ZnS薄膜参数对有机/无机复合发光器件特性的影响

半导体量子点(QDs)具有发光效率高和发光波长可调等特点。采用胶体CdSe QDs作电致发光器件的有源材料,TPD(N,N′-biphenyl-N,N′-bis-(3-methylphenyl)-1,1′-biphenyl-4,4′-diamine)作空穴传输层,ZnS作电子传输层,研究了有机/无机复合发光器件ITO/TPD/CdSe QDs/ZnS/Ag的电致发光特性。TPD和CdSe QDs薄膜采用旋涂方法、ZnS薄膜采用磁控溅射方法沉积,器件表面平整。CdSe QDs的光致发光和电致发光谱峰位波长均位于～580 nm,属于量子点的带边激子发光。我们与以前的ITO/ZnS/CdSe QDs/ZnS/Ag发光器件结构进行了对比,发现新的器件结构的电致发光谱没有观察到QDs表面态的发光,而且新器件的发光强度是ITO/ZnS/CdSe QDs/ZnS/Ag结构的～10倍。发光效率的提高归因于碰撞激发与载流子注入两种发光机制并存的结果：一方面电子经过ZnS 层加速后,碰撞激发CdSe QDs发光;另一方面,空穴从TPD层注入CdSe QDs 与QDs中激发的电子复合发光。我们进一步研究了ZnS电子加速层厚度对发光特性的影响,选择ZnS薄膜的厚度分别是80,120 和160 nm,发现随着ZnS层厚度增大,器件启亮电压升高,EL强度增大,但是击穿电压降低。EL峰位随着ZnS厚度的减小发生明显蓝移,对上述实验现象进行了机理解释。     

Low temperature deposition of transparent conducting ITO/Au/ITO films by reactive magnetron sputtering

Transparent conducting indium tin oxide/Au/indium tin oxide (ITO) multilayered films were deposited on unheated polycarbonate substrates by magnetron sputtering. The thickness of the Au intermediated film varied from 5 to 20 nm. Changes in the microstructure, surface roughness and optoelectrical properties of the ITO/Au/ITO films were investigated with respect to the thickness of the Au intermediated layer. X-ray diffraction measurements of ITO single layer films did not show characteristic diffraction peaks, while ITO/Au/ITO films showed an In₂O₃ (2 2 2) characteristic diffraction peak. The optoelectrical properties of the films were also dependent on the presence and thickness of the Au thin film. The ITO 50 nm/Au 10 nm/ITO 40 nm films had a sheet resistance of 5.6 Ω/□ and an average optical transmittance of 72% in the visible wavelength range of 400-700 nm. Consequently, the crystallinity, which affects the optoelectrical properties of ITO films, can be enhanced with Au intermediated films.     

Highly flexible transparent and conductive ZnS/Ag/ZnS multilayer films prepared by ion beam assisted deposition

ZnS/Ag/ZnS (ZAZ) multilayer films were prepared on polyethene terephthalate (PET) by ion beam assisted deposition at room temperature. The structural, optical and electrical characteristics of ZAZ multilayers dependent on the thickness of silver layer were investigated. The ZAZ multilayers exhibit a low sheet resistance of about 10 Ω/sq., a high transmittance of 92.1%, and the improved resistance stabilities when subjected to bending. When the inserted Ag thickness is over 12 nm, the ZAZ multilayers show good resistance stabilities due to the existence of a ductile Ag metal layer. The results suggest that ZAZ film has better optoelectrical and anti-deflection characteristics than conventional indium tin oxide (ITO) single layer.     

Experimental investigation of energy transfer between CdSe/ZnS quantum dots and different-sized gold nanoparticles

Hybrid nanostructures of quantum dots(QDs) and metallic nanostructure are attractive for future use in a variety of optoelectronic devices. For photodetection applications, it is important that the photoluminescence (PL) of QDs is quenched by the metallic nanostructures. Here, the quenching efficiency of CdSe/ZnS core-shell quantum dots (QDs) with different sized gold nanoparticles (NPs) films through energy transfer is investigated by measuring the PL intensity of the hybrid nanostructures. In our research, the gold NPs films are formed by the post-annealing of the deposited Au films on the quartz substrate. We find that the energy transfer from the QDs to the Au NPs strongly depends on the sizes of the Au NPs. For CdSe/ZnS QDs direct contact with the Au NPs films, the largest energy transfer efficiency are detected when the resonance absorption peak of the Au NPs is nearest to the emission peak of the CdSe/ZnS QDs. However, when there is a PMMA spacer between the QDs layer and the Au NPs films, firstly, we find that the energy transfer efficiency is weakened, and the largest energy transfer efficiency is obtained when the resonant absorption peak of the Au NPs is farthest to the emission peak wavelength of CdSe/ZnS QDs. These results will be useful for the potential design of the high efficiency QDs optoelectronic devices.     

ZnS/CdS复合窗口层对CdTe太阳能电池短波光谱响应的影响

采用磁控溅射法制备了ZnS/CdS复合窗口层,并将其应用于CdTe太阳能电池。对所制备薄膜的形貌和结构等进行了研究。测试了具有不同窗口层的CdTe太阳电池的量子效率和光Ⅰ-Ⅴ特性,分析了ZnS薄膜制备条件对CdTe电池器件性能影响;研究了CdS薄膜厚度和ZnS/CdS复合窗口层对短波区透过率以及CdTe太阳电池的光谱响应的影响。着重研究了具有ZnS/CdS复合窗口层的CdTe太阳电池的短波光谱响应。结果表明,CdS窗口层厚度从100 nm减至50 nm后,其对短波区光子透过率平均提高了18.3%,CdTe太阳电池短波区光谱响应平均提高了27.6%。衬底温度250 ℃条件下制备的ZnS晶粒尺寸小于室温下制备的ZnS。具有ZnS/CdS复合窗口层的CdTe电池中,采用衬底温度250 ℃沉积ZnS薄膜来制备窗口层的电池器件,其性能要优于室温下沉积ZnS制备窗口层的电池器件。这说明晶粒尺寸的大小对电子输运有一定影响。在相同厚度CdS的前提下,具有ZnS/CdS复合窗口层的CdTe电池比具有CdS窗口层在短波的光谱响应提高了约2%。这说明ZnS/CdS复合窗口层能够做到减少对短波光子的吸收,从而使更多的光子被CdTe电池的吸收层吸收。     

ZnS／PS异质结的光学和电学性质

用脉冲激光沉积（PLD）的方法在多孔硅衬底上沉积了ZnS薄膜,并在室温下研究了ZnS／PS异质结的结构、光学和电学性质。X射线衍射仪（XRD）测量结果表明．制备的ZnS薄膜在28．5°附近有一较强的衍射峰,对应于β-ZnS（111）晶向,说明薄膜沿该方向高度择优取向生长。ZnS／PS复合体系的光致发光谱表明,ZnS的发光与PS的发光叠加在一起,在可见光区形成一个450-700nm较宽的光致发光谱带。呈现较强的白光发射。对ZnS／PS异质结I-V,特性曲线的测量结果表明,异质结呈现出与普通二极管相似的整流特性。在正向偏置下,电流密度较大．电压降较低;在反向偏置下,电流密度接近于零。异质结的理想因子的值为77。     

Achieving desired quality of ZnS buffer layer by optimization using air annealing for solar cell applications

The possibility of maximum transmittance at lower thickness of light transmitting ZnS layer and its optimization by air-annealing as an alternative to hazardous and expensive CdS is reported in this communication in order to achieve better buffer layer for solar cells. Thin films of ZnS were deposited using e-beam evaporation on glass and ITO substrates and subjected to air-annealing followed by characterizations for physical properties. XRD patterns revealed amorphous behavior which transformed into cubic (111) plane with change of substrate and annealing whereas surface topography reveals hill and deep valley like structures. Optimal transmittance of maximum 95% in visible region, direct band gap of 3.38 eV and maximum electrical conductivity were observed for 200 °C annealed films. The study refers that films annealed at 200 °C are claimed to be suitable for buffer layer applications.     

核壳结构CdS/ZnS纳米微粒的制备与光学特性

用微乳液法制备CdS纳米微粒 ,以ZnS对其进行表面修饰 ,得到具有核壳结构的CdS/ZnS纳米微粒 .采用X射线衍射 (XRD)、透射电镜 (TEM )表征其结构、粒度和形貌 ,紫外 可见吸收光谱 (UV)、光致发光光谱(PL)表征其光学特性 .制得的CdS近似呈球形 ,直径为 3.3nm ;以XRD和UV证实了CdS/ZnS核壳结构的实现 .研究了不同ZnS壳层厚度对CdS纳米微粒光学性能的影响 ,UV谱表明随着壳层厚度的增加纳米微粒的吸收带边有轻微的红移 ,同时短波吸收增强 ;PL谱表明壳层ZnS的包覆可减少CdS纳米微粒的表面缺陷 ,带边直接复合发光的几率增大 ,具有合适的壳层厚度时发光效率大大提高 .     

Structural and optical properties of monodispersed ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles

Excellent luminescence properties of ZnS/CdS/ZnO and ZnO/ZnS/CdS nanocrystallites synthesized through a simple chemical method at room temperature are reported. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), UV–visible absorption and photoluminescence techniques were used to characterize the undoped ZnS, CdS and ZnO and the novel ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles. The optical properties of ZnS/CdS/ZnO and ZnO/ZnS/CdS nanoparticles reflect a combinational effect of the photoluminescent properties of ZnS, CdS and ZnO.     

Structure and magnetic properties of magnetron-sputtered [(Fe/Pt/Fe)/Au]n multilayer films

Using dc magnetron sputtering, Fe/Pt/Au multilayer films were prepared, and the effects of Au layer thickness and annealing temperature on structure and magnetic properties of the Fe/Pt/Au multilayer films were investigated. The as-deposited Fe/Pt/Au multilayer films have good periodic structure with composition modulation along the growth direction. The stress stored in the as-deposited films promoted the ordering of the films annealed at 400 °C. When the films were annealed at 500 °C, the thicker Au layer could restrain the order-disorder transformation region volume and lead to the decrease of the ordered volume fraction with Au layer thickness increasing.     

ZnS thin film deposited with chemical bath deposition process directed by different stirring speeds

In this combined film thickness, scanning electron microscopy (SEM), X-ray diffraction and optical properties study, we explore the effects of different stirring speeds on the growth and optical properties of ZnS film deposited by CBD method. From the disclosed changes of thickness of ZnS film, we conclude that film thickness is independent of the stirring speeds in the heterogeneous process (deposition time less than 40 min), but increases with the stirring speeds and/or deposition time increasing in the homogeneous process. Grazing incident X-ray diffraction (GIXRD) and the study of optical properties disclosed that the ZnS films grown with different stirring speeds show partially crystallized film and exhibit good transmittance (70-88% in the visible region), but the stirring speeds cannot give much effects on the structure and optical properties in the homogeneous process.     

Preparation and characterization of ZnS/CdS bi-layer for CdTe solar cell application

In this work, bilayer ZnS/CdS film was prepared as an improved window layer of CdTe solar cell. TEM was used to observe the cross section of the bilayer structure. The total thickness of ZnS/CdS film was about 60 nm, which could allow more photons to pass through it and contribute to the photocurrent. Optical properties of the bilayers were investigated using UV–vis spectroscopy. Compared with poor transmission of standard CdS film in the short wavelength range of 350–550 nm, the transmission of ZnS/CdS was improved and reached above 50%. The ZnS/CdS was annealed with CdCl₂. X-ray photoelectron spectroscopy (XPS) was used to investigate its chemical properties. A possible diffusion between CdS and ZnS was observed after annealing. The efficiency of standard CdS/CdTe solar cell was 9.53%. The device based on ZnS/CdS window layer had a poor 6% efficiency. With annealing treatment on ZnS/CdS layer, the performance was improved and reached 10.3%. In addition, the homogeneity of solar cell performance was improved using ZnS/CdS window layer. A thin ZnS layer was quite effective to reduce the possible shunt paths and short parts of window layer and consequently contributed to fabrication of a homogeneous CdTe solar cell.     

Green route fast synthesis and characterization of chemical bath deposited nanocrystalline ZnS buffer layers

Zinc sulphide (ZnS) thin films are deposited using chemical bath deposition method on the glass substrates in an aqueous alkaline reaction bath of zinc acetate and thiourea along with non-toxic complexing agent tri-sodium citrate at 95 °C. The results show noteworthy improvement in the growth rate of the deposited ZnS thin films and thickness of the film increases with the deposition time. From X-ray diffraction patterns, it is found that the ZnS thin films exhibit hexagonal polycrystalline phase reflecting from (101) and (0016) planes. The high resolution transmission electron microscopy studies confirmed the formation of hexagonal phase from the d-value calculation which was 0.3108 nm. X-ray photoelectron spectroscopy reveals that the Zn–S bonding energy is at 1022.5 and 162.1 eV for Zn 2p_3/2 and S 2p_1/2 states, respectively. Field emission scanning electron microscopy study shows that deposited thin films are highly uniform, with thin thickness and completely free from large ZnS clusters which usually form in aqueous solutions. Atomic force microscopy investigates that root mean square values of the ZnS thin films are from 3 to 4.5 nm and all the films are morphologically smooth. Energy dispersive spectroscopy shows that the ZnS thin films are relatively stoichiometric having Zn:S atomic ratio of 55:45. It is shown by ultraviolet–visible spectroscopy that ～90% transmittance and ～10% absorbance for the ZnS films in the visible region, which is significantly higher than that reported elsewhere and the band gap energy of the ZnS films is found to be 3.76, 3.74, and 3.71 eV, respectively.     

退火对ZnS/PS复合体系光致发光特性的影响

用脉冲激光沉积(PLD)技术以多孔硅(PS)为衬底生长了ZnS薄膜,分别测量了ZnS、PS以及ZnS/PS复合体系在室温下的光致发光(PL)光谱。结果发现,ZnS/PS复合体系的PL光谱中PS的发光峰位相对于新制备的PS有所蓝移。把该ZnS/PS样品分成三块,在真空400℃分别退火10,20,30 min,研究不同退火时间对ZnS/PS复合体系光致发光特性的影响。发现退火后样品的PL光谱中都出现了一个新的绿色发光带,归结为ZnS的缺陷中心发光。随着退火时间的延长,PS的发光强度逐渐降低且峰位红移。把ZnS的蓝、绿光与PS的红光相叠加,整个ZnS/PS复合体系在可见光区450~700 nm形成一个较宽的光致发光谱带,呈现较强的白光发射。     

Effects of ZnS:Mn/AlN multilayer structure on luminescent properties of nanostructured thin-film EL device

Effects of ZnS:Mn/AlN multilayer structure on luminescent properties of nanostructured (NS) thin-film electroluminescent (TFEL) device of which emission layer is a multilayer composed with ZnS:Mn layers and 0.7-nm-thick AlN interlayers were studied. The bandgap widening and the increased PL efficiency of Mn²⁺ 3d-3d transitions with a decrease in the ZnS:Mn single-layer thickness down to 5 nm were observed, which is ascribed to quantum confinement effects. Meanwhile, the multilayer with 2-nm-thick ZnS:Mn single-layers shows a drop of PL efficiency, indicating the presence of defective region just on AlN. The tendency of the luminous efficiency of the NS-TFEL device against the ZnS:Mn single-layer thickness is similar to the tendency found in the PL efficiency, indicating the importance of the ZnS:Mn/AlN interface for the device performance.     

Al-doped ZnS layers synthesized by solution growth method

ZnS is one of the potential candidates as a window/buffer layer for solar photovoltaic applications. Al-doped ZnS nanocrystalline films were grown by a simple and economic process, chemical solution growth method. The layers were prepared for different Al-dopant concentrations that vary in the range, 0-10 at. %. The effect of Al-doping on the composition, structure, optical, electrical and photoluminescence properties of the synthesized layers was determined using appropriate techniques. The elemental composition of a typical sample with 6 at. % ‘Al’ in ZnS was Zn = 44.9 at. %, S = 49.8 at. % and Al = 5.3 at. %. The films were nanocrystalline in nature and showed (111) plane of ZnS as the preferred orientation for all the doping concentrations. The layers with 6 at. % of Al showed a crystallite size of ∼9 nm. The FTIR studies confirmed the presence of ZnS in the layers. The layers showed an average transmittance of ∼75% in the visible region. The change of photoluminescence behaviour with dopant concentration was also studied. The electrical resistivity was considerably decreased from 10⁷ Ωcm to 10³ Ωcm with Al-doping. The detailed analysis of results will be presented and discussed.     

低温硫化制备ZnS薄膜的物理性质研究

采用磁控溅射方法先在玻璃衬底上室温下沉积Zn金属薄膜，接着先后在200和400 ℃温度下的硫蒸气和氩气流中进行退火，生长出 ZnS 薄膜。薄膜样品的微观结构、物相结构、表面形貌和光学性质分别采用正电子湮没技术 (PAT)、X射线衍射仪 (XRD)、扫描电子显微镜 (SEM)和紫外-可见分光光度计进行表征。该ZnS薄膜在可见光范围具有约80%的高透光率，随着硫化时间的增加，其带隙由3.55 增加到3.57 eV，S/Zn原子比从0.54上升至0.89，薄膜质量明显得到改善，相对于以前报道的真空封装硫化所制备的ZnS薄膜，硫过量问题得到了较好解决。此外，慢正电子湮没多普勒展宽谱对硫化前后薄膜样品中膜层结构缺陷研究表明，硫化后薄膜的S参数明显增大，生成的ZnS 薄膜结构缺陷浓度高于Zn薄膜。     

Enhancement in the photoluminescence of ZnS nanowires by TiO2 coating and thermal annealing

Influences of the TiO₂ coating and thermal annealing on the photoluminescence (PL) properties of ZnS nanowires were investigated. ZnS nanowires were synthesized by thermal evaporation of ZnS powder and then coated with TiO₂ by using the sputtering technique. The PL emission of ZnS nanowires can be significantly enhanced without nearly changing the wavelength of the emission by coating them with a TiO₂ layer with an appropriate thickness and then annealing them in an Ar atmosphere. The optimum TiO₂ coating layer thickness for the highest PL emission enhancement was found to be about 6.5 nm. The PL emission of the ZnS-core/TiO₂-shell coaxial nanowires is degraded by annealing in an oxygen atmosphere whereas it is enhanced by annealing in an argon atmosphere.     

Au层退火温度对ZnO/Au/ZnO多层膜的结构、光学及电学性质的影响

采用金属有机化学气相沉积(MOCVD)技术在蓝宝石衬底上制备出晶体质量较好的透明导电的ZnO/Au/ZnO(ZAZ)多层膜,其中,Au夹层是通过射频磁控溅射的方法获得。通过对Au夹层进行不同温度的退火处理,研究了Au层退火温度对ZAZ多层膜的结构特性、电学性能和光学特性的影响。利用原子力显微镜(AFM)、扫描电子显微镜(SEM)、X射线衍射(XRD)仪、霍尔效应测试和透射谱分析等测试手段对ZAZ多层膜的性质进行了分析。测试结果表明,在200 ℃下对Au夹层进行快速退火处理,多层膜的结构、电学和光学性质达到最优,表面等离子体效应也更明显。其中,XRD(002)衍射峰的半高宽为0.14°,电阻率为2.7×10^-3 Ω·cm,载流子浓度为1.07×10²⁰ cm^-3,可见光区平均透过率为75.3%。     

The study of structure and optoelectronic properties of ZnS and ZnO films on porous silicon substrates

ZnS and ZnO films were prepared on porous silicon (PS) substrates with the same porosity by pulsed laser deposition (PLD), and the structural, optical and electrical properties of ZnS and ZnO films on PS were investigated at room temperature by X-ray diffraction (XRD), scanning electron microscope (SEM), optical absorption measurement, photoluminescence (PL) and I–V characteristic studies. The prepared ZnS was obtained in the cubic phase along β-ZnS (1 1 1) orientation which showed a perfect match with the earlier report while ZnO films were obtained in c-axis orientation. There appeared some cracks in the surface of ZnS and ZnO films due to the roughness of PS substrates. Luminescence studies of ZnS/PS and ZnO/PS composites indicated room temperature emission in a broad, intense, visible photoluminescence band, which cover the blue emission to red emission, exhibiting intensively white light emission. Based on the I–V characteristic, ZnS/PS heterojunction exhibited the rectifying junction behavior, while the I–V characteristic of ZnO/PS heterostructure was different from that of the common diode, whose reverse current was not saturated.