Cd—Te薄膜的制备及表征

Cd-Te是一种重要的光电材料,它的禁带宽度为1·45eV,光吸收系数很大,厚度1μm的薄膜足以吸收能量大于CdTe禁带宽度的光所具有能量的99%[1],因此它是一种十分理想的太阳电池材料。Cd-Te薄膜制备的方法有喷涂法、电沉积法、丝网印刷法、分子束外延法、化学气相沉积法、近空间升华     

TiO2 band shift by nitrogen-containing heterocycles in dye-sensitized solar cells: a periodic density functional theory study

A density functional theory (DFT) method (periodic DMol3) with full geometry optimization was used to study the adsorption of nitrogen-containing heterocycles such as pyrazole, imidazole, 1,2,4-triazole, pyridine, pyrimidine, pyrazine, and 4-t-butylpyridine (TBP) on TiO2 anatase (101), (100), and (001) surfaces. All structures displayed a negative shift in the TiO2 Fermi level upon adsorption of N-containing heterocycles. Additionally, the heterocycles were examined as an additive in an I-/I3- redox electrolyte solution of dye-sensitized TiO2 solar cell. The DFT results indicated that the negative shift of TiO2 Fermi level was due to the adsorbate dipole moment component normal to the TiO2 surface plane, and corresponded to the enhanced open-circuit photovoltage (Voc) and the reduced short-circuit photocurrent density (Jsc) in a dye-sensitized solar cell.     

Characterization of solid-state dye-sensitized solar cells utilizing high absorption coefficient metal-free organic dyes

Solid-state dye-sensitized solar cells were fabricated using the organic hole-transporting medium (HTM) 2,2'7,7'-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene (spiro-MeOTAD), and three organic indoline-based sensitizer dyes with high molar extinction coefficients. The cells were characterized by several techniques, including spectral response measurements, photovoltage decay transients, intensity modulated photovoltage spectroscopy (IMVS), and charge extraction. The differences in apparent electron lifetime observed for cells fabricated using the three dyes are attributed in part to changes in the surface dipole potential at the TiO2/spiro-MeOTAD interface, which shift the TiO2 conduction band energy relative to the Fermi level of the HTM. These energy shifts influence both the open circuit voltage (as a result of changes in free electron density) and the short circuit current (as a consequence of changes in the overlap between the dye LUMO level and the conduction band). A self-consistent approach was used to derive the positions of the conduction band relative to the spiro-MeOTAD redox Fermi level for cells fabricated using the three dyes. The analysis also provided estimates of the free electron lifetime in spiro-MeOTAD cells. In order to evaluate the possible contribution of the adsorbed dyes to the observed changes in surface dipole potential, their dipole moments were estimated using ab initio density functional theory (DFT) calculations. Comparison of the calculated dipole contributions with the experimentally measured shifts in conduction band energy revealed that other factors such as proton adsorption may be predominant in determining the surface dipole potential.     

Chemisorption determines the photovoltage of a Ti/TiO2/Au/dye internal electron emission photovoltaic cell

The Ti/TiO2/Au junction forms the basis of a promising new type of photovoltaic cell, provided that a light-harvesting antenna layer can be deposited on the thin gold film. We report that the electrical diode characteristics of the TiO2/Au Schottky barrier deteriorate by deposition of a hydrophobic quantum dot film, Merbromin dye adsorption, or electron-hole photogeneration in TiO2 under inert conditions. In the presence of oxygen and water vapor, the Schottky barrier characteristics and high photovoltage are recovered. The strong influence of the TiO2 surface chemistry on the (photo)electrical characteristics of the solar cell is discussed on the basis of an existing microscopic model.     

Effect of additives on the photovoltaic performance of coumarin-dye-sensitized nanocrystalline TiO2 solar cells

The effects of deoxycholic acid (DCA) and 4-tert-butylpyridine (TBP) as additives on the photovoltaic performance of coumarin-dye-sensitized nanocrystalline TiO2 solar cells were investigated. DCA coadsorption improved both the photocurrent and photovoltage of the solar cells, even though it decreased the amount of dye adsorbed on the TiO2 electrode. The improved photocurrent may arise from suppression of the deactivation of the excited state via quenching processes between dye molecules or a more negative LUMO level of the dye in the presence of DCA, resulting in a high electron-injection yield from the dye into TiO2. The increased photovoltage is probably due to suppression of recombination between the injected electrons and I3- ions on the TiO2 surface (dark current). The addition of TBP to the electrolyte also markedly improved the photovoltage and fill factor of the solar cell, and consequently, the total conversion efficiency increased from 3.6% to 7.5%. FT-IR spectroscopy indicated that a large amount of TBP was adsorbed on the dye-coated TiO2 films in the presence of Li cations. This result suggests that TBP, like DCA, suppressed the dark current on the TiO2 surface, which resulted in the improved photovoltage.     

Preparation of sodium titanate nanotubes modified by CdSe quantum dots and their photovoltaic characteristics

Sodium titanate nanotubes have been prepared and modified chemically with CdSe quantum dots (QDs) using bifunctional modifiers (HS-COOH). Their photovoltaic characteristics have also been studied. The results indicate that the surface photovoltage response of nanotubes extends to the visible light region, and the intensity of surface photovoltage is enhanced after modification with CdSe QDs. The field-induced surface photovoltage spectroscopy (FISPS) shows that sodium titanate nanotubes have different photovoltaic response before and after modification. That is, the surface photovoltaic re-sponse of pure sodium titanate nanotubes increases with the enhancement of positive applied bias and decreases with the enhancement of negative applied bias. Meanwhile, the surface photovoltaic re-sponse of CdSe modified sodium titanate nanotubes is different from that of the pure sodium titanate nanotubes. The whole spectrum increases with the enhancement of applied bias at the first stage. However, when the applied bias reaches a certain value, the surface photovoltage response keeps in-creasing in some spectrum regions, while decreasing in other spectrum regions. This novel phe-nomenon is explained by using an electric field induced dipole model.     

Graphene quantum dots assisted photovoltage and efficiency enhancement in CdSe quantum dot sensitized solar cells

CdSe quantum dot sensitized solar cells(QDSCs) modified with graphene quantum dots(GQDs) have been successfully achieved in this work for the first time. Satisfactorily, the optimized photovoltage(Voc) of the modified QDSCs was approximately 0.04 V higher than that of plain CdSe QDSCs, consequently improving the photovoltaic performance of the resulting QDSCs. Served as a novel coating on the CdSe QD sensitized photoanode, GQDs played a vital role in improving Vocdue to the suppressed charge recombination which has been confirmed by electron impedance spectroscopy as well as transient photovoltage decay measurements. Moreover, different adsorption sequences, concentration and deposition time of GQDs have also been systematically investigated to boost the power conversion efficiency(PCE) of CdSe QDSCs. After the coating of CdSe with GQDs, the resulting champion CdSe QDSCs exhibited an improved PCE of 6.59% under AM 1.5G full one sun illumination.     

动态复合对染料敏化太阳电池性能的影响

本文通过设计一种特殊的电池结构,动态改变电解液与导电玻璃（Tc0）的接触面积,固定Ti02薄膜面积,将TCO／OL解液界面与TiO2／电解液界面两种复合途径进行区分,从实验和理论两方面研究了复合途径变化对染料敏化太阳电池（DSC）性能的影响．采用电化学阻抗谱（EIS）表征界面电荷交换过程,研究了不同途径在复合中的作用机理．通过单色光下,1-V性能测试,对不同界面复合主导下的DSC二极管特性进行数值分析,探讨了复合过程中界面电荷交换变化对光电压（‰）的影响．研究结果表明,高光强下（Voc=700mV）改变TCO／电解液接触面积对复合影响不明显,DSC电子复合主要经由TiO2／电解液界面,电池具有明显的二极管特征;而弱光下（Voc〈400mV）增加TCO／电解液接触面积将使复合大幅增加,此时电荷交换由TCO／电解液界面主导,电池填充因子大幅降低,整流作用减弱．由于TCO／OL解液界面电荷交换明显慢于TiO2／电解液界面,通过同一电池一定光强范围内的光电压变化对比发现,高光强下光电压变化较慢,而弱光下光电压变化较快．     

二联体卟啉的光致电荷转移行为

卟啉聚集体在光合作用和生物体新陈代谢过程中发挥着极为重要的作用[1,2 ] .但是在复杂的自然界体系中 ,研究卟啉聚集体中的电子转移行为非常困难 ,所以借助于简单的二联体卟啉和多聚体卟啉作为生物体新陈代谢过程中活性位点的模型来研究其间的电荷转移行为[3] .近年来 ,人们在二联体卟啉和多聚体卟啉合成及性质表征方面做了大量的工作 ,特别是利用各种光谱来研究它们的电子和光生电子行为以及它们与具有生物活性的分子和特殊气体分子之间的电荷转移过程 [4 ,5] .本文利用表面光电压谱 (SPS)技术对二联体卟啉的光伏响应进行了研究 ,发现二…     

Crossed BiOI flake array solar cells

We report a new kind of solar cell based on crossed flake-like BiOI arrays for the first time. The BiOI flake arrays were fabricated on an FTO glass with a TiO₂ block layer at room temperature by successive ionic layer adsorption and reaction (SILAR) method. The resulting BiOI flake array solar cell exhibited enhanced photovoltaic performance under solar illumination. This work provides an attractive and new solar cell system and a facile route to fabricate low cost and non-toxic solar cell.     

Mg(OOCCH(3))(2) as an electrolyte additive for quasi-solid dye-sensitized solar cells: with the purpose of enhancing both the photovoltage and photocurrent by modifying the TiO(2)/dye/electrolyte interfaces

The interface modification effect within quasi-solid dye-sensitized solar cells and the photovoltaic performance were investigated after the introduction of Mg(OOCCH(3))(2) as an additive into a polymer gel electrolyte. Electrochemical impedance spectroscopy showed that the addition of Mg(OOCCH(3))(2) into the polymer gel electrolyte can efficiently retard charge recombination at the TiO(2)/electrolyte interface. Mg(OOCCH(3))(2) in the electrolyte can also contribute to the enhancement of the incident photon-to-electron conversion efficiency by modifying the dye molecules. This results in an improvement in the photovoltage and photocurrent due to a barrier layer at the TiO(2)/electrolyte interface and the promotion of charge injection at the dye/TiO(2) interface, respectively. Photovoltaic measurements reveal that a conversion efficiency enhancement from 4.05% to 4.96% under 100 mW cm(-2) is obtained after the amount of Mg(OOCCH(3))(2) added was optimized.     

不同受体结构染料共敏化对染料敏化太阳电池性能的影响

为了拓宽染料敏化太阳电池对太阳光谱的响应范围,提高电池的光电转换效率,将两种含有不同受体结构（绕丹宁-3-乙酸基（RA）和氰基丙烯酸基（CA））的三苯胺染料（TR1和TC1）进行共敏化。TR1染料平伏吸附在TiO₂表面,而TC1染料直立吸附在TiO₂表面。将两种染料按照不同摩尔比共敏化TiO₂后,TC1占据TR1的部分位置,拓展光谱的同时也抑制了电荷复合,电子寿命较TR1敏化的太阳电池长。在TR1与TC1摩尔比为5：5的共敏剂溶液敏化的共敏电池器件中,短路光电流密度（J_sc）为11.7 mA/cm²,开路电压（V_oc）为704 mV,填充因子（FF）为0.73,光电转换效率（η）为6.03%。该结果明显优于单一染料敏化的电池器件。     

A novel concept for photovoltaic cells: clusters of titanium dioxide encapsulated within zeolites as photoactive semiconductors.

Discrete clusters of TiO(2) (of only a few titanium atoms) are prepared within the internal micropore space of zeolite Y (4.8 wt % Ti loading) and characterized by Raman spectroscopy (rutile- and anatase-like structures), electron microscopy combined with elemental analyses (coincident Si and Ti spatial distribution), and X-ray diffraction (minor zeolite crystallinity decrease). The parent TiO(2)@Y sample is modified either by adsorption of acid-organic compounds (benzoic and 4-aminobenzoic acids or catechol) or by nitrogen doping. After modification, the optical UV/Vis spectrum of the parent TiO(2)@Y (onset of the absorption band at wavelengths <300 nm and bandgap of 4.2 eV) changes, and the appearance of new bands expanding to the visible region is observed. In contrast to the inactive zeolite Y matrix, all the zeolite-encapsulated TiO(2) species exhibit a photovoltaic response. The influence of the I(2)/I(3) (-) concentration in the electrolyte solution on the temporal profile of the photovoltage clearly shows that I(2)/I(3) (-) is also a suitable carrier for the positive charge in zeolite-based photovoltaic devices. The photocurrent response and the efficiency of the photovoltaic cell based on zeolite-encapsulated TiO(2) materials depend on the nature of the organic modifier and on the N-doping. The most efficient photovoltaic cell is that based on N-doped TiO(2)@Y, which exhibits a V(OC) (voltage at open circuit) of 270 mV, an I(SC) of 5.8 muA (current at short circuit), and a fill factor (FF) of 0.4. Although these values are low compared to current dye-sensitized TiO(2) solar cells, our findings could open up a promise for a stimulating research on the photovoltaic activity of zeolite-based host-guest solids.     

Influence of pyrimidine additives in electrolytic solution on dye-sensitized solar cell performance

The influence of pyrimidine additives on the performance of a bis(tetrabutylammonium)cis-bis(thiocyanato)bis(2,2′-bipyridine-4-carboxylic acid, 4′-carboxylate)ruthenium(II) dye-sensitized TiO₂ solar cell with an I⁻/I₃⁻ redox electrolyte in acetonitrile was studied. The current–voltage characteristics were measured for more than 10 different pyrimidine derivatives under AM 1.5 (100 mW/cm²). The pyrimidine additives tested had varying effects on the performance of the cell. The additives drastically enhanced the open-circuit photovoltage (V_oc) and the solar energy conversion efficiency (η), but usually reduced the short circuit photocurrent density (J_sc) of the solar cell. Physical and chemical properties of the pyrimidines were computationally calculated in order to determine the reasons for the additive effects on cell performance. Consequently, the greater the calculated partial charge of the nitrogen atoms in the pyrimidine groups, the larger the V_oc but the smaller the J_sc values. The V_oc of the cell also increased as the ionization energy of the pyrimidine molecules decreased. Moreover, as the calculated dipole moment of the pyrimidine derivatives increased, the J_sc value was reduced, but the V_oc value was enhanced. These results suggest that the electron donicity of pyrimidine additives influenced the interaction with TiO₂ electrode and I⁻/I₃⁻ electrolyte, which lead to the changes in dye-sensitized solar cell performance.     

Effects of tethering alkyl chains for amphiphilic ruthenium complex dyes on their adsorption to titanium oxide and photovoltaic properties

Ruthenium (II) complex dye, Ru(4,4'-dicarboxyl-2,2'-bipyridine)(4-nonyl-2,2'-bipyridine) (NCS)(2), (denoted as RuC9) tethering single alkyl chain was synthesized and well characterized. Its adsorption behavior onto the mesoporous TiO(2) and photovoltaic properties were compared with Z907 which has similar chemical structure but tethers two alkyl chains. RuC9 dyes tend to aggregate into vesicles in the acetonitrile/t-butanol co-solvent as a result of the amphiphilic structure, whereas Z907 dyes aggregate into lamellae. The dye-sensitized solar cell (DSSC) with RuC9 dye showed higher short-circuit photocurrent than that with Z907, attributing to its higher molar optical extinction coefficient and more adsorption amount onto the mesoporous TiO(2). However, the DSSC with Z907 dye has higher open-circuit photovoltage and power conversion efficiency, presumably due to the fact that Z907 with more alkyl chains formed a molecular layer with higher hydrophobicity. It reduced the charge recombination in the interface between the dye-sensitized mesoporous TiO(2) and electrolyte as verified by the electrochemical impedance spectroscopy and intensity modulated photocurrent and photovoltage spectroscopies.     

The Photovoltage-gas Sensitive Properties of 7,7,8,8-Tetracyanoquinodimethane(TCNQ)

In this paper, surface photovoltage technique (SPV) was applied to the study of photovoltaic and gas sensitive properties of TCNQ polycrystal. It was found that SPV shows two peaks at 390 nm(P1) and 480 nm (P2) in the ultraviolet-visible range. And they are opposite in phase. The results of gaseous adsorption confirm that P, shows the acceptor characteristics, while PI shows that of donor. During adsorption, donor gas interacts with conjugated II * orbital, acceptor gas with the terminal group C=N .     

Molecularly controlled metal-semiconductor junctions on silicon surface: a dipole effect

Silicon surface was chemically modified by covalent attachment of homologous organic molecules having different dipole moments. Surface photovoltage measurements clearly confirm that organic molecules have a profound effect on surface band bending of semiconductor. Metal-molecules--silicon junctions were constituted for molecules belonging to ethynylbenzene series using soft mercury contact. These junctions show a systematic change in the electrical charge transport with dipole moment of molecules. Parameters such as ideality factor, barrier height, and density of interface states of various junctions are estimated to understand the role of organic molecules. These studies offer the prospect to develop molecular electronics, which may find potential applications in solar cells and chemical and biological sensors.     

Direct correlation between work function of indium-tin-oxide electrodes and solar cell performance influenced by ultraviolet irradiation and air exposure

We report on reversible changes of the work function (WF) values of indium-tin-oxide (ITO) under prolonged ultraviolet (UV) and air exposure. The WF of ITO is reduced from 4.7 eV to 4.2 eV by photon absorption in ITO under UV illumination or an air mass 1.5 solar simulator (100 mW cm(-2)). Air or oxygen exposure is found to increase the WF of ITO (UV-exposed) to a value of 4.6 eV. These changes of ITO's WF lead to reversible variations of the performance of organic photovoltaic devices where ITO acts primarily as the electron collecting or hole collecting electrode. These variations can be reflected in the disappearance (or appearance) of an S-shaped kink in the J-V characteristics upon continuous UV or solar simulator illumination (or air exposure). This reversible phenomenon is ascribed to the adsorption and desorption of oxygen on the surface and grain boundaries of ITO. The use of surface modifiers to either decrease or increase the WF of ITO in organic photovoltaic devices with inverted and conventional geometries is also shown to be an effective route to stabilize the device performance under UV illumination.     

Passive Gate-Tunable Kinetic Photovoltage along Semiconductor-Water Interfaces

Moving boundaries of electric double layer at solid–liquid interface enables unprecedented persistent energy conversion and provokes a kinetic photovoltaic effect by moving an illumination region along the semiconductor-water interface. Here, we report a transistor-inspired gate modulation of kinetic photovoltage by applying a bias at the semiconductor-water interface. The kinetic photovoltage of both p-type and n-type silicon samples can be facilely switched on/off, stemming from the electrical-field-modulated surface band bending. In contrast to the function of solid-state transistors relying on external sources, passive gate modulation of the kinetic photovoltage is achieved simply by introducing a counter electrode with materials of desired electrochemical potential. This architecture provides the ability to modulate the kinetic photovoltage over three orders of magnitude and opens up a new way for self-powered optoelectronic logic devices.     

Electron Transport in Quasi‐Two‐Dimensional Porous Network of Titania Nanoparticles,Incorporating Electrical and Optical Advantages in Dye‐Sensitized Solar Cells

The integration of fast electron transport and large effective surface area is critical to attaining higher gains in the nanostructured photovoltaic devices. Here, we report facilitated electron transport in the quasi‐two‐dimensional (Q2D) porous TiO₂. Liquid electrolyte dye‐sensitized solar cells were prepared by utilizing photoanodes based on the Q2D porous substructures. Due to electron confinement in a microscale porous medium, directional diffusion toward collecting electrode is induced into the electron transport. Our measurements based on the photocurrent and photovoltage time‐of‐flight transients show that at higher Fermi levels, the electron diffusion coefficient in the Q2D porous TiO₂ is about one order of magnitude higher when compared with the conventional layer of porous TiO₂. The results show that microstructuring of the porous TiO₂ leads to an approximately threefold improvement in the electron diffusion length. Such a modification may considerably affects the electrical functionality of moderate or low performance dye‐sensitized solar cells for which the internal gain or collection efficiency is typically low.