A facile low temperature synthesis of TiO2 nanorods for high efficiency dye sensitized solar cells

Titania (TiO₂) nanorods have been synthesized with controlled size for dye-sensitized solar cells (DSSCs) via hydrothermal route at low hydrothermal temperature of 100 °C for 24 h. The titania nanorods were characterized using XRD, SEM, TEM/HRTEM, UV-vis Spectroscopy, FTIR and BET specific surface area (S _BET), as well as pore-size distribution by BJH. The results indicated that the bulk traps and the surface states within the TiO₂ nanorods films have enhanced the efficiency of DSSCs. The size of the titania nanorods was 6.7 nm in width and 22 nm in length. The high surface area can provide more sites for dye adsorption, while the fast photoelectron-transfer channel can enhance the photogenerated electron transfer to complete the circuit. The specific surface area S _BET was 77.14 m²?g^?1 at the synthesis conditions. However, the band gap energy of the obtained titania nanorods was 3.2 eV. The oriented nanorods with appropriate lengths are beneficial in improving the electron transport property and thus leading to the increase of photocurrent, together enhancing the power conversion efficiency. A nearly quantitative absorbed photon-to-electrical current conversion achieved upon excitation at wave length of 550 nm and the power efficiency was enhanced from 5.6 % for commercial TiO₂ nanoparticles Degussa (P25) cells to 7.2 % for TiO₂ nanorods cells under AM 1.5 illumination (100 mW?cm^?2). The TiO₂ cells performance was improved due to their high surface area, hierarchically mesoporous structures and fast electron-transfer rate compared with the Degussa (P25).     

Natural dye-based photoelectrode for improvement of solar cell performance

In the present paper, photovoltaic studies of dye-sensitized solar cells (DSSCs) based on betacyanin/TiO₂ and betacyanin/WO₃–TiO₂ have been done. The cell performances were compared through I–V curves and wavelength dependant photocurrent measurements for the two new types of DSSCs. The TiO₂-coated DSSC showed the photovoltage and photocurrent of 300 mV and 4.96 mA/cm², whereas the cell employing WO₃–TiO₂ photoelectrode showed the values 435 mV and 9.86 mA/cm², respectively. The conversion efficiency of TiO₂ based dye-sensitized solar cell was found to be 0.69 %, while WO₃–TiO₂-based cell exhibited a higher conversion efficiency of 2.2 %. The better performance of the WO₃–TiO₂ dye-sensitized solar cell photoelectrode is thought to be due to an inherent energy barrier at the electrode/electrolyte interface leading to the reduced recombination of photoinduced electrons.     

Electrochemical properties of TiO2 nanoparticle/nanorod composite photoanode for dye-sensitized solar cells

A unique composite of TiO₂ nanoparticles (NPs) and nanorods (NRs) has been used to fabricate a photoelectrode for developing dye-sensitized solar cells (DSSCs) with higher sensitivity. The TiO₂ nanorods were synthesized using a mechanical process, in which electrospun TiO₂ nanofibers was grinded in a controlled way to obtain uniform size distribution. The characteristics of electron transport, recombination lifetime and charge collection were investigated by intensity-modulated photocurrent spectroscopy (IMPS) and intensity-modulated photovoltage spectroscopy (IMVS). Photoelectrodes prepared with the composites of NRs and NPs showed significant improvements in electron transportation compared to only NP photoelectrodes, which would enhance the photovoltaic performance of DSSCs. IMPS and IMVS measurements show that fast electron transport and slightly decreased recombination lifetime resulted in the improvement of efficiency. The highest energy conversion efficiency obtained from the photoelectrodes fabricated with the as-prepared rutile TiO₂ nanofibers at 5 wt% NR content was up to 6.1% under AM1.5G solar illumination. The results demonstrate that the composite nanostructure can take advantage of both the fast electron transport of the nanorods and the high surface area of the nanoparticles.     

Interfacial engineering of CuO nanorod/ZnO nanowire hybrid nanostructure photoanode in dye-sensitized solar cell

Developing efficient and cost-effective photoanode plays a vital role determining the photocurrent and photovoltage in dye-sensitized solar cells (DSSCs). Here, we demonstrate DSSCs that achieve relatively high power conversion efficiencies (PCEs) by using one-dimensional (1D) zinc oxide (ZnO) nanowires and copper (II) oxide (CuO) nanorods hybrid nanostructures. CuO nanorod-based thin films were prepared by hydrothermal method and used as a blocking layer on top of the ZnO nanowires’ layer. The use of 1D ZnO nanowire/CuO nanorod hybrid nanostructures led to an exceptionally high photovoltaic performance of DSSCs with a remarkably high open-circuit voltage (0.764 V), short current density (14.76 mA/cm² under AM1.5G conditions), and relatively high solar to power conversion efficiency (6.18%) . The enhancement of the solar to power conversion efficiency can be explained in terms of the lag effect of the interfacial recombination dynamics of CuO nanorod-blocking layer on ZnO nanowires. This work shows more economically feasible method to bring down the cost of the nano-hybrid cells and promises for the growth of other important materials to further enhance the solar to power conversion efficiency.     

Dye-sensitized solar cells based on ZnO nanowire array/TiO2 nanoparticle composite photoelectrodes with controllable nanowire aspect ratio

The ZnO nanowire (NW) array/TiO₂ nanoparticle (NP) composite photoelectrode with controllable NW aspect ratio has been grown from aqueous solutions for the fabrication of dye-sensitized solar cells (DSSCs), which combines the advantages of the rapid electron transport in ZnO NW array and the high surface area of TiO₂ NPs. The results indicate that the composite photoelectrode achieves higher overall photoelectrical conversion efficiency (η) than the ZnO NW alone. As a result, DSSCs based on the ZnO NW array/TiO₂ NP composite photoelectrodes get the enhanced photoelectrical conversion efficiency, and the highest η is also achieved by rational tuning the aspect ratio of ZnO NWs. With the proper aspect ratio (ca. 6) of ZnO NW, the ZnO NW array/TiO₂ NP composite DSSC exhibits the highest conversion efficiency (5.5 %). It is elucidated by the dye adsorption amount and interfacial electron transport of DSSCs with the ZnO NW array/TiO₂ NP composite photoelectrode, which is quantitatively characterized using the UV-Vis absorption spectra and electrochemical impedance spectra. It is evident that the DSSC with the proper aspect ratio of ZnO NW displays the high dye adsorption amount and fastest interfacial electron transfer.     

Effects of Gd<Superscript>3+</Superscript> modifications on the photoelectrochemical properties of TiO<Subscript>2</Subscript>-based dye-sensitized solar cells

In this paper, TiO₂ particles (~30 nm) modified with Gd₂O₃-coating layer (~2 nm) for dye-sensitized solar cells (DSSCs) were fabricated via the hydrothermal method. Among the solar cells based on the Gd³⁺-doped TiO₂ photoanodes, the optimal conversion efficiency was obtained from the 0.025Gd³⁺-modified TiO₂-based cell, with a 17.7% improvement in the efficiency as compared to the unmodified one (7.18%). This enhancement was probably due to the improved UV radiation harvesting via a down-conversion luminescence process by Gd³⁺ ions, enhancement of visible light absorption and improved dye loading capacity. In addition, after Gd modification, a thin coating could be formed on the TiO₂ nanoparticles, which worked as an energy barrier and resulted in a lower charge recombination.     

Interface modification of MoS2 counter electrode/electrolyte in dye-sensitized solar cells by incorporating TiO2 nanoparticles

To achieve the high efficiency in dye-sensitized solar cells (DSSCs), the interface modification of MoS₂ counter electrode (CE)/electrolyte should be carried out. Making the modified MoS₂ CE by incorporating TiO₂ nanoparticles provides possibilities to enhance electrocatalytic activity. The DSSCs with the MoS₂/TiO₂ CE show enhanced performance compared with DSSCs with the MoS₂ CE. The experimental results revealed that the MoS₂/TiO₂ nanocomposite influences on the power conversion efficiency by enhancing electrocatalytic activity and increasing the active surface area that serve to increase the short circuit current. This understanding can provide guidance for the development of highly efficient DSSCs with platinum-free CEs.     

GaN-nanowire-based dye-sensitized solar cells

GaN nanowires typically exhibit high electron mobility and excellent chemical stability. However, stability of GaN is detrimental for successful attachment of dye molecules and its application in dye-sensitized solar cells (DSSCs). Here we demonstrate DSSCs based on GaN/gallium oxide and GaN/TiO _x core–shell structures, and we show that coating of GaN nanowires with a TiO _x shell significantly increases dye adsorption and consequently photovoltaic performance. The best cells exhibited short circuit current density of 1.83 mA/cm² and power conversion efficiency of 0.44% under AM 1.5 simulated solar illumination.     

ZnO/TiO2 core–shell nanowire arrays for enhanced dye-sensitized solar cell efficiency

We present a new method of synthesizing ZnO/TiO₂ core–shell nanowire (NW) arrays for the fabrication of dye-sensitized solar cells (DSSCs). Vertically aligned ZnO NW arrays were obtained on Si substrates, and modified by a TiO₂ shell in order to solve the recombination problems via a cost-effective spin-coating method. The structure of the ZnO/TiO₂ composite NW arrays was characterized. The experimental results indicate that the TiO₂ shell enhances the performance of the DSSCs, through improving the stability of the ZnO NWs and decreasing the recombination of photogenerated electrons on the NW surface. The highest overall conversion efficiency of the cell reaches about 3.0 %.     

Modification and photovoltaic properties of reduced graphene oxide/acetylene black composite electrode

A simple and high efficient reduced graphene oxide/acetylene black (rGO/ACET) nano-composite electrode was prepared as the substitute of high-cost Pt counter electrode in dye-sensitized solar cells (DSSCs). Surface-modified method called solvent-substituting (SS) was firstly used to avoid agglomeration of rGO sheets. The Brunner-Emmet-Teller (BET)-specific surface area of rGO was increased from 195.823 to 355.210 m²/g after modifying with ethanol. Then ACET particles were introduced between rGO layers to improve the electronic transportation properties. The chemical compositions, microstructures, and pore size distributions of rGO/ACET composites were investigated. Electrochemical impedance spectroscopy (EIS) indicated that rGO/ACET counter electrode had a lower charge transfer resistance (R_ct) and its S-shaped current–voltage curves disappeared obviously. The highest power conversion efficiency up to 6.62% was achieved for the DSSCs with rGO/ACET nano-composite counter electrode.     

Performance of dye-sensitized solar cells based on natural dyes

The natural dyes were successfully extracted from spinach, pitaya pericarp, orange peel, ginkgo leaf, purple cabbage and carrot, and then fabricated a dye-sensitized solar cells (DSSCs). It suggested that the absorption properties of natural dyes were strongly dependent on the types and concentration of pigments, and the purple cabbage exhibited an obvious absorption at 317 nm. Meanwhile, a higher conversion efficiency of 0.157% was obtained as the DSSCs were prepared by using purple cabbage, but the DSSCs showed a poor performance when the carrot was used as natural dyes, just achieved 0.01%. FTIR spectra revealed that purple cabbage showed a better adsorption properties between TiO₂ films and dyes than carrot. The dipping time was further investigated and proved that an optimal dipping time was 6 min, the DSSCs using purple cabbage could achieve 0.146% in photoelectric conversion efficiency.     

The control of the diameter of the nanorods prepared by dc reactive magnetron sputtering and the applications for DSSC

The TiO₂ nanorod arrays, with about 1.8 μm lengths, have been deposited on ITO substrates by dc reactive magnetron sputtering at different target-substrate distances. The average diameter of these nanorods can be modified from about 45 to 85 nm by adjusting the target-substrate distance from 90 to 50 mm. These nanorods are highly ordered and perpendicular to the substrate. Both XRD and Raman measurements show that the nanorods prepared at different target-substrate distances have only an anatase TiO₂ phase. The nanorods prepared at the target-substrate distance less than 80 mm have a preferred orientation along the (2 2 0) direction. However, this preferred orientation disappears as the target-substrate distance is more than 80 mm. These TiO₂ nanorods have been used as the electrodes for dye-sensitized solar cells (DSSCs). The highest conversion efficiency, about 4.78%, has been achieved for TiO₂ nanorods prepared at 80 mm target-substrate distance.     

Preparation and improvement in photovoltaic performance of dye-sensitized solar cells using carbon dioxide

We report preparation and improvement in photovoltaic performance of N719-based dye-sensitized solar cells (DSSCs) using pressurized carbon dioxide (CO₂) as a co-solvent for the absorption process on the TiO₂ photoelectrode surface. Effective absorption of the N719 molecules on the TiO₂ surface was achieved using CO₂ processing, and the absorption time was shortened drastically from 24 h (in the dip process) to less than 3 h. The cells prepared under pressurized CO₂ for the absorption showed greater photovoltaic performance, especially higher short-circuit current density and conversion efficiency, compared with that from typical dip method. It was revealed that the suitable CO₂ pressure for the absorption was 5 MPa and the efficiency was achieved to be more than 7.5 %. Prevention of back electron transfer reactions from TiO₂ to oxidized dyes or iodides was caused currently, because the homogeneous coverage of N719 molecules on the TiO₂ surface was obtained by the use of pressurized CO₂.     

Influence of pyrazole on the photovoltaic performance of dye-sensitized solar cell with polyvinylidene fluoride polymer electrolytes

We investigate the influence of the pyrazole content on the polyvinylidene fluoride (PVDF)/KI/I₂ electrolytes for dye-sensitized solar cells (DSSCs). The solid polymer electrolyte films consisting of different weight percentage ratios (0 20, 30, 40, and 50 %) of pyrazole doped with PVDF/KI/I₂ have been prepared by solution casting technique using N,N-dimethyl formamide (DMF) as a solvent. The as-prepared polymer electrolyte films were characterized by various techniques such as Fourier transform infrared spectroscopy (FT-IR spectroscopy), differential scanning calorimetry (DSC), X-ray diffractometer (XRD), alternate current (AC)-impedance analysis, and scanning electron microscopy (SEM). The 40 wt% pyrazole-PVDF/KI/I₂ electrolyte exhibited the highest ionic conductivity value of 9.52?×?10^?5 Scm^?1 at room temperature. This may be due to the lower crystallinity of PVDF and higher ionic mobility of iodide ions in the electrolyte. The DSSC fabricated using this highest ion conducting electrolyte showed an enhanced power conversion efficiency of 3.30 % under an illumination of 60 mW/cm² than that of pure PVDF/KI/I₂ electrolyte (1.42 %).     

Minimizing structural deformation of gold nanorods in plasmon-enhanced dye-sensitized solar cells

Plasmonic metal nanoparticles have shown great promise in enhancing the light absorption of organic dyes and thus improving the performance of dye-sensitized solar cells (DSSCs). However, as the plasmon resonance of spherical nanoparticles is limited to a single wavelength maximum (e.g., ~ 520 nm for Au nanoparticles), we have here utilized silica-coated gold nanorods (Au@SiO₂ NRs) to improve the performance at higher wavelengths as well. By adjusting the aspect ratio of the Au@SiO₂ NRs, we can shift their absorption maxima to better match the absorption spectrum of the utilized dye (here we targeted the 600–800 nm range). The main challenge in utilizing anisotropic nanoparticles in DSSCs is their deformation during the heating step required to sinter the mesoporous TiO₂ photoanode and we show that the Au@SiO₂ NRs start to deform already at temperatures as low as 200 °C. In order to circumvent this problem, we incorporated the Au@SiO₂ NRs in a TiO₂ nanoparticle suspension that does not need high sintering temperatures to produce a functional photoanode. With various characterization methods, we observed that adding the plasmonic particles also affected the structure of the produced films. Nonetheless, utilizing this low-temperature processing protocol, we were able to minimize the structural deformation of the gold nanorods and preserve their characteristic plasmon peaks. This allowed us to see a clear redshift of the maximum in the incident photon-to-current efficiency spectra of the plasmonic devices (Δλ ~ 14 nm), which further proves the great potential of utilizing Au@SiO₂ NRs in DSSCs.

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Graphical Abstract Undeformed gold nanorods provide an enhanced performance of dye-sensitized solar cells at high wavelengths

     

Dye-sensitized solar cells based on trench structured TiO2 nanotubes in Ti substrate

We have proposed dye-sensitized solar cells (DSSCs) with trench-type TiO₂ nanotube structure to improve the low device efficiency of conventional TiO₂ nanotube DSSCs using Ti substrate. Compared to the conventional standing-type TiO₂ nanotube structure based DSSCs, the trench-type TiO₂ nanotube structure based DSSCs have shown an improvement of device efficiency of approximately 40% due to the large increase of Jsc. In the trench-type TiO₂ nanotube structure, the contact area between the TiO₂ nanotube sidewall and the Ti substrate is significantly increased. This increase of contact area provides more charge transport paths than exist in the conventional standing-type TiO₂ nanotube structure and reduces the electrical resistance between the Ti substrate and the TiO₂ nanotubes. Therefore, the remarkable increase of Jsc is the result of the charge collection efficiency, which is improved due to the increase of contact area between the TiO₂ nanotube sidewall and the Ti substrate in the trench-type TiO₂ nanotube structure. The fabrication of the trench-type TiO₂ nanotube structure is an effective manufacturing process for improving the device efficiency of TiO₂ nanotube based DSSCs using Ti substrate. DSSCs having an 11.9 μm thick trench-type TiO₂ nanotube structure have shown an efficiency of 5.74%.     

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.

     

TiO2 Wedgy Nanotubes Array Flims for Photovoltaic Enhancement

In this study, TiO₂ wedgy nanotubes with rectangular cross-sections were fabricated on transparent conductive substrates by using TiO₂ nanorods as the precursor via the anisotropic etching route. TiO2 nanotubes with V-shaped hollow structure and the special crystal plane exposed on the tube wall possess nature of high surface area for more dye molecules absorption, and the strong light scattering effects and dual-channel for effective electron transport of the TiO₂ V-shaped nanotubes based dye-sensitized solar cell exhibit a remarkable photovoltaic enhancement compared with the TiO₂ nanorods. The photoanode based on our V-shaped TiO₂ nanotubes with a length of 1.5 μm show a 123% increase of the dye loading and a 182% improvement in the overall conversion efficiency when compared with 4 μm rutile TiO₂ nanorods photoanode.     

MEH-PPV与TiO2共混体系太阳电池性能分析

以MEH-PPV(poly(2-methoxy-5-(2′-ethylhexoxy)-1,4-phenylene vinylene)为电子给体材料(Donor,D), TiO₂纳米线为电子受体材料(Acceptor,A),制成了共混体系太阳电池. 从D/A材料共混体系的紫外可见吸收光谱(UV-vis)、光荧光谱(PL)、器件的电荷传输的光导J-V图等方面,分析了MEH-PPV∶TiO₂体系器件性能变化的原因. 得出了当在纯MEH-PP 关键词： 太阳电池 聚合物 性能     

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%.