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1.
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   

2.
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.  相似文献   

3.
All‐organic dyes have shown promising potential as an effective sensitizer in dye‐sensitized solar cells (DSSCs). The design concept of all‐organic dyes to improve light‐to‐electric‐energy conversion is discussed based on the absorption, electron injection, dye regeneration, and recombination. How the electron‐donor–acceptor‐type framework can provide better light harvesting through bandgap‐tuning and why proper arrangement of acceptor/anchoring groups within a conjugated dye frame is important in suppressing improper charge recombination in DSSCs are discussed. Separating the electron acceptor from the anchoring unit in the donor–acceptor‐type organic dye would be a promising strategy to reduce recombination and improve photocurrent generation.  相似文献   

4.
A novel series of dipolar organic dyes containing diarylamine as the electron donor, 2‐cyanoacrylic acid as the electron acceptor, and fluorene and a heteroaromatic ring as the conjugating bridge have been developed and characterized. These metal‐free dyes exhibited very high molar extinction coefficients in the electronic absorption spectra and have been successfully fabricated as efficient nanocrystalline TiO2 dye‐sensitized solar cells (DSSCs). The solar‐energy‐to‐electricity conversion efficiencies of DSSCs ranged from 4.92 to 6.88 %, which reached 68–96 % of a standard device of N719 fabricated and measured under the same conditions. With a TiO2 film thickness of 6 μm, DSSCs based on these dyes had photocurrents surpassing that of the N719‐based device. DFT computation results on these dyes also provide detailed structural information in connection with their high cell performance.  相似文献   

5.
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   

6.
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 (Jsc) of 15.69 mA cm?2, an open‐circuit photovoltage (Voc) 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.  相似文献   

7.
A series of organic dyes were prepared that displayed remarkable solar‐to‐energy conversion efficiencies in dye‐sensitized solar cells (DSSCs). These dyes are composed of a 4‐tert‐butylphenylamine donor group (D), a cyanoacrylic‐acid acceptor group (A), and a phenylene‐thiophene‐phenylene (PSP) spacer group, forming a D‐π‐A system. A dye containing a bulky tert‐butylphenylene‐substituted carbazole (CB) donor group showed the highest performance, with an overall conversion efficiency of 6.70 %. The performance of the device was correlated to the structural features of the donor groups; that is, the presence of a tert‐butyl group can not only enhance the electron‐donating ability of the donor, but can also suppress intermolecular aggregation. A typical device made with the CB‐PSP dye afforded a maximum photon‐to‐current conversion efficiency (IPCE) of 80 % in the region 400–480 nm, a short‐circuit photocurrent density Jsc=14.63 mA cm?2, an open‐circuit photovoltage Voc=0.685 V, and a fill factor FF=0.67. When chenodeoxycholic acid (CDCA) was used as a co‐absorbent, the open‐circuit voltage of CB‐PSP was elevated significantly, yet the overall performance decreased by 16–18 %. This result indicated that the presence of 4‐tert‐butylphenyl substituents can effectively inhibit self‐aggregation, even without CDCA.  相似文献   

8.
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   

9.
Three new dyes with a 2‐(1,1‐dicyanomethylene)rhodanine (IDR‐ I , ‐ II , ‐ III ) electron acceptor as anchor were synthesized and applied to dye‐sensitized solar cells. We varied the bridging molecule to fine tune the electronic and optical properties of the dyes. It was demonstrated that incorporation of auxiliary acceptors effectively increased the molar extinction coefficient and extended the absorption spectra to the near‐infrared (NIR) region. Introduction of 2,1,3‐benzothiadiazole (BTD) improved the performance by nearly 50 %. The best performance of the dye‐sensitized solar cells (DSSCs) based on IDR‐ II reached 8.53 % (short‐circuit current density (Jsc)=16.73 mA cm?2, open‐circuit voltage (Voc)=0.71 V, fill factor (FF)=71.26 %) at AM 1.5 simulated sunlight. However, substitution of BTD with a group that featured the more strongly electron‐withdrawing thiadiazolo[3,4‐c]pyridine (PT) had a negative effect on the photovoltaic performance, in which IDR‐ III ‐based DSSCs showed the lowest efficiency of 4.02 %. We speculate that the stronger auxiliary acceptor acts as an electron trap, which might result in fast combination or hamper the electron transfer from donor to acceptor. This inference was confirmed by electrical impedance analysis and theoretical computations. Theoretical analysis indicates that the LUMO of IDR‐ III is mainly localized at the central acceptor group owing to its strong electron‐withdrawing character, which might in turn trap the electron or hamper the electron transfer from donor to acceptor, thereby finally decreasing the efficiency of electron injection into a TiO2 semiconductor. This result inspired us to select moderated auxiliary acceptors to improve the performance in our further study.  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.
Seven SGT organics dyes, containing bis‐dimethylfluoreneyl amino groups with a dialkoxyphenyl unit as an electron donor and a cyanoacrylic acid group as an anchoring group, connected with oligothiophenes, fused thiophenes and benzothiadiazoles as π‐bridges, were designed and synthesised for applications in dye‐sensitised solar cells (DSSCs). The photovoltaic performance of DSSCs based on organic dyes with oligothiophenes depends on the molecular structure of the dyes, in terms of the length change of the π‐bridging units. The best performance was found with a π‐bridge length of about 6 Å. To further enhance the photovoltaic performance associated with this concept, cyclopenta[1,2‐b:5,4‐b′]dithiophene (CPDT) and benzothiadiazole were introduced into the π‐bridge unit. As a result, the DSSC based on the organic dye containing the CPDT moiety showed the best photovoltaic performance with a short‐circuit photocurrent density (Jsc) of 14.1 mA cm?2, an open‐circuit voltage (Voc) of 0.84 V and a fill factor (FF) of 0.72, corresponding to an overall conversion efficiency (η) of 8.61 % under standard AM 1.5 irradiation.  相似文献   

12.
New hemicyanine dyes ( CM101 , CM102 , CM103 , and CM104 ) in which tetrahydroquinoline derivatives are used as electron donors and N‐(carboxymethyl)‐pyridinium is used as an electron acceptor and anchoring group were designed and synthesized for dye‐sensitized solar cells (DSSCs). Compared with corresponding dyes that have cyanoacetic acid as the acceptor, N‐(carboxymethyl)‐pyridinium has a stronger electron‐withdrawing ability, which causes the absorption maximum of dyes to be redshifted. The photovoltaic performance of the DSSCs based on dyes CM101 – CM104 markedly depends on the molecular structures of the dyes in terms of the n‐hexyl chains and methoxyl. The device sensitized by dye CM104 achieved the best conversion efficiency of 7.0 % (Jsc=13.4 mA cm?2, Voc=704 mV, FF=74.8 %) under AM 1.5 irradiation (100 mW cm?2). In contrast, the device sensitized by reference dye CMR104 with the same donor but the cyanoacetic acid as the acceptor gave an efficiency of 3.4 % (Jsc=6.2 mA cm?2, Voc=730 mV, FF=74.8 %). Under the same conditions, the cell fabricated with N719 sensitized porous TiO2 exhibited an efficiency of 7.9 % (Jsc=15.4 mA cm?2, Voc=723 mV, FF=72.3 %). The dyes CM101 – CM104 show a broader spectral response compared with the reference dyes CMR101 – CMR104 and have high IPCE exceeding 90 % from 450 to 580 nm. Considering the reflection of sunlight, the photoelectric conversion efficiency could be almost 100 % during this region.  相似文献   

13.
High‐performance Förster resonance energy transfer (FRET)‐based dye‐sensitized solar cells (DSSCs) have been successfully fabricated through the optimized design of a CdSe/CdS quantum‐dot (QD) donor and a dye acceptor. This simple approach enables quantum dots and dyes to simultaneously utilize the wide solar spectrum, thereby resulting in high conversion efficiency over a wide wavelength range. In addition, major parameters that affect the FRET interaction between donor and acceptor have been investigated including the fluorescent emission spectrum of QD, and the content of deposited QDs into the TiO2 matrix. By judicious control of these parameters, the FRET interaction can be readily optimized for high photovoltaic performance. In addition, the as‐synthesized water‐soluble quantum dots were highly dispersed in a nanoporous TiO2 matrix, thereby resulting in excellent contact between donors and acceptors. Importantly, high‐performance FRET‐based DSSCs can be prepared without any infrared (IR) dye synthetic procedures. This novel strategy offers great potential for applications of dye‐sensitized solar cells.  相似文献   

14.
This review focuses on our work on metal‐free sensitizers for dye‐sensitized solar cells (DSSCs). Sensitizers based on D?A′?π?A architecture (D is a donor, A is an acceptor, A′ is an electron‐deficient entity) exhibit better light harvesting than D?π?A‐type sensitizers. However, appropriate molecular design is needed to avoid excessive aggregation of negative charge at the electron‐deficient entity upon photoexcitation. Rigidified aromatics, including aromatic segments comprising fused electron‐excessive and ‐deficient units in the spacer, allow effective electronic communication, and good photoinduced charge transfer leads to excellent cell performance. Sensitizers with two anchors/acceptors, D(–π–A)2, can more efficiently harvest light, inject electrons, and suppress dark current compared with congeners with a single anchor. Appropriate incorporation of heteroaromatic units in the spacer is beneficial to DSSC performance. High‐performance, aqueous‐based DSSCs can be achieved with a dual redox couple comprising imidazolium iodide and 2,2,6,6‐tetramethylpiperidin‐N‐oxyl, and/or using dyes of improved wettability through the incorporation of a triethylene oxide methyl ether chain.

  相似文献   


15.
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   

16.
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   

17.
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.  相似文献   

18.
A series of platinum(II) alkynyl‐based sensitizers has been synthesized and found to show light‐to‐electricity conversion properties. These dyes were developed as sensitizers for the application in nanocrystalline TiO2 dye‐sensitized solar cells (DSSCs). Their photophysical and electrochemical properties were studied. The excited‐state property was probed using nanosecond transient absorption spectroscopy, which showed the formation of a charge‐separated state that arises from the intramolecular photoinduced charge transfer from the platinum(II) alkynylbithienylbenzothiadiazole moiety (donor) to the polypyridyl ligand (acceptor). A lifetime of 3.4 μs was observed for the charge‐separated state. A dye‐sensitized solar cell based on one of the complexes showed a short‐circuit photocurrent of 7.12 mA cm?2, an open circuit voltage of 780 mV, and a fill factor of 0.65, thus giving an overall power conversion efficiency of 3.6 %.  相似文献   

19.
Dye‐sensitized solar cells (DSSCs) based on organic dyes adsorbed on oxide semiconductor electrodes, such as TiO2, ZnO, or NiO, which have emerged as a new generation of sustainable photovoltaic devices, have attracted much attention from chemists, physicists, and engineers because of enormous scientific interest in not only their construction and operational principles, but also in their high incident‐solar‐light‐to‐electricity conversion efficiency and low cost of production. To develop high‐performance DSSCs, it is important to create efficient organic dye sensitizers, which should be optimized for the photophysical and electrochemical properties of the dyes themselves, with molecular structures that provide good light‐harvesting features, good electron communication between the dye and semiconductor electrode and between the dye and electrolyte, and to control the molecular orientation and arrangement of the dyes on a semiconductor surface. The aim of this Review is not to make a list of a number of organic dye sensitizers developed so far, but to provide a new direction in the epoch‐making molecular design of organic dyes for high photovoltaic performance and long‐term stability of DSSCs, based on the accumulated knowledge of their photophysical and electrochemical properties, and molecular structures of the organic dye sensitizers developed so far.  相似文献   

20.
In this study a novel symmetrical metal‐free organic dye for applications in dye‐sensitized solar cells (DSSCs) was synthesized. This dye ( D ) was designed with A–π–D–π–A framework and synthesized with 9,9‐dioctylfluorene as electron donor, phenylene as π‐spacer and cyanoacetic acid as electron acceptor. The chemical structure of product was determined using UV‐Vis, FT‐IR, CNMR, HNMR spectroscopy techniques. The presence of a phenylene π‐bridge between the donor and the acceptor units and the di‐anchoring moieties in this structure led to enhancement of conjugation lengths and molar extinction coefficient (ε) that is promising for further improvement of the conversion efficiency of DSSCs.  相似文献   

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