Ferromagnetism in noncompensated (Mn,Ga)-codoped ZnO films

Mn/Ga noncompensated codoped ZnO films were prepared on c-cut sapphire substrates via pulsed laser deposition. The structural, magnetic, transport, and optical properties of the films were then investigated. Addition of the Ga donor increases the electron concentration and enhances the magnetization in these films because of the net negative charge of the special noncompensated codoping, which can adjust the carrier concentration as well as the magnetic moment. Moreover, the Fermi level moves into the conduction band because of the increase in electron concentration, which results in an increase in the optical band gap value, from 3.28 eV for the undoped ZnO film to 3.61 eV for the (Mn,Ga)-codoped ZnO film.     

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.     

Study of the bandgap renormalization in Ga-doped ZnO films by means of optical absorption under high pressure and photoelectron spectroscopy

In this paper we investigate the band gap renormalization in heavily Ga-doped ZnO thin films deposited by pulsed laser deposition on C$C$-plane sapphire and mica substrates. Thin films were studied by ultraviolet photoelectron spectroscopy and also by optical measurements under high pressure. The Fermi-level shift, as obtained from ultraviolet photoelectron experiments, exhibits a relatively small and positive shift (about 0.3 eV) with respect to the valence band for increasing electron concentrations up to 10²¹ cm⁻³. The optical gap exhibits a much larger increase (0.6 eV) for the same concentration range. Absorption measurements under pressure show that the pressure coefficient of the optical gap is correlated to the electron concentration in films, decreasing with increasing electron concentration. As a consequence, the contributions of band filling and band renormalization to the optical gap shift can be separated on the basis of the different pressure behavior of the physical parameters involved in each effect.     

First-principle study of optical properties of (N,Ga) codoped ZnO

To analyze the electronic structure and optical properties of (N, Ga) codoped ZnO, the parameters such as band structure, density of states, dielectric constant, absorption and reflection spectra of pure ZnO, N–Ga and 2N–Ga codoped ZnO were calculated by using first-principle method based on DFT (Density Functional Theory). The results demonstrated that the band gap of (N, Ga) codoped ZnO narrows, and 2N–Ga codoping can obtain a high-quality and more stable p-type ZnO. Compared with pure ZnO, the real and imaginary part of dielectric function of (N, Ga) codoped ZnO move toward a lower energy side; in ultraviolet region, the absorption spectrum reduces greatly, and the blue shift of reflectivity spectrum is observed; while in infrared region, the reflectivity spectrum of 2N–Ga codoped ZnO is twice that of pure ZnO or N–Ga codoped ZnO. The results provided certain theoretical reference for the study of ZnO-based transparent conductive thin films.     

Growth characteristics and properties of ZnO:Ga thin films prepared by pulsed DC magnetron sputtering

Transparent conductive ZnO:Ga thin films were deposited on Corning 1737 glass substrate by pulsed direct current (DC) magnetron sputtering. The effects of process parameters, namely pulse frequency and film thickness on the structural and optoelectronic properties of ZnO:Ga thin films are evaluated. It shows that highly c-axis (0 0 2) oriented polycrystalline films with good visible transparency and electrical conductivity were prepared at a pulsed frequency of 10 kHz. Increasing the film thickness also enlarged the grain size and carrier mobility which will subsequently lead to the decrease in resistivity. In summary, ZnO:Ga thin film with the lowest electrical resistivity of 2.01 × 10⁻⁴ Ω cm was obtained at a pulse frequency of 10 kHz with 500 nm in thickness. The surface RMS (root mean square) roughness of the film is 2.9 nm with visible transmittance around 86% and optical band gap of 3.83 eV.     

Deposition and characterization of transparent and conductive sprayed ZnO:B thin films

Highly transparent and conductive Boron doped zinc oxide (ZnO:B) thin films were deposited using chemical spray pyrolysis (CSP) technique on glass substrate. The effect of variation of boron doping concentration in reducing solution on film properties was investigated. Low angle X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal wurtzite structure and have preferred orientation in [002] direction. The films with resistivity 2.54×10⁻³ Ω-cm and optical transmittance >90% were obtained at optimized boron doping concentration. The optical band gap of ZnO:B films was found ∼3.27 eV from the optical transmittance spectra for the as-deposited films. Due to their excellent optical and electrical properties, ZnO:B films are promising contender for their potential use as transparent window layer and electrodes in solar cells.     

Correlation between electrical and optical properties of Cr:ZnO thin films grown by pulsed laser deposition

Highly transparent and conducting Chromium doped ZnO (Cr:ZnO) thin films with preferential c-axis orientation were grown on (0 0 0 1) sapphire substrates using buffer assisted pulsed laser deposition. The resistivity of Cr:ZnO thin films was found to decrease to a minimum value of ∼1.13×10⁻³Ω cm with the increasing Cr concentration up to ∼1.9 at.% and then increase with further increase of Cr concentration. On the contrary, the band gap and carrier concentration of Cr:ZnO thin films increased up to ∼3.37 eV and ∼2×10²⁰ cm⁻³, respectively, with the increase of Cr concentration up to ∼1.9 at.%, then decreased with further increase of Cr concentration. The increase of carrier concentration and conductivity with Cr doping at low Cr concentrations (<1.9 at.%) could be attributed to the presence of Cr in +3 valence state in ZnO thus acting as donor while decrease of carrier concentration beyond ∼1.9 at.% of Cr concentration could be attributed to the charge compensating effect due to the presence of acceptor like point defects such as oxygen interstitials. This was experimentally confirmed using x-ray photoelectron spectroscopy. The observed variation in the band gap of Cr:ZnO thin films with increasing Cr doping was attributed to the competing effects of the high free carrier concentration induced Burstein-Moss blue shift and band gap narrowing.     

Room temperature transparent conducting oxides based on zinc oxide thin films

Doped zinc oxide thin films are grown on glass substrate at room temperature under oxygen atmosphere, using pulsed laser deposition (PLD). O₂ pressure below 1 Pa leads to conductive films. A careful characterization of the film stoichiometry and microstructure using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) concludes on a decrease in crystallinity with Al and Ga additions (≤3%). The progressive loss of the (0 0 2) orientation is associated with a variation of the c parameter value as a function of the film thickness and substrate nature. ZnO:Al and ZnO:Ga thin films show a high optical transmittance (>80%) with an increase in band gap from 3.27 eV (pure ZnO) to 3.88 eV and 3.61 eV for Al and Ga doping, respectively. Optical carrier concentration, optical mobility and optical resistivity are deduced from simulation of the optical data.     

Photoluminescence and absorption in sol-gel-derived ZnO films

Highly c-axis-oriented ZnO films were obtained on corning glass substrate by sol-gel technique. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption in the absorption (UV) spectra are closely related to the post-annealing treatment. The difference between PL peak position and the absorption edge, designated as Stokes shift, is found to decrease with the increase of annealing temperature. The minimum Stokes shift is about 150 meV. The decrease of Stokes shift is attributed to the decrease in carrier concentration in ZnO film with annealing. X-ray diffraction, surface morphology and refractive index results indicate an improvement in crystalline quality with annealing. Annealed films also exhibit a green emission centered at ∼520 nm with activation energy of 0.89 eV. The green emission is attributed to the electron transition from the bottom of the conduction band to the antisite oxygen O_Zn defect levels.     

Deposition and properties of B-N codoped p-type ZnO thin films by RF magnetron sputtering

B-N codoped p-type ZnO thin films have been realized by radio frequency (rf) magnetron sputtering using a mixture of argon and oxygen as sputtering gas. Types of conduction and electrical properties in codoped ZnO films were found to be dependent on oxygen partial pressure ratios in the sputtering gas mixture. When oxygen partial pressure ratio was 70%, the codoped ZnO film showed p-type conduction and had the best electrical properties. Additionally, the p-ZnO/n-Si heterojunction showed a clear p-n diode characteristic. XRD results indicate that the B-N codoped ZnO film prepared in 70% oxygen partial pressure ratio has high crystal quality with (0 0 2) preferential orientation. Meanwhile, the B-N codoped ZnO film has high optical quality and displays the stronger near band edge (NBE) emission in the temperature-dependent photoluminescence spectrum, the acceptor energy level was estimated to be located at 125 meV above the valence band.     

Growth of carbon nanofibers on aligned zinc oxide nanorods and their field emission properties

Carbon nanofibers were grown by electrodeposition technique onto aligned zinc oxide (ZnO) nanorods deposited by hybrid wet chemical route on glass substrates. X-ray diffraction traces indicated very strong peak for reflections from (0 0 2) planes of ZnO. The Raman spectra were dominated by the presence of G band at about 1597 cm⁻¹ corresponding to the E_2g tangential stretching mode of an ordered graphitic structure with sp² hybridization and a D band at about 1350 cm⁻¹ originating from disordered carbon. Fourier transformed infrared studies indicated the presence of a distinct characteristic absorption peak at ∼511 cm⁻¹ for Zn-O stretching mode. Photoluminescence spectra indicated band edge luminescence of ZnO at ∼3.146 eV along with a low intensity peak at ∼0.877 eV arising out of carbon nanofibers. Field emission properties of these films and their dependence on the CNF coverage on ZnO nanorods are reported here. The average field enhancement factor as determined from the slope of the FN plot was found to vary between 1 × 10³ and 3 × 10³. Both the values of turn-on field and threshold field for CNF/ZnO were lower than pure ZnO nanorods.     

Boron doped ZnO thin films fabricated by RF-magnetron sputtering

By using the radio frequency-magnetron sputtering (RF-MS) method, both pure ZnO and boron doped ZnO (ZnO:B) thin films were deposited on glass substrates at ambient temperature and then annealed at 450 °C for 2 h in air. It is found that both ZnO and ZnO:B thin films have wurtzite structure of ZnO with (0 0 2) preferred orientation and high average optical transmission (≥80%). Compared with the resistivity of 6.3 × 10² Ω cm for ZnO film, both as-deposited and annealed ZnO:B films exhibit much lower resistivity of 9.2 × 10⁻³ Ω cm and 7.5 × 10⁻³ Ω cm, respectively, due to increase in the carrier concentration. Furthermore, the optical band gaps of 3.38 eV and 3.42 eV for as-deposited and annealed ZnO:B films are broader than that of 3.35 eV for ZnO film. The first-principles calculations show that in ZnO:B thin films not only the band gap becomes narrower but also the Fermi level shifts up into the conduction band with respect to the pure ZnO film. These are consistent with their lower resistivities and suggest that in the process of annealing some substituted B in the lattice change into interstitial B because of its smaller ion radius and this transformation widens the optical band gap of ZnO:B thin film.     

Temperature dependence of the optical band gap and electrical conductivity of sol-gel derived undoped and Li-doped ZnO films

Undoped and lithium (Li)-doped ZnO films were prepared by sol-gel method using spin coating technique. The effects of Li content on the crystallinity and morphological properties of ZnO films were assessed by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). XRD patterns of the films showed the hexagonal wurtzite type polycrystalline structure and that the incorporation of lithium leads to substantial changes in the structural characteristics of ZnO films. The SEM and AFM measurements showed that the surface morphology of the films was affected from the lithium incorporation. The wrinkle network was observed on the surface from both SEM and AFM results for undoped ZnO. The wrinkle structure disappeared with increasing Li content. The absorption spectra of the ZnO and 5% Li-doped ZnO (LZO5) films were carried out between 140 and 400 K temperatures. The optical band gap of ZnO and LZO5 films (calculated at various temperatures) showed a linear dependence on the temperature. The absolute zero value optical band gap and the rate of change of the band gap with temperature of the ZnO and LZO5 films were found to be 3.339 and 3.322 eV, and 2.95 × 10⁻⁴ and 1.60 × 10⁻⁴ eV/K, respectively. The transport mechanisms in the ZnO and LZO5 films have been investigated by analyzing of the temperature (80-300 K) dependence of the conductivity. The activation energies of the ZnO film increased with Li content.     

Electroluminescence from a ZnO homojunction device grown by pulsed laser deposition

A ZnO homojunction light emitting device was grown on n+ GaAs substrate by pulsed laser deposition. As-doped ZnO film by diffusion of As from the substrate was used for the p-type side and Al-doped ZnO film for the n-type side of the device. A distinct electroluminescence emission consisting of a dominant emission peak at ∼2.5 eV and a weak shoulder centered at ∼3.0 eV was observed at room temperature. The I-V characteristic of the ZnO homojunction showed a good rectifying behavior with a turn-on voltage of ∼4.5 V and a reverse breakdown voltage of ∼9 V.     

Structural, electrical and optical properties of Gd doped and undoped ZnO:Al (ZAO) thin films prepared by RF magnetron sputtering

The influence of the gadolinium doping on the structural features and opto-electrical properties of ZnO:Al (ZAO) films deposited by radio frequency (RF) magnetron sputtering method onto glass substrates was investigated. X-ray analysis showed that the films were polycrystalline fitting well with a hexagonal wurtzite structure and have preferred orientation in [0 0 2] direction. The Gd doped ZAO film with a thickness of 140 nm showed a high visible region transmittance of 90%. The optical band gap was found to be 3.38 eV for pure ZnO film and 3.58 eV for ZAO films while a drop in optical band gap of ZAO film was observed by Gd doping. The lowest resistivities of 8.4 × 10⁻³ and 10.6 × 10⁻³ Ω cm were observed for Gd doped and undoped ZAO films, respectively, which were deposited at room temperature and annealed at 150 °C.     

Structural, optical and electrical properties of Al-N codoped ZnO films by RF-assisted MOCVD method

N-doped ZnO films were produced using N₂ as N source by metal-organic chemical vapor deposition (MOCVD) system which has been improved with radio-frequency (RF)-assisted equipments. The data of secondary ion mass spectroscopy (SIMS) indicate that the concentration of N in N-doped ZnO films is around 5 × 10²⁰ cm⁻³, implying that sufficient incorporation of N into ZnO can be obtained by RF-assisted equipment. On this basis, the structural, optical and electrical properties of Al-N codoped ZnO films were studied. Then, the effect of RF power on crystal quality, surface morphologies, optical properties was analyzed using X-ray diffraction, atomic force microscopy and photo-luminescence methods. The results illustrate that the RF plasma is the key factor for the improvement of crystal quality. Then the observation of A⁰X recombination associated with N_O acceptor in low-temperature PL spectrum proved that some N atoms have occupied the positions of O atoms in ZnO films. Hall measurements shown that p-type ZnO film deposited on quartz glasses was obtained when RF power was 150 W for the Al-N codoped ZnO films, while the resistivity of N-doped ZnO films was rather high. Compared with the Al-doped ZnO film, the obviously increased resistivity of codoped films indicates that the formation of N_O acceptors compensate some donors in ZnO films effectively.     

Structural and electrical properties of nitrogen and aluminum codoped p-type ZnO films

To resolve the problem of p-type doping in ZnO, nitrogen and aluminum (N-Al) codoped ZnO films were prepared by the ultrasonic spray pyrolysis (USP) technique. The structural and electrical properties of N-Al codoped ZnO films were investigated. The results demonstrate that the undoped ZnO films exhibit the preferential orientation of (002) plane, while ZnO films show high orientation of (101) plane after codoping with N and Al. The N-Al codoped ZnO films under optimum conditions show p-type conduction, with a low resistivity of 1.7×10⁻²Ω cm, carrier concentration of 5.09×10¹⁸ cm⁻³ and high Hall mobility of 73.6 cm² V⁻¹ s⁻¹. A conversion from p-type conduction to n-type was observed during the increase of measurement temperature.     

Transparent conductive ZnO:Ga films prepared by DC reactive magnetron sputtering at low temperature

Ga-doped ZnO (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. The structural, electrical, and optical properties of ZnO:Ga films were investigated in a wide temperature range from room temperature up to 400 °C. The crystallinity and surface morphology of the films are strongly dependent on the growth temperatures, which in turn exert an influence on the electrical and optical properties of the ZnO:Ga films. The film deposited at 350 °C exhibited the relatively well crystallinity and the lowest resistivity of 3.4 × 10⁻⁴ Ω cm. More importantly, the low-resistance and high-transmittance ZnO:Ga films were also obtained at a low temperature of 150 °C by changing the sputtering powers, having acceptable properties for application as transparent conductive electrodes in LCDs and solar cells.     

Effect of energetic electron beam treatment on Ga-doped ZnO thin films

Transparent conductive zinc oxide (ZnO) thin films were synthesized by a sol–gel spin coating method with the addition of Ga(NO₃)₃ in a Zn(CH₃COO)₂ solution and exposed to electron beam treatment. The UV–Vis spectra demonstrated that all of the films had transmittances of over 85% in the visible region. When Ga(NO₃)₃ was added to the ZnO precursor solution, the resistivity of the ZnO thin film decreased and the carrier concentration increased significantly. After electron beam treatment was performed on the 0.4 at.% Ga-doped ZnO film, the optical band gap increased and the resistivity significantly decreased resulting from the increases of the carrier concentration and mobility. By combining Ga doping and electron beam treatment, the resistivity of the ZnO thin film was reduced by a factor of nine hundred.     

Swift heavy ion induced modifications in cobalt doped ZnO thin films: Structural and optical studies

Modifications in the structural and optical properties of 100 MeV Ni⁷⁺ ions irradiated cobalt doped ZnO thin films (Zn_1−xCo_xO, x = 0.05) prepared by sol-gel route were studied. The films irradiated with a fluence of 1 × 10¹³ ions/cm² were single phase and show improved crystalline structure with preferred C-axis orientation as revealed from XRD analysis. Effects of irradiation on bond structure of thin films were studied by FTIR spectroscopy. The spectrum shows no change in bonding structure of Zn-O after irradiation. Improved quality of films is further supported by FTIR studies. Optical properties of the pristine and irradiated samples have been determined by using UV-vis spectroscopic technique. Optical absorption spectra show an appreciable red shift in the band gap of irradiated Zn_1−xCo_xO thin film due to sp-d interaction between Co²⁺ ions and ZnO band electrons. Transmission spectra show absorption band edges at 1.8 eV, 2.05 eV and 2.18 eV corresponding to d-d transition of Co²⁺ ions in tetrahedral field of ZnO. The AFM study shows a slight increase in grain size and surface roughness of the thin films after irradiation.