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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2012

Synthesis of TiO{sub 2} thin films using single molecular precursors by MOCVD method for dye-sensitized solar cells application and study on film growth mechanism

For dye-sensitized solar cells application, in this study, we have synthesized TiO{sub 2} thin films at deposition temperature in the range of 300–750 °C by metalorganic chemical vapor deposition (MOCVD) method. Titanium(IV) isopropoxide, (TIP, Ti(O{sup i}Pr){sub 4}) and Bis(dimethylamido)titanium diisopropoxide, (BTDIP, (Me{sub 2}N){sub 2}Ti(O{sup i}Pr){sub 2}) were used as single source precursors that contain Ti and O atoms in the same molecule, respectively. Crack-free, highly oriented TiO{sub 2} polycrystalline thin films with anatase phase were deposited on Si(1 0 0) with TIP at temperature as low as 450 °C. XRD and TED data showed that below 500 °C, the TiO{sub 2} thin films were dominantly grown in the [2 1 1] direction on Si(1 0 0), whereas with increasing the deposition temperature to 700 °C, the main film growth direction was changed to [2 0 0]. Above 700 °C, however, rutile phase TiO{sub 2} thin films have only been obtained. In the case of BTDIP, on the other hand, only amorphous film was grown on Si(1 0 0) below 450 °C while a highly oriented anatase TiO{sub 2} film in the [2 0 0] direction was obtained at 500 °C. With further increasing deposition temperatures over 600 °C, the main film growth direction shows a sequential change from rutile [1 0 1] to rutile [4 0 0], indicating a possibility of getting single crystalline TiO{sub 2} film with rutile phase. This means that the precursor together with deposition temperature can be one of important parameters to influence film growth direction, crystallinity as well as crystal structure. To investigate the CVD mechanism of both precursors in detail, temperature dependence of growth rate was also carried out, and we then obtained different activation energy of deposition to be 77.9 and 55.4 kJ/mol for TIP and BTDIP, respectively. Also, we are tested some TiO{sub 2} film synthesized with BTDIP precursor to apply dye-sensitized solar cell.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Improved performance of dye-sensitized solar cells with surface-treated TiO{sub 2} as a photoelectrode

We report on the effects of surface-modified TiO{sub 2} on the performance of dye-sensitized solar cells (DSSCs). TiO{sub 2} surface was modified with Na{sub 2}CO{sub 3} via a simple dip coating process and the modified TiO{sub 2} was applied to photoelectrodes of DSSCs. By dipping of TiO{sub 2} layer into aqueous Na{sub 2}CO{sub 3} solution, the DSSC showed a power conversion efficiency of 9.98%, compared to that (7.75%) of the reference device without surface treatment. The UV–vis absorption spectra, the impedance spectra and the dark current studies revealed that the increase of all parameters was attributed to the enhanced dye adsorption, the prolonged electron lifetime and the reduced interfacial resistance.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Template-free hydrothermal derived cobalt oxide nanopowders: Synthesis, characterization, and removal of organic dyes

Graphical abstract: XRD patterns of the products obtained by hydrothermal treatment at 160 °C for 24 h, and at different [Co{sup 2+}]/[CO{sub 3}{sup 2−}] ratios: (a) 1:6, (b) 1:3, (c) 1:1.5, (d) 1:1, (e) 1:0.5. Highlights: ► Spinel cobalt oxide nanoparticles with different morphologies were prepared by hydrothermal approach. ► The optical characteristics of the as-prepared cobalt oxide revealed the presence of two band gaps. ► Adsorption of methylene blue dye on Co{sub 3}O{sub 4} was investigated and the percent uptake was found to be >99% in 24 h. -- Abstract: Pure spinel cobalt oxide nanoparticles were prepared through hydrothermal approach using different counter ions. First, the pure and uniform cobalt carbonate (with particle size of 21.8–29.8 nm) were prepared in high yield (94%) in an autoclave in absence unfriendly organic surfactants or solvents by adjusting different experimental parameters such as: pH, reaction time, temperature, counter ions, and (Co{sup 2+}:CO{sub 3}{sup 2−}) molar ratios. Thence, the spinel Co{sub 3}O{sub 4} (with mean particle size of 30.5–47.35 nm) was produced by thermal decomposition of cobalt carbonate in air at 500 °C for 3 h. The products were characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FTIR), transmission electron microscope (TEM), scanning electron microscope (SEM), and thermal analysis (TA). Also, the optical characteristics of the as-prepared Co{sub 3}O{sub 4} nanoparticles revealed the presence of two band gaps (1.45–1.47, and 1.83–1.93 eV). Additionally, adsorption of methylene blue dye on Co{sub 3}O{sub 4} nanoparticles was investigated and the uptake% was found to be >99% in 24 h.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Applications of Cu{sub 2}O octahedral particles on ITO glass in photocatalytic degradation of dye pollutants under a halogen tungsten lamp

Graphical abstract: - Highlights: • Photocatalytic activity of Cu{sub 2}O octahedral microcrystals on ITO glass was studied. • They showed high abilities in degradation of methylene blue in the presence of H{sub 2}O{sub 2}. • H{sub 2}O{sub 2} amount could affect the degradation efficiency. • Such particles could be easily recycled and still kept high activity. • Many dye pollutants and their mixtures could be efficiently degraded. - Abstract: Cu{sub 2}O octahedral microcrystals were prepared on the ITO glass by galvanostatic electrodeposition in CuSO{sub 4} solution with poly(vinylpryrrolidone) as the surfactant. By controlling the electrodeposition time, the microcrystals could be randomly distributed on the ITO glass and separated from each other, resulting in as many as possible (1 1 1) crystalline planes were exposed. Such microcrystals immobilized on ITO glass were employed in photodegradation of dye pollutants in the presence of H{sub 2}O{sub 2} under a 150 W halogen tungsten lamp. The photodegradation of methylene blue was taken as an example to evaluate the photocatalytic activities of the octahedral Cu{sub 2}O microcrystals. Effects of electrodeposition time and H{sub 2}O{sub 2} amount on the degradation efficiency was discussed, giving the optimum conditions and the corresponding degradation mechanism. The catalyst showed high ability in degradation of methylene blue, methyl orange, rhodamine B, eosin B and their mixtures under identical conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2014

γ-Fe{sub 2}O{sub 3} nanoparticles: An easily recoverable effective photo-catalyst for the degradation of rose bengal and methylene blue dyes in the waste-water treatment plant

Graphical abstract: - Highlights: • γ-Fe{sub 2}O{sub 3} NPs from a single-source precursor and characterized by XRD, TEM, UV–vis spectra. • The NPs were tested as effective photocatalyst toward degradation of RB and MB dyes. • The possible pathway of the photocatalytic decomposition process has been discussed. • The active species, OH·, was detected by TA photoluminescence probing techniques. - Abstract: γ-Fe{sub 2}O{sub 3} nanoparticles (NPs) were synthesized from a single-source precursor complex [Fe{sub 3}O(C{sub 6}H{sub 5}COO){sub 6}(H{sub 2}O){sub 3}]NO{sub 3} by a simple thermal decomposition process and have been characterized by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM) and UV–vis spectroscopic techniques. The NPs were highly pure and well crystallized having hexagonal morphology with an average particle size of 35 nm. The prepared γ-Fe{sub 2}O{sub 3} (maghemite) NPs show effective photo-catalytic activity toward the degradation of rose bengal (RB) and methylene blue (MB) dyes under visible light irradiation and can easily be recoverable in the presence of magnetic field for successive re-uses. The possible photo-catalytic decomposition mechanism is discussed through the detection of hydroxyl radical (OH·) by terephthalic acid photo-luminescence probing technique.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Double-layer composite film based on hollow TiO{sub 2} boxes and P25 as photoanode for enhanced efficiency in dye-sensitized solar cells

Highlights: • A novel TiO{sub 2} double-layer composite film is successfully fabricated. • The TiO{sub 2}-HB overlayer exhibited intense scattering ability. • The P25 particles underlayer can enlarge the contact area and increase the contact points between TiO{sub 2}-HB and FTO glass. • TiO{sub 2}-DLL film cells have the maximum conversion efficiency. - Abstract: A TiO{sub 2} double-layer composite film consisting of hollow TiO{sub 2} boxes (HB-TiO{sub 2}) as overlayer and commercial-grade TiO{sub 2} nanoparticles (P25) as underlayer is designed as the photoelectrode of dye-sensitized solar cells (DSSCs). The hollow TiO{sub 2} box has been employed as light-scattering part to increase the optical length in the film and enhance light-harvesting. It was found that the double-layer film cell with lower absorbed dye achieved the highest conversion efficiency and reach up to a maximum value of 6.4%, which is 226% higher than that of pure HB-TiO{sub 2} film cell (η = 1.96%) and 57.2% higher than that of pure P25 particles film cell under identical film thickness at a constant irradiation of 100 mW cm{sup −2}. The enhanced efficiency of double-layer film can be attributed to its light-scattering capability.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Hierarchical TiO{sub 2} submicron-sized spheres for enhanced power conversion efficiency in dye-sensitized solar cells

Hierarchical TiO{sub 2} submicron-sized sphere scattering layer, with relatively large surface area and effective light scattering, shows enhanced power conversion efficiency in dye-sensitized solar cells. - Highlights: • Hierarchical TiO{sub 2} submicron-sized spheres (TiO{sub 2} HSSs) with diameters of 400–600 nm were synthesized. • The HSSs composed of nanoparticles of ∼14 nm have a relatively large surface area of ∼35 m{sup 2}/g. • DSC exhibited the highest cell efficiency (6.23%) compared with ones with pure P25 (5.50%) or HSS (2.00%) photoanodes. - Abstract: Hierarchical TiO{sub 2} submicron-sized spheres (TiO{sub 2} HSSs) with diameters of 400–600 nm were synthesized by a facile one-step solvothermal method in ethanol solvent. The HSSs composed of nanoparticles of ∼14 nm have a relatively large surface area of ∼35 m{sup 2}/g. When applied as the scattering overlayer in dye-sensitized solar cells (DSCs), such TiO{sub 2} HSSs effectively improved light harvesting and led to the increase of photocurrent in DSCs. Furthermore, bilayer-structured photoanode also provided fast electron transportation and long electron lifetime as confirmed by electrochemical impedance spectra. As a result, DSC based on P25 nanoparticle underlayer and HSS-2 overlayer exhibited the highest cell efficiency (6.23%) compared with ones with pure P25 (5.50%) or HSS-2 (2.00%) photoanodes.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Hierarchically macro–mesoporous TiO{sub 2} film via self-assembled strategy for enhanced efficiency of dye sensitized solar cells

Highlights: • A new hierarchically macro–mesoporous TiO{sub 2} film is fabricated via TiF{sub 4} hydrolysis. • TiF{sub 4} hydrolysis is accompanied with self-assembled process of TiO{sub 2} nanoparticles. • The hierarchically porous TiO{sub 2} films show higher performance than nonporous film. - Abstract: The hierarchically porous structure of TiO{sub 2} film plays an important role on improved photoelectric conversion efficiency in dye-sensitized solar cells (DSSCs). It is highly required to develop a facile strategy to prepare the hierarchical porous photoelectrode. In this study, a novel hierarchically macro–mesoporous TiO{sub 2} film as photoelectrode of DSSCs is fabricated by a self-assembled process of TiO{sub 2} nanoparticles via TiF{sub 4} hydrolysis. The hydrolysis of TiF{sub 4} is accompanied with self-assembled process of TiO{sub 2} nanoparticles on the surface of electrophoretic-deposited titanate nanotube film which provides effective active sites for the deposition of TiO{sub 2} nanoparticles owing to a large amount of hydroxyl groups, resulting in the formation of hierarchically porous structures. The hierarchically porous TiO{sub 2} film is mainly composed of mesopores with a size of 2–50 nm and macropores with a wide range of 0.5–5 μm, which contribute to an obviously higher conversion performance (6.70%) than nonporous P25-TiO{sub 2} film (4.01%). The main reasons for enhanced conversion efficiency of hierarchically porous TiO{sub 2} film can be attributed to adsorption of more dye molecules, rapid diffusion and efficient transport of electrolyte, and longer electron lifetime. This work may provide new insights into preparing porous structure of TiO{sub 2} films in DSSCs for modification of photoelectric conversion efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Enhancing photovoltaic performance of dye-sensitized solar cells by rare-earth doped oxide of SrAl{sub 2}O{sub 4}:Eu{sup 3+}

Graphical abstract: Current–voltage characteristics of DSSCs based on the photoanodes doping different SrAl{sub 2}O{sub 4}:Eu{sup 3+} and doping 3% SrAl{sub 2}O{sub 4}. - Highlights: • A down-conversion (DC) nanocrystal (SrAl{sub 2}O{sub 4}:Eu{sup 3+}) was synthesized. • The effect of SrAl{sub 2}O{sub 4}:Eu{sup 3+} doped in photoanode in DSSCs was investigated. • SrAl{sub 2}O{sub 4}:Eu{sup 3+} doped in photoanode appeared the better photovoltaic performances. • The dual function of DC and p-type doping effect were explained. - Abstract: SrAl{sub 2}O{sub 4}:Eu{sup 3+} down-conversion (DC) nanocrystals were synthesized by a sol–gel method and then doped in TiO{sub 2} as a photoanode in dye-sensitized solar cells (DSSCs). Differential thermal analysis, fourier transform infrared spectroscopy, X-ray diffraction and Brunauer–Emmet–Teller analysis confirmed the formation of SrAl{sub 2}O{sub 4}:Eu{sup 3+} nanocrystals with diameters of ∼47 nm, pore size of ∼25 nm, sintering temperature of 1300 °C. The photoluminescence and UV–vis absorption spectra of the SrAl{sub 2}O{sub 4}:Eu{sup 3+} revealed a DC from ultraviolet light to visible light which matched the strong absorbing region of the N719 dye. The photoelectric conversion efficiency of the DSSCs with a TiO{sub 2} photoanode doped with 3 wt% SrAl{sub 2}O{sub 4}:Eu{sup 3+} was 20% higher than that with a pure TiO{sub 2} photoanode. This phenomenon could be mainly explained by SrAl{sub 2}O{sub 4}:Eu{sup 3+} nanocrystals’ ability of DC and increased the short-circuit current density. It could be minorly due to the p-type doping effect and slightly improved the open-circuit voltage.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Enhanced photocatalytic degradation of methylene blue dye under UV-sunlight irradiation by cesium doped chromium oxide thin films

Highlights: • Cs doped thin films has been prepared by the low- cost spray pyrolysis technique. • Enhanced photocatalytic activity of Cr2O3 thin films for MB photogegradation(MB) dye was achieved through Cs doping. • 6 % Cs doped Cr{sub 2}O{sub 3} thin film photocatalyst with the merits of low band gap and more oxygen vacancies, exhibits the highest sun-light photocatalytic activity. • High photostability and recyclability was achieved under sun-light irradiation. - Abstract: The present contribution highlights the photocatalytic degradation of methylene blue dye over chromium oxide Cr{sub 2}O{sub 3} thin films based photocatalysts illuminated by ultraviolet and sunlight. Cr{sub 2}O{sub 3} photocatalyst was synthesized as thin film by the spray pyrolysis method on glass substrate at temperature of 350 °C. The physical properties of the thin films were studied by X-ray diffraction, scanning electron microscopy (SEM), infrared spectroscopy (IR), Raman spectroscopy, photoluminescence (PL) probing and UV–vis spectroscopy. XRD results showed that all samples were well crystallized with rhomoboedric curudum structure. Emissions of all films have been observed in visible region at 325 nm excitation. UV–vis-NIR spectrophotometry analysis showed that the band gap energy value of chromium oxide is shortened with cesium doping. Results indicate that both the cesium doping and the introduction of oxygen vacancies promote good photocatalytic activity of Cs doped Cr{sub 2}O{sub 3} thin films under sunlight for MB degradation.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Nickel doped graphitic carbon nitride nanosheets and its application for dye degradation by chemical catalysis

Highlights: • Nickel doped Graphitic carbon nitride (GCN) was synthesized chemically. • Mott-Schottky was done to calculate the flat band potentials and donor densities of pure and doped samples. • Toxic Methyl Orange dye was degraded efficiently by doped samples in the presence of NaBH{sub 4} accompanied by hydrogen evolution. • Enhancement of catalytic activity with increasing doping concentration was studied in presence of varying amount of NaBH{sub 4}. • A plausible mechanism for catalytic degradation was discussed in details. - Abstract: A facile synthesis of transition metal-nickel doped graphitic carbon nitride (NiGCN) nanosheets with varying doping concentrations has been reported. X-Ray diffraction and Fourier transformed infrared spectroscopic study were performed to analyse the structural phase formation and different bonds present in the samples, whereas, field emission and transmission electron microscopic study provided the morphological information. The thermal stability of the samples was measured from the TG-DTA analysis. Photoluminescence spectroscopy was performed to elucidate the emissive property of the samples. The flat band potential of the samples was measured by Mott-Schottky analysis. First principle study was carried out to delineate the probable doping site of the Ni atom along with the effect of doping on the pure material. The samples were effectively utilized to degrade toxic methyl orange (MO) dye from water in the presence of sodium borohydride (NaBH{sub 4}) without exploiting any visible light source. The plausible catalysis mechanism following a series of several chemical reactions has been discussed in details.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Improved photo-degradation of dyes over Ag-loaded NiTiO3:V nanorods on visible-light-irradiation

Highlights: • Ag/NiTiO{sub 3}:V nanorods were prepared by electrospinning synthesis. • The crystalline crystal structure was refined. • The optical absorption and band structure were clarified. • Photocatalysis was greatly enhanced in Ag/NiTiO{sub 3}:V nanorods. • The photocatalysis activities and mechanisms were discussed. - Abstract: Pure and V-doped NiTiO{sub 3} (NiTiO{sub 3}:V) nanorods were synthesized via electrospinning synthesis using sol–gel precursors, followed by sintering the samples at 600 °C. And the subsequent Ag-loaded NiTiO{sub 3}:V nanorods were prepared by the chemical precipitation method (Ag/NiTiO{sub 3}:V). The phase formations were studied via X-ray powder diffraction (XRD) measurements. The Rietveld refinements were conducted to investigate the structural characteristics. The surface property of the nanorods was measured via morphologies and X-ray photon spectrascope (XPS) measurements. The absorption spectra of products indicate sufficient optical response in visible wavelength region. The indirect allowed band gap (2.18 eV) of NiTiO{sub 3} originates from the characteristic charge-transfer (CT) transitions of O{sup 2−} → Ti{sup 4+} (UV region) and Ni{sup 2+} → Ti{sup 4+} (visible light region). While Ag/NiTiO{sub 3}:V composites have a smaller band energy of 2.09 eV. The photocatalytic activities were investigated by photo-degradation of Rhodamine B (RhB) dye solutions under visible-light irradiation. The Ag/NiTiO{sub 3}:V nanorods were efficient for the photo-degradation of RhB dye solutions. EIS measurements were used to analyze the charge-carrier migration at the interfaces. The improved photocatalysis of Ag/NiTiO{sub 3}:V is ascribed to the narrowed band energy and enhanced efficiencies of the charge separations due to the Ag-coupling and V-doping in NiTiO{sub 3} lattices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2024

Multivariate degradation modeling using generalized cauchy process and application in life prediction of dye-sensitized solar cells

Recently, the Generalized Cauchy (GC) process has been applied to capture a Long Memory (LM) phenomenon in product degradation modeling and life prediction. Compared with the traditional fractional Brownian motion that captures the LM using a single Hurst parameter, the GC process has two free parameters (Hurst and fractal dimension parameters) that flexibly capture both global LM and local irregularity. However, all existing GC-based degradation models are for a single Degradation Characteristic (DC). In this article, motivated by a real degradation problem of dye-sensitized solar cells that jointly exhibits multiple DCs, global LM, local irregularity and DC-wise cross-correlation, we propose a novel GC-based Multivariate Degradation Model (GC-MDM) to simultaneously capture the aforementioned effects. A maximum likelihood estimation approach is developed to estimate parameters of the GC-MDM. Subsequently, product life prediction based on the GC-MDM is developed. The proposed GC-MDM is validated through a simulation study and a physical experiment of dye-sensitized solar cells. Furthermore, results show that the proposed GC-MDM fundamentally improves the life prediction accuracy in comparison with conventional degradation models which significantly misestimate the uncertainty of product life.

14 SOLAR ENERGY↗
DOE OSTI2023

Correction to “Ruthenium Dye Excitations and Relaxations in Natural Sunlight”

An error in computing the optical rate coefficients for dye RuP was discovered in Table S4 of the Supporting Information Section S8 Model S? for this article, published in J. Phys. Chem. A, 2021, 125, 4365-4372, 10.1021/acs.jpca.1c02386. The optical rate coefficients include absorption, stimulated emission, and ground-state bleach associated with the ground state and the singlet and triplet excited states as well as for the excited-state absorption between the excited states and implicit higher-energy excited states. The optical rate coefficients for continuous solar irradiance were computed using eq 3 of the main text in which the product of the individual signal components and the solar spectrum are integrated and multiplied by the fundamental optical rate coefficient. We determined the incorrect signal components were used for RuP in the published Supporting Information Table S4. The corrected Table S4 column for RuP is presented with the reported values from the original paper in the corrected Supporting Information. New simulations have been performed using the corrected values, and the results were used to update Figures 5 and 6 and also Figure S9 in the corrected Supporting Information. The published conclusions are unchanged. The populations of RuP excited states, Figure 5, are only marginally smaller, which should be expected with minor changes to the optical rate coefficients. There is not a significant change in the results for the number of radiative and nonradiative interactions per dye per second (the optical transitions and nonradiative transitions increased, respectively, by approximately 2% and 10%, Figure 6A). The occurrence of excited-state absorption (ESA) and excited-state emission (ESE) events, Figure 6C, both decreased from the original simulation results by 20% and 33%. The most notable difference is exhibited in Figure 6B; the fraction of population moving from the lowest-energy singlet state (i.e., intersystem crossing or ultrafast nonradiative relaxation) and nonradiative relaxation from the triplet state have decreased from ~0.45 to ~0.4 and increased from ~0.35 to ~0.4, respectively..

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

One electron changes everything: a multispecies copper redox shuttle for dye-sensitized solar cells.

Dye-sensitized solar cells (DSCs) are an established alternative photovoltaic technology that offers numerous potential advantages in solar energy applications. However, this technology has been limited by the availability of molecular redox couples that are both noncorrosive/nontoxic and do not diminish the performance of the device. In an effort to overcome these shortcomings, a copper-containing redox shuttle derived from 1,8-bis(2'-pyridyl)-3,6-dithiaoctane (PDTO) ligand and the common DSC additive 4-tert-butylpyridine (TBP) was investigated. Electrochemical measurements, single-crystal X-ray diffraction, and absorption and electron paramagnetic resonance spectroscopies reveal that, upon removal of one metal-centered electron, PDTO-enshrouded copper ions completely shed the tetradentate PDTO ligand and replace it with four or more TBP ligands. Thus, the Cu(I) and Cu(II) forms of the electron shuttle have completely different coordination spheres and are characterized by widely differing Cu(II/I) formal potentials and reactivities for forward versus reverse electron transfer. Notably, the coordination-sphere replacement process is fully reversed upon converting Cu(II) back to Cu(I). In cells featuring an adsorbed organic dye and a nano- and mesoparticulate, TiO2-based, photoelectrode, the dual species redox shuttle system engenders performance superior to that obtained with shuttles based on the (II/I) forms of either of the coordination complexes in isolation.

Hoffeditz, William L.↗
DOE OSTI2025

Vibronic coupling-driven symmetry breaking and solvation in the photoexcited dynamics of quadrupolar dyes

Quadrupolar dyes, such as acceptor–donor–acceptor molecules, are highly relevant for applications in nonlinear optics and photovoltaics. They are also versatile models for exploring photoinduced charge-transfer dynamics. The interplay between electronic and vibronic couplings in these molecules may break excited-state symmetry, resulting in intramolecular charge separation and pronounced solvatochromism. Experimentally, distinguishing the roles of intramolecular vibronic coupling and solvent reorganization for the initial charge-transfer dynamics has been challenging so far. Here we investigate a prototypical quadrupolar dye in polar and non-polar solvents using ultrafast pump–probe and two-dimensional electronic spectroscopy. Our results reveal that vibronic couplings initiate excited-state symmetry breaking during the first ~50 fs of the photoinduced charge transfer, whereas solvent-induced charge localization sets in at later times. Quantum dynamics and electronic structure simulations support our experimental findings. Our results reveal the details of solvation dynamics in photoexcited molecules and suggest strategies for their manipulation through vibronic couplings.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Enhanced dye-sensitized solar cell photocurrent and efficiency using a Y-shaped, pyrazine-containing heteroaromatic sensitizer linkage

A new sensitizer motif for dye sensitized solar cells (DSSC) has been developed. A heteroaromatic moiety containing a pyrazine ring links two porphyrin chromophores to the metal oxide surface via two carboxylic acid attachment groups. A test DSSC sensitized with the new molecule was 3.5 times more efficient than a similar cell sensitized by a single porphyrin model compound. The open circuit photovoltage was increased by a modest factor of 1.3, but the photocurrent increased by a factor of 2.7. Most of the increase is attributed to a reduced rate of charge recombination of the charge separated state formed by photoinduced electron transfer from the excited sensitizer to the TiO 2 , although some of the difference is due to increased light absorption resulting from more dye on the photoanode. Increased light absorption due to the pyrazine-containing group may also play a role. The design illustrated here could also be used to link complementary sensitizers or antenna moieties in order to increase spectral coverage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Tuning the near infrared II emitting wavelength of small molecule dyes by single atom alteration

A series of small molecule dyes demonstrate the feasibility of manipulating Near Infrared II emission by simply altering the donors’ heteroatoms, which involved both electronegativity and intramolecular steric effects. Furthermore, these dyes show high resolution and stability for in vivo imaging after being complexed with human serum albumin.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗