Microstructures and optical properties of Cu-doped ZnO films prepared by radio frequency reactive magnetron sputtering

Pure and Cu-doped ZnO (ZnO:Cu) thin films were deposited on glass substrates using radio frequency (RF) reactive magnetron sputtering. The effect of substrate temperature on the crystallization behavior and optical properties of the ZnO:Cu films have been studied. The crystal structures, surface morphology and optical properties of the films were systematically investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and a fluorescence spectrophotometer, respectively. The results indicated that ZnO films showed a stronger preferred orientation toward the c-axis and a more uniform grain size after Cu-doping. As for ZnO:Cu films, the full width at half maxima (FWHM) of (0 0 2) diffraction peaks decreased first and then increased, reaching a minimum of about 0.42° at 350 °C and the compressive stress of ZnO:Cu decreased gradually with the increase of substrate temperature. The photoluminescence (PL) spectra measured at room temperature revealed two blue and two green emissions. Intense blue-green luminescence was obtained from the sample deposited at higher substrate temperature. Finally, we discussed the influence of annealing temperature on the structural and optical properties of ZnO:Cu films. The quality of ZnO:Cu film was markedly improved and the intensity of blue peak (∼485 nm) and green peak (∼527 nm) increased noticeably after annealing. The origin of these emissions was discussed.     

Structure and mechanical properties of reactive sputtering CrSiN films

CrSiN films with various Si contents were deposited by reactive magnetron sputtering using the co-deposition of Cr and Si targets in the presence of the reactive gas mixture. Comparative studies on microstructure and mechanical properties between CrN and CrSiN films with various Si contents were carried out. The structure of the CrSiN films was found to change from crystalline to amorphous structure as the Si contents increase. Amorphous phase of Si₃N₄ compound was suggested to exist in the CrSiN film. The growth of films has been observed from continuous columnar structure, granular structure to glassy-like appearance morphology with the increase of silicon content. The film fracture changed from continuous columnar structure, granular structure to glassy-like appearance morphology with the increase of silicon content. Two hardness peaks of the films as function of Si contents have been discussed.     

Mechanical and optical properties of CNx films with high N/C ratio

Nitrogen-rich carbon nitride films were prepared by three different deposition methods on fused silica, stainless steel and silicon cantilever substrates. Their optical properties were studied by spectroscopic ellipsometry and UV spectrometry. Mechanical properties such as plastic and Vickers microhardness, Young’s modulus, adhesion and film stress were also tested. The results were compared with the properties of films with lower nitrogen concentrations. Received: 26 January 2001 / Accepted: 29 January 2001 / Published online: 3 May 2001     

Structural and photoluminescent properties of ZnO films deposited by radio frequency reactive sputtering

Zinc oxide films with c-axis preferred orientation were deposited on silicon (100) substrates by radio frequency (RF) reactive sputtering. The properties of the sam- ples were characterized by X-ray diffractometer, X-ray photoelectron spectroscopy and fluorescent-spectrophotometer. The effect of sputtering power and substrate temperature on the structural and photoluminescent (PL) properties of the ZnO films was investigated. The results indicated that when the sputtering power is 100 W and the substrate temperature is 300-400℃, it is suitable for the growth of high c-axis orientation and small strain ZnO films. A violet peak at about 380 nm and a blue band at about 430 nm were observed in the room temperature photolumines- cence spectra, and the origin of blue emission was investigated.     

Effect of deposition parameters on structural, optical and electrical properties of nanocrystalline ZnSe thin films

This paper presents the chemical bath deposition of zinc selenide (n-ZnSe) nanocrystalline thin films on non-conducting glass substrates, in an aqueous alkaline medium using sodium selenosulphate as Se²⁻ ion source. The X-ray diffraction studies show that the deposited ZnSe material is nanocrystalline with a mixture of hexagonal and cubic phase. The direct optical band gap ‘E_g’ for the as-deposited n-ZnSe films is found to be 3.5 eV. TEM studies show that the ZnSe nanocrystals (NCs) are spherical in shape. Formation of ZnSe has been confirmed with the help of infrared (IR) spectroscopy by observing bands corresponding to the multiphonon absorption. We demonstrate the effect of the deposition temperature and reactant concentration on the structural, optical and electrical properties of ZnSe films.     

Effect of air post contamination on mechanical properties of amorphous carbon nitride thin films

We report in this study the mechanical, structural and compositional characteristics of amorphous carbon nitride films (a-CN_x) deposited on Si(100) using RF magnetron sputtering of graphite targets in pure nitrogen and under different RF powers. The properties of the films were determined in their as deposited state using nuclear reaction analysis (NRA), elastic recoil detection (ERDA), infrared (IR) absorption and Raman spectroscopy. The mechanical properties were obtained combining nanoindentation and residual stress measurements. The presence of various types of C-N bonds, as well as the post-deposition contamination of the deposited films by oxygen and water (voids) is revealed. The measured hardness and Young modulus were 0.9-2.03 and 23-27 GPa, respectively. These results have been analysed in term of the matrix flexibility which results from the nitrogen content and the porous character of the films, which can affect deeply the estimation of the physical-mechanical properties of the films.     

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.     

射频功率对辉光聚合物薄膜结构与光学性质的影响

采用三倍频射频辉光放电聚合技术,利用低压等离子聚合装置在不同功率条件下制备辉光放电聚合物(GDP)薄膜. 利用表面轮廓仪、Fourier变换红外光谱仪表征所制备薄膜在不同功率下的生长速率和化学结构, 讨论了功率变化对薄膜生长速度和化学结构的影响.利用元素分析仪和紫外可见光谱仪表征GDP薄膜中碳氢原子比和光学性质. 研究表明:薄膜的生长速率随射频功率的增大先增加后减少,功率为40 W时,生长速率可达到0.34 μm/h. 在波长大于500 nm的可见光区, GDP薄膜的光学透过率都在90%以上. GDP薄膜的光学间隙随射频功率的增大先减少后增加,射频功率为50 W时制备GDP薄膜的光学间隙最小.     

Structural and optical properties of sputtered gadolinium nitride films

Rare-earth (RE) materials have high magnetic moments and form a wide range of magnetic structures. There has been speculation in the literature that rare-earth nitrides may form half-metallic ferromagnetics. This is surprising because, based on a simple ionic model, trivalent rare-earth nitrides would be expected to be insulators with a similar electronic structure to the divalent rare-earth chalcogenides. However if it is the case that they are half-metallic or narrow gap insulators, then they have potential applications in spin-filtering devices. In the present investigation, We have deposited GdN films on glass substrate at room temperature by Ar/N₂ mixed gas plasma-radio frequency (rf) sputtering method. The structure and the complex optical properties as well as the energy gap of GdN thin films as a function of N₂ partial pressure are determined.     

Structural and optical properties of sputtered ZnO thin films

Zinc oxide (ZnO) and aluminium-doped zinc oxide (ZnO:Al) thin films were prepared by RF diode sputtering at varying deposition conditions. The effects of negative bias voltage and RF power on structural and optical properties were investigated. X-ray diffraction measurements (XRD) confirmed that both un-doped and Al-doped ZnO films are polycrystalline and have hexagonal wurtzite structure. The preferential 〈0 0 1〉 orientation and surface roughness evaluated by AFM measurements showed dependence on applied bias voltage and RF power. The sputtered ZnO and ZnO:Al films had high optical transmittance (>90%) in the wavelength range of 400-800 nm, which was not influenced by bias voltage and RF power. ZnO:Al were conductive and highly transparent. Optical band gap of un-doped and Al-doped ZnO thin films depended on negative bias and RF power and in both cases showed tendency to narrowing.     

Effect of oxygen partial pressure on the structural and optical properties of dc reactive magnetron sputtered molybdenum oxide films

Molybdenum oxide films (MoO₃) were deposited on glass and crystalline silicon substrates by sputtering of molybdenum target under various oxygen partial pressures in the range 8 × 10⁻⁵–8 × 10⁻⁴ mbar and at a fixed substrate temperature of 473 K employing dc magnetron sputtering technique. The influence of oxygen partial pressure on the composition stoichiometry, chemical binding configuration, crystallographic structure and electrical and optical properties was systematically studied. X-ray photoelectron spectra of the films formed at 8 × 10⁻⁵ mbar showed the presence of Mo⁶⁺ and Mo⁵⁺ oxidation states of MoO₃ and MoO_3−x. The films deposited at oxygen partial pressure of 2 × 10⁻⁴ mbar showed Mo⁶⁺ oxidation state indicating the films were nearly stoichiometric. It was also confirmed by the Fourier transform infrared spectroscopic studies. X-ray diffraction studies revealed that the films formed at oxygen partial pressure of 2 × 10⁻⁴ mbar showed the presence of (0 k 0) reflections indicated the layered structure of α-phase MoO₃. The electrical conductivity of the films decreased from 3.6 × 10⁻⁵ to 1.6 × 10⁻⁶ Ω⁻¹ cm⁻¹, the optical band gap of the films increased from 2.93 to 3.26 eV and the refractive index increased from 2.02 to 2.13 with the increase of oxygen partial pressure from 8 × 10⁻⁵ to 8 × 10⁻⁴ mbar, respectively.     

Investigation of thermal annealing effects on microstructural and optical properties of HfO2 thin films

In the present paper, we investigate the effect of thermal annealing on optical and microstructural properties of HfO₂ thin films (from 20 to 190 nm) obtained by plasma ion assisted deposition (PIAD). After deposition, the HfO₂ films were annealed in N₂ ambient for 3 h at 300, 350, 450, 500 and 750 °C. Several characterisation techniques including X-ray reflectometry (XRR), X-ray diffraction (XRD), spectroscopic ellipsometry (SE), UV Raman and FTIR were used for the physical characterisation of the as-deposited and annealed HfO₂ thin films. The results indicate that as-deposited PIAD HfO₂ films are mainly amorphous and a transition to a crystalline phase occurs at a temperature higher than 450 °C depending on the layer thickness. The crystalline grains consist of cubic and monoclinic phases already classified in literature but this work provides the first evidence of amorphous-cubic phase transition at a temperature as low as 500 °C. According to SE, XRR and FTIR results, an increase in the interfacial layer thickness can be observed only for high temperature annealing. The SE results show that the amorphous phase of HfO₂ (in 20 nm thick samples) has an optical bandgap of 5.51 eV. Following its transition to a crystalline phase upon annealing at 750 °C, the optical bandgap increases to 5.85 eV.     

The structure and optical properties of evaporated Samarium fluoride films

Samarium fluoride (SmF₃) films have been deposited on quartz, silicon and germanium substrates by vacuum evaporation method. The crystal structure of the films deposited on silicon substrate is examined by X-ray diffraction (XRD). The films deposited at 100 °C, 150 °C and 250 °C have the (1 1 1) preferred growth orientation, but the film deposited at 200 °C has (3 6 0) growth orientation. The surface morphology evolution of the films with different thickness is investigated with optical microscopy. It is shown that the microcrack density and orientation of thin film is different from that of thick film. The transmission spectrum of SmF₃ films is measured from 200 nm to 20 μm. It is found that this material has good transparency from deep violet to far infrared. The optical constants of SmF₃ films from 200 nm to 12 μm are calculated by fitting the transmission spectrum of the films using Lorentz oscillator model.     

射频反应磁控溅射法制备的氟化类金刚石薄膜摩擦特性研究

以高纯石墨做靶,CHF3和Ar气为源气体,采用射频反应磁控溅射法在不同流量比条件下制备了氟化类金刚石(F-DLC)薄膜.利用原子力显微镜、纳米压痕仪、拉曼光谱和红外光谱、摩擦磨损测试仪对薄膜的表面形貌、硬度、键结构以及摩擦性能做了具体分析.表面形貌测试结果表明,制备的薄膜整体均匀致密,表现出了良好的减摩性能.当CHF3与Ar气流量比r为1:6时,所得薄膜的摩擦系数减小至0.42,而纳米压痕结果显示,此时薄膜的硬度也最高.拉曼和红外光谱显示,随着r的增加,薄膜中的F浓度呈上升趋势,薄膜中的芳香环比例减小.研究表明,F原子的键入方式是影响F-DLC薄膜摩擦系数的一个重要因素,CF2反对称伸缩振动强度的减弱和CC中适量碳氢氟键的形成都能导致薄膜具有相对较低的摩擦系数.     

Effect of indium incorporation on the optical properties of spray pyrolyzed Cd0.22Zn0.78S thin films

In this study, effect of indium incorporation on the optical properties is investigated for the spray pyrolyzed onto glass substrates at 275°C substrate temperature undoped and indium doped Cd_0.22Zn_0.78S thin films. The average optical transmittance of all the films was over 77% in the wavelength range between 450 and 800 nm. The optical band gap energies of the thin films have been investigated by the measurement of the optical absorbance as a function of wavelength. The optical absorption studies reveal that the transitions are direct band gaps of 3.02 and 3.05 eV for undoped and doped indium Cd_0.22Zn_0.78S thin films, respectively. The Urbach tail parameter and optical constants such as refractive index, extinction coefficient, and dielectric constants were calculated for these films. The dispersion parameters such as single-oscillator energy and dispersive energy were discussed in terms oft he single-oscillator Wemple—DiDomenico model.     

Influence of size effect and sputtering conditions on the crystallinity and optical properties of ZnO thin films

The effects of the thickness variation, substrate type and annealing on the crystallinity parameters, luminescent and optical properties of the zinc oxide (ZnO) thin films were reported. The thin films were deposited on the glass and the amorphous quartz substrates by the standard RF-magnetron sputtering method using ZnO targets in the argon atmosphere. It has been found that the films deposited on the glass substrate manifest a clear size effect. Both the structural and the optical parameters show clearly minima on their thickness dependences. It has been shown that annealing of the comparatively thick ZnO films leads to increase of the crystallite sizes that are followed by a considerable rise of the cathodoluminescence intensity. The corresponding model of the crystallite growth is proposed.     

Microstructure and mechanical properties of reactive magnetron sputtered Ti-B-C-N nanocomposite coatings

Ti-B-C-N nanocomposite coatings with different C contents were deposited on Si (1 0 0) and high speed steel (W18Cr4V) substrates by closed-field unbalanced reactive magnetron sputtering in the mixture of argon, nitrogen and acetylene gases. These films were subsequently characterized ex situ in terms of their microstructures by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM), their nanohardness/elastic modulus and facture toughness by nano-indention and Vickers indentation methods, and their surface morphology using atomic force microscopy (AFM). The results indicated that, in the studied composition range, the deposited Ti-B-C-N coatings exhibit nanocomposite based on TiN nanocrystallites. When the C₂H₂ flow rate is small, incorporation of small amount of C promoted crystallization of Ti-B-C-N nanocomposite coatings, which resulted in increase of nano-grain size and mechanical properties of coatings. A maximum grain size of about 8 nm was found at a C₂H₂ flux rate of 1 sccm. However, the hardness, elastic modulus and fracture toughness values were not consistent with the grain size. They got to their maximum of 35.7 GPa, 363.1 GPa and 2.46 MPa m^1/2, respectively, at a C₂H₂ flow rate of 2 sccm (corresponding to about 6 nm in nano-grain size). Further increase of C content dramatically decreased not only grain size but also the mechanical properties of coatings. The presently deposited Ti-B-C-N coatings had a smooth surface. The roughness value was consistent with that of grain size.     

Annealing effects on electrical and optical properties of ZnO thin films synthesized by the electrochemical method

Microstructural and electrical properties of potentiostatically electrodeposited ZnO thin films from an aqueous bath were investigated after annealing at different temperatures in Ar and 5% H₂/Ar atmospheres. It is confirmed that the bandgap energy of ZnO thin films decreased with annealing from 3.42 to 3.27-3.29 eV by calculating the wavelength of the absorption region. The annealing at temperatures as low as 200 °C decreased the sheet resistance of ZnO thin films because of the extinction of Zn(OH)₂ in the atmosphere. In addition, the sheet resistance of ZnO thin films decreased by annealing in a 5% H₂ atmosphere, which caused an increase of carrier concentration by hydrogen reduction.     

Electrical and optical properties of silver doped indium oxide thin films prepared by reactive DC magnetron sputtering

Silver doped indium oxide (In_2−x Ag_x O_3−y) thin films have been prepared on glass and silicon substrates at room temperature (300 K) by reactive DC magnetron sputtering technique using an alloy target of pure indium and silver (80: 20 atomic %. The magnetron power (and hence the metal atom sputter flux) is varied in the range 40-80 W. The energy dispersive analysis of X-ray (EDAX) results show that the silver content in the film decreases with increasing magnetron power. The grain size of these films is of the order of 100 nm. The resistivity of these films is in the range 10⁻²-10⁻³ Ω cm. The work function of the silver-indium oxide films (by Kelvin Probe) are in the range: 4.64-4.55 eV. The refractive index of these films (at 632.8 nm) varies in the range: 1.141-1.195. The optical band gap of indium oxide (3.75 eV) shrinks with silver doping. Calculations of the partial ionic charge (by Sanderson's theory) show that silver doping in indium oxide thin films enhance the ionicity.     

Structural and optical properties of Au-implanted ZnO films

The structural and luminescence related optical behaviours of Au ion implanted ZnO films grown by magnetic sputtering and their post implantation annealing behaviours in the temperature range of 100-700 °C have been investigated. Optical absorption and transmittance spectra of the films indicate that band edge of Au-implanted ZnO has shifted to high energy range and optical band gap has increased, because the sharp difference of thermal expansion induces the lattice mismatch between ZnO and SiO₂. PL spectra reveal that UV and visible luminescence bands of ZnO films can be improved after thermal annealing due to recovery of defects and Au ions incorporation. Importantly, green luminescence band of 530 nm has been only observed in the Au-implanted and subsequently annealed ZnO films and it enhances with the increasing annealing temperature, which can be related to Au atoms or clusters in ZnO films. Furthermore, X-ray photoelectron spectroscopy measurements reveal that the Au⁰ is dominant state in Au implanted and annealed ZnO films. Possible mechanisms, such as optical transitions of Au atoms or clusters and deep level luminescence of ZnO, have been proposed for green emission.