal diffusivity. Optical properties of the thin films revealed that films with disorder in the deposition and gathered clusters showed poor transmittance in visible region with a pronounced peak in the near IR, and also a reduction in the band gap. A detailed parametric analysis using analytical solution of one-dimensional heat equation had been performed. A discontinuity in the temperature elevation at the ZnO-glass interface was found.     

Microstructure parameters and optical properties of cadmium ferrite thin films of variable thickness

CdFe₂O₄ thin films of different thicknesses were deposited onto glass substrates by the thermal evaporation technique. Their structural characteristics were studied by X-ray diffraction (XRD). The microstructure parameters, crystallite size, and microstrain were calculated. It is observed that both the crystallite size increases and microstrain increase with increasing with the film thickness. The fundamental optical parameters like absorption coefficient and optical band gap are calculated in the strong absorption region of transmittance and reflectance spectrum. The refractive indices have been evaluated in terms of the envelope method, which has been suggested by Swanepoel in the transparent region. The refractive index can be extrapolated by the Cauchy dispersion relationship over the whole spectra range, which extended from 400 to 2500 nm. The refractive index, n, increases on increasing the film thickness up to 733 nm and the variation of n with higher thickness lies within the experimental errors.     

Optical properties and adhesion of air oxidized vacuum evaporated bismuth thin films

Highly adhesive bismuth oxide thin films on glass have been prepared by air oxidation of vacuum evaporated bismuth thin films at various temperatures. The transmittance, optical band gap, refractive index and adhesion show temperature and oxidation time effects. The films show a direct band gap between 2 and 2.5 eV. The refractive indices are in the range 1.854-1.991. The transmittances of the bismuth oxide films are quite high in a large wavelength range. These bismuth oxide films can have potential use in optical waveguides.     

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.     

Optical parameters of epitaxial GaN thin film on Si substrate from the reflection spectrum

A method has been proposed for determining the optical properties of a thin film layer on absorbing substrates. The film optical parameters such as thickness, refractive index, absorption coefficient, extinction coefficient and the optical energy gap of an absorbing film are retrieved from the interference fringes of the reflection spectrum at normal incidence. The envelopes of the maxima of the spectrum E_M and of the minima E_m are introduced in analytical forms to find the reflectance amplitudes at the interfaces and approximate values of the thin film refractive index. Then, the interference orders and film thickness are calculated to get accurate values of the needed optical parameters. There are no complex fitting procedures or assumed theoretical refractive index dispersion relations. The method is applied to calculate the optical properties of an epitaxial gallium nitride thin film on a silicon (1 1 1) substrate. Good agreement between our results and the published data are obtained.     

Effect of thickness on structural, optical and electrical properties of nanostructured ZnO thin films by spray pyrolysis

Transparent conducting zinc oxide thin films were prepared by spray pyrolytic decomposition of zinc acetate onto glass substrates with different thickness. The crystallographic structure of the films was studied by X-ray diffraction (XRD). XRD measurement showed that the films were crystallized in the wurtzite phase type. The grain size, lattice constants and strain in films were calculated. The grain size increases with thickness. The studies on the optical properties show that the direct band gap value increases from 3.15 to 3.24 eV when the thickness varies from 600 to 2350 nm. The temperature dependence of the electrical conductivity during the heat treatment was studied. It was observed that heat treatment improve the electrical conductivity of the ZnO thin films. The conductivity was found to increase with film thickness.     

Influence of annealing temperature on optical properties of zinc oxide thin films analyzed by spectroscopic ellipsometry method

Zinc oxide (ZnO) thin films were sol–gel spin coated on glass substrates, annealed at various temperatures 300 °C, 400 °C and 500 °C and characterized by spectroscopic ellipsometry method. The optical properties of the films such as transmittance, refractive index, extinction coefficient, dielectric constant and optical band gap energy were determined from ellipsometric data recorded over the spectral range of 300–800 nm. The effect of annealing temperature in air on optical properties of the sol–gel derived ZnO thin films was studied. The transmission values of the annealed films were about 65% within the visible range. The optical band gap of the ZnO thin films were measured between 3.25 eV and 3.45 eV. Also the dispersion parameters such as single oscillator energy and dispersive energy were determined from the transmittance graph using the Wemple and DiDomenico model.     

Preparation and optical properties of nanocrystalline thin films in the ZnO-TiO<Subscript>2</Subscript> system

Nanocrystalline compound thin films of ZnO-TiO₂ with different Zn/Ti atomic ratios were prepared by radio frequency magnetron reactive sputtering. The optical constants and the optical band gap were investigated using spectroscopic ellipsometry and the optical absorption spectrum. It was found that the cubic ZnTiO₃ phase can be obtained with the atomic ratio of Zn to Ti of about 1:1, and transforms to rhombohedral ZnTiO₃ phase and a phase mixture of rhombohedral ZnTiO₃ and ZnO with increasing Zn content. The refractive index decreases with the increase of Zn content, and the extinction coefficient in the visible range is near zero. The optical band gap was derived from the modeling of ellipsometry data and extinction coefficient spectra, and compared with that obtained from optical absorption spectrum, and it was found that the optical band gaps obtained by these three methods are consistent with each other. PACS 42.70.-a; 68.55.Jk; 78.20.Ci; 81.15.Cd     

Optical properties of zinc peroxide and zinc oxide multilayer nanohybrid films

Zinc peroxide and zinc oxide nanoparticles were prepared and self-assembled hybrid nanolayers were built up using layer-by-layer (LbL) technique on the surface of glass substrate using the layer silicate hectorite and an anionic polyelectrolyte, sodium polystyrene sulfonate (PSS). Light absorption, interference and morphological properties of the hybrid films were studied to determine their thickness and refractive index. The influence of layer silicates and polymers on the self-organizing properties of ZnO₂ and ZnO nanoparticles was examined. X-ray diffraction revealed that ZnO₂ powders decomposed to ZnO (zincite phase) at relatively low temperatures (less than 200 °C). The optical thickness of the films ranged from 190 to 750 nm and increased linearly with the number of layers. Band gap energies of the ZnO₂/hectorite films were independent from the layer thickness and were larger than that of pure ZnO₂ nanodispersion. Decomposition of ZnO₂ to ZnO and O₂ at 400 °C resulted in the decrease of the band gap energy from 3.75 to 3.3 eV. Concomitantly, the refractive index increased in correlation with the formation of the zincite ZnO phase. In contrast, the band gap energies of the ZnO₂/PSS hybrid films decreased with the thickness of the nanohybrid layers. We ascribe this phenomenon to the steric stabilization of primary ZnO₂ particles present in the confined space between adjacent layers of hectorite sheets.     

Analysis of codeposited Gd2O3/SiO2 composite thin films by phase modulated spectroscopic ellipsometric technique

Tailoring of the refractive index of optical thin films has been a very fascinating as well as challenging topic for developing new generation optical coatings. In the present work a novel Gd₂O₃/SiO₂ composite system has been experimented and probed for its superior optical properties through phase modulated spectroscopic ellipsometry, spectrophotometry and atomic force microscopy. The optical parameters of the composite films have been evaluated using Tauc-Lorentz (TL) formulations. In order to derive the growth dependent refractive index profiles, each sample film has been modeled as an appropriate multilayer structure where each sub-layer was treated with the above TL parameterizations. All codeposited films demonstrated superiority with respect to the band gap and morphological measurements. At lower silica mixing compositions such as in 10-20% level, the composite films depicted superior spectral refractive index profile, band gap as well as the morphology. This aspect highlighted the fact that microstructural densifications in composite films can override the chemical compositions while deciding the refractive index and optical properties in such thin films.     

多孔阳极氧化铝薄膜光学常数的确定

根据多孔阳极氧化铝(AAO)薄膜的实验透射谱(200—2500nm)，采用极值包络线算法确定其光学常数，并由此较精确地计算出AAO薄膜样品在该波段的光学常数.结果表明，多孔氧化铝薄膜表现出直接带隙(能隙约4．5eV)半导体的光学特性，且其光学常数与制样中的重要工艺参数阳极氧化电压有显著的相关性，即随阳极氧化电压的增加，AAO薄膜的厚度、折射率和光学能隙变大，消光系数减小．同时，计算得到的薄膜厚度与实测值相吻合，则说明计算结果和实验值是自洽的. 关键词： 薄膜光学 光学常数 多孔阳极氧化铝 阳极氧化电压     

Synthesis and optical characterization of nanocrystalline CdTe thin films

From several years the study of binary compounds has been intensified in order to find new materials for solar photocells. The development of thin film solar cells is an active area of research at this time. Much attention has been paid to the development of low cost, high efficiency thin film solar cells. CdTe is one of the suitable candidates for the production of thin film solar cells due to its ideal band gap, high absorption coefficient. The present work deals with thickness dependent study of CdTe thin films. Nanocrystalline CdTe bulk powder was synthesized by wet chemical route at pH≈11.2 using cadmium chloride and potassium telluride as starting materials. The product sample was characterized by transmission electron microscope, X-ray diffraction and scanning electron microscope. The structural characteristics studied by X-ray diffraction showed that the films are polycrystalline in nature. CdTe thin films with thickness 40, 60, 80 and 100 nm were prepared on glass substrates by using thermal evaporation onto glass substrate under a vacuum of 10⁻⁶ Torr. The optical constants (absorption coefficient, optical band gap, refractive index, extinction coefficient, real and imaginary part of dielectric constant) of CdTe thin films was studied as a function of photon energy in the wavelength region 400–2000 nm. Analysis of the optical absorption data shows that the rule of direct transitions predominates. It has been found that the absorption coefficient, refractive index (n) and extinction coefficient (k) decreases while the values of optical band gap increase with an increase in thickness from 40 to 100 nm, which can be explained qualitatively by a thickness dependence of the grain size through decrease in grain boundary barrier height with grain size.     

厚度对未掺杂ZnO薄膜光谱性能的影响

X射线衍射光谱、拉曼光谱和紫外可见透射光谱技术是薄膜材料检测的重要技术手段。通过对薄膜材料光谱性能的分析,可以获得薄膜材料的物相、晶体结构和透光性能等信息。为了解厚度对未掺杂ZnO薄膜的X射线衍射光谱、拉曼光谱和紫外可见透射光谱性能的影响,利用溶胶-凝胶法在石英衬底上旋涂制备了不同厚度的未掺杂ZnO薄膜样品,并对薄膜样品进行了X射线衍射光谱、拉曼光谱和紫外可见透射光谱的检测。首先,通过X射线衍射光谱检测发现,薄膜样品呈现出（002）晶面的衍射峰,ZnO薄膜为六角纤锌矿结构,均沿着C轴择优取向生长,且随着薄膜厚度的增加,衍射峰明显增强,ZnO薄膜的晶粒尺寸随着膜厚的增加而长大。利用扫描电子显微镜对薄膜样品的表面形貌分析显示,薄膜表面致密均匀,具有纳米晶体的结构,其晶粒具有明显的六角形状。通过拉曼光谱检测发现,薄膜样品均出现了437 cm-1的拉曼峰,这是ZnO纤锌矿结构的特征峰,且随着薄膜厚度的增加,其特征拉曼峰强度也增加,进一步说明了随着ZnO薄膜厚度的增加,ZnO薄膜晶化得到了加强。最后,通过紫外可见透射光谱测试发现,随着膜厚的增加,薄膜的吸收边发生一定红移,薄膜样品在可见光区域内的透过率随着膜厚度增加而略有降低,但平均透过率都超过90%。通过对薄膜样品的紫外-可见透射光谱进一步分析,估算了薄膜样品的折射率,定量计算了薄膜样品的光学禁带宽度,计算结果表明：厚度的改变对薄膜样品的折射率影响不大,但其禁带宽度随着薄膜厚度的增加而变窄,且均大于未掺杂ZnO禁带宽度的理论值3.37 eV。进一步分析表明,ZnO薄膜厚度的变化与ZnO晶粒尺寸的变化呈正相关,本质上,吸收边或光学禁带宽度的变化是由于ZnO晶粒尺寸变化引起的。     

Optical constants of Na-doped ZnO thin films by sol-gel method

The structural and optical properties of pure and Na-doped ZnO thin films have been investigated by X-ray diffraction (XRD), atom force microscopy and UV-Vis spectrophotometer. The crystal structure of all the thin films is the hexagonal wurtzite. The average grain size and surface roughness increases with the increase of the Na/Zn ratio. The optical band gap of the thin films decreases from 3.26 to 3.12 eV by increasing the Na/Zn ratio from 0.0 to 0.10. Transmittance spectra were used to determine the optical constants of the thin films, and the effect of Na/Zn ratio on the optical constants was investigated. With the increase of Na/Zn ratio, the refractive index decreases and the extinction coefficient increases in the 380-700 nm spectral range.