微量Mg掺杂ZnO薄膜的光致发光光谱和带隙变化机理研究

利用射频磁控溅射(RF-MS)法在450℃玻璃基底上制备了Mg掺杂量分别为0.81at%,2.43at%和4.05at%的ZnO薄膜,对其微观结构、室温光致发光光谱(PL)、光学和电学性质进行了研究.结果发现,微量Mg掺杂ZnO薄膜晶体具有六方纤锌矿结构并保持高结晶质量;掺杂0.81at%和2.43at%Mg的ZnO薄膜室温PL谱中近带边发射(NBE)峰的短波方向出现了高能发射带与NBE峰同时存在;随着Mg掺杂量增加至4.05at%,这个高能发射带逐步将NBE峰掩盖.推测在Mg掺杂ZnO薄膜中,Mg2+替代Zn2+附近核外电子的能量增大并产生了一个高能级.而未被Mg2+替代的Zn2+周围的核外电子能量状态不变,带间能级依然存在,随着Mg掺杂量的增加处于高能级的电子数目逐步增加并占绝对优势.因此,ZnO薄膜随着Mg掺杂量增加薄膜禁带宽度增大,这是由于Mg掺杂后周围电子能量增大与Burstein-Moss效应共同作用的结果.另外,薄膜在可见光区域的平均透射率均大于85%,随着Mg掺杂量的增加,薄膜禁带宽度增大并在3.36—3.52eV内变化;Mg掺杂量为0.81at%,2.43at%和4.05at%时,薄膜电阻率分别为2.2×10-3,3.4×10-3和8.1×10-3Ω.cm.     

溶胶-凝胶法制备MgxZn1-xO薄膜的结构及光学特性

用溶胶-凝胶法制备了一系列的Mg_xZn_1-xO(0≤x≤0.3)薄膜,并用X射线衍射(XRD)和光致发光(PL)研究了不同的退火温度和Mg的掺杂含量对Mg_xZn_1-xO薄膜的结构和光学性质的影响.研究表明:Mg_xZn_1-xO薄膜为单相六角纤锌矿结构,并且具有沿c轴的择优取向;发现了中间热处理温度为350℃的Mg_xZn_1-xO薄膜退火温度的转折点为700℃,低于这个温度时随退火温度的升高,(002)衍射峰强度增强且掺Mg的薄膜既有紫外光又有绿光发射;800℃退火时,薄膜的(002)衍射峰强度减小,出现了(100)和(101)衍射峰,且掺Mg的薄膜只有紫外发光峰.不同的掺杂浓度对于发光也有影响,低于700℃退火时,ZnO薄膜只出现紫外发光峰,掺Mg的薄膜却出现了紫外和绿光两个发光峰.     

射频磁控溅射ZnO薄膜的结构和光学特性

采用射频（RF）反应磁控溅射法在n-Si(001)衬底上外延生长ZnO薄膜。XRD谱测量显示出较强的（002）衍射峰，表明ZnO薄膜为c轴择优取向生长的。室温PL谱测量观察到了较强的紫外光发射和深能级发射。     

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.     

氧气压强对PLD制备MgZnO薄膜光学性质的影响(英文)

使用准分子脉冲激光沉积(PLD)方法在Si(100)基片上制备了高度c轴取向的MgZnO薄膜。分别使用SEM、XRD、XPS、PL谱和吸收谱表征了薄膜的形貌、结构、成分和光学性质。实验发现氧气压强对MgZnO薄膜的结构和光学性质有重要影响。当氧气压强由5 Pa增大到45 Pa时,薄膜的PL谱紫外峰蓝移了86meV,表明氧气压强的增大提高了MgZnO薄膜中Mg的溶解度。在15 Pa氧气压强下制备的薄膜显示了独特、均匀的六角纳米柱状结构,其PL谱展示了优异的发光特性,具有比其他制备条件下超强的紫外发射和微弱的可见发光。500~600 nm范围内的绿光发射,我们讨论其机理可能源于深能级中与氧相关的缺陷。使用PLD得到纳米柱状结构表明:优化制备条件,可望使用PLD制备ZnO纳米阵列的外延衬底;可使用PLD技术开发基于ZnO纳米结构的高效发光器件。     

退火对ZnO薄膜的结构和光学性质的影响

采用射频磁控溅射法在Si衬底上制备了高c轴择优取向的ZnO薄膜,研究了退火对ZnO薄膜的晶粒尺度和发光光谱的影响。XRD结果显示退火可以改善ZnO薄膜的结构特性,PL谱结果显示退火对ZnO薄膜的发光强度产生很大影响。     

MOCVD法制备Cu掺杂ZnO薄膜

通过金属有机物化学气相沉积(MOCVD)设备,在c-Al2 03衬底上生长本征和Cu掺杂ZnO( ZnO∶ Cu)薄膜.X射线衍射(XRD)谱观察到未掺杂的ZnO和ZnO∶ Cu样品都呈现出较好的c轴择优取向生长.X射线光电子能谱(XPS)表明Cu已掺入到ZnO薄膜中.利用光致发光(PL)测试对本征ZnO和ZnO∶ C...     

过渡金属与F共掺杂ZnO薄膜结构及磁、光特性

采用溶胶-凝胶法在玻璃衬底上制备了过渡金属元素与F共掺杂Zn_0.98-xTM_xF_0.02O (TM_x=Cu_0.02, Ni_0.01, Mn_0.05, Fe_0.02, Co_0.05)薄膜, 进而利用X射线衍射仪、扫描电子显微镜、紫外-可见透过谱、光致发光及振动样品磁强计等研究了薄膜的表面形貌、微结构、禁带宽度及光致发光(PL)和室温磁学特性. 研究表明: 掺杂离子都以替位的方式进入了ZnO晶格, 掺杂不会破坏ZnO的纤锌矿结构. 其中Zn_0.93Co_0.05F_0.02O薄膜样品的颗粒尺寸最大, 薄膜的结晶度最好且c轴择优取向明显; Zn_0.93Mn_0.05F_0.02O薄膜样品的颗粒尺寸最小, 薄膜结晶度最差且无明显的c轴择优取; Cu, Ni, Fe与F共掺杂样品的颗粒尺寸大小几乎相同. TM掺杂样品均表现出很高的透过率, 同时掺杂后的薄膜样品的禁带宽度都有不同程度的红移. PL谱观察到Zn_0.98-xTM_xF_0.02O薄膜的发射峰主要由较强的紫外发射峰和较弱的蓝光发射峰组成. Zn_0.93Mn_0.05F_0.02O薄膜样品的紫外发光峰最弱, 蓝光发射最强, 饱和磁化强度最大; 与之相反的是Zn_0.96Cu_0.02F_0.02O薄膜, 其紫外发光峰最强, 蓝光发射最弱, 饱和磁化强度最小. 结合微结构和光学性质对Zn_0.98-xTM_xF_0.02O薄膜的磁学性质进行了讨论.     

MOCVD生长中载气H2对N掺杂ZnO性质的影响

采用MOCVD方法在石英衬底上生长ZnO。实验使用二乙基锌(DEZn)为锌源,N2O作为氧和氮源,H2作为载气。采用PL和Raman光谱方法对ZnO样品进行表征,结果表明H2的加入大幅度减少薄膜中碳的掺入,明显改善了薄膜的光学质量。采用N2O离化技术,可以进一步提高其带边峰的强度,抑制带内发光。XRD测量表明,生长的ZnO薄膜具有c轴择优取向。目前生长高质量N掺杂的p型ZnO薄膜是很困难的,而H2作为载气的加入明显改善了ZnO薄膜的光学性质,在生长过程中加入H2将为获得高质量N掺杂的p型ZnO薄膜提供一种途径。     

利用P-MBE制备高质量MgxZn1-xO的结构和光学特性

利用等离子体辅助分子束外延(P-MBE)的方法,在c平面的蓝宝石衬底上制备了高质量的MgxZn1-xO合金薄膜。通过改变Mg源的温度,得到了不同Mg组份的MgxZn1-xO合金薄膜;通过引入ZnO的低温缓冲层,有效地提高了MgxZn1-xO合金薄膜的结晶质量。随着Mg组份的增加,MgxZn1-xO的X射线衍射的(002)衍射峰逐渐向大角度方向移动。对样品进行光致发光(PL)谱的测量,在室温下观察到了较强的紫外发光。随Mg浓度的增加,紫外发光峰向高能侧移动,并且发光峰逐渐展宽。通过对x=0.15的样品进行变温光谱的测量研究了紫外发光峰起因,得到了MgxZn1-xO的发光是来自于自由激子的发光。自由激子束缚能为54meV。     

Thickness effect on the evolution of morphology and optical properties of ZnO films

N-Al co-doped ZnO films with various thicknesses were deposited on glass substrates by ultrasonic spray pyrolysis (USP). The crystalline microstructure, morphology, distribution of elements and photoluminescence properties of ZnO films were characterized by X-ray diffraction (XRD), field emission scanning microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS) and photoluminescence (PL) spectroscopy. The XRD and FESEM results show that with the increase of film thickness the grain size increases and the grain shape changes from regular hexagonal sheet-like to wedge-shaped, even pyramidal. The PL spectra illustrate that there is an obvious red-shift for the emission center from ultraviolet to blue region, and the intensities of defects emissions increase with the increase of thickness. In addition, the electrical properties are proved to be strongly affected by film thickness.     

退火对ZnO:Al薄膜光致发光性能的影响

 采用溶胶-凝胶工艺在石英衬底上制备ZnO:Al（AZO）薄膜，通过不同温度的退火处理，研究了退火对AZO薄膜结构和光致发光特性的影响。XRD图谱表明：所制备的薄膜具有c轴高度择优取向，随着退火温度的升高，(002)峰的强度逐渐增强，同时(002)峰的半高宽逐渐减小,表明晶粒在不断增大。未退火样品的光致发光（PL）谱由361 nm附近的紫外带边发射峰和500 nm附近的深能级发射峰组成。样品经退火后，以500 nm为中心的绿带发射逐渐减弱，而带边发射强度有所增强,并且逐渐红移到366 nm附近，与吸收边移动的测试结果相吻合。对经过不同时间退火的样品分析表明，AZO薄膜的发光特性与退火时间也有很大关系，时间过短可见波段的发射较强，但时间过长会使晶粒发生团聚，导致紫外发射峰强度减弱。     

射频反应磁控溅射法退火生长Na-N共掺杂p-ZnO薄膜

采用射频反应磁控溅射法退火生长得到了Na-N共掺杂p-ZnO薄膜。XRD测试结果表明,退火前后均得到c轴择优取向的ZnO薄膜。Hall测试结果表明:退火后薄膜的电学性能明显改善,得到了p-ZnO薄膜,退火温度为450℃时取得最佳电学性能:室温电阻率为139.2Ω.cm,迁移率为0.2cm2.V-1.s-1,空穴浓度为2.5×1017cm-3。XPS分析表明:Na掺入ZnO中作为受主NaZn而存在,N主要以N—H键的形式存在,其受主NO的作用不明显,但是否存在NaZn-NO受主复合体,还需进一步的研究。     

退火温度对ZnO薄膜结构和发光特性的影响

采用反应射频磁控溅射法在 Si(100)基片上制备了高c轴择优取向的ZnO薄膜，研究了退火温度对ZnO薄膜的晶粒尺度、应力状态、成分和发光光谱的影响，探讨了ZnO薄膜的紫外发光光谱和可见发光光谱与薄膜的微观状态之间的关系.研究结果显示,在600—1000℃退火温度范围内，退火对薄膜的织构取向的影响较小，但薄膜的应力状态和成分有比较明显的变化.室温下光致发光光谱分析发现，薄膜的近紫外光谱特征与薄膜的晶粒尺度和缺陷状态之间存在着明显的对应关系；而近紫外光谱随退火温度升高所呈现的整体峰位红移是各激子峰相对比例变 关键词： ZnO薄膜 退火 光致发光 射频反应磁控溅射 可见光发射     

高质量ZnO及BeZnO薄膜的发光性质

用分子束外延设备插入缓冲层在c面蓝宝石上生长得到高质量ZnO和BeZnO薄膜。XRD测试显示薄膜具有六方结构和c轴取向,并具有良好的晶体质量,其中ZnO薄膜的半高宽仅为108 arcsec,Be_xZn_1-xO薄膜的半高宽小于600 arcsec。对ZnO和BeZnO薄膜的拉曼光谱进行对比研究发现,随着Be元素的掺入,A₁(LO)、A₁(2LO)声子模频率往大波数方向移动,并且首次发现了与Be元素掺杂有关的局域振动模。利用变温光致发光光谱研究了薄膜的发光性质,结果显示ZnO薄膜室温光致发光只出现一个紫外发发光峰(378 nm),而低温光谱(80 K)则出现了很强的自由激子发光峰。随着温度的升高,束缚激子发光逐渐湮灭向自由激子发光转变,并且峰值位置红移。相对于ZnO薄膜,BeZnO薄膜的紫外发光主峰位置蓝移,并且由于Be元素的掺入导致薄膜晶体质量下降,在低温(80 K)光致发光光谱中没有出现强的自由激子发光峰。另外,在低温光致发光及拉曼光谱中,主峰位置在100~200 K之间有局部最大值,推测为由于合金晶格热膨胀系数失配而引起的应力效应。     

Dopant induced morphology changes in ZnO nanocrystals

Zinc oxide (ZnO) nanocrystals doped with different groups of impurities, e.g., Li, Na, Cu, Pr and Mg synthesized by solid-state reaction method under similar conditions exhibit different morphology. XRD showed monophasic wurtzite structure but change in lattice parameters and Zn-O bond length indicates incorporation of dopant ion in ZnO lattice. The morphology of ZnO nanocrystals exhibited striking dependence on type of dopant ion with the shape changing from nanorods, spherical to petal like particles. Photoluminescence (PL) shows pronounced UV emission and negligible visible emission for Li, Na and Cu doped ZnO nanocrystals with peak positions coinciding with that of undoped ZnO. Whereas signature emission of Pr³⁺ ion as well as broad visible emission from Mg doped ZnO revealed the role of intra gap metastable states formed by the dopant ion in the emission process.     

Preparation and characterization of Mg-doped ZnO thin films by sol-gel method

Undoped and Mg-doped ZnO thin films were deposited on Si(1 0 0) and quartz substrates by the sol-gel method. The thin films were annealed at 873 K for 60 min. Microstructure, surface topography and optical properties of the thin films have been measured by X-ray diffraction (XRD), atomic force microscope (AFM), UV-vis spectrophotometer, and fluorophotometer (FL), respectively. The XRD results show that the polycrystalline with hexagonal wurtzite structure are observed for the ZnO thin film with Mg:Zn = 0.0, 0.02, and 0.04, while a secondary phase of MgO is evolved for the thin film with Mg:Zn = 0.08. The ZnO:Mg-2% thin film exhibits high c-axis preferred orientation. AFM studies reveal that rms roughness of the thin films changes from 7.89 nm to 16.9 nm with increasing Mg concentrations. PL spectra show that the UV-violet emission band around 386-402 nm and the blue emission peak about 460 nm are observed. The optical band gap calculated from absorption spectra and the resistivity of the ZnO thin films increase with increasing Mg concentration. In addition, the effects of Mg concentrations on microstructure, surface topography, PL spectra and electrical properties are discussed.     

射频磁控溅射法制备ZnO薄膜的发光特性

利用射频磁控溅射法在硅衬底上制备出具有（002）择优取向的氧化锌薄膜，用波长为300nm的光激发，观察到在446nm处有一强的光致发光峰，它来自于氧空位浅施主能级上的电子到价带上的跃迁。并讨论了发光峰与氧压的关系以及退火对它的影响，且给出了解释。     

Low temperature synthesis wide optical band gap Al and (Al, Na) co-doped ZnO thin films

Al-doped ZnO (AZO) and (Al, Na) co-doped ZnO (ANZO) thin films were prepared via sol-gel technique with an annealing process at temperatures between 450 and 550 °C for 60 min in air ambient, and their structural and optical properties have been investigated. The deposited films exhibited hexagonal zinc oxide structure except annealing at 450 °C. For the 500 °C-annealed samples, the surface morphology was analyzed via scanning electron microscopy, Photoluminescence (PL) of different Na content ANZO thin films showed that there were very obvious violet and blue emission bands between 400 and 500 nm, and intensity of which were enhanced with Na content increasing. Transparency of the films was improved along with increasing Na content. The result of UV indicated the absorb bands appeared obviously red shift with Na doping into ZnO, the optical gaps of all films far beyond 3.37 eV of pure ZnO, and gradually decreased with Na content increasing, this is very virtual for improving photoelectricity performance of transparent conduct oxide (TCO) film. The possible origins responsible for structure and optical properties also had been discussed.