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     

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.     

赝能隙导致的YBa2(Cu1－xMx)3O7-δ(M=Co,Zn)薄膜的输运性质异常

报道了两类典型元素替代的超导Y123相体系-YBa2(Cu1-xCox)3O7-δ(x=001,002)和YBa2(Cu1-yZny)3O7-δ(y=0005,0010)薄膜的电阻率温度特性(ρ(T))和Hall效应(RH(T)).研究表明,Co掺杂的Y123相体系十分类似于氧欠掺杂的情况,对Co掺杂的薄膜样品,由电阻率温度特性定义的赝能隙打开的温度T分别为193和225K.而Zn掺杂的样品没有观察到赝能隙打开对电阻率温度特性的影响.由Hall效应的测量和Hall角(cotθH)定义了另一个特征温度T0, 关键词： 赝能隙 Y123相 Hall效应     

铬掺杂氧化锌薄膜的超声喷雾法制备及其光学与磁学性质

用注射超声喷雾法将前驱体由针管直接送入超声喷头内,在石英基板上制备Zn_(1-x)Cr_xO(x=0.0,0.01,0.03,0.05)薄膜。采用X射线衍射仪、扫描电子显微镜、荧光光谱仪、紫外-可见分光光度计、振动样品磁强计(VSM)等对薄膜的结构、光学和磁学性质进行测量。实验结果表明,未掺杂的ZnO薄膜为六角纤锌矿结构,沿着c轴(002)择优取向,而Cr掺杂抑制了薄膜的c轴择优取向性;掺杂后的薄膜平均晶粒尺寸均增大,且当x=3%时,晶粒尺寸最大,达31.4nm。扫描电镜(SEM)下薄膜呈球形颗粒状,并且在x=5%下,薄膜出现了长条状的微观形貌。Cr掺杂使样品的光致发光谱(PL)发生了很大的变化:未掺杂的样品的PL谱在378nm处存在一个紫外发射峰,对应于550nm附近还存在一个由于缺陷态引起的绿光发射峰;掺Cr样品只有在350~550nm的很宽的范围内存在一个发射峰,对其进行高斯拟合后,发现掺Cr量为x=1%,3%,5%下样品均存在V_(Zn)(锌空位)、Zn_i(Zn间隙位)、V_(Zn)~-(带一个电子的锌空位)内部缺陷态,且当x=3%时,V_(Zn)最多。Cr的掺杂使得薄膜的带隙增大,并且x=3%时,禁带宽度最大,达到3.374eV。掺Cr的三个样品均具有室温铁磁性,且x=3%样品的磁化强度最大,其与V_(Zn)(锌空位)最大相对应,验证了Cr~(3+)和V_(Zn)的缺陷复合体是ZnO∶Cr样品具有稳定的铁磁有序的最有利条件的理论预测。     

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     

退火对多晶ZnO薄膜结构与发光特性的影响

用射频反应溅射法在Si（111）衬底上制备了C轴取向的多晶ZnO薄膜，通过不同温度的退火处理，研究了退火对多晶ZnO薄膜结构和发光特性的影响.由x射线衍射得知，随退火温度的升高，晶粒逐渐变大，薄膜中压应力由大变小至出现张应力.光致发光测量发现，样品在430nm附近有一光致发光峰, 峰的强度随退火温度升高而减弱，联合样品电阻率随退火温度升高而逐渐变大的测量及能级图，推测出ZnO薄膜中的蓝光发射主要来源于锌填隙原子缺陷能级与价带顶能级间的跃迁. 关键词： ZnO薄膜 退火 光致发光 射频反应溅射     

电泳沉积法制备的Zn_(1-x)Cu_xO薄膜的结构及阻变性能

采用电泳沉积法在FTO导电玻璃基片上制备Zn_(1-x)Cu_xO薄膜,并对其微观结构、光致发光谱、伏安特性、保持特性和转换电压分布进行探讨。PL谱表明,Cu掺杂在禁带中引入深受主能级,降低氧空位浓度,导致ZnO薄膜的紫外发光、蓝光发光和绿光发光峰强度降低。所得薄膜的晶粒细小、致密、均匀,具有稳定的双极性阻变特性,开关比R_(off)/R_(on)最高达到10~5,其低阻态(LRS)和高阻态(HRS)的阻变机理分别符合欧姆定律和空间电荷限制传导理论。器件经100次循环测试后开关比无明显变化,呈现出较为良好的抗疲劳特性。Cu掺杂对LRS影响不大,但显著改善了HRS的分散性以及转换电压V_(SET)的分散性。当Cu掺杂量x=0.04时,器件表现出良好的综合性能:R_(off)≈10~6Ω,R_(off)/R_(on)≈10~4,V_(SET)介于0.4~3.03 V之间。     

铜位锌替代对DyBa_2Cu_3O_(7-δ)体系超导电性的影响

利用X射线衍射(XRD)技术对DyBa2Cu3-xZnxO7-δ(x=0.0~0.4)系列样品的晶体结构进行探测,研究体系相结构的掺杂效应。结果发现,在整个掺杂范围体系保持了正交相的晶体结构。采用四引线法对掺杂样品DyBa2Cu3-xZnxO7-δ的超导电性能进行了系统测量,发现随着Zn掺杂量的增加,样品的超导转变温度总体呈明显降低趋势,分析了铜位锌掺杂对超导电性抑制的原因。     

退火处理对LaAlO_3薄膜发光特性的影响

在室温下,采用射频磁控溅射法在p-Si(100)衬底上制备了铝酸镧(LaAlO3)薄膜,分别在800℃,900℃和950℃下进行退火处理。利用X射线衍射(XRD)仪、原子力显微镜(AFM)、荧光分光光度计等研究了不同温度退火处理对LaAlO3薄膜结构、表面形貌及光学性质的影响。研究结果表明,LaAlO3薄膜样品在900℃开始由非晶向晶体转变,说明高温退火有利于提高结晶质量。光致发光(PL)谱测量发现样品在368,470nm位置处分别出现发光峰,各峰的强度随退火温度的升高逐渐增强,但峰位基本保持不变。根据吸收光谱和缺陷能级图,推测出368nm紫外光峰来源于电子从氧空位形成的缺陷能级到价带顶能级的跃迁,470nm附近的蓝光峰归因于电子从负价AlLa错位缺陷能级到价带顶能级的跃迁。     

磁性和非磁性元素掺杂的自旋梯状化合物Sr_(14)(Cu_(0.97)M_(0.03))_(24)O_(41)(M=Zn,Ni,Co)的结构和电输运性质

利用固相反应法制备了Sr14Cu24O41及其系列B位掺杂Sr14(Cu0.97M0.03)24O41(M=Zn,Ni,Co)的样品.X射线衍射分析显示,所有样品均为纯相,晶格常数a与c没有明显的变化;Zn掺杂样品晶格常数b没有明显变化,而Ni,Co掺杂样品晶格常数b分别稍有增加.选区电子衍射研究揭示:磁性元素Ni,Co及非磁性元素Zn掺杂,可能主要替代了Sr14Cu24O41结构中自旋链上的Cu原子,从而影响了自旋链上的dimer排列,破坏电荷有序超结构.电输运测量显示:Zn2+,Ni2+,Co3+离子掺杂样品的电阻率降低,但仍体现半导体行为,所有的掺杂样品都存在一个渡越温度Tρ,当TTρ时,其导电机理是以单空穴热激发导电占主要地位,在TTρ时,配对的局域化空穴的一维变程跳跃导电占主要优势;在相同的掺杂量下,非磁性元素Zn掺杂对电阻率值的影响大于磁性元素Ni,Co掺杂的影响,而磁性元素Ni,Co掺杂对渡越温度Tρ的影响大于非磁性元素Zn掺杂的影响.     

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.     

Influence of excitation light wavelength on the photoluminescence properties for ZnO films prepared by magnetron sputtering

Highly orientated polycrystalline ZnO films were deposited on sapphire, silicon and quartz substrates at room temperature by r.f. magnetron sputtering. Different photoluminescence (PL) spectra were observed when excited with different wavelength light. A UV emission peak (356 nm) and a blue peak (446 nm) were generated for the films on sapphire, silicon and quartz substrates, and only the 446 nm blue emission appeared for the films on glass substrates when the wavelength of the excitation light was 270 nm. With increasing the wavelength of the excitation light up to 300 and 320 nm, the UV emission disappeared for films on various substrates and the wavelength of the PL peaks increased up to 488 and 516 nm, respectively. When the wavelength of the excitation light increased to 398 nm, the PL spectrum becomes a wide band that is consistent with three emission peaks.     

纳米ZnO薄膜的光致发光性质

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)、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薄膜呈多晶状态,具有六角纤锌矿晶体结构和良好的C轴取向．观察到二个荧光发射带,中心波长分别位于395 nm的紫带、524 nm的绿带和450 nm附近的蓝带．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;450 nm附近的蓝带来自电子从VO的浅施主能级到价带顶或锌填隙(Zni) 到价带顶或导带底到VZn的浅受主能级的复合．     

Effect of solution concentrations on crystal structure,surface topographies and photoluminescence properties of ZnO thin films

Zinc oxide thin films were deposited on silicon substrates via hydrothermal method. Microstructures, surface topographies and optical properties of ZnO thin films were systematically investigated by X-ray diffraction, atomic force microscopy and fluorescence spectrophotometer. The mean grain size and surface roughness of the thin films decrease first and then increase with increasing the concentration of zinc nitrate hexahydrate. The photoluminescence spectra of ZnO thin films, excited by the 240, 320, 360, 380 and 400 nm excitation wavelength, were investigated in detail. Based on our analysis, it can be noted that mechanisms of the ultraviolet, violet and blue emissions are attributed to the transitions from the localized levels below the conduction band, zinc vacancy, interstitial zinc and extended interstitial zinc levels to the valance band, respectively. Blue–violet emissions of ZnO have great potential in light emitting and biological fluorescence labeling applications.     

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。     

Structural and optical properties of ZnO thin films on (111) CaF2 substrates grown by magnetron sputtering

ZnO thin films were grown on (111) CaF₂ substrates by magnetron sputtering at room temperature. Structural and optical properties of the ZnO thin films were studied. XRD analysis showed that the ZnO thin films had the (002) preferential orientation. The transmittance of ZnO thin films was over 80% in the visible range. The optical band gap of the ZnO thin films was 3.26 eV. The optical constants (n,k)$(n,k)$ of the ZnO thin films in the wavelength range 300–1000 nm were obtained by infrared spectroscopic ellipsometry measurement. PL spectra of ZnO thin films showed strong UV near-band-edge emission peak at 376.5 nm and weak visible red emission at 643.49 nm using He–Cd laser as the light source, using a synchrotron radiation light source PL spectra showed three emission peak at 320 nm, 410 nm and 542 nm respectively.     

退火对溶胶-凝胶法制备的ZnO薄膜结构和光致发光的影响

采用溶胶-凝胶法在n-Si(100)衬底上制备ZnO薄膜并从三个方面对其研究。X射线衍射结果表明,在含氧气氛中退火的ZnO薄膜为多晶六角纤锌矿结构,有明显的c轴择优结晶取向;退火时间的长短和温度的高低对结晶取向性和粒径均有较大影响,通过进一步的研究发现最佳处理温度在500℃左右。用扫描电子显微镜观察样品的表面和侧面形貌,晶体的生长比较均匀,粒径平均在70~160nm范围内,与XRD测量结果相一致。室温下ZnO胶体的光致发光谱表明,随着胶体老化时间的延长,胶体的紫外峰位发生了蓝移。室温下ZnO薄膜的光致发光谱表明,紫外部分的发光峰位在365,390nm,发光强度较强;在可见光区的发光强度相对较弱,但是还没有被氧完全抑制掉。     

Hydrothermal synthesis and optical properties of full-color-emission ZnS:Cu, Al nanocrystals

ZnS:Cu, Al nanocrystals were synthesized by a hydrothermal method at 200 degrees C and their optical properties were studied. The analysis of XRD and TEM show that the spherical-like nanocrystals had a grain size of approximately 15 nm and were well dispersed, with a zinc blende structure. The energy dispersive X-ray spectroscopy (EDX) and atomic absorption spectrometry were applied to the analysis of S, Zn and Cu content in the sample. The results proved that a large number of zinc vacancies exist and Cu is incorporated into the sample lattice. The photoluminescence (PL) spectra were investigated. The PL mechanism is discussed. The excitation spectrum is broad. Under 337 nm excitation the sample emits bright green light. Under 370-410 nm excitation the sample emits white light. The broad emission spectra are almost coincident with any excitation wavelength of between 370 and 410 nm making them attractive as conversion phosphors for LED applications and full-color fluorescence display devices. The emitted white light under 375 nm excitation was found to be the result of blue, green, and orange emission bands. For Cu/Zn, Cu/Al and S/Zn molar ratios of 3 x 10(-4), 2 and 3, respectively, the near blue white light can be observed with the naked eye in daylight.