Fabrication of dye-sensitized solar cells using ordered and vertically oriented TiO2 nanotube arrays with open and closed ends

Highly ordered and vertically oriented TiO₂ nanotube arrays were prepared and applied to dye sensitized solar cell (DSSC) as working electrodes. The nanotube arrays were fabricated using atomic layer deposition and AAO template. The two types of nanotube's end, closed-end and open-end, were produced by reactive ion etching (RIE) process. The structure of nanotube arrays was characterized by FE-SEM, TEM, and XRD. DSSCs using the TiO₂ nanotube arrays as working electrodes were fabricated and characterized. The DSSCs prepared from the TiO₂ nanotubes with open end exhibited higher power conversion efficiency of 1.17% than that with closed end. This result is attributed to that the open-ended TiO₂ nanotubes provided larger surface area, leading to more amount of dye molecules to adsorb followed by the higher light absorption.     

Surface modification of electron transport layers based on TiO2 nanorod boosts efficiency of perovskite solar cells

In this work, TiO₂ heterostructure thin films including rutile TiO₂ nanorods (TNRs) and anatase TiO₂ nanoparticles (TNPs) on fluorine-doped tin oxide (FTO) glass are fabricated by the hydrothermal method and are applied as electron transport layers (ETLs) in MAPbI₃-based perovskite solar cells (PSCs). To enhance the surface area of ETL, TNRs are first etched in acidic solution by another hydrothermal process for different reaction times before coating with TNPs. The morphological and structural properties of TNRs after etching are carefully investigated. Interestingly, the surface modification of TNR thin film by appropriate TNP deposition and etching improves significantly the efficiency of PSC devices by more than 1.6 times. To further improve the performance of PSC, phenyl-C61-butyric acid methyl ester (PCBM) is used to enhance the charge transfer efficiency at the ETL/perovskite interface, and the optimal PSC device shows the champion efficiency of 18.50% with low charge transfer resistance (11.56 ohms).     

Dye-sensitized solar cells based on a nanoparticle/nanotube bilayer structure and their equivalent circuit analysis

Dye-sensitized solar cells (DSSCs) were prepared by capitalizing on a TiO(2) bilayer structure composed of P-25 nanoparticles and freestanding crystalline nanotube arrays as photoanodes. After being subjected to sequential TiCl(4) treatment and O(2) plasma exposure, the bilayer photoanode was sensitized with N719 dye. DSSCs based on a 20 μm TiO(2) nanoparticle film solely and a bilayer of 13 μm TiO(2) nanoparticles and 7 μm TiO(2) nanotubes exhibited the highest power conversion efficiency, PCE, of 8.02% and 7.00%, respectively, compared to the devices made of different TiO(2) thicknesses. On the basis of J-V parameter analysis acquired by equivalent circuit model simulation, in comparison to P-25 nanoparticles, charge transport in nanotubes was found to be facilitated due to the presence of advantageous nanotubular structures, while photocurrent was reduced owing to their small surface area, which in turn resulted in low dye loading, as well as the lack of cooperative effect of anatase and rutile phases.     

A facile route to fabricate an anodic TiO(2) nanotube-nanoparticle hybrid structure for high efficiency dye-sensitized solar cells

The relatively low internal surface area of anodized TiO(2) nanotube arrays (TNAs) limits dye adsorption and light capturing in TNA-based dye-sensitized solar cells (DSSCs). Here, water treatment of as-anodized TNAs at room temperature was used to tailor the geometry of TNA walls in a controllable way, leading to a hybrid tube wall structure with the outer shell in a tubular morphology and the inner surface consisting of small particles. To enable front-side illumination in DSSCs, the TNAs with porous inner walls were transferred to transparent conductive oxide substrates by a self-detaching and transfer technique. The roughened water-treated TNAs show significantly enhanced internal surface area, leading to improved dye-loading and light-harvesting capabilities. Optimized performance was achieved after water treatment for 2 days, with a power conversion efficiency of 6.06%, increased by ～33% compared to conventional TNAs. Furthermore, the hybrid TNA nanostructure provides excellent electron transfer and recombination characteristics, thus promising for high efficiency DSSCs.     

Slope-tunable Si nanorod arrays with enhanced antireflection and self-cleaning properties

Slope-tunable Si nanorod arrays (NRAs) were fabricated with colloidal lithography and reactive ion etching (RIE). Sharpened NRAs fabricated by increasing the SF6/O2 flow ratio during RIE exhibit enhanced antireflection (AR) and hydrophobic properties, which are attributed to the smooth gradient in the effective refractive index of NRAs, and the enlarged water/air interface of the water drops in the NRA layers, respectively. Enhanced AR characteristics via modifying the slope of NRAs are accompanied by broad-band working ranges, omnidirectionality, and polarization insensitivity. Detailed experimental and theoretical analysis of slope-tunable NRAs should benefit the development of various self-cleaning optoelectronic devices with efficient light management.     

The influence of anatase-rutile mixed phase and ZnO blocking layer on dye-sensitized solar cells based on TiO2nanofiberphotoanodes

High performance is expected in dye-sensitized solar cells (DSSCs) that utilize one-dimensional (1-D) TiO₂ nanostructures owing to the effective electron transport. However, due to the low dye adsorption, mainly because of their smooth surfaces, 1-D TiO₂ DSSCs show relatively lower efficiencies than nanoparticle-based ones. Herein, we demonstrate a very simple approach using thick TiO₂ electrospun nanofiber films as photoanodes to obtain high conversion efficiency. To improve the performance of the DSCCs, anatase-rutile mixed-phase TiO₂ nanofibers are achieved by increasing sintering temperature above 500°C, and very thin ZnO films are deposited by atomic layer deposition (ALD) method as blocking layers. With approximately 40-μm-thick mixed-phase (approximately 15.6?wt.% rutile) TiO₂ nanofiber as photoanode and 15-nm-thick compact ZnO film as a blocking layer in DSSC, the photoelectric conversion efficiency and short-circuit current are measured as 8.01% and 17.3?mA?cm^?2, respectively. Intensity-modulated photocurrent spectroscopy and intensity-modulated photovoltage spectroscopy measurements reveal that extremely large electron diffusion length is the key point to support the usage of thick TiO₂ nanofibers as photoanodes with very thin ZnO blocking layers to obtain high photocurrents and high conversion efficiencies.     

Preparation of TiO₂ nanowires/nanotubes using polycarbonate membranes and their uses in dye-sensitized solar cells

Track-etched polycarbonate (PC) membranes were used as a soft template to synthesize mesoporous TiO(2) for use in dye-sensitized solar cells (DSSCs). The Ti precursor infiltrated into the cylindrical confined spaces of PC membranes. Upon calcination at 500 °C, TiO(2) nanowires (15TNW) were obtained from PC with a 15 nm pore diameter, whereas TiO(2) nanotubes (50TNT and 100TNT) were generated from PC with 50 and 100 nm diameter pores, respectively. TNW and TNT were used as photoelectrodes in DSSCs employing a polymer electrolyte. The ranking of the cell efficiencies of the 200 nm thick TiO(2) films was 50TNT (1.1%) > 15TNW (0.8%) ? 100TNT (0.7%), which was mostly attributed to different amounts of dye adsorption due to different surface areas. These TNW and TNT films were further coated with the graft copolymer-directed mesoporous TiO(2) and were used as interfacial layers between the FTO glass and the 4 μm thick nanocrystalline TiO(2) film. As a result, the order of energy conversion efficiency was 15TNW (5.0%) ? 50TNT (4.8%) > 100TNT (4.1%). The improved performance of 15TNW was due to a higher transmittance through the electrode and a longer electron lifetime for recombination. The DSSC performance was systematically investigated in terms of interfacial resistance and charge recombination using electrochemical impedance spectroscopy.     

The effect of dye-sensitized solar cell based on the composite layer by anodic TiO2 nanotubes

TiO₂ nanotube arrays are very attractive for dye-sensitized solar cells (DSSCs) owing to their superior charge percolation and slower charge recombination. Highly ordered, vertically aligned TiO₂ nanotube arrays have been fabricated by a three-step anodization process. Although the use of a one-dimensional structure provides an enhanced photoelectrical performance, the smaller surface area reduces the adsorption of dye on the TiO₂ surface. To overcome this problem, we investigated the effect of DSSCs constructed with a multilayer photoelectrode made of TiO₂ nanoparticles and TiO₂ nanotube arrays. We fabricated the novel multilayer photoelectrode via a layer-by-layer assembly process and thoroughly investigated the effect of various structures on the sample efficiency. The DSSC with a four-layer photoelectrode exhibited a maximum conversion efficiency of 7.22% because of effective electron transport and enhanced adsorption of dye on the TiO₂ surface.     

Controllable growth of dendritic ZnO nanowire arrays on a stainless steel mesh towards the fabrication of large area, flexible dye-sensitized solar cells

Well-defined ZnO nanowire (NW) arrays with controlled dendritic structures were successfully built on a stainless steel mesh and utilized as photoanodes for the fabrication of large-area, flexible dye-sensitized solar cells (DSSCs). The dendritic nanostructure proves favorable for the improvement of the overall light conversion efficiency of the DSSC. An optimized etching time for the affixion of ZnO seeds on the ZnO backbone of the dendritic "tree" and the controlled growth conditions of the branch NW are critical to achieve high conversion efficiency solar cells.     

Strong light coupling effect for a glancing-deposited silver nanorod array in the Kretschmann configuration

In this work, three slanted silver nanorod arrays (NRAs) with different thicknesses are fabricated using the glancing angle deposition method. Each silver NRA in the Kretschmann configuration is arranged to form a prism/NRA/air system. Attenuated total reflection occurs over the visible wavelengths and wide incident angles of both s- and p-polarization states. The extinctance is inversely proportional to the thickness of the Ag NRA. The thinnest NRA, with a thickness of 169 nm, exhibits strong extinctance of more than 80% over the visible wavelengths. The associated forward scatterings from the three NRAs are measured and compared under illumination with a laser beam with a wavelength of 632.8 nm.     

Effects of dye etching on the morphology and performance of ZnO nanorod dye-sensitized solar cells

Dye-sensitized solar cells based on electrodeposited ZnO nanorod arrays were fabricated and tested. Field-emission scanning electron microscopy (FESEM) and X-ray powder diffraction (XRD) were used to identify the characters of ZnO nanorod arrays. The effects of dye etching on the morphology and performance of ZnO nanorod dye-sensitized solar cells were studied. It was found that the surfaces of ZnO nanorods were both etched by dye solutions, no matter N3 or N719. Compared with N3, N719 had a larger damage to the structure of ZnO nanorod photoanode, and the photoelectric conversion efficiency of cells decreased quickly with the sensitizing time increasing. In a certain range, the increasing length of ZnO nanorods can clearly improve the photoelectric conversion efficiency of cells.     

Effect of compressed TiO2 nanoparticle thin film thickness on the performance of dye-sensitized solar cells

In this study, dye-sensitized solar cells (DSSCs) were fabricated using nanocrystalline titanium dioxide (TiO₂) nanoparticles as photoanode. Photoanode thin films were prepared by doctor blading method with 420 kg/cm² of mechanical compression process and heat treatment in the air at 500°C for 30 min. The optimal thickness of the TiO₂ NP photoanode is 26.6 μm with an efficiency of 9.01% under AM 1.5G illumination at 100 mW/cm². The efficiency is around two times higher than that of conventional DSSCs with an uncompressed photoanode. The open-circuit voltage of DSSCs decreases as the thickness increases. One DSSC (sample D) has the highest conversion efficiency while it has the maximum short-circuit current density. The results indicate that the short-circuit current density is a compromise between two conflict factors: enlargement of the surface area by increasing photoanode thickness and extension of the electron diffusion length to the electrode as the thickness increases.     

A facile method to prepare SnO2 nanotubes for use in efficient SnO2-TiO2 core-shell dye-sensitized solar cells

A high-efficiency photoelectrode for dye-sensitized solar cells (DSSCs) should combine the advantageous features of fast electron transport, slow interfacial electron recombination and large specific surface area. However, these three requirements usually cannot be achieved simultaneously in the present state-of-the-art research. Here we report a simple procedure to combine the three conflicting requirements by using porous SnO(2) nanotube-TiO(2) (SnO(2) NT-TiO(2)) core-shell structured photoanodes for DSSCs. The SnO(2) nanotubes are prepared by electrospinning of polyvinyl pyrrolidone (PVP)/tin dichloride dihydrate (SnCl(2)·2H(2)O) solution followed by direct sintering of the as-spun nanofibers. A possible evolution mechanism is proposed. The power conversion efficiency (PCE) value of the SnO(2) NT-TiO(2) core-shell structured DSSCs (～5.11%) is above five times higher than that of SnO(2) nanotube (SnO(2) NT) DSSCs (～0.99%). This PCE value is also higher than that of TiO(2) nanoparticles (P25) DSSCs (～4.82%), even though the amount of dye molecules adsorbed to the SnO(2) NT-TiO(2) photoanode is less than half of that in the P25 film. This simple procedure provides a new approach to achieve the three conflicting requirements simultaneously, which has been demonstrated as a promising strategy to obtain high-efficiency DSSCs.     

In situ electrochemical synthesis of a poly(o‐anisidine) counter electrode for a dye‐sensitized solar cell

Poly(o‐anisidine) (POA) counter electrodes (CEs) were fabricated by potentiodynamic deposition and incorporated into platinum (Pt)‐free dye‐sensitized solar cells (DSSCs). A different sweep number had great impact on the morphology and electrocatalytic activity of the POA films. The POA film fabricated by 25 sweep cycles was observed to have a highly porous morphology, and this resulted in a lower charge‐transfer resistance of 57 cm² in comparison with the Pt CE. The DSSC assembled with the POA CE showed a higher photovoltaic conversion efficiency of 1.67% compared to 1.2% for the DSSC with the Pt CE under full sunlight illumination. Therefore, the high active surface area of the 25‐sweep‐segmented POA film could be considered a promising alternative CE for use in DSSCs because of its high electrocatalytic performance and electrochemical stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42041.     

Effect of Annealing Temperature on TiO2 Nanorod Films Prepared by dc Reactive Magnetron Sputtering for Dye-Sensitized Solar Cells

Anatase TiO₂ nanorod films have been prepared on ITO coated glass substrates at room temperature by dc reactive magnetron sputtering technique. The nanorods are highly ordered and are perpendicular to the substrate. XRD measurements show that the anatase nanorods have a preferred orientation along the [110] direction. The prepared nanorods were annealed at different temperatures (200?C500 °C) in air for 1 h. The dye-sensitized solar cells (DSSC) have been made using the as-deposited and annealed TiO₂ nanorods as working electrodes. It has been found that annealing improves the efficiency of the DSSC. An optimum conversion efficiency of 2.13%, at 100 mW/cm² light intensity has been achieved with TiO₂ nanorods annealed at 300 °C.     

Open-ended TiO2 nanotubes formed by two-step anodization and their application in dye-sensitized solar cells

We demonstrate a simple method to fabricate open-ended TiO(2) nanotube (NT) based dye-sensitized solar cells (DSSCs), where the NTs are attached to either TiO(2) nanorods (NRs) grown on fluorine-doped tin oxide (FTO) or FTO directly by nanoparticles (NPs). A completely hole-through TiO(2) NT layer is fabricated via a two-step anodization with heat treatment immediately after the first anodization. DSSCs with the open-ended NTs show better photovoltaic performance than those with close-ended NTs, due to the enhanced charge transport in the open-ended structure. Under optimum conditions, DSSCs fabricated with the open-ended NT layer exhibit a short circuit current density (J(sc)) of 19.10 mA cm(-2), an open circuit voltage (V(oc)) of 0.68 V, a fill factor (FF) of 0.49, and a power conversion efficiency (eff) of 6.3%.     

Graphene oxide modified TiO2 nanotube arrays: enhanced visible light photoelectrochemical properties

Novel nanocomposite films, based on graphene oxide (GO) and TiO(2) nanotube arrays, were synthesized by assembling GO on the surface of self-organized TiO(2) nanotube arrays through a simple impregnation method. The composite films were characterized with field emission scanning electron microscopy, X-ray diffraction, Raman spectroscopy and UV-vis diffuse reflectance spectroscopy. The photoelectrochemical properties of the composite nanotube arrays were investigated under visible light illumination. Remarkably enhanced visible light photoelectrochemical response was observed for the GO decorated TiO(2) nanotube composite electrode compared with pristine TiO(2) nanotube arrays. The sensitizing effect of GO on the photoelectrochemical response of the TiO(2) nanotube arrays was demonstrated and about 15 times enhanced maximum photoconversion efficiency was obtained with the presence of GO. An enhanced photocatalytic activity of the TiO(2) nanotube arrays towards the degradation of methyl blue was also demonstrated after modification with GO. The results presented here demonstrate GO to be efficient for the improved utilization of visible light for TiO(2) nanotube arrays.     

Growth and optical properties of ZnO nanorod arrays on Al-doped ZnO transparent conductive film

ZnO nanorod arrays (NRAs) on transparent conductive oxide (TCO) films have been grown by a solution-free, catalyst-free, vapor-phase synthesis method at 600°C. TCO films, Al-doped ZnO films, were deposited on quartz substrates by magnetron sputtering. In order to study the effect of the growth duration on the morphological and optical properties of NRAs, the growth duration was changed from 3 to 12 min. The results show that the electrical performance of the TCO films does not degrade after the growth of NRAs and the nanorods are highly crystalline. As the growth duration increases from 3 to 8 min, the diffuse transmittance of the samples decreases, while the total transmittance and UV emission enhance. Two possible nanorod self-attraction models were proposed to interpret the phenomena in the sample with 9-min growth duration. The sample with 8-min growth duration has the highest total transmittance of 87.0%, proper density about 75 μm⁻², diameter about 26 nm, and length about 500 nm, indicating that it can be used in hybrid solar cells.     

Improved photocurrent of a poly (3,4-ethylenedioxythiophene)-ClO₄⁻/TiO₂ thin film-modified counter electrode for dye-sensitized solar cells

We prepared a poly(3,4-ethylenedioxythiophene) (PEDOT)-ClO??-supported TiO? thin-film electrode as a counter electrode on a transparent conductive oxide glass electrode for a dye-sensitized solar cell (DSSC) using a combination of sol-gel and electropolymerization methods. The photocurrent-voltage characteristics indicate that DSSCs with PEDOT-ClO??/TiO? thin-film counter electrodes had a high photovoltaic conversion efficiency similar to that of PEDOT-ClO??/TiO? particle composite-film electrodes. Furthermore, it was found that the photocurrent was increased by attaching a reflector to the opposite side of the transparent counter electrode.     

大小颗粒Ti02复合制备纳晶薄膜电极及其性能研究

选用大小粒径分别为200nm和21nm的TiO2颗粒,采用刮涂法制备了几种不同条件的TiOz薄膜电极,研究了大小颗粒Ti02的复合方式和质量比对其所组装染料敏化太阳能电池光电性能的影响。应用红外吸收光谱仪和扫描电子显微镜对Ti02薄膜电极进行了表征,在100mW／cm^2（AM1．5G）光照下,测试了电池的光电性能。结果表明：将大颗粒Ti02作为光散射层,且大颗粒Ti02和小颗粒Ti02质量比为1：3时,所制薄膜不但可以保持纳米粉体高比表面积的优点,同时可以提高对太阳光的散射率,用其组装的电池光电性能最好,转换效率达到2．46％。