射频磁控溅射沉积的ZnO薄膜的光致发光中心与漂移

利用射频磁控溅射法在n型单晶硅衬底上制备了ZnO薄膜.通过改变源气体中氩气和氧气的流量比制备了具有不同化学计量比的ZnO薄膜，并且将它们在真空中作了加热后处理来研究ZnO薄膜的光致发光特性.这些在常温衬底上沉积的薄膜可发出强的蓝光，其峰位会随氧流量的减少而发生红移.从导带底到锌缺陷形成的受主能级之间的跃迁可能是产生蓝光发射的原因. 关键词： ZnO薄膜 光致发光 退火 蓝光发射     

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。     

氧氩比对纳米ZnO薄膜蓝光发射光谱的影响

利用射频磁控溅射方法,在石英表面上制备了具有良好的c轴取向的纳米ZnO薄膜。室温下,在300 nm激发下,在450 nm附近观测到ZnO薄膜的蓝光发射谱(430~460 nm)。分析了气氛中氧气与氩气比对薄膜质量及蓝光发射光谱的影响,给出了纳米ZnO薄膜光致发光谱(PL)的积分强度和峰值强度与氧氩比关系。探讨了纳米ZnO薄膜的蓝光光谱的发射机制,初步证实了ZnO蓝光发射(2.88~2.69 eV)来自氧空位(VO)形成的浅施主能级上的电子至价带顶的跃迁。     

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     

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。     

蓝光ZnO薄膜的特性研究

采用反应溅射法在n型硅（100）衬底上制备了ZnO薄膜,分别用X射线衍射仪、原子力显微镜和荧光分光光度计对样品的结构、表面形貌和光致发光特性进行了表征。X射线衍射结果表明,实验中制备出了应变小的c轴择优取向的ZnO薄膜;原子力显微镜观察表明,薄膜表面平整,颗粒大小约为50nm,为柱状结构,颗粒垂直于硅衬底表面生长;在室温光致发光（PL）谱中观察到了波长位于434nm处的较窄的强蓝光发射峰,该蓝光峰的半峰全宽约为50meV。对蓝光峰的发光机制进行了讨论,并推断出该蓝光峰来源于电子从Zn填隙缺陷能级向价带顶跃迁。     

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。     

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。     

Si基CeO_2薄膜的发光特性

利用电子束蒸发技术在p型硅衬底上沉积了200 nm厚的CeO2薄膜样品,将样品置于弱还原气氛中高温退火后,观察到薄膜在385,418 nm以及445 nm左右出现三个明显的发光峰。结合激发光谱、吸收光谱以及XRD分析表明:CeO2薄膜在高温下容易发生失氧反应,出现Ce4+→Ce3+离子转变,Ce3+离子在紫外光的激发下,电子由O2p跃迁到5d能级,再由5d能级向4f能级跃迁,从而产生强烈的蓝紫外发射,而445 nm左右的发光峰则来自于SiO2薄膜的缺陷发光。样品选择900~1 200℃不同温度退火,并且在1 200℃下进行了不同时间的退火。研究结果显示:在1 200℃下进行2 h的退火,薄膜发光强度达到最大。     

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。     

Photoluminescence of ZnO films prepared by r.f. sputtering on different substrates

Polycrystalline ZnO films with good orientation were deposited on sapphire, quartz, Si and 7059 glass substrates by r.f. magnetron sputtering. A strong UV photoluminescence (PL) peak (located at 356 nm) and a weak blue emission peak (located at 446 nm) were observed at room temperature (RT) for the films deposited on sapphire, quartz and Si substrates when excited with 270 nm light. For the films prepared on Corning 7059 glass, only a strong 446 nm blue emission peak was found, and the PL intensity decreased with increasing oxygen pressure during films deposition. The intensity of the UV emission increased 7 and 14 times, respectively, for the films on sapphire and quartz substrates after high temperature annealing in vacuum. The UV emission originates from the inter-band transition of electrons and the blue emission is due to transition of electrons from the shallow donor level of the oxygen vacancies to the valence band.     

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.     

Structural and PL properties of Cu-doped ZnO films

Cu-doped ZnO films with hexagonal wurtzite structure were deposited on silicon (1 1 1) substrates by radio frequency (RF) sputtering technique. An ultraviolet (UV) peak at ∼380 nm and a blue band centered at ∼430 nm were observed in the room temperature photoluminescent (PL) spectra. The UV emission peak was from the exciton transition. The blue emission band was assigned to the Zn interstitial (Zn_i) and Zn vacancy (V_Zn) level transition. A strong blue peak (∼435 nm) was observed in the PL spectra when the α_Cu (the area ratio of Cu-chips to the Zn target) was 1.5% at 100 W, and ZnO films had c-axis preferred orientation and smaller lattice mismatch. The influence of α_Cu and the sputtering power on the blue band was investigated.     

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。     

Effects of substrate on surface morphology, crystallinity, and photoluminescence properties of sputtered ZnO nano films

Effects of substrate on crystallinity, surface morphology, and luminescence properties of radio frequency sputtered zinc oxide (ZnO) thin films were investigated. A variety of materials such as Si (100), Si (111), Al₂O₃, quartz, and silicon carbide (SiC) wafers were examined as substrates for deposition of ZnO thin films. The results showed smooth and uniform growth of c-axis orientation films. The thickness of the layers was about 50 nm. The average grain sizes of films were about 10, 13, and 12 nm for Si (111), quartz, and SiC samples, respectively. The deposited film on Al₂O₃ showed the largest grain size, about 500 nm. Grazing incidence x-ray diffraction patterns of the samples revealed that sputtered layers on Al₂O₃ and quartz had better crystallinity with higher peak at (002) orientation compared to Si and SiC substrates. Moreover, the Al₂O₃ sample exhibited a weak peak at position of (100) planes of ZnO too. The photoluminescence spectra of the samples showed a typical luminescence behavior with a broad UV band, including a main peak at around 388 nm and a weak shoulder peak at around 381 nm, corresponding with bound excitonic recombination and free excitonic recombination, respectively. The luminescence peak revealed that the intensity of UV emission is not necessarily dependent on the grain sizes and the micro-structural quality of ZnO films.     

Near infrared to UV dielectric functions of Al doped ZnO films deposited on c-plane sapphire substrate using pulsed laser deposition

Transparent conducting polycrystalline Al-doped ZnO (AZO) films were deposited on sapphire substrates at substrate temperatures ranging from 200 to 300 °C by pulsed laser deposition (PLD). X-ray diffraction measurement shows that the crystalline quality of AZO films was improved with increased substrate temperature. The electrical and optical properties of the AZO films have been systematically studied via various experimental tools. The room-temperature micro-photoluminescence (µ-PL) spectra show a strong ultraviolet (UV) excitonic emission and weak deep-level emission, which indicate low structural defects in the films. A Raman shift of about 11 cm⁻¹ is observed for the first-order longitudinal-optical (LO) phonon peak for AZO films when compared to the LO phonon peak of bulk ZnO. The Raman spectra obtained with UV resonant excitation at room temperature show multi-phonon LO modes up to third order. Optical response due to free electrons of the AZO films was characterized in the photon energy range from 0.6 to 6.5 eV by spectroscopic ellipsometry (SE). The free electron response was expressed by a simple Drude model combined with the Cauchy model are reported.     

Dependence of photoconductivity on the crystallite orientations and porosity of polycrystalline ZnO films

Hexagonal ZnO films deposited on quartz glass, sapphire and glass substrates by sol–gel coating are found to be randomly oriented; maximum randomness is found in the film on quartz glass substrate. All the films are ultra-violet (UV) sensitive at around 360 nm sensitivity being maximum for the film with maximum randomness in the crystallite orientations. The film on quartz showed the lowest dark current and maximum photoresponse, which is related to the lowering of the barrier heights, introduced by the adsorbed oxygen at the grain boundaries. Faster decay in photocurrent is observed for the film deposited on glass, which is attributed due to the smaller crystallite sizes with porous microstructure of the film. PACS 73.61.Ga; 68.55.Jk; 73.50.Pz     

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.     

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。     

退火对Ga_2O_3薄膜特性的影响

采用金属有机物化学气相沉积法在c面蓝宝石衬底上生长了高质量的β-Ga_2O_3薄膜,并将样品分别在真空、氧气、氮气氛围下退火30 min,研究了各类退火工艺对Ga_2O_3薄膜特性的影响,对退火所得的薄膜进行了X射线衍射、光致发光谱、紫外透射谱和原子力显微镜扫描的研究。结果表明,各类退火工艺均能够优化薄膜的晶体质量和表面形貌,同时有效改善了薄膜的光学性质。其中,氧气退火后的样品在可见光波段透射率高达83%,且吸收边更加陡峭;表面粗糙度降至0.564 nm,其表面更为平整。这些结果说明氧气退火对晶体质量的提高最为显著。氮气、真空退火的样品在光致发光谱中出现365 nm的发光峰,这是大量氧空位的存在导致的。