Solution grown nanocrystalline ZnO thin films for UV emission and LPG sensing

Nanocrystalline ZnO thin films were successfully deposited by a simple and inexpensive solution growth technique. Photoluminescence (PL) and liquefied petroleum gas (LPG) sensing properties were investigated. Films were found to be uniform, pinhole free, and well adherent. As deposited and heat treated (at 673 K for 2 h) films were characterized by XRD, SEM, and EDAX. The dc electrical resistivity and LPG sensing property were measured. The change in morphology, from spherical particle to rod-like, was observed after air annealing. XRD results revealed that the obtained films were nanocrystalline and had a hexagonal wurtzite structure. The absorption edge was found to be at around 366 nm for the as-deposited film and 374 nm for the annealed film. The band gaps were found to be 3.29 and 2.9 eV for the as-deposited and annealed films, respectively. PL spectra of ZnO thin films showed strong peak at 384 nm, which corresponds to near band edge emission (UV emission) and a relatively weak peak at 471 nm. Further, the annealed film was used for detection of LPG in air. Maximum response was observed at 673 K. The maximum sensitivity of sensor was found to be 4.5 for 0.6 vol.% LPG. Sensing response got saturated after 0.6 vol.% of gas concentration. A possible mechanism of LPG sensing has been explained.     

Characterizations of ferromagnetic Zn1−xCoxO thin films grown on Al2O3 (0001) by reactive radio-frequency magnetron sputtering coupled with post-growth annealing

High-quality ferromagnetic Zn_1−xCo_xO thin films were deposited on a sapphire (0001) substrate at 600 °C by using reactive radio-frequency magnetron sputtering coupled with post-annealing treatment for 1 h at 580 °C under an Ar atmosphere. High resolution X-ray diffraction patterns show that hexagonal wurzite crystal structures of undoped ZnO film were maintained even after Co doping up to 4.5 at.% without forming Co clusters or oxides. X-ray photoelectron spectroscopy spectra represent the energy difference of 15.42 eV between Co2p_3/2 and Co2p_1/2, which is different from 15.05 eV of Co clusters. The characteristic absorption bands near 658, 616, and 568 nm wavelengths out of UV-VIS-IR spectroscopy spectra are correlated with the d-d transitions of tetrahedrally coordinated Co²⁺ ions. The low temperature photoluminescence spectrum for undoped ZnO shows a strong near-band edge (NBE) emission peak of 3.42 eV without deep level emission peaks. But, Co content increases in Zn_1−xCo_xO film, the NBE emission peak intensity decreases and another emission peak at 3.37 eV as well as a broad green emission peak at around 2.5 eV starts to appear with larger intensity due to the more actively creating oxygen vacancies. The emission peak at 3.37 eV proves the interaction between Co ions and the hydrogenic electrons in the impurity band and also supports the typical ferromagnetic hysteresis curves obtained by superconducting quantum interface device magnetometry at 300 K for Zn_1−xCo_xO films. High insulator characteristics are observed for as-grown Zn_1−xCo_xO films whereas it exhibits n-type characteristics with the increased carrier concentration, mobility, and resistivity after post-growth annealing. The spintronic devices could be fabricated with the utilization of Zn_1−xCo_xO films grown by the economically feasible reactive radio-frequency magnetron sputtering coupled with the post annealing treatment.     

Structure and optical properties of ZnO:V thin films with different doping concentrations

A series of ZnO thin films doped with various vanadium concentrations were prepared on glass substrates by direct current reactive magnetron sputtering. The results of the X-ray diffraction (XRD) show that the films with doping concentration less than 10 at.% have a wurtzite structure and grow mainly along the c-axis orientation. The residual stress, estimated by fitting the XRD diffraction peaks, increases with the doping concentration and the grain size also has been calculated from the XRD results, decreases with increasing the doping concentration. The surface morphology of the ZnO:V thin films was examined by SEM. The optical constants (refractive index and extinction coefficient) and the film thickness have been obtained by fitting the transmittance. The optical band gap changed from 3.12 eV to 3.60 eV as doping concentration increased from 1.8 at.% to 13 at.% mol. All the results have been discussed in relation with doping concentration.     

Preparation,characterization, and photoluminescence study of PVA/ZnO nanocomposite films

ZnO nanoparticles with average diameter of 25 nm were synthesized by a modified sol–gel method and used in the preparation of (in wt.%) (100 − x) poly(vinyl alcohol) (PVA)/x ZnO nanocomposite films, with x = 0, 1, 2, 3, 4, and 5. The PVA/ZnO films were exposed to UV radiation for 96 h and their thermal, morphological, and spectroscopic properties were investigated. In inert atmosphere, the nanocomposite films showed lower thermal stability than the pure PVA film, and the calorimetric data suggest an interaction between PVA and ZnO in the nanocomposite films. Some crystalline phases could be seen in the films with ZnO, and a direct dependence on the ZnO concentration was also observed. The original structure of ZnO nanoparticles remained unaltered in the PVA matrix and they were uniformly distributed on the film surface. The roughness of the PVA film was not modified by the addition of ZnO; however, it increased after 96 h of UV irradiation, more significantly in the nanocomposite films. The films showed an absorption band centered at 370 nm and a broad emission band in the UV–vis region when excited at 325 nm.     

Influence of substrate temperature on N-doped ZnO films deposited by RF magnetron sputtering

Nitrogen-doped ZnO films were deposited by RF magnetron sputtering in 75% of N₂ / (Ar + N₂) gas atmosphere. The influence of substrate temperature ranging from room temperature (RT) to 300 °C was analyzed by X-ray diffractometry (XRD), spectrophotometry, X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectrometry (SIMS) and Hall measurements setup. The XRD studies confirmed the hexagonal ZnO structure and showed that the crystallinity of these films increased with increasing substrate temperature (T_s). The optical studies indicate the average visible transmittance in the wavelength ranging 500-800 nm increases with increasing T_s. A minimum transmittance (9.84%) obtained for the films deposited at RT increased with increasing T_s to a maximum of 88.59% at 300 °C (500-800 nm). Furthermore, it was understood that the band gap widens with increasing T_s from 1.99 eV (RT) to 3.30 eV (250 °C). Compositional analyses (XPS and SIMS) confirmed the nitrogen (N) incorporation into the ZnO films and its decreasing concentration with increasing T_s. The negative sign of Hall coefficients confirmed the n-type conducting.     

Study of structural and optical properties of Ge doped ZnO films

The Ge doped ZnO films were deposited on quartz substrates by radio frequency magnetron sputtering. The effects of doping and substrate temperature on the structural and optical properties of the Ge doped ZnO films were investigated by means of X-ray diffraction (XRD), UV-visible transmission spectra, X-ray photoelectron spectroscopy and photoluminescence (PL) spectra. The XRD patterns showed that Zn₂GeO₄ phases were formed in the films. With the increase of substrate temperature the crystallization of Zn₂GeO₄ was improved, and that of ZnO phases turned worse, and no diffraction peak of ZnO was observed when the substrate temperature was 700 °C. Obvious ultraviolet (UV) light emission was found due to ZnO grains, and it was much stronger than that of un-doped ZnO films. The enhancement of UV light emission at about 380 nm may be caused by excitons which were formed at the interface between Zn₂GeO₄ and ZnO grains. In the visible region of the PL spectra, the green light emission peak of samples at about 512 nm was associated with defects in ZnO. A red shift of the green light emission peak was observed which can be explained by the fact that there is a luminescence center at about 548 nm taking the place of the defect emission of ZnO with the increase of substrate temperature. The red shift of the green light emission peak and the 548 nm green light emission peaks of the PL spectrum show that some Ge²⁺ should replace the Zn²⁺ positions during the Zn₂GeO₄ grains growth and form the Ge²⁺ luminescence centers in Zn₂GeO₄ grains.     

Characterization of gallium-nitrogen co-doped zinc oxide thin films prepared by RF diode sputtering

We investigated the possibility of achieving p-type zinc oxide (ZnO) by RF diode sputtering and gallium-nitrogen co-doping. ZnO:Ga:N thin films were prepared with a different N₂ content in Ar/N₂ working gas, ranging from 0 to 100%, and at a varying substrate temperature, from room temperature (RT) to 300 °C. A hole conduction with maximum carrier concentration of 2.6 × 10¹⁸ cm⁻³, mobility of 2 cm²/Vs and resistivity of 1.5 Ω cm resulted from deposition at RT with 100% N₂. It arose from N incorporation and formation of N_O acceptors. In the secondary ion mass spectrometry (SIMS) depth profiles of the co-doped films were observed NO/NO₂ negative ions. Average transmittance (including Corning glass substrate) across the visible spectrum varied (60 ÷ 66%) with increasing nitrogen content (50 ÷ 100% N₂). As the substrate temperature increased (RT - 300 °C), highly transparent (T ∼72-83%) and conductive (electron concentrations of 10¹⁷-10¹⁹ cm⁻³) n-type ZnO:Ga:N films were attained. Reduction of optical band gap (E_g) (∼3.13-3.08 eV) was observed for co-doped ZnO films. Atomic force microscopy (AFM) images revealed that the films grown at RT have roughness of approximately 5.3 nm while roughness of those grown at 300 °C is approximately 3.9 nm.     

Deposition of nanocrystalline ZnO by wire explosion technique and characterization of the films' properties

ZnO films deposited on glass, quartz and Al on silicon mono-crystal Si (100) substrates by using the wire explosion technique were investigated by X-ray diffraction (XRD), UV–VIS spectroscopy, scanning electron (SEM) and atomic force microscopy (AFM) measurements. X-ray diffraction measurements have shown that ZnO films are mainly composed of (100), (002) and (101) orientation crystallites. The post-deposition thermal treatment at 600 °C temperature in air has shown that the composite of Zn/ZnO film was fully oxidized to ZnO film. The XRD spectra of the film deposited in oxygen atmosphere at room temperature present high intensity dominating peak at 2h = 36, 32° corresponding to the (101) ZnO diffraction peak. The small fraction of the film (7%) corresponds to the (002) peak intensity at 2h = 34, 42°. This result indicates the good crystal quality of the film and hexagonal wurtzite-type structure deposited by zinc wire explosion. The optical absorption spectra shows the bands at 374, 373 and 371 nm corresponding to deposition conditions. The SEM analysis shows that ZnO films presented different morphologies from fractal network to porous films depending on deposition conditions. AFM analysis revealed the grain size ranges from 50 nm to 500 nm. The nanoneedles up to 300 nm in length were found as typical structures in the film. It was demonstrated that the wire explosion technique is a feasible method to produce ZnO crystalline thin films and nanostructures.     

Effect of precursor concentration on structural and optical properties of ZnO microrods by spray pyrolysis

ZnO films have been prepared by spray pyrolysis technique on glass substrate at 500 °C. Zinc Chloride has been used as a precursor. Effect of precursor concentration on structural and optical properties has been investigated. Homogenous films are obtained with precursor concentration rating between 0.1 M and 0.4 M. X-ray diffraction patterns show that ZnO films are polycrystalline with (002) plane as preferential orientation. Field emission scanning electron microscopy images show that ZnO films consist of microrods that their length increases with increasing precursor concentration and tallest microrods obtain by spraying precursor with 0.3 M concentration. The optical transmittance spectrum shows that transmittance increases with decreasing of the concentration and transmittance reaches to a maximum value of about 80% for the visible region ZnO films prepared with 0.1 M. Photoluminescence spectra at room temperature show an ultraviolet emission at 3.21 eV that can be related to band gap and two visible emissions at 2.88 eV and 2.38 eV.     

Effect of GaN doping on ZnO films by pulsed laser deposition

The present study reveals the codoping of Ga and N into ZnO films on sapphire substrates by pulsed laser deposition (PLD) with GaN doped ZnO targets. The glow discharge mass spectroscopy (GDMS) spectra confirm the presence of Ga and N in the doped films. The XRD measurements show that for GaN concentration up to 0.8 mol%, the full width at half maximum (FWHM) is almost unchanged thereby maintaining the crystallinity of the films, while for 1 mol% the FWHM increases. The PL spectra only show the strong near band edge (NBE) emission, whereas the deep level emissions are almost undetectable, indicating that they have been considerably suppressed. Our Hall measurements indicate that all the GaN doped ZnO films are of n-type. However, as the GaN concentration is greater than 0.6 mol%, the film shows a decrease in the carrier concentration, suggesting that N acceptors are not sufficient to compensate the native donor defects.     

Synthesis,structural and optical characterization of Ni-doped ZnO nanoparticles

Nanocrystalline Zn_1−x Ni _x O (x = 0.00, 0.02, 0.04, 0.06, 0.08) powders were synthesized by a simple sol–gel autocombustion method using metal nitrates of zinc, nickel and glycine. Structural and optical properties of the Ni-doped ZnO samples annealed at 800 °C are characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive analysis using X-rays (EDAX), UV–visible spectroscopy and photoluminescence (PL). X-ray diffraction analysis reveals that the Ni-doped ZnO crystallizes in a hexagonal wurtzite structure and secondary phase (NiO) was observed with the sensitivity of XRD measurement with the increasing nickel concentration (x ≥ 0.04). The lattice constants of Ni-doped ZnO nanoparticles increase slightly when Ni²⁺ is doped into ZnO lattice. The optical absorption band edge of the nickel doped samples was observed above 387 nm (3.20 eV) along with well-defined absorbance peaks at around 439 (2.82 eV), 615(2.01 eV) and 655 nm (1.89 eV). PL measurements of Ni-doped samples illustrated the strong UV emission band at ~3.02 eV, weak blue emission bands at 2.82 and 2.75 eV, and a strong green emission band at 2.26 eV. The observed red shift in the band gap from UV–visible analysis and near band edge UV emission with Ni doping may be considered to be related to the incorporation of Ni ions into the Zn site of the ZnO lattice.     

Synthesis and optical characterization of n-ZnO and p-Cu2ZnSnS4 nanocrystalline thin films for low cost solar cells

High quality ZnO/Cu₂ZnSnS₄ thin films as a window/absorber layers were successfully synthesized via spin coating the sol-gel precursor of each composition without using any vacuum facilities. In this study, the impact of annealing temperature (400 °C, 3 h) on the ZnO window layer and different thickness (3 and 5 layers) of the Cu₂ZnSnS₄ (CZTS) absorber layer were investigated. X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), scanning electron microscope (SEM) and UV–vis–NIR spectroscopy were used for the structural, compositional, morphological and optical absorption analysis of each layer. ZnO exhibits wurtzite hexagonal crystal structure with particle size equals to 8.60 and 28.59 nm for fresh and annealed films, respectively. Micro-strain and dislocations density decreased with the annealing temperature. X-ray diffraction patterns for CZTS films show small peak at (112) according to the kesterite structure with particle size in nano-scale for the two thicknesses. ZnO films demonstrated direct optical band gap of 3.23 and 3.21 eV for fresh and annealed films, respectively. CZTS films (3 and 5 layers) also have direct optical band with optimum value (1.51 eV) for thickness of 5 layers. The J-V characteristics of the CZTS-based thin film solar cells (CZTS/ZnO/ZnO:Ag) were measured under air mass AM 1.5 and 100 mW/cm² illumination. The values of the short circuit current (J_sc), open circuit voltage (V_oc) and fill factor (FF) also have been obtained.     

Dependence of photoluminescence and electrical properties with rapid thermal annealing in nitrogen-implanted ZnO films

Undoped (as-grown) ZnO films grown by pulsed laser deposition on Al₂O₃ (0001) substrates were doped with nitrogen by means of an ion implantation process. Post-implantation annealing behavior in the temperature range between 500 and 700 °C has been studied by photoluminescence and Hall effect measurements. The implanted films show no peak other than the excitonic recombination emission in the as-implanted state, however, after rapid thermal annealing at 700 °C they reveal a nitrogen acceptor related emission at 3.273 eV. The as-implanted ZnO films show more electron concentrations than the as-grown, unimplanted ZnO film. In contrast, after annealing, the electron concentration in the implanted films is significantly reduced, indicating that the incorporated nitrogen becomes activated after the thermal annealing, then produces holes and eventually compensates for certain amount of electrons. The results imply that a proper nitrogen implantation and subsequent annealing may be a way to produce p-type ZnO films.     

Enhanced free exciton and direct band-edge emissions at room temperature in ultrathin ZnO films grown on Si nanopillars by atomic layer deposition

Room-temperature ultraviolet (UV) luminescence was investigated for the atomic layer deposited ZnO films grown on silicon nanopillars (Si-NPs) fabricated by self-masking dry etching in hydrogen-containing plasma. For films deposited at 200 °C, an intensive UV emission corresponding to free-exciton recombination (~3.31 eV) was observed with a nearly complete suppression of the defect-associated broad visible range emission peak. On the other hand, for ZnO films grown at 25 °C, albeit the appearance of the defect-associated visible emission, the UV emission peak was observed to shift by ~60 meV to near the direct band edge (3.37 eV) recombination emission. The high-resolution transmission electron microscopy (HRTEM) showed that the ZnO films obtained at 25 °C were consisting of ZnO nanocrystals with a mean radius of 2 nm embedded in a largely amorphous matrix. Because the Bohr radius of free-exictons in bulk ZnO is ~2.3 nm, the size confinement effect may have occurred and resulted in the observed direct band edge electron-hole recombination. Additionally, the results also demonstrate order of magnitude enhancement in emission efficiency for the ZnO/Si-NP structure, as compared to that of ZnO directly deposited on Si substrate under the same conditions.     

Co-emission of UV, violet and green photoluminescence of ZnO/TiO2 thin film

ZnO/TiO₂ thin films were fabricated on quartz glass substrates by E-beam evaporation. The structural and optical properties were investigated by X-ray diffraction (XRD), Raman spectra, optical transmittance and photoluminescence. XRD analysis indicates that the TiO₂ buffer layer can increase the preferential orientation along the (002) plane of the ZnO film. PL measurements suggest that co-emission of strong UV peak at 378 nm, violet peak at 423 nm and weak green luminescence at 544 nm is observed in the ZnO/TiO₂ thin film. The violet luminescence emission at 423 nm is attributed to the interface trap in the ZnO film grain boundaries.     

Growth,chemical composition,and structure of thin La x Hf1 − x O y films on Si

The chemical structure, phase composition, and crystal structure of La _x Hf_{1 ? x} O _y films grown on Si using volatile metalorganic compounds as Hf and La precursors have been studied by X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive X-ray microanalysis, and atomic force microscopy. By varying the lanthanum and hafnium source temperatures, we were able to grow films with 2 at % < C_La < 30 at %. The Hf 4f and La 3d peak positions in the XPS spectra of the films correspond to hafnium and lanthanum in the Hf⁴⁺ and La³⁺ states. With increasing La concentration, the reflections in the X-ray diffraction patterns of the films shift to smaller 2θ angles, indicating the formation of solid solutions. At 18 at % La, we observed a transition from a fluorite-like structure to the pyrochlore structure (La₂Hf₂O₇). The film containing 30 at % La consisted of a mixture of c-La₂O₃ and La₂Hf₂O₇. The surface roughness of the films was shown to increase with increasing La concentration. Capacitance-voltage (C-V) measurements were used to assess the relative permittivity (k) of the films as a function of La concentration. The minimum k value was obtained at the La concentration corresponding to the transition from the fluorite structure to an ordered pyrochlore structure (second-order phase transition).     

Optical and photoluminescent properties of sol-gel Al-doped ZnO thin films

Al-doped zinc oxide (AZO) thin films have been prepared via a sol-gel process. Optical and photoluminescent properties of the AZO films have been investigated. The UV absorption edge was blue shifted with increasing Al doping concentration. Efficient green–yellow emission was obtained after annealing at 850 °C. For the 850 °C-annealed samples, the green peak was red shifted from 518 to 565 nm as the Al doping concentration increased from 0 to 2.0 at.%. In addition, violet emission in the range of 400–450 nm was observed in the 850 °C-annealed AZO films. The possible origins responsible for these emission bands have been discussed.     

Structure, luminescence and electrical properties of ZnO thin films annealed in H2 and H2O ambient: A comparative study

Undoped ZnO films were grown on a c-plane sapphire by plasma-assisted molecular-beam epitaxy technique, and subsequently annealed at 200-500 °C with steps of 100 °C in water vapour and hydrogen ambient, respectively. It is found that the c-axis lattice constant of the ZnO films annealed in hydrogen or water vapour at 200 °C increases sharply, thereafter decreases slowly with increasing annealing temperature ranging from 300 °C to 500 °C. The stress in the as-grown ZnO films was more easily relaxed in water vapour than in hydrogen ambient. Interestingly, the controversial luminescence band at 3.310 eV, which is often observed in photoluminescence (PL) spectra of the ZnO films doped by p-type dopants, was observed in the PL spectra of the annealed undoped ZnO films and the PL intensity increases with increasing annealing temperature, indicating that the 3.310 eV band is not related to p-type doping of ZnO films. The electron concentration of the ZnO films increases sharply with increasing annealing temperature when annealed in hydrogen ambient but decreases slowly when annealed in water vapour. The mechanisms of the effects of annealing ambient on the properties of the ZnO films are discussed.     

Size and defect related broadening of photoluminescence spectra in ZnO:Si nanocomposite films

Nanocomposite films of zinc oxide and silicon were grown by thermal evaporation technique using varying ratios of ZnO:Si in the starting material. Structural analyses reveal the role of ZnO and amorphous silicon interface in contributing to the relatively less common blue photoluminescence emissions (at ～410 and 470 nm). These blue peaks are observed along with the emissions resulting from band edge transition (370 nm) and those related to defects (520 nm) of ZnO. Careful analysis shows that along with the grain size of ZnO, a suitable compositional ratio of ZnO to silicon is critical for the coexistence of all the four peaks. Proper selection of conditions can give comparable photoluminescence peak intensities leading to broad-band emission.     

Effect of Ga Doping Concentration on Electrical and Optical Properties of Nano-ZnO:Ga Transparent Conductive Films

Transparent conductive nano ZnO thin films with different Ga doping concentrations (1, 3, 5, 7 at.%) were prepared on glass substrate by RF magnetron sputtering. The influence of Ga doping concentration on the structural, electrical and optical properties of ZnO:Ga films was investigated by XRD, SEM, Hall measurement and optical-transmission spectroscopy. It shows that the nano ZnO:Ga films are dense and flat, and have polycrystalline structure with preferential (002) and weak (101) orientation. The grain sizes, carrier concentration and Hall mobility changes non-linearly with the increase of Ga-content. The lowest resistivity of 1.44×10⁻³ Ωcm appears at 3 at.% Ga doping concentration. The average transmittance of the films is about 80∼90% in the visible range. The optical band gap obtained for these films is larger than for pure ZnO (∼3.37 eV).