Formation of organic crystalline nanopillar arrays and their application to organic photovoltaic cells

To enhance the performance of organic photovoltaic (OPV) cells, preparation of organic nanometer-sized pillar arrays is fascinating because a significantly large area of a donor/acceptor heterointerface having continuous conduction path to both anode and cathode electrodes can be realized. In this study, we grew cupper phthalocyanine (CuPc) crystalline nanopillar arrays by conventional thermal gradient sublimation technique using a few-nanometer-sized trigger seeds composed of a CuPc and 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) stacked layer. We optimized the pillar density by tuning crystal growth condition in order to apply it to OPV cells.     

Performance of polymer/ZnO hybrid photovoltaic devices determined by reaction time for oriented ZnO nanorod growth

The performance of hybrid polymer/metal oxide photovoltaic devices based on poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) and oriented ZnO nanorods is studied. The ZnO nanorods on indium tin oxide-coated glass were prepared by hydrothermal method, where the length and the defect concentration of ZnO nanorods were controlled by the reaction time (T_r) for nanorod growth. Increasing T_r results in longer ZnO nanorods and higher defect concentration. Results show that both photocurrent and electron lifetime have strong dependence on the nanorod length (i.e., growth time) due to the exponential attenuation of incident light intensity in the device, offering a peak conversion efficiency of 0.337% under 1.5 AM illumination for T_r = 120 min. Combinational analyses of the data in this experiment and the previous data for the electrodeposited ZnO nanorods provide the insights into the dependence of the device performance on the intrinsic property of the ZnO nanorods.     

Hybrid photovoltaic devices of polymer and ZnO nanofiber composites

Organic semiconductor-based photovoltaic devices offer the promise of a low-cost photovoltaic technology that could be manufactured via large-scale, roll-to-roll printing techniques. Existing organic photovoltaic devices have currently achieved solar power conversion efficiencies greater than 3%. Although encouraging, the reasons higher efficiencies have not been achieved are poor overlap between the absorption spectrum of the organic chromophores and the solar spectrum, non-ideal band alignment between the donor and acceptor species, and low charge carrier mobilities resulting from the disordered nature of organic semiconductors. To address the latter issues, we are investigating the development of nanostructured oxide/conjugated polymer composite photovoltaic (PV) devices. These composites can take advantage of the high electron mobilities attainable in oxide semiconductors and can be fabricated using low-temperature solution-based growth techniques. Additionally, the morphology of the composite can be controlled in a systematic way through control of the nanostructured oxide growth. ZnO nanostructures that are vertically aligned with respect to the substrate have been grown. Here we discuss the fabrication of such nanostructures and present results from ZnO nanofiber/poly(3-hexylthiophene) (P3HT) composite PV devices. The best performance with this cell structure produced an open circuit voltage (V_oc) of 440 mV, a short circuit current density (J_sc) of 2.2 mA/cm², a fill factor (FF) of 0.56, and a conversion efficiency (η) of 0.53%. Incorporation of a blend of P3HT and (6,6)-phenyl C₆₁ butyric acid methyl ester (PCBM) into the ZnO nanofibers produced enhanced performance with a V_oc of 475 mV, J_sc of 10.0 mA/cm², FF of 0.43, and η of 2.03%. The power efficiency is limited in these devices by the large fiber spacing and the reduced V_oc.     

Photosensitization of ZnO nanowires with CdSe quantum dots for photovoltaic devices

We combine CdSe semiconductor nanocrystals (or quantum dots) and single-crystal ZnO nanowires to demonstrate a new type of quantum-dot-sensitized solar cell. An array of ZnO nanowires was grown vertically from a fluorine-doped tin oxide conducting substrate. CdSe quantum dots, capped with mercaptopropionic acid, were attached to the surface of the nanowires. When illuminated with visible light, the excited CdSe quantum dots injected electrons across the quantum dot-nanowire interface. The morphology of the nanowires then provided the photoinjected electrons with a direct electrical pathway to the photoanode. With a liquid electrolyte as the hole transport medium, quantum-dot-sensitized nanowire solar cells exhibited short-circuit currents ranging from 1 to 2 mA/cm2 and open-circuit voltages of 0.5-0.6 V when illuminated with 100 mW/cm2 simulated AM1.5 spectrum. Internal quantum efficiencies as high as 50-60% were also obtained.     

Fabrication of flower-like ZnO microstructures from ZnO nanorods and their photoluminescence properties

In the present work, we reported a novel method for the synthesis of well-dispersed flower-like ZnO microstructures derived from highly regulated, well-dispersed ZnO nanorods by using low temperature (100 °C) hydrothermal process and without using any additional surfactant, organic solvents or catalytic agent. The phase and structural analysis were carried out by X-ray diffraction (XRD) which confirms the high crystal quality of ZnO with hexagonal (wurtzite-type) crystal structure. The morphological and structural analyses were carried out by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) which indicate the formation of well-dispersed ZnO nanorods as well as flower-like ZnO. It has been shown that flower-like ZnO is made up of dozen of ZnO nanorods building block units. The high resolution transmission electron microscopy (HRTEM) and their corresponding selected area electron diffraction (SAED) pattern show that both ZnO nanorods and flower-like ZnO microstructures are single crystalline in nature and preferentially grow along [0 0 0 1] direction. Their optical property was characterized by photoluminescence spectroscopy; shows ZnO nanorods have only violet emission and no other emission while flower-like ZnO microstructures have a weak violet emission and a strong visible emission. A plausible growth mechanism of ZnO nanorods as well as flower-like ZnO microstructures has been given.     

ZnO compact layers used in third-generation photovoltaic devices: a review

Journal of Materials Science - ZnO is a well-known semitransparent semiconductor with wide applicability in semiconducting devices such as solar cells, LEDs, MOSFETs, gas sensor devices, or...     

Improved efficiency of organic/inorganic photovoltaic devices by electrospun ZnO nanofibers

The efficiency of the photovoltaic (PV) device based on P3HT and PCBM bulk heterojunction is improved by introducing small-diameter electrospun ZnO diffused nanofibers network. Diameter, diffusion and melting of nanofibers are controlled by calcination temperature. The thickness of the active layer is optimized for efficient PV devices by varying electrospinning (ES) time. Increased nanofiber's mat thickness by an increase in electrospinning time beyond a certain optimum value reduces the device performance due to increased series resistance, increased traps and reduced blend infiltration through the nanofiber pores. ES time suggests optimized active area for energy absorption and exciton dissociation. In this study, we report the improvement in power conversion efficiency (PCE) from 0.9% to 2.23%, for optimum ES time (∼300 s).     

Fabrication and characterization of highly c-axial oriented ZnO films by chemical solution deposition

Highly c-axial oriented ZnO thin films were successfully fabricated on glass substrates at a very low pre-heating temperature by chemical solution deposition using polyvinyl alcohol (PVA) as the solvent. Effect of deposition parameters on the crystalline of ZnO films was investigated including atmosphere, pre-treating temperature and annealing temperature. It was found that all the samples were c-axial oriented regardless of growth conditions, attributing to the dominating mechanism of the PVA-Zn network. In addition, the optical properties of ZnO films were correlated with the surface morphology.     

ZnO纳米棒阵列膜的制备及其光电化学性能研究

采用化学溶液沉积法,在ZnO纳米颗粒膜修饰的FTO导电玻璃基底上,制备了ZnO纳米棒阵列。用X射线衍射仪（XRD）、场发射扫描电子显微镜（FESEM）、透射电子显微镜（TEM）对样品进行表征。研究结果表明所制备的ZnO纳米棒为六方纤锌矿相单晶结构,沿c轴择优取向生长,平均直径约为40nm,长度约为900nm;ZnO纳米棒阵列生长致密,取向性较一致。以曙红Y敏化的ZnO纳米棒阵列膜为光阳极制作了染料敏化太阳能电池原型器件,在光照强度为100mW/cm2下,其开路电压为0.418V,短路电流为0.889mA/cm2,总的光电转换效率为0.133%。     

Effect of ZnO film deposition methods on the photovoltaic properties of ZnO–Cu2O heterojunction devices

The effect of ZnO film depositions using various film deposition methods such as magnetron sputtering (MSP), pulsed laser deposition (PLD) and vacuum arc plasma evaporation (VAPE) on the photovoltaic properties of ZnO–Cu₂O heterojunction solar cells is described in this report. In addition, the relationship between the resulting photovoltaic properties and the film deposition conditions such as supply power and substrate arrangement was investigated in Al-doped ZnO (AZO)–Cu₂O heterojunction devices fabricated using AZO thin films prepared by d.c. magnetron sputtering (d.c.MSP) or r.f. magnetron sputtering (r.f.MSP). The results showed that the measured photovoltaic properties of devices fabricated with films deposited on substrates oriented perpendicular to the target were better than those of devices fabricated with films deposited on substrates oriented parallel to the target. It was also found that ZnO film depositions under conditions where a relatively weaker oxidizing atmosphere was used yield better properties than films derived from MSP, which utilizes a high-density and high-energy plasma. Using VAPE and PLD, for example, high efficiencies of 1.52 and 1.42%, respectively, were obtained under AM2 solar illumination in devices fabricated at a substrate temperature around 200 °C.     

Fabrication of high sensitivity ZnO thin film ultrasonic devices byelectrochemical etch techniques

In this experiment, high quality thin film acoustic devices were constructed utilizing zinc oxide (ZnO) thin film deposition, integrated circuit (IC), and electrochemical etch techniques. The bridge type ZnO thin film ultrasonic devices produced showed acute high frequency response sensitivity, with the high frequency response at 600 KHz attaining -124 dBV μBar. The highest response was near 8 MHz. Sensitivity increased in direct proportion to frequency, indicating that the bridge-type ZnO thin film acoustic devices were suitable for application as ultrasonic wave sensors at high operating frequencies. Further experimentation verified that the bridge-type ZnO thin film acoustic devices fabricated also had ultrasonic signal transmitting capability and signal bidirectional devices having both transmission and reception functions were successfully constructed. Therefore, bridge-type ZnO thin film acoustic devices will continue to be developed in the future due to the reliable control possible over the structural transformations involved; and, since IC fabrication techniques can be readily adopted in the process, the manufacturing of such devices will be greatly assisted     

纳米金刚石表面择优取向生长的氧化锌纳米棒阵列制备及在DNA检测中的应用

研制了基于氧化锌纳米棒阵列的高稳定性和高特异性DNA荧光传感器．首先在纳米金刚石表面制备一层择优取向生长的氧化锌纳米棒，然后通过共缩聚方法在氧化锌表面修饰一层带氨基的硅层．用SEM和XPS对其进行了表征．通过非共价键或共价键方式把探针DNA固定在氧化锌和氨基修饰的氧化锌表面．并对荧光标记DNA进行了检测。实验结果表明共价固定方法比非共价固定方法有更好的特异性。此外，共价固定方法有好的稳定性和较高的灵敏度．     

Fabrication and resistive switching characteristics of high compact Ga-doped ZnO nanorod thin film devices

This study investigates the resistive switching behavior of Ga-doped ZnO (GZO) nanorod thin films with various Ga/Zn molar ratios. Vertically well-aligned and uniform GZO nanorod thin films were successfully grown on Au/Ti/SiO(2)/p-Si substrates using an aqueous solution method. X-ray diffraction (XRD) results indicate that GZO nanorods have [0001] highly preferred orientation. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations show the formation of highly ordered and dense nanorod thin films. These compact GZO nanorod thin films can be used to make resistive switching memory devices. Such memory devices can be reversibly switched between ON and OFF states, with a stable resistance ratio of ten times, narrow dispersion of ON and OFF voltages, and good endurance performance of over 100 cycles. The resistive switching mechanism in these devices is related to the formation and rupture of conducting filaments consisting of oxygen vacancies, occurring at interfaces between GZO nanorods (grain boundaries). Results show that the resulting compact GZO nanorod thin films have a high potential for resistive memory applications.     

Fabrication of highly oriented (002) ZnO film on glass by sol-gel method

In this study high quality (002) ZnO films were deposited on glass substrate by a sol-gel spin coating process. The as-coated films were post-annealed at different temperatures in air to investigate the effect of annealing temperature in particular. The chemical composition of the precursor sol and the intermediates produced in the films heating process were analyzed by thermo gravimetric analysis/differential thermal analysis (TGA/DTA). The microstructure and its optical properties of ZnO films were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), ultraviolet-visible spectroscopy (UV-Vis) and photoluminescence. TGA/DTA showed that a significant weight loss occurred at around 200-300 °C and the weight stabilized at 300 °C. An extremely sharp (002) diffracted peak in XRD patterns indicated the high preference in crystallinity of these films. FESEM micrographs revealed that the films were filled with particulates with size ranging from 10 to 25 nm as post annealing temperature increased from 400 to 500 °C and turned into porous films at 600 °C. UV-Vis has shown that the films were highly transparent under visible light and had a sharp absorption edge in the ultraviolet region at 380 nm. The measured optical band gap values of the ZnO thin films were around 3.24-3.26 eV. Photoluminescence spectra revealed a strong UV emission centered at about 390 nm corresponding to the near-band-edge emission with a weak defect-related emission at about 520 nm. The intensity of UV emission increased with the annealing temperature. This may be attributed to a higher quality ZnO film while annealed at higher temperature.     

Blue fluorescent OLED materials and their application for high-performance devices

The authors applied two technologies to improve the efficiency of fluorescent blue organic light-emitting diodes (OLEDs). First, an efficiency-enhancement layer (EEL) was introduced to boost triplet–triplet fusion (TTF). Second, new blue dopants with a higher orientation factor in the emitting layer were developed. Consequently, the external quantum efficiency (EQE) was increased up to 11.5% with Commission Internationale de l’Eclairage (CIE) 1931 color coordinates of (0.138, 0.092). The reported results may lead to EQEs that exceed 14% with fluorescent blue emitters.     

Complex and oriented ZnO nanostructures

Extended and oriented nanostructures are desirable for many applications, but direct fabrication of complex nanostructures with controlled crystalline morphology, orientation and surface architectures remains a significant challenge. Here we report a low-temperature, environmentally benign, solution-based approach for the preparation of complex and oriented ZnO nanostructures, and the systematic modification of their crystal morphology. Using controlled seeded growth and citrate anions that selectively adsorb on ZnO basal planes as the structure-directing agent, we prepared large arrays of oriented ZnO nanorods with controlled aspect ratios, complex film morphologies made of oriented nanocolumns and nanoplates (remarkably similar to biomineral structures in red abalone shells) and complex bilayers showing in situ column-to-rod morphological transitions. The advantages of some of these ZnO structures for photocatalytic decompositions of volatile organic compounds were demonstrated. The novel ZnO nanostructures are expected to have great potential for sensing, catalysis, optical emission, piezoelectric transduction, and actuations.     

Fabrication and application in hybrid solar cell of ZnO nanorod arrays

Well-aligned ZnO nanorod arrays (ZNRAs) were grown on coated indium tin oxide coated glass substrates from aqueous solutions at low temperature. Morphologies, crystalline structure and optical transmission were investigated by a scanning electron microscope, X-ray diffraction and UV–Visible transmission spectra, respectively. The results showed that ZNRAs grew vertically from the substrates, having uniform thickness and length distribution, ZnO nanorods were wurtzite-structured (hexagonal) ZnO. The high optical transmission in the visible region was also achieved. Furthermore, a hybrid solar cell was be constructured using ZNRAs as inorganic layer, and a power conversion efficiency of 0.47 % was achieved.     

Formation of aligned ZnO nanotube arrays by chemical etching and coupling with CdSe for photovoltaic application

High density aligned ZnO nanotube (NT) arrays were synthesized using a facile chemical etching of electrochemically deposited ZnO nanorods (NRs). The influence of etching time and solution concentration on the ZnO NT formation was investigated. Moreover, cadmium selenide (CdSe) nanoparticles as sensitizers were assembled onto the ZnO NT and NR arrays for solar cell application. A conversion efficiency (η) of 0.44% was achieved for CdSe/ZnO NT-based solar cell under the white light illumination intensity of 85 mW/cm². An 8% enhancement in η was observed between the CdSe/ZnO NT-based and NR-based solar cell due to the enhancement of the photocurrent density. ZnO NT arrays have been proved to have a superior ability as compared with ZnO NR arrays when employed as a semiconductor film.     

A simple and cheap way to produce porous ZnO ribbons and their photovoltaic response

A simple and cheap method is proposed to achieve porous ZnO ribbons by oxidation of ZnS ribbons in the air. ZnS has a fully transformation to ZnO at an annealing temperature of 700°C from energy dispersive X-ray spectra and X-ray diffraction patterns. Scanning electron microscopy images indicate that ZnO ribbons keep the original shapes of ZnS, but produce some ordered and uniform pores on their surfaces. The photovoltage spectrum of ZnO/N3 indicates such dye-porous ZnO ribbons may be used in the dye-sensitized solar cells. The porous ZnO ribbons may also find potential applications in catalyst, sensor, and molecular selection. This technique to produce porous ribbons may also be applied to prepare other porous metal oxide ribbons.