高质量纳米ZnO薄膜的光致发光特性研究

报道了利用低压-金属有机物化学气相沉积技术生长纳米ZnS薄膜，然后，将ZnS薄膜在氧气中于800℃温度下进行热氧化制备高质量纳米ZnO薄膜.x射线衍射结果表明，纳米ZnO薄膜具有六角纤锌矿多晶结构.室温下观察到一束强的紫外(3.26 eV) 光致发光和很弱的深能级发射.根据激子峰的半高宽度与温度的关系确定了激子-纵向光学声子（LO）的耦合强度（ГLO）.由于量子限域效应使ГLO减少较多. 关键词： 光致发光 热氧化 激子 纳米ZnO薄膜     

磁控溅射制备ZnO薄膜的受激发射特性的研究

用射频磁控反应溅射法在二氧化硅衬底上制备ZnO薄膜。得到了在不同温度下ZnO薄膜的吸收与光致发光。观测到了纵光学波 (LO)声子吸收峰与自由激子吸收峰 ;室温 (30 0K)下 ,PL谱中仅有自由激子发光峰。这些结果证实了ZnO薄膜具有较高的质量。探讨了变温ZnO薄膜的发光特性。研究了ZnO薄膜的受激发射特性。     

MBE生长ZnO薄膜的结构和光学特性的研究

用等离子体源辅助分子束外延(P-MBE)方法在蓝宝石(0001)面上生长出了高质量的ZnO薄膜,并对其结构和发光特性进行了研究。在XRD中只观察到ZnO薄膜的(0002)衍射峰,其半高宽(FWHM)值为0.18°;而在共振Raman散射光谱中观测到1LO(579 cm-1 )和2LO(1 152 cm-1 )两个峰位,这些结果表明ZnO薄膜具有单一c轴取向和高质量的纤维锌矿晶体结构。在吸收光谱中观测到自由激子吸收和激子-LO声子吸收峰,这表明在ZnO薄膜中激子稳定的存在于室温,并且两峰之间能量间隔为71.2 meV,与文献上报道的ZnO纵向光学声子能量(71 meV)相符。室温下在光致发光光谱(PL)中仅观测到位于376 nm处的自由激子发光峰,而没有观测到与缺陷相关的深能级发射峰,表明ZnO薄膜具有较高的质量和低的缺陷密度。     

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。     

扩散掺杂的p型ZnO薄膜的光学性质研究

采用原子层沉积技术(atomic layer deposition)在InP衬底上生长ZnO薄膜,并在不同温度下(500和700 ℃)进行热退火处理,将P掺杂进入ZnO,得到p型ZnO薄膜。样品的光学特性通过光致发光光谱(photoluminescence, PL)来测定,得出热退火温度是影响P扩散掺杂的重要因素,低温PL光谱中,700 ℃热退火1 h样品的光谱展现出四个与受主相关的发射峰：3.351,3.311,3.246和3.177 eV,分别来自受主束缚激子的辐射复合(A°X)、自由电子到受主的发射(FA)、施主受主对的发射(DAP)以及施主受主对的第一纵向声子伴线(DAP-1LO),计算得到受主束缚能为122 meV,与理论计算结果一致。通过热扩散方式实现了ZnO薄膜的p型掺杂,解决了制约ZnO基光电器件发展的主要问题, 对ZnO基半导体材料及其光电器件的发展有重要意义。     

非掺杂ZnO薄膜中紫外与绿色发光中心

用直流反应溅射方法在硅衬底上淀积了ZnO薄膜,测量它们的光致发光(PL)光谱,观察到两个发光峰,峰值能量分别为3.18(紫外峰,UV)和2.38eV(绿峰).样品用不同温度分别在氧气、氮气和空气中热处理后,测量了PL光谱中绿峰和紫外峰强度随热处理温度和气氛的变化,同时比较了用FP-LMT方法计算的ZnO中几种本征缺陷的能级位置.根据实验和能级计算的结果,推测出ZnO薄膜中的紫外峰与ZnO带边激子跃迁有关,而绿色发光主要来源于导带底到氧错位缺陷(O_Zn)能级的跃迁,而不是通常认为的氧空 关键词： ZnO薄膜 热处理 光致发光光谱 缺陷能级     

MOCVD法生长ZnO薄膜的结构及光学特性

采用MOCVD方法在c Al2 O3衬底上生长出了具有单一c轴取向的ZnO薄膜 ,采用X射线衍射 (XRD)、Raman散射、X射线光电子能谱 (XPS)及光致发光 (PL)谱等方法对ZnO薄膜的结构及光学特性进行分析测试。XRD分析只观察到ZnO薄膜 (0 0 0 2 )衍射峰 ,其FWHM数值为 0 1 84°。Raman散射谱中 ,4 35 32cm- 1 处喇曼峰为ZnO的E2 (high)振动模 ,A1 (LO)振动模位于 5 75 32cm- 1 处。XPS分析表明 :ZnO薄膜表面易吸附游离态氧 ,刻蚀后ZnO薄膜O1s光电子能谱峰位于 5 30 2eV ,更接近Zn—O键中O1s电子结合能 (5 30 4eV)。PL谱中 ,在3 2 8eV处观察到了自由激子发射峰 ,而深能级跃迁峰位于 2 5 5eV ,二者峰强比值为 4 0∶1 ,表明生长的ZnO薄膜具有较高的光学质量     

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.     

非晶态Nb氧化物纳米薄膜可见光区的光玫发光

在低真空及亚高温(200～300℃)下.通过热氧化法在Si单晶基底上合成了呈准直阵列的椎形结构的氧化铌(NbOx)非晶结构纳米薄膜,薄膜经热处理后室温下在可见光区具有很好的光致发光.实验研究了退火温度与发光强度规律,对铌氧化物纳米薄膜的光致发光(PL)机制进行了初步分析和讨论.变功率光致发光(PL)实验有力地支持了初步讨论结果.     

ZnO/Zn界面对纳米ZnO薄膜光学性质的影响

采用氧等离子体辅助电子束蒸发金属Zn后低温退火的方法制备纳米ZnO薄膜。利用X射线衍射(XRD)谱、拉曼(Raman)谱、X射线光电子能谱(XPS)以及光致发光(PL)谱等手段,分析了退火温度及ZnO/Zn界面对样品的结构和发光性质的影响。Raman结果表明随着退火温度的升高,界面模式(Es)振动减弱并向低波数方向移动。当退火温度为400℃时,界面振动消失,Zn全部转化成具有六方纤锌矿结构的ZnO,得到化学配比的纳米ZnO薄膜。PL谱表明,经400℃退火处理的样品紫外发射最强,发光性质最好。     

Temperature dependence of excitonic luminescence from nanocrystalline ZnO films

The properties of the excitonic luminescence for nanocrystalline ZnO thin films are investigated by using the dependence of excitonic photoluminescence (PL) spectra on temperature. The ZnO thin films are prepared by thermal oxidation of ZnS films prepared by low-pressure metalorganic chemical vapor deposition (LP-MOCVD) technique. The X-ray diffraction (XRD) indicates that ZnO thin films have a polycrystalline hexagonal wurtzite structure with a preferred (0 0 2) orientation. A strong ultraviolet (UV) emission peak at 3.26 eV is observed, while the deep-level emission band is barely observable at room temperature. The strength of the exciton-longitudinal-optical (LO) phonon coupling is deduced from the temperature dependence of the full-width at half-maximum (FWHM) of the fundamental excitonic peak, decrease in exciton-longitudinal-optical (LO) phonon coupling strength is due to the quantum confinement effect.     

Fabrication and low-temperature photoluminescence spectra of Mn-doped ZnO nanowires

Mn-doped ZnO nanowires have been fabricated through a high temperature vapor-solid deposition process. The low-temperature photoluminescence spectra of the samples show that there are multipeak emissions at the ultraviolet (UV) region (about 3.4?C3.0?eV). The excitonic and phonon-assisted transitions in Mn-doped ZnO nanowires were investigated. The results show that there is an obvious oscillatory structure emission at the UV region under low temperature from 12?C125?K. The oscillatory structure has an energy periodicity about 70?meV and the oscillatory structure is mainly attributed to longitudinal optical (LO) phonon replicas of free excitons?(FX). The multipeak emissions at 12?K are attributed to a donor-bound exciton (DBX, 3.3617?eV), 1LO-phonon replicas of a free exciton (FX-1LO, 3.3105?eV), 2LO-phonon replicas of a free exciton (FX-2LO, 3.2396?eV), and 3LO-phonon replicas of a free exciton (FX-3LO, 3.1692?eV), respectively. The intensity of UV emission and the efficiency of emission from the Mn-doped ZnO nanowires are improved.     

ZnO薄膜近带边紫外发光的研究

用ZnO陶瓷靶,采用脉冲激光沉积(PLD)技术在c-Al₂O₃衬底上制备了ZnO薄膜。通过不同温度下光致发光(PL)光谱的测量,对样品的紫外发光机理进行研究。 在较低温度(10 K)下的PL光谱中,观测到一个位于3.354 eV处的束缚激子(D⁰X)发射,随着温度的升高(~50 K),在D⁰X的高能侧观测到了自由激子的发射峰。在10 K温度下,3.309 eV处出现了一个较强的发光带A,此发光带强度随着温度升高先增大然后减小,并且一直延续到室温。重点讨论了此发光带的起源,并认为A带可归属于自由电子-受主之间的复合发射。     

Ti缓冲层及退火处理对Si(111)基片上生长的ZnO薄膜结构和发光特性的影响

采用反应磁控溅射法在Si（111）基片上制备了带有Ti缓冲层的高c轴取向ZnO薄膜.通过X射线衍射分析和光致荧光光谱测量,研究了Ti缓冲层厚度和退火处理对ZnO薄膜结晶质量和光致荧光特性的影响.研究结果表明,Ti缓冲层的引入可以有效改善Si基片上ZnO薄膜的发光性能,但缓冲层存在一个最佳的厚度.薄膜应力是影响ZnO薄膜紫外荧光发射性能的重要因素,较小的残余应力对ZnO薄膜的紫外荧光发射是有利的,残余应力的存在可以改变ZnO薄膜紫外荧光发射能量.随着退火温度的增加,薄膜中的张应力增大,导致带隙宽度减小以及激子复合跃迁峰逐渐向低能方向移动. 关键词： ZnO薄膜 缓冲层 退火处理 应力分析     

Cesium doped and undoped ZnO nanocrystalline thin films: a comparative study of structural and micro‐Raman investigation of optical phonons

Undoped and cesium‐doped zinc oxide (ZnO) thin films have been deposited on sapphire substrate (0001) using the sol–gel method. Films were preheated at 300 °C for 10 min and annealed at 600 and 800 °C for 1 h. The grown thin films were confirmed to be of wurtzite structure using X‐ray diffraction. Surface morphology of the films was analyzed using scanning electron microscopy. The photoluminescence (PL) spectra of ZnO showed a strong ultraviolet (UV) emission band located at 3.263 eV and a very weak visible emission associated with deep‐level defects. Cesium incorporation induced a blue shift of the optical band gap and quenching of the near‐band‐edge PL for nanocrystalline thin film at room temperatures because of the band‐filling effect of free carriers. A shift of about 10–15 cm⁻¹ is observed for the first‐order longitudinal‐optical (LO) phonon Raman peak of the nanocrystals when compared to the LO phonon peak of bulk ZnO. The UV resonant Raman excitation at RT shows multiphonon LO modes up to fifth order. Copyright © 2010 John Wiley & Sons, Ltd.     

Excitonic polaron and phonon assisted photoluminescence of ZnO nanowires

The coupling strength of the radiative transition of hexagonal ZnO nanowires to the longitudinal optic (LO) phonon polarization field is deduced from temperature dependent photoluminescence spectra. An excitonic polaron formation is discussed to explain why the interaction of free excitons with LO phonons in ZnO nanowires is much stronger than that of bound excitons with LO phonons. The strong exciton-phonon coupling in ZnO nanowires affects not only the Haung-Ray S factor but also the FXA-1LO phonon energy spacing, which can be explained by the excitonic polaron formation.     

Photoinduced Effects in the ZnO Luminescence Spectra

The effect of intense UV irradiation on the photoluminescence (PL) spectra of ZnO powders and nanocrystalline films obtained by atomic layer deposition (ALD) was investigated. At room temperature, the behavior of the spectra under continuous UV irradiation in multiple vacuum-atmosphere cycles was studied. The changes in the intensities of exciton radiation and radiation in the “green” band region, associated with the phenomena of oxygen photodesorption and photoadsorption, are discussed. In the temperature range of 5–300 K, the effect of strong UV irradiation on the near-edge luminescence spectrum of ZnO films was studied. The nature of a new line arising in the photoluminescence spectra of an irradiated film in the region of emission of bound excitons is discussed.