PbS量子点/ZnO纳米片复合膜的制备及其光电化学性能

通过两步法合成PbS量子点(QDs)修饰ZnO纳米片复合膜. 首先利用电化学法在掺氟的SnO₂导电玻璃(FTO)上生长ZnO纳米片, 然后在ZnO纳米片上通过逐次化学浴法沉积PbS量子点形成PbS/ZnO复合膜. 利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)详细表征了样品的表面形貌和晶体结构, 并研究了PbS/ZnO复合膜作为量子点敏化太阳能电池光阳极的紫外-可见吸收谱、光电化学性能和表面光电压谱. 对比ZnO纳米片经PbS量子点修饰前后, 发现PbS量子点修饰后光阳极的光吸收和光伏响应均从紫外区拓宽到了可见光区, 同时光电化学性能有了显著提高, 短路电流密度从敏化前的0.1 mA/cm²增加到0.7 mA/cm², 效率由0.04%增加到0.57%. 与单一ZnO纳米片相比, PbS/ZnO复合膜的表面光伏响应强度明显增强, 说明PbS与ZnO之间形成了有利于光生电荷分离的异质结, 从而导致了PbS/ZnO复合膜光电性能的增加.     

Optical and field-emission properties of ZnO nanostructures deposited using high-pressure pulsed laser deposition

ZnO nanostructures were deposited on GaN (0001), Al2O3 (0001), and Si (100) substrates using a high-pressure pulsed laser deposition (PLD) method. Vertically aligned hexagonal-pyramidal ZnO nanorods were obtained on the Al2O3 and Si substrates whereas interlinked ZnO nanowalls were obtained on the GaN substrates. A growth mechanism has been proposed for the formation of ZnO nanowalls based on different growth rates of ZnO polar and nonpolar planes. Both ZnO nanorods and nanowalls exhibit a strong E2H vibration mode in the micro-Raman spectra. The corresponding fluorescence spectra of ZnO nanorods and nanowalls showed near band emission at 3.28 eV. The ZnO nanorods grown on the Si substrates exhibited better crystalline and optical properties compared with the ZnO structures grown on the GaN and Al2O3 substrates. The high aspect ratio, good vertical alignment, and better crystallinity of the ZnO nanorods with tapered tips exhibited promising field emission performance with a low turn-on field of 2 V/μm, a high current density of 7.7 mA/cm2, and a large field enhancement factor.     

Synthesis of ZnO nanowires by the hydrothermal method,using sol–gel prepared ZnO seed films

Zinc oxide (ZnO) nanowires with various morphologies are synthesized by the hydrothermal method on silicon substrates coated with ZnO thin films. The ZnO films are used as the seed layer and are prepared using the sol–gel technique. Experimental results demonstrate that the synthesis of ZnO nanowires is dependent on the crystalline properties of the ZnO seed-layer films. Sol concentration is the controlled parameter for the preparation of ZnO seed-layer films in this study. The ZnO films are found to have the hexagonal wurtzite structure with highly preferred growth along the c-axis at suitable sol concentrations. The vertically aligned ZnO nanowire arrays on the substrates are believed to be the result of the epitaxial growth of the ZnO seed layer. Scanning electron microscopy shows that nanowires with uniform distribution in length, diameter, and density are obtained. X-ray diffraction patterns clearly reveal that the ZnO nanowires are primarily grown along the c-axis direction. Transmission electron microscopy and selected-area electron diffraction measurements show that the nanowires have good crystalline properties. The well-aligned and high surface areas of the ZnO nanowires make them a potential candidate for applications in solar cells, field emission devices, and ultra-sensitive gas sensors.     

化学浴沉积过程中的氧化锌微米棒与纳米棒研究

采用化学浴沉积法在氧化锌种子层上制备了整齐有序且具有c轴取向的氧化锌纳米棒,同时还出现了自由分布的微米棒,其生长速度高于纳米棒,且生长模式符合扩散控制"Ostwald熟化"机制,但纳米棒生长过程的影响因素除扩散过程外还有形核密度、生长界面的反应动力学等.并研究了氧化锌纳米棒的微观结构和光学性质.     

Structure and physical properties of undoped ZnO and vanadium doped ZnO films deposited by pulsed laser deposition

Undoped ZnO films were deposited using pulsed laser deposition technique on Si and glass substrates in different O2 partial pressures (ranging from 10(-5) mbar to 3 mbar) and substrate temperatures. When the substrate temperature is 500 degrees C and O2 partial pressure (pp) approximately 3 mbar, randomly oriented ZnO hexagons were observed on glass substrate, whereas, dense ZnO hexagonal rod like structures (diameter ranging from 200-500 nm) were observed on Si substrate. The photoluminescence (PL) characterization of ZnO film grown on Si exhibited an intense defect free narrow excitonic emission in the UV region (Full width half maximum (FWHM) approximately 11.26 nm) as compared to broad emission (FWHM approximately 57.06 nm) from that grown on glass. The parent film emission was found to shift from UV to blue region on doping ZnO with Vanadium.     

Dramatically enhanced ultraviolet photosensing mechanism in a n-ZnO nanowires/i-MgO/n-Si structure with highly dense nanowires and ultrathin MgO layers

This study reports that the visible-blind ultraviolet (UV) photodetecting properties of ZnO nanowire based photodetectors were remarkably improved by introducing ultrathin insulating MgO layers between the ZnO nanowires and Si substrates. All layers were grown without pause by metal organic chemical vapor deposition and the density and vertical arrangement of the ZnO nanowires were strongly dependent on the thickness of the MgO layers. The sample in which an MgO layer with a thickness of 8 nm was inserted had high density nanowires with a vertical alignment and showed dramatically improved UV photosensing performance (photo-to-dark current ratio = 1344.5 and recovery time = 350 ms). The photoresponse spectrum revealed good visible-blind UV detectivity with a sharp cut off at 378 nm and a high UV/visible rejection ratio. A detailed discussion regarding the developed UV photosensing mechanism from the introduction of the i-MgO layers and highly dense nanowires in the n-ZnO nanowires/i-MgO/n-Si substrates structure is presented in this work.     

不同衬底上低温生长的ZnO晶体薄膜的结构及光学性质比较

采用电子束反应蒸发方法,在单晶Si(001)及玻璃衬底上低温外延生长了沿c轴高度取向的单晶ZnO薄膜,并对沉积的ZnO晶体薄膜的结构和光学性质进行了分析比较。通过对ZnO薄膜的X射线衍射(XRD)分析及光致荧光激发谱(PLE)测量,研究了衬底材料结构特性、生长温度及反应气氛中充O     

Wire-shaped quantum dots-sensitized solar cells based on nanosheets and nanowires

Wire-shaped quantum dots-sensitized solar cells (WS-QDSCs) based on nanosheets and nanowires were fabricated and investigated for this paper. The nanosheets grown on stainless steel (SS) wire by electrodeposition were mainly composed of Zn?(OH)?Cl?·H?O and most of the Zn?(OH)?Cl?·H?O was converted to ZnO by post-treatment, and ZnO nanowires were directly grown on SS wire by the hydrothermal method. CdS QDs were deposited on nanosheets and nanowires by successive ionic layer adsorption and reaction method. The results of photoelectrochemical performance indicated that WS-QDSCs showed a similar conversion efficiency in polysulfide and Na?SO? electrolytes, while the WS-QDSCs based on the Cu2S counter electrode achieved much higher performance than those based on SS and Cu counter electrodes. By optimizing electrodeposition duration, the WS-QDSCs based on nanosheets presented the highest conversion efficiency of 0.60% for the duration of 20 min. Performance comparison indicated that the WS-QDSC based on nanosheets showed very superior performance to that based on the nanowires with similar film thickness.     

Controlled growth of ZnO nanomaterials via hydrothermal method: effect of buffer layer

We report a facile solution-based method for the controlled growth of ZnO nanomaterials on an AIN/Si substrate. A ZnO buffer layer was coated on the substrate before growing the ZnO nano-materials. The shape of the ZnO nanomaterials changed from nanosheet to nanorod as the thickness of the ZnO buffer layer increased. Doping of the buffer layer with Ga decreased the average grain size of the ZnO buffer layer, which resulted in the growth of longer and thinner ZnO nanorods on the buffer layer. The UV sensing results of the ZnO nanorod-based device revealed that the aspect ratio of the ZnO nanorods is crucial for enhancing the performance of the device.     

Selective MOCVD growth of ZnO nanotips

ZnO is a wide bandgap semiconductor with a direct bandgap of 3.32eV at room temperature. It is a candidate material for ultraviolet LED and laser. ZnO has an exciton binding energy of 60 meV, much higher than that of GaN. It is found to be significantly more radiation hard than Si, GaAs, and GaN, which is critical against wearing out during field emission. Furthermore, ZnO can also be made as transparent and highly conductive, or piezoelectric. ZnO nanotips can be grown at relatively low temperatures, giving ZnO a unique advantage over the other nanostructures of wide bandgap semiconductors, such as GaN and SiC. In the present work, we report the selective growth of ZnO nanotips on various substrates using metalorganic chemical vapor deposition. ZnO nanotips grown on various substrates are single crystalline, n-type conductive and show good optical properties. The average size of the base of the nanotips is 40 nm. The room temperature photoluminescence peak is very intense and sharp with a full-width-half-maximum of 120 meV. These nanotips have potential applications in field emission devices, near-field microscopy, and UV photonics.     

ZnO薄膜的晶体性能的分析

在硅基上制备出了c轴取向高度一致的ZnO薄膜 ,这将有可能成为新型GaN单晶薄膜的过渡层。对ZnO薄膜的晶体性能进行了分析 ,研究不同衬底和不同衬底温度对ZnO薄膜的结晶状况的影响 ,并着重用TEM研究了硅基ZnO薄膜的晶体性能。     

Seed-layer controlled synthesis of well-aligned ZnO nanowire arrays via a low temperature aqueous solution method

A simple and controllable method has been developed to synthesize well-aligned ZnO nanowire arrays on silicon and glass substrates in aqueous solution. A thin ZnO seed-layer coated with colloidal ZnO nanocrystals was introduced to control the density and orientation of ZnO nanowires. X-ray diffraction (XRD) and scanning electron microscopy (SEM) result show the high dense and well-aligned character of ZnO nanowires. The photoluminescence (PL) reveals the high crystal quality of the nanowires. It was found that the ZnO seed-layer can effect the size distribution, density and crystal structure of the nanowires. The growth mechanism of ZnO nanowires was also discussed.     

Electrodeposition of hierarchical ZnO nanorod-nanosheet structures and their applications in dye-sensitized solar cells

We present a two-step electrochemical deposition process to synthesize hierarchical zinc oxide (ZnO) nanorod-nanosheet structures on indium tin oxide (ITO) substrate, which involves electrodeposition of ZnO nanosheet arrays on the conductive glass substrate, followed by electrochemical growth of secondary ZnO nanorods on the backbone of the primary ZnO nanosheets. The formation mechanism of the hierarchical nanostructure is discussed. It is demonstrated that annealing treatment of the primary nanosheets synthesized by the first-step deposition process plays a key role in synthesizing the hierarchical nanostructure. Photovoltaic properties of dye-sensitized solar cells (DSSCs) based on hierarchical ZnO nanostructures are investigated. The hierarchical ZnO nanorod-nanosheet DSSC exhibits improved device performance compared to the DSSC constructed using photoelectrode of bare ZnO nanosheet arrays. The improvement can be attributed to the enhanced dye loading, which is caused by the enlargement of internal surface area within the nanostructure photoelectrode. Furthermore, we perform a parametric study to determine the optimum geometric dimensions of the hierarchical ZnO nanorod-nanosheet photoelectrode through adjusting the preparation conditions of the first- and second-step deposition process. By utilizing a hierarchical nanostructure photoelectrode with film thickness of about 7 μm, the DSSC with an open-circuit voltage of 0.74 V and an overall power conversion efficiency of 3.12% is successfully obtained.     

Selective growth of ZnO nanorods on SiO2/Si substrates using a graphene buffer layer

A promising strategy for the selective growth of ZnO nanorods on SiO₂/Si substrates using a graphene buffer layer in a low temperature solution process is described. High densities of ZnO nanorods were grown over a large area and most ZnO nanorods were vertically well-aligned on graphene. Furthermore, selective growth of ZnO nanorods on graphene was realized by applying a simple mechanical treatment, since ZnO nanorods formed on graphene are mechanically stable on an atomic level. These results were confirmed by first principles calculations which showed that the ZnO-graphene binding has a low destabilization energy. In addition, it was found that ZnO nanorods grown on SiO₂/Si with a graphene buffer layer have better optical properties than ZnO nanorods grown on bare SiO₂/Si. The nanostructured ZnO-graphene materials have promising applications in future flexible electronic and optical devices.     

Effects of substrate parameters on structure and optical properties of ZnO thin films fabricated by pulsed laser deposition

Highly oriented zinc oxide thin films have been grown on quartz, Si (1 1 1) and sapphire substrates by pulsed laser deposition (PLD). The effect of temperature and substrate parameter on structural and optical properties of ZnO thin films has been characterized by X-ray diffraction (XRD), atomic force microscopy (AFM), optical transmission spectra and PL spectra. The experimental results show that the best crystalline thin films grown on different substrate with hexagonal wurtzite structure were achieved at growth temperature 400–500 °C. The growth temperature of ZnO thin film deposited on Si (1 1 1) substrate is lower than that of sapphire and quartz. The band gaps are increasing from 3.2 to 3.31 eV for ZnO thin film fabricated on quartz substrate at growth temperature from 100 to 600 °C. The crystalline quality and UV emission of ZnO thin film grown on sapphire substrate are significantly higher than those of other ZnO thin films grown on different substrates.     

Structure, photoluminescence and wettability properties of well arrayed ZnO nanowires grown by hydrothermal method

Well aligned ZnO nanowire arrays with high crystal quality were grown on Si substrates at a low temperature (50 degrees C) by hydrothermal method using a pre-formed ZnO seed layer. ZnO seeds were prepared via radio-frequency magnetron sputtering onto Si substrates. The morphologies of the ZnO nanowire arrays were shown by field emission scanning electron microscopy. X-ray diffraction spectra showed that the full width at the half maximum of the (0002) peak of the nanowire arrays without any heat treatment was only 0.07 degrees, indicating very high crystal quality. Furthermore, the room-temperature photoluminescence spectra of the ZnO nanowire arrays exhibited excellent UV emission. The special micro/nano surface structure of the ZnO nanowire arrays can enhance the dewettability for surfaces modified via low surface energy materials such as long chain fluorinated organic compounds. The surface of the ZnO nanowire arrays is also found to be superhydrophobic with a contact angle of 165 degrees +/- 1 degrees, while the sliding angle is 3 degrees.     

Position and density control in hydrothermal growth of ZnO nanorod arrays through pre-formed micro/nanodots

Position-?and density-controlled ZnO nanorod arrays (ZNAs) were successfully grown on a Si substrate through a low temperature (90?°C) hydrothermal approach assisted by pre-formed ZnO micro/nanodots. The ZnO dots on Si substrates were prepared by a spin-coating technique, through which the pattern and density of the dots could be easily changed. Accordingly, the position-?and density-controlled growth of ZNAs was achieved. For the resulting density-controlled ZNAs, the density could range from (5.6 ± 0.01) × 10(2) to (1.2 ± 0.01) × 10(2)?rods?μm(-2). The room-temperature photoluminescence (PL) spectrum of ZNAs exhibited excellent UV emission. The water wettability measurements of the ZNAs with different density showed good hydrophobicity, and the ZNAs with the lowest density revealed a superhydrophobic characteristic with a water contact angle of 166.1°.     

Carrier transport mechanism on ZnO nanorods/p-Si heterojunction diodes with various atmospheres annealing hydrothermal seed-layer

Annealing in various atmospheres (vacuum, N₂, and O₂) was employed for a hydrothermal seed-layer. The influence on ZnO nanorods (NRs) and carrier transport of ZnO NRs/p-Si heterojunction diodes (HJDs) was investigated. In this work, a hydrothermal method was employed to prepare a seed-layer on a Si substrate, and then annealing at 450 °C in various atmospheres was carried out to improve the subsequent growth of ZnO NRs according to the same method. Observations indicated that ZnO NRs with an O₂-annealed seed-layer have a higher nucleation density and absorb fewer OH groups or O₂⁻ ions, and hence they have fewer defect-level centres. This leads to a very large rectification ratio of 1.9 × 10⁵ in the ZnO NRs/p-Si HJDs because oxygen atoms compensate for the oxygen vacancy-related defects. More band-gap states are present at the ZnO/p-Si interface for the vacuum annealing sample, and this enables recombination-tunnelling transport with a rather large ideality factor of 7 at forward voltage less than 0.7 V. In contrast, diffusion-recombination transport was obtained in the N₂- and O₂-annealed samples with ideality factors as low as 2.4 and 2.2, respectively.     

Ultraviolet lasing action in ZnO nanosheets

We report room-temperature ultraviolet lasing action in large quantities of uniform multilayer ZnO nanosheets grown by a vapor-transport method via thermal evaporation of Zn powder. An excellent multimode lasing emission at a center wavelength of 390 nm with a mode linewidth less than 0.33 nm occurs above an excitation threshold of 8 mJ pulse(-1) cm(-2). The observed multimode lasing action may be attributed to microcavity effect and low concentration of defects in the nanosheets. We believe that the single-mode lasing emission can be obtained by growing completely uniform nanosheets. ZnO nanosheet is an attractive candidate as gain medium to realize ultraviolet semiconductor diode lasers.     

热处理温度对溶胶-凝胶法制备ZnO薄膜晶体结构和发光特性的影响

采用溶胶-凝胶(Sol-Gel)旋涂法在Si(100)衬底上制备ZnO薄膜,利用X射线衍射(XRD)、光致发光谱(PL)、扫描电子显微镜(SEM)等手段分析制得的ZnO薄膜的晶体结构和发光特性。着重考察了热分解温度对ZnO薄膜晶体结构和发光特性的影响。结果表明,溶胶-凝胶旋涂法制备的ZnO薄膜样品厚度约为220nm,属六方纤锌矿结构,其c轴取向度与热分解温度有很大关系;ZnO薄膜在室温下均有较强的紫外带边发射峰,且紫外带边发射峰与样品c轴取向度没有直接关系,与缺陷有关的可见发射带很弱。