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     

Co，Cu共掺杂ZnO薄膜的结构及发光特性

采用电子束蒸发沉积成膜工艺在单晶Si(111)衬底上制备出Co,Cu共掺杂的Zn0.85-xCo0.15CuxO(x=0,0.04,0.06)多晶膜。采用X射线衍射(XRD)研究了Co、Cu掺杂对其微结构的影响;室温下测量了Zn0.85-xCo0.15CuxO薄膜的光致发光谱,发现随着Cu掺杂量的增加,样品发光增强,当Cu掺杂x=0.06时,Zn0.85-xCo0.15CuxO薄膜的PL谱中出现了较强的双峰蓝光发射;分析了掺杂含量对其发光性能的影响,并对样品的发光机制进行了探讨,并推断出蓝光峰来源于电子由导带底到锌空位(VZn)能级的跃迁及锌填隙(Zni)能级到价带顶的跃迁。     

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。     

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.     

N掺杂ZnO薄膜的荧光特性研究

以N2为掺杂源,通过改变O2∶N2比,利用射频磁控溅射法在玻璃衬底上制备了具有[002]择优取向的N掺杂ZnO薄膜,研究了ZnO薄膜的光致发光谱随着N掺入量的不同而变化的规律.结果表明,薄膜主衍射峰为402 nm处的发光峰;由于N掺杂量的不同,有的薄膜在445 nm和524 nm处也有发光发存在,但随着薄膜N含量的不同,其发光峰强度明显不同,其峰位也发生了相应的红移或者蓝移.当O2∶N2为10∶ 15时,制备的薄膜N掺杂量最大,光学性能最好,此工艺为研究ZnO薄膜的缺陷类型及导电类型提供了重要的研究参考.     

Na-Mg共掺杂ZnO薄膜的结构和光学性质

利用溶胶-凝胶法,在普通载玻片上使用旋转涂膜技术制备了具有c轴择优取向生长的Na-Mg共掺杂的ZnO薄膜。用XRD、SEM、光致发光(PL)及透射光谱对薄膜样品进行了表征。结果表明:Na-Mg共掺杂有利于ZnO薄膜的c轴择优取向生长,并且随着Na+掺杂浓度的增加,晶粒尺寸先增大后减小;通过比较不同掺杂浓度ZnO薄膜的PL谱,推测发光峰值位于380nm的紫外发射与ZnO的自由激子复合有关;发现掺入Mg的确能使ZnO禁带宽度增大,掺杂组分为Na0.04Mg0.2Zn0.76O时,其PL谱只有一个很强的紫光发射峰,其近带边紫外光发射强度较未掺杂的ZnO增强了近10倍,极大地提高了薄膜紫外发光性能;并且随Na+浓度增加薄膜透光性减弱。     

反应溅射氧化锌薄膜的结构特点及性质

以金属Zn(纯度为99.99%)作为靶材,采用离子束反应溅射法在玻璃衬底上溅射沉积了一系列ZnO薄膜样品。通过对薄膜样品X射线衍射(XRD)谱的分析,发现尽管溅射条件不同,但是ZnO薄膜只沿(0002)晶面取向生长。衬底温度和溅射气体的氧分压对薄膜沿c轴取向生长有影响,其中衬底温度的影响较明显。溅射过程中发现衬底温度为360℃最适合(0002)晶面的生长,在此温度下溅射获得了完全沿c轴取向生长且衍射峰最强的ZnO薄膜。室温下测量了ZnO薄膜的发射光谱,发现薄膜在紫外区(364nm附近)、蓝绿区(470nm附近)有较强的发光峰,在紫光区(398nm附近)、蓝光区(452nm附近)和红外区(722nm附近)有较弱的发光峰。ZnO薄膜在空气中退火,对薄膜的结构、发光和电学性质都有一定影响。合适的退火温度可以促进薄膜沿c轴的取向生长;退火后ZnO多晶薄膜的晶粒比未退火的略大;退火使部分发光峰的位置发生偏移并使薄膜的发光强度增强;退火使薄膜的电阻率显著增大,薄膜的电阻率随氧分压的增大而增大。     

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。     

RF磁控溅射条件对ZnO薄膜结构的影响

采用RF磁控溅射法在Si（001）衬底上制备ZnO薄膜。研究发现了工作中溅射频率、氧气和氩气流量比对样品结构的影响。样品的XRD图谱显示了强的（002）ZnO衍射峰，表明ZnO薄膜为c轴高取向生长。比较不同条件下制备的ZnO薄膜，研究发现当氧气和氩气的流量比相同时，随着溅射功率的增加，样品的（002）衍射峰增强，半高全宽变小。而当溅射功率相同时，随着氧气和氩气的流量比增加，样品的（002）衍射峰也增强，半高全宽同样变小。此外，本文还分析了溅射工艺和薄膜晶体质量之间关系，发现在相同的功率条件下，溅射率低时晶粒尺寸更大且薄膜的结晶性更好。     

射频磁控溅射法制备的Eu掺杂ZnO薄膜的结构及其发光性质

用射频磁控溅射法在石英衬底上制备了ZnO:Eu3+薄膜,通过X射线衍射仪、扫描电子显微镜和荧光光谱仪测试了薄膜结构、形貌以及发光性能,重点考察了溅射功率和退火工艺对其组织结构和发光性能的影响.结果表明:样品均呈现ZnO的六角纤锌矿结构,增大溅射功率有利于形成ZnO的c轴择优取向;增大溅射功率以及高温退火会使晶粒尺寸增大...     

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.     

Structural and photoluminescent properties of ZnO films deposited by radio frequency reactive sputtering

Zinc oxide films with c-axis preferred orientation were deposited on silicon (100) substrates by radio frequency (RF) reactive sputtering. The properties of the sam- ples were characterized by X-ray diffractometer, X-ray photoelectron spectroscopy and fluorescent-spectrophotometer. The effect of sputtering power and substrate temperature on the structural and photoluminescent (PL) properties of the ZnO films was investigated. The results indicated that when the sputtering power is 100 W and the substrate temperature is 300-400℃, it is suitable for the growth of high c-axis orientation and small strain ZnO films. A violet peak at about 380 nm and a blue band at about 430 nm were observed in the room temperature photolumines- cence spectra, and the origin of blue emission was investigated.     

Microstructures and optical properties of Cu-doped ZnO films prepared by radio frequency reactive magnetron sputtering

Pure and Cu-doped ZnO (ZnO:Cu) thin films were deposited on glass substrates using radio frequency (RF) reactive magnetron sputtering. The effect of substrate temperature on the crystallization behavior and optical properties of the ZnO:Cu films have been studied. The crystal structures, surface morphology and optical properties of the films were systematically investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and a fluorescence spectrophotometer, respectively. The results indicated that ZnO films showed a stronger preferred orientation toward the c-axis and a more uniform grain size after Cu-doping. As for ZnO:Cu films, the full width at half maxima (FWHM) of (0 0 2) diffraction peaks decreased first and then increased, reaching a minimum of about 0.42° at 350 °C and the compressive stress of ZnO:Cu decreased gradually with the increase of substrate temperature. The photoluminescence (PL) spectra measured at room temperature revealed two blue and two green emissions. Intense blue-green luminescence was obtained from the sample deposited at higher substrate temperature. Finally, we discussed the influence of annealing temperature on the structural and optical properties of ZnO:Cu films. The quality of ZnO:Cu film was markedly improved and the intensity of blue peak (∼485 nm) and green peak (∼527 nm) increased noticeably after annealing. The origin of these emissions was discussed.     

不同衬底上的ZnO薄膜紫外光致发光

用射频磁控溅射法在蓝宝石、硅和石英衬底上沉积出具有好的择优取向的多晶ZnO薄膜. 在270 nm波长的光激发下室温下可观察到显著的紫外光发射（波长为356 nm）和较弱的蓝光发射（波长为446 nm）. 经高温退火后薄膜的结晶质量显著提高, 在蓝宝石、石英衬底上沉积的薄膜，其积分发光强度分别增加了7倍和14倍.而硅衬底上的膜发光强度增强不太显著.紫外光发射源于电子的带间跃迁，而蓝光发射是由电子从氧空位浅施主能级到价带顶的跃迁引起的. 关键词： ZnO薄膜 射频磁控溅射 紫外发光 退火     

Violet and blue-green luminescence from Ti-doped ZnO films deposited by RF reactive magnetron sputtering

Pure and Ti-doped zinc oxide (TZO) films are deposited using radio frequency (RF) reactive magnetron sputtering at different RF powers. Micro-structural and optical properties in doped ZnO films are systematically investigated by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electronic microscopy (SEM), and a fluorescence spectrophotometer. The results indicate that ZnO films show stronger preferred orientation toward the c$c$-axis and smoother surface roughness after Ti doping. As for TZO films, the full width at half maxima (FWHM) of (002) diffraction peaks decreased first and then increased, reaching a minimum of about 0.92° at 150 W, while the residual compressive stress of the TZO film prepared at 150 W became the largest. The photoluminescent (PL) spectra measured at room temperature reveal a violet, a blue and two green emissions. Intense violet and blue-green luminescence is obtained for the sample deposited at higher RF power. The origin of these emissions is discussed.     

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。     

Ti-incorporated ZnO films synthesized via magnetron sputtering and its optical properties

Undoped and Ti-doped ZnO films were deposited using radio frequency reactive magnetron sputtering at various sputtering powers. The crystal structures, surface morphology, chemical state and optical properties in Ti-doped ZnO films were systematically investigated via X-ray diffraction (XRD), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and ultraviolet visible (UV–Vis) spectrophotometer. Results indicated that titanium atoms may replace zinc atomic sites substitutionally or incorporate interstitially in the hexagonal lattices, and a moderate quantity of Ti atoms exist in the form of sharing the oxygen with Zn atoms and hence improve the (0 0 2) orientation. The photoluminescence (PL) spectra of the Ti-doped ZnO films contain one main blue peak, whose intensity increased with the increase of sputtering power. Our results indicated that a higher compressive stress in Ti-doped ZnO films results in a lower optical band gap and a lower transmittance, and various Ti impurities can affect the concentration of the interstitial Zn and O vacancies.     

Cu掺杂ZnO薄膜的光学性质

采用射频反应磁控溅射方法,在Si(100)和石英基片上使用双靶溅射的方法制备了Cu掺杂ZnO薄膜。利用X射线衍射、透射光谱和光致发光光谱分析了薄膜的晶体结构及光学性质,并与密度泛函理论计算的结果进行了对比。研究结果显示:Cu掺杂ZnO薄膜均具有高的c轴择优取向,无Cu及其氧化物相关相析出,掺杂对晶格参数的影响较小,与理论计算结果一致。Cu掺杂显著改变了ZnO薄膜在近紫外及可见光波段的吸收特性,其光学带隙随着Cu掺杂量的增加有所减小,带隙宽度的变化趋势与理论结果有着很好的一致性。Cu掺杂显著降低了ZnO薄膜的发光效率,具有明显的发光猝灭作用,但并不影响光致发光的发光峰位。说明Cu掺杂导致的吸收特性的改变可能与杂质能级有关,这与能带结构计算发现的Cu-3d电子态位于价带顶附近的禁带中是一致的。     

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.     

Photoluminescence and Raman scattering of Cu-doped ZnO films prepared by magnetron sputtering

The Cu-doped ZnO films were prepared by direct current reactive magnetron sputtering using a zinc target with various Cu-chips attached. The influences of Cu-doping on the microstructure, photoluminescence, and Raman scattering of ZnO films were systematically investigated. The results indicate that ZnO films doped with moderate Cu dopant (2.0-4.4 at.%) can obtain wurtzite structure with strong c-axis orientation. The near band edge (NBE) emission of ZnO film can be enhanced by Cu dopant with a concentration of 2.0 at.% and quench quickly with further increase of doping concentration. Two additional modes at about 230 and 575 cm⁻¹, which could be induced by Cu dopant, can be observed in Raman spectra of the Cu-doped ZnO films.