Efficient and stable panchromatic squaraine dyes for dye-sensitized solar cells

A new series of stable, unsymmetrical squaraine near-IR sensitizers (JK-216 and JK-217), which are assembled using both thiophenyl pyrrolyl and indolium groups, exhibit a panchromatic light harvesting up to 780 nm. The JK-216 based cell exhibited a record efficiency of 6.29% for near-IR DSSCs. In addition, the JK-217 device showed an excellent stability under a light soaking test at 60 °C for 1000 h.     

DFT and TD-DFT calculation of new thienopyrazine-based small molecules for organic solar cells

Background

Novel six organic donor-π-acceptor molecules (D-π-A) used for Bulk Heterojunction organic solar cells (BHJ), based on thienopyrazine were studied by density functional theory (DFT) and time-dependent DFT (TD-DFT) approaches, to shed light on how the π-conjugation order influence the performance of the solar cells. The electron acceptor group was 2-cyanoacrylic for all compounds, whereas the electron donor unit was varied and the influence was investigated.

Methods

The TD-DFT method, combined with a hybrid exchange-correlation functional using the Coulomb-attenuating method (CAM-B3LYP) in conjunction with a polarizable continuum model of salvation (PCM) together with a 6-31G(d,p) basis set, was used to predict the excitation energies, the absorption and the emission spectra of all molecules.

Results

The trend of the calculated HOMO–LUMO gaps nicely compares with the spectral data. In addition, the estimated values of the open-circuit photovoltage (V_oc) for these compounds were presented in two cases/PC₆₀BM and/PC₇₁BM.

Conclusion

The study of structural, electronics and optical properties for these compounds could help to design more efficient functional photovoltaic organic materials.

     

DFT/TD-DFT molecular design of porphyrin analogues for use in dye-sensitized solar cells

Density functional theory (DFT) and time-dependent DFT calculations have been employed to model Zn meso-tetraphenylporphyrin (ZnTPP) complexes having different beta-substituents, in order to design an efficient sensitizer for dye-sensitized solar cells. To calculate the excited states of the porphyrin analogues, at least the TD-B3LYP/6-31G* level of theory is needed to replicate the experimental absorption spectra. Solvation results were found to be invariant with respect to the type of model used (PCM vs. C-PCM). Most of the electronic transitions based on Gouterman's four-orbital model of ZnTPP-A and ZnTPP-B are pi --> pi* transitions, so that cell efficiency can be enhanced by increasing the pi-conjugation and electron-withdrawing capability of the beta-substituent. This proposition was tested by inserting thiophene into the beta-substituent of ZnTPP-A to form a new analogue, ZnTPP-C. Compared with ZnTPP-A and ZnTPP-B, ZnTPP-C has a smaller band gap, which brings LUMO closer to the conduction band of TiO(2), and a red-shifted absorption spectrum with higher extinction coefficients, especially in the Q-band position.     

Design of NIR-absorbing simple asymmetric squaraine dyes carrying indoline moieties for use in dye-sensitized solar cells with Pt-free electrodes

Novel near-infrared (NIR)-sensitizing (up to 800 nm) simple asymmetric squaraine dyes (Sq 31 and Sq 33) carrying indoline moieties that did not require the introduction of any linker groups were developed. DSSCs fabricated with Sq 33 exhibited remarkable characteristics in the long-wavelength visible and NIR region (up to 800 nm), such as a conversion efficiency of 3.75% (AM 1.5G) with an incident photon-to-current conversion efficiency of 63% (650 nm), a short-circuit photocurrent density of 13.64 mA, an open-circuit photovoltage of 0.48, and a fill factor of 0.57.     

Dye-sensitized nanocrystalline solar cells

The basic physical and chemical principles behind the dye-sensitized nanocrystalline solar cell (DSC: also known as the Gr?tzel cell after its inventor) are outlined in order to clarify the differences and similarities between the DSC and conventional semiconductor solar cells. The roles of the components of the DSC (wide bandgap oxide, sensitizer dye, redox electrolyte or hole conductor, counter electrode) are examined in order to show how they influence the performance of the system. The routes that can lead to loss of DSC performance are analyzed within a quantitative framework that considers electron transport and interfacial electron transfer processes, and strategies to improve cell performance are discussed. Electron transport and trapping in the mesoporous oxide are discussed, and a novel method to probe the electrochemical potential (quasi Fermi level) of electrons in the DSC is described. The article concludes with an assessment of the prospects for future development of the DSC concept.     

Optimizing dyes for dye-sensitized solar cells

Dye-sensitized solar cells (DSSCs) have emerged as an important cheap photovoltaic technology. Charge separation is initiated at the dye, bound at the interface of an inorganic semiconductor and a hole-transport material. Careful design of the dye can minimize loss mechanisms and improve light harvesting. Mass application of DSSCs is currently limited by manufacturing complexity and long-term stability associated with the liquid redox electrolyte used in the most-efficient cells. In this Minireview, dye design is discussed in the context of novel alternatives to the standard liquid electrolyte. Rapid progress is being made in improving the efficiencies of such solid and quasi-solid DSSCs which promises cheap, efficient, and robust photovoltaic systems.     

DFT and TD-DFT calculations on thieno[2,3-b]indole-based compounds for application in organic bulk heterojunction (BHJ) solar cells

Research on Chemical Intermediates - Eight novel organic compounds with donor–π–acceptor (D–π–A) structure were designed for use as donors in organic bulk...     

Coumarin derivatives for dye sensitized solar cells: a TD-DFT study

Time dependent density functional theory (TD-DFT) calculations have been carried out to study the electronic structure and the optical properties of five coumarin based dyes: C343, NKX-2311, NKX-2586, NKX-2753 and NKX-2593. We have found out that the position and width of the first band in the electronic absorption spectra, the absorption threshold and the LUMO energy with respect to the conduction band edge are key parameters in order to establish some criteria that allow evaluating the efficiency of coumarin derivatives as sensitizers in Dye Sensitized Solar Cells (DSSC). Those criteria predict the efficiency ordering for the coumarin series in good agreement with the experimental evidence. Presumably, they might be used in the design of new efficient organic based DSSC.     

Arylamine-based dyes for p-type dye-sensitized solar cells

New arylamine-based sensitizers for p-type dye-sensitized solar cells (DSSCs) have been synthesized and used for p-type DSSCs. The best conversion efficiency reaches ～0.1%. Sensitizers with two anchoring carboxylic acids lead to higher open-circuit voltages, short-circuit currents, and energy conversion efficiencies.     

Enhanced energy transfer from diolefinic laser dyes to meso-tetrakis (4-sulfonatophenyl) porphyrin immobilized on silver nanoparticles: DFT,TD-DFT and spectroscopic studies

Porphyrin derivatives are known singlet oxygen sensitizers in photodynamic therapy (PDT). Energy transfer from a class of diolefinic laser dyes (DOLDs) as energy donors to the sodium salt of meso-tetrakis (4-sulfonatophenyl) porphyrin (TPPS) as the accepter of energy would extend the range of photon harvesting down to the UV-region. Energy transfer was substantially enhanced in the presence of metallic silver nanoparticles (AgNPs), as revealed by steady-state emission spectroscopy, lifetimes, and quantum mechanics. DOLDs under investigation are 2,5-distyrylpyrazine (DSP), 1,4-bis (β-pyridyl-2 vinyl) benzene (P2VB), and 1,4 bis (2-methylstyryl) benzene (MSB) as efficient donors of intense absorption in the UV-region. AgNPs enhance the rate of energy transfer from DOLDs to TPPS via bringing donor and acceptor into close- proximity with a concomitant increase in dipole–dipole interaction between excited state donor and ground-state acceptor. The DOLDs molecular structures were optimized using the DFT/CAM-B3LYP/6-311G++ (d, p) level of theory. The calculated electronic absorption spectra for the studied DOLDs in the gaseous phase and methanol solvent were studied using the time-dependent density functional theory (TD-DFT) at M06-2X/6-311G++ (2d,2p) level. The calculated absorption/emission spectra for DSP laser dye in methanol are obtained at the TD/ M06-2X/6-311G++(2d, 2p) method. Notably, all theoretical results of the molecular structures under study highly agreed with the practical optical results. Energy transfer rate constants (k_ET) amid energy donor/acceptor pairs were determined by Stern-Volmer constants (KSV) and donors' lifetime measurements. The KSV values indicate an enhanced Fluorescence Resonance Energy Transfer (FRET) efficiencies in the presence of negatively charged AgNPs. The critical transfer distances R_o were determined from the spectral overlap between the emission spectrum of donor and absorption spectrum of TTPS. These outcomes propose the application of designed metal-enhanced FRET for energy-transfer-based assays and photodynamic therapy (PDT) applications.     

New tetrazole-based organic dyes for dye-sensitized solar cells

A series of new metal-free organic dyes that contain donors with triphenylamine or its derivatives and tetrazole-based acceptors were synthesized and characterized by photophysical, electrochemical, and theoretical computational methods. They were applied in nanocrystalline TiO_2 solar cells(DSSCs). It is found that the introduction of diphenylamine units as antennas in the as-synthesized dyes could improve photovoltaic performance compared with phenothiazine and carbazole units as antennas in DSSCs. The dye with(2H-tetrazol-5-yl) acrylonitrile electron acceptor also displayed the highest solar-to-electrical energy conversion efficiency.     

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%.     

Oligothiophene-containing coumarin dyes for efficient dye-sensitized solar cells

We have developed oligothiophene-containing coumarin dyes fully functionalized for dye-sensitized nanocrystalline TiO(2) solar cells (DSSCs). DSSCs based on the dyes gave good performance in terms of incident photon-to-current conversion efficiency (IPCE) in the range of 400-800 nm. A solar energy-to-electricity conversion efficiency (eta) of 7.4% was obtained with a DSSC based on 2-cyano-3-[5'-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-[2,2']bithiophenyl-5-yl]acrylic acid (NKX-2677) under simulated AM 1.5G irradiation (100 mW cm(-2)) with a mask: short-circuit current density (J(sc)) = 13.5 mA cm(-2); open-circuit voltage (V(oc)) = 0.71 V; fill factor (FF) = 0.77. Transient absorption spectroscopy measurements indicated that electron injection from NKX-2677 to the conduction band of TiO(2) is very rapid (<100 fs), which is much faster than the emission lifetime of the dye (1.0 ns), giving a highly efficient electron injection yield of near unity.     

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.     

Y-shaped dyes based on triphenylamine for efficient dye-sensitized solar cells

Three new triphenylamine-based dyes with Y-shaped conformation bearing triphenylamino-vinyl, 10-octyl-10H-phenothiazine-vinyl and 9-octyl-9H-carbazole-vinyl as arms (TT, TP, and TC) have been synthesized. From electrochemical investigations it is found that they can be employed in DSSCs due to the balanced HOMO and LUMO energy levels. Notably, the photo-to-electrical conversion efficiency of the DSSCs sensitized with branched TT, TP, and TC reach 5.12%, 4.84%, and 3.63%, which are higher than that sensitized with T (2.79%), and the DSSC sensitized with TT shows higher IPCE response and better photovoltaic performances (J_sc=12.37 mA/cm², V_oc=0.72 V and ff=0.58) than others. These results reveal that the introduction of branched Y-shaped extended π-conjugated donors to D-π-A dyes cannot only enlarge the spectral response range, but also suppress the molecular aggregation on TiO₂ films to a certain extent, which would enhance the performance of DSSCs.     

Fluorine substituent effect on organic dyes for sensitized solar cells

Two sets of organic dyes containing a stilbene backbone with fluorine substituents were designed for a study on the quantum efficiency of dye-sensitized solar cells (DSSCs). The results revealed that adding a fluorine substituent on the phenyl group ortho to the cyanoacrylate can enhance the light-harvesting performance in comparison with the unsubstituted one. However, when the two ortho-positions were both substituted by fluorine atoms, the performance of DSSCs was substantially reduced. The reason was mainly ascribed to a distortion from a planar geometry caused by steric hindrance. The π-conjugation was therefore disturbed, and the result led to a substantial reduction of the short-circuit photocurrent density (J_sc). Another effect was found that the open-circuit photovoltage (V_oc) of the doubly substituted derivative was lower than that of the mono-substituted one. The more flexible conformation of the difluoro-substituted dyes induced an undesired nonradiative decay, therefore led to a reduction of open-circuit photovoltage. The phenomenon can be verified by electrochemical impendence spectrum. The non-planar geometry was realized by a computation using the density function theory (DFT) model. The slight blue shift of absorption band was also consistent with the calculated transition energy by a time dependent DFT model.     

Organic dyes containing thienylfluorene conjugation for solar cells

New organic dyes that contain variable lengths of conjugation featuring alternating thiophene and fluorene segments have been synthesized and efficient nano-crystalline TiO2 based dye-sensitized solar cells were fabricated using these molecules as light-harvesting sensitizers.     

Highly-efficient metal-free organic dyes for dye-sensitized solar cells

A solar-to-electric conversion efficiency of 6.1% is achieved with this new dye, compared to 6.3% for N3 dye under the same experimental conditions. Although these indoline dyes are slightly less efficient than N3 dye, the cost of indoline dye is much less than for N3 due to ease of preparation. Furthermore, indoline dyes are shown to be highly stable to photoredox processes by cyclic voltammogram.