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1.
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.  相似文献   

2.
Benzimidazole‐branched bi‐anchoring organic dyes that contained triphenylamine/phenothiazine donors, 2‐cyanoacrylic acid acceptors, and various π linkers were synthesized and examined as sensitizers for dye‐sensitized solar cells. The structure–activity relationships in these dyes were systematically investigated by using absorption spectroscopy, cyclic voltammetry, and density functional theory calculations. The wavelength of the absorption peak was more‐heavily influenced by the nature of the π linker than by the nature of the donor. For a given donor, the absorption maximum (λmax) was red‐shifted on changing the π linker from phenyl to 2,2′‐bithiophene, whilst the dyes that contained triphenylamine units displayed higher molar extinction coefficients (?) than their analogous phenothiazine‐based triphenylamine dyes, which led to good light‐harvesting properties in the triphenylamine‐based dyes. Electrochemical data for the dyes indicated that the triphenylamine‐based dyes possessed relatively low‐lying HOMOs, which could be beneficial for suppressing back electron transfer from the conduction band of TiO2 to the oxidized dyes, owing to facile regeneration of the oxidized dye by the electrolyte. The best performance in the DSSCs was observed for a dye that possessed a triphenylamine donor and 2,2′‐bithiophene π linkers. Electron impedance spectroscopy (EIS) studies revealed that the use of triphenylamine as the donor and phenyl or 2,2′‐bithiophene as the π linkers was beneficial for disrupting the dark current and charge‐recombination kinetics, which led to a long electron lifetime of the injected electrons in the conduction band of TiO2.  相似文献   

3.
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 TiO2 conduction band to I3? in the electrolyte, and enhance the electron lifetime, resulting in a decreased dark current and enhanced open circuit voltage (Voc) 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 (Jsc) of 15.65 mA cm?2, a Voc 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.  相似文献   

4.
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 TiO2 surface, rapid dye regeneration, and effective retardation of charge recombination.  相似文献   

5.
Organic dyes that contain a 2,7‐diaminofluorene‐based donor, a cyanoacrylic‐acid acceptor, and various aromatic conjugation segments, which are composed of benzene, fluorene, carbazole, and thiophene units, as a π‐bridge have been synthesized and characterized by optical, electrochemical, and theoretical investigations. The trends in the absorption and electrochemical properties of these dyes are in accordance with the electron‐donating ability of the conjugating segment. Consequently, the dyes that contained a 2,7‐carbazole unit in the π‐spacer exhibited red‐shifted absorption and lower oxidation potentials than their corresponding fluorene‐ and phenylene‐bridged dyes. However, the enhanced power‐conversion efficiency that was exhibited by the fluorene‐bridged dyes in the DSSCs was attributed to their broader and intense absorption. Despite the longer‐wavelength absorption and reasonable optical density, carbazole‐bridged dyes exhibited lower power‐conversion efficiencies, which were ascribed to the poor alignment of the LUMO level in these dyes, thereby leading to the inhibition of electron injection into the TiO2 conduction band.  相似文献   

6.
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.  相似文献   

7.
Due to the ease of tuning its redox potential, the cobalt‐based redox couple has been extensively applied for highly efficient dye‐sensitized solar cells (DSSCs) with extraordinarily high photovoltages. However, a cobalt electrolyte needs particular structural changes in the organic dye components to obtain such high photovoltages. To achieve high device performance, specific requirements in the molecular tailoring of organic sensitizers still need to be met. Besides the need for large electron donors, studies of the auxiliary acceptor segment of donor–acceptor–π‐acceptor (D‐A‐π‐A) organic sensitizers are still rare in molecular optimization in the context of cobalt electrolytes. In this work, two novel organic D‐A‐π‐A‐type sensitizers ( IQ13 and IQ17 ) have been developed and exploited in cobalt‐ and iodine‐based redox electrolyte DSSCs, specifically to provide insight into the effect of π‐bridge modification in different electrolytes. The investigation has been focused on the additional electron‐withdrawing acceptor capability with grafted long alkoxy chains. Optoelectronic transient measurements have indicated that IQ17 containing a pyrido[3,4‐b]pyrazine moiety bearing long alkoxyphenyl chains is more suitable for application in cobalt‐based DSSCs.  相似文献   

8.
In an attempt to shed light on how the addition of a benzothiadiazole (BTD) moiety influences the properties of dyes, a series of newly designed triphenylamine‐based sensitizers incorporating a BTD unit as an additional electron‐withdrawing group in a specific donor–acceptor–π‐acceptor architecture has been investigated. We found that different positions of the BTD unit provided significantly different responses for light absorption. Among these, it was established that the further the BTD unit is away from the donor part, the broader the absorption spectra, which is an observation that can be applied to improve light‐harvesting ability. However, when the BTD unit is connected to the anchoring group a faster, unfavorable charge recombination takes place; therefore, a thiophene unit was inserted between these two acceptors, providing redshifted absorption spectra as well as blocking unfavorable charge recombination. The results of our calculations provide valuable information and illustrate the potential benefits of using computation‐aided sensitizer design prior to further experimental synthesis.  相似文献   

9.
Thieno[3,4‐c]pyrrole‐4,6‐dione‐based organic sensitizers with triphenylamine ( FNE38 and FNE40 ) or julolidine ( FNE39 and FNE41 ) as electron‐donating unit have been designed and synthesized. A linear hexyl group or a branched alkyl chain, the 2‐ethylhexyl group, is incorporated into molecular skeleton of the dyes to minimize intermolecular interactions. The absorption, electrochemical, and photovoltaic properties for these sensitizers were then systematically investigated. It is found that the sensitizers have similar photophysical and electrochemical properties, such as absorption spectra and energy levels, owing to their close chemical structures. However, the quasi‐solid‐state dye‐sensitized solar cells (DSSCs) based on the two types of sensitizers exhibit very different performance parameters. Upon the incorporation of the short ethyl group on the hexyl moiety, enhancements in both open‐circuit voltage (Voc) and short‐circuit current (Jsc) are achieved for the quasi‐solid‐state DSSCs. The Voc gains originating from the suppression of charge recombination were quantitatively investigated and are in good agreement with the experimentally observed Voc enhancements. Therefore, an enhanced solar energy conversion efficiency (η) of 6.16 %, constituting an increase by 23 %, is achieved under standard AM 1.5 sunlight without the use of coadsorbant agents for the quasi‐solid‐state DSSC based on sensitizer FNE40 , which bears the branched alkyl group, in comparison with that based on FNE38 carrying the linear alkyl group. This work presents a design concept for considering the crucial importance of the branched alkyl substituent in novel metal‐free organic sensitizers.  相似文献   

10.
A series of metal‐free organic donor–π bridge–acceptor dyes are studied computationally using density functional theory (DFT) and time‐dependent DFT (TDDFT) approaches to explore their potential performances in dye‐sensitized solar cells (DSSCs). Taking triphenylamine (TPA) and cyanoacrylic acid moieties as donor and acceptor units, respectively, the effects of different substituents of the π linkers in the TPA‐based dyes on the energy conversion efficiency of the DSSCs are theoretically evaluated through optimized geometries, charge distributions, electronic structures, simulated absorption spectra, and free energies of injection. The results show that the molecular orbital energy levels and electron‐injection driving forces of the TPA dyes can be tuned by the introduction of substituents with different electron‐withdrawing or ‐donating abilities. The electron‐withdrawing substituent always lowers the energies of both frontier orbitals, while the electron‐donating one heightens them simultaneously. The efficiency trend of these TPA derivatives as sensitizers in DSSCs is also predicted by analyzing the light‐harvesting efficiencies and the free energies of injection. The following substituents are shown to increase the efficiency of the dye: OMe, OEt, OHe, and OH.  相似文献   

11.
A series of porphyrin sensitizers that featured two electron‐donating groups and dual anchoring groups that were connected through a porphine π‐bridging unit have been synthesized and successfully applied in dye‐sensitized solar cells (DSSCs). The presence of electron‐donating groups had a significant influence on their spectroscopic, electrochemical, and photovoltaic properties. Overall, the dual anchoring groups gave tunable electronic properties and stronger attachment to TiO2. These new dyes were readily synthesized in a minimum number of steps in gram‐scale quantities. Optical and electrochemical data confirmed the advantages of these dyes for use as sensitizers in DSSCs. Porphyrins with electron‐donating amino moieties provided improved charge separation and better charge‐injection efficiencies for the studied dual‐push–pull dyes. Attenuated total reflectance–Fourier‐transform infrared (ATR‐FTIR) and X‐ray photoelectron spectroscopy of the porphyrin dyes on TiO2 suggest that both p‐carboxyphenyl groups are attached onto TiO2, thereby resulting in strong attachment. Among these dyes, cis-Zn2BC2A , with two electron‐donating 3,6‐ditertbutyl‐phenyl‐carbazole groups and dual‐anchoring p‐carboxyphenyl groups, showed the highest efficiency of 4.07 %, with JSC=9.81 mA cm?2, VOC=0.63 V, and FF=66 %. Our results also indicated a better photostability of the studied dual‐anchored sensitizers compared to their mono‐anchored analogues under identical conditions. These results provide insight into the developments of a new generation of high‐efficiency and thermally stable porphyrin sensitizers.  相似文献   

12.
A series of novel metal‐free organic dyes containing the thiazolo[5,4‐d]thiazole moiety were designed and synthesized for quasi‐solid‐state dye‐sensitized solar cells (DSSCs). Different alkoxy chains were introduced into the electron donor part of the dye molecules for comparison. The optical, electrochemical, and photovoltaic properties for all sensitizers were systematically investigated. It was found that the sensitizers with the different alkoxy groups have similar photophysical and electrochemical properties, such as absorbance and energy levels, owing to their close chemical structures. However, the quasi‐solid‐state DSSCs based on the resulting sensitizers exhibit different performance parameters. The quasi‐solid‐state DSSC based on sensitizer FNE74 with two octyloxy chains possessed the highest solar energy conversion efficiency of 5.10 % under standard AM 1.5G sunlight illumination without the use of coadsorbant agents.  相似文献   

13.
(Dibenzoylmethanato)boron difluoride derivatives containing triphenylamine moieties were synthesized as a new type of electron‐donor/π‐acceptor system. These new compounds exhibited long‐wavelength absorptions in the UV/Vis spectra, and reversible oxidation and reduction waves in cyclic voltammetry experiments. Their amphoteric redox properties are based on their resonance hybrid forms, in which a positive charge is delocalized on the triphenylamine moieties and a negative charge is localized on the boron atoms. Molecular orbital (MO) calculations indicate that their HOMO and LUMO energies vary with the number of phenylene rings connected to the difluoroboron‐chelating ring. This is useful for optimizing the HOMO and LUMO levels to an iodine redox (I?/I3?) potential and a titanium dioxide conduction band, respectively. Dye‐sensitized solar cells fabricated by using these compounds as dye sensitizers exhibited solar‐to‐electric power conversion efficiencies of 2.7–4.4 % under AM 1.5 solar light.  相似文献   

14.
New organic dyes containing pyrenylamine donors in a cascade arrangement and cyanoacrylic acid acceptors have been synthesized and characterized by optical, electrochemical, and theoretical studies. The dyes inherit a D ‐π1‐D ‐π2‐A (D=donor, A=acceptor) molecular architecture where the π linkers π1 are changed from phenyl to biphenyl and fluorene, whereas the π linker π2 that connects the donor fragment with the acceptor is a phenyl unit. The conjugation pathway linking the two donor segments has been found to play a major role in the optical and electrochemical properties. Shorter π linkers such as phenyl groups facilitate the donor–acceptor interaction while the nonplanar biphenyl spacer decreases the electronic communication between the donors and enhances the oxidation propensity of the corresponding dye. All the dyes display an intense longer wavelength electronic transition,which is attributable to the amine‐to‐cyanoacrylic acid charge transfer. The extinction coefficient of this peak grows dramatically on increasing the conjugation pathway length between the two donor segments. The dyes were used as sensitizers in nanocrystalline TiO2‐based dye‐sensitized solar cells (DSSCs) and the cascade donor system contributed to the enhancement in the device efficiency due to favorable absorption and redox properties.  相似文献   

15.
A conjugated polymer containing an electron donating backbone (triphenylamine) and an electron accepting side chain (cyanoacetic acid) with conjugated thiophene units as the linkers has been synthesized. Dye‐sensitized solar cells (DSSCs) are fabricated utilizing this material as the dye sensitizer, resulting a typical power conversion efficiency of 3.39% under AM 1.5 G illumination, which represents the highest efficiency for polymer dye‐sensitized DSSCs reported so far. The results show the good promise of conjugated polymers as sensitizers for DSSC applications.

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16.
With perovskite‐based solar cells (PSCs) now reaching efficiencies of greater than 20 %, the stability of PSC devices has become a critical challenge for commercialization. However, most efficient hole‐transporting materials (HTMs) thus far still rely on the state‐of‐the‐art methoxy triphenylamine (MOTPA) donor unit in which methoxy groups usually reduce the device stability. Herein, a carbazole‐fluorene hybrid has been employed as a methoxy‐free donor to construct organic HTMs. The indeno[1,2‐b]carbazole group not only inherits the characteristics of carbazole and fluorene, but also exhibits additional advantages arising from the bulky planar structure. Consequently, M129, endowed with indeno[1,2‐b]carbazole simultaneously exhibits a promising efficiency of over 20 % and superior long‐term stability. The hybrid strategy toward the methoxy‐free donor opens a new avenue for developing efficient and stable HTMs.  相似文献   

17.
Four novel donor ? π‐bridge ? acceptor (D ? π ? A) polymeric metal complexes (P1–P4) based on 8‐hydroxyquinoline metal complexes were synthesized and tested for their performance in dye‐sensitized solar cells (DSSCs). The polymeric metal complexes dyes use alkoxy benzene or alkyl fluorene as the electron donor and C=C as π linker; the 8‐hydroxyquinoline derivative complex part was used as the electron acceptor and diaminomaleonitrile was used as ancillary ligand. The two strongly electron‐withdrawing cyano groups in the polymer structure can provide an efficient charge transport in the intramolecular between donor and acceptor parts. The thermal, photophysical, electrochemical and photovoltaic properties of these copolymers were investigated by TGA, differential scanning calorimetry, cyclic voltammetry and cureent density‐voltage curves, and the results showed that dye containing complex Zn(II) and alkoxy benzene unit benefited the generation of photocurrent and open‐circuit voltages, and a maximum power conversion efficiency of 1.91% (P2) was obtained, with an open‐circuit voltage of 0.71 V, a short‐circuit current density of 4.23 mA cm?2, and a fill factor of 38.6% under AM1.5G irradiation. The study results also show that the four polymers exhibit good thermal stability, indicating that these polymeric metal complexes are suitable for the fabrication processes of optoelectronic devices. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

18.
The high performances of dye‐sensitized solar cells (DSSCs) based on seven new dyes are disclosed. Herein, the synthesis and electrochemical and photophysical properties of a series of intentionally designed dipolar organic dyes and their application in DSSCs are reported. The molecular structures of the seven organic dyes are composed of 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 DSSCs based on the dye DJ104 gave the best overall cell performance of 8.06 %; the efficiency of the DSSC based on the standard N719 dye under the same experimental conditions was 8.82 %. The spectral coverage of incident photon‐to‐electron conversion efficiencies extends to the onset at the near‐infrared region due to strong internal charge‐transfer transition as well as the effect of electron‐deficient diphenylquinoxaline to lower the energy gap in these organic dyes. A combined tetraphenyl segment as a hydrophobic barrier in these organic dyes effectively slows down the charge recombination from TiO2 to the electrolyte and boosts the photovoltage, comparable to their RuII counterparts. Detailed spectroscopic studies have revealed the dye structure–cell performance correlations, to allow future design of efficient light‐harvesting organic dyes.  相似文献   

19.
The syntheses of [3]‐ and [4]cyclo‐9,9‐dimethyl‐2,7‐fluorenes ([3] and [4]CFRs), cyclic trimer, and tetramers of 9,9‐dimethyl‐2,7‐fluorene (FR), respectively, were achieved by the platinum‐mediated assembly of FR units and subsequent reductive elimination of platinum. A triangle‐shaped tris‐platinum complex and a square‐shaped tetra‐platinum complex were obtained by changing the platinum ligand. The structure of the triangle complex was unambiguously determined by X‐ray crystallographic analysis. Reductive elimination of each complex gave [3] and [4]CFRs. Two rotamers of [3]CFR were sufficiently stable at room temperature and were separated by chromatography. The physical properties of the CFRs were also investigated theoretically and experimentally.  相似文献   

20.
Two donor–acceptor molecular tweezers incorporating the 10‐(1,3‐dithiol‐2‐ylidene)anthracene unit as donor group and two cyanoacrylic units as accepting/anchoring groups are reported as metal‐free sensitizers for dye‐sensitized solar cells. By changing the phenyl spacer with 3,4‐ethylenedioxythiophene (EDOT) units, the absorption spectrum of the sensitizer is red‐shifted with a corresponding increase in the molar absorptivity. Density functional calculations confirmed the intramolecular charge‐transfer nature of the lowest‐energy absorption bands. The new dyes are highly distorted from planarity and are bound to the TiO2 surface through the two anchoring groups in a unidentate binding form. A power‐conversion efficiency of 3.7 % was obtained with a volatile CH3CN‐based electrolyte, under air mass 1.5 global sunlight. Photovoltage decay transients and ATR‐FTIR measurements allowed us to understand the photovoltaic performance, as well as the surface binding, of these new sensitizers.  相似文献   

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