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.     

Photovoltaic Performance of Triphenylamine Dyes-sensitized Solar Cells Employing Cobalt Redox Shuttle and Influence of π-conjugated Spacers

Developing photosensitizers suitable for the cobalt electrolyte and understanding the structure-property relationship of organic dyes is warranted for the dye-sensitized solar cells (DSSCs). The DSSCs incorporating tris(1,10-phenanthroline)cobalt(II/III)-based redox elec-trolyte and four synthesized organic dyes as photosensitizers are described. The photovoltaic performance of these dyes-sensitized solar cells employing the cobalt redox shuttle and the influences of the π-conjugated spacers of organic dyes upon the photovoltage and photocur-rent of mesoscopic titania solar cells are investigated. It is found that organic dyes with thiophene derivates as linkers are suitable for DSSCs employing cobalt electrolytes. DSSCs sensitized with the as-synthesized dyes in combination with the cobalt redox shuttle yield an overall power conversion efficiency of 6.1% under 100 mW/cm² AM1.5 G illumination.     

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 organic dye sensitizers containing fluorenyl and biphenyl moieties for solar cells

Three novel triarylamine dyes(AFL1-AFL3) containing fluorenyl and the biphenyl moieties have been designed and synthesized for application in dye-sensitized solar cells.The light-harvesting capabilities and photovoltaic performance of these dyes were investigated systematically through comparison of different π-bridges.The dye with a furan linker exhibited a higher open-circuit voltage(V_(OC)) and monochromatic incident photon-to-current conversion efficiency(IPCE) compared to thiophene and benzene linker.Thus,AFL3 containing a furan linker exhibited the maximum overall conversion efficiency of 5.81%(V_(OC) = 760 mV,J_(SC) = 11.36 mA cm~2 and ff=0.68) under standard global AM 1.5 G solar condition.     

High-Performance Dipolar Organic Dyes with an Electron-Deficient Diphenylquinoxaline Moiety in the π-Conjugation Framework for Dye-Sensitized Solar Cells

We report here the synthesis and electrochemical and photophysical properties of a series of easily prepared dipolar organic dyes and their application in dye-sensitized solar cells (DSSCs). For the six organic dyes, the molecular structures comprised a triphenylamine group as an electron donor, a cyanoacrylic acid as an electron acceptor, and an electron-deficient diphenylquinoxaline moiety integrated in the π-conjugated spacer between the electron donor and acceptor moieties. The incorporation of the electron-deficient diphenylquinoxaline moiety effectively reduces the energy gap of the dyes and broadly extends the spectral coverage. DSSCs based on dye 6 produced the best overall cell performance of 7.35?%, which translates to approximately 79?% of the intrinsic efficiency of the DSSCs based on the standard N719 dye under identical experimental conditions. The high performance of DSSCs based on dye 6 among the six dyes explored is attributed to the combined effects of high dye loading on a TiO(2) surface, rapid dye regeneration, and effective retardation of charge recombination.     

Rapid Synthesis of Thiophene‐Based,Organic Dyes for Dye‐Sensitized Solar Cells (DSSCs) by a One‐Pot,Four‐Component Coupling Approach

This one‐pot, four‐component coupling approach (Suzuki–Miyaura coupling/C?H direct arylation/Knoevenagel condensation) was developed for the rapid synthesis of thiophene‐based organic dyes for dye‐sensitized solar cells (DSSCs). Seven thiophene‐based, organic dyes of various donor structures with/without the use of a 3,4‐ethylenedioxythiophene (EDOT) moiety were successfully synthesized in good yields based on a readily available thiophene boronic acid pinacol ester scaffold (one‐pot, 3‐step, 35–61 %). Evaluation of the photovoltaic properties of the solar cells that were prepared using the synthesized dyes revealed that the introduction of an EDOT structure beside a cyanoacrylic acid moiety improved the short‐circuit current (J_sc) while decreasing the fill factor (FF). The donor structure significantly influenced the open‐circuit voltage (V_oc), the FF, and the power conversion efficiency (PCE). The use of a n‐hexyloxyphenyl amine donor, and our originally developed, rigid, and nonplanar donor, both promoted good cell performance (η=5.2–5.6 %).     

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.     

Starburst triarylamine based dyes for efficient dye-sensitized solar cells

We report here on the synthesis and photophysical/electrochemical properties of a series of novel starburst triarylamine-based organic dyes (S1, S2, S3, and S4) as well as their application in dye-sensitized nanocrystalline TiO2 solar cells (DSSCs). For the four designed dyes, the starburst triarylamine group and the cyanoacetic acid take the role of electron donor and electron acceptor, respectively. It was found that the introduction of starburst triarylamine group to form the D-D-pi-A configuration brought about superior performance over the simple D-pi-A configuration, in terms of bathochromically extended absorption spectra, enhanced molar extinction coefficients and better thermo-stability. Moreover, the HOMO and LUMO energy levels tuning can be conveniently accomplished by alternating the donor moiety, which was confirmed by electrochemical measurements and theoretical calculations. The DSSCs based on the dye S4 showed the best photovoltaic performance: a maximum monochromatic incident photon-to-current conversion efficiency (IPCE) of 85%, a short-circuit photocurrent density (J(sc)) of 13.8 mA cm(-2), an open-circuit photovoltage (V(oc)) of 0.63 V, and a fill factor (ff) of 0.69, corresponding to an overall conversion efficiency of 6.02% under 100 mW cm(-2) irradiation. This work suggests that the dyes based on starburst triphenylamine donor are promising candidates for improvement of the performance of the DSSCs.     

Highly efficient organic indolocarbazole dye in different acceptor units for optoelectronic applications—a first principle study

A series of novel organic dyes (ICZA1, ICZA2, ICZA3, ICZA4) with D-π-A structural configuration incorporating indolo[3,2,1-jk]carbazole moiety as donor (D) unit, thiophene as π-linker and 2-cyanoacrylic acid as acceptor unit were investigated using density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. Indolo[3,2,1-jk]carbazole-based D-π-A dyes composed of different acceptor groups were designed. By modulating acceptor unit, the efficiency of D-π-A dye-based dye-sensitized solar cells (DSSCs) can be further improved. In the present work, four novel push-pull organic dyes only differing in electron acceptor, have been designed based on the experimental literature value of IC-2. In order to further improve the light harvesting capability of indolo[3,2,1-jk]carbazole dyes, the acceptor influence on the dye performance were examined. The NLO property of the designed dye molecules can be derived as polarizability and hyperpolarizability. The calculated value of ICZA2 dye is the best candidate for NLO properties. Furthermore, the designed organic dyes exhibit good photovoltaic performance of charge transfer characteristics, driving force of electron injection, dye regeneration, global reactivity, and light harvesting efficiency (LHE). From the calculated value of ICZA4 dye, it has been identified as a good candidate for DSSCs applications. Finally, it is concluded that the both ICZA2 and ICZA4 dyes theoretically agrees well with the experimental value of IC-2 dye. Hence, the dyes ICZA2 and ICZA4 can serve as an excellent electron withdrawing groups for NLO and DSSCs applications.     

Enhancements of Trifluoroacetic Acylated Five‐membered Heterocyclic Compounds Using as Additives in Dye Sensitized Solar Cells

In this study, five‐membered heterocyclic compounds are trifluoroacetic acylated for the purpose of providing more long pairs to enhance electrolyte in dye sensitized solar cells (DSSCs). Four five‐membered heterocyclic compounds will be trifluoroacetic acylated with trifluoroacetic anhydride by Friedel‐Crafts acylation: furan, thiophene, pyrrole and N‐methylpyrrole. The properties will be measured by cyclic voltage (CV), Fourier transform infrared spectroscopy (FTIR), solar simulator, and electrochemical impedance spectroscopy (EIS). We find out that furan and thiophene which we add in electrolyte as additives can increase short circuit current and photovoltaic efficiency, and furthermore, all the trifluoroacetic acylated heterocyclic compounds perform better photoelectric abilities than non‐trifluoroacetic acylated one. The photovoltaic efficiency will be increased from 4.439% to 5.197% when 1wt% trifluoroacetic acylated thiophene is added in electrolyte as additives.     

Novel carboxylated oligothiophenes as sensitizers in photoelectric conversion systems

Novel carboxylated oligothiophenes with different thiophene units were designed and synthesized as photosensitizers in dye-sensitized solar cells (DSSCs) for efficient opto-electric materials. The introduction of -COOH into thiophene molecules can lead to a red shift of UV-visible absorption, increase light-harvesting efficiency, and enhance photoinduced charge transport by forming efficient covalent bonds to the substrate surface. A red shift of the absorption spectrum of oligothiophene is also achieved by the increase in the number of thiophene units. The DSSCs based on the oligomers have excellent photovoltaic performances. Under 100 mW cm(-2) irradiation a short-circuit current of 10.57 mA cm(-2) and an overall energy conversion efficiency of 3.36 % is achieved when pentathiophene dicarboxylated acid was used as a sensitizer. The incident photo-to-current conversion efficiency (IPCE) has a maximum as high as 80 %. In addition, photovoltage and photocurrent transients show that slow charge recombination in DSSCs is important for efficient charge separation and excellent photoelectric conversion properties of the oligomers. These initial and promising results suggest that carboxylated oligothiophenes are efficient photosensitizers.     

Fine-tuning the Electronic Structure of Organic Dyes for Dye-Sensitized Solar Cells

A series of metal-free organic dyes exploiting different combinations of (hetero)cyclic linkers (benzene, thiophene, and thiazole) and bridges (4H-cyclopenta[2,1-b:3,4-b']dithiophene (CPDT) and benzodithiophene (BDT)) as the central π-spacers were synthesized and characterized. Among them, the sensitizer containing the thiophene and CPDT showed the most broad incident photon-to-current conversion efficiency spectra, resulting in a solar energy conversion efficiency (η) of 6.6%.     

Dye‐Sensitized Solar Cells Based on (Donor‐π‐Acceptor)2 Dyes With Dithiafulvalene as the Donor

Dipolar metal‐free sensitizers (D‐π‐A; D=donor, π=conjugated bridge, A=acceptor) consisting of a dithiafulvalene (DTF) unit as the electron donor, a benzene, thiophene, or fluorene moiety as the conjugated spacer, and 2‐cyanoacrylic acid as the electron acceptor have been synthesized. Dimeric congeners of these dyes, (D‐π‐A)₂, were also synthesized through iodine‐induced dimerization of an appropriate DTF‐containing segment. Dye‐sensitized solar cells (DSSCs) with the new dyes as the sensitizers have cell efficiencies that range from 2.11 to 5.24 %. In addition to better light harvesting, more effective suppression of the dark current than the D‐π‐A dyes is possible with the (D‐π‐A)₂ dyes.     

Unsymmetric Platinum(II) Bis(aryleneethynylene) Complexes as Photosensitizers for Dye‐Sensitized Solar Cells

Four new unsymmetric platinum(II) bis(aryleneethynylene) derivatives have been designed and synthesized, which showed good light‐harvesting capabilities for application as photosensitizers in dye‐sensitized solar cells (DSSCs). The absorption, electrochemical, time‐dependent density functional theory (TD‐DFT), impedance spectroscopic, and photovoltaic properties of these platinum(II)‐based sensitizers have been fully characterized. The optical and TD‐DFT studies show that the incorporation of a strongly electron‐donating group significantly enhances the absorption abilities of the complexes. The maximum absorption wavelength of these four organometallic dyes can be tuned by various structural modifications of the triphenylamine and/or thiophene electron donor, improving the light absorption range up to 650 nm. The photovoltaic performance of these dyes as photosensitizers in mesoporous TiO₂ solar cells was investigated, and a power conversion efficiency as high as 1.57 % was achieved, with an open‐circuit voltage of 0.59 V, short‐circuit current density of 3.63 mA cm^?2, and fill factor of 0.73 under simulated AM 1.5G solar illumination.     

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.     

Thiophene-fused coplanar sensitizer for dye-sensitized solar cells

We have designed and synthesized a novel ladder-type heteroacene dye consisting uniquely of thiophene segments as a photosensitizer for the dye-sensitized solar cells (DSSCs). The onset of the IPCE spectrum for the dye not only reaches up to 700 nm with a high IPCE (>60%) but also a solar energy-to-electricity conversion efficiency of 2.31% is achieved. Even though the efficiency is slightly lower than those of other dyes reported previously, this work opens up a new strategy to design heteroaromatic fused photosensitizers for DSSCs.     

Adamantyl Side Chains as Anti-Aggregating Moieties in Dyes for Dye-Sensitized Solar Cells

Designing and evaluating novel dye concepts is crucial for the development of the field of dye-sensitized solar cells (DSSCs). In our recent report, the novel concept of tethering the anti-aggregation additive chenodeoxycholic acid (CDCA) to dyes for DSSC was introduced. Based on the performance improvements seen for this modification, the aim of this study is to see if a simplified anti-aggregation unit could achieve similar results. The following study reports the synthesis and photovoltaic characterization of two novel dyes decorated with the steric ethyladamantyl moiety on the π-spacer, and on the triarylamine donor. This modification is demonstrated to be successful in increasing the photovoltages in devices employing copper-based electrolytes compared to the non-modified reference dye. The best photovoltaic performance is achieved by a device prepared with the adamantyl decorated donor dye and CDCA, this device achieves a power conversion efficiency of 6.1 % (Short-circuit current=8.3 mA cm⁻², Open-circuit voltage=1054 mV, Fill factor=0.69). The improved photovoltaic performance seen for the adamantyl decorated donor demonstrate the potential of ethyladamantyl side chains as a tool to ensure surface protection of TiO₂.     

Constructing organic D-A-π-A-featured sensitizers with a quinoxaline unit for high-efficiency solar cells: the effect of an auxiliary acceptor on the absorption and the energy level alignment

Four organic D-A-π-A-featured sensitizers (TQ1, TQ2, IQ1, and IQ2) have been studied for high-efficiency dye-sensitized solar cells (DSSCs). We employed an indoline or a triphenylamine unit as the donor, cyanoacetic acid as the acceptor/anchor, and a thiophene moiety as the conjugation bridge. Additionally, an electron-withdrawing quinoxaline unit was incorporated between the donor and the π-conjugation unit. These sensitizers show an additional absorption band covering the broad visible range in solution. The contribution from the incorporated quinoxaline was investigated theoretically by using DFT and time-dependent DFT. The incorporated low-band-gap quinoxaline unit as an auxiliary acceptor has several merits, such as decreasing the band gap, optimizing the energy levels, and realizing a facile structural modification on several positions in the quinoxaline unit. As demonstrated, the observed additional absorption band is favorable to the photon-to-electron conversion because it corresponds to the efficient electron transitions to the LUMO orbital. Electrochemical impedance spectroscopy (EIS) Bode plots reveal that the replacement of a methoxy group with an octyloxy group can increase the injection electron lifetime by a factor of 2.4. IQ2 and TQ2 can perform well without any co-adsorbent, successfully suppress the charge recombination from TiO(2) conduction band to I(3)(-) in the electrolyte, and enhance the electron lifetime, resulting in a decreased dark current and enhanced open circuit voltage (V(oc)) values. By using a liquid electrolyte, DSSCs based on dye IQ2 exhibited a broad incident photon-to-current conversion efficiency (IPCE) action spectrum and high efficiency (η=8.50?%) with a short circuit current density (J(sc)) of 15.65?mA?cm(-2), a V(oc) value of 776?mV, a fill factor (FF) of 0.70 under AM 1.5 illumination (100?mW?cm(-2)). Moreover, the overall efficiency remained at 97% of the initial value after 1000?h of visible-light soaking.     

Synthesis and photovoltaic properties of new [1,2,5]thiadiazolo[3,4-c]pyridine-based organic Broadly absorbing sensitizers for dye-sensitized solar cells

In this paper, by introducing [1,2,5]thiadiazolo[3,4-c]pyridine (PT) as an auxiliary acceptor into the molecular design of organic sensitizers, we have synthesized four new dyes (PT1–PT4) for dye-sensitized solar cells (DSSCs) with triphenylamine or N,N-diphenylthiophen-2-amine as the donor units and thiophene or benzene as the π-bridges, respectively. All the structures, optical and electrochemical properties were fully characterized. Nanocrystalline TiO₂ dye-sensitized solar cells were also fabricated using these dyes. Among them, PT2-based DSSCs showed the highest overall conversion efficiency of 6.11% with V_oc=668 mV, J_sc=12.61 mA cm⁻² and a fill factor (FF)=0.74 after a chenodeoxycholic acid (CDCA) treatment under standard illumination condition (100 mW cm⁻² simulated AM 1.5 solar light).