Preparation and investigation of optical, structural, and morphological properties of nanostructured ZnO:Mn thin films

Nanostructured ZnO:Mn thin films have been prepared by sol–gel dip coating method. The content of Mn in the sol was varied from 0 to 12 wt%. The effect of Mn concentration on the optical, structural, and morphological properties of ZnO thin films were studied by using Fourier Transform Infrared (FTIR), UV–visible and photoluminescence (PL) spectroscopy, X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM). XRD results showed that the films have hexagonal wurtzite structure at lower content of Mn. The diffraction peaks corresponding to ZnO disappeared and two diffraction peaks of MnO₂ and Mn₃O₄ appeared at the highest value of doping concentration (viz., 12 wt%). SEM results revealed that the surface smoothness of the films improved at higher content of Mn. The optical band gap of the films decreased from 3.89 to 3.15 eV when the Mn concentration increased from 0 to 12 wt%. The PL spectra of the films showed the characteristic peaks linked to band-to-band, green and yellow emissions. Besides, the PL intensity of the samples decreased with increase in Mn concentration.     

Effect of substrate and annealing on the structural and optical properties of ZnO:Al films

ZnO:Al thin films with c-axis preferred orientation were deposited on glass and Si substrates using RF magnetron sputtering technique. The effect of substrate on the structural and optical properties of ZnO:Al films were investigated. The results showed a strong blue peak from glass-substrate ZnO:Al film whose intensity became weak when deposited on Si substrate. However, the full width at half maxima (FWHM) of the Si-substrate ZnO:Al (0 0 2) peaks decreased evidently and the grain size increased. Finally, we discussed the influence of annealing temperature on the structural and optical properties of Si-substrate ZnO:Al films. After annealing, the crystal quality of Si-substrate ZnO:Al thin films was markedly improved and the intensity of blue peak (∼445 nm) increased noticeably. This observation may indicate that the visible emission properties of the ZnO:Al films are dependent more on the film crystallinity than on the film stoichiometry.     

A comparative study on structural and optical properties of ZnO and Al-doped ZnO thin films obtained by ultrasonic spray method using different solvents

Transparent conducting ZnO and Al doped ZnO thin films were deposited on glass substrate by ultrasonic spray method. The thin films with concentration of 0.1 M were deposited at 350 °C with 2 min of deposition time. The effects of ethanol and methanol solution before and after doping on the structural, optical and electrical properties were examined. The DRX analyses indicated that ZnO films have nanocrystalline nature and hexagonal wurtzite structure with (1 0 0) and (0 0 2) preferential orientation corresponding to ZnO films resulting from methanol and ethanol solution, respectively. The crystallinity of the thin films improved with methanol solution after doping to (0 0 2) oriented. All films exhibit an average optical transparency about 90%, in the visible range. The band gaps values of ZnO thin films are increased after doping from 3.10 to 3.26 eV and 3.27 to 3.30 eV upon Al doping obtained by ethanol and methanol solution, respectively. The electrical conductivity increase from 7.5 to 15.2 (Ω cm)⁻¹ of undoped to Al doped ZnO thin films prepared by using ethanol solution. However, for the methanol solution; the electrical conductivity of the film is stabilized after doping.     

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.     

Effects of hydrogen flow on properties of hydrogen doped ZnO thin films prepared by RF magnetron sputtering

The hydrogen doped ZnO (ZnO:H) thin films were deposited on quartz glass substrates by radio frequency magnetron sputtering. The doping characteristics of ZnO:H thin films with varied hydrogen flow ratio were investigated. At low hydrogen flow ratio (H₂/(H₂+Ar)≤0.02), the ZnO:H thin films exhibited dominant (002) peaks from X-ray diffraction and the lattice constants became smaller. The particles were mainly a columnar structure. The particles’ size became smaller, and the island-like structure appeared on the thin films surface. In addition, the low resistivity properties of ZnO:H thin films was ascribed to the increase of the carriers concentration and carriers mobility; When the hydrogen flow ratio was more than 0.02 (M≥0.02), two absorption bands at 1400–1800 cm^?1 and 3200–3900 cm^?1 were observed from the FT-IR spectra, which indicated that the ZnO:H thin films had typical Zn–H bonding, O–H bonding (hydroxyl), and Zn–H–O bonding (like-hydroxyl). The scanning electron microscope (SEM) results show that a large number of hydroxyl agglomeration formed an island-like structure on the thin films surface. The absorption peak at about 575 cm^?1 in the Raman spectra indicated that oxygen vacancies (V_O) defects were produced in the process of high hydrogen doping. In this condition, the low resistivity properties of ZnO:H thin films were mainly due to the increasing electron concentration resulted from V_O. Meanwhile, the Raman absorption peaks at approximately 98 cm^?1 and 436 cm^?1 became weaker, and the (002) XRD diffraction peak quenched and the lattice constants increased, which shows that the ZnO:H thin films no longer presented a typical ZnO hexagonal wurtzite structure. With the increasing of hydrogen flow ratio, the optical transmittance of ZnO:H thin films in the ultraviolet band show a clear Burstein–Moss shift effect, which further explained that electron concentration was increased due to the increasing V_O with high hydrogen doping concentration. Moreover, the optical reflectance of the thin films decreased, indicating the higher roughness of the films surface. It was noteworthy that etching effect of H plasma was obvious in the process of heavy hydrogen doping.     

Influence of substrate temperature and Cobalt concentration on structural and optical properties of ZnO thin films prepared by Ultrasonic spray technique

Pure and Cobalt doped zinc oxide were deposited on glass substrate by Ultrasonic spray method. Zinc acetate dehydrate, Cobalt chloride, 4-methoxyethanol and monoethanolamine were used as a starting materials, dopant source, solvent and stabilizer, respectively. The ZnO samples and ZnO:Co with Cobalt concentration of 2 wt.% were deposited at 300, 350 and 400 °C. The effects of substrate temperature and presence of Co as doping element on the structural, electrical and optical properties were examined. Both pure and Co doped ZnO samples are (0 0 2) preferentially oriented. The X-ray diffraction results indicate that the samples have polycrystalline nature and hexagonal wurtzite structure with the maximum average crystallite size of ZnO and ZnO:Co were 33.28 and 55.46 nm. An increase in the substrate temperature and presence doping the crystallinity of the thin films increased. The optical transmittance spectra showed transmittance higher than 80% within the visible wavelength region. The band gap energy of the thin films increased after doping from 3.25 to 3.36 eV at 350 °C.     

Influence of Mn doping on structural and optical properties of ZnO nano thin films synthesized by sol–gel technique

Undoped and Mn-doped ZnO samples with different percentages of Mn content (1, 5 and 10?at%) were synthesized by a dip-coating sol?Cgel method. We have studied the structural, chemical and optical properties of the samples by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-visible spectroscopy. The XRD spectra show that all the samples are hexagonal wurtzite structures. We note that doping favors c-axis orientation along (002) planes. Up to 5?at% of Mn doping level, the c-axis lattice parameter shifts towards higher values with the increase of manganese content in the films. The expansion of the lattice constant of ZnO?CMn indicates that Mn is really doped into the ZnO. The SEM investigations of all samples revealed that the crystallites are of nanometer size. The surface quality of the ZnO?CMn film increases with Mn doping but no significant change of the grain size is observed from SEM images. The transmittance spectra show that the transparency of all the samples is greater than 85?%. We note, also, that a small doping (1?%) lowered the refractive index while the thickness of the layers and the gap increase. However, on raising the proportion of Mn beyond 5?%, practically the same values of index and gap as pure ZnO are found.     

Quantum cutting effect and photoluminescence emission at about 1,000 nm from Er–Yb co-doped ZnO nanoplates prepared by wet chemical precipitation method

ZnO nanoplates with Er-doping concentrations varying in the range from 3 to 7 wt% and co-doped with (Er–Yb) (7 + 7 wt%) were successfully prepared by wet chemical precipitation method. The effects of doping on the structural and optical properties of ZnO nanostructures have been systematically investigated. The structural morphology of the prepared nanostructures was found to change with increasing Er-doping concentrations. The visible photoluminescence and infrared photoluminescence of the prepared nanostructures were measured at room temperature. The intensity of visible emission spectra was found to increase with increasing Er-doping concentrations and was further enhanced for (Er–Yb) co-doped ZnO nanoplate samples. Additionally, Er-doped (7 wt%) and Yb-doped (7 wt%) ZnO nanoplates showed an enhanced emission peak at 950 nm, whereas two enhanced emission peaks at 950 and 980 nm have been found for (Er–Yb)-co-doped (7 + 7 wt%) ZnO nanoplates samples when excited at 310, 365 and 371 nm excitation wavelengths.     

Influence of Al doping on microstructure,morphology, optical and photoluminescence properties of pyrolytic ZnO thin films prepared in an ambient atmosphere

Zinc oxide (ZnO) and aluminium (Al) doped zinc oxide (AZO) thin films have been fabricated by spray pyrolysis technique in normal atmospheric condition. Samples of different Al-concentrations (0–5% Al) were deposited at 350 °C onto glass substrate to study the structural, morphological, optical and photoluminescence properties. X-ray diffraction study confirms that the films are polycrystalline having hexagonal structure. SEM images show that the films have rope and tube like morphology. Optical properties, such as transmittance, optical band gap, extinction coefficient, refractive index, optical conductivity, dielectric constants and electron energy loss functions were analyzed and discussed. Results show that the optical parameters have been changed significantly with Al-doping concentration. The photoluminescence spectra indicate that the PL peaks originated from deep level emissions (DLE) with different intensities for ZnO and Al-doped ZnO films.     

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.     

Ta掺杂对ZnO光电材料性能影响的研究

采用基于密度泛函理论第一性原理的方法, 研究了Ta掺杂ZnO的电子结构和光学性质. 计算结果表明: 掺入Ta原子后, 费米能级进入导带, 随着掺杂浓度的增加, 带隙逐渐变窄, 介电函数虚部、吸收系数、反射率和折射率均发生明显变化, 介电函数虚部和反射率均向高能方向移动, 吸收边发生红移, 从理论上指出了光学性质和电子结构的内在联系.     

Mn doped ZnO nanostructured thin films prepared by ultrasonic spray pyrolysis method

Mn-doped ZnO thin films with different percentage of Mn content (0, 1, 3 and 5 at.%) and substrate temperature of 350 °C, were deposited by a simple ultrasonic spray pyrolysis method under atmospheric pressure. We have studied the structural and optical properties by using X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and ultra-violet visible near infrared (UV–Vis-NIR) spectroscopy. The lattice parameters calculated for the Mn-doped ZnO from XRD pattern were found to be slightly larger than those of the undoped ZnO, which indicate substitution of Mn in ZnO lattice. Compared with the Raman spectra for ZnO pure films, the Mn-doping effect on the spectra is revealed by the presence of additional peak around 524 cm⁻¹ due to Mn incorporation. With increasing Mn doping the optical band gap increases indicating the Burstein–Moss effect.     

Microstructure and electro-optical properties of sol–gel derived Cd-doped ZnO films

The microstructure, and the electrical and optical properties of undoped zinc oxide (ZnO) and cadmium-doped ZnO (CZO) films deposited by a sol–gel method have been investigated. The films have a polycrystalline structure with hexagonal wurtzite ZnO. Scanning electron microscopy (SEM) images indicated that the films have a wrinkle network with uniform size distributions. The elemental analyses of the CZO films were carried out by energy dispersive X-ray analysis. The fundamental absorption edge changed with doping. The optical band gap of the films decreased with Cd dopant. The optical constants of the films such as refractive index, extinction coefficient and dielectric constants changed with Cd dopant. A two-probe method was used to investigate the electrical properties, and the effect of Cd content on the electrical properties was investigated. The electrical conductivity of the films was improved by incorporation of Cd in the ZnO film.     

Nitrogen doping in pulsed laser deposited ZnO thin films using dense plasma focus

Pulsed laser deposition synthesized ZnO thin films, grown at 400 °C substrate temperature in different oxygen gas pressures, were irradiated with 6 shots of pulsed nitrogen ions obtained from 2.94 kJ dense plasma focus to achieve the nitrogen doping in ZnO. Structural, compositional and optical properties of as-deposited and nitrogen ion irradiated ZnO thin films were investigated to confirm the successful doping of nitrogen in irradiated samples. Spectral changes have been seen in the nitrogen irradiated ZnO thin film samples from the low temperature PL measurements. Free electron to acceptor emissions can be observed from the irradiated samples, which hints towards the successful nitrogen doping in films. Compositional analysis by X-ray photoelectron spectroscopy and corresponding shifts in binding energy core peaks of oxygen and nitrogen confirmed the successful use of plasma focus device as a novel source for nitrogen ion doping in ZnO thin films.     

Preparation and characterization of thin films of ZnO:Al by nebulized spray pyrolysis

Pure and Al-doped nanocrystalline ZnO films have been deposited on Si(100) substrate by nebulized spray pyrolysis. UV–NIR reflections, microstructure and electrical properties were investigated in some detail. The effects of Al doping and annealing at higher temperatures (1073 K) on these properties were investigated. The orientation and the microstructure were revealed by X-ray diffraction patterns and scanning electron microscopy (SEM). The resistivity of the films was inversely proportional to the intensity of the (002) peak. Also, as grain sizes increased, their mobility decreased; therefore, the resistivity value of the films became lower. The values of the non-linear I–V coefficient, , lay in the range 2–4 for all the samples. A great increase in the NIR reflectance (25 to 45%) was observed upon 0.3% Al doping. PACS 78.65; 78.50; 81.50; 78.2.-e     

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.     

A comparative ab initio study of the structural,mechanical, electronic and optical behaviors of ZnO:Ni thin films with nanometer scale

The electronic and optical properties of undoped and Ni–doped ZnO thin films with nanometer scale have been studied in the wurtzite phase, by first–principle approach. Density functional theory has been employed to calculate the fundamental properties of the films using full–potential linearized augmented plane–wave method. Ni doping was found to reduce the bandgap value of the material. Additionally, DOS effective mass of the electrons was evaluated. It was revealed that the effective mass of the electrons at the bottom of conduction band increased with Ni doping. Decrease of reflectance for thin films with nanometer scale in the UV–vis region was observed. The substitution by Ni decreased the intensity of the peaks, and a red shift was observed in the absorption peak. Moreover, the static dielectric constant, and static refractive index decreased with Ni content. Energy loss function of the modeled compounds was also evaluated. All calculated parameters were compared with the available experimental and other theoretical results.     

Effect of annealing temperature on the structural and optical properties of ZnO thin films prepared by sol–gel method

In this work, ZnO thin films were synthesized by sol–gel method on glass substrates followed by calcinations on different temperatures. The effect of annealing temperature on the structure and optical properties of the films was studied. The structural characteristics of the samples were analyzed by X-ray diffraction and atomic force microscope. The optical properties were studied by a UV-visible spectrophotometer. The results show that all the prepared ZnO thin films have a high preferential oriented c-axis orientation with compact hexagonal wurtzite structure. With the increasing annealing temperature (mse.ufl.edu), the intensity of (002) peak, particle size, surface RMS roughness, and absorbance of the ZnO thin films were increased as well. On the contrary, the transmittance and optical band gaps were decreased.     

Effect of molybdenum doping on the electrochromic properties of tungsten oxide thin films by RF magnetron sputtering

Thin films of pure and molybdenum (Mo)-doped tungsten trioxide (WO₃) were deposited on indium tin oxide (ITO)-coated glass and Corning glass substrates by RF magnetron sputtering technique. The effect of Mo doping on the structural, morphological, optical and electrochromic properties of WO₃ films was studied systematically. The energy dispersive X-ray analysis (EDAX) revealed that the films consist of molybdenum concentrations from 0 to 2 at.%. X-ray diffraction (XRD) studies indicated that with the increase of Mo concentration the structural phase transformation takes place from polycrystalline to amorphous phase. The crystallite size of the films decreased from 24 to 12 nm with increase of doping concentration of Mo in WO₃. Scanning electron microscope (SEM) analysis revealed that Mo dopant led to significant changes in the surface morphology of the films. The electrochemical and electrochromic performance of the pure and Mo-doped WO₃ were studied. The WO₃ films formed with 1.3 at.% Mo dopant concentration exhibited high optical modulation of 44.3 % and coloration efficiency of 42.5 cm²/C.