Low operating temperature of oxygen gas sensor based on undoped and Cr-doped ZnO films

Undoped and doped ZnO with 1 at.% (atomic percentage) chromium (Cr) was synthesized by RF reactive co-sputtering for oxygen gas sensing applications. The prepared films showed a highly c-oriented phase with a dominant (0 0 2) peak at a Bragg angle of around 34.2°. The operating temperature of the prepared ZnO sensor was around 350 °C and shifted to around 250 °C for the doped ZnO sensor which is lower than that of previously reported work. The sensitivity of the sensor toward oxygen gas was enhanced by doping ZnO with 1 at.% Cr. Good stability and repeatability of the sensor were demonstrated when tested under different concentration of oxygen atmosphere.     

Determination of electrical types in the P-doped ZnO thin films by the control of ambient gas flow

Phosphorus (P)-doped ZnO thin films with amphoteric doping behavior were grown on c-sapphire substrates by radio frequency magnetron sputtering with various argon/oxygen gas ratios. Control of the electrical types in the P-doped ZnO films was achieved by varying the gas ratio without post-annealing. The P-doped ZnO films grown at a argon/oxygen ratio of 3/1 showed p-type conductivity with a hole concentration and hole mobility of 1.5 × 10¹⁷ cm⁻³ and 2.5 cm²/V s, respectively. X-ray diffraction showed that the ZnO (0 0 0 2) peak shifted to lower angle due to the positioning of P³⁻ ions with a larger ionic radius in the O²⁻ sites. This indicates that a p-type mechanism was due to the substitutional P_O. The low-temperature photoluminescence of the p-type ZnO films showed p-type related neutral acceptor-bound exciton emission. The p-ZnO/n-Si heterojunction light emitting diode showed typical rectification behavior, which confirmed the p-type characteristics of the ZnO films in the as-deposited status, despite the deep-level related electroluminescence emission.     

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.     

Relationship between the photoluminescence and conductivity of undoped ZnO thin films grown with various oxygen pressures

The pulsed laser deposition (PLD) technique is used to deposit undoped ZnO thin films on glass substrates at 150 °C with different oxygen pressures of 40, 80, 100 and 150 mTorr. X-ray diffraction (XRD) and atomic force microscopy (AFM) studies indicated that the obtained ZnO thin films were hexagonal wurtzite-type structures with strong (0 0 2) c-axis orientation. The relationship between photoluminescence and the conductivity of the ZnO thin films grown by pulsed laser deposition at various oxygen pressures was also discussed. The intensity of the deep-level-emission (DLE) and conductivity generally increased as the oxygen pressure decreased. The intensity of DLE peak was generally proportional to the conductivity. The band gap energy values, determined from transmittance spectra, were around 3.30-3.34 eV, and decreased when the oxygen pressure increased.     

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.     

Radio frequency plasma enhanced chemical vapor based ZnO thin film deposition on glass substrate: A novel approach towards antibacterial agent

In the present study, the structural, optical and antibacterial properties of ZnO thin films are reported. ZnO thin films are deposited on borosilicate glass substrates by radio frequency plasma enhanced chemical vapor deposition (PECVD) using oxygen as process gas. The crystallinity of the deposited films is improved upon annealing at 450 °C in air for 1.5 h and the polycrystalline nature of the films is further confirmed by selected area electron diffraction. The particle size of the annealed film (thickness 476 nm) is found to be ∼34 nm from the transmission electron microscopic observation. Energy dispersive X-ray spectrum indicates the stoichiometric deposition of ZnO films. The films are highly transparent (transmittance >85%) in the visible region of electromagnetic spectrum. The films exhibit excellent antibacterial effect towards the growth of Escherichia coli and Pseudomonas aeruginosa.     

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.     

Structural and optical properties of nanocrystalline ZnO thin films synthesized by the citrate precursor route

Nanocrystalline zinc oxide (ZnO) thin films have been deposited by spin-coating polymeric precursors synthesized by the citrate precursor route using ethylene glycol and citric acid as chelating agents. The ZnO thin films were annealed in air at different temperatures for 10 min. The films were characterized by different structural and optical techniques, including X-ray diffraction (XRD), atomic force microscopy (AFM), optical transmission spectroscopy, and photoluminescence (PL). The thermal decomposition of polymeric precursor was studied by thermogravimetric analysis (TGA). XRD analysis with grazing incidence and rocking curves indicate that the ZnO films are polycrystalline with preferential orientation along the c-axis direction with a full-width at half-maximum (FWHM) of 0.31° for 600 °C-annealed samples. On annealing, the texturing in films increased along with a decrease in FWHM. AFM micrographs illustrate that the ZnO films are crack-free with well-dispersed homogeneous and uniformly distributed spherical morphology. The synthesized ZnO thin films have transparency >85% in the visible region exhibiting band edge at 375 nm, which becomes sharper with anneal. Room temperature PL spectra of these films show strong ultraviolet (UV) emission around 392 nm with an increase in intensity with annealing temperature, attributed to grain growth. Deconvolution of the PL spectra reveals that there is coupling of free excitons with higher orders of longitudinal optical (LO) phonon replicas leading to a broad asymmetric near-band-edge peak.     

Effect of different dopant elements (Al,Mg and Ni) on microstructural,optical and electrochemical properties of ZnO thin films deposited by spray pyrolysis (SP)

In the present work we studied the influence of the dopant elements and concentration on the microstructural and electrochemical properties of ZnO thin films deposited by spray pyrolysis. Transparent conductive thin films of zinc oxide (ZnO) were prepared by the spray pyrolysis process using an aqueous solution of zinc acetate dehydrate [Zn(CH₃COO)₂·2H₂O] on soda glass substrate heated at 400 ± 5 °C. AlCl₃, MgCl₂ and NiCl₂ were used as dopant. The effect of doping percentage (2–4%) has been investigated. Afterwards the samples were thermally annealed in an ambient air during one hour at 500 °C. X-ray diffraction showed that films have a wurtzite structure with a preferential orientation along the (0 0 2) direction for doped ZnO. The lattice parameters a and c are estimated to be 3.24 and 5.20 ?, respectively. Transmission allowed to estimate the band gaps of ZnO layers. The electrochemical studies revealed that the corrosion resistance of the films depended on the concentration of dopants.     

Photoluminescence study of pure and Li-doped ZnO thin films grown by sol-gel technique

The effect of annealing atmosphere, temperature and aging on the photoluminescence of pure and Li-doped ZnO thin films has been investigated. Annealing the pure ZnO in N₂ and He above 800 °C results in green emission centered at ca. 500 nm; however annealing in air red-shifts the green emission to 527 nm. The visible emission of the Li-doped ZnO is found to be largely dependent on the annealing atmosphere. Warm-white photoluminescence with a broad emission band covering nearly the whole visible spectrum is obtained for the Li-doped ZnO films annealed in helium. The substitutional and interstitial extrinsic point defects created by lithium doping may mediate the relative concentration of the intrinsic defects and thereby tune the intrinsic-defect-related visible emission. The enhanced intensity ratio of near-band-edge ultraviolet emission to deep-level visible emission with aging time may be ascribed to both in-diffusion of oxygen from air and self-diffusion of oxygen interstitials to heal the oxygen vacancies during the aging process.     

Properties of Zn3N2-doped ZnO films deposited by pulsed laser deposition

The optical properties of N-doped ZnO films grown by pulsed laser deposition are examined for which zinc nitride is used as the source of nitrogen. The motivation for this study is to determine if nitrogen-related acceptor state formation can be achieved in ZnO films using Zn₃N₂ doping in the ablation target. The films were deposited in oxygen or nitrogen on c-plane sapphire. Photoluminescence measurements at 20 K reveal a 3.31 eV acceptor-bound exciton emission due to nitrogen substitution on the oxygen site, donor-acceptor pair emission at 3.23 ± 1 eV and free electron-acceptor at 3.27 eV. The binding energy of the N-related acceptor is estimated to be in the range of 170-15 meV. While the as-deposited films were n-type, thermal annealing in oxygen yielded insulating behavior, consistent with compensating acceptor states.     

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.     

Effect of annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films on sapphire (0 0 0 1) substrates by magnetron sputtering

ZnO thin films were epitaxially grown on sapphire (0 0 0 1) substrates by radio frequency magnetron sputtering. ZnO thin films were then annealed at different temperatures in air and in various atmospheres at 800 °C, respectively. The effect of the annealing temperature and annealing atmosphere on the structure and optical properties of ZnO thin films are investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), photoluminescence (PL). A strong (0 0 2) diffraction peak of all ZnO thin films shows a polycrystalline hexagonal wurtzite structure and high preferential c-axis orientation. XRD and AFM results reveal that the better structural quality, relatively smaller tensile stress, smooth, uniform of ZnO thin films were obtained when annealed at 800 °C in N₂. Room temperature PL spectrum can be divided into the UV emission and the Visible broad band emission. The UV emission can be attributed to the near band edge emission (NBE) and the Visible broad band emission can be ascribed to the deep level emissions (DLE). By analyzing our experimental results, we recommend that the deep-level emission correspond to oxygen vacancy (V_O) and interstitial oxygen (O_i). The biggest ratio of the PL intensity of UV emission to that of visible emission (I_NBE/I_DLE) is observed from ZnO thin films annealed at 800 °C in N₂. Therefore, we suggest that annealing temperature of 800 °C and annealing atmosphere of N₂ are the most suitable annealing conditions for obtaining high quality ZnO thin films with good luminescence performance.     

Effects of Cr doping on physical properties of amorphous In-Ga-Zn-O films

Amorphous thin films of InGaZnO₄ (a-IGZO) doped with Cr have been fabricated by using pulsed-laser deposition (PLD). The electrical, optical and magnetic properties of Cr-doped a-IGZO films grown at 25 °C and 150 °C were investigated. The conductivity, optical transmission and band gap of films are remarkably enhanced by increasing the growth temperature. Conductivity, carrier concentration and mobility decrease with increasing the Cr content. However, the optical transmission and band gap are not significantly affected by Cr doping. Moreover, all Cr-doped films exhibit room-temperature ferromagnetism.     

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.     

Structural, optical and magnetic properties of (ZnO)1−x(MnO2)x thin films deposited at room temperature

The structural, magnetic and optical properties of (ZnO)_1−x(MnO₂)_x (with x = 0.03 and 0.05) thin films deposited by pulsed laser deposition (PLD) were studied. The pellets used as target, sintered at different temperatures ranging from 500 °C to 900 °C, were prepared by conventional solid state method using ZnO and MnO₂ powders. The observation of non-monotonic shift in peak position of most preferred (1 0 1) ZnO diffraction plane in XRD spectra of pellets confirmed the substitution of Mn ions in ZnO lattice of the sintered targets. The as-deposited thin film samples are found to be polycrystalline with the preferred orientation mostly along (1 1 0) diffraction plane. The UV-vis spectroscopy of the thin films revealed that the energy band gap exhibit blue shift with increasing Mn content which could be attributed to Burstein-Moss shift caused by Mn doping of the ZnO. The deposited thin films exhibit room temperature ferromagnetism having effective magnetic moment per Mn atom in the range of 0.9-1.4μ_B for both compositions.     

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%.     

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.     

Highly conductive and transparent laser ablated nanostructured Al: ZnO thin films

Al doped ZnO thin films are prepared by pulsed laser deposition on quartz substrate at substrate temperature 873 K under a background oxygen pressure of 0.02 mbar. The films are systematically analyzed using X-ray diffraction, atomic force microscopy, micro-Raman spectroscopy, UV-vis spectroscopy, photoluminescence spectroscopy, z-scan and temperature-dependent electrical resistivity measurements in the temperature range 70-300 K. XRD patterns show that all the films are well crystallized with hexagonal wurtzite structure with preferred orientation along (0 0 2) plane. Particle size calculations based on XRD analysis show that all the films are nanocrystalline in nature with the size of the quantum dots ranging from 8 to 17 nm. The presence of high frequency E₂ mode and longitudinal optical A₁ (LO) modes in the Raman spectra suggest a hexagonal wurtzite structure for the films. AFM analysis reveals the agglomerated growth mode in the doped films and it reduces the nucleation barrier of ZnO by Al doping. The 1% Al doped ZnO film presents high transmittance of ∼75% in the visible and near infrared region and low dc electrical resistivity of 5.94 × 10⁻⁶ Ω m. PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. Nonlinear optical measurements using the z-scan technique shows optical limiting behavior for the 5% Al doped ZnO film.     

The gas response enhancement from ZnO film for H2 gas detection

ZnO thin films were prepared by thermal oxidation of Zn metal at 400 °C for 30 and 60 min. The XRD results showed that the Zn metal was completely converted to ZnO with a polycrystalline structure. The sensors had a maximum response to H₂ at 400 °C and showed stable behavior for detecting H₂ gases in the range of 40 to 160 ppm. The film oxidized for 60 min in oxygen flow exhibited higher response than that of the 30 min oxidation which was approximately 4000 for 160 ppm H₂ gas concentration. The sensing mechanism was modeled according to the oxygen-vacancy model.