N掺杂ZnO薄膜的荧光特性研究

以N2为掺杂源,通过改变O2∶N2比,利用射频磁控溅射法在玻璃衬底上制备了具有[002]择优取向的N掺杂ZnO薄膜,研究了ZnO薄膜的光致发光谱随着N掺入量的不同而变化的规律.结果表明,薄膜主衍射峰为402 nm处的发光峰;由于N掺杂量的不同,有的薄膜在445 nm和524 nm处也有发光发存在,但随着薄膜N含量的不同,其发光峰强度明显不同,其峰位也发生了相应的红移或者蓝移.当O2∶N2为10∶ 15时,制备的薄膜N掺杂量最大,光学性能最好,此工艺为研究ZnO薄膜的缺陷类型及导电类型提供了重要的研究参考.     

Cu掺杂Ga2O3薄膜的光学性能

采用射频磁控溅射和N₂气氛退火处理制备了多晶Ga₂O₃薄膜和Cu掺杂Ga₂O₃薄膜.用X射线衍射仪、紫外-可见分光光度计、荧光光谱仪对Ga₂O₃薄膜和Cu掺杂Ga₂O₃薄膜的结构和光学性能进行了表征.结果表明,Cu掺杂后Ga₂O₃薄膜的结晶质量变差,透过率明显降低,吸收率增加,光学带隙减小.本征Ga₂O₃薄膜在紫外、蓝光和绿光出现了发光带,Cu掺杂后紫外和蓝光发射增强,且在475 nm 处出现了一个新的发光峰.     

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。     

退火温度对N+注入ZnO:Mn薄膜结构及室温铁磁性的影响

采用射频磁控溅射法在石英玻璃衬底上制备了ZnO:Mn薄膜, 结合N⁺ 注入获得Mn-N共掺ZnO薄膜, 进而研究了退火温度对其结构及室温铁磁性的影响. 结果表明, 退火后ZnO:(Mn, N) 薄膜中Mn²⁺和N^3-均处于ZnO晶格位, 没有杂质相生成. 退火温度的升高 有助于修复N⁺注入引起的晶格损伤, 同时也会让N逸出薄膜, 导致受主(N_O)浓度降低. 室温铁磁性存在于ZnO:(Mn, N)薄膜中, 其强弱受N_O浓度的影响, 铁磁性起源可采用束缚磁极化子模型进行解释.     

溶胶-凝胶法Er2O3薄膜的结构和光学特性

针对稀土Er掺杂Si光源中Er离子掺杂浓度低的问题,采用溶胶-凝胶（Sol-gel）法在Si(100)和SiO2/Si(100)基片上旋涂法制备Er₂O₃光学薄膜,Er离子浓度与以前掺杂方法相比提高了2个数量级.900 ℃热处理获得单一立方结构的Er₂O₃薄膜材料.光致发光（PL）特性研究表明在654 nm波长的激光泵浦下,Er₂O₃薄膜材料获得了1.535 μm的发光峰,并具有较小的温度猝灭1/5.在SiO₂/Si(100)基体上制备的Er2O3薄膜材料的光致发光强度比Si(100)基体上制备的薄膜提高2-3倍.研究结果表明具有强光致发光特性的Er₂O₃薄膜是一种有前景的硅基光源和放大器材料.     

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.     

掺铋BaF2晶体的制备及其近红外发光研究

通过温度梯度法制备了Bi₂O₃:BaF₂以及BiF₃:BaF₂晶体.在Bi₂O₃:BaF₂晶体中观察到了发光峰位于961 nm,半高宽202 nm的超宽带红外发光.在BiF₃:BaF₂晶体中检测到Bi²⁺和Bi³⁺可见区的发光,但是没有观察到红外发光.通过γ射线辐照实现了BiF₃:BaF₂晶体的近红外发光, 发光峰位于1135 nm,半高宽192 nm.讨论了Bi₂O₃和BiF₃掺杂BaF₂晶体的红外发光的机理.     

a-C∶H(N)薄膜结构的X射线光电子能谱分析

采用直流-射频等离子增强化学汽相沉积技术制备a-C∶H(N)薄膜，用X射线光电子能谱研究了混合气体中N₂含量对薄膜成分与结构的影响.a-C∶H(N)薄膜中含氮量可达9.09%.对a-C∶H(N)薄膜的C1s和N1s结合能谱的分析表明a-C∶H(N)薄膜的结构是由C₃N₄相镶嵌在sp²键结合的CN_x基体中组成.其中C₃N₄相中N和C原子比接近4∶3，不随薄     

退火对He注入及随后208Pb27+辐照的Al2O3单晶PL谱的影响

利用高能离子研究了110 keV 的He⁺注入Al₂O₃单晶及随后230 MeV的²⁰⁸Pb²⁷⁺辐照并在不同温度条件下退火样品的光致发光的特性. 从测试结果可以清楚地看到在375 nm，390 nm，413 nm 和450 nm 出现了强烈的发光峰. 经过600 K退火2 h后测试结果显示，390 nm发光峰增强剧烈，而别的发光峰显示不明显. 在900 K退火条件下，390 nm的发光峰开始减弱相反在510 nm出现了较强的发光峰，到1100 K退火完毕后390 nm的发光峰完全消失，而510 nm的发光峰相对增强. 从辐照样品的FTIR谱中看到，波数在460—510 cm^-1间的吸收是振动模式，经过离子辐照后，吸收带展宽，随着辐照量的增大，Al₂O₃振动吸收峰消失，说明Al₂O₃振动模式被完全破坏. 1000—1300 cm^-1之间为Al-O-Al桥氧的伸缩振动模式，辐照后吸收带向高波数方向移动. 退火后的FTIR谱变化不大.     

Gd3Ga5O12:Ag薄膜电致发光材料的制备及其发光性质

研究了Gd₃Ga₅O₁₂:Ag材料的制备及其发光性质.Gd₃Ga₅O₁₂:Ag材料通过固相反应法制得,采用X射线衍射法分 析了材料的结晶度及成分.用电子束蒸发将该材料制备成交流的薄膜电致发光器件,得到了 较好的蓝紫色发光,发光峰分别位于397和467nm.通过对材料的光致发光和激发光谱的研究 和比较,得出397和467nm分别来自于氧空位和Ag⁺的发光.     

Photoluminescence properties of thin nitrogen- and phosphorus-doped ZnO films fabricated using pulsed laser deposition

The production of n- and p-type high-quality film structures is a foreground task in tackling the problem of growing the light-emitting p-n junctions based on zinc oxide. The ZnO:N and ZnO:P thin-film samples are produced from ceramic targets using the pulsed laser deposition. Zn₃N₂, MgO, and Zn₃P₂ are introduced in the ZnO ceramic targets for the fabrication of the p-type ZnO films. Gases O₂ and N₂O are used as buffer gases. The thermal annealing of the ZnO films is employed. The resistance and photoluminescence (PL) spectra of the ZnO films are measured prior to and after annealing. The dependence of the ZnO PL peak amplitude and position prior to and after annealing on the level of doping with nitrogen and phosphorus is established. The PL characteristics of the films are studied at cw optical excitation using a He-Cd laser with a radiation wavelength of 325 nm. The PL spectra in the interval 300–700 nm are recorded by an HR4000 Ocean Optics spectrometer in the temperature range 10–400 K. The effect of the conditions for the film deposition on the PL spectra is analyzed. The effect of the N- and P-doping level of the ZnO films on the PL intensity of the films and the position of the PL bands in the UV region is investigated. The short-wavelength (250–400 nm) transmission spectra of the ZnO:P films are measured. The effect of the P-doping level on the band gap of the ZnO films is studied.     

Structural, optical and electrical properties of Al-N codoped ZnO films by RF-assisted MOCVD method

N-doped ZnO films were produced using N₂ as N source by metal-organic chemical vapor deposition (MOCVD) system which has been improved with radio-frequency (RF)-assisted equipments. The data of secondary ion mass spectroscopy (SIMS) indicate that the concentration of N in N-doped ZnO films is around 5 × 10²⁰ cm⁻³, implying that sufficient incorporation of N into ZnO can be obtained by RF-assisted equipment. On this basis, the structural, optical and electrical properties of Al-N codoped ZnO films were studied. Then, the effect of RF power on crystal quality, surface morphologies, optical properties was analyzed using X-ray diffraction, atomic force microscopy and photo-luminescence methods. The results illustrate that the RF plasma is the key factor for the improvement of crystal quality. Then the observation of A⁰X recombination associated with N_O acceptor in low-temperature PL spectrum proved that some N atoms have occupied the positions of O atoms in ZnO films. Hall measurements shown that p-type ZnO film deposited on quartz glasses was obtained when RF power was 150 W for the Al-N codoped ZnO films, while the resistivity of N-doped ZnO films was rather high. Compared with the Al-doped ZnO film, the obviously increased resistivity of codoped films indicates that the formation of N_O acceptors compensate some donors in ZnO films effectively.     

Effects of substrate on surface morphology, crystallinity, and photoluminescence properties of sputtered ZnO nano films

Effects of substrate on crystallinity, surface morphology, and luminescence properties of radio frequency sputtered zinc oxide (ZnO) thin films were investigated. A variety of materials such as Si (100), Si (111), Al₂O₃, quartz, and silicon carbide (SiC) wafers were examined as substrates for deposition of ZnO thin films. The results showed smooth and uniform growth of c-axis orientation films. The thickness of the layers was about 50 nm. The average grain sizes of films were about 10, 13, and 12 nm for Si (111), quartz, and SiC samples, respectively. The deposited film on Al₂O₃ showed the largest grain size, about 500 nm. Grazing incidence x-ray diffraction patterns of the samples revealed that sputtered layers on Al₂O₃ and quartz had better crystallinity with higher peak at (002) orientation compared to Si and SiC substrates. Moreover, the Al₂O₃ sample exhibited a weak peak at position of (100) planes of ZnO too. The photoluminescence spectra of the samples showed a typical luminescence behavior with a broad UV band, including a main peak at around 388 nm and a weak shoulder peak at around 381 nm, corresponding with bound excitonic recombination and free excitonic recombination, respectively. The luminescence peak revealed that the intensity of UV emission is not necessarily dependent on the grain sizes and the micro-structural quality of ZnO films.     

The morphology and optical properties of Cr-doped ZnO films grown using the magnetron co-sputtering method

Undoped ZnO and Zn_0.9Cr_0.1O films were prepared on Al₂O₃ (0 0 0 1) substrates using the magnetron co-sputtering technique. X-ray diffraction scans show that all films exhibit nearly single-phase wurtzite structure with c-axis orientation. Both chromium doping and growth ambient have a significant impact on the lattice constants and nucleation processes in ZnO film. A large quantity of subgrains (10 nm in size) has been observed on Zn_0.9Cr_0.1O film grown under Ar + O₂, while irregular plateau-like grains 40-50 nm in size were observed on Zn_0.9Cr_0.1O film grown under Ar + N₂. The ultraviolet-visible transmittance and optical bandgap of all films were also examined. The photoluminescence spectra of all films exhibit a broad emission located around 400 nm, which is composed of one weak ultraviolet luminescence and another rather intense near-violet one, as determined by Gaussian peak fitting. The near-violet emission centered on 400 nm might originate from the electron transition between the band tail state levels of surface defects and/or lattice imperfection in the ZnO film.     

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     

Formation Mechanisms of Electrical Conductivity and Optical Properties of ZnO:N Film Produced by Annealing Treatment

The effects of annealing on the chemical states of N dopant, electrical, and optical properties of N-doped ZnO film grown by molecular beam epitaxy (MBE) are investigated. Both the as-grown ZnO:N film and the film annealed in N₂ are of n-type conductivity, whereas the conductivity converts into p-type conductivity for the film annealed in O₂. We suggest that the transformation of conductivity is ascribed to the change in ratio of the N molecular number on O site (N₂)_O to the N atom number on O site (N_O) in ZnO:N films under the various annealed atmosphere. For the ZnO:N film annealed in N₂, the percentage content of (N₂)_O is larger than that of N_O, i.e.the ratio >1, resulting in the n-type conductivity. However, in the case of the ZnO:N film annealed in O₂, the percentage content of (N₂)_O is fewer than that of N_O, i.e., the ratio <1, giving rise to the p-type conductivity. There is an obvious difference between low-temperature (80K) PL spectra of ZnO:N film annealed in N₂ and that of ZnO:N film annealed in O₂. An emission band located at 3.358eV is observed in the spectra of the ZnO:N film after annealed in N₂, this emission band is due to donor-bound exciton (D⁰X). After annealed in O₂, the PL of the donor-bound exciton disappeared, an emission band located at 3.348eV is observed, this emission band is assigned to acceptor-bound exciton (A⁰X).     

Effects of annealing ambience on ZnO:N films grown by MOCVD and the p-type doping mechanism of ZnO:N films investigated by XANES

ZnO:N thin films were deposited on sapphire substrate by metal organic chemical vapor deposition with NH₃ as N-doping sources. The reproducible p-type ZnO:N film with hole concentration of ∼10¹⁷ cm⁻³ was successfully achieved by subsequent in situ thermal annealing in N₂O plasma protective ambient, while only weak p-type ZnO:N film with remarkably lower hole concentration of ∼10¹⁵ cm⁻³ was obtained by annealing in O₂ ambient. To understand the mechanism of the p-type doping behavior of ZnO:N film, X-ray photoelectron spectroscopy (XPS) and soft X-ray absorption near-edge spectroscopy (XANES) measurements have been applied to investigate the local electronic structure and chemical states of nitrogen atoms in ZnO:N films.     

Successive chemical solution deposition of ZnO films on flexible steel substrate: structure, photoluminescence and optical transitions

Zinc oxide is an attractive optoelectronic material with wide applications. Thin ZnO films were prepared on steel foil by successive chemical solution deposition (SCSD). The film structure, room-temperature photoluminescence (PL) and optical absorption characteristics were investigated. This study revealed that films of high structural and optical quality can be prepared by the SCSD method. PL of as-grown films shows a weak green peak at 560 nm and a strong UV peak at 380 nm. Annealing in either air or argon suppresses the green peak and red shifts the UV emission towards 390 nm. The presence of chlorine in the deposition solution destroys the PL of as-grown films. A strong UV emission, however, develops after annealing the films in air. Several optical transitions measured from the film PL and optical absorption coefficients are shown to be related to transitions through the known defect levels in ZnO, such as E₁, L₁, E₃ and V_O ²⁺ levels. PACS 81.16.Be; 81.05.Dz; 78.55.Et; 78.66.Hf; 68.55.Jk