退火温度对Cu:ZnO薄膜绿光发射的影响

利用溶胶-凝胶法在Si衬底上制备了不同退火温度的Cu:ZnO薄膜.利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜和光致发光谱研究了样品的晶格结构、表面形貌、成分及其发光特性.结果表明:所有样品均具有高度的c轴择优取向,随着退火温度的升高,样品的结晶质量变好,样品的表面都被晶粒覆盖,强而稳定的绿光发射被观察到.绿光强度随退火温度的升高先增加后减小,发光中心位置不随退火温度的变化而改变,这样的绿光发射强而稳定.XRD和XPS结果表明,随退火温度的升高Cu2+还原为Cu+,导致Cu:ZnO薄膜形成的缺陷是VZn,所以绿光发射是由VZn引起的.Cu2+还原为Cu+时,Cu:ZnO薄膜中VZn浓度增加,使绿光发射强度增大.当退火温度超过800?C时,Cu2+的还原能力变差,绿光发射强度减弱.     

(Li,Cu)掺杂ZnO薄膜的发光性质

利用溶胶-凝胶(Sol-gel)法在n型si(100)衬底上制备(Li,Cu)掺杂ZnO薄膜,研究了室温下薄膜的结构、形貌和光致发光性能.研究结果表明,随着Li掺杂浓度的增加,可见光发光强度增加,可见光发射可能是源于单电离氧窄位到价带顶以及单电离氧空位到Li替位Zn(Lizn)受主跃迁的双重作用.与此类似,Cu掺杂Zn...     

Fe掺杂对溶胶凝胶法制备的ZnO: Ni薄膜结构及发光特性的影响

采用溶胶凝胶法在玻璃基片上制备了ZnO及Ni, Fe共掺杂的Zn_0.95-xNi_0.05Fe_xO (x=0, 0.005, 0.01, 0.03, 0.05) 薄膜. 通过扫描电镜(SEM) 和X射线衍射(XRD) 研究了薄膜样品的表面形貌和晶体结构. 结果表明所有样品都具有(002) 择优取向, Fe掺杂导致ZnO: Ni薄膜的晶体质量变差, 晶粒尺寸减小, 但适当的Fe掺杂有利于获得致密、 均匀的薄膜. XPS测试结果表明样品中Ni离子的价态为+2价, Fe离子的价态为+2价和+3价.室温光致发光(PL) 测量表明, 所有样品均观察到较强的紫外发光峰, 蓝光双峰和绿光发光峰. ZnO: Ni薄膜的发光强度可以通过Fe掺杂进行有效调节. 进而我们讨论了Ni, Fe共掺杂ZnO样品的发光机理.     

Effect of aging time of ZnO sol on the structural and optical properties of ZnO thin films prepared by sol-gel method

In this work, ZnO thin films were prepared by sol-gel method and the effect of aging time of ZnO sol on the structural and optical properties of the films was studied. The structural characteristics of the samples were analyzed by an atomic force microscope and an X-ray diffractometer. The optical properties were studied by a UV-vis spectrophotometer and a fluorophotometer. The results show that the ZnO thin film prepared by the as-synthesized ZnO sol had relatively poor crystalline quality, low optical transmittance in the visible range and relatively weak ultraviolet emission performance. After the as-synthesized ZnO sol was aged for 24 h, the degree of the preferred crystal orientation along the c-axis of the ZnO thin film prepared by this aged sol was improved. At the same time, this film had a very smooth surface with uniform grains and both its visible range transmittance and ultraviolet emission intensity were obviously increased. These results suggest that appropriate aging of ZnO sol is very important for the improvement of structural and optical quality of ZnO thin films derived from sol-gel method.     

Co,Sn共掺ZnO薄膜结构与光致发光的研究

采用溶胶-凝胶旋涂法在玻璃衬底上制备了Co,Sn掺杂ZnO系列薄膜.通过金相显微镜和X射线衍射(XRD)研究了Co与Sn掺杂对薄膜的表面形貌和微结构的影响.XRD结果表明,所有ZnO薄膜样品都存在(002)择优取向,特别Sn单掺ZnO薄膜的c轴择优取向最为显著,而且晶粒尺寸最大.XPS测试表明样品中Co和Sn的价态分别为2+和4+,证实Co²⁺,Sn⁴⁺进入了ZnO的晶格.室温光致发光谱(PL)显示在所有的样品中都有较强的蓝光双峰发射和较弱的绿光发 关键词： ZnO薄膜 溶胶-凝胶 掺杂 光致发光     

纳米ZnO薄膜可见发射机制研究

利用溶胶－凝胶法 （Sol-Gel）制备了纳米ZnO薄膜，获得了高强的近紫外发射室温下测量了样品的光致发光谱(PL )、吸收谱(ABS)、X射线衍射谱(XRD).X射线衍射(XRD)的结果表明：纳米ZnO薄膜呈多晶态，具有六角纤锌矿结构和良好的C轴取向；发现随退火温度升高，（002）衍射峰强度显著增强，衍射峰的半高宽（FWHM）减小、纳米颗粒的粒径增大.由吸收谱(ABS)给出了样品室温下带隙宽度为3.30 eV.在PL谱中观察到二个荧光发射带，一个是中心波长位于392 nm附近强而尖的紫带，另一个是519 nm附近弱而宽的绿带研究了不同退火温度样品的光致发光峰值强度的变化关系，发现随退火温度升高，紫带峰值强度增强、绿带峰值强度减弱，均近似呈线性变化.证实了纳米ZnO薄膜绿光发射主要来自氧空位(Vo)形成的浅施主能级与锌空位(VZn)形成的浅受主能级之间的复合，或氧空位(Vo)形成的深施主能级上的电子至价带顶的跃迁；紫带来自于导带中的电子与价带中的空位形成的激子复合.     

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.     

The effect of heat treatment on the physical properties of sol-gel derived ZnO thin films

Zinc oxide (ZnO) thin films were deposited on microscope glass substrates by sol-gel spin coating method. Zinc acetate (ZnAc) dehydrate was used as the starting salt material source. A homogeneous and stable solution was prepared by dissolving ZnAc in the solution of monoethanolamine (MEA). ZnO thin films were obtained after preheating the spin coated thin films at 250 °C for 5 min after each coating. The films, after the deposition of the eighth layer, were annealed in air at temperatures of 300 °C, 400 °C and 500 °C for 1 h. The effect of thermal annealing in air on the physical properties of the sol-gel derived ZnO thin films are studied. The powder and its thin film were characterized by X-ray diffractometer (XRD) method. XRD analysis revealed that the annealed ZnO thin films consist of single phase ZnO with wurtzite structure (JCPDS 36-1451) and show the c-axis grain orientation. Increasing annealing temperature increased the c-axis orientation and the crystallite size of the film. The annealed films are highly transparent with average transmission exceeding 80% in the visible range (400-700 nm). The measured optical band gap values of the ZnO thin films were between 3.26 eV and 3.28 eV, which were in the range of band gap values of intrinsic ZnO (3.2-3.3 eV). SEM analysis of annealed thin films has shown a completely different surface morphology behavior.     

Comparison of ZnO thin films grown on a polycrystalline 3C-SiC buffer layer by RF magnetron sputtering and a sol-gel method

Zinc oxide (ZnO) thin films were deposited on a polycrystalline (poly) 3C-SiC buffer layer using RF magnetron sputtering and a sol-gel method. The post-deposition annealing was performed on ZnO thin films prepared using both methods. The formation of ZnO piezoelectric thin films with less residual stress was due to a close lattice mismatch of the ZnO and SiC layers as obtained by the sputtering method. Nanocrystalline, porous ZnO film prepared using the sol-gel method showed strong ultraviolet UV emission at a wavelength of 380 nm. The 3C-SiC buffer layer improved the optical and piezoelectric properties of the ZnO film produced by the two deposition methods. Moreover, the different structures of the ZnO films on the 3C-SiC intermediate layer caused by the different deposition techniques were also considered and discussed.     

Al掺杂原子分数及退火温度对ZnO薄膜光学特性的影响

 采用溶胶凝胶法在（0001）Al₂O₃衬底上制备了不同掺杂原子分数的ZnO:Al薄膜，在Ar气氛中进行了600～950 ℃不同温度的退火处理，研究了掺杂原子分数和退火温度对薄膜光致发光、光吸收和透射的影响。结果显示，薄膜的紫外峰强度随掺杂原子分数和退火温度的提高而增强，与缺陷相关的绿光强度却随着掺杂原子分数和退火温度的提高而降低；薄膜光学带隙随掺杂原子分数的提高从3.21 eV增大到3.25 eV；光吸收在可见光区随着退火温度的升高而增大，在紫外区却随着退火温度的升高而减小，透射与吸收的变化规律相反；薄膜吸收边随退火温度的升高出现轻微的红移。     

Influence of glucose on the structural and optical properties of ZnO thin films prepared by sol-gel method

In this work, ZnO thin films were prepared by sol-gel method on glass substrates followed by calcinations at 500 °C for an hour. The effect of glucose on the structure and optical properties of the films was studied. The structural characteristics of the samples were analyzed by X-ray diffractometer (XRD) and atomic force microscope (AFM). The optical properties were studied by a UV-visible spectrophotometer. The results show that some of the prepared ZnO thin films have a high preferential oriented c-axis orientation with compact hexagonal wurtzite structure due to a proper amount of glucose introducing. After introducing the glucose additive in ZnO colloids, the intensity of (002) peak, the transmittance, and the optical band gap of the ZnO thin films increases because of the enhanced ZnO crystallization. On the contrary, the absorbance, the film thickness, and the surface root-mean-square (RMS) roughness of the ZnO thin films decreases. The glucose additive could not only improve the surface RMS roughness and microstructure of ZnO thin films, but also enhance the transmittance and the energy band gap more easily.     

退火对溶胶-凝胶法制备的ZnO薄膜结构和光致发光的影响

采用溶胶-凝胶法在n-Si(100)衬底上制备ZnO薄膜并从三个方面对其研究。X射线衍射结果表明,在含氧气氛中退火的ZnO薄膜为多晶六角纤锌矿结构,有明显的c轴择优结晶取向;退火时间的长短和温度的高低对结晶取向性和粒径均有较大影响,通过进一步的研究发现最佳处理温度在500℃左右。用扫描电子显微镜观察样品的表面和侧面形貌,晶体的生长比较均匀,粒径平均在70~160nm范围内,与XRD测量结果相一致。室温下ZnO胶体的光致发光谱表明,随着胶体老化时间的延长,胶体的紫外峰位发生了蓝移。室温下ZnO薄膜的光致发光谱表明,紫外部分的发光峰位在365,390nm,发光强度较强;在可见光区的发光强度相对较弱,但是还没有被氧完全抑制掉。     

Structural and optical properties of ZnO thin films prepared by sol-gel method with different thickness

In this work, ZnO thin films with different thickness were prepared by sol-gel method on glass substrates and the structural and optical properties of these films were studied by X-ray diffractometer, atomic force microscope, UV-visible spectrophotometer, ellipsometer and fluorophotometer, respectively. The structural analyses show that all the samples have a wurtzite structure and are preferentially oriented along the c-axis perpendicular to the substrate surface. The growth process of highly c-axis oriented ZnO thin films derived from sol-gel method is a self-template process. With the increase of film thickness, the structural disorder decreases and the crystalline quality of the films is gradually improved. A transition of crystal growth mode from vertical growth to lateral growth is observed and the transition point is found between 270 and 360 nm thickness. The optical analyses show that with the increase of film thickness, both the refractive index and ultraviolet emission intensity are improved. However, the transmittance in the visible range is hardly influenced by the film thickness, and the averages are all above 80%.     

Excimer laser processing of ZnO thin films prepared by the sol-gel process

ZnO thin films were prepared on soda-lime glass from a single spin-coating deposition of a sol-gel prepared with anhydrous zinc acetate [Zn(C₂H₃O₂)₂], monoethanolamine [H₂NC₂H₄OH] and isopropanol. The deposited films were dried at 50 and 300 °C. X-ray analysis showed that the films were amorphous. Laser annealing was performed using an excimer laser. The laser pulse repetition rate was 25 Hz with a pulse energy of 5.9 mJ, giving a fluence of 225 mJ cm⁻² on the ZnO film. Typically, five laser pulses per unit area of the film were used. After laser processing, the hexagonal wurtzite phase of zinc oxide was observed from X-ray diffraction pattern analysis. The thin films had a transparency of greater than 70% in the visible region. The optical band-gap energy was 3.454 eV. Scanning electron microscopy and profilometry analysis highlighted the change in morphology that occurred as a result of laser processing. This comparative study shows that our sol-gel processing route differs significantly from ZnO sol-gel films prepared by conventional furnace annealing which requires temperatures above 450 °C for the formation of crystalline ZnO.     

Structure distortion, optical and electrical properties of ZnO thin films co-doped with Al and Sb by so--gel spin coating

ZnO thin films co-doped with Al and Sb with different concentrations and a fixed molar ratio of AlCl₃ to SbCl₃ at 1:2, are prepared by a sol--gel spin-coating method on glass annealed at 550 ℃ for 2 h in air. The x-ray diffraction results confirm that the ZnO thin films co-doped with Al and Sb are of wurtzite hexagonal ZnO with a very small distortion, and the biaxial stresses are 1.03×10⁸, 3.26×10⁸, 5.23×10⁸, and 6.97×10⁸ Pa, corresponding to those of the ZnO thin films co-doped with Al and Sb in concentrations of 1.5, 3.0, 4.5, 6.0 at% respectively. The optical properties reveal that the ZnO thin films co-doped with Al and Sb have obviously enhanced transmittance in the visible region. The electrical properties show that ZnO thin film co-doped with Al and Sb in a concentration of 1.5 at% has a lowest resistivity of 2.5Ω·cm.     

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.     

Fe,Co共掺杂ZnO薄膜结构及发光特性研究

采用溶胶凝胶法在玻璃衬底上制备了Fe,Co共掺Zn0.9FexCo0.1-xO(x=0,0.03,0.05,0.07)系列薄膜.通过扫描电镜(SEM)、X射线衍射(XRD)、X射线光电子谱(XPS)和光致发光(PL)谱对薄膜样品的表面形貌、晶体结构、成分和光学性能进行了研究.XRD结果表明所有ZnO薄膜样品都呈六方纤锌矿结构,在样品中没有观察到与Fe和Co相关的团簇,氧化物及其他杂相的衍射峰,表明共掺杂改善了Fe或Co在ZnO的分散性.XPS测试结果揭示样品中Co离子的价态为+2价;Fe离子的价态为+2价和+3价共存,但Fe相对浓度的增大导致Fe3+含量增加.所有样品的室温光致发光谱(PL)均观察到紫外发光峰和蓝光双峰,其中Fe,Co共掺ZnO薄膜的紫外发光峰较本征ZnO出现蓝移,蓝光双峰峰位没有变化,但发光强度有所减弱;而掺杂ZnO薄膜的绿光发光峰几乎消失.最后,结合微结构和成分分析对薄膜样品的发光机理进行了讨论.     

热处理参数对溶胶-凝胶法制备氧化锌薄膜特性的影响

采用溶胶-凝胶旋涂法在Si(111)衬底上生长了ZnO薄膜，并用荧光光谱、原子力显微镜和XRD对ZnO薄膜样品进行了分析.结果表明，溶胶-凝胶旋涂法制备的ZnO薄膜为纤锌矿结构，其c轴取向程度与热处理温度有很大的关系.当热处理温度小于550℃时，氧化锌薄膜在室温下均有较强的紫外带边发射峰，而可见波段的发射很弱；当热处理温度高于550℃时，可见波段发射明显增强.对经过不同时间热处理的ZnO薄膜样品分析表明，氧化锌薄膜的荧光特性及表面形貌与热处理时间也有很大关系，时间过短可见波段的发射较强，但时间过长会导致晶 关键词： ZnO薄膜 光致发光     

Blue luminescence from Ce-doped ZnO thin films prepared by magnetron sputtering

The photoluminescence properties of undoped and Ce-doped ZnO thin films that were prepared by DC magnetron sputtering were investigated. It was found that the incorporation of Ce could intensively affect the structural, optical, and photoluminescence properties of the ZnO thin films. The undoped ZnO thin films showed a sharp UV luminescence, whereas the Ce-doped ZnO thin films showed a broad blue luminescence. The effects of excitation wavelength and annealing atmosphere on the photoluminescence properties of Ce-doped ZnO thin films were also studied. After post-annealing in air and oxygen atmospheres, the blue emissions of the prepared films were drastically suppressed. Our results indicate that the blue emissions of Ce-doped ZnO thin films are related to zinc interstitials and the intrinsic transition of Ce³⁺ ions.     

溶胶-凝胶法制备ZnO薄膜及其光致发光性质

利用溶胶-凝胶法在石英衬底上制备了ZnO薄膜,通过测量样品的透射谱、X射线衍射谱、扫描电子显微镜(SEM)图像和光致发光谱研究了其结构特征和发光性质.结果表明:在衍射角2θ=34.32°处出现了对应(002)晶面的强衍射峰,ZnO膜呈多晶状态,具有六角纤矿晶体结构和良好的C轴择优取向,薄膜中颗粒的平均粒径为56nm;光致发光呈多发光峰状,有中心波长为378nm的紫带,520nm绿带,446nm附近的蓝带以及发现未见报道过的绿带以后中心波长为586nm和570nm两个弱发射峰.实验结果表明,制备的ZnO薄膜具有发光特性,但内部与深能级发射相关的结构缺陷浓度还是较高,样品中两个低能量光致发光应来源于晶粒间界的缺陷能级,多缺陷能级导致了多发射峰的光致发光谱.