多孔硅的不同制备方法及其光致发光

目前，多孔硅的制备方法已有许多种。我们用电化学方法、光化学方法和化学方法分别制备出了室温下在可见光区发射光荧光的多孔硅。通过对实验装置、制备条件、样品的成膜过程及其光致发光(PL)光谱的比较，分析解释了其成膜机理和PL光谱的特点。认为虽然这三种方法都可以制备出多孔硅，但相比较而言，通过电化学方法制备的样品最均匀、实验的可重复性较强、因而电化学方法是被普遍采用的一种方法。另外在多孔硅的成膜过程中，自由载流子起着至关重要的作用。     

闪烁晶体碘化铯在紫外光和X射线激发下的发光特性

室温下掺铊碘化铯(CsI∶Tl)晶体的吸收谱在230~320 nm范围内有3个特征峰:310 nm(4 eV)、270nm(4.6 eV)和245 nm(5.1 eV)。采用这3种不同激发能量(对应不同激发机制)的近紫外(UV)光激发得到的荧光(PL)光谱相同。这些PL谱与钨(W)靶X射线激发的辐照致荧光(RL)谱也类似。经分峰计算,PL和RL均含有4种熟知的3.1 eV(400 nm)、2.55 eV(486 nm)、2.25 eV(550 nm)和2.1 eV(590 nm)发光组分,但RL中2.1 eV组分高于PL,同时2.55 eV组分又低于PL。分析认为,这一差异来自于X射线对晶体的辐照损伤Tl+Va+、Tl0Va+,相关的2.1 eV吸收峰与2.55 eV发光带重叠。结果表明:X射线比紫外光更易产生损伤从而影响晶体CsI∶Tl的发光特性。     

Cu掺杂氧化锌薄膜的发光特性研究

通过射频反应溅射法在Si（111）衬底上制备了不同Cu掺杂量的ZnO薄膜.室温下测量了样品的光致发光（PL）谱，所有样品的PL谱中均观察到435?nm左右的蓝光发光带，该发光带的强度与Cu掺杂量和溅射功率有关.当溅射功率为150?W，Cu掺杂量为2.5%时，ZnO薄膜的PL谱中出现了较强的蓝光双峰，而溅射功率为100?W，Cu掺杂量为1.5%时，出现了位于437nm（2.84eV）处较强的蓝光峰，后者的取向性较好.还研究了掺杂量和溅射功率对发光特性的影响，并对样品的蓝光发光机制进行了探讨. 关键词： ZnO薄膜 Cu掺杂 光致发光谱 射频反应共溅射     

8-羟基喹啉锂的合成、表征及发光特性

通过液相反应合成了高纯度、高产率的8-羟基喹啉锂(Liq)粉体,制备了Liq薄膜,通过IR光谱、UV吸收谱、X射线衍射谱、荧光光谱对其结构和性能进行了表征,并利用UV吸收谱、电化学循环伏安法、荧光光谱研究了它的电子能级结构。结果表明,pH值和溶剂对Liq的合成有很大影响,而温度的影响不大。利用真空热蒸镀很容易制备高质量、无定性薄膜,Liq的熔点365℃,具有很高的热稳定性。Liq的LUMO能级2．94eV,HOMO能级5．95eV,光学禁带宽度3．01eV．在363nm紫外光的激发下。产生发光峰在452nm附近、半峰全宽为69．4nm的蓝光发射,发光亮度高,色纯度高。由于电子与声子的强耦合作用以及带隙态的影响,产生了5424cm^-1的斯托克斯频移。     

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。     

CVD两步法生长ZnO薄膜及其光致发光特性

用CVD两步法在常压下于p型Si(100)衬底上沉积出具有较好择优取向的多晶ZnO薄膜。在325nm波长的光激发下,室温下可观察到显著的紫外光发射(峰值波长381nm)。高温退火后氧空位缺陷浓度增加,出现了一个450~600nm的绿光发光带,发光峰值在510nm。作为比较,用一步法生长的ZnO薄膜结晶质量稍差。在其PL谱中不仅有峰值波长389nm的紫外发射而且还出现了一个很强的蓝光发光中心(峰值波长437nm),退火后同样产生绿光发光带。对这两种绿光发光带的发光机制进行了研究,认为前者源于VO,而后者与O_Zn有密切的关系。     

低束流Nd3+注入硅基薄膜结构及光致发光的研究

采用金属蒸气真空弧离子源（MEVVA）制备了掺Nd^3 硅基薄膜材料。用扫描电镜和X射线衍射观测了表面形貌及物相结构随注入条件、退火温度的变化，样品经1000℃退火处理形成NdSi相钕硅化合物。测试了样品的光致荧光谱，在254nm（－5.0eV）光激发下获得了紫蓝光区（410－430nm）和红光区（746nm）蒌光发射，随着退火温度的升高，荧光强度增大。746nm红光光谱显示了Nd^3 特征光发射跃迁（^4F7/2,^4S3/2→^4I9/2），讨论了注入层结构与荧光发射的相关性。     

多孔硅在30~180℃温区光致发光谱的研究

对长期存放在空气中的多孔硅样品和即时制备的多孔硅样品分别在室温~180℃下进行了光致发光（PL）温度效应的研究.两类样品的PL呈现不同的变化规律.前者的PL还表现为双峰,且长波PL峰随温度升高蓝移;后者的PL表现为单峰,且PL峰位随温度升高红移.基于量子限制效应对后者进行了解释;而前者难以用分立的量子限制和表面发光中心模型来解释,实验结果表明两种机制之间可能有较复杂的耦合效应发生.     

掺AlZnO纳米线阵列的光致发光特性研究

采用化学气相沉积方法，以金做催化剂，在Si (100)衬底上制备了掺AlZnO纳米线阵列.扫描电子显微镜(SEM)表征发现ZnO纳米线的直径在30nm左右.X射线衍射(XRD)图谱上只存在ZnO的(002)衍射峰，说明ZnO纳米线沿c轴择优取向.掺AlZnO纳米线阵列的室温光致发光(PL)谱中出现了3个带边激子发射峰：373nm，375nm，389nm.运用激子理论推算出掺AlZnO纳米线的禁带宽度为3.343eV ，束缚激子结合能为0.156eV；纯ZnO纳米线阵列PL谱中3个带边激子发射 关键词： 光致发光 化学气相沉积(CVD) 激子 ZnO纳米线阵列     

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1h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3.177eV,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122meV,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。     

非晶氧化硅薄膜带尾发光特性

采用等离子体增强化学气相沉积技术,通过改变CO2流量制备了不同氧含量的非晶氧化硅薄膜。利用紫外可见吸收谱、傅里叶红外吸收谱和稳态/瞬态光致发光谱等技术研究了薄膜的微观结构和光学特性。实验结果表明,随着氧含量的增加,薄膜的带隙增大,光致发光强度增加、峰值朝高能方向移动、光谱半峰全宽展宽。时间分辨光谱显示薄膜发光峰值处的衰减时间随氧含量的增加从6.2ns单调增加到21ns,而同一样品的发光寿命随发射波长能量增加而减小。综合分析光学吸收、发射及发光衰减特性表明,薄膜的发光机制主要归结为非晶材料带尾态之间的辐射复合。     

Effect of contact with air on the photoluminescence spectrum of porous silicon

A study has been made of the transformation of photoluminescence (PL) spectra of porous silicon (PS) induced by its ageing, including the early stages of contact with air. The sample was prepared under conditions that minimized this contact, and spectral measurements were carried out in a high vacuum or in liquid nitrogen. The PS PL spectra obtained under continuous measurement in high vacuum are always dominated by one emission band of PS nanoelements, which shifts toward shorter wavelengths with ageing by 150 nm. At 80 K, the band intensity is considerably higher than at 300 K, and this difference grows with ageing. Exposure of a sample to air for a few tens of seconds is long enough to strongly transform its time-resolved PL spectra, which is evidence of a change in the sample surface. The effect of immersion of PS samples in liquid nitrogen on PL spectra is associated not only with their cooling, but also with the field of adsorbed nitrogen molecules, whose influence becomes weaker with increasing thickness of the oxidized near-surface layer. The variation of the spectral properties and kinetics of the long-wavelength PS PL band with temperature, medium (liquid nitrogen or vacuum), and exposure time suggest that these factors affect carrier migration between silicon nanoelements.     

光声谱研究多孔碳化硅的能带特性

报道了用UV光照射和不用UV光照射条件下形成的p型α PSC以及原始SiC的光声光谱（PAS）.从光声Rosenwaig Gersho理论出发，计算出多孔SiC的吸收系数与能量的关系，得到多孔SiC的能隙低于原始SiC的能隙，并深入分析了能隙的变化原因，同时，对吸收边附近的吸收情况进行了讨论. 关键词： 光声光谱 多孔碳化硅 能隙     

多孔硅的表面碳膜钝化

报道对多孔硅（ＰＳ）进行碳膜（ＣＦ）钝化处理的结果。红外吸收光谱表明,经钝化处理样品的表面由Ｓｉ－Ｃ、Ｓｉ－Ｎ和Ｓｉ－Ｏ键所覆盖;荧光我谱表明,经钝化处理的样品较未处理的样品发光强度提高４￣４．５倍,且发光峰位明显蓝移;存放实验显示,经钝化处理的样品发光强度稳定、发光峰位不变。这些结果表明正丁胺可以在多孔硅表面形成优良的钝化碳膜,是一种十分有效的多孔硅后处理途径。     

532 nm纳秒激光辐照下的单晶硅表面微结构及荧光特性

采用Nd:YAG纳秒脉冲激光对单晶硅在空气中进行辐照,研究了表面微结构在不同能量密度和扫描速度下的演化情况。扫描电子显微镜测量表明,激光在相对较低能量密度下辐照硅表面诱导出鱼鳞状波纹结构,激光能量密度相对较大时,诱导出絮状多孔的不规则微结构。光致荧光谱（PL）表明,激光扫描区域在710 nm附近有荧光发射。用氢氟酸腐蚀掉样品表面的SiOx后,荧光峰的强度显著降低,说明SiOx在光致发光增强上起重要作用。能量色散X射线谱（EDS）表明氧元素的含量随激光能量密度的增大而增加。研究表明:纳秒激光的能量密度和扫描速度对微结构形成起着决定性作用,改变了硅材料表面微结构尺寸,增大了光吸收面积; 氧元素在光致发光增强上起重要作用,微构造硅和SiOx对光致荧光的发射都有贡献。     

多孔硅的制备条件对其光致发光特性的影响

不同的实验条件下制备的多孔硅的光致发光(PL)特性是不同的,这是许多研究产生分歧的主要原因。对比分析了阳极氧化电流密度、阳极氧化时间、溶液浓度以及自然氧化时间对多孔硅光致发光光谱的影响。认为在一定的范围内,多孔硅的发光峰位会随电流密度的增大而蓝移,要获得较强的发光,需要选择合适的电流密度;随着腐蚀时间的延长,多孔硅的发光峰位也发生蓝移。当HF酸的浓度较小时,峰位随浓度的增大表现为向低能移动;而当HF酸的浓度较大时,峰位随浓度的增大则表现为移向高能。多孔硅在空气中自然氧化,其发光峰位发生蓝移,而发射强度随放置时间的延长而降低。并用量子限制模型和发光中心模型对实验结果进行解释。     

MOCVD法制备的p-ZnO/n-SiC 异质结器件及其电致发光性能

采用光辅助金属有机化学汽相沉积(PA-MOCVD)法在n-SiC(6H)衬底上制备出As掺杂的p型ZnO薄膜,并制备出相应的p-ZnO:As/n-SiC异质结器件。X射线衍射(XRD)和光致发光(PL)测试表明,ZnO薄膜具有较好的结构和光学特性。电流-电压(I-V)测试结果表明,该型异质结器件具有良好的整流特性,开启电压为5.0 V,反向击穿电压约为-13 V。正向偏压下,器件的电致发光(EL)谱表现出两个分别位于紫外和可见光区域的发光峰,通过和ZnO、SiC的PL谱对照,证实异质结器件的发光峰来源于ZnO侧的辐射复合。     

Tuning the cathodoluminescence of porous silicon films

We have obtained intense cathodoluminescence (CL) emission from electron beam modified porous silicon films by excitation with electrons with kinetic energies below 2 keV. Two types of CL emissions were observed, a stable one and a non-stable one. The first type is obtained in well-oxidized samples and is characterized by a spectral peak that is red shifted with respect to the photoluminescence (PL) peak. The physically interesting and technologically promising CL is however the CL that correlates closely with the PL. Tuning of this CL emission was achieved by controlling the average size of the nanostructure thus showing that the origin of this CL emission is associated with the quantum confinement and the surface chemistry effects that are known to exist in the porous silicon system. We also found that the electron bombardment causes microscale morphological modifications of the films, but the nanoscale features appear to be unchanged. The structural changes are manifested by the increase in the density of the nanoparticles which explains the significant enhancement of the PL that follows the electron irradiation.     

热退火、激光束和电子束等作用对纳米硅制备及其局域态发光特性的影响

在纳米晶体硅制备的过程中, 晶化处理是影响和提高纳米硅发光效率的重要制备环节. 热退火、激光退火和电子束辐照是使纳米硅样品晶化的不同方式. 实验表明: 选取适当的晶化方式和参量对制备纳米硅晶体结构至关重要, 特别是在制备硅量子点和量子面的过程中控制好参量, 可以得到较高的发光效率. 有趣的是, 在实验中发现: 当晶化时间较短(如低于20 min)时, 可以获得较好的纳晶硅结构(如量子点结构), 对应于较好的纳晶硅光致发光(PL)和掺杂局域态发光; 当晶化时间较长(如超过30 min)时, 纳米晶体硅结构被破坏, 致使PL谱逐渐减弱与消失. 结合热退火、激光退火和电子束辐照对纳米硅晶化过程, 本文建立起晶化时间对纳米硅局域态发光影响机理的物理模型, 解释了晶化时间对纳米硅局域态发光的影响.     

Quenching of porous silicon photoluminescence by molecular oxygen and dependence of this phenomenon on storing media and method of preparation of pSi photosensitizer

The quenching of porous silicon photoluminescence (pSi PL) by molecular oxygen has been studied in different storing media in an attempt to clarify the mechanism of the energy transfer from the silicon photosensitizer to the oxygen acceptor. Luminescent materials have been prepared by two methods: electrochemical anodizing and chemical etching. Different structural forms were used: porous layers on silicon wafer and two kinds of differently prepared powder. Dry air and liquid water were employed as storing media; quenching behaviour was under observation until total degradation of quenching properties. Singlet oxygen molecules generation through energy transfer from photoluminescent pSi was the only photosensitizing mechanism observed under dry gas conditions. This PL quenching process was preferentially developed at 760 nm (1.63 eV) that corresponds to the formation of the ¹Σ singlet oxygen state. Oxidation of the pSi photosensitizer was the main factor that led to its total deactivation in a time scale of few weeks. Regarding water medium, different photosensitizing behaviour was observed. In watery conditions, two preferred energy levels were found: the one detected in dry gas and another centred at approximately 2.2 eV (550 nm). Formation of reactive oxygen species (ROS) different from singlet oxygen, such as superoxide anion or superoxide radical, can be responsible for the second one. This second quenching process developed gradually after the initial contact of pSi photosensitizer with water and then degraded. The process lasted only several hours. Therefore, functionalization of the pSi photosensitizer is probably required to stabilize its PL and quenching properties in the watery physiological conditions required for biomedical applications.