Integrated Design of Organic Hole Transport Materials for Efficient Solid‐State Dye‐Sensitized Solar Cells

A series of triphenylamine‐based small molecule organic hole transport materials (HTMs) with low crystallinity and high hole mobility are systematically investigated in solid‐state dye‐sensitized solar cells (ssDSCs). By using the organic dye LEG4 as a photosensitizer, devices with X3 and X35 as the HTMs exhibit desirable power conversion efficiencies (PCEs) of 5.8% and 5.5%, respectively. These values are slightly higher than the PCE of 5.4% obtained by using the state‐of‐the‐art HTM Spiro‐OMeTAD. Meanwhile, transient photovoltage decay measurement is used to gain insight into the complex influences of the HTMs on the performance of devices. The results demonstrate that smaller HTMs induce faster electron recombination in the devices and suggest that the size of a HTM plays a crucial role in device performance, which is reported for the first time.     

Spray Deposition of Silver Nanowire Electrodes for Semitransparent Solid‐State Dye‐Sensitized Solar Cells

Transparent top electrodes for solid‐state dye‐sensitized solar cells (ssDSCs) allow for fabrication of mechanically stacked ssDSC tandems, partially transparent ssDSCs for building integration, and ssDSCs on metal foil substrates. A solution‐processed, highly transparent, conductive electrode based on PEDOT:PSS [poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate)] and spray‐deposited silver nanowires (Ag NWs) is developed as an effective top contact for ssDSCs. The electrode is solution‐deposited using conditions and solvents that do not damage or dissolve the underlying ssDSC and achieves high performance: a peak transmittance of nearly 93% at a sheet resistance of 18 Ω/square – all without any annealing that would harm the ssDSC. The role of the PEDOT:PSS in the electrode is twofold: it ensures ohmic contact between the ssDSC 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenylamine)9,9′‐spirobifluorene (Spiro‐OMeTAD) overlayer and the silver nanowires and it decreases the series resistance of the device. Semitransparent ssDSCs with D35 dye fabricated using this Ag NW/PEDOT:PSS transparent electrode show power conversion efficiencies of 3.6%, nearly as high as a reference device using an evaporated silver electrode (3.7%). In addition, the semitransparent ssDSC shows high transmission between 700–1100 nm, a necessity for use in efficient tandem devices. Such an electrode, in combination with efficient ssDSCs or hybrid perovskite‐sensitized solar cells, can allow for the fabrication of efficient, cost‐effective tandem photovoltaics.     

The Effect of Hole Transport Material Pore Filling on Photovoltaic Performance in Solid‐State Dye‐Sensitized Solar Cells

A detailed investigation of the effect of hole transport material (HTM) pore filling on the photovoltaic performance of solid‐state dye‐sensitized solar cells (ss‐DSCs) and the specific mechanisms involved is reported. It is demonstrated that the efficiency and photovoltaic characteristics of ss‐DSCs improve with the pore filling fraction (PFF) of the HTM, 2,2’,7,7’‐tetrakis‐(N, N ‐di‐ p ‐methoxyphenylamine)9,9’‐spirobifluorene(spiro‐OMeTAD). The mechanisms through which the improvement of photovoltaic characteristics takes place were studied with transient absorption spectroscopy and transient photovoltage/photocurrent measurements. It is shown that as the spiro‐OMeTAD PFF is increased from 26% to 65%, there is a higher hole injection efficiency from dye cations to spiro‐OMeTAD because more dye molecules are covered with spiro‐OMeTAD, an order‐of‐magnitude slower recombination rate because holes can diffuse further away from the dye/HTM interface, and a 50% higher ambipolar diffusion coefficient due to an improved percolation network. Device simulations predict that if 100% PFF could be achieved for thicker devices, the efficiency of ss‐DSCs using a conventional ruthenium‐dye would increase by 25% beyond its current value.     

Design‐to‐Device Approach Affords Panchromatic Co‐Sensitized Solar Cells

Data‐driven materials discovery has become increasingly important in identifying materials that exhibit specific, desirable properties from a vast chemical search space. Synergic prediction and experimental validation are needed to accelerate scientific advances related to critical societal applications. A design‐to‐device study that uses high‐throughput screens with algorithmic encodings of structure–property relationships is reported to identify new materials with panchromatic optical absorption, whose photovoltaic device applications are then experimentally verified. The data‐mining methods source 9431 dye candidates, which are auto‐generated from the literature using a custom text‐mining tool. These candidates are sifted via a data‐mining workflow that is tailored to identify optimal combinations of organic dyes that have complementary optical absorption properties such that they can harvest all available sunlight when acting as co‐sensitizers for dye‐sensitized solar cells (DSSCs). Six promising dye combinations are shortlisted for device testing, whereupon one dye combination yields co‐sensitized DSSCs with power conversion efficiencies comparable to those of the high‐performance, organometallic dye, N719. These results demonstrate how data‐driven molecular engineering can accelerate materials discovery for panchromatic photovoltaic or other applications.     

Masked red-emitting carbopyronine dyes with photosensitive 2-diazo-1-indanone caging group

Caged near-IR emitting fluorescent dyes are in high demand in optical microscopy but up to now were unavailable. We discovered that the combination of a carbopyronine dye core and a photosensitive 2-diazo-1-indanone residue leads to masked near-IR emitting fluorescent dyes. Illumination of these caged dyes with either UV or visible light (λ < 420 nm) efficiently generates fluorescent compounds with absorption and emission at 635 nm and 660 nm, respectively. A high-yielding synthetic route with attractive possibilities for further dye design is described in detail. Good photostability, high contrast, and a large fluorescence quantum yield after uncaging are the most important features of the new compounds for non-invasive imaging in high-resolution optical microscopy. For use in immunolabelling the caged dyes were decorated with a (hydrophilic) linker and an (activated) carboxyl group.     

Effect of chemical structures of acridine and triphenylmethane dyes on the induced optical activity of DNA-dye complexes

Fifteen symmetrically substituted acridine dyes, all of which are interrelated by their chemical structures, each belonging to a C_2v symmetry, and three triphenylmethane dyes with amino or dimethylamino substituents are utilized to study necessary conditions for the appearance of extrinsic Cotton effects upon their binding to native and heat-denatured deoxyribonucleic acid (DNA). Three different kinds of the DNA–dye complexes, i.e., (1) dye added to native DNA, (2) heat-denatured DNA–dye complex, and (3) dye added to preheated DNA, were examined for each dye at a fixed P/D value of about 4. Optical activity was always observed for the compelexes of type (1) in each absorption band of the dyes in the visible and near-ultraviolet region. Two exceptions are 9-acetamido- and 9-hydroxyacridine, both being nonionic in aqueous solution at a pH range of 6. Acridinium chloride was unable to exhibit any definite extrinsic Cotton effect for complexes (2) and (3). Thus, the monocationic form of a dye due to the protonation or quaternization of the ring nitrogen in acridines or exonuclear amino nitrogen in triphenylmethane dyes is concluded to be an essential factor for extrinsic Cotton effect to appear. Changes in the absorption spectra upon complex formation are also related to the structure of dyes. Hypochromism and bathochromism are associated with the induced optical activity in all cases in the presence of native and denatured DNA.     

Photo-bleaching and photon saturation in flow cytometry.

In flow cytometry, small particles travel at a high speed through a bright light spot. The high light intensity at the point of measurement causes measurable photon saturation. This observation indicates that the rate at which individual dye molecules emit photons is close to the maximum emission rate. Despite the short exposure time, individual molecules may go through a few hundred excitation cycles while they are in the light beam. The absorbed light dose causes significant dye destruction. This article presents experimental procedures to determine the extent of photon saturation and photo-bleaching of dyes bound to cell nuclei in a flow cytometer. Measurements of Hoechst and propidium iodide bound to chromatin show that the amount of dye bleached per emitted photon is the same at low and high illumination intensities. This finding indicates that photon emission and dye destruction are both the result of the absorption of single excitation photons. The experimental observations allow rough estimates of the lifetime of the excited state and the lifetime of the molecule. The lifetime of the Hoechst 33258 bound to DNA is estimated to be 100 excitation-relaxation cycles. The average propidium iodide molecule lasts approximately 200 excitation-relaxation cycles. The theoretical considerations show that the optimal illumination conditions are different for bleaching and nonbleaching dyes. An optical arrangement for high precision measurements of bleaching dyes is presented.     

Molecule design and screening of novel unsymmetrical zinc phthalocyanine sensitizers for dye-sensitized solar cells

The molecular orbital and optical properties of the dyes PCH001 and TT1 reported previously were studied using the density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations. The results show that the electronic spectra simulated for PCH001 and TT1 in ethanol were in good agreement with the experimental data. The molecular orbital spatial orientation was used to interpret the discrepancy of the photovoltaic performances of the PCH001 and TT1 sensitized solar cells. The conjugation between the carboxyl group and the phthalocyanine ring in TT1 was found to be better than that through the C-C single bond in PCH001, which may contribute to TT1’s improved performance. Four new unsymmetrical phthalocyanine molecules with the peripheral substituents as donors and anchoring groups as acceptors, namely CZ1, CZ2, trans- and cis-CZ3, were designed and compared to PCH001 and TT1. The new molecules CZ2 and cis-CZ3 were promising and may challenge the current record of PCH001 and TT1 in phthalocyanine-sensitized solar cells.     

Two Channels of Charge Generation in Perylene Monoimide Solid‐State Dye‐Sensitized Solar Cells

The mechanism of charge generation in solid‐state dye‐sensitized solar cells using triarylamine‐substituted perylene monoimide dyes is studied by vis‐NIR broadband pump‐probe transient absorption spectroscopy. The experiments demonstrate that photoinduced electron injection into the TiO₂ can only occur in regions where Li⁺, from the commonly used Li‐TFSI additive salt, is present on the TiO₂ surface. Incomplete surface coverage by Li⁺ means that some dye excitons cannot inject their electron into the TiO₂. However it is observed in the solar cell structure that some of the dye excitons that cannot directly inject an electron still contribute to free charge generation by the previously hypothesized reductive quenching mechanism (hole transfer to the solid‐state hole transporter followed by electron injection from the dye anion into the TiO₂). The contribution of reductive quenching to the quantum efficiency of charge generation is significant, raising it from 68% to over 80%. Optimization of this reductive quenching pathway could be exploited to maintain high quantum efficiency in dyes with greater NIR absorption to achieve overall enhancements in device performance. It is demonstrated that broadband NIR transient spectroscopy is necessary to obtain population kinetics in these systems, as strong Stark effects distort the population kinetics in the visible region.     

Evaluation of Voltage-Sensitive Fluorescence Dyes for Monitoring Neuronal Activity in the Embryonic Central Nervous System

Using an optical imaging technique with voltage-sensitive dyes (VSDs), we investigated the functional organization and architecture of the central nervous system (CNS) during embryogenesis. In the embryonic nervous system, a merocyanine-rhodanine dye, NK2761, has proved to be the most useful absorption dye for detecting neuronal activity because of its high signal-to-noise ratio (S/N), low toxicity and small dye bleaching. In the present study, we evaluated the suitability of fluorescence VSDs for optical recording in the embryonic CNS. We screened eight styryl (hemicyanine) dyes in isolated brainstem–spinal cord preparations from 7-day-old chick embryos. Measurements of voltage-related optical signals were made using a multiple-site optical recording system. The signal size, S/N, photobleaching, effects of perfusion and recovery of neural responses after staining were compared. We also evaluated optical responses with various magnifications. Although the S/N was lower than with the absorption dye, clear optical responses were detected with several fluorescence dyes, including di-2-ANEPEQ, di-4-ANEPPS, di-3-ANEPPDHQ, di-4-AN(F)EPPTEA, di-2-AN(F)EPPTEA and di-2-ANEPPTEA. Di-2-ANEPEQ showed the largest S/N, whereas its photobleaching was faster and the recovery of neural responses after staining was slower. Di-4-ANEPPS and di-3-ANEPPDHQ also exhibited a large S/N but required a relatively long time for recovery of neural activity. Di-4-AN(F)EPPTEA, di-2-AN(F)EPPTEA and di-2-ANEPPTEA showed smaller S/Ns than di-2-ANEPEQ, di-4-ANEPPS and di-3-ANEPPDHQ; but the recovery of neural responses after staining was faster. This study demonstrates the potential utility of these styryl dyes in optical monitoring of voltage changes in the embryonic CNS.     

Histological, Chromatographic and Spectrophotometric Studies of Toluidine Blue

Chromatographic analysis of commercial batches of toluidine blue shows these to be dye mixtures. Histologically, some samples were found to be poor metachromatic dyes. These unsatisfactory stains contained blue dyes with little or no metachromatic properties as well as a metachromatic fraction. On the other hand, contaminating dyes in histologically satisfactory samples had poor staining qualities and hence did not interfere with the color produced by the metachromatic fraction.

Chromatographic fractionation of different commercial batches of toluidine blue yielded identical, homogeneous metachromatic dyes. These purified dyes had a peak absorption at 615 mμ in contrast to that of purified azure A whose peak absorption was at 622.5 mμ.     

Transforming Benzophenoxazine Laser Dyes into Chromophores for Dye‐Sensitized Solar Cells: A Molecular Engineering Approach

The refunctionalization of a series of four well‐known industrial laser dyes, based on benzophenoxazine, is explored with the prospect of molecularly engineering new chromophores for dye‐sensitized solar cell (DSC) applications. Such engineering is important since a lack of suitable dyes is stifling the progress of DSC technology. The conceptual idea involves making laser dyes DSC‐active by chemical modification, while maintaining their key property attributes that are attractive to DSC applications. This molecular engineering follows a stepwise approach. First, molecular structures and optical absorption properties are determined for the parent laser dyes: Cresyl Violet ( 1 ), Oxazine 170 ( 2 ), Nile Blue A ( 3 ), Oxazine 750 ( 4 ). These reveal structure‐property relationships which define the prerequisites for computational molecular design of DSC dyes; the nature of their molecular architecture (D‐π‐A) and intramolecular charge transfer. Second, new DSC dyes are computationally designed by the in silico addition of a carboxylic acid anchor at various chemical substitution points in the parent laser dyes. A comparison of the resulting frontier molecular orbital energy levels with the conduction band edge of a TiO₂ DSC photoanode and the redox potential of two electrolyte options I^?/I₃^? and Co^(II/III)tris(bipyridyl) suggests promise for these computationally designed dyes as co‐sensitizers for DSC applications.     

Organic Sensitizers with Bridged Triphenylamine Donor Units for Efficient Dye‐Sensitized Solar Cells

Bridged triphenylamine was chosen as the donor unit for metal‐free organic sensitizers in dye‐sensitized solar cells (DSSCs). The easily constructed alkene linkage between the donor and the spacer improves the molecule's delocalization and causes a large red shift in its absorption peaks. Planarization of the donor and the use of alkene linkage have proven powerful in extending the red light response of the sensitizer, leading to a significant enhancement in photocurrent density of the device. As a result, devices sensitized with target sensitizers LC‐2 (η = 7.51%) and LC‐3 (η = 8.00%) exhibited more than 70% efficiency increase over devices sensitized with the reference sensitizer LC‐1 (η = 4.44%).     

Mechanism of potential-dependent light absorption changes of lipid bilayer membranes in the presence of cyanine and oxonol dyes

Summary The mechanism by which the light absorption of cyanine and oxonol dyes changes in response to changes in transmembrane electrical potential has been studied. Trains of membrane potential steps produce changes in the intensity of light passing through glycerylmonooleate (GMO) bilayer lipid membranes (BLM) in the presence of these dyes. The size of the signal-averaged absorbance change for one of the cyanine dyes diS-C₂-(5) is 10^–5. The response time for the absorbance change of all of the dyes was 10 sec. In order for an absorption signal to be observed, the concentration of dye on both sides of the membrane must be different. Since GMO bilayer membranes are permeable to the charged dyes that were studied, the dye concentration asymmetry necessary for the optical signal had to be maintained with a constant dc membrane potential, onto which the trains of potential steps were superimposed. The more hydrophobic dyes were the most permeant. Inclusion of cholesterol in the GMO bilayers decreased the permeance of the positively charged cyanine dyes, but increased the permeance of the negatively charged oxonol dyes. The magnitude and the size of the BLM absorbance change depended on the wavelength of illumination. Comparisons of the wavelength dependence of the BLM spectra with absorption difference spectra obtained with model membrane systems allow us to postulate a mechanism for a BLM absorbance change. For the cyanine and oxonol dyes, the data are consistent with an ON-OFF mechanism where a quantity of dye undergoes a rapid potential-dependent movement between a hydrocarbon-like binding site on the membrane and the aqueous salt solution near the membrane. For some dyes, which readily aggregate on the membrane, part of the absorbance change may possibly be explained by a potential dependent change in the state of aggregation of dye molecules localized on the membrane. Mechanisms involving a potential dependent change in the polarizability of the environment of membrane-localized dye molecules cannot be excluded, but seem unlikely.     

Intrinsic fluorescence of B and Z forms of poly d(G-m5C).poly d(G-m5C), a synthetic double-stranded DNA: spectra and lifetimes by the maximum entropy method.

A study has been made of the fluorescence of poly d(G-m5C).poly d(G-m5C), a synthetic double-stranded DNA, in buffered neutral aqueous solution at room temperature, excited by synchrotron radiation at 280 nm and 250 nm and by a frequency-doubled pulse dye laser at 290 nm. Exciting at 280 nm, the B form shows a uni-modal UV spectrum with lambdaf(max) approximately 340 nm. The Z form has in addition a visible emission lambdaf(max) at 450 nm. The spectral positions remain unchanged on exciting at 250 nm but the relative intensities change considerably. Decay profiles have been obtained at 360 nm and 450 nm for both the B and Z forms and have been analyzed by fitting to a pseudo-continuous distribution of 100 (and occasionally 200) exponentials, ranging from 10 ps to 20 ns, by optimizing the 'entropy' of the signal (the method of maximum entropy). We find the mean lifetimes for both wavelengths of emission and for both structural forms fall into three well-separated regions in the ranges indicated tau1 approximately 0.04-0.21 ns, tau2 approximately 0.9-1.26 ns, and tau3 approximately 5.1-6.5 ns. The UV emission, from its spectral position and half-width, correlates with monomeric emission from m5C (and from C for poly d(G-C)). However the lifetime tau1 is approximately 2 orders of magnitude longer than the monomers and points to an involvement of protonated guanosine (GH+, tauf approximately 200 ps) in the overall absorption/emission sequence. In the UV the tau3 emission is predominant, with fractional time-integrated emission approximately 86% for B DNA and approximately 64% for Z. We suggest it results from exciton (stacked) absorption followed by dissociative emission. For Z DNA the visible (450 nm) emission is dominated by a tau3 species (approximately 91%) with a lifetime of 6.5 ns and we suggest it represents a hetero-excimer emission consequent upon absorption by the strongly overlapped base-stacking, which differs from that in B DNA. The weak emission corresponding to tau2 is made more apparent by scanned gated detection of the emission from laser excitation (290 nm) of single-crystal d(m5C-G)3. A central role is attributed to the tight stacking of the bases in the Z form which correlates with enhanced hypochromism at 250 nm vs. 280 nm and with the reversal of the fluorescence intensity ratios UV-visible between these wavelengths.     

Orientation and spectral properties of two stilbazolium merocyanine dyes in stretched and unstretched polyvinyl alcohol films

Spectral properties (anisotropy coefficients calculated for absorption, emission and fluorescence decay time) of two stilbazolium merocyanine dyes have been determined to evaluate the applicability of these dyes as sensitizers in photodynamic therapy. The dyes were embedded in an anisotropic polymer matrix. Analysis of the emission decay components measured in polarized light provides information on the interactions of the dye molecules with the polymer matrix being a model of an anisotropic biological system. Different values of the emission anisotropies obtained from various polarized components of fluorescence decays have shown that the orientations of the dye molecules influence their interactions with the polymer. This means that differently oriented dye molecules located in biological systems should exhibit different interactions with membranes. The chain length and type of side groups attached as well as the salt form of the dye molecule were shown to influence the dye-polymer interactions and should be taken into account before the application of merocyanine dyes in medicine. These dyes seem to be promising optical sensors with spectral properties, including the calculated anisotropy coefficients, sensitive to the molecular environment, useful to study orientation and interaction with neighbouring molecules in biological membranes.     

Comparative study of the optical and heat generation properties of IR820 and indocyanine green

AbstractNear-infrared (NIR) fluorophores are the focus of extensive research for combined molecular imaging and hyperthermia. In this study, we showed that the cyanine dye IR820 has optical and thermal generation properties similar to those of indocyanine green (ICG) but with improved in vitro and in vivo stability. The fluorescent emission of IR820 has a lower quantum yield than ICG but less dependence of the emission peak location on concentration. IR820 demonstrated degradation half-times approximately double those of ICG under all temperature and light conditions in aqueous solution. In hyperthermia applications, IR820 generated lower peak temperatures than ICG (4-9%) after 3-minute laser exposure. However, there was no significant difference in hyperthermia cytotoxicity, with both dyes causing significant cell growth inhibition at concentrations ≥ 5 μM. Fluorescent images of cells with 10 μM IR820 were similar to ICG images. In rats, IR820 resulted in a significantly more intense fluorescence signal and significantly higher organ dye content than for ICG 24 hours after intravenous dye administration (p < .05). Our study shows that IR820 is a feasible agent in experimental models of imaging and hyperthermia and could be an alternative to ICG when greater stability, longer image collection times, or more predictable peak locations are desirable.     

Structural parameters controlling the performance of organized mesoporous TiO2 films in dye sensitized solar cells

Titanium dioxide films with organized mesoporous structure were investigated as photoanodes in dye sensitized solar cells. High-quality films were grown on FTO supports by implementing the protocol of supramolecular templating with an amphiphilic triblock copolymer, Pluronic P123. Thicker films were obtained by repeated dip-coating and calcination cycles of up to 10 layers. The TiO₂ films were crack-free, optically transparent, and had thicknesses exceeding 2 μm, while still preserving the organized mesoporous morphology. Their roughness factors, determined from Kr-adsorption isotherms, exceeded 500. The sorption of N-3 and N-719 dyes was fitted to a surface coverage of 0.31 molecules/nm², which is about one third of the ideal dye loading assumed for the (1 0 1) anatase face. The solar performance of multilayer films sensitized with N-945 dye scaled linearly for 1-3 layer films, but approached a plateau for thicker films.     

Complexation of polymethine dyes with human serum albumin: a spectroscopic study

Non-covalent interactions between polymethine dyes of various types (cationic and anionic thiacarbocyanines as well as anionic oxonols and tetracyanopolymethines) and human serum albumin (HSA) were studied by means of absorption, fluorescence and circular dichroism (CD) spectroscopies. Complexation with the protein leads to a red shift of the dye absorption spectra and, in most cases, to a growth of the fluorescence quantum yield (Phif; for oxonols this growth is very small). The binding constants (K) obtained from changing the absorption spectra and Phif vary from 10(4) to (5-6) x 10(7) M(-1). K for the anionic dyes is much higher than for the cationic dyes (the highest K was found for oxonols). Interaction of meso-substituted anionic thiacarbocyanines with HSA results in cis-->trans isomerization and, as a consequence, an appearance and a steep rise of dye fluorescence. Binding to HSA gives rise to dye CD signals and in many cases is accompanied by aggregation of the dyes. These aggregates often exhibit biphasic CD spectra. The aggregates formed by the dyes alone are decomposed in the presence of HSA.     

Thermoacoustic molecular imaging of small animals

We have designed, constructed, and tested a thermoacoustic computed tomography (TCT) scanner for imaging optical absorption in small animals in three dimensions. The device utilizes pulsed laser irradiation (680-1064 nm) and a unique, 128-element transducer array. We quantified the isotropic spatial resolution of this scanner to be 0.35 mm. We describe a dual-wavelength subtraction technique for isolating optical dyes with TCT. Phantom experiments demonstrate that we can detect 5 fmol of a near-infrared dye (indocyanine green, ICG) in a 1-microL volume using dual-wavelength subtraction. Initial TCT imaging in phantoms and in two sacrificed mice suggests that three-dimensional, optical absorption patterns in small animals can be detected with an order of magnitude better spatial resolution and an order of magnitude better low-contrast detectability in small animals when compared to fluorescence imaging or diffusion optical tomography.