Enhanced photosplitting of water using ultrathin cobalt sulfide nanoflakes-sensitized zinc oxide nanorods array

We report synthesis and characterization of ultrathin cobalt sulfide nanoflakes (CoS_x-NFs) sensitized zinc oxide nanorods (Z-NRs) array based thin films and their implementation as photoanodes for photoelectrochemical (PEC) splitting of water. Cobalt sulfide nanoflakes-sensitized zinc oxide nanorods (CoS_x-NFs/Z-NRs) array based photoanodes were grown on fluorine-doped tin oxide substrate by a simple and versatile electrodeposition method. Maximum conversion efficiency of PEC cell was found 0.37% with a photocurrent density of 0.48 mA/cm² at a bias of 0.3 V/SCE in CoS_x-NFs/Z-NRs-15 (loading of CoS_x-NFs on Z-NRs by cyclic voltammetry for 15 cycles) based photoanodes. The photo-activity is 2.7 times larger than that of Z-NRs array-based photoanode. Experimental results reveal that sensitization by CoS_x-NFs causes red shift in the band gap energy of Z-NRs photoanode. Lower band gap energy, suitable band redox potential, and marked absorption in visible light make CoS_x-NFs/Z-NRs-15 thin films a promising material for photoanodes in PEC cells. A detailed analysis using X-ray diffraction (XRD), UV-Visible (UV-Visible) spectroscopy, field emission scanning electron microscope (FE-SEM), energy-dispersive analysis (EDX), electron impedance spectroscopy (EIS), Mott-Schottky (MS) analysis, applied bias photon-to-current conversion efficiency (ABPE), and incident photon to current conversion efficiency (IPCE) measurements has been carried out to substantiate our observations. The excellent performance of CoS_x-NFs/Z-NRs allows the composite photoelectrode to have many potential applications as a photoanode material for H₂ production, nanoflakes-sensitized solar cells, and UV photodetector.     

The Dynamic Resistance of CdS/CdSe/ZnS Co-Sensitized TiO2 Solar Cells

Quantum dots' sensitized solar cells (QDSSCs) can create the high-performance and low-cost photovoltaic in the future. In this study, we synthesized the film of TiO₂/CdS/CdSe/ZnS photoanodes by successive ionic layer adsorption reaction (SILAR) method. The absorption spectra, photoluminescent spectra and electrochemical impedance spectra (EIS) of the film TiO₂/CdS/CdSe/ZnS photoanodes show that the structure of energy levels in the conduction band (CB) of photoanode materials CdS, CdSe, and ZnS quantum dots (QDs) can absorb a great number of photons in each region and inject stimulated electrons quickly into the conduction band (CB) of TiO₂. Furthermore, we also studied the influence of the SILAR cycles on the dynamic resistance, the lifetime of electrons in QDSSCs through Nyquist and Bode.     

A novel TiO2 nanoparticles/nanowires composite core with ZrO2 nanoparticles shell coating photoanode for high-performance dye-sensitized solar cell based on different electrolytes

The novel TiO₂ nanopartilces/nanowires (TNPWs) composite with ZrO₂ nanoparticles (ZNPs) shell-coated photoanodes were prepared to fabricate high-performance dye-sensitized solar cell (DSSC) based on different types of electrolytes. Hafnium oxide (HfO₂) is a new and efficient blocking layer material applied over the TNPWs-ZNPs core-shell photoanode film. TiO₂ nanoparticles (TNPs) and TiO₂ nanowires (TNWs) were characterized by X-ray diffractometer (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). DSSCs were fabricated using the novel photoanodes with an organic sensitizer D149 dye and different types of electrolytes namely liquid electrolyte, ionic liquid electrolyte, solid-state electrolyte, and quasi-solid-state electrolyte. The DSSC-4 made through the novel core-shell photoanode using quasi-solid-state electrolyte showed better photocurrent efficiency (PCE) as compared to the other DSSCs. It has such photocurrent-voltage characteristics: short circuit photocurrent (Jsc)?=?19 mA/cm², the open circuit voltage (Voc)?=?650 mV, fill factor (FF)?=?65 %, and PCE (η)?=?8.03 %. The improved performance of DSSC-4 is ascribed to the core-shell with blocking layer photoanode could increased electron transport and suppressed recombination of charge carriers at the TNPWs-ZNPs/dye/electrolyte interface.     

Dependence of photovoltaic parameters on the size of cations adsorbed by TiO2 photoanode in dye-sensitized solar cells

The effects of “pre-adsorbed cations” in photoanodes on the performances of dye-sensitized solar cells (DSSCs) were studied using two different size cations (K⁺ and guanidine cation (G⁺)). While the DSSCs with optimized K⁺ ions pre-adsorbed photoanodes showed a maximum efficiency of 7.04%, the DSSCs with G⁺ ions pre-adsorbed photoanodes showed an efficiency of 6.73%. DSSCs fabricated with conventional photanodes (without pre-cation adsorption) showed an efficiency of 6.21%. Differences in efficiencies are very likely due to the cation pre-adsorption effects and could be due to a higher number of K⁺ cation adsorption per unit area of TiO₂ surface of the photoanode compared to a smaller number of G⁺ cation adsorption in TiO₂, due to their difference in sizes. This pre-cation adsorption technique can be used to improve the overall efficiency of a DSSC by about 14% fold over the conventional photoanodes use in DSSCs, specially using smaller cations.

     

Thickness effect of the TiO2 nanofiber scattering layer on the performance of the TiO2 nanoparticle/TiO2 nanofiber-structured dye-sensitized solar cells

TiO₂ nanofibers (NFs) were fabricated by an electrospinning process and were used as scattering layers in dye-sensitized solar cells (DSSCs). The NF-coated photoanodes of the DSSCs were prepared with a variety of scattering layer thicknesses. The thickness effect of the scattering layer on the double-layered TiO₂ nanoparticle (NP)/TiO₂ NF structure was investigated through structural, morphological, and optical measurements. In the double-layered photoanode, the TiO₂ NP layer plays a major role in dye adsorption and light transmission, and the TiO₂ NF scattering layer improves the absorption of visible light due to the light scattering effects. The scattering effect of TiO₂ NFs layer was examined by the incident monochromatic photon-to-electron conversion efficiency (IPCE) and UV–Vis spectrometry. The conversion efficiency for the 12 μm-thick photoanode composed of a 2 μm-thick TiO₂ NF layer and 10 μm-thick TiO₂ NP layer was higher than that of DSSCs with only TiO₂ NPs photoanode by approximately 33%.     

纳米TiO2颗粒/亚微米球多层结构薄膜内电荷传输性能研究

本文主要利用TiO₂亚微米球较强的光散射特性设计了纳米TiO₂颗粒/亚微米球多层结构光阳极, 并借助强度调制光电流谱(intensity-modulated photocurrent spectroscopy)、电化学阻抗谱(electrochemical impedance spectroscopy)和入射单色光光电转化效率(incident photon-to-current conversion efficiency), 研究亚微米球的引入对多层结构薄膜内缺陷态、电子传输时间、电子收集效率和界面电荷转移性能的影响. 强度调制光电流谱反映出亚微米球表面缺陷态少, 但其颗粒间接触不紧密, 导致在接触部位形成了势垒, 阻碍了电子的传输, 导致电子传输时间增长. 电化学阻抗谱结果表明不同多层结构电池界面复合无明显差别, 同时底层采用纳米TiO₂ 透明薄膜结构的电池, 其光利用率要明显高于底层采用亚微米球薄膜结构的电池, TiO₂费米能级电子填充水平也相对增大, 使得电池的光电转换效率得到提升. 多层结构复合薄膜电荷传输和光伏特性的研究, 为高效染料敏化太阳电池光阳极设计提供了实验基础.     

Anodic TiO<Subscript>2</Subscript> nanotubes powder and its application in dye-sensitized solar cells

An increasing energy demand and environmental pollution create a pressing need for clean and sustainable energy solutions. TiO₂ semiconductor material is expected to play an important role in helping solve the energy crisis through effective utilization of solar energy based on photovoltaic devices. Dye-sensitized solar cells (DSSCs) are potentially lower cost alternative to inorganic silicon-based photovoltaic cells. In this study, we report on the fabrication of DSSCs from anodic TiO₂ nanotubes (NT) powder, produced by rapid breakdown potentiostatic anodization of Ti foil in 0.1 M HClO₄ electrolyte, as photoanode. TiO₂ NT powders with a typical NT outer diameter of approximately 40 nm, wall thickness of approximately 8–15 nm, and length of about 20–25 μm, have been synthesized. The counter electrode was made by electrodeposition of Pt from an aqueous solution of 5 mM H₂PtCl₆ onto fluorine-doped tin oxide (FTO) glass substrate. The above front-side illuminated DSSCs were compared with back-side illuminated DSSCs fabricated from anodic TiO₂ NTs that were grown on the top of Ti foil as photoanode. The highest cell efficiency was 3.54% under 100 mW/cm² light intensity (1 sun AM 1.5G light, Jsc = 14.3 mA/cm², Voc = 0.544 V, FF = 0.455). To the best of our knowledge, this is the first report on the fabrication of DSSC from anodic TiO₂ NTs powder. The TiO₂/FTO photoanodes were characterized by FE-SEM, XRD, and UV–Visible spectroscopy. The catalytic properties of Pt/FTO counter electrodes have been examined by cyclic voltammetry.     

Synthesis and Characterization of a Novel Ternary Hematite Nanocomposites Structure with Fullerene and 2D‐Electrochemical Reduced Graphene Oxide for Superior Photoelectrochemical Performance

In this study, a novel ternary hematite nanocomposites photoanode structure with superior photoelectrochemical (PEC) performance consisting of fullerene (C₆₀) and 2D‐electrochemical reduced graphene oxide (eRGO) used as the effective surface passivators is developed. The introduction of both the electron scavenging C₆₀ and highly conducting eRGO has mitigated the high interfacial recombination rate of hematite and led to the superior enhancement in PEC performance. UV–vis analysis reveals that the incorporation of C₆₀ and eRGO can provide a stronger light absorption at the visible light (400 nm < λ < 700 nm) and near infrared (IR) region (λ > 700 nm). Through the electrochemical impedance spectroscopy measurements, it can be concluded that the introduction of C₆₀ and eRGO onto hematite photoanode improves electron transfer and collection, reduces charge‐carrier recombination efficiency, and enhances PEC activity. The resultant ternary hematite photoanode structure exhibits 16.8‐fold enhancement in photocurrent density and 0.8‐fold reduction in charge transfer resistance when compared to the bare hematite structure only. This study has shown that the application of C₆₀, 2D‐eRGO, or in combination as a ternary structure provides the plasmonic effect that can enhance the PEC performance in hematite photoanode structure.     

Molecular dynamics simulation of displacement damage in 6H-SiC

ABSTRACT

As a new generation of low-loss components, 6H-SiC is widely used in optoelectronic devices, electronic devices and other fields, especially in high temperature and strong radiation environment. Radiation will lead to a great large of defects generated in the material, then forming permanent displacement damage which will result in performance down or failure. In this paper, the molecular dynamics method was used to study the spatial distribution of defects and the effect of temperature and PKA energy on the various properties of the point defects. The main contributions were the evolution of defects in 6H-SiC crystal, the influence of PKA energy and temperature on the defect distribution and the number of point defect. In this paper, the spatial distribution of point defects in 6H-SiC crystal after PKA incidence was obtained, the recombination rate under four kinds of energy PKA was calculated, and the effect of temperature and incident PKA energy on the number of defects, the rate of the vacancy cluster and the rate of vacancy defects at steady state were investigated. The results show that the number of defects at steady-state increases linearly with the increase of incident PKA energy, the effect of temperature and energy on defects producing and the rate of clusters are insignificant.     

Plasmon enhanced CdS-quantum dot sensitized solar cell using ZnO nanorods array deposited with Ag nanoparticles as photoanode

CdS-quantum dot sensitized solar cell using ZnO nanorods (ZnO NRs) array deposited with Ag nanoparticles (Ag NPs) as photoanode was fabricated. Light absorption effect of Ag NPs on improvement of the cell performance was investigated. Performance improvement of metal nanoparticles (MNPs) was controlled by the structure design and architecture. Different decorations and densities of Ag NPs were utilized on the photoanode. Results showed that using 5% Ag NPs in the photoanode results in the increased efficiency, fill factor, and circuit current density from 0.28% to 0.60%, 0.22 to 0.29, and 2.18 mA/cm² to 3.25 mA/cm², respectively. Also, incident photon-to-current efficiencies (IPCE) results showed that cell performance improvement is related to enhanced absorption in the photoanode, which is because of the surface plasmonic resonance and light scattering of Ag NPs in the photoanode. Measurements of electrochemical impedance spectroscopy revealed that hole transfer kinetics increases with introduction of Ag NPs into photoanode. Also, it is shown that chemical capacitance increases with introduction of Ag NPs. Such increase can be attributed to the surface palsmonic resonance of Ag NPs which leads to absorption of more light in the photoanode and generation of more photoelectron in the photoanode.     

Nanostructured ZnO thin films by chemical bath deposition in basic aqueous ammonia solutions for photovoltaic applications

This paper presents further insights and observations of the chemical bath deposition (CBD) of ZnS thin films using an aqueous medium involving Zn-salt, ammonium sulfate, aqueous ammonia, and thioure. Results on physical and chemical properties of the grown layers as a function of ammonia concentration are reported. Physical and chemical properties were analyzed using scanning electron microscopy (SEM), X-ray energy dispersive (EDX), and X-ray diffraction (XRD). Rapid growth of nanostructured ZnO films on fluorine-doped SnO₂ (FTO) glass substrates was developed. ZnO films crystallized in a wurtzite hexagonal structure and with a very small quantity of Zn(OH)₂ and ZnS phases were obtained for the ammonia concentration ranging from 0.75 to 2.0 M. Flower-like and columnar nanostrucured ZnO films were deposited in two ammonia concentration ranges, respectively: one between 0.75 and 1.0 M and the other between 1.4 and 2.0 M. ZnS films were formed with a high ammonia concentration of 3.0 M. The formation mechanisms of ZnO, Zn(OH)₂, and ZnS phases were discussed in the CBD process. The developed technique can be used to directly and rapidly grow nanostructured ZnO film photoanodes. Annealed ZnO nanoflower and columnar nanoparticle films on FTO substrates were used as electrodes to fabricate the dye sensitized solar cells (DSSCs). The DSSC based on ZnO-nanoflower film showed an energy conversion efficiency of 0.84%, which is higher compared to that (0.45%) of the cell being constructed using a photoanode of columnar nanoparticle ZnO film. The results have demonstrated the potential applications of CBD nanostructured ZnO films for photovoltaic cells.     

Hydrothermal synthesis of TiO2 nanocrystals in different basic pHs and their applications in dye sensitized solar cells

In this research TiO₂ nanocrystals with sizes about 11–70 nm were grown by hydrothermal method. The process was performed in basic autoclaving pH in the range of 8.0–12.0. The synthesized anatase phase TiO₂ nanocrystals were then applied in the phtoanode of the dye sensitized solar cells. It was shown that the final average size of the nanocrystals was larger when the growth was carried out in higher autoclaving pHs. The photoanodes made of TiO₂ nanocrystals prepared in the pHs of 8.0 and 9.0 represented low amounts of dye adsorption and light scattering. The performance of the corresponding dye sensitized solar cells was also not acceptable. Nevertheless, the energy conversion efficiency was better for the state of pH of 9.0. For the photoanodes made of TiO₂ nanocrystals prepared at autoclaving pH of 10.0, the dye adsorption and light scattering were quite higher. The photovoltaic characteristics of the best cell in this state were 15.25 mA/cm², 740 mV, 0.6 and 6.8% for the short-circuit current density, open-circuit voltage, fill factor and efficiency, respectively. The photoanodes composed of TiO₂ nanocrystals prepared in autoclaving pHs of 11.0 and 12.0 demonstrated lower amount of dye adsorption and higher light scattering. This was quite considerable for the state of pH of 12.0. The energy conversion efficiencies were consequently decreased compared to that of the pH of 10.0. The optimum situation was finally discussed based on the nanocrystals size and its influence on the sensitization and light harvesting efficiency.     

Dye-sensitized solar cells with polymer bindings based on titanium dioxide

An urgent task in the field of sensitized solar cells (DSSC) is to decrease the temperature of thermal annealing of titanium dioxide photoanode. In this work, we use a titania based polymer as organic “polylinker,” which allows low temperature annealing. This polylinker, which is obtained by means of partial hydrolysis of titanium polybutyltitanate or tianium 2-methoxyethoxide allowed us to decrease the annealing temperature of titanium dioxide down to 150–180°C. This permits the manufacture of DSSC on flexible polymer substrates. DSSC samples with efficiency of energy conversion up to 1% are obtained.     

电荷俘获存储器数据保持特性第一性原理研究

本文研究HfO₂掺入Al替位Hf杂质和氧空位共同掺杂对电荷俘获型存储器存储特性的影响. HfO₂作为高介电常数材料由于具有缩小器件尺寸、提高器件性能等优势, 被广泛用于CTM的俘获层. 采用MS和VASP研究了HfO₂俘获层中掺入Al对氧空位形成能的影响. 同时计算了两种缺陷在不同距离下的相互作用能. 计算结果表明在HfO₂中掺入Al使得氧空位的形成能降低, 并且三配位氧空位的形成能比四配位氧空位的形成能降低的更多. 通过研究Al和三配位氧空位两种缺陷间不同距离的三种情况, 计算结果表明当缺陷间距为2.107 Å时, 体系的电荷俘获能最大; 量子态数最多; 布居数最小、Al–O键最长. 通过研究三种体系写入空穴后键长的变化, 得出当缺陷间距为2.107 Å时, 写入空穴后体系的Al–O键长变化最小. 以上研究结果表明, 掺入Al后可以有效提高电荷俘获型存储器的数据保持能力. 因而本文的研究为改善电荷俘获型存储器数据保持特性提供一定的理论指导.     

Mineralization of flexible mesoporous TiO2 photoanodes using two low‐temperature dielectric barrier discharges in ambient air

Two types of dielectric barrier discharges (DBDs), volume DBD (called Industrial Corona) and coplanar DBD, were used for low temperature (70 °C) atmospheric pressure plasma mineralization of mesoporous methyl‐silica/titanium dioxide nanocomposite photoanodes. The photoanodes with a thickness of approx. 300 nm were inkjet‐printed on flexible polyethylene terephthalate (PET) foils. Plasma treatments of both DBDs led to changes in the chemical stoichiometry and morphology of the mesoporous photoanodes, resulting in a significant increase of the work function from approx. 4.0 to 4.3 eV and 4.8 eV, after plasma mineralization with volume DBD and coplanar DBD, respectively. We also studied the effect of plasma mineralization on the photoelectrochemical properties of the flexible mesoporous TiO₂ photoanodes. Plasma mineralization with volume DBD and coplanar DBD showed different effects on the generated photocurrent in the photoanodes. Although the plasma mineralization with volume DBD showed only a minor effect on the photocurrent, plasma mineralization with coplanar DBD led to significantly higher photocurrents. We found that the enhancement of the photoelectrochemical properties was related to the homogeneity of the plasma‐treated surfaces—arising from different spatial properties of the plasma between volume and coplanar DBDs. Furthermore, the results showed that plasma mineralization using coplanar DBD can effectively change the energy levels of the surface. This resulted in the enhancement of the work function and the photoelectrochemical properties of the mesoporous TiO₂ photoanodes. This contribution shows that coplanar arrangement of electrodes in DBDs generates plasma of higher efficacy compared with standard volume DBD that is currently often used in industrial processes.     

Synthesis of two-dimensional nanowall of Cu-Doped TiO2 and its application as photoanode in DSSCs

Two-dimensional nanowall of Cu-doped TiO₂ (CuTNW) has been prepared in this work to study the role of Cu doping on its photoactivity properties and its photovoltaic performance as photoanode in a dye-sensitized solar cell (DSSC). TiO₂ nanowall with five Cu ion doping, i.e. 6.25, 12.5, 25.0, 50.0 and 100.0 mM, were prepared via a liquid-phase deposition method using ammoniumhexafluorotitanate and hexamethylenetetramine as the reagents with a growth temperature of 90 °C. The X-Ray Diffraction (XRD), X-ray energy dispersion (EDX) and diffuse optical reflectance spectroscopy analysis results confirmed the successfulness of the Cu doping process in the TiO₂ nanowall and effective modification on the photoactivity of the TiO₂ nanowall. We found that the power conversion efficiency of the DSSC utilizing TiO₂ nanowall as photoanode can be enhanced up to 2 times, i.e. from 0.2% to 0.44%, when the TiO₂ nanowall doped with Cu ion. The nanostructure preparation, device fabrication and the mechanism for the device performance enhancement will be discussed.     

Defect repairing in two-dimensional transition metal dichalcogenides

Atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDCs) have stimulated enormous research interest due to rich phase structure, high theoretical carrier mobility and layer-dependent bandgap. In view of the close correlation between defects and properties in 2D TMDCs, more attentions have been paid on the defect engineering in recent years, however the mechanism is still unclear. Herein, we review the critical progress of defect engineering and provide an extensive way to modulate the properties depressed by defects. To insight into the defect engineering, we firstly introduce two common kinds of defects during the growth progress of TMDCs and the possible distribution of energy levels those defects could induce. Then, various methods to improve point defects and grain boundaries during the period of growth are discussed intensively, with the assistance of which more large-area TMDCs films can be obtained. Considering the defects in TMDCs are inevitable regardless of concentration, we also highlight strategies to heal the defects after growth. Through dry methods or wet methods, the chalcogen vacancies can be repaired and thus, the performance of electronic device would be significantly enhanced. Finally, we propose the challenges and prospective for defect engineering in 2D TMDCs materials to support the optimization of device and lead them to wide applied fields.     

深能级缺陷对半绝缘InP材料电学补偿的影响

对铁掺杂和高温退火非掺杂磷化铟制备的两种半绝缘材料的电学补偿和深能级缺陷进行了分析和比较.根据热激电流谱(TSC)测得的深能级缺陷结果，分析了这两种半绝缘InP材料中深能级缺陷对电学补偿的影响.在掺铁半绝缘InP材料中，由于存在高浓度的深能级缺陷参与电学补偿，降低了材料的补偿度和电学性能.相比之下，利用磷化铁气氛下高温退火非掺InP获得的半绝缘材料的深能级缺陷浓度很低，通过扩散掺入晶格的铁成为唯一的深受主补偿中心钉扎费米能级，材料表现出优异的电学性质.在此基础上给出了一个更为广泛的半绝缘InP材料的电学补偿模型.     

Hybrid photoanode films based on sparse ZnO rod array-TiO2 nanoparticles in dye-sensitized solar cells

ZnO-TiO2 hybrid photoanodes were fabricated via the doctor-blade method by integrating vertically-grown sparse ZnO arrays with hydrothermal TiO2 nanoparticles. A special surface-coating technique was developed to deposit a thin TiO2 layer on the surface of ZnO rods. Microstructure, optical and photoelectrochemical performance of the hybrid photoanodes were investigated. The denser ZnO array exhibited bad filling behavior of nanoparticles in the interspace of ZnO rods, strong scattering and low conversion efficiency (0.27%). The sparser array showed a much better integrated microstructure, improved transmittance and high conversion efficiency (2.68%). The surface modification of ZnO rods by the TiO2 thin layer was found useful in improving the interfacial microstructure between the ZnO rod and the TiO2 bulk film, and the total conversion efficiency of 3.01% was achieved, higher than that of the pure TiO2 nanoparticle cell (2.93%). The increased scattering effects on the incident light, the enhanced electron transportation at TiO2/dye/electrolyte interface, and the inhabited recombination were responsible for this improvement.