联氨对化学水浴沉积ZnS薄膜的影响

在A(ZnSO4、SC(NH2)2、NH4OH)和含有联氨的B(ZnSO4、SC(NH2)2、NH4OH、(NH2)2)两种水溶液中采用化学水浴法沉积ZnS薄膜,研究了联氨对薄膜沉积过程和薄膜性质的影响.结果表明,加入少量联氨以后,薄膜沉积速度明显增加.两种溶液沉积的ZnS都为立方相结构,且含有联氨的B溶液沉积的ZnS薄膜表面附着颗粒较少.在含有联氨的B溶液中沉积的ZnS薄膜结晶度和短波区的透过率均高于A溶液沉积的ZnS薄膜.将两种溶液沉积的ZnS薄膜作为电池缓冲层制备铜铟镓硒(CIGS)薄膜太阳电池,加入联氨沉积的ZnS制备的CIGS电池转换效率达到7.77%,比不加联氨沉积的ZnS制备的CIGS电池转换效率提高了1.3%.     

退火温度对ZnS/PS薄膜的晶体结构和光电性质的影响

用脉冲激光沉积法(PLD)在多孔硅(PS)衬底上生长ZnS薄膜,分别在300℃、400℃和500℃下真空退火。用X射线衍射(XRD)和扫描电子显微镜(SEM)研究了退火对ZnS薄膜的晶体结构和表面形貌的影响,并测量了ZnS/PS复合体系的光致发光(PL)谱和异质结的I-V特性曲线。研究表明,ZnS薄膜仅在28.5°附近存在着(111)方向的高度取向生长,由此判断薄膜是单晶立方结构的-βZnS。随着退火温度的升高,-βZnS的(111)衍射峰强度逐渐增大,且ZnS薄膜表面变得更加均匀致密,说明高温退火可以有效地促进晶粒的结合并改善结晶质量。ZnS/PS复合体系的PL谱中,随着退火温度升高,ZnS薄膜的自激活发光强度增大,而PS的发光强度减小,说明退火处理更有利于ZnS薄膜的发光。根据三基色叠加的原理,ZnS的蓝、绿光与PS的红光相叠加,ZnS/PS体系可以发射出较强的白光。但过高的退火温度会影响整个ZnS/PS体系的白光发射。ZnS/PS异质结的I-V特性曲线呈现出整流特性,且随着退火温度的升高其正向电流增加。     

退火温度对电子束蒸发的ZnS薄膜性能的影响

为了获得光电性能好的ZnS窗口层薄膜,采用电子束蒸发法在玻璃基片上沉积ZnS薄膜,研究退火温度(200~500℃)对ZnS薄膜的结构和光电性能的影响。结果表明:所制备的薄膜均为闪锌矿结构的β-ZnS多晶薄膜,导电类型为n型。随着退火温度的增高,薄膜结晶度和光电性能都变好。但是,当退火温度过高(500℃)时,薄膜的半导体特性反而变差。退火温度为400℃时,ZnS薄膜的性能最佳,此时薄膜的透过率较高;电阻率较低,为246.2?.cm。     

Zn沉积时间对低温硫化制备ZnS薄膜性能的影响

采用磁控溅射方法在不同时间下沉积了Zn薄膜,接着先后在200℃和400℃温度下的硫蒸气和氩气氛中进行了低温硫化退火,时间都为1 h,最后得到不同厚度的六方相ZnS薄膜。以XRD、SEM、EDS和紫外可见分光光度计对薄膜进行表征。研究表明:随着Zn沉积时间的增加,硫化制备的ZnS薄膜的晶粒尺寸、光透过率、带隙、S/Zn摩尔比都发生了明显变化,但变化趋势不同。并且,对其低温硫化生长ZnS薄膜的机理进行了讨论。此外,硫化前的抽真空处理可以明显改善ZnS薄膜的质量。所有低温硫化制备的ZnS薄膜在400~1100 nm范围光透过率约为70%,带隙值为3.49~3.57 eV。其中,3 min沉积的Zn在抽真空后低温硫化生长的ZnS薄膜质量最佳。     

硫化法制备ZnS薄膜的结构和光学性能研究

采用直流反应磁控溅射法,在玻璃衬底上沉积了ZnO薄膜,然后在H2S气氛和500℃温度下退火制备了六方ZnS薄膜。利用X射线衍射仪(XRD)、UV-VIS分光光度计、扫描电子显微镜(SEM)对样品进行了表征。结果表明:ZnO经0.5 h硫化就能全部生成ZnS,适当提高硫化时间可改善ZnS的结晶性,但硫化时间超过2 h后,结晶性会有所降低;所有制得ZnS薄膜都沿c轴择优生长,其晶粒明显比ZnO更大。此外,这些ZnS薄膜在500~1 100nm波长范围内的光透过率均高达约75%,带隙为3.65~3.70 eV。     

硫化法制备ZnS薄膜的结构和光学性能研究

采用直流反应磁控溅射法,在玻璃衬底上沉积了ZnO薄膜,然后在H2S气氛和500℃温度下退火制备了六方ZnS薄膜。利用X射线衍射仪(XRD)、UV-VIS分光光度计、扫描电子显微镜(SEM)对样品进行了表征。结果表明:ZnO经0.5 h硫化就能全部生成ZnS,适当提高硫化时间可改善ZnS的结晶性,但硫化时间超过2 h后,结晶性会有所降低;所有制得ZnS薄膜都沿c轴择优生长,其晶粒明显比ZnO更大。此外,这些ZnS薄膜在500~1 100nm波长范围内的光透过率均高达约75%,带隙为3.65~3.70 eV。     

ZnS/CuInS2/Mo/钠钙玻璃衬底上射频溅射ZnO:Al薄膜的SEM研究

结合ZnO薄膜在Cu-Ⅲ-Ⅵ2基薄膜太阳电池上的应用,采用射频磁控溅射技术以陶瓷ZnOAl2O3为靶材在ZnS/CuInS2/Mo/钠钙玻璃衬底上于固定沉积条件下低温(200℃)制备了铝掺杂氧化锌(ZnOAl)薄膜.运用扫描电子显微镜研究了底层材料特别是ZnS和CuInS2的生长参数对沉积的ZnOAl薄膜的表面形貌的影响.实验发现,衬底材料中硫含量的增加(无论来自ZnS还是来自CuInS2),都会引起沉积ZnOAl薄膜结晶质量的提高,而金属含量的增大将有利于薄膜均匀性的改进.     

PLD法制备ZnO薄膜的退火特性和蓝光机制研究

通过脉冲激光沉积(PLD)方法,在O2中和100～500℃衬底温度下,用粉末靶在Si(111)衬底上制备了ZnO薄膜,在300℃温度下生长的薄膜在400～800℃温度和N2氛围中进行了退火处理,用X射线衍射(XRD)谱、原子力显微镜(AFM)和光致发光(PL)谱表征薄膜的结构和光学特性。XRD谱显示,在生长温度300℃时获得较好的复晶薄膜,在退火温度700℃时获得最好的六方结构的结晶薄膜;AFM显示,在此退火条件下,薄膜表面平整、晶粒均匀;PL谱结果显示,在700℃退火时有最好的光学特性。     

不同温度硫化生长ZnS薄膜的性能

采用磁控溅射方法在玻璃衬底上室温下沉积了Zn薄膜,接着将薄膜在硫蒸气和氩气氛中于200℃预热1 h,然后升温至250~500℃退火1 h。以XRD、SEM、EDS和紫外可见分光光度计对薄膜进行表征,并结合热力学计算结果研究了Zn薄膜硫化生长机理。Zn转变为ZnS的过程包括硫化反应以及S原子和Zn原子的扩散。研究还表明:第一步的200℃预热可在Zn薄膜表面形成ZnS,随后第二步退火的硫化温度对硫化薄膜光透过率、S/Zn摩尔比和结晶性都有明显影响;在大于或等于300℃的硫化温度下制备的ZnS薄膜在400~1100 nm范围光透过率高达约80%,带隙为3.54~3.60 eV,晶体结构为六方。     

退火对磁控溅射法制备半导体Mg2Si薄膜的影响

通过磁控溅射和氩气氛围退火,在Si(111)衬底上制备环境友好半导体Mg2Si薄膜,并采用XRD和SEM研究了退火对Mg2Si薄膜形成和微结构的影响。结果表明Mg2Si薄膜的质量取决于退火温度、退火时间和沉积的薄膜厚度。制备Mg2Si薄膜,400℃退火5h是最优退火条件。XRD和SEM结构表明Mg2Si是通过沉积的Mg和Si衬底原子的相互扩散形成的。退火减少薄膜缺陷,也影响薄膜的表明粗糙度。     

Cu(In,Ga)Se2太阳电池缓冲层ZnS薄膜性质及应用

在含有ZnSO4,SC(NH2)2,NH4OH的水溶液中采用CBD法沉积ZnS薄膜,XRF和热处理前后的XRD测试表明,ZnS沉积薄膜为立方相结构,薄膜含有非晶态的Zn(OH)2.光学透射谱测试表明,制备的薄膜透过率(λ＞500nm)约为90%,薄膜的禁带宽度约为3.51eV.ZnS薄膜沉积时间对Cu(In,Ga)Se2太阳电池影响显著,当薄膜沉积时间在25～35min时,电池的综合性能最好.对比了不同缓冲层的电池性能,采用CBD-CdS为缓冲层的电池转换效率、填充因子、开路电压稍高于CBD-ZnS为缓冲层的无镉电池,但无镉电池的短路电流密度高于前者,两者转换效率相差2%左右.ZnS可以作为CIGS电池的缓冲层,替代CdS,实现电池的无镉化.     

ZnS薄膜制备和光学性能研究

采用化学水浴法,以硫酸锌、硫脲、联氨、氨水和去离子水为反应前驱物制备ZnS薄膜。采用SEM、EDS、XRD和透射光谱分析方法,研究反应前驱物中氨水以及联氨的浓度对ZnS薄膜形貌、成分、结构和光学性能的影响,同时对ZnS薄膜的形成机理做进一步分析。结果表明:ZnS薄膜由纳米颗粒组成,这些ZnS纳米颗粒为非晶态结构。ZnS薄膜中S与Zn原子比最大为0.79∶1,薄膜中夹杂少量ZnO或Zn(OH)2。ZnS薄膜在可见光波段的透过率大于80%,禁带宽度为3.74～3.84 eV。氨水和联氨浓度对薄膜形貌、成分和光学性能有较大的影响。当反应前驱物中氨水浓度为0.5～0.8 mol/L、联氨浓度为0.5～1.0 mol/L时,溶液中的化学反应以在衬底上发生的离子-离子反应占主导作用,能在衬底上形成致密且颗粒大小分布均匀的ZnS薄膜,S与Zn的原子比接近1∶1。     

Preparation and characterization of ZnS thin films prepared by chemical bath deposition

Zinc sulfide thin films were prepared by chemical bath deposition technique using zinc sulfate (ZnSO₄·7H₂O) and thiourea [SC(NH₂)₂] as sources of Zn²⁺ and S^2– ions, and ammonia (NH₃) and hydrazine hydrate (N₂H₄) as complexing agents. The structural, stoichiometric proportion, morphology and optical properties of the ZnS thin films were investigated as a function of thiourea and ammonia concentrations using X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), scanning electron microscopy (SEM) and UV-visible spectrophotometry measurements. The deposition mechanism is discussed. The results reveal that the ZnS films exhibit poor crystallinity. The ammonia concentration had an obvious effect on the surface morphology, optical properties and deposition mechanism. The S/Zn atomic ratio and optical bandgap of the ZnS thin films first increased and then decreased with increasing ammonia or thiourea concentration.     

Effect of four different zinc salts and annealing treatment on growth,structural, mechanical and optical properties of nanocrystalline ZnS thin films by chemical bath deposition

ZnS thin films were deposited from four different zinc salts on glass substrates by chemical bath deposition method. Different anions of zinc salts affect the deposition mechanism and growth rate, which influence the properties of the films significantly. The ZnS thin film deposited from ZnSO₄ is smoother, thicker, more homogeneous and compact, nearly stoichiometric, comparing with the films deposited from Zn(CH₃COO)₂ and Zn(NO₃)₂, and ZnCl₂. The scratch test of bonding force between ZnS film and substrate shows that the ZnS film deposited from ZnSO₄ has the most excellent adhesion with the substrate. The presence of SO₄²⁻ promotes heterogeneous ZnS thin film growth via ions by ions deposition, and the films deposited from Zn(CH₃COO)₂ and Zn(NO₃)₂ are formed via clusters by clusters deposition. XRD and HRTEM results show that cubic ZnS films are obtained after single deposition, and the grain size of ZnS thin film deposited from ZnSO₄ for 2.5 h is 10 nm. The average transmission of all films is greater than 85% in the wavelength ranging from 600 to 1100 nm, and the transmission of films deposited from ZnSO₄ or Zn(NO₃)₂ for 1.5, 2 and 2.5 h is greater than 85% in the wavelength varying from 340 to 600 nm, which can enhance the blue response. The band gaps of all ZnS thin films are in the range of 3.88–3.99 eV. After annealing treatment, the mechanical and optical properties of the ZnS thin film deposited from ZnSO₄ are improved significantly.     

Optimising conditions for the growth of nanocrystalline ZnS thin films from acidic chemical baths

The growth of nanocrystalline zinc sulfide thin films onto glass substrates by chemical bath deposition has been optimized at acidic pH. Powder X-ray diffraction (p-XRD) confirms the deposition of sphalerite, the cubic phase of ZnS. The crystallite size calculated by Scherrer equation was found to be 4.0 nm. Scanning Electron Microscopy (SEM) show clusters of spherical nanoparticles uniformly distributed over the surface of the glass substrates. Energy Dispersive X-ray (EDX) analysis of the deposited thin films show the zinc to sulfur ratio close to 1:1. The observed band gap (3.78 eV) of the deposited thin films is higher than that reported for cubic phase of bulk ZnS (3.54 eV) as expected due to nano-size crystallites. Binding energies calculated by X-ray Photoelectron Spectroscopy (XPS) confirm the material as ZnS and the photoluminescence measurements show the blue shift in emission maximum.     

倾斜角沉积技术制备ZnS双折射雕塑薄膜

使用倾斜角沉积(GLAD)的电子束蒸发技术,制备了倾斜角度在60°~85°之间的ZnS双折射雕塑薄膜(STF)。使用X射线衍射(XRD)和扫描电镜(SEM)检测了ZnS薄膜的结晶状态和断面形貌,使用Lamda-900分光光度计测量了薄膜在不同的偏振光入射时的透过率。研究发现,室温下倾斜沉积ZnS薄膜断面为倾斜柱状结构,且薄膜的结晶程度不高。在相同的监控厚度时,随倾斜角度增大,沉积到基片上的薄膜厚度逐渐变小,但仍然大于余弦曲线显示的理论厚度。根据偏振光垂直入射时薄膜的透过光谱计算了不同角度沉积的薄膜的折射率和双折射。结果显示当倾斜角度为75°时,薄膜的双折射效应最显著,此时Δn=0.044。     

ZnS thin film deposition on Silicon and glass substrates by Thermionic vacuum Arc

In this study, Silicon (Si) and glass substrates were coated with Zinc sulfide (ZnS) using Thermionic Vacuum Arc (TVA) technique for the first time. With this technique, the coating time of the samples is very short and film thickness can be controlled during the coating process. Moreover, TVA provides many advantages to deposited thin films than other techniques such as compactness, low roughness, nanostructures, homogeneities as compared to other deposition techniques. This paper presents a different technique for deposition of high-quality ZnS thin films. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and atomic force microscopy (AFM) were used to characterize the coated silicon and glass surface morphologies. Additionally, transmittances, thickness and refractive indices of coated glass samples with ZnS were measured by ultraviolet–visible spectrophotometer and interferometer to characterize their optical properties.     

Optical and electrical properties of copper-incorporated ZnS films applicable as solar cell absorbers

Un-doped and Cu-doped ZnS (ZnS:Cu) thin films were synthesized by Successive Ion Layer Absorption and Reaction (SILAR) method. The UV-visible absorption studies have been used to calculate the band gap values of the fabricated ZnS:Cu thin films. It was observed that by increasing the concentration of Cu²⁺ ions, the Fermi level moves toward the edge of the valence band of ZnS. Photoluminescence spectra of un-doped and Cu-doped ZnS thin films was recorded under 355 nm. The emission spectrum of samples has a blue emission band at 436 nm. The peak positions of the luminescence showed a red shift as the Cu²⁺ ion concentration was increased, which indicates that the acceptor level (of Cu²⁺) is getting close to the valence band of ZnS.