Thermal stress induced band gap variation of ZnO thin films

The growth temperature and post annealing-dependent optical and structural effect of RF magnetron sputtered ZnO thin films were examined. As the growth temperature increased, the lattice constant increased and approached the bulk value, suggesting a decrease in interfacial strain between the substrate and thin film. For the post annealed samples, the interfacial strain decreased further and was close to the bulk value regardless of the post annealing environments (in air and O₂). The optical properties of all ZnO thin films examined and revealed higher transparency (>90%). Furthermore, the optical band gap varied according to the growth temperature and post annealing environments due to a decrease in the interfacial strain effect.     

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.     

Direct current magnetron sputter-deposited ZnO thin films

Zinc oxide (ZnO) is a very promising electronic material for emerging transparent large-area electronic applications including thin-film sensors, transistors and solar cells. We fabricated ZnO thin films by employing direct current (DC) magnetron sputtering deposition technique. ZnO films with different thicknesses ranging from 150 nm to 750 nm were deposited on glass substrates. The deposition pressure and the substrate temperature were varied from 12 mTorr to 25 mTorr, and from room temperature to 450 °C, respectively. The influence of the film thickness, deposition pressure and the substrate temperature on structural and optical properties of the ZnO films was investigated using atomic force microscopy (AFM) and ultraviolet-visible (UV-Vis) spectrometer. The experimental results reveal that the film thickness, deposition pressure and the substrate temperature play significant role in the structural formation and the optical properties of the deposited ZnO thin films.     

An influence of deposition temperature on structural,optical and electrical properties of sprayed ZnO thin films of identical thickness

Nanocrystalline ZnO thin films were deposited at different temperatures (T_s = 325 °C–500 °C) by intermittent spray pyrolysis technique. The thickness (300 ± 10 nm) independent effect of T_s on physical properties was explored. X-Ray diffraction analysis revealed the growth of wurtzite type polycrystalline ZnO films with dominant c-axis orientation along [002] direction. The crystallite size increased (31 nm–60 nm) and optical band-gap energy decreased (3.272 eV–3.242 eV) due to rise in T_s. Scanning electron microscopic analysis of films deposited at 450 °C confirmed uniform growth of vertically aligned ZnO nanorods. The films deposited at higher T_s demonstrated increased hydrophobic behavior. These films exhibited high transmittance (>91%), low dark resistivity (～10^?2 Ω-cm), superior figure of merit (～10^?3 Ω^?1) and low sheet resistance (～10² Ω/□). The charge carrier concentration (η -/cm³) and mobility (μ – cm²V^?1s^?1) are primarily governed by crystallinity, grain boundary passivation and oxygen desorption effects.     

Effects of the substrate and oxygen partial pressure on the microstructures and optical properties of Ti-doped ZnO thin films

Ti-doped ZnO (ZnO:Ti) thin films were deposited on the glass and Si substrates using radio frequency reactive magnetron sputtering. The effects of substrate on the microstructures and optical properties of ZnO:Ti thin films were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and a fluorescence spectrophotometer. The structural analyses of the films indicated that they were polycrystalline and had a hexagonal wurtzite structure on different substrates. When ZnO:Ti thin film was deposited on Si substrate, the film had a c-axis preferred orientation, while preferred orientation of ZnO:Ti thin film deposited on glass substrate changed towards (1 0 0). Finally, we discussed the influence of the oxygen partial pressures on the structural and optical properties of glass-substrate ZnO:Ti thin films. At a high ratio of O₂:Ar of 18:10 sccm, the intensity of (0 0 2) diffraction peak was stronger than that of (1 0 0) diffraction peak, which indicated that preferred orientation changed with the increase of O₂:Ar ratios. The average optical transmittance with over 93% in the visible range was obtained independent of the O₂:Ar ratio. The photoluminescence (PL) spectra measured at room temperature revealed four main emission peaks located at 428, 444, 476 and 527 nm. Intense blue-green luminescence was obtained from the sample deposited at a ratio of O₂:Ar of 14:10 sccm. The results showed that the oxygen partial pressures had an important influence for PL spectra and the origin of these emissions was discussed.     

Physical properties of ZnO thin films deposited by spray pyrolysis technique

Thin films of ZnO have been prepared on glass substrates at different thicknesses by spray pyrolysis technique using 0.2 M aqueous solution of zinc acetate. X-ray diffraction reveals that the films are polycrystalline in nature having hexagonal wurtzite type crystal structure. The resistivity at room temperature is of the order 10⁻² Ω cm and decreased as the temperature increased. Films are highly transparent in the visible region. The dependence of the refractive index, n, and extinction coefficient, k, on the wavelength for a sprayed film is also reported. Optical bandgap, E_g, has been reported for the films. A shift from E_g = 3.21 eV to 3.31 eV has been observed for deposited films.     

Effect of precursors on structure, optical and electrical properties of chemically deposited nanocrystalline ZnO thin films

Nanocrystalline ZnO thin films were chemically deposited on glass substrates using two different precursors namely, zinc sulphate and zinc nitrate. XRD studies confirm that the films are polycrystalline zinc oxide having hexagonal wurtzite structure with crystallite size in the range 25-33 nm. The surface morphology of film prepared using zinc sulphate exhibits agglomeration of small grains throughout the surface with no visible holes or faulty zones, while the film prepared using zinc nitrate shows a porous structure consisting of grains with different sizes separated by empty spaces. The film prepared using zinc sulphate shows higher reflectance due to its larger refractive index which is related to the packing density of grains in the film. Further, the film prepared using zinc sulphate is found to have normal dispersion for the wavelength range 550-750 nm, whereas the film prepared using zinc nitrate has normal dispersion for the wavelength range 450-750 nm. The direct optical band gaps in the two films are estimated to be 3.01 eV and 3.00 eV, respectively. The change in film resistance with temperature has been explained on the basis of two competing processes, viz. thermal excitation of electrons and atmospheric oxygen adsorption, occurring simultaneously. The activation energies of the films in two different regions indicate the presence of two energy levels - one deep and one shallow near the bottom of the conduction band in the bandgap.     

Effect of intrinsic stress on the optical properties of nanostructured ZnO thin films grown by rf magnetron sputtering

In this paper we report the effect of deposition temperature on the structural and optical properties of ZnO thin films prepared by rf magnetron sputtering. The films grown at lower deposition temperatures were in a state of large compressive stress, whereas the films grown at higher temperature (450 °C) were almost stress free. In the absorption spectra, the ZnO excitonic and the Zn surface plasmon resonance (SPR) peaks have been observed. A redshift in the optical band gap of ZnO films has also been observed with the increase in the deposition temperature. The shift in the band gap calculated from the size effect did not match with the observed shift values and the observed shift has been attributed to the compressive stress present in the films.     

The influence of using different substrates on the structural and optical characteristics of ZnO thin films

ZnO thin films with thikness d = 100 nm were deposited onto different substrates such as glass, kapton, and silicon by radio frequency magnetron sputtering. The structural analyses of the films indicate they are polycrystalline and have a wurtzite (hexagonal) structure.The ZnO layer deposited on kapton substrate shows a stronger orientation of the crystallites with (0 0 2) plane parallel to the substrate surface, as compared with the other two samples of ZnO deposited on glass and silicon, respectively.All three layers have nanometer-scale values for roughness, namely 1.7 nm for ZnO/glass, 2.4 nm for ZnO/silicon, and 6.8 nm for ZnO/kapton. The higher value for the ZnO layer deposited on kapton substrate makes this sample suitable for solar cells applications. Transmission spectra of these thin films are strongly influenced by deposition conditions. With our deposition conditions the transparent conducting ZnO layer has a good transmission (78-88%) in VIS and NIR domains. The values of the energy gap calculated from the absorption spectra are 3.23 eV for ZnO sample deposited onto glass substrate and 3.30 eV for the ZnO sample deposited onto kapton polymer foil substrate. The influence of deposition arrangement and oxidation conditions on the structural, morphological, and optical properties of the ZnO films is discussed in the present paper.     

Effects of Ti-doped concentration on the microstructures and optical properties of ZnO thin films

The Ti-doped ZnO (ZnO:Ti) thin films have been deposited on glass substrates by radio frequency (RF) reactive magnetron sputtering technique with different Ti doping concentrations. The effect of Ti contents on the crystalline structure and optical properties of the as-deposited ZnO:Ti films was systematically investigated by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and fluorescence spectrophotometer. The XRD measurements revealed that all the films had hexagonal wurtzite type structure with a strong (100) preferential orientation and relatively weak (002), (101), and (110) peaks. It was found that the intensity of the (100) diffraction peaks was strongly dependent on the Ti doping concentration. And the full width at half-maximum (FWHM) of (002) diffraction peaks constantly changed at various Ti contents, which decreased first and then increased, reaching a minimum of about 0.378° at 1.43 at.% Ti. The morphologies of ZnO:Ti films with 1.43 at.% Ti showed a denser texture and better smooth surface. All the films were found to be highly transparent in the visible wavelength region with an average transmittance over 90%. Compared with E_g = 3.219 eV for pure ZnO film, all the doping samples exhibited a blue-shift of E_g. It can be attributed to the incorporation of Ti atoms and raising the concentration of carriers. Five emission peaks located at 412, 448, 486, 520, and 550 nm were observed from the photoluminescence spectra measured at room temperature and the origin of these emissions was discussed.     

Structural and optical characteristics of spin-coated ZnO thin films

Zinc oxide (ZnO) thin films were deposited onto glass substrates by spin-coating method, from a precursor solution containing zinc acetate, ethanol and ammonium hydroxide. After deposition, the films were heated at a temperature of 100 °C in order to remove unwanted materials. Finally, the films were annealed at 500 °C for complete oxidation. X-ray diffraction showed that ZnO films were polycrystalline and have a hexagonal (wurtzite) structure. The crystallites are preferentially oriented with (0 0 2) planes parallel to the substrate surface. The films have a high transparency (more than 75%) in the spectral range from 450 nm to 1300 nm. The analysis of absorption spectra shows the direct nature of band-to-band transitions. The optical bandgap energy ranges between 3.15 eV and 3.25 eV.Some correlations between the processing parameters (spinning speed, temperature of post deposition heat treatment) and structure and optical characteristics of the respective thin films were established.     

Effect of the oxygen pressure on the microstructure and optical properties of ZnO films prepared by laser molecular beam epitaxy

A series of ZnO films were prepared on the Si (1 0 0) or glass substrate at 773 K under various oxygen pressures by using a laser molecular beam epitaxy system. The microstructure and optical properties were investigated through the X-ray diffraction, Raman spectrometer, scanning electron microscope, ultraviolet–visible spectrophotometer and spectrofluorophotometer. The results showed that ZnO thin film prepared at 1 Pa oxygen pressure displayed the best crystalinity and all ZnO films formed a columnar structure. Meanwhile, all ZnO films exhibited an abrupt absorption edge near the wavelength of 380 nm in transmission spectra. With increasing the oxygen pressure, the transmission intensity changed non-monotonically and reached a maximum of above 80% at 1 Pa oxygen pressure, based on which the band gaps of all ZnO films were calculated to be about 3.259–3.315 eV. Photoluminescence spectra indicated that there occurred no emission peak at a low oxygen pressure of 10⁻⁵ Pa. With the increment of the oxygen pressure, there occurred a UV emission peak of 378 nm, a weak violet emission peak of 405 nm and a wide green emission band centered at 520 nm. As the oxygen pressure increased further, the position of UV emission peak remained and its intensity changed non-monotonically and reached a maximum at 1 Pa. Meanwhile the intensity of green emission band increased monotonically with increasing the oxygen pressure. In addition, it was also found that the intensity of UV emission peak decreased as the measuring temperature shifted from 80 to 300 K. The analyses indicated that the UV emission peak originated from the combination of free excitons and the green emission band originated from the energy level jump from conduction band to O_Zn defect.     

Nanoporous structures on ZnO thin films

Porous structures were formed on ZnO thin films which were grown by an electrochemical deposition (ECD) method. The growth processes were carried out in a solution of dimethylsulfoxide (DMSO) zinc perchlorate, Zn(ClO₄)₂, at 120 ^°C on indium tin oxide (ITO) substrates. Optical and structural characterizations of electrochemically grown ZnO thin films have shown that the films possess high (0002) c$c$-axis orientation, high nucleation, high intensity and low FWHM of UV emission at the band edge region and a sharp UV absorption edge. Nanoporous structures were formed via self-assembled monolayers (SAMs) of hexanethiol (C₆SH) and dodecanethiol (C₁₂SH). Scanning electron microscope (SEM) measurements showed that while a nanoporous structure (pore radius 20 nm) is formed on the ZnO thin films by hexanathiol solution, a macroporous structure (pore radius 360 nm) is formed by dodecanethiol solution. No significant variation is observed in X-ray diffraction (XRD) measurements on the ZnO thin films after pore formation. However, photoluminescence (PL) measurements showed that green emission is observed as the dominant emission for the macroporous structures, while no variation is observed for the thin film nanoporous ZnO sample.     

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.     

Influence of sputter-etching of substrate on the microstructural and optical properties of ZnO films deposited by RF magnetron sputtering

ZnO films were prepared using radio frequency magnetron sputtering on Si(1 1 1) substrates that were sputter-etched for different times ranging from 10 to 30 min. As the sputter-etching time of the substrate increases, both the size of ZnO grains and the root-mean-square (RMS) roughness decrease while the thickness of the ZnO films shows no obvious change. Meanwhile, the crystallinity and c-axis orientation are improved by increasing the sputter-etching time of the substrate. The major peaks at 99 and 438 cm⁻¹ are observed in Raman spectra of all prepared films and are identified as E₂(low) and E₂(high) modes, respectively. The Raman peak at 583 cm⁻¹ appears only in the films whose substrates were sputter-etched for 20 min and is assigned to E₁(LO) mode. Typical ZnO infrared vibration peak located at 410 cm⁻¹ is found in all FTIR spectra and is attributed to E₁(TO) phonon mode. The shoulder at about 382 cm⁻¹ appearing in the films whose substrates were sputter-etched for shorter time (10-20 min) originates from A₁(TO) phonon mode. The results of photoluminescence (PL) spectra reveal that the optical band gap (Eg) of the ZnO films increases from 3.10 eV to 3.23 eV with the increase of the sputter-etching time of the substrate.     

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.     

Effect of Er doping on optical band gap energy of TiO2 thin films prepared by spin coating

In order to evaluate the effect of Er doping in the range of 0–1.0 mol% on optical indirect band gap energy (E_g) of the film, the Er-doped TiO₂ (Er-TiO₂) thin films were spin-coated onto fluorine-doped SnO₂ coated (FTO) glasses. Glancing angle X-ray diffraction (GAXRD) results indicated that the films whose thickness was 550 nm consisted of pure anatase and FTO substrate. The anatase (101) TiO₂ peaks became broader and weaker with the rise in Er content. The apparent crystallite size decreased from 12 nm to 10 nm with increasing the amount of Er from 0 mol% to 1.0 mol%. UV–vis spectrophotometry showed that the values of E_g decreased from 3.25 eV to 2.81 eV with the increase of Er doping from 0 to 0.7 mol%, but changed to 2.89 eV when Er content was 1.0 mol%. The reduction in E_g might be attributed to electron and/or hole trapping at the donor and acceptor levels in the TiO₂ band structure.     

Effect of boron ion implantation on the structural, optical and electrical properties of ZnSe thin films

Zinc Selenide (ZnSe) thin films were deposited onto well cleaned glass substrates using vacuum evaporation technique under a vacuum of 3×10⁻⁵ mbar. The prepared ZnSe samples were implanted with mass analyzed 75 keV B⁺ ions at different doses ranging from 10¹² to 10¹⁶ ions cm⁻². The composition, thickness, microstructures, surface roughness and optical band gap of the as-deposited and boron-implanted films were studied by Rutherford backscattering (RBS), grazing incidence X-ray diffraction, Atomic force microscopy, Raman scattering and transmittance measurements. The RBS analysis indicates that the composition of the as-deposited and boron-implanted films is nearly stoichiometric. The thickness of the as-deposited film is calculated as 230 nm. The structure of the as-deposited and boron-implanted thin films is cubic. It is found that the surface roughness increases on increasing the dose of boron ions. In the optical studies, the optical band gap value decreases with an increase of boron concentration. In the electrical studies, the prepared device gave a very good response in the blue wavelength region.     

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.