Novel D-π-A system based on zinc porphyrin dyes for dye-sensitized solar cells: Synthesis, electrochemical, and photovoltaic properties

We have designed and synthesized novel zinc porphyrin dyes which have a D-π-A system based on porphyrin derivatives containing a triphenylamine (TPA) electron-donating group and a phenyl carboxyl anchoring group substituted at the meso position of the porphyrin ring, yielding the push-pull porphyrins as the most efficient green dye for dye-sensitized solar cell (DSSC) applications. The synthesis and characterization of a novel D-π-A system based on zinc-porphyrin derivatives have been investigated through their photophysical and photoelectrochemical studies. A large red-shift of the absorption maxima due to introduction of the TPA moiety at the meso position of the porphyrin ring was expected in the D-π-A porphyrins, but the absorption maxima of HKK-Por dyes were a little red-shifted in contrast to Zn[5,-10,15-triphenyl-20-(4-carboxylphenyl)-porphyrin], due to the tilted structure between TPA and the porphyrin unit. Under the photovoltaic performance measurement, the maximum incident photon-to-current conversion efficiency (IPCE) value of the DSSC based on HKK-Por 5 was slightly higher than the efficiencies of the DSSCs based on other HKK-Por dyes due to the introduction of the alkoxy group into the TPA moiety at the meso position of the porphyrin ring. A maximum photon-to-electron conversion efficiency of 3.36% was achieved with the DSSC based on HKK-Por 5 dye (J_SC = 9.04 mA/cm², V_OC = 0.57 V, FF = 0.66) under AM1.5 irradiation (100 m Wcm⁻²).     

Optical properties of donor-π-(acceptor)n merocyanine dyes with dicyanovinylindane as acceptor group and triphenylamine as donor unit

Donor-π–(Acceptor)_n (D-π-A) type dyes were synthesized and their absorption and emission spectra investigated in different solvents. Strong acceptor units imparted large red-shifts in absorption; the twisting of the dye's structure imposed by an acceptor unit quenched fluorescence. Electron delocalization before and after excitation was observed according to molecular orbital calculations. The results indicated potential use of the dyes as electro-optical materials.     

Synthesis of new N, N-diphenylhydrazone dyes for solar cells: Effects of thiophene-derived π-conjugated bridge

Four novel D-π-A hydrazone dyes (HT, HM, HE, and HO) with an N, N-diphenylhydrazone moiety as the electron donor, different thiophene-derived π-conjugated bridges and a cyanoacrylic acid moiety as the electron acceptor have been designed and synthesized for the application in dye-sensitized solar cells. The influences of thiophene-derived bridges on the photoelectrochemical and photovoltaic performance of these hydrazone dyes were investigated. Results demonstrate that the introduction of 3,4-dialkyloxythiophene could red-shift the dye’s absorption spectrum due to the enhancement of the electron-donating ability of π-conjugated bridges. Importantly, electrochemical impedance spectroscopy analysis reveal that 3,4-dialkyloxythiophene bridge could change the charge recombination resistance at the TiO₂/dye/electrolyte interface and as a result to improve the open-circuit photovoltage. Among the four dyes, HO exhibits the maximum power conversion efficiency of 5.83% (V_oc = 0.65 V, J_sc = 12.69 mA/cm², FF = 0.707) under simulated AM 1.5 irradiation (100 mW/cm²).     

两个新的2-萘酮衍生物的合成与光物理性质

以咔唑为电子给体、羰基为电子受体,合成了一个新的D-π-A型有机染料1(1-(2-萘基)-3-(N-乙基咔唑)-丙烯酮)和一个新的以咔唑为电子给体中心的A-π-D-π-AV型双枝有机染料2(3,6-二[1-(2-萘基)丙烯酮]-N-丁基咔唑)。系统研究了它们在不同溶剂和聚合物基质中的光物理性质。研究发现,双枝有机染料2相对于单枝染料1吸收和荧光强度大大增强,在聚合物基质中的荧光强度相对于溶液中大大增强,即使掺杂浓度较高时也没有因生成分子的聚集体而发生明显的荧光猝灭。     

Triphenylamine-based organic dyes containing benzimidazole derivatives for dye-sensitized solar cells

The synthesis and application to dye-sensitized solar cells of two new triphenylamine-based organic dyes containing benzimidazole derivatives as secondary donors together with a simple triphenylamine derived dye for the purpose of comparison is reported. The photophysical and electrochemical properties of the dyes were investigated by UV–vis spectroscopy and cyclic voltammetry. The introduction of benzimidazole derivatives in the phenyl ring of the triphenylamine core increases the molar extinction coefficients and λ_max because of the extension of the π-conjugation structures of the dyes. Overall conversion efficiencies of ∼2.5% under full sunlight (AM 1.5G, 100 mW cm⁻²) irradiation were obtained for DSSCs based on these new dyes, under the same conditions, the reference dye and di-tetrabutylammonium cis-bis(isothiocyanato) bis(2,2′-bipyridyl-4,4′-dicarboxylato) ruthenium(II) (N719) gave overall conversion efficiencies of 1.23% and 5.61%, respectively. Our findings demonstrate that the introduction of benzimidazole derivatives as secondary donors in triphenylamine-based dye can improve their photovoltaic performance compared to the unsubstituted reference dye in DSSCs.     

Effect of side chain substituents on the electron injection abilities of unsymmetrical perylene diimide dyes

Three near-infrared (NIR) absorbing unsymmetrical perylene diimide D-A-D type dyes containing 6-undecanoxy as donor group were utilized in dye-sensitized nanocrystalline TiO₂ solar cells. Structure of the acceptor side of the molecules were improved by adding 4-[2-methyl-5-(cyanoacrylic acid)-3-thienyl]-phenyl (V), 3-carboxy-2-pyridil (VI) and 3-carboxy-2-pyrazyl (VII) moieties attached to one of the N-side of the dye. The relationship between the molecular structure of the acceptor sites of the dyes and the photovoltaic performances were discussed. Electrochemical measurements indicated that band gaps of the dyes were energetically favorable for electron injection from the excited state of the dyes to the conduction band of TiO₂ nanoparticles. However, three dyes gave lower conversion efficiency on DSSC applications. Strong electron-withdrawing nature of perylene core might not permit to transfer the photo-generated electrons to the carboxyl groups anchoring to TiO₂ surface, and then solar-to-electricity conversion efficiencies of the dyes were reduced.     

含异靛单元染料的合成及在DSSC中的研究

我们以三苯胺为电子给体,氰基丙烯酸为电子受体和锚定基团,首次使用窄带隙共轭单元异靛设计合成了一个D-π-A型全有机染料TPAID1,对其进行在染料敏化太阳能电池中的性能进行了一些列的表征,测定了染料在氯仿溶剂中的紫外-可见吸收光谱,并对其进行了DSSC器件表征,在AM 1.5 G,100 mW/cm2下,染料TPAID1的电池能量转换效率为0.59%(Jsc=1.59 mA/cm2,Voc=0.55 V,FF=0.69)。     

Design and Synthesis of Novel Chromophore with Multi-Carboxyl Groups

In order to explore the application of organic conjugated small molecules in bioimaging, a novel functional chromophore with A-π-D-π-A structure (Cr-3) was synthesized through Knoevenagel condensation reaction, consisting of carbazole unit as electron donor and cyanoacetic acid as electron acceptor groups. To improve the water solubility of this conjugated molecule, three carboxyl groups were introduced to chromophore Cr-3. Compared to the traditional D-π-A chromophores, chromophore Cr-3 showed the great improvement in water with the solubility of 2000 ppm. Also, the thermal stability of chromophore Cr-3 was also studied. The thermal decomposition temperature (Td) of Cr-3 was approximately 180°C, which was attributed to the dehydration of the carboxyl groups. Though the second harmonic generation (SHG) effect was not very high, it is large enough for the detection of SHG signal in water solution (0.28 pm/V).     

D-A-π-A型有机敏化染料的光谱调控与稳定性提升

有机功能染料在新型光电子领域具有重要的应用前景,染料的光学特性与稳定性是影响其应用价值的重要因素。应用于有机太阳电池的敏化染料是决定电池器件光电转换效率和长期稳定性的关键组分。传统有机敏化染料的设计主要遵循电子给体-共轭桥连-电子受体(D-π-A)模型,但其对设计宽光谱、高效率、高稳定性的有机敏化染料存在明显的局限性。近年来系统引入额外的强吸电子基团作为电荷分离“阱”受体,成功发展高稳定性敏化染料,显著提升敏化染料稳定性及光电转换效率,创新地提出D-A-π-A型纯有机敏化染料概念。本文主要依据在纯有机敏化染料设计与合成方面的相关工作,简单介绍D-A-π-A模型中额外受体对染料能级、光谱等性能的调控机制,以及该模型对提升有机敏化染料稳定性方面的作用及原理。     

微环境对“D-π-A”型荧光分子发光行为的影响

本文通过研究自制的6种“D-π-A”型共轭有机盐类染料在不同环境中的发光行为,讨论了环境和分子结构对其发光行为的影响。研究结果表明:(1)巴比妥酸盐类可看出引入羟基发生较明显的荧光淬灭现象,且发光峰位显著蓝移;(2)通过比较喹啉盐类吡啶盐类荧光光谱,可知吡啶基受体具有良好的发光特性;(3)三类有机盐的荧光强度均随着溶剂极性的增大而减小,且有不同程度的蓝移。     

N-Aryl stilbazolium dyes as sensitizers for solar cells

Eight new N-arylstilbazolium chromophores with electron donating -NR₂ (R = Me or Ph) substituents have been synthesized via Knoevenagel condensations and isolated as their PF₆⁻ salts. These compounds have been characterized by using various techniques including ¹H NMR and IR spectroscopies and electrospray mass spectrometry. UV-vis absorption spectra recorded in acetonitrile are dominated by intense, low energy π → π* intramolecular charge-transfer (ICT) bands, and replacing Me with Ph increases the ICT energies. Cyclic voltammetric studies show irreversible reduction processes, together with oxidation waves that are irreversible for R = Me, but reversible for R = Ph. Single crystal X-ray structures have been determined for three of the methyl ester-substituted stilbazolium salts and for the Cl⁻ salts of their picolinium precursors. Time-dependent density functional theory calculations afford reasonable predictions of ICT energies, but greater rigour is necessary for -NPh₂ derivatives. The four new acid-functionalized dyes give moderate sensitization efficiencies (ca. 0.2%) when using TiO₂-based photoanodes, with relatively higher values for R = Ph vs Me, while larger efficiencies (up to 0.8%) are achieved with ZnO substrates.     

Three new five-coordinated mercury (II) dyes: Structure and enhanced two-photon absorption

A new donor-bridge-acceptor (D-π-A) type ligand (L: 4′-(4-[4-(imidazole)styryl]phenyl)-2,2′:6′,2″-terpyridine) with two-photon absorption and coordination ability was designed and synthesized. Self-assembly of the ligand with HgX₂ (X = Cl, Br, I) yielded a series of new coordination complexes (Dyes 1-3) with five-coordinated mercury (ΙΙ), which were characterized by single crystal X-ray diffraction determination. Solvent molecules and various weak interactions, including hydrogen bonds (C-H···N, C-H···X) and π-π interactions played significant roles in the final topological structures. Linear and nonlinear optical properties of the ligand and three dyes were described. Experimental results revealed that two-photon absorption cross sections of three dyes are extraordinary stronger than that of ligand.     

Organic dyes incorporating low-band-gap chromophores based on π-extended benzothiadiazole for dye-sensitized solar cells

A series of new π-conjugated organic dyes (HKK-BTZ1, HKK-BTZ2, HKK-BTZ3 and HKK-BTZ4), comprising triphenylamine (TPA) moieties as the electron donor and benzothiadiazole moieties as the electron acceptor/anchoring groups, was synthesized for the use in dye-sensitized solar cells (DSSCs). TPA units are bridged to benzothiadiazole with single(S), double(D) and triple bonds(T) in different derivatives. And HKK-BTZ1 was modified by introducing alkoxy group of TPA unit, because the bulky alkoxy group is a strong donating group for the more red shift and for reducing aggregation of dyes in TiO₂ film. The structure-property relationship was investigated. Under standard global AM 1.5 G illumination, a maximum photo-to-electron conversion efficiency of 7.30% was achieved with the DSSC based on dye HKK-BTZ4 (J_SC = 17.9 mA/cm⁻², V_OC = 0.62 V, FF = 0.66), while the Ru dye N719-sensitized DSSC showed an efficiency of 7.82% with a J_SC of 17.5 mA/cm⁻², a V_OC of 0.62 V, and a FF of 0.72.     

D-π-A 星型分子的合成及非线性光学性质

以苯基为中心, 通过 Suzuki 偶联反应引入两个电子给体(D)单元三苯胺和电子受体(A)单元菲并咪唑, 合成了新的 D-π-A 星型分子(Y), 其结构通过NMR、ESI-MS 及元素分析进行了表征;通过紫外可见吸收光谱、荧光光谱、荧光量子产率、理论计算以及 Z 扫描测试技术对该分子的三阶非线性光学性质进行了研究。结果表明, 分子Y的荧光量子产率 (ϕ) 可达 0.77, 双光子吸收截面 (σ₂) 为120GM, 三阶非线性折射率(n₂)为9.0×10^-7cm²/GW, 可见该化合物具有较好的非线性光学性质, 为非线性光学材料的分子设计提供了一定的思路。     

Multi-alkylthienyl appended porphyrins for efficient dye-sensitized solar cells

Four porphyrin dyes, incorporating multi-alkylthienyl appended porphyrins as the electron donor, the 2-cyanoacrylic acid as the electron acceptor, and different π-conjugated spacer, have been synthesized for dye-sensitized solar cells (DSSCs). All the porphyrin dyes studied in this work exhibit red-shifted and broadened electronic spectra respect to the reference P_Zn as expected. By the introduction of thienyl groups at the meso-positions, the energy level of E_ox (excited-state oxidation potentials) is significantly shifted to the positive compared with the reference P_Zn, indicating a decreased HOMO–LUMO gap. The highest power conversion efficiency of the four dyes based on DSSCs reached 5.71% under AM 1.5 G irradiation.     

Multi-alkylthienyl appended porphyrins for efficient dye-sensitized solar cells

Four porphyrin dyes, incorporating multi-alkylthienyl appended porphyrins as the electron donor, the 2-cyanoacrylic acid as the electron acceptor, and different π-conjugated spacer, have been synthesized for dye-sensitized solar cells (DSSCs). All the porphyrin dyes studied in this work exhibit red-shifted and broadened electronic spectra respect to the reference P_Zn as expected. By the introduction of thienyl groups at the meso-positions, the energy level of E_ox (excited-state oxidation potentials) is significantly shifted to the positive compared with the reference P_Zn, indicating a decreased HOMO-LUMO gap. The highest power conversion efficiency of the four dyes based on DSSCs reached 5.71% under AM 1.5 G irradiation.     

Fluorescence and photophysical properties of D-π-A push-pull systems featuring a 4,5-dicyanoimidazole unit

Absorption and fluorescence spectra and fluorescence quantum yields of 18 D-;π-A push-pull compounds were measured. The investigated chromophores consist of 4,5-dicyanoimidazole — bearing donor — substituted and systematically extended π-conjugated spacers. The influence of temperature and solvent polarity on the spectral and photophysical properties was investigated. Employing INDO/S calculations, the structure-property relationships were discussed.     

Fluorescence and photophysical properties of D-π-A push-pull systems featuring a 4,5-dicyanoimidazole unit

Absorption and fluorescence spectra and fluorescence quantum yields of 18 D-;π-A push-pull compounds were measured. The investigated chromophores consist of 4,5-dicyanoimidazole — bearing donor — substituted and systematically extended π-conjugated spacers. The influence of temperature and solvent polarity on the spectral and photophysical properties was investigated. Employing INDO/S calculations, the structure–property relationships were discussed.     

The design and synthesis of a novel 1,8-naphthalimide PAMAM light-harvesting dendron with fluorescence “off-on” switching core

A novel polyamidoamine dendron core, peripherally functionalized with 1,8-naphthalimide fluorophores, was configured as a light harvesting antenna in which the system surface was labelled with blue emitting 4-allyloxy-1,8-naphthalimide “donor” dyes capable of both absorbing light and efficiently (96%) transferring the energy to a single, yellow-green emitting 4-N-methylpiperazinyl-1,8-naphthalimide “acceptor” dye. The 1,8-naphthalimide core was designed on the “fluorophore-spacer-receptor” format and was able to function as a fluorescence photoinduced electron transfer sensor. Two different photoinduced electron transfer effects were observed in the new antenna namely that from the receptor to the core fluorophore and that from the polyamidoamine backbone to the peripheral 1,8-naphthalimides. Althogh the core emission intensity of the system was enhanced > four times by reducing the pH from 10 to 2, the fluorescence enhancement of the system in acidic medium, excited within the periphery (λ_ex = 360 nm), was approximately twice that of the core fluorescence enhancement after direct excitation of the focal 1,8-naphthalimide (λ_ex = 420 nm), because of more efficient energy transfer. The observed “off-on” switching of the core fluorescence over a wid pH scale indicates that the novel light harvesting antenna would be able to act as a highly efficient fluorescent sensor.     

Tunable molecular weights of poly(triphenylamine‐2,2′‐bithiophene) and their effects on photovoltaic performance as sensitizers for dye‐sensitized solar cells

Despite the huge progress achieved over the past decade, the relationship between the molecular weights of dyes and the performance of dye‐sensitized solar cells (DSSCs) remains unclear. In this article, we report on the fine control of the number‐average molecular weight (M_n) of poly(triphenylamine‐2,2′‐bithiophene) (PPAT) dyes with cyanoacrylic acid moieties as acceptors. We found a correlation between the M_n and photovoltaic performance of these polymers when they were used for DSSC applications. In this study, three samples (PPAT‐01, PPAT‐02, and PPAT‐03) with different M_n values (M_ns = 1700, 2800, and 3500 g/mol) were prepared through the control of the polymerization time and characterized by analytical gel permeation chromatography and NMR. Under the same experimental conditions, the overall cell efficiency of the oligomer dyes showed a nonmonotonic tendency with increasing molecular weight. The power‐conversion efficiencies were 2.81% for PPAT‐01, 4.72% for PPAT‐02, and 1.88% for PPAT‐03. UV absorption measurements proved that PPAT‐03 formed aggregation, whereas PPAT‐01 and PPAT‐02 were in the monolayer state adsorbed on TiO₂. The larger aggregation decreased charge transfer; thus, poor photoelectric conversion performance was observed. Furthermore, a higher molecular weight reduced the amount of PPAT‐03 adsorbed on TiO₂, and this had a crucial effect on the performance of the cells because of the reduced photocurrent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44182.