Small-signal response of nanocrystalline-titanium dioxide/poly(3-hexylthiophene) heterojunction solar cells

Admittance spectra of nanocrystalline titanium dioxide/poly(3-hexyl thiophene), heterojunction solar cells have been measured in air and under vacuum. In air, a 3-orders of magnitude increase in capacitance is observed when the measurement frequency is decreased from 1 MHz to 0.1 Hz. The frequency-dependence of the loss tangent with zero bias voltage indicates the presence of two processes, the weaker of which is attributed to adsorbed water molecules on the surface of the nanocrystalline titanium dioxide. The second process which becomes dominant in forward bias is believed to arise from the presence of an interfacial capacitance. In air, the capacitance is seen to depend strongly on applied forward bias consistent with the presence of an interfacial depletion region. However, a number of inconsistencies indicate that a mechanism related to carrier interaction with oxygen-related interface states may be the cause. At high forward bias and low frequencies, a negative incremental capacitance is observed similar to that seen in organic light emitting diodes following the onset of double-injection.     

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.     

Conversion efficiency versus sensitizer for electrospun TiO(2) nanorod electrodes in dye-sensitized solar cells

The electrochemical and optical properties of three indoline dyes, namely C(35)H(28)N(2)O(2) (D131), C(37)H(30)N(2)O(3)S(2) (D102), and C(42)H(35)N(3)O(4)S(3) (D149), were studied and compared with that of the N3 dye. D131 has the largest bandgap and lowest unoccupied molecular orbital (LUMO) energies compared to the other dyes. A size-dependent variation in the absorptivity of the indoline dyes was observed-the absorptivity increased with increase in the molecular size. The dyes were anchored onto TiO(2) nanorods. The TiO(2) nanorods were obtained by electrospinning a polymeric solution containing titanium isopropoxide and polyvinylpyrrolidone and subsequent sintering of the as-spun composite fibers. Absorption spectral measurements of the dye-anchored TiO(2) showed blue shifts in the excitonic transition of the indoline dyes, the magnitude of which increased with decrease in the molecular size. Dye-sensitized solar cells (DSSCs) were fabricated using the indoline dyes, TiO(2) nanorods, and iodide/triiodide electrolyte. The D131 dye showed comparable energy conversion efficiency (η) to that of the N3 dye. A systematic change in the short circuit current density (J(SC)) and η of the indoline DSSCs was observed. The observed variation in J(C) is most likely originated from the difference in the electronic coupling strengths between the dye and the TiO(2).     

Approach to a block polymer precursor from poly(3-hexylthiophene) nitroxide-mediated in situ polymerization for stabilization of poly(3-hexylthiophene)/ZnO hybrid solar cells

A cross-linked block copolymer poly(3-hexylthiophene)-b-poly(zinc dimethacrylate) (P3HT-b-PZn(MA)₂), which acted as precursor for the preparation of poly(3-hexylthiophene)/ZnO (P3HT/ZnO) hybrid film by in-situ hydrolysis, was rationally designed and synthesized via nitroxide-mediated in-situ polymerization of zinc methacrylate (Zn(MA)₂) using poly(3-hexylthiophene) alkoxyamine (P3HT-TIPNO) as macroinitiator for the purpose of stabilizing the P3HT/ZnO hybrid solar cells. The cross-linking was confirmed by the insolubility of the film in organic solvents and Fourier-transform infrared experiment. With the function of the cross-linked template, the diffusion of ZnO nanoparticles prepared by in-situ hydrolysis could be lowered to suppress the formation of large aggregations, which favored the formation of a better and more stable interpenetrating network and provided more heterojunction interfaces for exciton dissociation. As a result, the inverted device based on cross-linked P3HT/ZnO hybrid film obtained by in situ hydrolyzing P3HT-b-PZn(MA)₂ block copolymer yielded a power conversion efficiency of 0.45% under AM 1.5G illumination from a calibrated solar simulator with an intensity of 100 mW/cm², and the deterioration of the photoconversion performance was suppressed in the hybrid solar cells with the cross-linked P3HT/ZnO compared to cells with non-cross-linked P3HT/ZnO obtained by in situ hydrolyzing P3HT-TIPNO/Zn(MA)₂ blend film.     

Synergistic effect of carbon microstructure and topography of TiO2 nanorod arrays on hemocompatibility of carbon/TiO2 nanorod arrays composites

This study systematically investigated the synergistic effect of material’s surface topography and electronic structure on fibrinogen adsorption and platelet activation. Three kinds of oriented TiO₂ nanorod arrays (TNA) were synthesized by the hydrothermal method by changing the growth parameters in order to adjust the surface topography and roughness. The carbon thin films with various sp³ C contents were deposited onto the top of TNA with the DC magnetic-filtered cathodic vacuum arc deposition. The structure, the surface topography, and the roughness of TNA were characterized by X-ray diffraction, scanning electron microscopy, and atomic force microscopy, respectively. The sp³ C content in carbon films was estimated using Raman spectroscopy. The results demonstrated that the amount of fibrinogen adsorbed on surface was influenced merely by surface topography and roughness of TNA, but independent of surface carbon coating. In addition, the platelet adhesion decreased significantly with the increase of the sp³ C content in carbon coating at the same degree of roughness or adsorbed fibrinogen. The lowest platelet adhesion and activation was observed on the specific surface topography associated with the highest sp³ C content in carbon coating.     

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.     

Time-evolution of poly(3-hexylthiophene) as an energy relay dye in dye-sensitized solar cells

Energy relay dyes (ERD) and F?rster resonant energy transfer (FRET) are useful techniques for increasing absorption in dye-sensitized solar cells. We use femtosecond transient absorption spectroscopy to monitor charge generation processes in a solid-state DSC containing poly(3-hexylthiophene) (P3HT) as both the hole-transporter and the ERD with a zinc phthalocyanine dye (TT1) as the sensitizer. We observe efficient FRET occurring on picosecond time scales and subsequent hole transfer from TT1 to P3HT occurring onward from 100 ps.     

Sputtered highly ordered TiO2 nanorod arrays and their applications as the electrode in dye-sensitized solar cells

For the first time, the TiO2 nanorod arrays have been prepared on ITO substrates at room temperature by dc reactive magnetron sputtering technique. These TiO2 nanorods have a preferred orientation along the (220) direction and are perpendicular to the ITO substrate. Both the X-ray diffraction and Raman scattering measurements show that the highly ordered TiO2 nanorod arrays have an anatase crystal structure. The diameter of the nanorod varies from 30 nm to 100 nm and the nanorod length can be varied from several hundred nanometers to several micrometers depending on the deposition time. The TiO2 nanorod arrays with about 3 micrometers length have been used as an electrode for dye-sensitized solar cell (DSSC). Short-circuit photocurrent density, open-circuit voltage, fill factor and light-to-electricity conversion efficiency at 100 mW/cm2 light intensity are estimated to be 12.76 mA/cm2, 0.65 V, 0.63 and 5.25%, respectively, for the DSSC made of the TiO2 nanorods.     

TiO2 nanorod arrays functionalized with In2S3 shell layer by a low-cost route for solar energy conversion

We report the fabrication and characterization of a TiO(2)-In(2)S(3) core-shell nanorod array structure for application of semiconductor-sensitized solar cells. Hydrothermally synthesized TiO(2) nanorod arrays on FTO glass substrates are functionalized with a uniform In(2)S(3) shell layer by using the successive ion layer adsorption and reaction (SILAR) method. This low-cost technique promotes a uniform deposition of In(2)S(3) nanoshells on the surface of TiO(2) nanorods, thus forming an intact interface between the In(2)S(3) shell and TiO(2) core. Results show that the thickness of In(2)S(3) shell layers as well as the visible light absorption threshold can be effectively controlled by varying the coating cycles during the SILAR process. The best reproducible performance of the sandwich solar cell using the TiO(2)-In(2)S(3) core-shell nanorod arrays as photoelectrodes was obtained after 30 SILAR cycles, exhibiting a short-circuit current (I(sc)) of 2.40 mA cm(-2), an open-circuit voltage (V(oc)) of 0.56 V, a fill factor (ff) of 0.40 and a conversion efficiency (η) of 0.54%, respectively. These results demonstrate a feasible and controllable route towards In(2)S(3) coating on a highly structured substrate and a proof of concept that such TiO(2)-In(2)S(3) core-shell architectures are novel and promising photoelectrodes in nanostructured solar cells.     

Sol-gel assisted ZnO nanorod array template to synthesize TiO(2) nanotube arrays

A TiO(2) nanotube array with a large surface area is fabricated on a glass substrate using a ZnO nanorod array and sol-gel process, and the structural characteristics of the TiO(2) nanotube array are investigated. The well-aligned ZnO nanorod array, which is deposited on ZnO seed layer coated glass substrates by the wet-chemical route, is used as a template to synthesize TiO(2)/ZnO composite nanostructures through the sol-gel process. Then, by selectively removing the ZnO template, a TiO(2) nanotube with contours of the ZnO nanorods is fabricated on the ZnO seed layer coated glass. The resultant TiO(2) nanotubes are 1.5?μm long and 100-120?nm in inner diameter, with a wall thickness of ～10?nm. In addition, by adjusting the experimental parameters, such as the dip-coating cycle number or heating rate, porous TiO(2) thick films can also be obtained.     

Controlled fabrication of TiO2 rutile nanorod/anatase nanoparticle composite photoanodes for dye-sensitized solar cell application

We present a straightforward procedure to prepare composite photoanodes which consisted of TiO2 rutile nanorods/anatase nanoparticles synthesized under hydrothermal conditions, with the ratio of rutile to anatase controlled simply by adjusting the volume of nitric acid. The as-prepared TiO2 composites exhibited high specific surface area, light-scattering effect, and good crystallinity. The dye-sensitized solar cells (DSCs) using the TiO2 composites showed higher short-circuit photocurrent and overall conversion efficiency than the DSC from pure-anatase nanoparticles. The highest conversion efficiency was achieved from the DSC based on TiO2 nanocomposites with 24 wt% rutile nanorods, which was attributed to improved light harvesting caused by the enhancement of specific surface area and scattering effect from rutile nanorods.     

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%.     

Growth of TiO2 nanowire bundle arrays and their application in dye-sensitized solar cells

Highly oriented single-crystalline TiO₂ nanowire bundle arrays on transparent conductive fluorine-doped tin oxide substrates are prepared by hydrothermal method using the precursors of titanium butoxide, deionized water and hydrochloric acid. The structure and morphology characteristics of all the samples have been analyzed by X-ray diffraction (XRD), scanning electron microscopy and transmission electron microscopy. Results show that the diameter, length, and density of the nanowire bundle arrays can be varied by changing the growth parameters, such as growth time, initial reactant concentration and acidity. The enhanced (002) peak in XRD patterns indicate that the nanowire is well crystallized and grow perpendicular to the substrate. The high resolution transmission electron microscope images and selected-area electron diffraction patterns confirm that there are approximately 10–30 nanowires in each bundle. The nanowire is single crystalline. Dye-sensitized solar cells assembled from oriented TiO₂ nanowire bundle arrays as the photoanode are studied. The light-to-electricity conversion efficiency is about 2.17 %.     

Nanostructured TiO2 films for dye-sensitized solar cells prepared by the sol-gel method

TiO2 films were prepared on glass substrates using the sol-gel process for a dye-sensitized solar cell application. The TiO2 sol was prepared using hydrolysis/polycondensation. Titanium (IV) Tetra Isopropoxide (TTIP) was used as precursor and Nitric acid (HNO3) was used as a catalyst for the peptization. The crystal structure and morphology of the prepared materials were characterized by XRD, and an SEM. The observations confirmed the nanocrystalline nature of the TiO2. The reaction parameters, such as the catalyst concentrations, the calcination time, and the calcination temperature were varied during the synthesis in order to achieve nanosize TiO2 particles. The prepared TiO2 particles were coated onto FTO glass using a screen printing technique. The prepared TiO2 films were characterized by UV-vis. The TiO2 particles calcinated at low temperatures showed an anatase phase they grew into a rutile phase when the calcination temperature increased. The size and structure of the TiO2 particles were adjusted to specific surface areas. It was found that the conversion efficiency of the DSSC was highly affected by the properties of the TiO2 particles.