Effect of strain on the structural and optical properties of Cu-N co-doped ZnO thin films

Polycrystalline ZnO thin films co-doped with Cu and N have been obtained by chemical bath deposition. Introduction of Cu and N causes the change of strained stress in ZnO films, which subsequently affects the structural and optical properties. The dependence of structural and optical properties of the ZnO films on lattice strained stress is investigated by XRD measurement, SEM, PL spectrum, optical reflection and Raman spectrum. The result of photoluminescence of Cu-N co-doped ZnO films indicates that the UV emission peaks shift slightly towards higher energy side with decrease in tensile strain and vise versa. The blue-shift of the absorption edge and up-shift of E2 (high) mode of the films can be observed in the optical reflection and Raman spectra.     

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.     

Improvement of electrical and optical properties of Ga and N co-doped p-type ZnO thin films with thermal treatment

Ga and N co-doped p-type ZnO thin films were epitaxially grown on sapphire substrate using magnetron sputtering technique. The process of synthesized Ga and N co-doped ZnO films was performed in ambient gas of N₂O. Hall measurement shows a significant improvement of p-type characteristics with rapid thermal annealing (RTA) process in N₂ gas flow, where more N acceptors are activated. The film rapid thermal annealed at 900 °C in N₂ ambient revealed the highest carrier concentration of 9.36 × 10¹⁹ cm⁻³ and lowest resistivity of 1.39 × 10⁻¹ Ω cm. In room and low temperature photoluminescence measurements of the as grown and RTA treated film, donor acceptor pair emission and exciton bound to acceptor recombination at 3.25 and 3.357 eV, respectively, were observed.     

Structural,optical and magnetic properties of Cu and V co-doped ZnO nanoparticles

Zn_0.98−xCu_xV_0.02O (x=0, 0.01, 0.02 and 0.03) samples were synthesized by the sol–gel technology to dope up to 3% Cu in ZnO. Investigations of structural, optical and magnetic properties of the samples have been done. The results of X-ray diffraction (XRD), transmission electron microscope (TEM) and X-ray photoelectron spectroscopy (XPS) indicated that the V and Cu ions were incorporated into the crystal lattices of ZnO. With Cu doping concentration increasing up to 2 at%, the XRD results showed that all diffraction peaks corresponded to the wurtzite structure of ZnO. Photoluminescence (PL) measurements showed that Zn_0.98−xCu_xV_0.02O powders exhibited that the position of the ultraviolet (UV) emission peak of the samples showed an obvious red-shift and the green emission peak enhanced significantly with Cu doping in ZnVO nanoparticle. Magnetic measurements indicated that room temperature ferromagnetism (RTFM) of Zn_0.98−xCu_xV_0.02O was an intrinsic property when Cu concentration was less than 3 at%. The saturation magnetization (M_s) of Zn_0.98−xCu_xV_0.02O (x=0, 0.01 and 0.02) increased with the increase of the Cu concentration.     

Mn掺杂ZnO薄膜的结构及光学性能研究

通过脉冲激光沉积(PLD)法在SiO₂基片上制备了不同含量的Mn掺杂ZnO薄膜.X射线衍射、X射线能谱、原子力显微镜与紫外-可见分光光度计测试结果表明：少量的Mn离子的掺杂并没有改变薄膜的结构，薄膜具有(103)面的择优取向；PLD法制备的ZnO薄膜的成分与靶材基本一致，实现了薄膜的同组分沉积；薄膜表面比较平坦，起伏度小于80nm，颗粒尺寸主要集中在25nm附近；但是Mn离子的掺杂改变了ZnO薄膜的禁带宽度，随Mn掺杂含量的增加，ZnO薄膜的禁带宽度增加；当薄膜中Mn含量从6%增加到 关键词： PLD ZnO薄膜 Mn掺杂 吸收谱     

Investigation of structural and optical properties of ZnO films co-doped with fluorine and indium

Undoped ZnO film and ZnO films, which are co-doped with F and In (FIZO) at different concentrations, were synthesized by sol–gel technique and the effects of co-doping of F and In on structural and optical properties of ZnO thin films were investigated. The concentration ratio of [F]/[Zn] was altered from 0.25 to 1.75 with 0.50 step at.% mole and [In]/[Zn] was altered from 0.25 to 1.00 with 0.25 step at.% mole. X-ray diffraction analysis indicates that the films have polycrystalline nature and the (0 0 2) preferred orientation is the stronger peak. No extra phases involving zinc, fluorine and indium compounds were observed even at high F and In content. The grain size of undoped ZnO and FIZO thin films varied between 15 and 20 nm with a small fluctuation. From the SEM images, although the undoped ZnO had a smooth and particle-shaped surface, FIZO films had nanofiber-networks shapes over the surface with average size of 500 nm. The surface morphologies and crystallite sizes for the F and In doped films were slightly different from than those of undoped film. From the optical study, a slight shrinkage of band gap was backwardly observed from 3.36 to 3.25 eV with the increasing of F and In content.     

Structure distortion, optical and electrical properties of ZnO thin films co-doped with Al and Sb by so--gel spin coating

ZnO thin films co-doped with Al and Sb with different concentrations and a fixed molar ratio of AlCl₃ to SbCl₃ at 1:2, are prepared by a sol--gel spin-coating method on glass annealed at 550 ℃ for 2 h in air. The x-ray diffraction results confirm that the ZnO thin films co-doped with Al and Sb are of wurtzite hexagonal ZnO with a very small distortion, and the biaxial stresses are 1.03×10⁸, 3.26×10⁸, 5.23×10⁸, and 6.97×10⁸ Pa, corresponding to those of the ZnO thin films co-doped with Al and Sb in concentrations of 1.5, 3.0, 4.5, 6.0 at% respectively. The optical properties reveal that the ZnO thin films co-doped with Al and Sb have obviously enhanced transmittance in the visible region. The electrical properties show that ZnO thin film co-doped with Al and Sb in a concentration of 1.5 at% has a lowest resistivity of 2.5Ω·cm.     

Structure distortion,optical and electrical properties of ZnO thin films co-doped with Al and Sb by sol-gel spin coating

ZnO thin films co-doped with Al and Sb with different concentrations and a fixed molar ratio of AlCl 3 to SbCl 3 at 1:2, are prepared by a sol-gel spin-coating method on glass annealed at 550°C for 2 h in air. The x-ray diffraction results confirm that the ZnO thin films co-doped with Al and Sb are of wurtzite hexagonal ZnO with a very small distortion, and the biaxial stresses are 1.03×10 8 , 3.26×10 8 , 5.23×10 8 , and 6.97×10 8 Pa, corresponding to those of the ZnO thin films co-doped with Al and Sb in concentrations of 1.5, 3.0, 4.5, 6.0 at% respectively. The optical properties reveal that the ZnO thin films co-doped with Al and Sb have obviously enhanced transmittance in the visible region. The electrical properties show that ZnO thin film co-doped with Al and Sb in a concentration of 1.5 at% has a lowest resistivity of 2.5Ω·cm.     

Structural and optical properties of pulsed laser deposited ZnO thin films

Nanocrystalline ZnO thin films were grown by means of pulsed laser deposition. The ablation process was carried out at relatively low background oxygen gas pressure (10 Pa) and by varying the substrate temperature up to 600 °C. Information on the structural and morphological properties of the deposited thin films have been obtained by means of X-ray photoelectron, Raman spectroscopies, X-ray diffraction (XRD) and atomic force microscopy (AFM). The results showed that all the deposited films are sub-stoichiometric in oxygen and with a hexagonal wurtzite crystalline structure, characterized by features of some tens of nanometers in size. An improvement of the films' crystalline quality was observed for the deposition temperature of 300 °C while the further increase of the deposition temperature up to 600 °C induces a worsening of the material's structural properties with the development of a large amount of nanoparticle's clusters. The analysis of the XRD patterns shows a growth crystallographic preferential direction as a function of the deposition temperature, in agreement with the appearance of the only E₂ optical phonon mode in the Raman spectra. Such findings are compatible with the changes observed in the photoluminescent (PL) optical response and was related to the modification of the ZnO thin film structural quality.     

纳米ZnO和ZnO-SiO2复合薄膜的光学性质研究

通过溶胶凝胶(sol-gel)法分别在玻璃衬底上制备了ZnO纳米薄膜和ZnO-SiO2纳米复合薄膜,并利用紫外.可见光分光光度计对薄膜的光学性能进行了分析.可见光一紫外透射谱显示,随着Zn0溶胶浓度从0.7 mol/L降低到0.006 mol/L,制备的ZnO薄膜从只出现一个380 nm(对应的光学禁带宽度为3.27 eV)左右的吸收边到在380和320nm(对应的光学禁带宽度为3.76 ev)左右各出现一个吸收边,并且随着ZnO溶胶浓度的降低,在380-320 nm波段内的透过率明显提高.而ZnO-SiO2复合薄膜只在310 nm左右出现一个吸收边.SiOO2的包覆宽化了ZnO的禁带宽度,包覆后的禁带宽度可达到3.87 ev.     

Effect of K-doping on structural and optical properties of ZnO thin films

In this work, K-doped ZnO thin films were prepared by a sol–gel method on Si(111) and glass substrates. The effect of different K-doping concentrations on structural and optical properties of the ZnO thin films was studied. The results showed that the 1 at.% K-doped ZnO thin film had the best crystallization quality and the strongest ultraviolet emission ability. When the concentration of K was above 1 at.%, the crystallization quality and ultraviolet emission ability dropped. For the K-doped ZnO thin films, there was not only ultraviolet emission, but also a blue emission signal in their photoluminescent spectra. The blue emission might be connected with K impurity or/and the intrinsic defects (Zn interstitial and Zn vacancy) of the ZnO thin films.     

Electrical and optical properties of Al-doped ZnO thin films by sol-gel process

Al-doped ZnO (AZO) thin films oriented along the (0 0 2) plane have been prepared by the sol-gel process and their electrical and optical properties with post-deposition heating temperature were investigated. The preferred c-axis orientation along the (0 0 2) plane was enhanced with increasing post-deposition heating temperature and the surface of the films showed a uniform and nano-sized microstructure. The electrical resistivity of the films decreased from 73 to 22 Ω cm as the post-deposition heating temperature increased from 500 to 650 °C; however, the film postheated at 700 °C increased greatly to 580 Ω cm. The optical transmittance of the films postheated below 650 °C was over 86%, but it decreased at 700 °C. The electrical and optical properties of the AZO films with post-deposition heating temperature are discussed.     

Engineering of electronic and optical properties of ZnO thin films via Cu doping

ZnO thin films doped with different Cu concentrations are fabricated by reactive magnetron sputtering technique. XRD analysis indicates that the crystal quality of the ZnO:Cu film can be enhanced by a moderate level of Cu-doping in the sputtering process. The results of XPS spectra of zinc, oxygen, and copper elements show that Cu-doping has an evident and complicated effect on the chemical state of oxygen, but little effect on those of zinc and copper. Interestingly, further investigation of the optical properties of ZnO:Cu samples shows that the transmittance spectra exhibit both red shift and blue shift with the increase of Cu doping, in contrast to the simple monotonic behavior of the Burstein–Moss effect. Analysis reveals that this is due to the competition between oxygen vacancies and intrinsic and surface states of oxygen in the sample. Our result may suggest an effective way of tuning the bandgap of ZnO samples.     

The crystalline structure,conductivity and optical properties of Co-doped ZnO thin films

Transparent conductive Co-doped ZnO thin films were deposited by ultrasonic spray technique. Conditions of preparation have been optimized to get good quality. A set of cobalt (Co)-doped ZnO (between 0 and 3 wt%) thin films were grown on glass substrate at 350 °C. The thin films were annealed at 500 °C for improvement of the physical properties. Nanocrystalline films with hexagonal wurtzite structure and a strong (0 0 2) preferred orientation were obtained. The maximum value of grain size G = 63.99 nm is attained with undoped ZnO film. The optical transmissions spectra showed that both the undoped and doped ZnO films have transparency within the visible wavelength region. The band gap energy decreased after doping from 3.367 to 3.319 eV when Co concentration increased from 0 to 2 wt% with slight increase of electrical conductivity of the films from 7.71 to 8.33 (Ω cm)⁻¹. The best estimated structure, optical and electrical results are achieved in Co-doped ZnO film with 2 wt%.     

Electrical and optical properties of Sb-doped ZnO thin films synthesized by sol–gel method

Sb-doped ZnO thin films with different values of Sb content （from 0 to 1.1 at.%） are deposited by the sol-gel dip- coating method under different sol concentrations. The effects of Sb-doping content, sol concentration, and annealing ambient on the structural, optical, and electrical properties of ZnO films are investigated. The results of the X-ray diffraction and ultraviolet-visible spectroscopy （UV-VIS） spectrophotometer indicate that each of all the films retains the wurtzite ZnO structure and possesses a preferred orientation along the c axis, with high transmittance （〉 90%） in the visible range. The Hall effect measurements show that the vacuum annealed thin films synthesized in the sol concentration of 0.75 mol/L each have an adjustable n-type electrical conductivity by varying Sb-doping density, and the photoluminescence （PL） spectra revealed that the defect emission （around 450 nm） is predominant. However, the thin films prepared by the sol with a concentration of 0.25 mol/L, despite their poor conductivity, have priority in ultraviolet emission, and the PL peak position shows first a blue-shift and then a red-shift with the increase of the Sb doping content.     

Characteristics of ZnO:Al thin films co-doped with hydrogen and fluorine

Fluorine and hydrogen co-doped ZnO:Al (AZO) films were prepared by radio frequency (rf) magnetron sputtering of ZnO targets containing 1 wt.% Al₂O₃ on Corning glass at substrate temperature of 150 °C with Ar/CF₄/H₂ gas mixtures, and the structural, electrical and optical properties of the as-deposited and the vacuum-annealed films were investigated. In as-deposited state, films with fairly low resistivity of 3.9-4 × 10⁻⁴ Ω cm and very low absorption coefficient below 900 cm⁻¹ when averaged in 400-800 nm could be fabricated. After vacuum-heating at 300 °C, the minimum resistivity of 2.9 × 10⁻⁴ Ω cm combined with low absorption loss in visible region, which enabled the figure of merit to uplift as high as 4 Ω⁻¹, could be obtained for vacuum-annealed film. It was shown that, unlike hydrogenated ZnO films which resulted in degradation upon heating in vacuum at moderately high temperature, films with fluorine addition could yield improved electrical properties mostly due to enhanced Hall mobility while preserving carrier concentration level. Furthermore, stability in oxidizing environment could be improved by fluorine addition, which was ascribed to the filling effect of dangling bonds at the grain boundaries. These results showed that co-doping of hydrogen and fluorine into AZO films with low Al concentration could be remarkably compatible with thin film solar cell applications.     

The microstructure, optical, and electrical properties of sol–gel-derived Sc-doped and Al–Sc co-doped ZnO thin films

Transparent conductive ZnO:Al–Sc (1:0.5, 1:1, 1:1.5 at.% Al–Sc) thin films were prepared on glass substrates by sol–gel method. The microstructure, optical, and electrical properties of ZnO:Sc and ZnO:Al–Sc films were investigated. Results show that Sc-doping alone obviously decreases grain size and degrades the crystallinity; there is an amorphous phase on the surface of ZnO grains; the transmittance spectra fluctuate dramatically with a large absorption valley at about 430–600 nm. However, Al–Sc co-doping can stabilize grain size and improve the microstructure; an average visible transmittance of above 73% is obtained with no large absorption valley; the amorphous phase does not appear. The optical band gaps of ZnO:Sc and ZnO:Al–Sc films (3.30–3.32 eV) are blue-shifted relative to pure ZnO film (3.30 eV). Hall effects show that the lowest resistivity of 2.941 × 10⁻² Ω cm and the maximum Hall mobility of 24.04 cm²/V s are obtained for ZnO:Al–Sc films while ZnO:Sc films do not exhibit any electrical conductivity. Moreover, there is an optimum atomic ratio with Al to Sc of 1:0.5–1 at.%. Although the resistivities are increased compared with that of ZnO:Al film, the Hall mobilities are raised by one order of magnitude.     

Low temperature synthesis wide optical band gap Al and (Al, Na) co-doped ZnO thin films

Al-doped ZnO (AZO) and (Al, Na) co-doped ZnO (ANZO) thin films were prepared via sol-gel technique with an annealing process at temperatures between 450 and 550 °C for 60 min in air ambient, and their structural and optical properties have been investigated. The deposited films exhibited hexagonal zinc oxide structure except annealing at 450 °C. For the 500 °C-annealed samples, the surface morphology was analyzed via scanning electron microscopy, Photoluminescence (PL) of different Na content ANZO thin films showed that there were very obvious violet and blue emission bands between 400 and 500 nm, and intensity of which were enhanced with Na content increasing. Transparency of the films was improved along with increasing Na content. The result of UV indicated the absorb bands appeared obviously red shift with Na doping into ZnO, the optical gaps of all films far beyond 3.37 eV of pure ZnO, and gradually decreased with Na content increasing, this is very virtual for improving photoelectricity performance of transparent conduct oxide (TCO) film. The possible origins responsible for structure and optical properties also had been discussed.     

Microstructure and optical properties of nanocrystalline ZnO and ZnO:(Li or Al) thin films

Zinc oxide thin films (ZnO, ZnO:Li, ZnO:Al) were deposited on glass substrates by a sol-gel technique. Zinc acetate, lithium acetate, and aluminum chloride were used as metal ion sources in the precursor solutions. XRD analysis revealed that Li doped and undoped ZnO films formed single phase zincite structure in contrast to Al:ZnO films which did not fully crystallize at the annealing temperature of 550 °C. Crystallized films had a grain size under 50 nm and showed c-axis grain orientation. All films had a very smooth surface with RMS surface roughness values between 0.23 and 0.35 nm. Surface roughness and optical band tail values increased by Al doping. Compared to undoped ZnO films, Li doping slightly increased the optical band gap of the films.