射频磁控溅射法制备ZnO薄膜的绿光发射

用射频磁控溅射法,在硅衬底上制备出具有良好的(002)择优取向的多晶ZnO薄膜。研究了室温下薄膜的光致发光特性,观察到显著的单绿光发射(波长为514nm)峰。在氧气中830℃高温退火后,薄膜结晶质量明显提高,绿光发射峰强度变弱;在真空中830℃高温退火后,绿光发射峰强度增加。绿光发射源于氧空位深施主能级到价带顶的电子跃近。     

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。     

A面(11-20)ZnO薄膜中杂质的偏振PL谱研究

本文通过分析A面(11-20)ZnO薄膜的低温PL(光致发光)光谱偏振特性来研究ZnO光致发光谱中杂质峰的来源。低温(4 K)下观察到476、479 nm两处新的杂质峰以及390 nm处激子峰,根据两个杂质峰的偏振特性,初步判定476nm峰来源于氧空位能级到价带轻空穴的跃迁,479 nm峰来源于氧空位价带重空穴的跃迁。     

磁控溅射制备ZnO薄膜的结构及发光特性研究

采用射频反应磁控溅射法在玻璃衬底上制备出具有c轴高择优取向的ZnO薄膜,利用X射线衍射、扫描探针显微镜及荧光分光光度法研究了生长温度对ZnO薄膜微观结构及光致发光特性的影响。结果表明,合适的衬底温度有利于提高ZnO薄膜的结晶质量;在室温下测量样品的光致发光谱(PL),观察到波长位于400 nm左右的紫光、446 nm左右的蓝色发光峰及502 nm左右微弱的绿光峰,随衬底温度升高,样品的PL谱中紫光及蓝光强度逐渐增大,同时,绿光峰的强度也表现出一定程度的增强。经分析得出紫光应是激子发光所致,而锌填隙则是引起蓝光发射的主要原因,502 nm左右的绿光峰应该是氧的深能级缺陷造成的。此外,还测量了样品的吸收谱,并结合样品吸收谱的拟合结果对光致发光机理的分析作了进一步的验证。     

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.     

RF溅射钕掺杂ZnO薄膜的结构与发光特性

通过射频磁控溅射技术在Si(111)衬底上制备了未掺杂ZnO薄膜和Nd掺杂ZnO薄膜。应用XRD分析了ZnO:Nd薄膜的晶格结构,通过AFM观察了ZnO:Nd薄膜的表面形貌。结果表明,Nd掺入了ZnO晶格中,由于Nd原子半径大于Zn原子半径,Nd以替位原子的形式存在于ZnO晶格中。ZnO:Nd薄膜为纳米多晶薄膜,表面形貌粗糙。ZnO:Nd薄膜的室温光致发光谱表明,相同条件下制备的未掺杂ZnO薄膜和Nd掺杂ZnO薄膜都出现了395nm的强紫光带和495nm的弱绿光带。我们认为,紫光发射峰窄而锐且强度远大于绿光峰,源于薄膜中激子复合;绿光峰强度较弱,源于薄膜中的氧空位(VO)及氧反位锌缺陷(OZn)。Nd掺杂没有影响ZnO:Nd薄膜的PL谱的发射峰的峰位。由于Nd3 离子电荷数与Zn2 离子电荷数不相等,为了保持ZnO薄膜的电中性,间隙锌(VZn)可以作为Nd替位补偿性的受主杂质而存在,影响ZnO薄膜的激子浓度。同时,Nd掺入使ZnO的晶格畸变缺陷浓度改变增强,因而发射峰的强度随Nd掺杂浓度不同而变化。     

溶胶-凝胶法纳米ZnO薄膜的绿光发射

利用溶胶-凝胶法制备了纳米ZnO薄膜,室温下测量了样品的光致发光谱(PL)和X射线衍射谱(XRD),观测到中心波长在523 nm附近的绿色荧光发射,研究了纳米ZnO薄膜的绿光发射机制,证实了纳米ZnO薄膜绿光可见发射带来自氧空位(Vo)形成的浅施主能级和锌空位(Vzn)形成的浅受主能级之间的复合。     

Co与Cu掺杂ZnO薄膜的制备与光致发光研究

采用溶胶-凝胶旋涂法在玻璃衬底上制备了Co, Cu单掺杂及Co,Cu共掺杂ZnO薄膜.用金相显微镜观察了Co与Cu掺杂对ZnO薄膜形貌的影响.X射线衍射（XRD）研究揭示所有ZnO薄膜样品都存在（002）择优取向,在Cu单掺的ZnO薄膜中晶粒尺寸最大.对所有样品的室温光致发光测量都观察到较强的蓝光双峰发射和较弱的绿光发射,其中长波长的蓝光峰和绿光峰都能够通过掺杂进行控制.对不同掺杂源的ZnO薄膜发光性能进行了分析,认为蓝光峰来源于电子由导带底到锌空位能级的跃迁及锌填隙到价带顶的跃迁,绿光峰是由于掺杂造成的 关键词： ZnO薄膜 溶胶-凝胶 Co Cu掺杂 光致发光     

沉淀法制备In/ZnO纳米粉及其发光特性

采用沉淀法制备In/ZnO纳米粉,通过XRD和光致发光谱等分析手段,详细讨论了不同In掺杂浓度、煅烧温度、反应物配比,以及沉淀剂种类对In/ZnO纳米粉微结构及光致发光特性的影响。实验结果表明,随着In掺杂浓度的增加,In/ZnO纳米粉的结晶性能和紫外发光强度因杂质缺陷的增多而逐渐减弱;同时观察到该发光峰位从389nm红移至419nm,这可能是由于施主能级和导带的合并,以及杂质能级的潜在波动因素的影响所致。当煅烧温度从500℃升至600℃时,晶粒尺寸逐渐变大,紫外发射强度也因结晶性的增强而逐渐增大;当温度继续升高至800℃时,结晶性的进一步提高导致紫外发射强度增强,同时由于温度的升高使得ZnO晶格中离子动能变大而更易于产生氧空位,从而导致525nm绿光发射也大大增强;当温度升高至1 000℃时,紫外发射强度由于过多的氧空位而被极大抑制,此时525nm绿光发射成为了发光主成份。随着反应物NH4HCO3/Zn(NO3)2摩尔比的增加,由于反应速率的加快,使得In/ZnO纳米粉晶粒变小,紫外发光强度下降。沉淀剂种类(NH4HCO3或NaOH)对前驱体粉末的结晶性能有着显著的影响,但对最终纳米粉产物的发光性能影响不大。     

热处理对ZnO∶Zn荧光薄膜结晶性能的影响

用热处理方法对电子束蒸发制备的ZnO∶Zn荧光薄膜分别进行400,600℃退火处理。采用X射线衍射、X射线光电子能谱、扫描电子显微镜、光致发光光谱等方法,表征了ZnO∶Zn荧光薄膜的结构、成分、形貌、发光性能。在ZnO∶Zn荧光薄膜的X射线衍射谱和扫描电子显微镜照片中,可以看出经退火处理后结晶状况大大改善,多晶结构趋于规则,晶粒更加均匀且膜层结构更加致密。在ZnO∶Zn荧光薄膜的光致发光谱中,检测到490 nm处发光峰,认为一价氧空位(VO)充当发光中心,且薄膜的光致发光强度受热处理温度的影响很大。实验表明随着退火温度的升高,薄膜的结晶程度提高,弥补了薄膜晶体表面的表面缺陷,薄膜的发光性能不断提高。     

Preparation of nanocone ZnO thin film and its aging effect of photoluminescence

In this work, a nanocone ZnO thin film was prepared by electron beam evaporation on a Si (1 0 0) substrate. The structural properties of the film were investigated by X-ray diffraction (XRD), atomic force microscopy and laser Raman scattering, respectively. The aging effect of the nanocone ZnO thin film was studied by photoluminescence spectra. The structural analyses show that the prepared ZnO thin film has a hexagonal wurtzite structure and is preferentially oriented along the c-axis perpendicular to the substrate surface. The photoluminescence spectra show that with the increase of aging time, the green emission of the nanocone ZnO thin film gradually decreases while the ultraviolet emission somewhat increases. The reason for this phenomenon is likely that the green-emission-related oxygen vacancies in the film are gradually filled up. The Raman scattering analyses also suggest that the intensity of the Raman peak related to oxygen vacancies in the nanocone ZnO thin film declines after the film is aged in air for a year. Therefore, the authors think the green emission is mainly connected with oxygen vacancy defects.     

Luminescence mechanism of ZnO thin film investigated by XPS measurement

The effects of annealing environment on the luminescence characteristics of ZnO thin films that were deposited on SiO₂/Si substrates by reactive RF magnetron sputtering were investigated by X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL). An analysis of the O 1s peak of ZnO film revealed that the concentration of oxygen vacancies increased with the annealing temperature from 600 °C to 900 °C under an ambient atmosphere. The PL results demonstrated that the intensity of green light emission at 523 nm also increased with temperature. Under various annealing atmospheres, the analyses of PL indicated that only one emission peak (523 nm) was obtained, indicating that only one class of defect was responsible for the green luminescence. The green light emission was strongest and the concentration of oxygen vacancies was highest when the ZnO film was annealed in ambient atmosphere at 900 °C. The results in this investigation show that the luminescence mechanism of the emission of green light from a ZnO thin film is associated primarily with oxygen vacancies. PACS 81.15.Cd; 81.40.Ef; 78.55.-m; 78.55.Et     

Ni掺杂ZnO薄膜的结构与光学特性研究

使用射频磁控溅射法成功制备了不同掺杂浓度（0—7at.%）的ZnO:Ni薄膜.X射线衍射的θ-2θ和摇摆曲线扫描结果表明,5at.%Ni掺杂ZnO薄膜具有沿c轴方向最佳的择优取向生长特性,（002）衍射峰向大角度方向移动揭示了Ni杂质被掺入ZnO晶格中占据Zn位.ZnO:Ni薄膜具有较好的可见光透明特性,拟合发现薄膜的光学带隙随Ni掺杂量的增加由3.272 eV线性降低到3.253 eV.未掺杂薄膜在550 nm处呈现出一个绿色发光峰,掺入Ni杂质后薄膜主要表现了以430 nm为中心的蓝色发光,分析认为它们分别源于薄膜中O空位和Zn填隙缺陷发光. 关键词： ZnO:Ni薄膜 结构特性 光学带隙 光致发光     

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     

两步溶液法制备亚微米ZnO棒阵列及其退火后的发光

通过改变溶液浓度、酸碱度等生长条件,用两步化学溶液沉积法在玻璃衬底上制备出有序排列的亚微米级ZnO棒阵列,棒的截面呈正六边形,直径约为200~500nm。测量了样品的XRD谱和扫描电镜像,证明这些样品都是六方纤锌矿结构的ZnO单晶,且以[002]方向择优生长。将样品退火前后的PL光谱进行比较分析,发现退火后样品的发射光谱中紫外峰消失而长波段的红色发光峰红移并且增强(峰位由630nm左右移到720nm),而其激发光谱中的室温激子激发峰也增强。当退火时间增加到6h后,出现了由430nm的蓝峰和505nm绿峰组成的宽谱带蓝绿色发射。并对发光机理进行了讨论。     

Photoluminescence and positron annihilation spectroscopic investigation on a H(+) irradiated ZnO single crystal

Low temperature photoluminescence and room temperature positron annihilation spectroscopy have been employed to investigate the defects incorporated by 6?MeV H(+) ions in a hydrothermally grown ZnO single crystal. Prior to irradiation, the emission from donor bound excitons is at 3.378?eV (10?K). The irradiation creates an intense and narrow emission at 3.368?eV (10?K). The intensity of this peak is nearly four times that of the dominant near band edge peak of the pristine crystal. The characteristic features of the 3.368?eV emission indicate its origin as a 'hydrogen at oxygen vacancy' type defect. The positron annihilation lifetime measurement reveals a single component lifetime spectrum for both the unirradiated (164?±?1?ps) and irradiated crystal (175?±?1?ps). It reflects the fact that the positron lifetime and intensity of the new irradiation driven defect species are a little higher compared to those in the unirradiated crystal. However, the estimated defect concentration, even considering the high dynamic defect annihilation rate in ZnO, comes out to be ～4?×?10(17)?cm(-3) (using SRIM software). This is a very high defect concentration compared to the defect sensitivity of positron annihilation spectroscopy. A probable reason is the partial filling of the incorporated vacancies (positron traps), which in ZnO are zinc vacancies. The positron lifetime of ～175?ps (in irradiated ZnO) is consistent with recent theoretical calculations for partially hydrogen-filled zinc vacancies in ZnO. Passivation of oxygen vacancies by hydrogen is also reflected in the photoluminescence results. A possible reason for such vacancy filling (at both Zn and O sites) due to irradiation has also been discussed.     

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.