Dye‐Sensitized TiO2 Nanotube Solar Cells: Rational Structural and Surface Engineering on TiO2 Nanotubes

Owing to well‐defined structural parameters and enhanced electronic properties, highly ordered TiO₂ nanotube arrays have been employed to substitute TiO₂ nanoparticles for use in dye‐sensitized solar cells. To further improve the performance of dye‐sensitized TiO₂ nanotube solar cells, efforts have been directed toward the optimization of TiO₂ photoanodes, dyes, electrolytes, and counter electrodes. Herein, we highlight recent progress in rational structural and surface engineering on anodic TiO₂ nanotube arrays and their effects on improving the power conversion efficiency of dye‐sensitized TiO₂ nanotube solar cells.     

SiO2/TiO2 Hollow Nanoparticles Decorated with Ag Nanoparticles: Enhanced Visible Light Absorption and Improved Light Scattering in Dye‐Sensitized Solar Cells

Hollow SiO₂/TiO₂ nanoparticles decorated with Ag nanoparticles (NPs) of controlled size (Ag@HNPs) were fabricated in order to enhance visible‐light absorption and improve light scattering in dye‐sensitized solar cells (DSSCs). They exhibited localized surface plasmon resonance (LSPR) and the LSPR effects were significantly influenced by the size of the Ag NPs. The absorption peak of the LSPR band dramatically increased with increasing Ag NP size. The LSPR of the large Ag NPs mainly increased the light absorption at short wavelengths, whereas the scattering from the SiO₂/TiO₂ HNPs improved the light absorption at long wavelengths. This enabled the working electrode to use the full solar spectrum. Furthermore, the SiO₂ layer thickness was adjusted to maximize the LSPR from the Ag NPs and avoid corrosion of the Ag NPs by the electrolyte. Importantly, the power conversion efficiency (PCE) increased from 7.1 % with purely TiO₂‐based DSSCs to 8.1 % with HNP‐based DSSCs, which is an approximately 12 % enhancement and can be attributed to greater light scattering. Furthermore, the PCEs of Ag@HNP‐based DSSCs were 11 % higher (8.1 vs. 9.0 %) than the bare‐HNP‐based DSSCs, which can be attributed to LSPR. Together, the PCE of Ag@HNP‐based DSSCs improved by a total of 27 %, from 7.1 to 9.0 %, due to these two effects. This comparative research will offer guidance in the design of multifunctional nanomaterials and the optimization of solar‐cell performance.     

Photocurrent Enhancement of Dye‐Sensitized Solar Cells owing to Increased Dye‐Adsorption onto Silicon‐Nanoparticle‐Coated Titanium‐Dioxide Films

The inverse‐micellar preparation of Si nanoparticles (Nps) was improved by utilizing sodium naphthalide. The Si Nps were subsequently functionalized with 4‐vinylbenzoic acid for their attachment onto TiO₂ films of dye‐sensitized solar cells (DSSCs). The average diameter of the COOH‐functionalized Si (Si? COOH) Nps was 4.6(±1.7) nm. Depth profiling by secondary‐ion mass spectrometry revealed that the Si Nps were uniformly attached onto the TiO₂ films. The number of Ru^II dye molecules adsorbed onto a TiO₂ film that was treated with the Si? COOH Nps was 42 % higher than that on the untreated TiO₂ film. As a result, DSSCs that incorporated the Si? COOH Nps exhibited higher short‐circuit photocurrent density and an overall energy‐conversion efficiency than the untreated DSSCs by 22 % and 27 %, respectively. This enhanced performance, mostly owing to the intramolecular charge‐transfer to TiO₂ from the dye molecules that were anchored to the Si? COOH Nps, was confirmed by comparing the performance with two different Ru^II–bipyridine dyes (N719 and N749).     

Multifunctional Ag‐Decorated Porous TiO2 Nanofibers in Dye‐Sensitized Solar Cells: Efficient Light Harvesting,Light Scattering,and Electrolyte Contact

Designing the photoanode structure in dye‐sensitized solar cells (DSSCs) is vital to realizing enhanced power conversion efficiency (PCE). Herein, novel multifunctional silver‐decorated porous titanium dioxide nanofibers (Ag/pTiO₂ NFs) made by simple electrospinning, etching, and chemical reduction processes are introduced. The Ag/pTiO₂ NFs with a high surface area of 163 m² g^?1 provided sufficient dye adsorption for light harvesting. Moreover, the approximately 200 nm diameter and rough surface of the Ag/pTiO₂ NFs offered enough light scattering, and the enlarged interpores among the NFs in the photoanode also permitted electrolyte circulation. Ag nanoparticles (NPs) were well dispersed on the surface of the TiO₂ NFs, which prevented aggregation of the Ag NPs after calcination. Furthermore, a localized surface plasmon resonance effect by the Ag NPs served to increase the light absorption at visible wavelengths. The surface area and amount of Ag NPs was optimized. The PCE of pTiO₂ NF‐based DSSCs was 27 % higher (from 6.2 to 7.9 %) than for pure TiO₂ NFs, whereas the PCE of Ag/pTiO₂ NF‐based DSSCs increased by about 12 % (from 7.9 to 8.8 %). Thus, the PCE of the multifunctional pTiO₂ NFs was improved by 42 %, that is, from 6.2 to 8.8 %.     

Brookite TiO2 Nanoparticle Films for Dye‐Sensitized Solar Cells

Brookite TiO₂ nanoparticles have been synthesized at low temperature by a soft solution growth method and have been used as building blocks to prepare pure brookite nanoparticle porous films. The film brookite structure was confirmed by XRD and Raman spectroscopy. By spectrophotometry, it was shown that the films had a direct band gap of 3.4 eV. After sensitization by the N719 dye, efficient cells have been produced. A best overall conversion efficiency of 5.97 %, without a scattering layer, was found for the larger TiO₂ starting nanoparticles. The cell open‐circuit voltage was improved compared with that of anatase cells and a lower electron diffusion coefficient was found in the photoanodes made of smaller brookite particles. Lanthanum‐doped brookite nanoparticle films were also studied. They showed a marked decreased in the amount of dye loading, and hence, the solar cells had a reduced current density that was not compensated for by the increased open‐circuit voltage of the cells.     

The Origin of Higher Open‐Circuit Voltage in Zn‐Doped TiO2 Nanoparticle‐Based Dye‐Sensitized Solar Cells

Zn‐doped anatase TiO₂ nanoparticles are synthesized by a one‐step hydrothermal method. Detailed electrochemical measurements are undertaken to investigate the origin of the effect of Zn doping on the performance of dye‐sensitized solar cells (DSSCs). It is found that incorporation of Zn²⁺ into an anatase lattice elevates the edge of the conduction band (CB) of the photoanodes and the Fermi level is shifted toward the CB edge, which contributes to the improvement in open‐circuit voltage (V_OC). Charge‐density plots across the cell voltage further confirm the increase in the CB edge in DSSCs directly. Photocurrent and transient photovoltage measurements are employed to study transport and recombination dynamics. The electron recombination is accelerated at higher voltages close to the CB edge, thus leading to a negative effect on the V_OC.     

A Novel Improved Method to Increase the Efficiency of Dye‐Sensitized Solar Cells

A novel improved method which employs a reflective mirror at the back of the Pt counter electrode is used in dye‐sensitized solar cells (DSSC). The direction of the light propagation in the cells was changed because of adding a mirror and the light reflected back into the DSSC in order to enhance the optical absorption of the DSSCs. Therefore, the performance of the cells was improved distinctively. The TiO₂ electrodes were characterized by X‐ray diffraction, scanning electron microscopy and I‐V properties of the cells measured by Linear Sweep Voltammetry system. The results indicates that the conversion efficiency can be increased from 4.81% to 5.43% under AM 1.5 illumination when a mirror is added at the back of the Pt counter electrode in the same cell. Meanwhile, the Jsc, Voc and the fill factor can be obtained 18.65 mA/cm², 0.728 V and 0.561, respectively.     

Nanosilver‐Decorated TiO2 Nanofibers Coated with a SiO2 Layer for Enhanced Light Scattering and Localized Surface Plasmons in Dye‐Sensitized Solar Cells

Enhanced harvesting of visible light is vital to the development of highly efficient dye‐sensitized solar cells (DSSCs). Nanosilver‐decorated TiO₂ nanofibers (Ag@TiO₂ NFs) were synthesized by depositing chemically reduced Ag ions onto the surface of electrospun TiO₂ nanofibers (TiO₂ NFs). The prepared Ag@TiO₂ NFs were coated with SiO₂ (SiO₂@Ag@TiO₂ NFs) by using PVP as coupling agent for protecting corrosion of Ag nanoparticle by I^?/${{\rm I}{{- \hfill \atop 3\hfill}}}$ solution. The fabricated SiO₂@Ag@TiO₂ NFs demonstrated a synergistic effect of light scattering and surface plasmons, leading to an enhanced light absorption. Moreover, an anode consisting of SiO₂@Ag@TiO₂ NFs incorporating TiO₂ nanoparticles (NPs) increased light harvesting without substantially sacrificing dye attachment. The power conversion efficiency increased from 6.8 to 8.7 % for a thick film (10 μm), that is, 28 %. These results suggest that SiO₂@Ag@TiO₂ NFs are promising materials for enhanced light absorption in dye‐sensitized solar cells.     

Photoanode Based on Chain‐Shaped Anatase TiO2 Nanorods for High‐Efficiency Dye‐Sensitized Solar Cells

Anatase TiO₂ nanorods with large specific surface areas and high crystallinity have been synthesized by surfactant‐free hydrothermal treatment of water‐soluble peroxotitanium acid (PTA). X‐ray diffraction and TEM analysis showed that all TiO₂ nanorods derived from PTA in different hydrothermal processes were in the anatase phase, and high aspect ratio TiO₂ nanorods with chain‐shaped structures were formed at 150 °C for 24 h by oriented growth. The nanorods were fabricated as photoanodes for high‐efficiency dye‐sensitized solar cells (DSSCs). DSSCs fabricated from the chain‐shaped TiO₂ nanorods gave a highest short‐circuit current density of 14.8 mA cm^?2 and a maximum energy conversion efficiency of 7.28 %, as a result of the presence of far fewer surface defects and grain boundaries than are present in commercial P25 TiO₂ nanoparticles. Electrochemical impedance spectroscopy also confirmed that DSSCs based on the TiO₂ nanorods have enhanced electron transport properties and a long electron lifetime.     

Influence of Solvent and Bridge Structure in Alkylthio‐Substituted Triphenylamine Dyes on the Photovoltaic Properties of Dye‐Sensitized Solar Cells

Three new triphenylamine dyes that contain alkylthio‐substituted thiophenes with a low bandgap as a π‐conjugated bridge unit were designed and synthesized for organic dye‐sensitized solar cells (DSSCs). The effects of the structural differences in terms of the position, number, and shape of the alkylthio substituents in the thiophene bridge on the photophysical properties of the dye and the photovoltaic performance of the DSSC were investigated. The introduction of an alkylthio substituent at the 3‐position of thiophene led to a decrease in the degree of redshift and the value of the molar extinction coefficient of the charge‐transfer band, and the substituent with a bridged structure led to a larger redshift than that of the open‐chain structure. The introduction of bulky and hydrophobic side chains decreased the short‐circuit photocurrent (J_sc), which was caused by the reduced amount of dye adsorbed on TiO₂. This resulted in a decrease in the overall conversion efficiency (η), even though it could improve the open‐circuit voltage (V_oc) due to the retardation of charge recombination. Furthermore, the change in solvents for TiO₂ sensitization had a critical effect on the performance of the resulting DSSCs due to the different amounts of dye adsorbed. Based on the optimized dye bath and molecular structure, the ethylene dithio‐substituted dye ( ATT3 ) showed a prominent solar‐to‐electricity conversion efficiency of 5.20 %.     

Fabrication of Au‐Nanoparticle/TiO2‐Nanotubes Electrodes Using Electrochemical Methods and Their Application for Electrocatalytic Oxidation of Hydroquinone

Gold nanoparticle (Au‐NPs)‐Titanium oxide nanotube (TiO₂‐NTs) electrodes are prepared by using galvanic deposition of gold nanoparticles on TiO₂‐NTs electrodes as support. Scanning electron microscopy and energy‐dispersive X‐ray spectroscopy results indicate that nanotubular TiO₂ layers consist of individual tubes of about 60–90 nm diameters and gold nanoparticles are well‐dispersed on the surface of TiO₂‐NTs support. The electrooxidation of hydroquinone of Au‐NPs/TiO₂‐NTs electrodes is investigated by different electrochemical methods. Au‐NPs/TiO₂‐NTs electrode can be used repeatedly and exhibits stable electrocatalytic activity for the hydroquinone oxidation. Also, determination of hydroquinone in skin cream using this electrode was evaluated. Results were found to be satisfactory and no matrix effects are observed during the determination of hydroquinone content of the “skin cream” samples.     

Effects of Dye‐Adsorption Solvent on the Performances of the Dye‐Sensitized Solar Cells Based on Black Dye

The effects of the dye‐adsorption solvent on the performances of the dye‐sensitized solar cells (DSSCs) based on black dye have been investigated. The highest conversion efficiency (10.6 %) was obtained in the cases for which 1‐PrOH and the mixed solvent of EtOH and tBuOH (3:1 v/v) were employed as dye‐adsorption solvents. The optimized value for the dielectric constant of the dye‐adsorption solvent was found to be around 20. The DSSCs that used MeOH as a dye‐adsorption solvent showed inferior solar‐cell performance relative to the DSSCs that used EtOH, 1‐PrOH, 2‐PrOH, and 1‐BuOH. Photo‐ and electrochemical measurements of black dye both in solution and adsorbed onto the TiO₂ surface revealed that black dye aggregates at the TiO₂ surface during the adsorption process in the case for MeOH. Both the shorter electron lifetime in the TiO₂ photoelectrode and the greater resistance in the TiO₂–dye–elecrolyte interface, attributed to the dye aggregation at the TiO₂ surface, cause the decrease in the solar‐cell performance of the DSSC that used MeOH as a dye adsorption solvent.     

Highly Catalytic Carbon Nanotube/Pt Nanohybrid‐Based Transparent Counter Electrode for Efficient Dye‐Sensitized Solar Cells

Low‐cost transparent counter electrodes (CEs) for efficient dye‐sensitized solar cells (DSSCs) are prepared by using nanohybrids of carbon nanotube (CNT)‐supported platinum nanoparticles as highly active catalysts. The nanohybrids, synthesized by an ionic‐liquid‐assisted sonochemical method, are directly deposited on either rigid glass or flexible plastic substrates by a facile electrospray method for operation as CEs. Their electrochemical performances are examined by cyclic voltammetry, current density–voltage characteristics, and electrochemical impedance spectroscopy (EIS) measurements. The CNT/Pt hybrid films exhibit high electrocatalytic activity for I^?/I₃^? with a weak dependence on film thickness. A transparent CNT/Pt hybrid CE film about 100 nm thick with a transparency of about 70 % (at 550 nm) can result in a high power conversion efficiency (η) of over 8.5 %, which is comparable to that of pyrolysis platinum‐based DSSCs, but lower cost. Furthermore, DSSC based on flexible CNT/Pt hybrid CE using indium‐doped tin oxide‐coated polyethylene terephthalate as the substrate also exhibits η=8.43 % with J_sc=16.85 mA cm^?2, V_oc=780 mV, and FF=0.64, and this shows great potential in developing highly efficient flexible DSSCs.     

Well‐Dispersed CoS Nanoparticles on a Functionalized Graphene Nanosheet Surface: A Counter Electrode of Dye‐Sensitized Solar Cells

With a facile electrophoretic deposition and chemical bath process, CoS nanoparticles have been uniformly dispersed on the surface of the functionalized graphene nanosheets (FGNS). The composite was employed as a counter electrode of dye‐sensitized solar cells (DSSCs), which yielded a power conversion efficiency of 5.54 %. It is found that this efficiency is higher than those of DSSCs based on the non‐uniform CoS nanoparticles on FGNS (4.45 %) and built on the naked CoS nanoparticles (4.79 %). The achieved efficiency of our cost‐effective DSSC is also comparable to that of noble metal Pt‐based DSSC (5.90 %). Our studies have revealed that both the exceptional electrical conductivity of the FGNS and the excellent catalytic activity of the CoS nanoparticles improve the conversion efficiency of the uniformly FGNS‐CoS composite counter electrode. The electrochemical impedance spectra, cyclic voltammetry, and Tafel polarization have evidenced the best catalytic activity and the fastest electron transport. Additionally, the dispersion condition of CoS nanoparticles on FGNS plays an important role for catalytic reduction of I₃^?.     

Benzoporphyrins: Selective Co‐sensitization in Dye‐Sensitized Solar Cells

A novel class of dyes, namely benzoporphyrins, was synthesized and implemented into dye‐sensitized solar cells. They feature complementary absorptions compared to N719 , which renders them promising candidates for co‐sensitization in DSSCs. Notably, metallated benzoporphyrins reveal a TiO₂–nanoparticle attachment that is size and aggregation dependent. Therefore, unproductive energy‐transfer events between the selectively attached dyes can be prevented. In light of the latter, an efficiency improvement of 39 % has been achieved upon selective adsorption of benzoporphyrins and N719 onto different layers of TiO₂ photoelectrode.     

钌配合物敏化La3+掺杂纳米多孔TiO2电极的光电性能研究

在染料敏化太阳能电池中,TiO2膜和敏化剂决定着电池的总体效率和机械性能。本文以4-甲基吡啶为原料,经过偶联、氧化、配位和配体交换反应合成了cis-RuL2(SCN)2, (L=2,2’-联吡啶-4,4’-二羧酸),通过溶胶-凝胶法制备了TiO2膜。为了提高TiO2膜的光电性能,将不同浓度的La(NO3)3 (0.1%、0.3%、0.5%和0.7%) 加入到溶胶中,采用cis-RuL2(SCN)2将掺杂前后的TiO2膜进行敏化。利用X射线衍射仪、原子力显微镜和X射线光电子能谱对所得薄膜进行结构表征。结果表明,当La离子的浓度为0.5%时,太阳能电池的效率最高,短路电流和开路电压比未掺杂的分别提高了0.54 mA/cm2和30.41 mV。     

The Influence of Charge Transport and Recombination on the Performance of Dye‐Sensitized Solar Cells

Electrochemical impedance spectroscopy (EIS) and transient voltage decay measurements are applied to compare the performance of dye sensitized solar cells (DSCs) using organic electrolytes, ionic liquids and organic‐hole conductors as hole transport materials (HTM). Nano‐crystalline titania films sensitized by the same heteroleptic ruthenium complex NaRu(4‐carboxylic acid‐4′‐carboxylate) (4,4′‐dinonyl‐2,2′‐bipyridyl)(NCS)₂ , coded Z‐907Na are employed as working electrodes. The influence of the nature of the HTM on the photovoltaic figures of merit, that is, the open circuit voltage, short circuit photocurrent and fill factor is evaluated. In order to derive the electron lifetime, as well as the electron diffusion coefficient and charge collection efficiency, EIS measurements are performed in the dark and under illumination corresponding to realistic photovoltaic operating conditions of these mesoscopic solar cells. A theoretical model is established to interpret the frequency response off the impedance under open circuit conditions, which is conceptually similar to photovoltage transient decay measurements. Important information on factors that govern the dynamics of electron transport within the nanocrystalline TiO₂ film and charge recombination across the dye sensitized heterojunction is obtained.     

Efficiency enhancement of solid‐state dye sensitized solar cell by in situ deposition of CuI

Solid‐state dye‐sensitized solar cells based on nanocrystalline TiO₂ thin film with the structures TiO₂/dye/CuI/Pt and TiO₂/dye/In situ CuI/CuI/Pt were developed in order to compare the use of In situ deposited CuI (In situ CuI). Porosity of the screen‐printed nanoporous TiO₂ thin film was enhanced by the addition of polystyrene balls. Evidence of decrease in interfacial resistance was observed by electrochemical impedance measurement for the device with In situ deposited CuI as compared to that without In situ deposited CuI as hole conductor. This was attributed to good interfacial contacts and better charge transfer between CuI and dye‐sensitized TiO₂ nanoparticles, which resulted in the enhancement of power conversion efficiency from 0.058 to 1.01%. Copyright © 2008 John Wiley & Sons, Ltd.     

Enhancing Electron Collection Efficiency and Effective Diffusion Length in Dye‐Sensitized Solar Cells

Intensity‐modulated photocurrent spectroscopy and intensity‐modulated photovoltage spectroscopy are employed to measure the dynamics of electron transport and recombination in the ZnO nanowire (NW) array‐ZnO/layered basic zinc acetate (LBZA) nanoparticle (NP) composite dye‐sensitized solar cells (DSSCs). The roles of the vertical ZnO NWs and insulating LBZA in the electron collection and transport in DSSCs are investigated by comparing the results to those in the TiO₂–NP, horizontal TiO₂–NW and vertical ZnO–NW‐array DSSCs. The electron transport rate and electron lifetime in the ZnO NW/NP composite DSSC are superior to those in the conventional TiO₂–NP cell due to the existence of the vertical ZnO NWs and insulating LBZA. It indicates that the ZnO NW/NP composite anode is able to sustain efficient electron collection over much greater thickness than the TiO₂–NP cell does. Consequently, a larger effective electron diffusion length is available in the ZnO composite DSSC.     

High‐Performance Förster Resonance Energy Transfer (FRET)‐Based Dye‐Sensitized Solar Cells: Rational Design of Quantum Dots for Wide Solar‐Spectrum Utilization

High‐performance Förster resonance energy transfer (FRET)‐based dye‐sensitized solar cells (DSSCs) have been successfully fabricated through the optimized design of a CdSe/CdS quantum‐dot (QD) donor and a dye acceptor. This simple approach enables quantum dots and dyes to simultaneously utilize the wide solar spectrum, thereby resulting in high conversion efficiency over a wide wavelength range. In addition, major parameters that affect the FRET interaction between donor and acceptor have been investigated including the fluorescent emission spectrum of QD, and the content of deposited QDs into the TiO₂ matrix. By judicious control of these parameters, the FRET interaction can be readily optimized for high photovoltaic performance. In addition, the as‐synthesized water‐soluble quantum dots were highly dispersed in a nanoporous TiO₂ matrix, thereby resulting in excellent contact between donors and acceptors. Importantly, high‐performance FRET‐based DSSCs can be prepared without any infrared (IR) dye synthetic procedures. This novel strategy offers great potential for applications of dye‐sensitized solar cells.