磁控溅射制备ZnO薄膜及其掺杂的研究

利用磁控溅射制备了纯ZnO薄膜,并在NH3O-2A-r气氛中溅射Zn靶实现了ZnO薄膜的N掺杂;利用双靶共溅的方法分别制备了Al掺杂和N+Al掺杂样品。原子力显微镜(AFM)观察显示各ZnO薄膜样品具有较好的晶粒分布,退火处理能够显著提高薄膜的结构状态,N+Al共掺杂样品具有较好的表面平整度;在438cm-1附近观察到了喇曼谱特征峰;透射光谱揭示了激子的吸收特征和掺杂样品的吸收边向短波方向移动;发射光谱测试表明,掺杂样品比未掺杂样品有更强的紫外发射;同时分析了ZnO薄膜的掺杂机理。     

Sn掺杂量对Sn-Al共掺ZnO薄膜光学性能的影响

利用溶胶-凝胶(sol-gel)法在玻璃和硅衬底上制备了不同Sn掺杂量的Sn-Al共掺的ZnO薄膜。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、紫外可见分光光度计(UV-Vis)、光致发光谱(PL)等测试手段,对薄膜的结构、形貌和光学性能进行了表征。结果表明:所制备的样品晶粒均沿(002)方向择优生长,且随着Sn元素掺杂量的增加,择优取向性先增强后减弱,同时薄膜的半高宽先减小后增大,半高宽最小时,薄膜的结晶质量最好。与只掺Al元素的ZnO薄膜相比,共掺后的薄膜近紫外发光峰的强度明显降低,出现了轻微的蓝移,且在600 nm处的缺陷发光强度明显增强;随着Sn掺杂量的增加薄膜的透过率先增加后减小。与AZO薄膜相比,当Sn的掺杂量为0.020时,薄膜的结晶质量更好,缺陷发光更强,光透过率更高。     

Properties of nanostructured Al doped ZnO thin films grown by spray pyrolysis technique

Aluminium doped zinc oxide thin films were deposited on glass substrate by using spray pyrolysis technique. The X-ray diffraction study of the films revealed that the both the undoped and Al doped ZnO thin films exhibits hexagonal wurtzite structure. The preferred orientation is (002) for undoped and up to 3 at % Al doping, further increase in the doping concentration to 5 at % changes the preferred orientation to (101) direction. The surface morphology of the films studied by scanning electron microscope, reveal marked changes on doping. Optical study indicates that both undoped and Al doped films are transparent in the visible region. The band gap of the films increased from 3.24 to 3.36 eV with increasing Al dopant concentration from 0 to 5 at % respectively. The Al doped films showed an increase in the conductivity by three orders of magnitude with increase in doping concentration. The maximum value of conductivity 106.3 S/cm is achieved for 3 at % Al doped films.     

Effect of Al dopant concentration on structural,optical and photoconducting properties in nanostructured zinc oxide thin films

Thin films of undoped and doped ZnO, with different Al concentrations (1–5 wt%) were deposited onto glass substrates, by the sol–gel spin coating method. Grazing incidence X-ray diffraction (GIXRD) studies confirmed the nature of films as poly-crystalline, with typical hexagonal wurtzite structure. The films showed variation in crystallite size and change in relative intensities, upon different Al doping concentrations. The surface morphology of the films examined using FE-SEM, showed the grain size becoming smaller upon Al doping. The influence of Al with different concentrations, onto ZnO on the optical absorption and transmittance was studied using UV–Vis–NIR spectrophotometer in the wavelength range 300–2500 nm. The UV absorption shifted towards shorter wavelength upon Al doping. The average transmittance in the visible region increased for Al doped films up to 1–2 wt% and decreased for other concentration. The dark and photo conductivity measurements of the films indicated increase in the current values upon doping up to 1–2 wt% of Al and decreased for further concentrations. The rise and decay time measured from the photoresponse study, indicate larger values of rise time for the doped films compared to undoped ZnO. However, the film with 1–2 wt% doping of Al showed better response within the doping concentration. The thermal activation energy obtained from temperature-dependant conductivity showed decrease in the value upon Al doping up to 2 wt% and increased beyond this concentration in the temperature range 300–400 K.     

N Doping and Al-N Co-doping in Sol–Gel ZnO Films: Studies of Their Structural,Electrical, Optical,and Photoconductive Properties

We have studied the structural, electrical, optical, and optoelectronic properties of N-doped and Al-N co-doped ZnO films grown by sol–gel technique. Both the undoped and doped films have a hexagonal wurtzite-type structure. The undoped film shows a very low electron concentration. The N-doped film exhibits an anomalous conduction type, while the Al-N co-doped film shows relatively stable p-type conduction. Though the transparency in the visible region is retained in the doped films, its optical qualities are degraded as indicated by photoluminescence results. The N-doped film has better response to ultraviolet light compared with the undoped and co-doped films. These results are important for the growth and development of p-type ZnO films using the very low-cost sol–gel method.     

Li、Mg掺杂ZnO薄膜PL特性研究

采用溶胶-凝胶法在玻璃基片上制备了Li、Mg掺杂的ZnO薄膜,研究了薄膜的光致发光(PL)性能。结果表明,由氧缺位引起的深能级发光峰(450~470 nm)的强度随Li和Mg掺杂量的增加而下降。Mg的添加会使薄膜的带边发射(NBE)增强,而Li的掺杂抑制了NBE峰,同时引发403 nm的Li杂质能级峰,该能级位于价带顶0.29 eV处。     

Optical and electrical properties of epitaxial (Mg,Cd)xZn1−xO, ZnO, and ZnO:(Ga,Al) thin films on c-plane sapphire grown by pulsed laser deposition

A consistent set of epitaxial, n-type conducting ZnO thin films, nominally undoped, doped with Ga or Al, or alloyed with Mg or Cd, was grown by pulsed laser deposition (PLD) on single-crystalline c-plane sapphire (0 0 0 1) substrates, and characterized by Hall measurement, and UV/VIS optical transmission spectroscopy.The optical band gap of undoped ZnO films at nearly 3.28 eV was shifted by alloying with Mg up to 4.5 eV and by alloying with Cd down to 3.18 eV, dependent on the alloy composition. In addition, highly doped ZnO:Al films show a blue-shifted optical absorption edge due to filling of electronic states in the conduction band.The Hall transport data of the PLD (Mg,Zn,Cd)O:(Ga,Al) thin films span a carrier concentration range of six orders of magnitude from 3 × 10¹⁴ to 3 × 10²⁰ cm⁻³, which corresponds to a resistivity from 5 × 10⁻⁴ to 3 × 10³ Ω cm. Structurally optimized, nominally undoped ZnO films grown with ZnO nucleation and top layer reached an electron mobility of 155 cm²/V s (300 K), which is among the largest values reported for heteroepitaxial ZnO thin films so far.Finally, we succeeded in combining the low resistivity of ZnO:Ga and the band gap shift of MgZnO in MgZnO:Ga thin films. This results demonstrate the unique tunability of the optical and electrical properties of the ZnO-based wide-band gap material for future electronic devices.     

The effects of Al doping and post-annealing via intrinsic defects on photoluminescence properties of ZnO:Eu nanosheets

Europium (Eu) and Aluminum (Al) co-doped ZnO nanosheets were synthesized by a hydrothermal method. The effects of Al concentration as a dopant and post-annealing of ZnO:Eu nanosheets on its structural, electrical and optical properties were investigated in detail. Prepared samples were characterized structurally using X-ray diffraction (XRD), morphologically using scanning electron microscopy (SEM) and optically using photoluminescence (PL) spectroscopy analyses. No diffraction peak related to dopants in XRD spectrum along with shift in peaks angles relevant to ZnO proved that Al and Eu ions were doped successfully into ZnO nanosheets. This study recommends that extrinsic doping and intrinsic defects have impressive roles on transferring energy to Eu ions at indirect excitations. Based on photoluminescence observations, intra-4f transitions of Eu³⁺ ions at an excitation wavelength of 390 nm allow a sharp red luminescence. Also the results showed that optical properties of ZnO can be tuned by varying the amount of Al concentration. In comparison with annealed Al doped ZnO:Eu nanostructures, as-grown samples showed the stronger PL peaks which indicated the effective role of intrinsic defects beside of extrinsic doping on energy transfer from ZnO host to Eu³⁺ ions which consequently led to producing the strong red emission from these sites.     

Effect of seed layers (Al,Ti) on optical and morphology of Fe-doped ZnO thin film nanowires grown on Si substrate via electron beam evaporation

The effects of Al and Ti seed layers were studied for undoped and Fe-doped ZnO thin films deposited on n-type Si substrates by electron beam (e-beam) evaporation. The films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). The films grown on seed layers showed wurtzite hexagonal crystal nanorod and nanowire structures. A higher angle phase shift was observed in the doped thin films compared to the pristine ZnO films. Microstructural studies confirmed the growth of nanorods and nanowires with average widths of ~32 nm and ~8–29 nm, respectively. The nanostructures were denser and more crystalline on the Al seed layer than on the Ti seed layer for the doped thin films. However, in the undoped thin films, a more crystalline nature was observed on the Ti seeded layer than the Al seeded layer.     

脉冲激光双光束沉积掺Mg的GaN薄膜的研究

采用脉冲激光双光束沉积系统在Si(111)衬底上生长了掺Mg的GaN薄膜和未掺杂GaN薄膜。利用X射线衍射(XRD)、原子力显微镜(AFM)、室温范德堡霍尔测量及光致发光(PL)光谱对两类薄膜进行对比分析，结果显示，所生长的GaN薄膜均为六方纤锌矿晶体结构，掺Mg可细化所生长的GaN薄膜晶粒。随着掺Mg量的增加，GaN薄膜无需后处理即可由”型导电转化为p型导电，GaN薄膜的光学性能随p型载流子浓度增大而提高；然而掺Mg却导致GaN薄膜结晶质量下降，掺镁量过大的GaN薄膜中p型载流子浓度反而减少，光致发光中黄发射峰增强较大。研究表明通过优化脉冲激光双光束沉积参数无需任何后处理可直接获得高空穴载流子浓度的p型GaN薄膜。     

The effect of Mg and Al co-doping on the structural and photoelectric properties of ZnO thin film

Mg–Al co-doped ZnO thin films were prepared via radio-frequency reactive magnetron sputtering technique. X-ray diffraction investigation showed all the thin films with different Mg:Al ratio had hexagonal wurtzite structure. All the thin films showed (100) preferential orientation of ZnO. When Al concentration was kept constant but Mg concentration was increased, the grain size decreased at first and then increased. When Mg:Al ratio was 3:1, the grain size reached a maximum. Ultraviolet–visible spectra showed the thin films had a high average transmittance of 80% in the visible range. The optical band gaps of the thin films were obtained as follows: 3.31, 3.32, and 3.37 eV, corresponding to the Mg:Al ratio of 0:1, 1:1, and 3:1, respectively. Photoluminescence spectroscopy showed all the thin films had four main peaks located at 386, 410, 463, and 499 nm. The origin of blue peak is oxygen vacancy. When Mg concentration was kept constant but Al concentration was increased, I–V curve presented that for both of the heterojunctions the rectifying behavior was formed. The conductivity of Mg:Al=1:1 thin film is higher than that of Mg:Al=1:0 thin film. After illumination, light I–V curve deviated from rectifying character.     

Al掺杂半导体Mg2Si薄膜的制备及光学带隙研究

用磁控溅射方法在Si衬底上制备了Al掺杂Mg2Si薄膜,通过X射线衍射仪(XRD)、扫描电镜(SEM)、原子力显微镜(AFM)和分光光度计研究了掺杂含量对Mg2Si薄膜组分、表面形貌、粗糙度及光学带隙值的影响,XRD结果表明随着Al掺杂量的增加, Mg2Si衍射峰先增强后减弱. SEM及AFM的结果表明随掺杂量的增加,结晶度先增加后降低,晶粒尺寸减小,粗糙度先增加后降低.得到掺杂后薄膜间接跃迁带隙范围为0.423～0.495 eV,直接跃迁带隙范围为0.72～0.748 eV,掺杂前薄膜间接跃迁带隙和直接跃迁带隙分别为0.53 eV、0.833 eV.     

Electrical and optical properties of ZnO/Si heterojunctions as a function of the Mg dopant content

Undoped and Mg-doped ZnO thin films prepared by a sol–gel process were deposited on p-Si and glass substrates via spin coating. The electrical and optical properties of the films were investigated. Atomic force microscopy images revealed that the ZnO films are formed from fibers consisting of nanoparticles. The electrical conductivity mechanism of the films was investigated. The I–V characteristics of Al/ZnO/p-Si samples showed rectification behavior with a rectification ratio that depended on the applied voltage and the Mg doping ratio. ZnO/p-Si heterojunction diodes exhibited non-ideal behavior with an ideality factor greater than unity that could be ascribed to the interfacial layer, interface states, and series resistance. The barrier height for undoped and Mg-doped ZnO/p-Si diodes was in the range 0.78–0.84 eV. The results demonstrate that the electrical properties of ZnO/p-Si heterojunction diodes are controlled by the Mg dopant content and suggest that the optical bandgap of these ZnO films can be tuned using the Mg level.     

Co与Cu掺杂ZnO磁性薄膜的溶胶-凝胶旋涂法制备

用溶胶-凝胶旋涂法在玻璃衬底上制备了Co,Cu单掺杂及(Co,Cu)共掺杂ZnO薄膜.磁性测量表明,无论是单掺还是共掺的ZnO薄膜都具有室温铁磁性,且Co掺杂和共掺杂ZnO薄膜的磁性相近,而Cu单掺ZnO薄膜磁性稍弱一点.用原子力显微镜和X射线衍射研究了Co,Cu掺杂对ZnO薄膜表面形貌和晶体结构的影响,在薄膜中没有发现第二相和磁性团簇的存在,且所有ZnO薄膜样品都存在(002)择优取向.室温光致发光测量在所有的样品中都观察到447和482 nm附近的蓝光发射,认为是由于氧空位浅施主能级上的电子到价带上的跃迁所导致的.     

Structure,luminescence and photocatalytic activity of Mg-doped ZnO nanoparticles prepared by auto combustion method

A series of Zn_1−xMg_xO nanoparticles with x=0 to 0.15 were prepared by auto combustion method using citric acid as the fuel and chelating agent. Structure, luminescence and photocatalytic properties were systematically investigated by means of X-ray diffraction, scanning electron microscopy, photoluminescence spectra, ultraviolet–visible absorbance measurement and photochemical reactions etc. The samples retained hexagonal wurtzite structure of ZnO and single phase below x=0.13, and the sizes of the nanoparticles were 60–70 nm. The photoluminescence spectroscopy demonstrated blue shift of ultraviolet emission with increasing Mg doping concentration. Both optical measurements of the as grown and Mg doped ZnO nanoparticles showed that the optical band gap could be modified from ~3.28 eV to 3.56 eV as the Mg content x increased from 0 to 0.13. The photocatalytic activities of the samples were evaluated by photocatalytic degradation of methyl orange, and the results showed that the doping of Mg into ZnO nanoparticles could enhance photocatalytic activity compared to the undoped ZnO nanoparticles, which was attributed to increased band gap and superior textural properties. In addition, according to the PL and photocatalytic studies, the critical doping content of effective Mg in ZnO is up to 0.09.     

Study on the structural, electrical and optical properties of Al-F co-doped ZnO thin films prepared by RF magnetron sputtering

Al and F co-doped ZnO(ZnO:(Al,F)) thin films on glass substrates are prepared by the RF magnetron sputtering with different F doping contents.The structural,electrical and optical properties of the deposited films are sensitive to the F doping content.The X-ray analysis shows that the films are c-axis orientated along the(002) plane with the grain size ranging from 9 nm to 13 nm.Micrographs obtained by the scanning electron microscope(SEM) show a uniform surface.The best films obtained have a resistivity of 2.16×10-3Ω·cm,while the high optical transmission is 92.0% at the F content of 2.46 wt.%.     

ZnO薄膜的丙酮气敏特性研究

用直流磁控反应溅射法,分别在Si(111)基片及Al2O3陶瓷基片上制备了ZnO薄膜,并进行TiO2、SnO2、Al2O3或CuO的掺杂和退火处理。用XRD分析了退火前后晶型的变化,利用气敏测试系统对各样品进行了气敏特性测试。结果表明:经过700℃退火后的样品,在最佳工作温度为220℃时,对丙酮有很好的选择性和很高的灵敏度(34.794)。掺杂TiO2或SnO2,可提高ZnO薄膜传感器对丙酮的灵敏度(57.963)。     

Influence of Ti dopant on the properties and dye sensitized solar cell performance of ZnO chunk-shaped nanostructures

This paper presents the results of photoanode constructed with undoped and Ti-doped ZnO chunk shaped nanostructures for dye sensitized solar cells (DSSC). Nanostructures are prepared by simple chemical method and moreover the structural, morphological, optical and photovoltaic performances are investigated by XRD, SEM, UV–Vis, PL, and I–V measurements, respectively. The experimental observations demonstrate that the Ti is effectively doped into Zn site, which increases free electron concentration, hereby expected an enhancement in the DSSC performance. Fabricated DSSCs are tested and the results reveal that undoped ZnO shows conversion efficiency of 0.42% with better photocurrent density and photovoltage but the fill factor gets enhance up to 0.447 with 3 mole% (dilute) of Ti doping. Comparably, PEO/KI/LiI/I₂ electrolyte matches well for Ti doped ZnO DSSC due to the easier diffusion path offered by KI salt rather than TiO₂ and PEG additives.     

氧化锌宽禁带半导体薄膜的发光及其p-n结特性

报道了用直流反应溅射法制备的氧化锌薄膜的近紫外发射以及热处理条件对受激发射谱的影响。同时用化学反应辅助掺杂方法生长了 p型和 n型 Zn O薄膜 ,研究了 Zn O/ Si异质结和氧化锌同质 p-n结的电压 -电流特性 (I-V特性 )     

Al掺杂对ZnO薄膜形貌和光学性能的影响

采用溶胶-凝胶旋涂法在FTO玻璃衬底上制备得到了不同Al掺杂浓度的ZnO薄膜(AZO)。利用XRD、FESEM、UV-vis和PL等测试手段对样品结构、形貌和光学性能进行了表征。结果表明,合成的AZO薄膜均为六方纤锌矿结构且峰强随掺杂浓度的升高而减弱;同时,颗粒形貌由不规则向规则球形转变且尺寸逐渐减小;PL谱中的近紫外发射峰和晶格缺陷峰值随掺杂浓度的升高先增大后降低;由UV-vis吸收光谱可知,AZO薄膜在设定波长内的光吸收处于波动状态,且当Al掺杂浓度为3%时,光吸收强度最高,禁带宽度减小到3.12eV。