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.     

缓冲层厚度对透明导电薄膜ZnO:Zr性能的影响

利用直流磁控溅射法在有ZnO:Zr缓冲层的水冷玻璃衬底上成功制备出了ZnO:Zr透明导电薄膜,缓冲层的厚度介于35～208 nm.利用XRD、SEM、四探针测试仪和紫外-可见分光光度计研究ZnO:Zr薄膜的结构、形貌、电光性能.结果表明,薄膜的颗粒尺寸和电阻率对缓冲层厚度具有较强的依赖性.当缓冲层厚度从35 nm增加到103 nm时,薄膜的颗粒尺寸增大,电阻率减小.而当缓冲层厚度从103 nm增加到208 nm时,薄膜的颗粒尺寸减小,电阻率增大.当缓冲厚度为103 nm时,薄膜的电阻率最小为2.96×10-3 Ω·cm,远小于没有缓冲层时的12.9×10-3 Ω·cm.实验结果表明,在沉积薄膜之前先沉积一层适当的缓冲层是提高ZnO:Zr薄膜质量的一种有效方法.     

A Method for Fabricating an Ultrathin Multilayer Film Composed of Poly(p‐phenylenevinylene) and Reduced Graphene Oxide on a Plastic Substrate for Flexible Optoelectronic Applications

The photoconductive properties of a uniform ultrathin multilayer film composed of alternating poly(p‐phenylene vinylene) (PPV) and reduced graphene oxide (RGO) layers, fabricated on a poly(ethylene terephthalate) (PET) sheet are reported. The assembly of the two electron‐rich layer components on the temperature‐sensitive substrate is realized using a layer‐by‐layer‐deposition technique under mild conditions and HI/H₂O vapor treatment at 100 °C. This protocol is established to simultaneously convert the layer components to their conjugated counterparts, PPV and RGO in the multilayer films, whose total thicknesses shrinks to 50% of their original values due to lattice contraction. Furthermore, the surface roughness decreases significantly, in contrast to the results obtained from general chemical treatments. The PET sheets coated with (PPV/RGO)₁₅ films exhibit a photocurrent of 115 μA at an illumination intensity of 1.1 mW and a photoresponsivity of 111.1 mA W^?1 at an illumination intensity of 0.5 mW; these are among the best values yet achieved in carbon‐based materials. The establishment of a method for fabricating (PPV/RGO) films on a temperature‐sensitive transparent flexible sheet is crucial for the development of organic‐based portable electronic devices.     

Thermally Conductive Reduced Graphene Oxide Thin Films for Extreme Temperature Sensors

Reduced graphene oxide (RGO) films are promising in applications ranging from electronics to flexible sensors. Though high electrical and thermal conductivities have been reported for RGO films, existing thermal conductivity data for RGO films show large variations from 30 to 2600 W m^?1 K^?1. Further, there is a lack of data at low temperatures (<300 K), which is critical for the understanding of thermal transport mechanisms. In this work, a temperature‐dependent study of thermal (10–300 K) and electrical (10–3000 K) transport in annealed RGO films indicates the potential application of RGO films for sensing temperatures across an extremely wide range. The room‐temperature thermal conductivity increases significantly from 46.1 to 118.7 W m^?1 K^?1 with increasing annealing temperature from 1000 to 3000 K with a corresponding increase in the electrical conductivity from 5.2 to 1481.0 S cm^?1. In addition, films reduced at 3000 K are promising for sensing extreme temperatures as demonstrated through the measured electrical resistivity from 10 to 3000 K. Sensors based on RGO films are advantageous over conventional temperature sensors due to the wide temperature range and flexibility. Thus, this material is useful in many applications including flexible electronics and thermal management systems.     

Near‐Infrared Light‐Driven,Highly Efficient Bilayer Actuators Based on Polydopamine‐Modified Reduced Graphene Oxide

Near‐infrared (NIR) light‐driven bilayer actuators capable of fast, highly efficient, and reversible bending/unbending motions toward periodic NIR light irradiation are fabricated by exploiting the photothermal conversion and humidity‐sensitive properties of polydopamine‐modified reduced graphene oxide (PDA‐RGO). The bilayer actuator comprises a PDA‐RGO layer prepared by a filtration method, and this layer is subsequently spin‐coated with a layer of UV‐cured Norland Optical Adhesive (NOA)‐63. Given the hydrophilicity of PDA, the PDA‐RGO layer can absorb water to swell and lose water to shrink. The intrinsic NIR absorbance of RGO sheets convertes NIR light into thermal energy, which transfers the humidity‐responsive PDA‐RGO layer to be NIR light‐responsive. Considering that the shape of the NOA‐63 layer remains unchanged under NIR light, periodic NIR light irradiation leads to asymmetric shrinkage/expansion of the bilayer, which enables fast and reversible bending/unbending motions of the bilayer actuator. We demonstrate that compared with a poly(ethylenimine)‐modified graphene oxide layer, the PDA‐RGO layer is unique in fabricating highly efficient bilayer actuators. A NIR light‐driven walking device capable of performing quick worm‐like motion on a ratchet substrate is built by connecting two polyethylene terephthalate plates as claws on opposite ends of the PDA‐RGO/NOA‐63 bilayer actuator.     

Highly Stable Graphene‐Based Multilayer Films Immobilized via Covalent Bonds and Their Applications in Organic Field‐Effect Transistors

Highly stable graphene oxide (GO)‐based multilayered ultrathin films can be covalently immobilized on solid supports through a covalent‐based method. It is demonstrated that when (3‐aminopropyl) trimethoxysilane (APTMS), which works as a covalent cross‐linking agent, and GO nanosheets are assembled in an layer‐by‐layer (LBL) manner, GO nanosheets can be covalently grafted on the solid substrate successfully to produce uniform multilayered (APTMS/GO)N films over large‐area surfaces. Compared with conventional noncovalent LBL films constructed by electrostatic interactions, those assembled using this covalent‐based method display much higher stability and reproducibility. Upon thermal annealing‐induced reduction of the covalent (APTMS/GO)N films, the obtained reduced GO (RGO) films, (APTMS/RGO)N, preserve their basic structural characteristics. It is also shown that the as‐prepared covalent (APTMS/RGO)N multilayer films can be used as highly stable source/drain electrodes in organic field‐effect transistors (OFETs). When the number of bilayers of the (APTMS/RGO)N film exceeds 2 (ca. 2.7 nm), the OFETs based on (APTMS/RGO)N electrodes display much better electrical performance than devices based on 40 nm Au electrodes. The covalent protocol proposed may open up new opportunities for the construction of graphene‐based ultrathin films with excellent stability and reproducibility, which are desired for practical applications that require withstanding of multistep post‐production processes.     

RGO-CdSe纳米复合材料的制备及其光学非线性吸收特性

通过两相法制备了氧化石墨烯 -硒化镉(GO-CdSe)纳米复合材料,并进一步通过水合肼还原, 制备了还原氧化石墨烯-硒化镉(RGO-CdSe)纳米复合材料。通过透射电镜(TEM)、 X射线衍射仪(XRD)、紫外可见光吸收(UV-Vis)光谱和荧光(PL)光谱对复合材料的 形貌、结 构和光学特性进行了表征。CdSe量子点为闪锌矿结构,粒径在6nm左右,基本均匀的分布在 RGO片上。在波长为532nm、脉冲宽度为30ps 的激光作用下,采用单光束Z扫描 技术,对复合材料的三阶光学非线性吸收性质进行了研究。研究发现,RGO-CdSe纳米复合 材料展现出反饱和吸收的非线性光学特性;相对于未附着CdSe量子点的 RGO,复合材料的光学非线性吸收特性有所增强。RGO-CdSe纳米复合材料的非线性吸收系数 为18.3cm/GW,高于纯RGO的11.2cm/GW。实 验 结果表明,RGO-CdSe纳米复合材料在光限幅器、光开关等光学器件方面有着潜在的应用前 景。     

Study on the fluorescence quenching of ZnO by graphene oxide

Zinc oxide (ZnO) microrod arrays were synthesized on Si substrate by a vapor phase transport (VPT) method in a tube furnace. The obtained ZnO microrods are characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The photoluminescence (PL) measurement indicates that the ZnO microrods have a strong ultraviolet (UV) emission centered at ~391 nm and a defect-related emission centered at ~530 nm. After the microrods were coated with graphene oxide (GO), the PL intensity of the hybrid microstructure is quenched compared with that of the bare one at the same excitation condition, and the PL intensity changes with the concentration of the GO. The fluorescence quenching mechanism is also discussed in this work.     

Metal oxide sandwiched dye-sensitized solar cells with enhanced power conversion efficiency fabricated by a facile and cost effective method

Developing efficient and cost effective photoanode and counter electro materials have been a persistent objective by a wide community for efficient, cost effective and stable dye-sensitized-solar cells (DSSCs). We have developed a unique and inexpensive way of co-electroplating-annealing method to synthesize metal oxides and employed it to prepare ZnO material on top of doctor bladed TiO₂ as photoanode and CuO on top of reduced graphene oxide (RGO) as counter electrode. By sandwiching these two electrodes with I^-/I₃ redox couple in-between we have shown the improvement of photovoltaic properties with ZnO barrier layer using Pt or cost effective CuO/RGO counter electrodes (CEs). This paper provides a comprehensive guide to prepare those electrodes cost effectively and fabricate metal oxide sandwiched DSSCs providing up to 6.91% power conversion efficiency with 26.5% enhancement compared to the conventional DSSCs with TiO₂ photoanode and Pt CE under AM1.5 simulated solar light. This work also addresses the reduction of fabrication cost of the cells to make them more economically viable as it is     

衬底温度对磁控溅射法制备的ZnO:In薄膜光电性能的影响

以粉末靶为溅射源,采用射频磁控溅射法在玻璃衬底上制备掺铟氧化锌(ZnO:In)透明导电膜.利用X射线衍射仪、原子力显微镜、霍尔测试仪,以及分光光度计等对不同衬底温度下生长的ZnO:In薄膜的结构、光电性能进行表征.结果表明,所有制备的ZnO:In薄膜均为六角纤锌矿结构的多晶膜,具有(002)择优取向.ZnO:In薄膜的电阻率随着衬底温度的升高先减小后增大,当衬底温度为100℃时,薄膜的最低电阻率为3.18×10~(-3)Ω·cm.制备的薄膜可见光范围内透过率均在85%以上.

Abstract：

Indium doped zinc oxide (ZnO : In) films were deposited on glass substrates by RF magnetron sputtering method using a powder target.The influence of the substrate temperature on the structure,optical and electrical properties was investigated by X-ray diffraction (XRD),atom force microscope (AFM),Hall measurement and optical transmission spectroscopy.The results show all the obtained films are polycrystalline with a hexagonal wurtzite structure and grow preferentially in the (002) direction,and the grain size is about 22～29 nm.The conductivity of the ZnO : In films change with the substrate temperature,and the lowest electrical resistivity is about 3.18 × 10~3 Ω·cm for the samples deposited at substrate temperature 100 ℃.The transmittance of our films in the visible range is all higher than 85%.     

Electrodeposition and characterization of ZnO thin films using sodium thiosulfate as an additive for photovoltaic solar cells

Zinc oxide thin films have been grown by electrodeposition technique onto Cu and ITO-coated glass substrates from an aqueous zinc nitrate solution with addition of sodium thiosulfate at 90℃.The effects of sodium thiosulfate on the electrochemical deposition of ZnO were investigated by cyclic voltammetry and chronoamperometry techniques.Deposited films were obtained at -0:60 V vs.SCE and characterized by XRD,SEM,FTIR, optical,photoelectrochemical and electrical measurements.Thickness of the deposited film was measured to be 357 nm.X-ray diffraction results indicated that the synthesized ZnO has a pure hexagonal wurtzite structure with a marked preferential orientation along (002) plane.FTIR results confirmed the presence of ZnO films at peak 558 cm^-1.SEM images showed uniform,compact morphology without any cracks and films composed of large flower-like ZnO agglomerates with star-shape.Optical properties of ZnO reveal a high optical transmission (>80%) and high absorption coefficient (α>105 cm^-1)in visible region.The optical energy band gap was found to be 3.28 eV.Photoelectrochemical measurements indicated that the ZnO films had n-type semiconductor conduction.Electrical properties of ZnO films showed a low electrical resistivity of 6.54 Ω·cm,carrier concentration of -1.3×10¹⁷cm^-3 and mobility of 7.35 cm²V^-1s^-1.     

ZnO薄膜对于CdTe太阳电池的影响*

通过直流磁控溅射法在ITO薄膜上沉积的ZnO薄膜可以作为CdTe太阳电池的高阻层。通过XRD,可见-红外可见光谱仪和四探针法分析了制备薄膜的结构,光学和电学性质。通过紫外光电子能谱和X射线光电子能谱深度刻蚀法分析了ITO/ZnO和ZnO/CdS薄膜的界面性质。结果表明：ZnO 作为高阻层有良好的光学和电学性质。ZnO 薄膜降低了ITO和CdS之间的势垒。 制备出来电池有ZnO（没有ZnO）的能量转换效率和量子效率是12.77% (8.9%) 和 >90% (79%)。 进一步,通过AMPS-1D模拟分析了ZnO薄膜厚度对于CdTe太阳电池的影响。     

退火温度对ZnO掺杂ITO薄膜性能的影响

利用电子束蒸镀方法,在K8玻璃衬底上沉积ZnO掺杂ITO(ZnO-ITO)与ITO薄膜。研究不同退火温度对ZnO-ITO薄膜的微观结构的影响;对比分析了在不同退火温度条件下,ZnO-ITO和无掺杂ITO薄膜的光电性能。结果发现,ZnO-ITO薄膜具有较大的晶粒尺寸,随着退火温度的上升,晶体结构得到改善,表面粗糙度减小,薄膜的光电性能显著提高。ZnO-ITO薄膜经过500℃退火后得到最佳的综合性能,其表面均方根粗糙度(RMS)为32.52nm,电阻率为1.43×10-4Ω.cm;对442nm波长的光,透射率可达98.37%;与ITO薄膜相比,ZnO-ITO薄膜具有显著的抗PEDOT:PSS溶液腐蚀的能力。     

玻璃和聚酰亚胺衬底上磁控溅射沉积的ZnO:Al透明导电膜的结构、电学和光学性能(英文)

利用射频磁控溅射方法在玻璃和聚酰亚胺膜(PI)衬底上沉积了氧化铝质量分数为2%的掺铝氧化锌透明导电薄膜(ZnO∶Al)。系统地研究了不同衬底材料对薄膜的结构、电学以及光学性能的影响。分析表明,衬底材料对薄膜的结晶性和电学性能有较大的影响,对可见光透射率却影响不大。X射线衍射(XRD)分析得出所有的ZnO∶Al具有良好的c轴择优取向性,在可见光区(400～800nm)两种衬底上的薄膜都达到了85%的透射率。玻璃衬底上的薄膜呈现出更强的(002)衍射峰及相对更小的半峰全宽(FWHM),薄膜电阻率达到了2.352×10-4Ω.cm。电镜分析表明,相对于PI上的ZnO∶Al膜,玻璃上ZnO∶Al膜表面有更致密的微观结构及更大的晶粒尺寸。PI衬底上的ZnO∶Al膜也有相对较好的电、光学性能,其中电阻率达到了6.336×10-4Ω.cm,而且由于PI衬底柔性可弯曲,使得它适于在柔性太阳电池和柔性液晶显示中做窗口层材料及透明导电电极。玻璃上的ZnO∶Al膜则可应用在平板显示和太阳电池技术中。     

High rate (~7 nm/s), atmospheric pressure deposition of ZnO front electrode for Cu(In,Ga)Se2 thin‐film solar cells with efficiency beyond 15%

Undoped zinc oxide (ZnO) films have been grown on a moving glass substrate by plasma‐enhanced chemical vapor deposition at atmospheric pressure. High deposition rates of ~7 nm/s are achieved at low temperature (200 °C) for a substrate speed from 20 to 60 mm/min. ZnO films are highly transparent in the visible range (90%). By a short (~minute) post‐deposition exposure to near‐ultraviolet light, a very low resistivity value of 1.6·10⁻³ Ω cm for undoped ZnO is achieved, which is independent on the film thickness in the range from 180 to 1200 nm. The photo‐enhanced conductivity is stable in time at room temperature when ZnO is coated by an Al₂O₃ barrier film, deposited by the industrially scalable spatial atomic layer deposition technique. ZnO and Al₂O₃ films have been used as front electrode and barrier, respectively, in Cu(In,Ga)Se2 (CIGS) solar cells. An average efficiency of 15.4 ± 0.2% (15 cells) is obtained that is similar to the efficiency of CIGS reference cells in which sputtered ZnO:Al is used as electrode. Copyright © 2013 John Wiley & Sons, Ltd.     

溅射功率对PET衬底上ZnO:Zr薄膜性能的影响

采用直流磁控溅射法在室温下柔性PET衬底上制备出了高质量的掺锆氧化锌(ZnO:Zr)透明导电薄膜。研究了溅射功率对ZnO:Zr薄膜表面形貌、结构、电学和光学性能的影响。溅射功率对ZnO:Zr薄膜的电阻率影响显著:当溅射功率从60W增加到90W时,薄膜的电阻率先减小后增大,在最佳功率80W时,电阻率具有最小值3.67×10-3Ω·cm。所制备的ZnO:Zr薄膜具有良好的附着性能,在可见光区平均透射率高达90%。     

溅射压强对柔性PET衬底ZnO薄膜性能的影响

利用直流磁控溅射法,在室温水冷柔性PET衬底上成功制备出了掺钛氧化锌(ZnO:Ti,TZO)透明导电薄膜。通过X射线衍射(XRD)研究了薄膜的结构,用扫描电镜(SEM)研究了薄膜的表面形貌,用四探针和紫外-可见分光光度计等仪器对薄膜的特性进行测试分析,研究了溅射压强对ZnO:Ti薄膜表面结构、形貌、力学、电学和光学性能的影响。结果表明,溅射压强对PET衬底上的TZO薄膜的性能有显著的影响,实验制备的ZnO:Ti薄膜为具有C轴择优取向的六角纤锌矿结构的多晶薄膜;当溅射压强从2Pa增加到4Pa时,薄膜的电阻率由10.87×10-4Ω.cm快速减小到4.72×10-4Ω.cm,随着溅射压强由4Pa继续增大到6Pa,薄膜的电阻率变化平缓,溅射压强为5Pa时薄膜的电阻率最小,为4.21×10-4Ω.cm;经计算得到6Pa时样品薄膜应力最小,为0.785 839GPa;所有样品都具有高于91%的可见光区平均透过率。     

π‐Conjugated Molecules Crosslinked Graphene‐Based Ultrathin Films and Their Tunable Performances in Organic Nanoelectronics

Graphene‐based ultrathin films with tunable performances, controlled thickness, and high stability are crucial for their uses. The currently existing protocols, however, could hardly simultaneously meet these requirements. Using amino‐substituted π‐conjugated compounds, including 1,4‐diaminobenzene (DABNH2), benzidine (BZDNH2), and 5,10,15,20‐tetrakis (4‐aminophenyl)‐21H,23H‐porphine (TPPNH2), as cross‐linkages, a new protocol through which graphene oxide (GO) nanosheets can be anchored on solid supports with a high stability and controlled thickness via a layer‐by‐layer method is presented. A thermal annealing leads to the reduction of the films, and the qualities of the samples can be inherited by the as‐produced reduced GO films (RGO). When RGO films are integrated as source/drain electrodes in OFETs, tunable performances can be realized. The devices based on the BZDNH2‐crosslinked RGO electrodes exhibit similar electrical behaviors as those based on the non‐π‐conjugated compound crosslinked electrodes, while improved performances can be gained when those crosslinked by DABNH2 are used. The performances can be further improved when RGO films crosslinked by TPPNH2 are employed. This work likely paves a new avenue for graphene‐based films of tunable performances, controlled thickness, and high stability.     

Indium doped zinc oxide thin films deposited by ultrasonic spray pyrolysis technique: Effect of the substrate temperature on the physical properties

Indium doped zinc oxide (ZnO:In) thin solid films were deposited on soda-lime glass substrates by the ultrasonic spray pyrolysis technique. The effect of the substrate temperature on the electrical, morphology, and optical characteristics of ZnO:In thin films was studied. It was found that, as the substrate temperature increases, the electrical resistivity decreases, reaching a minimum value in the order of 7.3×10⁻³ Ω cm, at 415 °C. Further increase in the substrate temperature results on an increment on the electrical resistivity of the thin solid films. All the samples were polycrystalline with a well-defined wurtzite structure. The preferred growth shows a switching from a random orientation at low substrates temperatures to (0 0 2) in the case of films deposited at the highest substrate temperature used. As the substrate temperature increases, the corresponding surface morphology changes from an almost faceted pyramidal to round-shaped form. The optical transmittance of the films in a interval of 400 to 700 nm is around 70%, with a band gap value in the order of 3.45 eV.     

WZO薄膜生长及氧流量对其特性的影响

采用直流脉冲反应磁控溅射方法生长W掺杂ZnO(ZnO:W,即WZO)透明导电氧化物(TCO)薄膜并研究了氧气流量对薄膜微观结构、组分、表面形貌以及光电性能的影响。实验结果表明,WZO薄膜具有良好的(002)晶面择优取向生长,且适当的氧气流量是制备优质WZO薄膜的关键因素。WZO薄膜表面形貌受薄膜结晶质量的影响。当氧气流量为2.08×10-7 m3/s时,WZO薄膜在400～1 500nm透过率达到84.5%,电阻率为4.61×10-3Ω.cm,迁移率为20.5cm2v-1s-1。XPS测试表明WZO薄膜中Zn和W均处于氧化态,其中W元素呈现W6+价态。