Phase transformation from cubic ZnS to hexagonal ZnO by thermal annealing

We have investigated the mechanism of phase transformation from ZnS to hexagonal ZnO by hightemperature thermal annealing. The ZnS thin films were grown on Si(001) substrate by thermal evaporation system using ZnS powder as source material. The grown films were annealed at different temperatures and characterized by X-ray diffraction(XRD), photoluminescence(PL), four-point probe, scanning electron microscope(SEM) and energy dispersive X-ray diffraction(EDX). The results demonstrated that as-deposited ZnS film has mixed phases but high-temperature annealing leads to transition from ZnS to ZnO. The observed result can be explained as a twostep process:(1) high-energy O atoms replaced S atoms in lattice during annealing process, and(2) S atoms diffused into substrate and/or diffused out of the sample. The dissociation energy of ZnS calculated from the Arrhenius plot of 1000/T versus log(resistivity) was found to be 3.1 eV. PL spectra of as-grown sample exhibits a characteristic green emission at 2.4 eV of ZnS but annealed samples consist of band-to-band and defect emission of ZnO at 3.29 eV and 2.5 eV respectively. SEM and EDX measurements were additionally performed to strengthen the argument.     

超声喷雾热解法制备ZnO：Eu薄膜

以醋酸锌（Zn（CH3COO）2）、氯化铕（EuCl3）水溶液为前驱体,采用超声喷雾热解（USP）方法在ITO导电玻璃衬底上沉积Eu掺杂ZnO（ZnO：Eu）薄膜。通过扫描电镜（SEM）、X射线衍射（XRD）和光致发光（PL）谱对ZnO：Eu薄膜的形貌、结构和光学性质进行了研究。SEM测试结果表明,超声喷雾热解法制备的...     

Optoelectronic properties of solution synthesis of carbon nanotube/ZnO:Al:N nanocomposite and its potential as a photocatalyst

A novel multiwalled carbon nanotubes/aluminum–nitrogen co-doped ZnO (MWCNT/ZnO:Al:N) nanocomposite film was synthesized by a sol–gel deposition method and used for the photodegradation of organic dye under UV light illumination. The MWCNT/ZnO:Al:N composite film was extensively characterized through scanning electron microscope (SEM), Energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence measurements (PL) and UV–vis spectroscopy. Photocatalytic measurements reveal that the addition of MWCNT enhances photocatalytic degradation of MB by providing conduction path for electron transfer and reactive oxygen groups.     

Microstructural and photoluminescence properties of Co-doped ZnO films fabricated using a simple solution growth method

Nanocrystalline 2% cobalt doped ZnO films were successfully prepared using a simple chemical solution method on glass substrates and subsequently annealed in air at 300 and 500 °C. Structural, morphology, chemical composition and photoluminescence properties of the films were characterized using X-ray diffractometry (XRD), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS) and Fourier transform infra-red spectroscopy (FTIR) and photoluminescence (PL) spectroscopy. X-ray diffraction studies of the annealed films reveal the formation of polycrystalline hexagonal wurtzite structure of ZnO crystals without any co-related secondary phases. SEM micrographs of the films show the formation of spherical nanoparticles. Photoluminescence of the films showed a weak UV and defect related visible emissions like blue, blue–green, yellow and relatively intense orange–red emissions and their mechanism was discussed in detail.     

纳米ZnO薄膜的热蒸发法制备及其光电特性研究

以醋酸锌为原料、O/Ar的混合气体为携载气体,在500℃的温度下应用热蒸发法在p型Si基片上生长纳米ZnO薄膜,并研究了其形貌、结构和光电特性.X-射线(XRD)衍射结果显示所制备ZnO纳米晶体呈六角纤锌矿结构;扫描电子显微镜(SEM)观察发现生长的Zn0薄膜平整均匀,纳米晶体颗粒平均尺寸为25nm.应用紫外-可见光吸收谱分析了其吸收特性,发现该ZnO薄膜在紫外波段具有很强的吸收,其吸收边位于320nm处.由于量子限制效应,与体材料相比,该吸收边存在明显的蓝移.应用光致发光谱(PL)研究了其发光特性,发现该ZnO薄膜在近紫外以及蓝-绿光波段具有强烈的受激发射.最后,还研究了ZnO薄膜的电容-电压(C-V)特性.     

ZnO纳米晶须的形态控制及其结构表征

采用激光分子束外延法先在Si(111)衬底上制备Zn薄膜,在不同的氧气体积流量和生长温度下,用热蒸发法在镀有Zn薄膜的Si(111)衬底上制备了不同形貌的ZnO纳米晶须。分别用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)和高分辨透射电子显微镜(HRTEM)对样品的成分、微结构和形貌进行了表征。Zn薄膜在高温下被氧化,并为晶体生长提供均匀的成核点,有利于形成一定大小和数量的ZnO晶核。研究结果表明,氧气体积流量和生长温度对ZnO纳米晶须的形貌有一定的影响。     

酞菁染料ZnPc和Q-PbS复合敏化纳米晶ZnO薄膜电极的研究

利用溶胶-凝胶旋涂镀膜法结合热处理工艺在FTO玻璃上制备了ZnO薄膜,并通过X射线衍射(XRD)、扫描电子镜(SEM)对其晶相及表面形貌进行了表征;以酞菁染料ZnPc和窄禁带半导体PbS量子点(Q-PbS)为敏化剂,分别制备了FTO/ZnO/ZnPc电极、FTO/ZnO/Q-PbS电极和FTOZnO/Q-PbS/ZnPc电极,结果表明,ZnPc和Q-PbS对ZnO纳米颗粒膜产生了良好的敏化作用,且两者的复合敏化效果最好;制备了FTO/ZnO/Q-PbS/ZnPc为光阳极的染料敏化太阳能电池(DSSC),在模拟太阳光下,电池的开路电压为304mV,短路电流为1.42mA,光电转换效率为0.696%,填充因子为0.348。     

Fabrication of porous ZnO via electrochemical etching using 10 wt% potassium hydroxide solution

We described the fabrication of porous ZnO using the electrochemical etching method. ZnO thin films deposited by radiofrequency sputtering were etched electrochemically using 10 wt% KOH solution as an etching medium to obtain porous ZnO surface structure. A constant voltage of 15 V was applied to enhance the etching process. The etched samples were then characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence (PL) spectroscopy to examine their structural and optical properties. XRD spectra showed that by performing the electrochemical etching process, porous ZnO could be obtained without severely deteriorating the crystallinity of the samples. Moreover, SEM characterization revealed that hillock-type porous ZnO was fabricated successfully. In addition, the cross-sectional SEM images revealed that there were only minimal changes in the layer thickness after the ZnO had been etched for various lengths of time. This finding shows the dominance of the vertical etching process. Notably, the intensity of PL spectra increased and the PL excitation peak exhibited a red shift trend as the etching time increased. These observations are due to the increase of the surface to volume ratio of the ZnO surface and the strain relaxation along the dislocation and grain boundary.     

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。     

Preparation and characterization of cubic lattice ZnS：Na Films with （111） preferred orientation

ZnS：Na thin films with （111） preferred orientation were deposited on glass substrates by vacuum evaporation method. The as-prepared films were annealed in flowing argon at 400--500 ℃ to improve the film crystallinity and electrically activate the dopants. The structural, optical and electrical properties of ZnS：Na films are investigated by X-ray diffrac- tion （XRD）, photoluminescence （PL）, optical transmittance measurements and the four-point probe method. Results show that the as-prepared ZnS：Na films are amorphous, and exhibit （111） preferred orientation after annealing at 400 --500 ℃. The PL emissions at 414 nm and 439 nm are enhanced due to the increase of the intrinsic defects induced by the thermal annealing. However, all the samoles exhibit high resistivitv due to the heavy self-compensation.     

氧分压对PLD法生长Si(111)基ZnO薄膜性能的影响

在不同氧分压下用脉冲激光沉积(PLD)法在n型硅(111)衬底上生长ZnO薄膜。通过对其进行XRD、傅里叶红外吸收(FTIR)和光致发光谱(PL)的测量,研究了氧分压对PLD法制备的ZnO薄膜的结晶质量和发光性质的影响。XRD显示,氧分压为6.50Pa时可以得到结晶质量最佳的ZnO薄膜。PL谱显示,当氧分压由0.13Pa上升至6.50Pa时,位于380nm附近的主发光峰的强度最大。当氧分压进一步上升至13.00Pa时,主发光峰减弱,与氧空位有关的发光峰消失,显示出ZnO薄膜的PL谱和氧分压的大小密切相关。     

Investigation of the blue–green emission and UV photosensitivity of Cu-doped ZnO films

Cu-doped zinc oxide (ZnO:Cu) films were deposited on p-Si (100) substrates using radio-frequency reactive magnetron sputtering. The structure and optical properties of the films were characterized by X-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and fluorescence spectroscopy. XRD and SEM results revealed that ZnO:Cu film had a better preferential orientation along the c-axis compared with pure ZnO film. The chemical state of copper and oxygen in ZnO:Cu films was investigated by XPS. The results suggest that the Cu ion has a mixed univalent and bivalent state. The integrated Cu²⁺/Cu⁺ intensity ratio increased with the O₂ partial pressure. Photoluminescence measurements at room temperature revealed a double peak in the blue regions and a green emission peak. The close relationship between the valence state of Cu ions and the blue–green emission is discussed in detail. A higher photocurrent was observed for ZnO:Cu films under UV illumination. UV photodetectors based on ZnO:Cu films have high sensitivity and fast response and recovery times. Under periodic UV illumination at 380 nm the ZnO:Cu films showed stable photocurrent growth and decay, so the films are potential candidate materials for UV photodetectors.     

ZnO:Ag薄膜的制备及其光学性能研究

采用蒸镀与氧化二步法,以高纯混合金属Zn:Ag作蒸发源,在石英衬底上沉积Zn:Ag金属薄膜,经不同热氧化处理生长Ag掺杂ZnO薄膜。结果显示,以Ag含量为质量分数3%的蒸发源沉积的Zn:Ag薄膜经500℃氧化后,生成的ZnO:Ag薄膜在380 nm附近出现很强的近带边紫外发光峰,在438~470 nm附近出现较弱的深能级缺陷发光峰,该薄膜在360 nm有接近垂直的吸收边,其载流子浓度为1.810×1021cm–3,表现出p型导电特性和较好的光学质量。     

Deposition of morphology-tailored PbS thin films by surfactant-enhanced aerosol assisted chemical vapor deposition

In this work, we report the results of deposition of PbS thin films using single molecular precursor, bis(O-isobutylxanthato)lead(II), in the presence of additives namely: sodium dodecyl sulfate (SDS), Tween and Triton x-100, via aerosol assisted chemical vapor deposition (AACVD). The as-deposited PbS thin films are highly crystalline and exhibited superior adhesion to glass substrates. Powder X-ray diffraction (XRD) analysis confirmed the formation of pure cubic phase of PbS. Thin films deposited using 0.4 mM Triton X-100 as additive resulted in wire like structures while 0.8 mM Triton X-100 deposited thin films comprised of predominantly shoe shaped structures. Further, increase in concentration (1.2 mM) of Triton X-100 deposited films having rod like morphology. The scanning electron microscopy (SEM) confirmed that in the presence of SDS, thin films consist of spherical shaped crystallites. Energy dispersive X-ray spectroscopy (EDX) and X-ray photon electron microscopy (XPS) of as-deposited PbS thin films was used to study chemical composition of thin films.     

无机络合溶胶-凝胶法制备多孔ZnO薄膜

利用无机络合溶胶-凝胶法制备多孔ZnO薄膜,同时利用多种测试手段对薄膜的晶体结构、表面形貌、多孔和光学性能进行了研究.XRD和SEM的测试结果表明,ZnO薄膜的晶体结构为六方纤锌矿,薄膜表面呈多孔状.由孔径分布曲线得出薄膜的孔主要集中在介孔2.02nm和4.97nm;500℃煅烧得到的ZnO薄膜的比表面积是27.57m2/g;在不同温度下煅烧的薄膜在可见光区域透射率均高于85%,光学带宽为3.25eV.     

退火过程对c轴择优取向的ZnO薄膜的光学性质的影响

利用溶胶凝胶法在石英衬底上采用旋涂法制备出ZnO薄膜,通过X射线衍射仪发现不同的退火温度对ZnO薄膜的择优取向有很大影响;通过紫外可见分光光度计和室温发光谱可以看出,制备的薄膜有很好的光学透过性和很强的紫外发光特性,而不同的退火温度对其光学性质有很大的影响。实验发现采用此种方法在650℃左右退火是一个合适的退火温度,结构特性和光学性质都相对较好;采用热分析方法可知ZnO将在375℃左右从非晶转向结晶状态,因而在常规ZnO薄膜制备方法中增加一步500oC的热处理将有助于提高ZnO薄膜的结晶质量。     

One-pot synthesis of ZnO/reduced graphene oxide nanocomposite for supercapacitor applications

ZnO/reduced graphene oxide (RGO) nanocomposite films were prepared by the sol–gel deposition method using a combination of zinc acetate and graphite. The solution derived composite films were extensively characterized using high resolution transmission electron microscopy (HR-TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), UV–visible spectroscopy, photoluminescence emission measurements, and four probe measurements. It was found that a highly transparent film with low resistivity could be obtained with the addition of a small amount of RGO into the deposition precursor. The results also showed that the sintering temperature reduces the resistivity and transparency of the films. XRD measurements revealed that films sintered >500 °C exhibit additional peaks, and suggest nucleation of different phases of the films. As a demonstration, the ZnO/RGO composite was integrated into a supercapacitor, and the resulting energy storage performance was tested.     

氮化Si基ZnO/Ga_2O_3制备GaN薄膜

利用射频磁控溅射法在Si衬底上先溅射ZnO缓冲层,接着溅射Ga2O3薄膜,然后ZnO/Ga2O3膜在管式炉中常压下通氨气进行氮化,反应自组生成GaN薄膜。XRD测量结果表明,利用该方法制备的GaN薄膜是沿c轴方向择优生长的六角纤锌矿多晶结构的薄膜,利用SEM观测了其表面形貌,PL测量结果发现了位于351nm处的室温光致发光峰。     

Synthesis and photoluminescence properties of Mn-doped ZnS nanobelts

Mn-doped ZnS nanobelts have been prepared through a thermal evaporation method at 1100℃. The synthesized nanobelts are characterized with X-ray diffraction （XRD）, scanning electron microscopy （SEM）, selected area electron diffraction （SAED）, high-resolution transmission electron microscopy （HRTEM）, and photoluminescence （PL） spectroscopy. The results show that the nanobelts have an uniform single-crystal hexagonal wurtzite structure and grow along [0001 ] direction. Room-temperature photoluminescence reveals that the intrinsic PL of the nanobelts disappears and a new PL peak of the Mn-doped ZnS nanobelts emerges at 575 nm.     

Epitaxial growth of ZnO on GaN/sapphire substrate by radio-frequency magnetron sputtering

Zinc oxide (ZnO) thin films were grown on n-GaN/sapphire substrates by radio-frequency (RF) magnetron sputtering. The films were grown at substrate temperatures ranging from 400 to 700 ℃ for 1 h at a RF power of 80 W in pure Ar gas ambient. The effect of the substrate temperature on the structural and optical properties of these films was investigated by X-ray diffraction (XRD), atomic force microscopy (AFM) and photoluminescence (PL) spectra. XRD results indicated that ZnO films exhibited wurtzite symmetry and c-axis orientation when grown epitaxially on n-GaN/sapphire. The best crystalline quality of the ZnO film is obtained at a growth temperature of 600 ℃. AFM results indicate that the growth mode and degree of epitaxy strongly depend on the substrate temperature. In PL measurement, the intensity of ultraviolet emission increased initially with the rise of the substrate temperature, and then decreased with the temperature. The highest UV intensity is obtained for the film grown at 600 ℃ with best crystallization.