D-A-π-A organic sensitizers containing a benzothiazole moiety as an additional acceptor for use in solar cells

Three novel triphenylamine-based D-A-π-A-featured dyes (Z1-Z3) have been designed, synthesized and characterized for use in dye-sensitized solar cells. Benzothiazole was incorporated as an additional acceptor, which greatly enhanced the molar extinction coefficient of the dyes. Various conjugated linkers, such as benzene, furan and thiophene, were also introduced to configure the novel D-A-π-A framework in order to prolong electron flow and active transportation. Among all dyes, Z2 containing a thiophene linker exhibited the maximum overall conversion efficiency (η) of 4.16% (Jsc = 9.27 mA cm-2 , Voc = 642 mV, FF = 0.70) under standard global AM 1.5 G solar condition.     

Tuning the Electrical and Optical Properties of Diketopyrrolopyrrole Complexes for Panchromatic Dye‐Sensitized Solar Cells

A series of metal‐free organic dyes that were bridged by a diketopyrrolopyrrole moiety and were composed of indoline and triphenylamine as donor groups and furan and benzene as conjugated spacer groups were designed and synthesized for use in dye‐sensitized solar cells (DSCs). The photophysical properties, electrochemical properties, and performance of the DSCs were related to the structure of their corresponding dyes. Their absorption spectra broadened upon the introduction of the indoline and heterocyclic furan moieties through fine‐tuning of their molecular configuration. The overall conversion efficiencies of DSCs that were based on these dyes ranged from 5.14–6.53 %. Among the four dyes that were tested, indoline‐based ID01 and ID02 showed higher efficiencies (6.35 % and 6.53 %) as a result of their improved light‐harvesting efficiency and larger electron driving force. The ID01 dye, which contained an indoline moiety as an electron donor and a furan group as a π‐conjugated linker, showed an excellent monochromatic incident‐photon‐to‐current‐conversion efficiency (IPCE) spectrum (350–650 nm) with a maximum value of 78 % in the high plateau region and an onset value close to 800 nm. Intensity‐modulated photovoltage spectroscopy (IMVS) and impedance spectroscopy (IS) revealed that dyes that contained benzene conjugation spacers suppressed the charge‐recombination rate more efficiently than dyes that contained furan spacers, thereby resulting in improved photovoltage.     

New bithiazole-based sensitizers for efficient and stable dye-sensitized solar cells

A series of new push-pull organic dyes (BT-I-VI), incorporating electron-withdrawing bithiazole with a thiophene, furan, benzene, or cyano moiety, as π?spacer have been synthesized, characterized, and used as the sensitizers for dye-sensitized solar cells (DSSCs). In comparison with the model compound T1, these dyes containing a thiophene moiety between triphenylamine and bithiazole display enhanced spectral responses in the red portion of the solar spectrum. Electrochemical measurement data indicate that the HOMO and LUMO energy levels can be tuned by introducing different π?spacers between the bithiazole moiety and cyanoacrylic acid acceptor. The incorporation of bithiazole substituted with two hexyl groups is highly beneficial to prevent close π-π aggregation, thus favorably suppressing charge recombination and intermolecular interaction. The overall conversion efficiencies of DSSCs based on bithiazole dyes are in the range of 3.58 to 7.51?%, in which BT-I-based DSSCs showed the best photovoltaic performance: a maximum monochromatic incident photon-to-current conversion efficiency (IPCE) of 81.1?%, a short-circuit photocurrent density (J(sc)) of 15.69?mA?cm(-2), an open-circuit photovoltage (V(oc)) of 778?mV, and a fill factor (ff) of 0.61, which correspond to an overall conversion efficiency of 7.51?% under standard global AM 1.5 solar light conditions. Most importantly, long-term stability of the BT-I-III-based DSSCs with ionic-liquid electrolytes under 1000?h of light soaking was demonstrated and BT-II with a furan moiety exhibited better photovoltaic performance of up to 5.75?% power conversion efficiency.     

New Bithiazole‐Based Sensitizers for Efficient and Stable Dye‐Sensitized Solar Cells

A series of new push–pull organic dyes ( BT‐I – VI ), incorporating electron‐withdrawing bithiazole with a thiophene, furan, benzene, or cyano moiety, as π spacer have been synthesized, characterized, and used as the sensitizers for dye‐sensitized solar cells (DSSCs). In comparison with the model compound T1 , these dyes containing a thiophene moiety between triphenylamine and bithiazole display enhanced spectral responses in the red portion of the solar spectrum. Electrochemical measurement data indicate that the HOMO and LUMO energy levels can be tuned by introducing different π spacers between the bithiazole moiety and cyanoacrylic acid acceptor. The incorporation of bithiazole substituted with two hexyl groups is highly beneficial to prevent close π–π aggregation, thus favorably suppressing charge recombination and intermolecular interaction. The overall conversion efficiencies of DSSCs based on bithiazole dyes are in the range of 3.58 to 7.51 %, in which BT‐I ‐based DSSCs showed the best photovoltaic performance: a maximum monochromatic incident photon‐to‐current conversion efficiency (IPCE) of 81.1 %, a short‐circuit photocurrent density (J_sc) of 15.69 mA cm^?2, an open‐circuit photovoltage (V_oc) of 778 mV, and a fill factor (ff) of 0.61, which correspond to an overall conversion efficiency of 7.51 % under standard global AM 1.5 solar light conditions. Most importantly, long‐term stability of the BT‐I – III ‐based DSSCs with ionic‐liquid electrolytes under 1000 h of light soaking was demonstrated and BT‐II with a furan moiety exhibited better photovoltaic performance of up to 5.75 % power conversion efficiency.     

Benzotriazole-Bridged Sensitizers Containing a Furan Moiety for Dye-Sensitized Solar Cells with High Open-Circuit Voltage Performance

Two new benzotriazole-bridged sensitizers are designed and synthesized ( BTA-I and BTA-II ) containing a furan moiety for dye-sensitized solar cells (DSSCs). Two corresponding dyes ( BTA-III and BTA-IV ) with a thiophene spacer were also synthesized for comparison. All of these dyes performed as sensitizers for DSSCs, and the photovoltaic performance data of these benzotriazole-bridged dyes showed a high open-circuit voltage (V_oc: 804–834 mV). Among the four dyes, DSSCs based on BTA-II , with a furan moiety and branched alkyl chain, showed the highest V_oc (834 mV), a photocurrent density (J_sc) of 12.64 mA cm⁻², and a fill factor (FF) of 0.64, corresponding to an overall conversion efficiency (η) of 6.72 %. Most importantly, long-term stability of the BTA-I , BTA-II , BTA-III , BTA-IV -based DSSCs with ionic-liquid electrolytes under 1000 h light-soaking was demonstrated, and BTA-II exhibited better photovoltaic performance of up to 5.06 % power conversion efficiency.     

Effect of five-membered heteroaromatic linkers to the performance of phenothiazine-based dye-sensitized solar cells

Phenothiazine derivatives with various conjugated linkers (furan, thiophene, and 3,4-ethylenedioxythiophene) were synthesized and used in dye-sensitized solar cells to study the effect of conjugated linkers on device performance. Among them, one with furan as a conjugated linker showed a solar energy-to-electricity conversion efficiency (η) of 6.58%, an improvement of over 24% compared with the T2-1 reference cells' 5.29% under AM 1.5 G irradiation.     

Theoretical investigation of triphenylamine dye/titanium dioxide interface for dye-sensitized solar cells

The structural, electronic and optical features of two metal-free triphenylamine (TPA) organic dyes (namely C206 and C217) before and after binding to a TiO(2) anatase nanoparticle have been investigated in detail, as a model for the corresponding dye-sensitized solar cells (DSSCs). The combination of density functional tight-binding (DFTB), density functional theory (DFT), and time-dependent DFT (TDDFT) approaches are employed. To understand the effects of the linker part in the TPA organic dyes on the energy conversion efficiency of the DSSCs, C217 and C206, which share the same donor and anchor parts but different linker parts, are theoretically evaluated. Our results show that compared with C206 containing just one thienothiophene unit as the linker, for C217 the introduction of one electron-rich 3,4-ethylenedioxythiophene group to the linker part results in stronger couplings with the TiO(2) conduction band and more efficient electron transfer. This difference contributes to the higher efficiency of C217 in DSSCs experiments. This study is expected to assist the molecular design of new and more efficient TPA-based organic dyes for the optimization of the DSSCs.     

不同受体结构染料共敏化对染料敏化太阳电池性能的影响

为了拓宽染料敏化太阳电池对太阳光谱的响应范围,提高电池的光电转换效率,将两种含有不同受体结构（绕丹宁-3-乙酸基（RA）和氰基丙烯酸基（CA））的三苯胺染料（TR1和TC1）进行共敏化。TR1染料平伏吸附在TiO₂表面,而TC1染料直立吸附在TiO₂表面。将两种染料按照不同摩尔比共敏化TiO₂后,TC1占据TR1的部分位置,拓展光谱的同时也抑制了电荷复合,电子寿命较TR1敏化的太阳电池长。在TR1与TC1摩尔比为5：5的共敏剂溶液敏化的共敏电池器件中,短路光电流密度（J_sc）为11.7 mA/cm²,开路电压（V_oc）为704 mV,填充因子（FF）为0.73,光电转换效率（η）为6.03%。该结果明显优于单一染料敏化的电池器件。     

2,7-Diaminofluorene-based organic dyes for dye-sensitized solar cells: effect of auxiliary donor on optical and electrochemical properties

New organic dyes containing a diarylaminofluorene unit as an electron donor and cyanoacrylic acid as acceptor and anchoring group in a donor-π-donor-π-acceptor architecture have been synthesized and characterized as sensitizers for nanocrystalline TiO(2)-based dye-sensitized solar cells. They have shown three major electronic absorptions originating from the π-π* and charge-transfer transitions covering the broad visible range (250-550 nm) in solution. The charge-transfer transition of the dyes exhibited negative solvatochromism, suggesting a polarized ground state. They have also displayed acidochromism in solution owing to the presence of a protonation-deprotonation equilibrium. On comparison with the triphenylamine and carbazole-based parent dyes (E)-2-cyano-3-(4-(diphenylamino)phenyl)acrylic acid and (E)-2-cyano-3-(9-ethyl-9H-carbazol-3-yl)acrylic acid they exhibited longer wavelength absorptions and facile oxidation, indicating the stronger electron-donating ability of the auxiliary chromophores. In addition, they exhibited nearly two times larger light-to-electron conversion efficiency under simulated AM 1.5 G irradiation (100 mW cm(-2)) with an aperture mask when compared to the parent dyes. Among the new dyes, the one containing the naphthylphenylamine segment showed better device characteristics attributable to the higher HOMO energy level which probably facilitates the regeneration of the dye and effective suppression of the back reaction of the injected electrons with the I(3)(-) in the electrolyte. The optical properties of the dyes were modeled using TDDFT simulations employing different theoretical models (B3LYP, CAM-B3LYP, and MPW1K), and the best correlations with the observed parameters have been found for CAM-B3LYP and MPW1K calculations. The electron lifetimes extracted from the electrochemical impedance measurements of the dye-sensitized solar cells were used to interpret the solar cell efficiency alternations.     

Coplanar indenofluorene-based organic dyes for dye-sensitized solar cells

A series of new organic dyes, comprising indenofluorene moiety as a conjugated bridge, with an extended π-groups, such as thiophene and furan, diphenylamine as donor, cyanoacrylic acid group as an electron acceptor and anchoring group, have been synthesized. Photophysical and electrochemical measurements, and theoretical computation were carried out on these dyes. Dye-sensitized solar cells (DSSCs) using these dyes as the sensitizers exhibited photocurrent density (J_SC), open-circuit voltage (V_OC), and fill factor (FF) in the range of 6.95–8.20 mA/cm², 0.70–0.71 V, and 0.69–0.71, respectively, corresponding to an overall conversion efficiency of 3.36–4.05%. The best efficiency reached 56% of the standard cell based on N719.     

Novel pyrenoimidazole-based organic dyes for dye-sensitized solar cells

A novel class of organic dyes containing pyrenoimidazole donors, cyanoacrylic acid acceptors, and oligothiophene π-linkers has been synthesized and characterized. The electro-optical properties of these dyes can be tuned by changing the conjugation length of the π-linkers. A dye containing terthiophene in the conjugation pathway exhibited a solar energy-to-electricity conversion efficiency of 5.65%.     

Benzotriazole‐Containing D–π–A Conjugated Organic Dyes for Dye‐Sensitized Solar Cells

A series of metal‐free benzotriazole‐based dipolar dyes have been developed as sensitizers for dye‐sensitized solar cells (DSSCs). Different heteroaromatic rings such as furan, thiophene, and selenophene, were used in combination with benzotriazole as the conjugated spacer group. Light harvesting, charge recombination, and electron injection of the cells fabricated are affected by the heteroaromatic ring used in the spacer. The DSSC with the thiophene‐containing dye has the highest conversion efficiency of 6.20 %, which reaches 85 % of the standard cell based on N719.     

Macrocyclic triphenylamine based organic dyes for efficient dye-sensitized solar cells

A novel class of organic D-π-A dyes employing macrocyclic triphenylamine dimer as electron donor was designed and synthesized for dye-sensitized solar cells. The prepared compounds showed high chemical and elelctrochemical stabilities as well as good long-wave absorption. Photovoltaic devices based on these dyes showed high open circuit voltage (higher than that of N3) and achieved a solar energy to electricity conversion efficiency of 6.31%. All the performances indicate the dyes containing macrocyclic triphenylamine dimer is a good candidate for dyes sensitized solar cells.     

Absorption tuning of monosubstituted triazatruxenes for bulk heterojunction solar cells

A series of triazatruxene (TAT)-functionalized Bodipy dyes were prepared by a sequence of reactions involving either cross-coupling reactions promoted by Pd complexes or a Knoevenagel reaction leading to a vinyl linker. The new dyes show large absorption coefficients and fluorescence quantum yields as well as interesting electrochemical properties. The blue dyes of this series exhibit interesting photovoltaic effects (V(OC) = 0.83 V, J(SC) = 3.6 mA/cm(2), efficiency 0.9%) in bulk heterojunction solar cells, due to the good hole mobility imported by the TAT entity.     

应用于染料敏化太阳能电池的基于染料R6的含有不同吸电子基团的有机染料的理论研究

Dye-sensitized solar cells (DSSCs) are the most promising alternatives to traditional fossil energy because of their advantages of low production cost, facile structure, relatively low environmental impact, relatively high photoelectronic absorption efficiency, and overall high efficiency. In addition, several studies on sensitizers as vital components have been conducted over the last three decades. Compared to metal dyes, metal-free organic dyes have been considered as promising candidates because of their simple fabrication, multiple structures, high molar absorption coefficients, easily tunable properties, and environmental friendliness. In this study, we systematically investigated the optoelectronic properties of six metal-free organic donor-acceptor dyes (RD1–6) derived from the known dye R6 by using the density functional theory (DFT) and time-dependent DFT methods. Cell performance parameters were discussed, including the geometrical and electronic structures, absorption spectrum, adsorption energy, light harvesting efficiency (LHE) curve, predictive short circuit current density (J_sc^Pred.), predictive open circuit voltage (V_oc^Pred.), and theoretical power conversion efficiency (PCE). Results revealed that all the designed dyes exhibited high theoretical PCE. In particular, dyes RD1, 2, and 4–6 showed greater conjugations, and dyes RD1–3 had smaller energy gaps than those of the reference dye. In addition, dyes RD1–3, 5, and 6 exhibited better light harvesting capacities that covered the entire visible region and extended to the near-infrared region with obviously red-shift maximum absorption wavelengths (λ_max), wider LHE curves, and higher J_sc^Pred. as compared to the reference dye. It was critical that dyes RD1 and 2 not only have greater conjugations and narrow band gaps but also good light harvesting capacities with more than 56-nm red-shift maximum absorption wavelengths and broadened LHE curves than those of the reference dye. Notably, mainly because of an average increment of 12.0% of J_sc^Pred., a remarkable increment of the theoretical power conversion efficiency was observed from 12.6% for dye R6 to 14.1% for dyes RD1 and 2. Thus, dyes RD1 and 2 exhibited superior cell performances and could be promising sensitizer candidates for highly efficient DSSCs. These results could be used to guide effective synthetic efforts in the discovery of efficient metal-free organic dye sensitizers in DSSCs.     

Comparing spiro-OMeTAD and P3HT hole conductors in efficient solid state dye-sensitized solar cells

Two hole conductor materials, spiro-OMeTAD and P3HT, were compared in solid-state dye-sensitized solar cells. Two organic dyes containing one anchor unit (D35) or two anchor units (M3) were used in the comparison. Absorbed photon to current conversion efficiency close to unity was obtained for the devices with spiro-OMeTAD. Energy conversion efficiencies of 4.7% and 4.9% were measured for the devices with spiro-OMeTAD and the dyes D35 and M3, respectively. For the devices using the P3HT hole conductor the results were rather different comparing the two dye molecules, with energy conversion efficiencies of 3.2% and 0.5% for D35 and M3, respectively. Photo-induced absorption measurements suggest that the regeneration of the dyes, and the polymer infiltration, is not complete using P3HT, while spiro-OMeTAD regenerates the dyes efficiently. However, the TiO(2)/D35/P3HT system shows rather high energy conversion efficiency and electrochemical oxidation of the dyes on TiO(2) indicates that D35 have a more efficient dye to dye hole conduction than M3, which thereby might explain the higher performance. The dye hole conduction may therefore be of significant importance for optimizing the energy conversion in such hybrid TiO(2)/dye/polymer systems.     

Modulation of photovoltaic behavior of dye-sensitized solar cells by electron donors of porphyrin dyes and cosensitization

Porphyrin dyes have received great attention due to their excellent photovoltaic performance in dyesensitized solar cells(DSSCs). In this work, dyes XC1–XC3 were synthesized by introducing various numbers of bis(4-methoxyphenyl)amino and p-hexyloxyphenyl groups to porphyrin meso-positions.The XC1 molecule contains two p-hexyloxyphenyl groups, and its DSSCs showed the power conversion efficiency of 4.81%. For XC2 and XC3, the replacement of p-hexyloxyphenyl with diphenylamino groups can effectively enhance the light harvesting around 500 nm. However, the highest occupied molecular orbitals(HOMOs) were elevated too much, which suppressed the dye regeneration processes, leading to low cell efficiencies of 2.51% and 1.27% for XC2, and XC3, respectively. To further improve the cell performance, an anthracene derivative C1 was used as the cosensitizer for XC1, which increased both the Jscand Vocvalues, with an improved efficiency of 5.75%.     

Synthesis and Photovoltaic Properties of Boron β‐Ketoiminate Dyes Forming a Linear Donor‐π‐Acceptor Structure

Organoboron complexes are of interest as chromophores for dye sensitizers owing to their light‐harvesting and carrier‐transporting properties. In this study, compounds containing boron β‐ketoiminate (BKI) as a chromophore were synthesized and used as dye sensitizers in dye‐sensitized solar cells. The new dyes were orange or red crystals and showed maximum absorptions in the 410–450 nm wavelength region on titanium dioxide substrates. These electrodes exhibited maximum efficiencies of over 80% in incident photon‐to‐current conversion efficiency spectra, suggesting that the continuous process of light absorption‐excitation‐electron injection was effectively performed. Open‐circuit photovoltages were relatively high owing to the large dipole moments of the BKI dyes with a linear molecular structure. Thus, a maximum power conversion efficiency of 5.3% was successfully observed. Comparison of BKI dyes with boron β‐diketonate dyes revealed certain differences in solution stability, spectral properties, and photovoltaic characteristics.     

Synthesis and photovoltaic properties of efficient organic dyes containing the benzo[b]furan moiety for solar cells

New organic dyes composed of the benzo[b]furan donor, thiophene-conjugated bridge, and cyano acrylic acid acceptor have been newly synthesized through the one-pot coupling cyclization key step. Nanocrystalline TiO2 dye-sensitized solar cell was fabricated using this dye. A solar-to-electric conversion efficiency of 6.65% and 4.70% is achieved with 1 and 2, respectively.     

Novel organic dyes for efficient dye-sensitized solar cells

Two novel metal-free organic dyes containing thienothiophene and thiophene segments have been synthesized. Nano-crystalline TiO2 dye-sensitized solar cells were fabricated using these dyes as light-harvesting sensitizers, and a high solar energy-to-electricity conversion efficiency of 6.23% was achieved.