The Factors Influencing Nonlinear Characteristics of the Short‐Circuit Current in Dye‐Sensitized Solar Cells Investigated by a Numerical Model

A numerical model for interpretation of the light‐intensity‐dependent nonlinear characteristics of the short‐circuit current in dye‐sensitized solar cells is suggested. The model is based on the continuity equation and includes the influences of the nongeminate recombination between electrons and electron acceptors in the electrolyte and the geminate recombination between electrons and oxidized dye molecules. The influences of the order and rate constant of the nongeminate recombination reaction, the light‐absorption coefficient of the dye, the film thickness, the rate constant of geminate recombination, and the regeneration rate constant on the nonlinear characteristics of the short‐circuit current are simulated and analyzed. It is proposed that superlinear and sublinear characteristics of the short‐circuit current should be attributed to low electron‐collection efficiency and low dye‐regeneration efficiency, respectively. These results allow a deep understanding of the origin of the nonlinear characteristics of the short‐circuit current in solar cells.     

Photoinduced ultrafast dynamics of coumarin 343 sensitized p-type-nanostructured NiO films

Photoinduced electron transfer from the valence band of nanocrystalline NiO, a p-type semiconductor, to an excited bound dye, coumarin 343, and the subsequent recombination have been measured by femtosecond transient absorbance spectroscopy probing with white light. It was found that both processes are nonexponential. The photoinduced electron transfer from the semiconductor to the excited bound dye has an ultrafast component (approximately 200 fs), which is comparable to the time constants measured for photoinduced electron injection in C343-TiO2 colloid solutions. The process is very efficient and constitutes the main path of deactivation of the excited dye. Back electron transfer is also remarkably fast, with the main part of the recombination process happening with a time constant of approximately 20 ps. Dye-sensitized nanostructured p-type semiconductors are attractive materials due to their potential use as photocathodes in dye-sensitized solar cells and solid electrolytes in solid-state dye-sensitized solar cells. To our knowledge, this is the first time that the photoinduced electron-transfer kinetics of a sensitized p-type semiconductor has been studied.     

Alkyl chain barriers for kinetic optimization in dye-sensitized solar cells

The optimization of interfacial charge transfer is crucial to the design of dye-sensitized solar cells. In this paper we address the dynamics of the charge separation and recombination in liquid-electrolyte and solid-state cells employing a series of amphiphilic ruthenium dyes with varying hydrocarbon chain lengths, acting as an insulating barrier for electron-hole recombination. Dynamics of electron injection, monitored by time-resolved emission spectroscopy, and of charge recombination and regeneration, monitored by transient optical absorption spectroscopy, are correlated with device performance. We find that increasing dye alkyl chain length results in slower charge recombination dynamics to both the dye cation and the redox electrolyte or solid-state hole conductor (spiro-OMeTAD). These slower recombination dynamics are however paralleled by reduced rates for both electron injection into the TiO2 electrode and dye regeneration by the I-/I3- redox couple or spiro-OMeTAD. Kinetic competition between electron recombination with dye cations and dye ground state regeneration by the iodide electrolyte is found to be a key factor for liquid electrolyte cells, with optimum device performance being obtained when the dye regeneration is just fast enough to compete with electron-hole recombination. These results are discussed in terms of the minimization of kinetic redundancy in solid-state and liquid-electrolyte dye-sensitized photovoltaic devices.     

多吡啶钌染料和有机染料共染色的钴基敏化太阳电池

具有低费米能级的外球电子媒介体的开发带来了染料敏化太阳电池性能的重大进展.针对这种快复合器件,通过精细的调控二氧化钛表面的染料包覆层结构来有效抑制界面电荷复合是目前该领域的一个重要研究主题.在本文中,利用高吸收系数的多吡啶钌染料与具有三维立体结构的有机给受体染料对二氧化钛薄膜进行共染色.基于邻菲罗啉钴氧化还原电对,相对于纯钌基染料染色的器件,瞬态吸收与瞬态光电压衰减测试表明具有三维立体结构的有机染料的引入不仅提高了电子注入效率,还同时减慢了二氧化钛中的电子与氧化态染料及电解质中的电子受体之间的复合反应速率,使器件开路电压从808 mV提升到883 mV.这种界面光活性层微结构变化诱导的电子注入效率的改善和电荷复合的减慢还过补偿了因薄膜光吸收减弱带来的不利影响,获得了更大的光电流输出,在模拟AM1.5太阳光辐照条件下器件功率转换效率从8.5%提升到10.3%.     

Effect of chenodeoxycholic acid (CDCA) additive on phenothiazine dyes sensitized photovoltaic performance

The effects of chenodeoxycholic acid (CDCA) in a dye solution as a co-adsorbent on the photovoltaic performance of dye-sensitized solar cells (DSSCs) based on two organic dyes containing phenothiazine and triarylamine segments (P1 and P2) were investigated.It was found that the coadsorption of CDCA can hinder the formation of dye aggregates and improve electron injection yield and thus Jsc.This has also led to a rise in photovoltage,which is attributed to the decrease of charge recombination.The DSSC based ...     

Contribution from a hole-conducting dye to the photocurrent in solid-state dye-sensitized solar cells

The hole transporting medium in solid-state dye-sensitized solar cells can be utilized to harvest sunlight. Herein we demonstrate that a triphenylamine-based dye, used as hole-transporting medium, contributes to the photocurrent in a squaraine-sensitized solid-state dye-sensitized solar cell. Steady-state photoluminescence measurements have been used to distinguish between electron transfer and energy transfer processes leading to energy conversion upon light absorption in the hole-transporting dye.     

Modified phthalocyanines for efficient near-IR sensitization of nanostructured TiO(2) electrode

A zinc phthalocyanine with tyrosine substituents (ZnPcTyr), modified for efficient far-red/near-IR performance in dye-sensitized nanostructured TiO(2) solar cells, and its reference, glycine-substituted zinc phthalocyanine (ZnPcGly), were synthesized and characterized. The compounds were studied spectroscopically, electrochemically, and photoelectrochemically. Incorporating tyrosine groups into phthalocyanine makes the dye ethanol-soluble and reduces surface aggregation as a result of steric effects. The performance of a solar cell based on ZnPcTyr is much better than that based on ZnPcGly. Addition of 3alpha,7alpha-dihydroxy-5beta-cholic acid (cheno) and 4-tert-butylpyridine (TBP) to the dye solution when preparing a dye-sensitized TiO(2) electrode diminishes significantly the surface aggregation and, therefore, improves the performance of solar cells based on these phthalocyanines. The highest monochromatic incident photo-to-current conversion efficiency (IPCE) of approximately 24% at 690 nm and an overall conversion efficiency (eta) of 0.54% were achieved for a cell based on a ZnPcTyr-sensitized TiO(2) electrode. Addition of TBP in the electrolyte decreases the IPCE and eta considerably, although it increases the open-circuit photovoltage. Time-resolved transient absorption measurements of interfacial electron-transfer kinetics in a ZnPcTyr-sensitized nanostructured TiO(2) thin film show that electron injection from the excited state of the dye into the conduction band of TiO(2) is completed in approximately 500 fs and that more than half of the injected electrons recombines with the oxidized dye molecules in approximately 300 ps. In addition to surface aggregation, the very fast electron recombination is most likely responsible for the low performance of the solar cell based on ZnPcTyr.     

A fast approach to optimize dye loading of photoanode via ultrasonic technique for highly efficient dye-sensitized solar cells

A distinctive method is proposed by simply utilizing ultrasonic technique in TiO_2 electrode fabrication in order to improve the optoelectronic performance of dye-sensitized solar cells(DSSCs). Dye molecules are at random and single molecular state in the ultrasonic field and the ultrasonic wave favors the diffusion and adsorption processes of dye molecules. As a result, the introduction of ultrasonic technique at room temperature leads to faster and more well-distributed dye adsorption on TiO_2 as well as higher cell efficiency than regular deposition, thus the fabrication time is markedly reduced. It is found that the device based on40 kHz ultrasonic(within 1 h) with N719 exhibits a Vocof 789 mV, Jscof 14.94 mA/cm~2 and fill factor(FF)of 69.3, yielding power conversion efficiency(PCE) of 8.16%, which is higher than device regularly dyed for12 h(PCE = 8.06%). In addition, the DSSC devices obtain the best efficiency(PCE = 8.68%) when the ultrasonic deposition time increases to 2.5 h. The DSSCs fabricated via ultrasonic technique presents more dye loading,larger photocurrent, less charge recombination and higher photovoltage. The charge extraction and electron impedance spectroscopy(EIS) were performed to understand the influence of ultrasonic technique on the electron recombination and performance of DSSCs.     

Charge separation versus recombination in dye-sensitized nanocrystalline solar cells: the minimization of kinetic redundancy

In this paper we focus upon the electron injection dynamics in complete dye-sensitized nanocrystalline metal oxide solar cells (DSSCs). Electron injection dynamics are studied by transient absorption and emission studies of DSSCs and correlated with device photovoltaic performance and charge recombination dynamics. We find that the electron injection dynamics are dependent upon the composition of the redox electrolyte employed in the device. In a device with an electrolyte composition yielding optimum photovoltaic device efficiency, electron injection kinetics exhibit a half time of 150 ps. This half time is 20 times slower than that for control dye-sensitized films covered in inert organic liquids. This retardation is shown to result from the influence of the electrolyte upon the conduction band energetics of the TiO2 electrode. We conclude that optimum DSSC device performance is obtained when the charge separation kinetics are just fast enough to compete successfully with the dye excited-state decay. These conditions allow a high injection yield while minimizing interfacial charge recombination losses, thereby minimizing "kinetic redundancy" in the device. We show furthermore that the nonexponential nature of the injection dynamics can be simulated by a simple inhomogeneous disorder model and discuss the relevance of our findings to the optimization of both dye-sensitized and polymer based photovoltaic devices.     

Adaptive response by an electrolyte: resilience to electron losses in a dye-sensitized porous photoanode

Photovoltage and photocurrents below theoretical limits in dye-sensitized photoelectrochemical solar energy conversion systems are usually attributed to electron loss processes such as dye–electron and electrolyte–electron recombination reactions within the porous photoanode. Whether recombination is a major loss mechanism is examined here, using a multiscale reaction–diffusion computational model to evaluate system characteristics. The dye-sensitized solar cell with an I⁻/I₃⁻ redox couple is chosen as a simple, representative model system because of the extensive information available for it. Two photoanode architectures with dye excitation frequencies spanning 1–25 s⁻¹ are examined, assuming two distinct recombination mechanisms. The simulation results show that although electrolyte–electron reactions are very efficient, they do not significantly impact photoanode performance within the system as defined. This is because the solution-phase electrolyte chemistry plays a key role in mitigating electron losses through coupled reactions that produce I⁻ within the photoanode pores, thereby cycling the electrolyte species without requiring that all electrolyte reduction reactions take place at the more distantly located cathode. This is a functionally adaptive response of the chemistry that may be partly responsible for the great success of this redox couple for dye-sensitized solar cells. The simulation results provide predictions that can be tested experimentally.

Interfacial electrolyte reactions in the pores of a photoanode consume electrons. The losses are offset by compensating solution-phase reactions that generate I⁻ locally, and promote efficient dye cycling and photocurrent generation.     

Oxide thickness and roughness factor as parameters for TiO<Subscript>2</Subscript>-dye sensitized solar cells performance

Oxide surface roughness in connection to oxide thickness has proved to be a key parameter for the performance of a dye sensitised solar cell. In this work, the numerical simulation of the system TiO₂-photo sensitive dye of a dye sensitized TiO₂ solar cell focuses on these two parameters. The steady-state numerical model used is based on the continuity and transport equations for charge species involved in the system, in connection to Poisson’s equation. Light absorbance is set dependent upon TiO₂ porosity and resulting electron density after illumination is derived as a function of the illuminating beam characteristics and material properties. Electron lifetime in the bulk is set dependent upon electron distribution with electron lifetime at the surface taking into consideration surface recombination. An effective dielectric constant dependent also upon the porosity of TiO₂ is used in the model. Results for different values of the TiO₂ thickness and surface roughness leading to optimum values for the cell performance are found in accordance with results reported in the literature.     

Recent progress in interface modification for dye-sensitized solar cells

Interface modification on the TiO₂/dye/electrolyte interface of dye-sensitized solar cells (DSCs) is one of the most effective approaches to suppress the charge recombination, improve electron injection and transportation, and thus ameliorate the conversion efficiency and stability of DSCs. Conventional research focusing on the photoanodes interface modification before sensitization in dye-sensitized solar cells has been carried out and reviewed. However, recent studies showed that post-modification after sensitization of the TiO₂ electrode also plays a significant role on the TiO₂/dye/electrolyte interface. This post-modification using the immersing method could deprotonate dye molecules, prohibit the dye aggregation and retard the recombination reaction. As a result, it has great influence on the devices’ photovoltaic performance. This interface modification could also provide an approach to broaden the response of the solar spectrum by introducing an alternative assembling structure. An in-situ meaning of using a co-adsorbent is employed to modify the interface in the DSCs, which could retard the aggregation of the dye molecules and enhance the conversion efficiency. In addition, electrolyte additives can be used to modify the TiO₂/dye/electrolyte interface through some unique mechanisms. Based on the background of interface modification of photoanodes before sensitization, this review introduces various interface modifications after sensitization of dye-sensitized solar cells and their mechanisms.     

Kinetics of electron recombination of dye-sensitized solar cells based on TiO2 nanorod arrays sensitized with different dyes

The performance and electron recombination kinetics of dye-sensitized solar cells based on TiO(2) films consisting of one-dimensional nanorod arrays (NR-DSSCs) which are sensitized with dyes N719, C218 and D205, respectively, have been studied. It has been found that the best efficiency is obtained with the dye C218 based NR-DSSCs, benefiting from a 40% higher short-circuit photocurrent density. However, the open circuit photovoltage of the N719 based cell is 40 mV higher than that of the organic dye C218 and D205 based devices. Investigation of the electron recombination kinetics of the NR-DSSCs has revealed that the effective electron lifetime, τ(n), of the different dye based NR-DSSCs shows the sequence of C218 > D205 > N719. The higher V(oc) with the N719 based NR-DSSC is originated from the more negative energy level of the conduction band of the TiO(2) film. In addition, in comparison to the DSSCs with the conventional nanocrystalline particles based TiO(2) films, the NR-DSSCs have shown over two orders of magnitude higher τ(n) when employing N719 as the sensitizer. Nevertheless, the τ(n) of the DSSCs with the C218 based nanorod arrays is only ten-fold higher than that of the nanoparticles based devices. The remarkable characteristic of the dye C218 in suppressing the electron recombination of DSSCs is discussed.     

二氢吲哚类染料用于染料敏化太阳能电池光敏剂的比较

采用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)对四种二氢吲哚染料进行研究, 从中筛选出相对优秀的染料敏化太阳能电池光敏剂. 对前线分子轨道的计算表明, 二氢吲哚染料的前线分子轨道结构非常有利于染料激发态向TiO2电极的电子注入. 对真空中的紫外和可见光吸收光谱的计算表明, 二氢吲哚染料的吸收光谱与太阳辐射光谱匹配较好. 对染料分子的能级计算表明, 二氢吲哚染料的能级结构比较适合于I-/I-3作电解液的TiO2纳米晶太阳能电池的光敏剂. 二氢吲哚染料最低未占据分子轨道(LUMO) 能级均比TiO2晶体导带边能级高, 能够保证激发态染料分子高效地向TiO2电极转移电子. 二氢吲哚染料最高占据分子轨道(HOMO)的能级比I-/I-3能级低, 保证了失去电子的染料分子能够顺利地从电解液中得到电子. 与实验数据比较, 得出在提高染料敏化太阳能电池转换效率方面, 对染料的关键要求是LUMO能级的位置. 染料分子的稳定性是染料敏化太阳能电池使用寿命的关键因素. 通过对化学键键长的比较表明, 二氢吲哚染料的分子稳定性基本相同. 对计算结果的分析表明, 二氢吲哚染料1(ID1)的LUMO能级最高, 分子稳定性最好, 在酒精溶液中的吸收光谱与太阳辐射光谱匹配很好, 在同类染料中是较好的染料敏化太阳能电池光敏剂.     

Formation of N719 dye multilayers on dye sensitized solar cell photoelectrode surfaces investigated by direct determination of element concentration depth profiles

The structure of the dye layer adsorbed on the titania substrate in a dye-sensitized solar cell is of fundamental importance for the function of the cell, since it strongly influences the injection of photoelectrons from the excited dye molecules into the titania substrate. The adsorption isotherms of the N719 ruthenium-based dye were determined both with a direct method using the depth profiling technique neutral impact collision ion scattering spectroscopy (NICISS) and with the standard indirect solution depletion method. It is found that the dye layer adsorbed on the titania surface is laterally inhomogeneous in thickness and there is a growth mechanism already from low coverage levels involving a combination of monolayers and multilayers. It is also found that the amount of N719 adsorbed on the substrate depends on the titania structure. The present results show that dye molecules in dye-sensitized solar cells are not necessarily, as presumed, adsorbed as a self-assembled monolayer on the substrate.     

The influence of dye structure on charge recombination in dye-sensitized solar cells

Replacing the nonyl groups on the solar cell dye Ru(4,4'-carboxylic acid-2,2'-bipyridine)(4,4'-dinonyl-2,2'-bipyridine)(NCS)(2) (Z-907) with amino groups results in a marked decrease in solar cell performance. This is despite the fact that the amino derivative (Z-960) has more favourable light absorption characteristics than Z-907 when used with thick nanocrystalline TiO(2) layers. Electron transfer to the electrolyte from the exposed fluorine-doped tin oxide (FTO) substrate is particularly fast in cells employing the Z-960 dye if a compact TiO(2) blocking layer is not used. The kinetics of electron transfer from the nanocrystalline TiO(2) layer in DSCs employing Z-960 are comparable to those of bare TiO(2) and ca. 2 to 5 times faster than for cells employing Z-907. The faster charge recombination in cells employing Z-960 lowers open-circuit photovoltage and results in very significant charge collection losses that lower short-circuit photocurrent. Voltammetric measurements show that surface modification of FTO electrodes with Z-960 results in slightly more facile charge transfer to acceptor species in triiodide/iodide electrolytes in the dark. A simpler molecule, p-aminobenzoic acid, more dramatically catalyses this charge transfer reaction. Conversely, chemical modification of FTO electrodes with Z-907 or p-toluic acid retards charge transfer kinetics. Similar results are obtained for nanocrystalline TiO(2) electrodes modified with these benzoic acid derivatives. These results strongly imply that surface adsorbed molecules bearing amino groups, including dye molecules, can catalyse charge recombination in dye-sensitized solar cells.     

Charge transport versus recombination in dye-sensitized solar cells employing nanocrystalline TiO2 and SnO2 films

We report a comparison of charge transport and recombination dynamics in dye-sensitized solar cells (DSSCs) employing nanocrystalline TiO(2) and SnO(2) films and address the impact of these dynamics upon photovoltaic device efficiency. Transient photovoltage studies of electron transport in the metal oxide film are correlated with transient absorption studies of electron recombination with both oxidized sensitizer dyes and the redox couple. For all three processes, the dynamics are observed to be 2-3 orders of magnitude faster for the SnO(2) electrode. The origins of these faster dynamics are addressed by studies correlating the electron recombination dynamics to dye cations with chronoamperometric studies of film electron density. These studies indicate that the faster recombination dynamics for the SnO(2) electrodes result both from a 100-fold higher electron diffusion constant at matched electron densities, consistent with a lower trap density for this metal oxide relative to TiO(2), and from a 300 mV positive shift of the SnO(2) conduction band/trap states density of states relative to TiO(2). The faster recombination to the redox couple results in an increased dark current for DSSCs employing SnO(2) films, limiting the device open-circuit voltage. The faster recombination dynamics to the dye cation result in a significant reduction in the efficiency of regeneration of the dye ground state by the redox couple, as confirmed by transient absorption studies of this reaction, and in a loss of device short-circuit current and fill factor. The importance of this loss pathway was confirmed by nonideal diode equation analyses of device current-voltage data. The addition of MgO blocking layers is shown to be effective at reducing recombination losses to the redox electrolyte but is found to be unable to retard recombination dynamics to the dye cation sufficiently to allow efficient dye regeneration without resulting in concomitant losses of electron injection efficiency. We conclude that such a large acceleration of electron dynamics within the metal oxide films of DSSCs may in general be detrimental to device efficiency due to the limited rate of dye regeneration by the redox couple and discuss the implications of this conclusion for strategies to optimize device performance.     

Co-sensitization of organic dyes for efficient ionic liquid electrolyte-based dye-sensitized solar cells

The co-sensitization of two organic dyes (SQ1 and JK2), which are complementary in their spectral responses, shows enhanced photovoltaic performance compared with that of an individual organic dye-sensitized solar cell. The power conversion efficiency of the co-sensitized organic dye solar cell based on the newly developed binary ionic liquid (solvent-free) electrolyte gives 6.4% under AM 1.5 sunlight at 100 mW/cm2 irradiation, which is higher than that of individual dye-sensitized solar cells. The incident monochromatic photon-to-current conversion efficiency (IPCE) of the co-sensitized solar cell shows typical absorption peaks at 530 and 650 nm corresponding to the two dyes and displays a broad spectral response over the entire visible spectrum with IPCE of >40% in the 400-700 nm wavelength domain.     

Deposition of a thin film of TiOx from a titanium metal target as novel blocking layers at conducting glass/TiO2 interfaces in ionic liquid mesoscopic TiO2 dye-sensitized solar cells

In dye-sensitized TiO2 solar cells, charge recombination processes at interfaces between fluorine-doped tin oxide (FTO), TiO2, dye, and electrolyte play an important role in limiting the photon-to-electron conversion efficiency. From this point of view, a high work function material such as titanium deposited by sputtering on FTO has been investigated as an effective blocking layer for preventing electron leakage from FTO without influencing electron injection. X-ray photoelectron spectroscopy analysis indicates that different species of Ti (Ti4+, Ti3+, Ti2+, and a small amount of Ti0) exist on FTO. Electrochemical and photoelectrochemical measurements reveal that thin films of titanium species, expressed as TiOx, work as a compact blocking layer between FTO and TiO2 nanocrystaline film, improving Voc and the fill factor, finally giving a better conversion efficiency for dye-sensitized TiO2 solar cells with ionic liquid electrolytes.