Fe、Ni共掺杂ZnO薄膜的溶胶-凝胶法制备及性能研究

采用溶胶-凝胶法在玻璃基片上旋涂生长了ZnO、Fe, Ni单掺杂及(Fe,Ni)共掺杂ZnO薄膜.产物的显微照片及XRD图谱结果表明, 该方法所制备的ZnO薄膜表面均匀致密,都存在(002)择优取向,具有六角纤锌矿结构,晶粒尺寸平均在13 nm 左右,振动样品磁强计(VSM)测试结果显示掺杂ZnO薄膜均存在室温铁磁性.光致发光(PL)测量表明所有样品薄膜的PL谱主要由较强的紫外发光峰(394 nm)、蓝光峰(420 nm)、绿光峰(480 nm)组成.Fe、Ni单掺杂和共掺杂并不改变ZnO薄膜的发光峰位置,但掺杂后该紫外发光峰减弱,420 nm处的蓝光峰增强.     

p-ZnO薄膜及其异质结的光电性质

采用射频磁控溅射法,在不同的Ar∶O2条件下,以高掺磷n型Si衬底为磷掺杂源制备了p型ZnO薄膜和p-ZnO/n-Si异质结.对ZnO∶P薄膜进行了光致发光谱(PL)、霍尔参数、Ⅰ-Ⅴ特性、扫描电镜(SEM)和X射线衍射谱(XRD)等测试.结果表明,获得的ZnO∶P薄膜沿(0002)晶面高取向生长,以3.33 eV近带边紫外发光为主,伴有2.69 eV附近的深能级绿色发光峰,空穴浓度为8.982 × 1017/cm3,空穴迁移率为9.595 cm2/V·s,p-ZnO/n-Si异质结I-V整流特性明显,表明ZnO∶P薄膜具有p型导电特性.     

四足棒球棒状ZnO纳/微米材料的制备及其生长机理的研究

采用简单的碳热蒸发法在硅衬底上制备了四足棒球棒状ZnO纳/微米材料,结合光致发光谱(PL)、阴极射线发光谱(CL)、XRD谱、SEM以及TEM等分析了该材料的结构和发光特性.结果表明,制备的单晶ZnO纳/微米材料具有纤锌矿结构,并且沿着c轴方向择优生长;每个纳/微米结构有四个足,每个足的直径约为0.2～1.5 μm,长度约为3 ～10 μm;室温光致发光谱中包含一个384 nm附近的较弱的近紫外发光峰和一个519 nm附近的较强的绿色发光峰;在单个四足状ZnO纳/微米结构不同位置获得的阴极射线发光谱也被用于对比分析.最后讨论了Ni缓冲层的作用及ZnO四足棒球棒状的生长机理.     

溶胶-凝胶法制备MgxZn1-xO及其特性

采用溶胶-凝胶法制备了不同组分(x=0.1～0.3)的MgxZn1-xO前驱体,并对它进行不同温度的热处理(550℃～1000℃).X射线衍射(XRD)结果表明,Mg0.1Zn0.9O具有和ZnO一样的衍射谱,为六方纤锌矿结构,而且随着热处理温度的升高,ZnO衍射峰的强度逐渐增强,半高宽不断减小;Mg元素掺杂浓度增大后,出现了MgO的峰位.扫描电子显微镜(SEM)显示Mg0.1Zn0.9O晶粒粒径分布较均匀;热处理温度升高,晶粒的尺寸不断变大.用室温荧光光谱(PL)分析了经过550～1000℃热处理获得的Mg0.1Zn0.9O粉末,结果发现除了550℃下处理的样品,其它都有紫外发射峰(350nm左右),而且随着热处理温度的升高紫外峰有明显的蓝移现象.     

ZnO(110)单层膜对O的自吸附及其电子结构的研究

基于密度泛函理论方法研究分析了一种Zn顶位吸附O的ZnO(110)-O二维膜材料的结构、结合性质、磁性质、电子结构和光吸收性质.结果表明,ZnO(110)二维膜经过O吸附之后,Zn-O键长分别增大到0.1992 nm和0.1973 nm,Zn-O链之间的距离减小到0.5628 nm,O-Zn-O键角度为108.044°,ZnO(110)膜Zn顶位对O原子的吸附为倾斜的吸附.经过Zn顶位O的吸附,ZnO(110)二维膜内原子间离子性结合性增强,吸附的O与Zn也形成偏离子性结合键,Zn顶位吸附O原子之后能量有所降低,吸附体系为反铁磁性材料.O吸附的ZnO(110)-O二维膜为间接带隙型材料,带隙宽度为0.565 eV.材料中的p电子对费米能处态密度贡献较多.ZnO(110)-O二维膜最高吸收峰位于156 nm,吸收率为67181光吸收单位,其在445 nm以上具有宽的强吸收带.     

热处理对Ni0.7Zn0.3O薄膜结构及缺陷荧光特性的影响

采用脉冲激光沉积法在Si(100)衬底上制备了Ni0.7Zn0.3O薄膜,通过热处理改变薄膜的缺陷状态,并利用X射线衍射仪、扫描电子显微镜和荧光光谱仪表征薄膜的晶体结构、表面形貌和缺陷发光特性.结果表明:沉积态薄膜为立方结构的Ni0.7Zn0.3O单相,且沿着(200)面高度取向生长.经过热处理后,薄膜形成ZnO和Ni0.7Zn0.3O两相共存的镶嵌结构.样品具有非常丰富的室温荧光光谱,其发光峰主要来自Ni0.7Zn0.3O的缺陷能级跃迁,多缺陷能级导致了多发光峰的荧光光谱.热处理引起薄膜中缺陷的种类和浓度发生变化,严重影响其发光特性.     

不同Ag光照时间对ZnO纳米花荧光增强的影响

采用水浴结合光照法,在Si(100)衬底上制备了Ag/ZnO纳米花结构,研究了不同Ag光照时间对ZnO发光性质的影响.通过X射线衍射(XRD)、扫描电子显微镜(SEM)和光致发光谱(PL)对Ag/ZnO纳米花的结构、形貌和光学性能进行了研究.研究表明,由水浴法制得的ZnO纳米花结构长度约1.0 μm,直径为200nm左右;不同光照时间的Ag掺杂后Ag/ZnO纳米花的衍射峰强度都增强,当光照时间为5min时,出现了Ag3O4的衍射峰.当光照时间为5 min时,Ag/ZnO纳米花结构具有最强的可见发射强度.     

氮气压强对PLD制备ZnO薄膜形貌及光电性能的影响

研究了氮气压强对脉冲激光沉积(PLD)法制备ZnO薄膜形貌及光电学性能的影响.结果表明,当氮气压强较低时,ZnO薄膜是由尺寸为50 nm的薄片组成;当氮气压强增加后,ZnO薄膜变成多孔状,并且组成ZnO薄膜的颗粒尺寸逐渐减小.在氮气压强为20 Pa以上时,所制备的ZnO薄膜的光致荧光(PL)光谱是由380 nm的带边发光峰和520 nm的缺陷发光峰组成;当氮气压强较低时(5 Pa和2 Pa),ZnO薄膜的PL光谱只有一个位于400 nm或41O nm处的发光峰.电学方而,2Pa和5 Pa氮气压强下制备的ZnO薄膜的电阻率约为氮气压强为20 Pa和50 Pa下制备样品的104和105倍.研究表明,当氮气压强较低时,Zn离子和O离子具有较大平均自由程和较大平均动能,因此易使N2离子化,可以使部分N离子掺入ZnO晶格中.当氮气压强较高时,Zn离子和O离子平均动能较小,不易使N2离子化,氮难于掺入ZnO晶格中.     

等离子体增强分子束外延生长ZnO薄膜及光电特性的研究

利用等离子体辅助分子束外延设备(P-MBE)在蓝宝石(Al2O3)衬底上外延生长ZnO薄膜,研究了不同生长温度对结晶质量的影响.随着生长温度的升高,X射线摇摆曲线(XRC)半高宽从0.88°变窄至 0.29°,从原子力显微镜(AFM)图像中发现薄膜中晶粒从20nm左右增大至200nm,室温光致发光(PL)谱中显示了一个近带边的紫外光发射(UVE)和一个与深中心有关的可见光发射.随着生长温度升高,可见光发射逐渐变弱,薄膜的室温载流子浓度由1.06×1019/cm3减少到7.66×1016/cm3,表明在高温下生长的薄膜中锌氧化学计量比趋于平衡,高质量的ZnO薄膜被获得.通过测量变温光谱,证实所有样品在室温下PL谱中紫外发光都来自于自由激子发射;随着生长温度的变化UVE峰位蓝移与晶粒尺寸不同引起的量子限域效应相关.     

ITO玻璃衬底上生长的Zn0.9Mg0.1S多晶薄膜特性研究

以ZnS和Mg粉末为原料,采用真空蒸镀技术在ITO玻璃上成功地制备了宽禁带三元化合物Zn0.9Mg0.1S多晶薄膜.原子力显微镜和X射线衍射研究表明:薄膜生长形貌和结晶性能良好,为择优取向的立方闪锌矿结构,晶粒直径约20nm,薄膜的X射线衍射峰较之ZnS的衍射峰向大角度方向移动了0.46°;室温下的拉曼谱峰相对于ZnS的拉曼谱峰出现蓝移,且347.67cm-1谱峰比较强;光致发光谱显示,Zn0.9Mg0.1S薄膜在410nm处有一个较强的发光峰.良好的结晶质量和发光特性为开发多功能材料和器件提供了可能性.     

ZnO growth on Si with low-temperature ZnO buffer layers by ECR-assisted MBE

High-quality ZnO films were grown on Si(1 0 0) substrates with low-temperature (LT) ZnO buffer layers by an electron cyclotron resonance (ECR)-assisted molecular-beam epitaxy (MBE). In order to investigate the optimized buffer layer temperature, ZnO buffer layers of about 1.1 μm were grown at different growth temperatures of 350, 450 and 550 °C, followed by identical high-temperature (HT) ZnO films with the thickness of 0.7 μm at 550 °C. A ZnO buffer layer with a growth temperature of 450 °C (450 °C-buffer sample) was found to greatly enhance the crystalline quality of the top ZnO film compared to others. The root mean square (RMS) roughness (3.3 nm) of its surface is the smallest, compared to the 350 °C-buffer sample (6.7 nm), the 550 °C-buffer sample (7.4 nm), and the sample without a buffer layer (6.8 nm). X-ray diffraction (XRD), photoluminescence (PL) and Raman scattering measurements were carried out on these samples at room temperature (RT) in order to characterize the crystalline quality of ZnO films. The preferential c-axis orientations of (0 0 2) ZnO were observed in the XRD spectra. The full-width at half-maximum (FWHM) value of the 450 °C-buffer sample was the narrowest as 0.209°, which indicated that the ZnO film with a buffer layer grown at this temperature was better for the subsequent ZnO growth at elevated temperature of 550 °C. Consistent with these results, the 450 °C-buffer sample exhibits the highest intensity and the smallest FWHM (130 meV) of the ultraviolet (UV) emission at 375 nm in the PL spectrum. The ZnO characteristic peak at 438.6 cm⁻¹ was found in Raman scattering spectra for all films with buffers, which is corresponding to the E₂ mode.     

The photoluminescence of ZnO thin films grown on Si (1 0 0) substrate by plasma-enhanced chemical vapor deposition

High-quality ZnO thin films have been grown on a Si(1 0 0) substrate by plasma-enhanced chemical vapor deposition (PECVD) using a zinc organic source (Zn(C₂H₅)₂) and carbon dioxide (CO₂) gas mixtures at a temperature of 180°C. A strong free exciton emission with a weak defect-band emission in the visible region is observed. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption peak in the absorption spectra, are closely related to the gas flow rate ratio of Zn(C₂H₅)₂ to CO₂. Full-widths at half-maximum of the free exciton emission as narrow as 93.4 meV have been achieved. Based on the temperature dependence of the PL spectra from 83 to 383 K, the exciton binding energy and the transition energy of free excitons at 0 K were estimated to be 59.4 meV and 3.36 eV, respectively.     

Low temperature deposition of zinc oxide nanoparticles via zinc-rich vapor phase transport and condensation

ZnO nanoparticles as small as 80 nm were successfully synthesized using a modified vapor phase transport (VPT) process at substrate temperatures as low as 222 °C. Particle size distribution and morphology were characterized by scanning electron microscopy and atomic force microscopy. Energy dispersive X-ray spectroscopy and X-ray diffraction indicate the synthesis of high quality crystalline ZnO structures. Low temperature (4.2 K) photoluminescence (PL) spectroscopy was used to characterize the optical quality of the nanoparticles. Ultraviolet emission and a nanostructure specific feature at 3.366 eV are strong in the PL spectra. The 3.366 eV feature is observed to predominate the spectrum with decrease in particle size. This size effect corroborates the luminescence as a nanostructure-specific surface related exciton feature as previously speculated in the literature. In addition, self-assembled ZnO mesoparticles (>100 nm) were realized by increasing the growth time. Low growth temperatures of the particles allow for their potential utilization in flexible organic hybrid optoelectronics. However, this work focuses mainly on the modified synthesis and optical characterization of nanoparticles.     

The effects of ZnO coating on the photoluminescence properties of porous silicon for the advanced optoelectronic devices

In the present work we investigate, the role of zinc oxide (ZnO) thin films passivating layer deposited by rf magnetron sputtering at room temperature on low (18%) and high (80%) porosity porous silicon (PS). The micro-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM) analysis have been carried out to understand the effect of ZnO films coating on PS. A systematic investigation from Raman spectroscopy suggests the formation of a good quality ZnO wurtzite structure on PS. The photoluminescence (PL) measurements on PS and ZnO coated PS shows a red, blue and UV emission bands at around ～1.8, ～2.78 and ～3.2 eV. An enhancement of all PL emission bands have been achieved after ZnO films deposition on high porosity PS.     

Observation of a new photoluminescence band at 320 nm under 270 nm excitation in Ge-doped silica glass

We investigate the influence of temperature on photoluminescence (PL) in Ge-doped silica glass. Under 270 nm excitation, we observe only one PL band at 424 nm at room temperature (RT). This band shifts to 436 nm with cooling (4 K), and a new PL band is recorded at 320 nm. We assign these PL bands to triplet-to-singlet and singlet-to-singlet transitions of a same Ge-related defect, whose structure is still unknown. The shift of the PL band (from 424 nm at RT to 436 nm at 4 K) is explained by the decrease of the overlap between PLs from different centers.     

High intense UV-luminescence of nanocrystalline ZnO thin films prepared by thermal oxidation of ZnS thin films

High quality zinc oxide (ZnO) films were obtained by thermal oxidation of high quality ZnS films. The ZnS films were deposited on a Si substrate by a low-pressure metalorganic chemical vapor deposition technique. X-ray diffraction spectra indicate that high quality ZnO films possessing a polycrystalline hexagonal wurtzite structure with preferred orientation of (0 0 2) were obtained. A fourth order LO Raman scattering was observed in the films. In photoluminescence (PL) measurements, a strong PL with a full-width at half-maximum of 10 nm around 380 nm was obtained for the samples annealed at 900°C at room temperature. The maximum PL intensity ratio of the UV emission to the deep-level emission is 28 at room temperature, providing evidence of the high quality of the nanocrystalline ZnO films.     

Excitation intensity and temperature‐dependent photoluminescence and optical absorption in Tl4Ga3InSe8 layered crystals

Photoluminescence (PL) spectra of Tl₄Ga₃InSe₈ layered crystals grown by Bridgman method have been studied in the wavelength region of 600‐750 nm and in the temperature range of 17‐68 K. A broad PL band centered at 652 nm (1.90 eV) was observed at T = 17 K. Variations of emission band has been studied as a function of excitation laser intensity in the 0.13 to 55.73 mW cm^‐2 range. Radiative transitions from donor level located at 0.19 eV below the bottom of conduction band to shallow acceptor level located at 0.03 eV above the top of the valence band were suggested to be responsible for the observed PL band. From X‐ray powder diffraction and optical absorption study, the parameters of monoclinic unit cell and the energy of indirect band gap were determined, respectively. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Room-temperature luminescence study on the effect of Mg activation annealing on p-GaN layers grown by MOCVD

An Mg-doped p-GaN layer was grown by the metalorganic chemical vapor deposition method. The dissociation extent of hydrogen-passivated Mg acceptors in the p-GaN layer through Mg activation annealing was estimated by using room-temperature cathodoluminescence (CL) spectroscopy. The CL measurement revealed that the CL spectra intensities tend to increase with increasing the activation annealing temperature. The sample annealed at 925 °C showed the most intense emission and the narrowest width among the emission peaks. Consequently, it was the most excellent dissociation extent of Mg–H complexes caused by the Mg activation annealing. The hole concentration under this optimum condition was 1.3×10¹⁷ cm⁻³ at room temperature. The photoluminescence (PL) measurement showed a 2.8 eV band having characteristically a broad peak in heavily Mg-doped GaN at room temperature. By analyzing the PL results, we learned that this band was associated with the deep donor–acceptor pair (DAP) emission rather than with the emission caused by the transition from the conduction band to deep acceptor level. The four emission peaks in the resolved 2.8 eV band were emitted by transiting from deep donor levels of 0.14, 0.26, 0.40, and 0.62 eV below the conduction band to the shallow Mg acceptor level of 0.22 eV above the valence band.     

Flux Bridgman growth and the influence of annealing temperatures on PL properties of ZnO single crystals

Transparent ZnO crystals were obtained by the flux Bridgman method from high temperature solution of 22 mol% ZnO‐78 mol% PbF₂ system. The influence of annealing temperatures on the photoluminescence (PL) of ZnO crystal was investigated. An ultraviolet emission peak at about 379 nm was observed in PL spectra and the peak position has a weak blueshift for annealed samples. A green band centered at 523 nm appeared in the annealed samples and its intensity enhanced with the increase of annealing temperatures, while the intensity of the ultraviolet peak decreased considerably. However, the ultraviolet emission peak became the strongest after annealing at 1000 °C. This phenomenon was considered to be associated with oxygen vacancy and F^‐ impurities induced by the PbF₂ flux. The results show that high temperature annealing in air seems helpful for improving the PL properties of ZnO crystal. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Infrared photoluminescence from TlGaS2 layered single crystals

Photolimuniscence (PL) spectra of TlGaS₂ layered crystals were studied in the wavelength region 500‐1400 nm and in the temperature range 15‐115 K. We observed three broad bands centered at 568 nm (A‐band), 718 nm (B‐band) and 1102 nm (C‐band) in the PL spectrum. The observed bands have half‐widths of 0.221, 0.258 and 0.067 eV for A‐, B‐, and C‐bands, respectively. The increase of the emission band half‐width, the blue shift of the emission band peak energy and the quenching of the PL with increasing temperature are explained using the configuration coordinate model. We have also studied the variations of emission band intensity versus excitation laser intensity in the range from 0.4 to 19.5 W cm^‐2. The proposed energy‐level diagram allows us to interpret the recombination processes in TlGaS₂ crystals. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)