Elementary Photoelectronic Processes at a Porphyrin Dye/Single‐Walled TiO2 Nanotube Hetero‐interface in Dye‐Sensitized Solar Cells: A First‐Principles Study

A unique one‐dimensional (1D) sandwich single‐walled TiO₂ nanotube (STNT) is proposed as a photoanode nanomaterial with perfect morphology and large specific surface area. We have thoroughly examined the elementary photoelectronic processes occurring at the porphyrin dye/STNT hetero‐interface in dye‐sensitized solar cells (DSSCs) by theoretical simulation. It is desirable to investigate the interfacial photoelectronic processes to elucidate the electron transfer and transport mechanism in 1D STNT‐based DSSCs. We have found that the photoexcitation and interfacial charge separation mechanism can be described as follows. A ground‐state electron of the dye molecule (localized around the electron donor) is first promoted to the excited state (distributed electron donor), and then undergoes ultrafast injection into the conduction band of the STNT, leaving a hole around the oxidized dye. Significantly, the injected electron in the conduction band is transported along the STNT by means of Ti 3d orbitals, offering a unidirectional electron pathway toward the electrode for massive collection without the observation of trap states. Our study not only provides theoretical guidelines for the modification of TiO₂ nanotubes as a photoanode material, but also opens a new perspective for the development of a novel class of TiO₂ nanotubes with high power‐generation efficiency.     

Extensive enhancement in power conversion efficiency of dye-sensitized solar cell by using Al-doped TiO<Subscript>2</Subscript> photoanode

In this work, we have prepared Al-doped TiO₂ nanoparticles via a hydrothermal method and used it for making photoanode in dye-sensitized solar cell (DSSC). Material characterizations were done using XRD, AFM, SEM, TEM and EDAX. XPS results reveal that Al is introduced successfully into the structure of TiO₂ creating new impurity energy levels in the forbidden gap. This resulted in tuning of the conduction band of TiO₂ and reduced charge recombination which led to better current conversion efficiency of DSSC. Greater dye loading and enhanced surface area was obtained for Al-doped TiO₂ compared to un-doped TiO₂. I-V analysis, EIS and Bode plots are employed to evaluate photovoltaic performance. The short-circuit current density (J _sc) and efficiency (η) of cell employing Al-doped TiO₂ photoanode were extensively enhanced compared to the cell using un-doped TiO₂. The optical band gap (E _g) for Al-doped and un-doped TiO₂ was obtained as 2.8 and 3.2 eV, respectively. J _sc and η were 13.39 mAcm^?2 and 4.27%, respectively, under illumination of 100 mWcm^?2 light intensity when thin films of 1% Al-doped TiO₂ was employed as photoanode in DSSC using N719 as the sensitizer dye. With the use of un-doped TiO₂ as photoanode under similar conditions, J _sc 5.12 mAcm^?2 and η 1.06% only could be obtained. The maximum IPCE% obtained with Al-doped TiO₂ and un-doped TiO₂ was 67 and 38% respectively at the characteristic wavelength of dye (λ _max = 540 nm). The EIS analyses revealed resistive and capacitive elements that provided an insight into various interfacial processes in terms of the charge transport. It was observed that Al-doping reduced the interfacial resistance leading to better charge transport which has improved both photocurrent density and conversion efficiency. Higher electron mobility and fast diffusion resulting in greater charge collection efficiency was obtained for Al-doped TiO₂ compared to the un-doped TiO₂. Using the Mott–Schottky plot, the donor density was calculated for un-doped and Al-doped TiO₂. The work demonstrated that the Al-doped TiO₂ is potential photoanode material for low-cost and high-efficiency DSSC.     

Effect of N719 Dye Dipping Temperature on the Performance of Dye-Sensitized Solar Cell

Preparation parameter of dye plays important role in determining DSSC performance. This paper reports the influence of N719 dye dipping temperature on the optical properties and performance parameters of the DSSC utilizing TiO₂ films prepared via microwave technique. The TiO₂ coated N719 dye films were prepared at various temperatures, namely, 30, 50, 60, 70 and 80°C. It is found that the TiO₂ film dipped into N719 dye solution at 50°C possesses the broadest optical absorption window and the highest dye loading. It is also found that the dye dipping temperature does not affect the leak current in the device. The short-circuit current density (J_SC) and power conversion efficiency (η) are strongly influenced by the dipping temperature. The DSSC utilizing the sample prepared at 50°C demonstrated the highest J_SC and η of 4.06 mA cm^–2 and 1.36%, respectively due to highest dye loading and recombination resistance.     

Effect of Surface Protonation on Device Performance and Dye Stability of Dye-sensitized TiO2 Solar Cell

A flat thin TiO₂ film was employed as the photo-electrode of a dye sensitized solar cell (DSSC), on which only a geometrical mono-layer of dye was attached. The effect of sur-face protonation by HCl chemical treatment on the performance of DSSCs was studied. The results showed that the short-circuit current Jsc increased significantly upon the HCl treatment, while the open-circuit voltage Voc decreased slightly. Compared to the untreated DSSC, the Jsc and energy conversion efficiency was increased by 31% and 25%, respectively, for the 1 mol/L HCl treated cell. TiO₂ surface protonation improved electronic coupling between the chemisorbed dye and the TiO₂ surface, resulting in an enhanced electron in-jection. The decreased open-circuit voltage after TiO₂ surface protonation was mainly due to the TiO₂ conduction band edge downshift and was partially caused by increased electron recombination with the electrolyte. In situ Raman degradation study showed that the dye stability was improved after the TiO₂ surface protonation. The increased dye stability was contributed by the increased electron injection and electron back reaction with the electrolyte under the open-circuit condition.     

Synthesis of new dyes containing double tetrazole groups for sensitization of TiO<Subscript>2</Subscript> nanoparticles in dye-sensitized solar cells

Di(1H-tetrazol-5-yl)methane is employed as a new electron acceptor group in the synthesis of two metal-free organic dyes containing triphenylamine donor group. Dye-sensitized nanocrystalline TiO₂ solar cell (DSSC) applying these novel dyes is constructed for consideration of their photovoltaic properties. The electronic properties of the dyes are also considered with the aid of theoretical calculations. The DSSC constructed from 4-(2,2-di(1H-tetrazol-5-yl)vinyl)-N,N-diphenylaniline (T1) shows a short-circuit photocurrent density of 13.38 mA cm^?2, an open circuit voltage of 578 mV, and a fill factor of 0.54, with a resulted solar energy-to-electricity conversion efficiency of 4.18% under simulated 1 sun irradiation (100 mW cm^?2). This result reveals that the dye with the di(1H-tetrazol-5-yl)methane anchoring group injects more electrons to the conduction band of TiO₂ in comparison with its analogs with single tetrazole ring in their anchoring group. It is found that in spite of a red-shift of the absorption spectrum resulted from the lengthening of the molecule, the dye with two di(1H-tetrazol-5-yl)methane groups gives lower performance than the dye with a single electron acceptor.     

The fabrication of TiO<Subscript>2</Subscript> nanoparticle/ZnO nanowire arrays bi-filmed photoanode and their effect on dye-sensitized solar cells

Porous TiO₂ nanoparticles coated on ZnO nanowire arrays (TiO₂ NP/ZnO NW) as photoanode for dye-sensitized solar cell (DSSC) has been fabricated and investigated to improve the power conversion efficiency. The TiO₂ NP/ZnO NW photoanode consists of single crystalline ZnO NWs synthesized via hydrothermal method and porous TiO₂ NP film covered on the surface of ZnO NW arrays by screen printing technique. The effect of TiO₂ NPs thickness of the bi-filmed photoanode on the cell performance has been investigated, and TiO₂ NP/ZnO NW DSSC with NP thickness of ~5 μm exhibits the best efficiency of 4.68%, higher than 1.16% of ZnO NW DSSC and 3.18% of TiO₂ NPs DSSC, prepared and tested under identical conditions. The efficiency increase is attributed to the enlarged photocurrent, due to the greatly enhanced surface area for dye absorption and light harvesting efficiency resulted from TiO₂ NPs, and improved open-circuit voltage, due to reduced electron recombination by providing direct conduction pathway along ZnO NWs.     

Structural engineering of dipolar organic dyes with an electron-deficient diphenylquinoxaline moiety for efficient dye-sensitized solar cells

A series of new organic dyes containing an electron-deficient diphenylquinoxaline moiety was synthesized and employed as the photosensitizers in dye-sensitized solar cells (DSSCs). The multiple phenyl rings in the peripheral positions of the dye structure provide a hydrophobic barrier to slow down the charge recombination. The photophysical and electrochemical properties of these dyes were investigated in detail. The cell performance and the associated photophysical and electrochemical properties can be easily tuned by the modification of the aromatic fragments within the π spacer. Dye CR204-based DSSC reached the best energy conversion efficiency of 6.49% with an open-circuit voltage of 666 mV, a short-circuit photocurrent density of 14.9 mA cm⁻², and a fill factor of 0.66. The IPCE of CR204-based DSSC covers the light-harvesting to NIR region.     

Anion-enhanced excited state charge separation in a spiro-locked N-heterocycle-fused push-pull zinc porphyrin

A new type of push–pull charge transfer complex, viz., a spiro-locked N-heterocycle-fused zinc porphyrin, ZnP-SQ, is shown to undergo excited state charge separation, which is enhanced by axial F⁻ binding to the Zn center. In this push–pull design, the spiro-quinone group acts as a ‘lock’ promoting charge transfer interactions by constraining mutual coplanarity of the meso-phenol-substituted electron-rich Zn(ii) porphyrin and an electron deficient N-heterocycle, as revealed by electrochemical and computational studies. Spectroelectrochemical studies have been used to identify the spectra of charge separated states, and charge separation upon photoexcitation of ZnP has been unequivocally established by using transient absorption spectroscopic techniques covering wide spatial and temporal regions. Further, global target analysis of the transient data using GloTarAn software is used to obtain the lifetimes of different photochemical events and reveal that fluoride anion complexation stabilizes the charge separated state to an appreciable extent.

A new type of push–pull charge transfer complex, viz., a spiro-locked N-heterocycle-fused zinc porphyrin, ZnP-SQ, is shown to undergo excited state charge separation, which is enhanced by axial F⁻ binding to the Zn center.     

Improvement of dye-sensitized solar cell performance through electrodepositing a close-packed TiO2 film

A simple electrodepositing method was proposed for fabricating a uniform, tight, and close-packed TiO₂ nanocrystalline film on the ITO substrate. The electrode and dye-sensitized solar cell (DSSC) with electrodeposited TiO₂ layer were characterized by scanning electron microscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The phthalocyanin dye, zinc tetra-carboxyl phthalocyanin complex, was used as a model dye to evaluate the influence of close-packed TiO₂ blocking layer on the photocurrent–voltage property. On the electrodeposition, the close-packed TiO₂ layer could effectively inhibit the recombination of charges, and therefore improve the performances of the corresponding cells. The effects of film thickness on light transmittance and photocurrent density of the corresponding cell were also demonstrated. The optimum film thickness was found to be approximately 400 nm. At the optimum thickness, the photocurrent density greatly increased comparing with that of the screen printing TiO₂ film. These results imply that our proposition was a potential and feasible method for the fabrication of DSSC practically.     

Inclined Substrate Deposition of Nanostructured TiO2 Thin Films for DSSC Application

Nanostructured TiO₂ films were deposited onto Indium Tin Oxide (ITO) and glass substrates by dc reactive magnetron sputtering at different substrate inclination angles. The structural and optical properties of the deposited films were studied by X-ray diffraction, scanning electron microscopy and UV–Vis spectrophotometer, respectively. Dye-sensitized solar cells (DSSC) were assembled using these TiO₂ films as photoelectrodes and the effect of the substrate inclination angle in the preparing process of TiO₂ films on the DSSC conversion efficiency was studied.     

Synthesis and applications of novel acceptor-donor-acceptor organic dyes with dithienopyrrole- and fluorene-cores for dye-sensitized solar cells

Four novel symmetrical organic dyes (S1-S4) configured with acceptor-donor-acceptor (A-D-A) structures containing electron donating fluorene (S1 and S2) and N-alkyl dithieno[3,2-b:2′,3′-d]pyrrole (DTP) (S3 and S4) cores terminated with two anchoring cyanoacrylic acids (as electron acceptors) were synthesized and applied to dye-sensitized solar cells (DSSCs). The DSSC device based on S2 dye showed the best photovoltaic performance among S1-S4 dyes: a maximum monochromatic incident photon-to-current conversion efficiency (IPCE) of 76%, a short circuit current (J_SC) of 12.27 mA/cm², an open circuit voltage (V_OC) of 0.61 V, a fill factor (FF) of 0.63, and an overall power conversion efficiency (η) of 4.73%. Besides, the utilization of chenodoxycholic acid (CDCA) as a co-adsorbent in the DSSC device based on S3 dye showed a significant improvement in its η value (from 3.70% to 4.31%), which is attributed to the suppression of dye aggregation on TiO₂ surface and thus to increase the J_SC value eventually.     

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.     

Hyperbranched conjugated polymers with donor-π-acceptor architecture as organic sensitizers for dye-sensitized solar cells

Three novel hyperbranched conjugated polymers (H-tpa, H-cya, and H-pca) with the same conjugated core structure and different functional terminal units were synthesized and applied in dye-sensitized solar cells (DSSCs) as photosensitizers. The photophysical, electrochemical and photovoltaic properties of the three hyperbranched conjugated polymers (HBPs) were investigated in detail. The results showed that donor-π-acceptor architecture in hyperbranched molecule benefited intramolecular charge transfer and consequently increased the generation of photocurrent. The three-dimensional (3D) steric configuration of HBPs could effectively suppress the aggregation of dyes on TiO₂ film, which is beneficial for achieving good photovoltaic performances. Among the three hyperbranched dyes, the highest power conversion efficiency (η) of 3.93% (J_sc = 8.78 mA/cm², V_oc = 0.65 V, FF = 0.688) was obtained with a DSSC based on H-pca dye upon the addition of the same mass ratio chenodeoxycholic acid (CDCA) as coadsorbent under AM 1.5 irradiation with 100 mW/cm² simulated sunlight.     

Thieno[2,3-a]carbazole-based donor–π–acceptor organic dyes for efficient dye-sensitized solar cells

New donor–π–acceptor organic dyes K-1 and K-2 containing thieno[2,3-a]carbazole as an electron donor were designed and synthesized for dye-sensitized solar cells (DSCs). Photophysical and electrochemical properties of K-dyes were investigated. DSCs based on K-dyes showed a high conversion efficiency of 6.6–6.7% with a J_sc of 12.40–12.49 mA cm⁻² and a V_oc of 0.70–0.71 V. The molecular geometry calculation indicated that the existence of thienocarbazole donor in K-dyes enhanced the molecular planarity compared to the carbazole analogue dye MK-3. As a result, DSCs based on K-dyes showed high IPCEs, perhaps due to efficient intramolecular charge transfer and electron injection from excited dye to TiO₂ conduction band.     

Mini review on the performance of Schiff base and their metal complexes as photosensitizers in dye-sensitized solar cells

Abstract

For the requirement of clean and efficient energy, research toward the improvement of solar energy is increased because it directly converts the sunlight into electrical energy leaving no harmful effect on the environment. Dye-sensitized solar cells (DSSCs) are one of the best alternative approaches to conventional solar cells. The photosensitizer is one of the important components in DSSC and plays a key role to initiate the electrochemical process for electricity production by harvesting visible light. The power conversion efficiency of DSSC is typically based on the dye/sensitizer which is coated on the porous semiconductor TiO₂ film. Schiff base metal complexes have potential photosensitizing behavior, due to their photophysical properties. This article presents the current development attained in the designing and synthesis of Schiff base metal complexes and their application as photosensitizers and also co-sensitizers in dye-sensitized solar cells, and recent developments on the DSSC using Schiff based metal complexes.     

基于TiO2纳米管阵列的高效正面透光型染料敏化太阳能电池的制备及其光电性能

报道了一种基于TiO2纳米管(TNT)阵列正面透光型光阳极的高效染料敏化太阳能电池.将TNTs在450°C烧结后能避免其有序结构在HF处理过程中被破坏,使膜内高速电子传输通道被保留,有利于染料敏化太阳能电池(DSSC)实现高速电荷传输.再用HF、TiCl4、HF和TiCl4混合等溶剂对TNTs进行处理,提高其表面粗糙度以吸附更多染料.染料吸附量的增加能提高光阳极在300-570 nm波段光子捕获效率,该波段是染料吸收光子的主要区域.然而,在染料吸收光子较弱的长波段区域(570-800 nm)光子捕获效率的增加主要源于光阳极光散射率的提高.光阳极光子捕获效率的提高使DSSC的内外量子效率在全波段(300-800 nm)均有所增加,从而使短路电流明显提高.从电化学阻抗数据可知,与电子传输性能密切相关的电化学参数如电荷传输电阻、界面电荷复合电阻、电容、电子寿命、电子扩散长度和电子收集效率等在含处理过的TNTs光阳极DSSC中均有所改善,从而提高电池光电转换效率.含HF和TiCl4混合溶剂处理TNTs光阳极的DSSC最高光电转换效率能达到7.30%,比未处理的DSSC(5.38%)提高35.69%.     

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.     

Enhanced photovoltaic characterization and charge transport of TIO2 nanoparticles/nanotubes composite photoanode based on indigo carmine dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) have established themselves as an alternative to conventional solar cells owing to their remarkably high power conversion efficiency, longtime stability and low-cost production. DSSCs composed of a dyed oxide semiconductor photoanode, a redox electrolyte and a counter electrode. In these devices, conversion efficiency is achieved by ultra-fast injection of an electron from a photo excited dye into the conduction band of metal oxide followed by subsequent dye regeneration and holes transportation to the counter electrode. The energy conversion efficiency of DSSC is to be dependent on the morphology and structure of the dye adsorbed metal oxide photoanode. Worldwide considerable efforts of DSSCs have been invested in morphology control of photoanode film, synthesis of stable optical sensitizers and improved ionic conductivity electrolytes. In the present investigation, a new composite nano structured photoanodes were prepared using TiO₂ nano tubes (TNTs) with TiO₂ nano particles (TNPs). TNPs were synthesized by sol–gel method and TNTs were prepared through an alkali hydrothermal transformation. Working photoanodes were prepared using five pastes of TNTs concentrations of 0, 10, 50, 90, and 100 % with TNPs. The DSSCs were fabricated using Indigo carmine dye as photo sensitizer and PMII (1-propyl-3-methylimmidazolium iodide) ionic liquid as electrolyte. The counter electrode was prepared using Copper sulfide. The structure and morphology of TNPs and TNTs were characterized by X-ray diffraction and electron microscopes (TEM and SEM). The photocurrent efficiency is measured using a solar simulator (100 mW/cm²). The prepared composite TNTs/TNPs photoanode could significantly improve the efficiency of dye-sensitized solar cells owing to its synergic effects, i.e. effective dye adsorption mainly originated from TiO₂ nanoparticles and rapid electron transport in one-dimensional TiO₂ nanotubes. The results of the present investigation suggested that the DSSC based on 10 % TNTs/TNPs showed better photovoltaic performance than cell made pure TiO₂ nanoparticles. The highest energy-conversion efficiency of 2.80 % is achieved by composite TNTs (10 %)/TNPs film, which is 68 % higher than that pure TNPs film and far larger than that formed by bare TNTs film (94 %). The charge transport and charge recombination behaviors of DSSCs were investigated by electrochemical impedance spectra and the results showed that composite TNTs/TNPs film-based cell possessed the lowest transfer resistances and the longest electron lifetime. Hence, it could be concluded that the composite TNTs/TNPs photoanodes facilitate the charge transport and enhancing the efficiencies of DSSCs.     

SrTiO3/TiO2 Hybridstructure as Photoanode in Dye‐Sensitized Solar Cell

In dye‐sensitized solar cells (DSSCs), the charge recombination at the TiO₂/dye/electrolyte interface greatly influences the photoelectron conversion efficiency. Hybrid semiconductor materials with matched band potentials are designed to reduce the charge recombination. In this study, SrTiO₃/TiO₂ hybridstructure was synthesized by using TiO₂ nanoparticles as template in a hydrothermal, showing a negative shift in the flat band potential. The DSSC with the SrTiO₃/TiO₂ anode exhibits an increased photovoltage and a reduced photocurrent. The suppression of charge recombination at the TiO₂/dye/electrolyte interface was observed in the electrochemical impedance spectroscopy, causing an improvement in the photovoltage. However, the SrTiO₃/TiO₂ system shows an obstructed electrons injection from the dye to SrTiO₃/TiO₂, limiting the photocurrent performance. The photoelectrochemical properties of the SrTiO₃/TiO₂ system are discussed in detail herein.     

Computational studies on optoelectronic and charge transfer properties of some perylene‐based donor‐π‐acceptor systems for dye sensitized solar cell applications

We report DFT studies on some perylene‐based dyes for their electron transfer properties in solar cell applications. The study involves modeling of different donor‐π‐acceptor type sensitizers, with perylene as the donor, furan/pyrrole/thiophene as the π‐bridge and cyanoacrylic group as the acceptor. The effect of different π‐bridges and various substituents on the perylene donor was evaluated in terms of opto‐electronic and photovoltaic parameters such as HOMO‐LUMO energy gap, λ_max, light harvesting efficiency(LHE), electron injection efficiency (Ø_inject), excited state dye potential (E^dye*), reorganization energy(λ), and free energy of dye regeneration (). The effect of various substituents on the dye–I₂ interaction and hence recombination process was also evaluated. We found that the furan‐based dimethylamine derivative exhibits a better balance of the various optical and photovoltaic properties. Finally, we evaluated the overall opto‐electronic and transport parameters of the TiO₂‐dye assembly after anchoring the dyes on the model TiO₂ cluster assembly.