Use of highly-ordered TiO(2) nanotube arrays in dye-sensitized solar cells

We describe the use of highly ordered transparent TiO(2) nanotube arrays in dye-sensitized solar cells (DSCs). Highly ordered nanotube arrays of 46-nm pore diameter, 17-nm wall thickness, and 360-nm length were grown perpendicular to a fluorine-doped tin oxide-coated glass substrate by anodic oxidation of a titanium thin film. After crystallization by an oxygen anneal, the nanotube arrays are treated with TiCl(4) to enhance the photogenerated current and then integrated into the DSC structure using a commercially available ruthenium-based dye. Although the negative electrode is only 360-nm-thick, under AM 1.5 illumination the generated photocurrent is 7.87 mA/cm(2), with a photocurrent efficiency of 2.9%. Voltage-decay measurements indicate that the highly ordered TiO(2) nanotube arrays, in comparison to nanoparticulate systems, have superior electron lifetimes and provide excellent pathways for electron percolation. Our results indicate that remarkable photoconversion efficiencies may be obtained, possibly to the ideal limit of approximately 31% for a single photosystem scheme, with an increase of the nanotube-array length to several micrometers.     

Highly efficient solar cells using TiO(2) nanotube arrays sensitized with a donor-antenna dye

Donor antenna dyes provide an exciting route to improving the efficiency of dye sensitized solar cells owing to their high molar extinction coefficients and the effective spatial separation of charges in the charge-separated state, which decelerates the recombination of photogenerated charges. Vertically oriented TiO(2) nanotube arrays provide an optimal material architecture for photoelectrochemical devices because of their large internal surface area, lower recombination losses, and vectorial charge transport along the nanotube axis. In this study, the results obtained by sensitizing TiO(2) nanotube arrays with the donor antenna dye Ru-TPA-NCS are presented. Solar cells fabricated using an antenna dye-sensitized array of 14.4 microm long TiO(2) nanotubes on Ti foil subjected to AM 1.5 one sun illumination in the backside geometry exhibited an overall conversion efficiency of 6.1%. An efficiency of 4.1% was obtained in the frontside illumination geometry using a 1 microm long array of transparent TiO(2) nanotubes subjected to a TiCl(4) treatment and then sensitized with the Ru-TPA-NCS dye. Open circuit voltage decay measurements give insight into the recombination behavior in antenna-dye sensitized nanotube photoelectrodes, demonstrating outstanding properties likely due to a reduction in the influence of the surface traps and reduced electron transfer from TiO(2) to ions in solution.     

ZnO nanotube based dye-sensitized solar cells

We introduce high surface area ZnO nanotube photoanodes templated by anodic aluminum oxide for use in dye-sensitized solar cells (DSSCs). Atomic layer deposition is utilized to coat pores conformally, providing a direct path for charge collection over tens of micrometers thickness. Compared to similar ZnO-based devices, ZnO nanotube cells show exceptional photovoltage and fill factors, in addition to power efficiencies up to 1.6%. The novel fabrication technique provides a facile, metal-oxide general route to well-defined DSSC photoanodes.     

An integrated power pack of dye-sensitized solar cell and Li battery based on double-sided TiO2 nanotube arrays

We present a new approach to fabricate an integrated power pack by hybridizing energy harvest and storage processes. This power pack incorporates a series-wound dye-sensitized solar cell (DSSC) and a lithium ion battery (LIB) on the same Ti foil that has double-sided TiO(2) nanotube (NTs) arrays. The solar cell part is made of two different cosensitized tandem solar cells based on TiO(2) nanorod arrays (NRs) and NTs, respectively, which provide an open-circuit voltage of 3.39 V and a short-circuit current density of 1.01 mA/cm(2). The power pack can be charged to about 3 V in about 8 min, and the discharge capacity is about 38.89 μAh under the discharge density of 100 μA. The total energy conversion and storage efficiency for this system is 0.82%. Such an integrated power pack could serve as a power source for mobile electronics.     

High-efficiency solid-state dye-sensitized solar cells based on TiO(2)-coated ZnO nanowire arrays

Replacing the liquid electrolytes in dye-sensitized solar cells (DSCs) with solid-state hole-transporting materials (HTMs) may solve the packaging challenge and improve the long-term stability of DSCs. The efficiencies of such solid-state DSCs (ss-DSCs), however, have been far below the efficiencies of their counterparts that use liquid electrolytes, primarily due to the challenges in filling HTMs into thick enough sensitized films based on sintered TiO(2) nanoparticles. Here we report fabrication of high-efficiency ss-DSCs using multilayer TiO(2)-coated ZnO nanowire arrays as the photoanodes. The straight channel between the vertically aligned nanostructures combined with a newly developed multistep HTM filling process allows us to effectively fill sensitized films as thick as 50 μm with the HTMs. The resulting ss-DSCs yield an average power conversion efficiency of 5.65%.     

Efficient inverted solar cells using TiO(2) nanotube arrays

Using a vertical titania (TiO(2)) nanotube array, an inverted polymer solar cell was constructed with power conversion efficiency up to 2.71%. In this study, self-organized TiO(2) nanotubes arrays were grown by anodizing Ti metal in glycerol electrolyte containing 0.5?wt% NH(4)F and 1.0?wt% H(2)O with 20?V potential. The tube length (～100?nm) was controlled by the thickness of the sputtered titanium layer on the indium-tin oxide (ITO) substrate. The diameter of the tube was approximately 15-25?nm. After annealing in air at 500?°C for 1?h, nanotubes arrays were crystallized to the anatase phase from the initial amorphous state. Following the infiltration of polymeric semiconductor (poly(3-hexylthiophene) and (6,6)-phenyl C(60) butyric acid methyl ester, P3HT:PCBM), the filled TiO(2) layer had an optical absorption over a range from UV to visible light. The high surface-to-volume ratio of the nanotube arrays structure increased the effective area of the active region. The high efficiency of our solar cell is attributed to the vertical TiO(2) nanotube array's enhanced conduction of photo-induced current due to its charge transport capability.     

TiO2 coated urchin-like SnO2 microspheres for efficient dye-sensitized solar cells

Urchin-like SnO2 microspheres have been grown for use as photoanodes in dye-sensitized solar cells （DSSCs）. We observed that a thin layer coating of TiO2 on urchin-like SnO2 microsphere photoanodes greatly enhanced dye loading capability and light scattering ability, and achieved comparable solar cell per- formance even at half the thickness of a typical nanocrystalline TiO2 photoanode. In addition, this photoanode only required attaching -55% of the amount of dye for efficient light harvesting compared to one based on nanocrystalline TiO2. Longer decay of transient photovoltage and higher charge recombination resistance evidenced from electrochemical impedance spectroscopy of the devices based on TiO2 coated urchin-like SnO2 revealed slower recombination rates of electrons as a result of the thin blocking layer of TiO2 coated on urchin- like SnO2. TiO2 coated urchin-like SnO2 showed the highest value （76.1 ms） of electron lifetime （＇r） compared to 2.4 ms for bare urchin-like SnO2 and 14.9 ms for nanocrystalline TiO2. TiO2 coated SnO2 showed greatly enhanced open circuit voltage （Voc）, short-circuit current density （Jsc） and fill factor （FF） leading to a four-fold increase in efficiency increase compared to bare SnO2. Although TiO2 coated urchin-like SnO2 showed slightly lower cell efficiency than nanocrystalline TiO2, it only used a half thickness of photoanode and saved -45% of the amount of dye for efficient light harvesting compared to normal nanocrystalline TiO2.     

Fabrication of partially crystalline TiO2 nanotube arrays using 1, 2-propanediol electrolytes and application in dye-sensitized solar cells

We report the fabrication of self-organized partial crystalline TiO₂ nanotube arrays in 1, 2-propanediol containing fluoride ion. The influence of anodization parameters including NH₄F concentration, water content, anodization voltage and time on the morphology, diameter and length of TiO₂ nanotube were investigated in detail. The prepared TiO₂ nanotube has diameter in 30–120 nm and length in 0.6–3 μm. TiO₂ nanotube arrays are used as photoanode for the application in dye-sensitized solar cell and the photovoltaic performance of 1.91% is achieved with a TiO₂ nanotube sample of 2.2 μm in length combining with N719 dye, and the corresponding photovoltaic parameters of 3.6 mA cm^?2 in short circuit photocurrent density, 840 mV in open circuit potential, and 63.2% in fill factor.     

A facile way to fabricate graphene sheets on TiO2 nanotube arrays for dye-sensitized solar cell applications

Large-area graphene sheets on TiO₂ nanotube arrays (RGO/TNAs) were fabricated using a simple electrochemical method. The RGO content loaded on the arrays was controlled by changing the electrochemical reaction time. The microstructures and properties of RGO/TNAs were characterized and measured using field emission scanning electron microscopy, X-ray diffraction pattern, X-ray photoelectron spectroscopy, FT-IR spectra, and ultraviolet–visible (UV–Vis) spectroscopy. The results indicated that an appropriate reaction time clearly enhances photoelectrochemical properties, while excessive RGO loading significantly lowers their performance. Remarkably, in sharp contrast to the dye-sensitized solar cells prepared by TNAs as photoanode, the RGO/TNAs showed a significantly enhanced power conversion efficiency of 4.46 %. The improvement of light harvesting is due to the excellent property of RGO and the special structure of the composite.     

TiO2 nanotube membranes on transparent conducting glass for high efficiency dye-sensitized solar cells

Crack-free TiO(2) nanotube (NT) membranes were obtained by short time re-anodization of a sintered TiO(2) NT array on Ti foil, followed by dilute HF etching at room temperature. The resulting freestanding TiO(2) membranes were opaque with a slight yellow color having one end open and another end closed. The membranes were then fixed on transparent fluorine-tin-oxide glass using a thin layer of screen-printed TiO(2) nanoparticles (NPs) as a binding medium. It was found that low temperature treatment of the resulting NT/NP film under appropriate pressure before sintering at 450?°C was critical for successful fixation of the NT membrane on the NP layer. The resulting films with open-ends of NT membranes facing the NP layer (open-ends down, OED, configuration) exhibited better interfacial contact between NTs and NPs than those with closed-ends facing the NP layer (closed-ends down, CED, configuration). The cells with an OED configuration exhibit higher external quantum efficiency, greater charge transfer resistance from FTO/TiO(2) to electrolyte, and better dye loading compared to CED configurations. The solar cells with the OED configuration gave 6.1% energy conversion efficiency under AM1.5G condition when the commercial N719 was used as a dye and I(-)/I(3)(-) as a redox couple, showing the promise of this method for high efficiency solar cells.     

Highly flexible frontside-illuminated dye-sensitized solar cells using three-dimensional network TiO2 nanowires

Here we report a highly flexible frontside-illuminated dye-sensitized solar cell (FIDSSC) using Ti foils as the substrates. The laser-drilled microhole arrays (LDMAs) on Ti foil substrates as the photoanode provided an efficient pathway for the diffusion of liquid electrolyte, which would be particularly favorable for frontside illumination of FIDSSC designs. The three-dimensional (3D) network TiO2 nanowires (NWs) were directly grown on the Ti substrate with LDMAs via a simple hydrothermal method. Platinized Ti sheet was used as the counter electrode in the FIDSSC. The mechanical properties of the novel structured device were measured. It was shown that as-synthesized large-scale 3D network TiO2 NWs with a diameter of about 20-30 nm and a length of about 6 microm can prevent crack from generating efficiently when bended to an extreme angle of 120 degree. Furthermore, we demonstrated that the effects of the different bending angles on the performance of the 3D network TiO2 NWs-based FIDSSCs were slight, indicating NWs preferable advantages for the fabrication of flexible DSSCs. The results showed that the FIDSSC achieved an efficiency of 0.72% under front illumination of AM 1.5 simulated one sun light (100 mWcm(-2)).     

Application of TiO2 nanoparticles coated multi-wall carbon nanotube to dye-sensitized solar cells

This study uses the sol-gel method to prepare TiO2 nanoparticle, and further applies TiO2 nanoparticle coating on the surface of the multi-wall carbon nanotube (MWCNT). As a result, TiO2-CNT composite nanoparticles are prepared to serve as photoelectrode material in dye-sensitized solar cell (DSSC). First, after acid treatment of MWCNT is used to remove impurities. Then, the sol-gel method is employed to prepare TiO2-CNT composite nanopowder. X-ray diffraction (XRD) pattern shows that after the TiO2 in TiO2-CNT composite nanopowder has been thermally treated at 450 degrees C, it can be completely changed to anatase phase. Furthermore, as shown from the SEM image, TiO2 has been successfully coated on CNT. The photoelectrode of DSSC is prepared using the electrophoretic deposition method (EPD) to mix the Degassa P25 TiO2 nanoparticles with TiO2-CNT powder for deposition on the indium tin oxide (ITO) conductive glass. After secondary EPD, a thin film of TiO2/CNTs with thickness 17 microm can be acquired. For the prepared TiO2-CNT composite nanoparticles, since MWCNT can increase the short-circuit current density of DSSC, the light-to-electricity conversion efficiency of DSSC can be effectively increased. Experimental results show that the photoelectric conversion efficiency of DSSC using CNT/TiO2 photoelectrode and N719 dye is increased by 41% from the original 3.45% to 4.87%.     

Influence of TiO2 nanofiber additives for high efficient dye-sensitized solar cells

TiO2 nanofibers were prepared from a mixture of titanium-tetra-isopropoxide and poly vinyl pyrrolidone by applying the electrospinning method. The samples were characterized by XRD, FE-SEM, TEM and BET analyses. The diameter of electrospun TiO2 nanofibers is in the range of 70 approximately 160 nm. To improve the short-circuit photocurrent, we added the TiO2 nanofibers in the TiO2 electrode of dye-sensitized solar cells (DSSCs). TiO2 nanofibers added in DSSCs can make up to 20% more conversion energy than the conventional DSSC with only TiO2 films only.     

染料敏化TiO2纳米晶太阳能电池的研究

通过改变TiO2 膜热处理温度来研究染料RuL2 (SCN ) 2 敏化TiO2 纳米晶太阳能电池光电性能。得热处理温度对TiO2 膜的质量有很大的影响。染料RuL2 (SCN) 2 的吸收光谱表明 ,染料RuL2 (SCN) 2 在可见光有很宽且强的吸收 ,是一种很理想的敏化剂。用XRD和UV -Vis等手段分别表征了TiO2 膜和染料。     

TiO_2纳米管阵列电极染料敏化太阳能电池

采用电化学阳极氧化法在纯钛片表面制备了高度有序的TiO2纳米管阵列。利用SEM、XRD分别对TiO2纳米管阵列的形貌、晶型进行了表征,并通过线性扫描伏安法对N719染料敏化纳米管阵列电极的光电性能进行了研究。实验结果表明,纳米管阵列的管径和长度随着阳极氧化电压的升高和氧化时间的延长都分别相应增加。同时还发现,通过450℃热处理的TiO2纳米管阵列,具有较好的锐钛矿晶型结构,其光电转化效率为2.1%。     

Quasi-solid-state dye-sensitized solar cells based on TiO2/NiO core-shell nanocomposites

The core-shell nanocomposites of titanium dioxide (TiO2) and nickel oxide (NiO) used as modified photoelectrode materials in a quasi-solid-state dye-sensitized solar cell (quasi-DSSC) were synthesized using TiO2 P-25 and a nickel acetate precursor, via ball milling. The as-obtained intermediate products were annealed at 350, 450, and 550 degrees C. The structural properties of the NiO/TiO2 nanocomposites were well characterized via X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. The results imply that NiO-shell-coated TiO2 nanoparticles can be obtained with the assistance of sufficient thermal energy in the system. The crystallite size of the composite increased as the annealing temperature increased. Among all the prepared conditions, the composite with 0.1 wt% NiO exhibited the best performance, with an optimized solar-energy conversion efficiency of 2.29% and with a short-circuit current density of 7.21 mA/cm2. The significant enhancement of the device's current density may be associated with the charge recombination suppression by the NiO shell, which acted as a potential barrier in the composite. The decrease in the recombination of the photo-injected electrons, and the increase in the number of electrons tunneling through the NiO layer at the interface, may have resulted from the presence of a NiO layer on the TiO2 nanoparticles.     

Solid-state dye-sensitized solar cells based on ordered ZnO nanowire arrays

A solid-state dye-sensitized solar cell (DSC) is fabricated by using arrays of 11-12 μm long, vertically oriented ZnO nanowires as the anode and CuSCN as the solid hole-transport material. The fabricated DSC yields a remarkably higher photocurrent density (J(SC) = 8 mA cm(-2)) compared to previously reported data for solid-state DSCs based on either one-dimensional nanostructures (J(SC) = 0.34 mA cm(-2)) or nanoporous nanocrystalline structures (J(SC) = 4.5 mA cm(-2)) of ZnO. A power conversion efficiency of 1.7% under an irradiation of AM 1.5 G simulated sunlight is reported.     

Novel carbon-doped TiO2 nanotube arrays with high aspect ratios for efficient solar water splitting

The photocatalytic splitting of water into hydrogen and oxygen using solar light is a potentially clean and renewable source for hydrogen fuel.(1,2) There has been extensive investigation into metal-oxide semiconductors such as TiO(2), WO(3), and Fe(2)O(3), which can be used as photoanodes in thin-film form.(3-5) Of the materials being developed for photoanodes, TiO(2) remains one of the most promising because of its low cost, chemical inertness, and photostability.(6) However, the widespread technological use of TiO(2) is hindered by its low utilization of solar energy in the visible region. In this study, we report the preparation of vertically grown carbon-doped TiO(2) (TiO(2-x)C(x)) nanotube arrays with high aspect ratios for maximizing the photocleavage of water under white-light irradiation. The synthesized TiO(2-x)C(x) nanotube arrays showed much higher photocurrent densities and more efficient water splitting under visible-light illumination (> 420 nm) than pure TiO(2) nanotube arrays. The total photocurrent was more than 20 times higher than that with a P-25 nanoparticulate film under white-light illumination.