Electrical, structural and optical properties of fluorine-doped zinc oxide thin films: Effect of the solution aging time

In this paper ageing effects of the solution used to prepare fluorine-doped ZnO films by the spray pyrolysis technique were investigated, concerning its role on the structure, the electrical and optical properties of films produced. The data reveal that the sheet resistance of the ZnO:F thin film decreases with the age of the solution used, reaching a minimum of 24 Ω/□, after 15 days. On the other hand the optical transmittance increases for films deposited using 6 days aging solution, decreasing afterwards as the aging time increases, being the optical transmittance in the visible range below 55%, for films deposited from solutions 36 days in age. The X-ray diffraction spectra show that the aged films are polycrystalline in nature with a [100] predominant orientation. The data also show that the intensity of (100) peak increases as the time of solution age increases, which is related to an improvement of the film crystallinity.     

Thickness dependence of structural, electrical and optical properties of sprayed ZnO:Cu films

ZnO:Cu thin films have been deposited by spray pyrolysis techniques within two different (450 °C and 500 °C) substrate temperatures. The structural properties of ZnO:Cu thin films have been investigated by X-ray diffraction techniques. The X-ray diffraction spectra showed that ZnO:Cu thin films are polycrystalline with the hexagonal structure and show a good c-axis orientation perpendicular to the substrate. The most preferential orientation is along the (002) direction for all spray deposited ZnO:Cu films together with orientations in the (100) and (101) planes also being abundant. Some parameters of the films were calculated and correlated with the film thickness for two different substrate temperatures. The optical properties of ZnO:Cu thin films have been investigated by UV/VIS spectrometer and the band gap values were found to be ranging from 3.29 eV to 3.46 eV.     

Deposition of Na–N dual acceptor doped p-type ZnO thin films and fabrication of p-ZnO:(Na,N)/n-ZnO:Eu homojunction

Sodium and nitrogen dual acceptor doped p-type ZnO (ZnO:(Na, N)) films have been prepared by spray pyrolysis technique at a substrate temperature of 623 K. The ZnO:(Na, N) films are grown at a fixed N doping concentration of 2 at.% and varying the nominal Na doping concentration from 0 to 8 at.%. The XRD results show that all the ZnO:(Na, N) films exhibited (0 0 2) preferential orientation. The EDX and elemental mapping analysis shows the presence and distribution of Zn, O, Na and N in the deposited films. The Hall measurement results demonstrate that the Na–N dual acceptor doped ZnO films show excellent p-type conduction. The p-type ZnO:(Na, N) films with comparatively low resistivity of 5.60 × 10⁻² Ω cm and relatively high carrier concentration of 3.15 × 10¹⁸ cm⁻³ are obtained at 6 at.%. ZnO based homojunction is fabricated by depositing n-type layer (Eu doped ZnO) grown over the p-type layer ZnO:(Na, N). The current–voltage (I–V) characteristics measured from the two-layer structure show typical rectifying characteristics of p-n junction with a low turn on voltage of about 1.69 V. The ZnO:(Na, N) films exhibit a high transmittance (about >90%) and the average reflectance is 8.9% in the visible region. PL measurement shows near-band-edge (NBE) emission and deep-level (DL) emission in the ZnO:(Na, N) thin films.     

Structural and electrical properties of p-type ZnO films prepared by Ultrasonic Spray Pyrolysis

Effects of atomic ratio of Zn:N:Al and solution concentration on the structural and electrical characteristic of ZnO films deposited by Ultrasonic Spray Pyrolysis using N-Al co-doping technique were investigated. Hall measurement indicated that with increasing Al doping, conductive type of ZnO thin films changed from n-type to p-type and then to n-type again. However, the solution concentration almost has no effect on the structural and electrical properties of p-type ZnO films. X-ray Photoelectron Spectroscopy indicated that the presence of Al indeed facilitates the incorporation of N through the formation of N-Al bonds in co-doped ZnO films. In addition, Photoluminescence spectra showed p-type ZnO films with a low density of native defects.     

Structural, optical and electrical properties of Al-doped ZnO microrods prepared by spray pyrolysis

Al-doped ZnO thin films were obtained on glass substrates by spray pyrolysis in air atmosphere. The molar ratio of Al in the spray solution was changed in the range of 0-20 at.% in steps of 5 at.%. X-ray diffraction patterns of the films showed that the undoped and Al-doped ZnO films exhibited hexagonal wurtzite crystal structure with a preferred orientation along (002) direction. Surface morphology of the films obtained by scanning electron microscopy revealed that pure ZnO film grew as quasi-aligned hexagonal shaped microrods with diameters varying between 0.7 and 1.3 μm. However, Al doping resulted in pronounced changes in the morphology of the films such as the reduction in the rod diameter and deterioration in the surface quality of the rods. Nevertheless, the morphology of Al-doped samples still remained rod-like with a hexagonal cross-section. Flower-like structures in the films were observed due to rods slanting to each other when spray solution contained 20 at.% Al. Optical studies indicated that films had a low transmittance and the band gap decreased from 3.15 to 3.10 eV with the increasing Al molar ratio in the spray solution from 0 to 20 at.%.     

前驱体浓度对超声雾化热解法制备ZnO薄膜性能的影响

采用超声雾化技术,以醋酸锌水溶液为前驱体溶液,在加热的玻璃衬底上制备得到ZnO薄膜.研究了不同前驱体溶液浓度和不同加热温度条件下制得的ZnO薄膜的微观结构和光学性能.测试结果表明,ZnO薄膜为六角纤锌矿结构,在合适的条件下可以制备出沿(002)晶面取向生长的样品,具有优良的均匀性和致密性.同时在可见光区也表现出80%以上的高透过率.     

Stable p-type conductivity and enhanced photoconductivity from nitrogen-doped annealed ZnO thin film

We report on the growth of p-type ZnO thin films with improved stability on various substrates and study the photoconductive property of the p-type ZnO films. The nitrogen doped ZnO (N:ZnO) thin films were grown on Si, quartz and alumina substrates by radio frequency magnetron sputtering followed by thermal annealing. Structural studies show that the N:ZnO films possess high crystallinity with c-axis orientation. The as-grown films possess higher lattice constants compared to the undoped films. Besides the high crystallinity, the Raman spectra show clear evidence of nitrogen incorporation in the doped ZnO lattice. A strong UV photoluminescence emission at ~ 380 nm is observed from all the N:ZnO thin films. Prior to post-deposition annealing, p-type conductivity was found to be unstable at room temperature. Post-growth annealing of N:ZnO film on Si substrate shows a relatively stable p-type ZnO with room temperature resistivity of 0.2 Ω cm, Hall mobility of 58 cm²/V s and hole concentration of 1.95 × 10¹⁷ cm^− 3. A homo-junction p-n diode fabricated on the annealed p-type ZnO layer showed rectification behavior in the current-voltage characteristics demonstrating the p-type conduction of the doped layer. Doped ZnO films (annealed) show more than two orders of magnitude enhancement in the photoconductivity as compared to that of the undoped film. The transient photoconductivity measurement with UV light illumination on the doped ZnO film shows a slow photoresponse with bi-exponential growth and bi-exponential decay behaviors. Mechanism of improved photoconductivity and slow photoresponse is discussed based on high mobility of carriers and photodesorption of oxygen molecules in the N:ZnO film, respectively.     

Investigation of precursors concentration in spray solution on the optoelectronic properties of CuInSe2 thin films deposited by spray pyrolysis method

Copper indium selenide CuInSe₂(CISe) thin films were deposited by chemical spray pyrolysis (CSP) method of CuInS₂(CIS) and subsequent selenization process. To study the effects of solution concentration, we prepared different precursors solution of CIS including different amount of indium salts from 0.025 to 0.100 M with In/Cu 1.25 and S/In 4. These results propose that solution concentration is critical for inflecting the morphological, optical, electrical, and electrochemical characteristics of solution-processed CISe films and device performance. The studied morphological properties of deposited samples were homogenous, crack-free with large grains in indium salt concentrations more than 0.075 M. The deposited film thickness depends on the spray precursor concentration and increases for higher concentration. In addition with increasing of indium precursor concentration from 0.025 to 0.100 M in spray solution, the optical bandgap of deposited film decreases from 1.40 to 1.35 eV. Also the films mobility and carrier density were notably influenced by any change in the solution concentration. Electrical and electrochemical properties showed a decrease in carrier density from?~?10²⁰ to?~?10¹⁷ cm^?3 and the increase in mobility of order?~?10^–7 to?~?10^–2 cm²/V s, respectively, for 0.025 M, 0.100 M CISe films. All films exhibited p-type conductivity owing to different concentrations. However, it seems that the concentration of the ideal solution is 0.100 molars.

     

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.     

Simple way for preparation of ZnO films by surfactant mediated spray pyrolysis

Nanocrystalline porous ZnO films are deposited onto alumina foil substrates by polyvinyl alcohol (PVA) modified spray pyrolysis. Water and ethanol–water mixture were used for preparation of the sols. The effect of polyvinyl alcohol on the morphological and photocatalytical properties of ZnO films was studied. It was found that the polyvinyl alcohol plays important role in formation of porous films structure with ganglia like morphology. Relatively compact granular morphology was observed for the ZnO samples, grown without organic surfactant. The X-ray diffraction patterns revealed the formation of phase-pure ZnO thin films. The FTIR spectra and DTA-TG analyses of the precursor mixtures: Zn(CH₃COOH)₂·2H₂O and Zn(NO₃)₂·6H₂0 with PVA revealed that ZnO is formed before the final decomposition of the polymer at 350 °C.     

Electrical and optical properties of P-doped ZnO thin films by annealing temperatures in Nitrogen ambient

The effects of post-annealing temperature on the optical and electrical properties of P-doped ZnO thin films, grown on sapphire substrate, have been investigated when the annealing is performed under nitrogen ambient. Analysis of the XRD shows that regardless of the post-annealing temperature, the P-doped ZnO thin films have grown the (002) peak. The full width of half maximum decreases from 0.194 to 0.181° as the annealing temperature increases from 700 to 900 °C. This phenomenon means that the increase of annealing temperature causes enhancement of the thin film’s crystalline properties. The results of Hall effect measurements indicate that the P-doped ZnO thin films, annealed at 750 and 800 °C exhibit p-type behavior, with hole concentrations of 5.71 × 10¹⁷ cm⁻³ and 1.20 × 10¹⁸ cm⁻³, and hole mobilities of 0.12 cm²/Vs and 0.08 cm²/Vs, respectively. The low-temperature (10 K) photoluminescence results reveal that the peaks related to the neutral-acceptor exciton (A⁰X) at 3.355 eV, free electrons to neutral acceptor (FA) at 3.305 eV and donor acceptor pair (DAP) at 3.260 and 3.170 eV are observed in the films showing p-type behavior with the acceptors. Because P atoms replace O atoms to produce acceptors from P-doped ZnO thin films by the thermal activation process at the appropriate annealing temperature with nitrogen ambient, the p-type ZnO thin films can be fabricated in this way.     

Structural,Optical and Electrical Properties of ZnO Thin Films Prepared by Spray Pyrolysis: Effect of Precursor Concentration

ZnO thin films have been prepared using zinc acetate precursor by spray pyrolytic decomposition of zinc acetate on glass substrates at 450 °C. Effect of precursor concentration on structural and optical properties has been investigated. ZnO films are polycrystalline with (002) plane as preferential orientation. The optical transmission spectrum shows that transmission increases with decrease in the concentration and the maximum transmission in visible region is about 95% for ZnO films prepared with 0·1 M. The direct bandgap value decreases from 3·37 to 3·19 eV, when the precursor concentration increases from 0·1 to 0·4 M. Photoluminescence spectra at room temperature show an ultraviolet (UV) emission at 3·26 eV and two visible emissions at 2·82 and 2·38 eV. Lowest resistivity is obtained at 2·09 Ω cm for 0·3 M. The current– voltage characteristic of the ZnO thin films were measured in dark and under UV illumination. The values of photocurrent and photoresponsivity at 5 V are increased with increase in precursor concentration and reaches to maximum value of 1148 μA and 0·287 A/W, respectively which is correlated to structural properties of ZnO thin films.     

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.     

Transparent conducting properties of Ni doped zinc oxide thin films prepared by a facile spray pyrolysis technique using perfume atomizer

Undoped and Ni doped zinc oxide (Ni–ZnO) thin films were prepared by a facile spray pyrolysis technique using perfume atomizer from aqueous solution of anhydrous zinc acetate (Zn(CH₃COOH)₂ and hexahydrated nickel chloride (NiCl₂·6H₂O) as sources of zinc and nickel, respectively. The films were deposited onto the amorphous glass substrates kept at (450 °C). The effect of the [Ni]/[Zn] ratio on the structural, morphological, optical and electrical properties of Ni doped ZnO thin film was studied. It was found from X-ray diffraction (XRD) analysis that both the undoped and Ni doped ZnO films were crystallized in the hexagonal structure with a preferred orientation of the crystallites along the [002] direction perpendicular to the substrate. The scanning electron microscopy (SEM) images showed a relatively dense surface structure composed of crystallites in the spherical form whose average size decreases when the [Ni]/[Zn] ratio increases. The optical study showed that all the films were highly transparent. The optical transmittance in the visible region varied between 75 and 85%, depending on the dopant concentrations. The variation of the band gap versus the [Ni]/[Zn] ratio showed that the energy gap decreases from 2.95 to 2.72 eV as the [Ni]/[Zn] ratio increases from 0 to 0.02 and then increases to reach 3.22 eV for [Ni]/[Zn] = 0.04. The films obtained with the [Ni]/[Zn] ratio = 0.02 showed minimum resistivity of 2 × 10⁻³ Ω cm at room temperature.     

Doping induced structural and compositional changes in ZnO spray pyrolysed films and the effects on optical and electrical properties

Highly transparent, conductive ZnO films have been deposited by spray pyrolysis of a zinc acetate based solution. Quality films are yielded as our process is analogous to an aerosol assisted chemical vapour deposition rather than a droplet deposition spray pyrolysis technique. The properties of the films are governed by the additives to the base precursor solution. When aluminium acetylacetonate is added to the precursor solution, ZnO:Al films are grown with free charge carrier concentrations of more than 10²⁰ cm⁻³. The carrier density and mobility are measured by both Hall probe and near infrared spectroscopy. Film growth and grain size, morphology and orientation are altered using an increased percentage of ZnCl₂ in the precursor, which results in a 10 fold increase in charge carrier mobility. An investigation is presented correlating the composition of the precursor solution with the chemical, structural, electrical and optical properties of the grown films.     

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.     

喷雾热解法生长N掺杂ZnO薄膜机理分析

通过超声喷雾热解工艺,以醋酸锌和醋酸铵的混合水溶液为前驱溶液,在单晶Si(100) 衬底上制备了N掺杂ZnO薄膜,采用热质联用分析(TG—DSC—MS)、X射线衍射(XRD)、场发射扫描电镜(FESEM)和霍耳效应(Hall-effect)测试等手段研究了喷雾热解工艺下N掺杂ZnO薄膜的生长机理、晶体结构和电学性能.结果表明,随衬底温度的不同,薄膜呈现出不同的生长机理,从而影响薄膜的晶体结构和电学性能.在优化的衬底温度下,实现了ZnO薄膜的p型掺杂,得到的p型ZnO薄膜具有优异的电学性能,载流子浓度为3.21×10¹⁸cm^-3,霍耳迁移率为110cm²·V^-1s^-1,电阻率为1.76×10^-2Ω·cm.     

Growth and characterisation of electrodeposited ZnO thin films

The electrochemical method has been used to deposit zinc oxide (ZnO) thin films from aqueous zinc nitrate solution at 80 °C onto fluorine doped tin oxide (FTO) coated glass substrates. ZnO thin films were grown between − 0.900 and − 1.025 V vs Ag/AgCl as established by voltammogram. Characterisation of ZnO films was carried out for both as-deposited and annealed films in order to study the effect of annealing. Structural analysis of the ZnO films was performed using X-ray diffraction, which showed polycrystalline films of hexagonal phase with (002) preferential orientation. Atomic force microscopy was used to study the surface morphology. Optical studies identified the bandgap to be ∼ 3.20 eV and refractive index to 2.35. The photoelectrochemical cell signal indicated that the films had n-type electrical conductivity and current-voltage measurements showed the glass/FTO/ZnO/Au devices exhibit rectifying properties. The thickness of the ZnO films was found to be 0.40 μm as measured using the Talysurf instrument, after deposition for 3 min. Environmental scanning electron microscopy was used to view the cross-section of glass/FTO/ZnO layers.     

Synthesis and characterization of nanostructured nickel oxide thin films prepared with chemical spray pyrolysis

Nickel oxide thin films have been deposited in an open atmosphere onto glass substrates by chemical spray pyrolysis using aqueous nickel acetate solutions and air as driving gas. The films show a strong variation in the surface morphology depending on the substrate temperature and the precursor solution flux. At 350 °C substrate temperature, a reticular tissue-like film morphology is obtained, becoming the reticular nickel oxide fibres of the film thicker with increasing precursor solution flux. At 450 °C substrate temperature, the film growth rate is 4 times slower and a highly symmetric self-ordering of the material at nanometer length scale occurs. These films consist of interconnected grains separated by pores, both of about 100 nm in size. XRD and TEM revealed that the films are cubic NiO, being the crystallite size around 10 nm. The optical band gap of the films decreases strongly for increasing film thickness from 4.3 eV to 3.65 eV.     

Orientation enhancement of polycrystalline ZnO thin films through thermal oxidation of electrodeposited zinc metal

The polycrystalline ZnO thin films with (002) orientation enhancement were prepared by annealing of electrodeposited metallic Zn films from the ethylene glycol solution of zinc acetate without using any catalyst and template. The morphologies of the thin films were evolved from the nanoplate to the nanocolumn structures with increasing of annealing temperature from 100 °C to 500 °C. SEM and XRD studies indicated that the ZnO nanocolumns were enhanced in the (002) orientation along their length direction. The UV-vis absorption spectra of the ZnO films obtained by annealing at 300 °C and 500 °C were carried out and their band gaps were 3.18 eV and 3.20 eV, respectively. A possible growth mechanism of the ZnO nanostructures responsible for the morphologies and orientation evolution was discussed.