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.     

Structural and optical properties of ZnO thin films on (111) CaF2 substrates grown by magnetron sputtering

ZnO thin films were grown on (111) CaF₂ substrates by magnetron sputtering at room temperature. Structural and optical properties of the ZnO thin films were studied. XRD analysis showed that the ZnO thin films had the (002) preferential orientation. The transmittance of ZnO thin films was over 80% in the visible range. The optical band gap of the ZnO thin films was 3.26 eV. The optical constants (n,k)$(n,k)$ of the ZnO thin films in the wavelength range 300–1000 nm were obtained by infrared spectroscopic ellipsometry measurement. PL spectra of ZnO thin films showed strong UV near-band-edge emission peak at 376.5 nm and weak visible red emission at 643.49 nm using He–Cd laser as the light source, using a synchrotron radiation light source PL spectra showed three emission peak at 320 nm, 410 nm and 542 nm respectively.     

Effect of excimer laser annealing on the properties of ZnO thin film prepared by sol-gel method

Pristine ZnO thin films have been deposited with zinc acetate [Zn(CH₃COO)₂], mono-ethanolamine (stabilizer), and isopropanol solutions by sol-gel method. After deposition, pristine ZnO thin films have been irradiated by excimer laser (λ = 248, KrF) source with energy density of 50 mJ/cm² for 30 sec. The effect of excimer laser annealing on the optical and structural properties of ZnO thin films are investigated by photoluminescence and field emission scanning electron microscope. As-grown ZnO thin films show a huge peak of visible region and a wide full width at half maximum (FWHM) of UV region due to low quality with amorphous ZnO thin films. After KrF excimer laser annealing, ZnO thin films show intense near-band-edge (NBE) emission and weak deep-level emission. The optically improved pristine ZnO thin films have demonstrated that excimer laser annealing is novel treatment process at room temperature.     

Fabrication of ZnO thin film-nanowires hybrid homojunction on silicon substrate

In this paper, the formation of a p–n ZnO thin film-nanowires hybrid homojunction on silicon substrate has been investigated. P-type ZnO thin film is formed by both e-beam evaporation and RF magnetron sputtering techniques. In order to fabricate 3-dimentional hybrid structures, ZnO nanowires were grown on p-type ZnO films by metal organic chemical vapor deposition techniques. The X-ray diffraction results showed that both ZnO thin films and nanowires are $c$-axis oriented. The formation of p–n ZnO homojunction is verified by current–voltage measurements. Typical diode behavior and photoconductivity were observed in both designs.     

纳米ZnO和ZnO-SiO2复合薄膜的光学性质研究

通过溶胶凝胶(sol-gel)法分别在玻璃衬底上制备了ZnO纳米薄膜和ZnO-SiO₂纳米复合薄膜,并利用紫外-可见光分光光度计对薄膜的光学性能进行了分析.可见光-紫外透射谱显示,随着ZnO溶胶浓度从0.7mol/L降低到0.006mol/L,制备的ZnO薄膜从只出现一个380nm(对应的光学禁带宽度为3.27eV)左右的吸收边到在380和320nm(对应的光学禁带宽度为3.76eV)左右各出现一个吸收边,并且随着ZnO溶胶浓度的降低,在380—320nm波段内的透过率明显提高.而Z 关键词： 纳米ZnO 2复合薄膜')" href="#">ZnO-SiO₂复合薄膜 溶胶凝胶法 透射率     

Effects of annealing treatment on the formation of CO2 in ZnO thin films grown by metal-organic chemical vapor deposition

Post-growth annealing was carried out on ZnO thin films grown by metal-organic chemical vapor deposition (MOCVD). The grain size of ZnO thin film increases monotonically with annealing temperature. The ZnO thin films were preferential to c-axis oriented after annealing as confirmed by X-ray diffraction (XRD) measurements. Fourier transformation infrared transmission measurements showed that ZnO films grown at low temperature contains CO₂ molecules after post-growth annealing. A two-step reaction process has been proposed to explain the formation mechanism of CO₂, which indicates the possible chemical reaction processes during the metal-organic chemical vapor deposition of ZnO films.     

Ag掺杂p型ZnO薄膜及其光电性能研究

采用超声喷雾热分解法在石英衬底上以醋酸锌水溶液为前驱体,以硝酸银水溶液为Ag掺杂源生长了Ag掺杂ZnO(ZnO：Ag)薄膜.研究了衬底温度对所得ZnO：Ag薄膜的晶体结构、电学和光学性质的影响规律.所得ZnO：Ag薄膜结构良好,在室温光致发光谱中检测到很强的近带边紫外发光峰,透射光谱中观测到非常陡峭的紫外吸收截止边和较高的可见光区透过率,表明薄膜具有较高的晶体质量与较好的光学特性.霍尔效应测试表明,在500℃下获得了p型导电的ZnO：Ag薄膜,载流子浓度为5.30×10¹⁵cm关键词： ZnO：Ag薄膜 p型掺杂 超声喷雾热分解 霍尔效应     

Nanocrystalline ZnO film deposited by ultrasonic spray on textured silicon substrate as an anti-reflection coating layer

A ZnO thin film was successfully synthesized on glass, flat surface and textured silicon substrates by chemical spray deposition. The textured silicon substrate was carried out using two solutions (NaOH/IPA and Na₂CO₃). Textured with Na₂CO₃ solution, the sample surface exhibits uniform pyramids with an average height of 5 μm. The properties and morphology of ZnO films were investigated. X-ray diffraction (XRD) spectra revealed a preferred orientation of the ZnO nanocrystalline film along the c-axis where the low value of the tensile strain 0.26% was obtained. SEM images show that all films display a granular, polycrystalline morphology. The morphology of the ZnO layers depends dramatically on the substrate used and follows the contours of the pyramids on the substrate surface. The average reflectance of the textured surface was found to be around 13% and it decreases dramatically to 2.57% after deposition of a ZnO antireflection coating. FT-IR peaks arising from the bonding between Zn–O are clearly represented using a silicon textured surface. A very intense photoluminescence (PL) emission peak is observed for ZnO/textured Si, revealing the good quality of the layer. The PL peak at 380.5 nm (UV emission) and the high-intensity PL peak at 427.5 nm are observed and a high luminescence occurs when using a textured Si substrate.     

Nanostructures and luminescence properties of porous ZnO thin films prepared by sol–gel process

ZnO thin films containing nano-sized pores were synthesized on solid substrates through a sol–gel process by accommodating cetyl-trimethyl-ammonium bromide (CTAB) as an organic template in the precursor solution. By X-ray diffraction the resultant ZnO films were found to possess ordered pore arrays forming lamellar structure with the spacing between two adjacent pores being ∼3.0 nm. Photoluminescence measurements indicated that the surfactants effectively passivated the surface defects of the ZnO films responsible for the green emission. Al doping was found to improve not only the lamellar structure of the pore arrays but also the near-band-gap emission intensity while the suppression effect of CTAB on the green emission remained undisturbed. With a proper control of doping level, the optical property as well as the structural integrity can be tailored to augment the potential of ZnO films for the optoelectronics and sensor applications.     

溶胶-凝胶制备ZnO-SiO2复合膜的量子效应和上转换发光

采用溶胶-凝胶技术在玻璃衬底上制备了ZnO薄膜和ZnO-SiO₂复合膜.原子力显微镜照片显示ZnO薄膜具有球状纳米晶粒;可见光-紫外透射光谱表明ZnO-SiO₂复合膜在可见光区的透过率大约是85%,透过率从330 nm开始下降,到290 nm附近降为零.由于量子效应,吸收边出现明显的蓝移.在室温下用不同波长的光激发ZnO-SiO₂复合膜,光致发光谱显示ZnO-SiO₂复合膜对应于激子发射的290 nm附近的紫外发光峰与透射谱所显示的吸收边位置一致,没有出现斯托克斯红移.同时,ZnO-SiO₂复合膜出现了双光子和三光子吸收现象和上转换发光现象. 关键词： 2')" href="#">ZnO-SiO₂ 量子效应 双光子和三光子吸收 上转换发光     

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

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

Comparative study on structural and optical properties of ZnO thin films prepared by PLD using ZnO powder target and ceramic target

Zinc oxide thin films have been obtained in O₂ ambient at a pressure of 1.3 Pa by pulsed laser deposition (PLD) using ZnO powder target and ceramic target. The effect of temperature on structural and optical properties of ZnO thin films was investigated systematically by XRD, SEM, FTIR and PL spectra. The results show that the best structural and optical properties can be achieved for ZnO thin film fabricated at 700 °C using powder target and at 400 °C using ceramic target, respectively. The PL spectrum reveals that the efficiency of UV emission of ZnO thin film fabricated by using powder target is low, and the defect emission of ZnO thin film derived from Zn_i and O_i is high.     

衬底对原位氧化制备的ZnO薄膜结构和光学性质的影响

 采用射频反应溅射法在不同衬底上制备Zn₃N₂薄膜,然后对其原位氧化制备ZnO薄膜。利用X射线衍射分析(XRD)、扫描电子显微镜(SEM)和光致发光谱(PL)等表征技术研究了不同衬底对ZnO薄膜的结晶特性和发光性能的影响。XRD研究结果显示:Zn₃N₂薄膜在500 ℃原位氧化3 h后完全转变为ZnO薄膜,在玻璃和熔融石英衬底上制备的多晶ZnO薄膜无择优取向,而单晶硅（100）衬底上的多晶ZnO薄膜具有较好的沿（002）方向的择优取向。PL测试结果显示:硅和熔融石英衬底上的多晶ZnO薄膜发光性能良好,激子复合产生的紫外发光峰很强,且半高宽较窄,而来自于深能级发射的绿色发光峰很弱;而玻璃衬底上的多晶ZnO薄膜发光性能较差。     

Pure UV photoluminescence from ZnO thin film by thermal retardation and using an amorphous SiO2 buffer layer

ZnO/SiO₂ thin films were fabricated on Si substrates by E-beam evaporation with thermal retardation. The as-prepared films were annealed for 2 h every 100 °C in the temperature range 400-800 °C under ambient air. The structural and optical properties were investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL). The XRD analysis indicated that all ZnO thin films had a highly preferred orientation with the c-axis perpendicular to the substrate. From AFM images (AFM scan size is 1 μm×1 μm), the RMS roughnesses of the films were 3.82, 5.18, 3.65, 3.40 and 13.2 nm, respectively. PL measurements indicated that UV luminescence at only 374 nm was observed for all samples. The optical quality of the ZnO film was increased by thermal retardation and by using an amorphous SiO₂ buffer layer.     

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.     

Influence of post-deposition annealing on the structural and optical properties of ZnO thin films prepared by sol–gel and spin-coating method

Thin films of zinc oxide have been deposited onto (0001) sapphire substrate by sol–gel and spin-coating methods. The XRD pattern showed that the crystallinity of the annealed ZnO films had improved in comparison with that of the as-grown films. Photoluminescence spectra revealed a two-line structure, which is identified in terms of UV emission and defect-related emission. The emission intensity was found to be greatly dependent on heat treatment. Host phonons of ZnO and a shift of the _E2$E_2$ (high) peak from its position have been observed from Raman spectra. The surface morphologies of the film had been improved after annealing was observed from AFM images.     

Characterization and ammonia sensing properties of pure and?modified ZnO films

Zinc oxide (ZnO) films have been prepared by thermal oxidation of pre-deposited zinc films on the glass substrate kept at room temperature. These films were surface modified by dipping them into an aqueous solution (0.1 M) of lithium chloride (LiCl) and aluminium chloride (AlCl₃) followed by firing at 500°C. Based on X-ray diffraction results it is observed that modification of pure ZnO by lithium and aluminium precursor results a change in the lattice parameters. Li and Al ions appear to enhance the a-axis orientation and c-axis orientation of pure ZnO films, respectively. Field emission scanning electron micrographs of lithium-modified ZnO film indicate the presence of nanoneedles, while nanorods are observed in case of aluminium-modified ZnO film. The electrical resistance measurements of modified ZnO films also show variation in resistance as compared to pure ZnO film. Pure and Al-modified films of ZnO are sensitive to ammonia at room temperature, while Al-modified ZnO film is found to be more sensitive with 99% of response at 250 ppm.     

Reduction of dislocation density and improvement of optical quality in ZnO layers by MgO-buffer annealing

Optical properties of ZnO thin films with/without MgO-buffer annealing were investigated by low and room temperature photoluminescence measurements. The ZnO films were grown on c-sapphire substrates by plasma-assisted molecular-beam epitaxy employing a thin MgO-buffer layer. Dislocation density of ZnO layer was reduced from 5.3 × 10⁹ to 1.9 × 10⁹ cm⁻² by annealing MgO-buffer prior to the growth of ZnO. The intensity of free exciton emission from the sample with MgO-buffer annealing was almost twice of that from the sample without annealing, while the deep level emission from the sample with MgO-buffer annealing was about 1/3 of that without annealing. The MgO-buffer annealing improves optical quality of overgrown ZnO films.     

Structural, defect and optical properties of ZnO films grown under various O2/Ar gas ratios

Thin wurtzite (0 0 2) textured ZnO thin films were deposited on glass substrates by radio frequency magnetron sputtering under O₂/Ar ratios R varying from 0.05 to 1.0 at room temperature. The structure of, and defects in, the films were investigated by XRD, SEM and slow positron beam techniques. The XRD spectra showed that ZnO thin films were polycrystalline with hexagonal structure and a good c-axis orientation perpendicular to the substrate. The thickness, grain size and the crystalline quality of the films strongly depended on R; the larger grain size and thicker ZnO films were grown when R was lower. Positron beam Doppler broadening measurements showed that in low R films additional vacancy-type defects (e.g. Zn-related vacancy complexes or clusters) were formed. Photoluminescence spectra found that the film with R = 0.4 had the highest luminescence efficiency, in good agreement with the best c-axis preferential orientation. The transmittance spectra of the films decreased with decreasing R, due to the thickness effect. Correlations between microstructure, defect and optical properties are discussed.