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Charge Recombination (charge + recombination)
Selected AbstractsOff the Back or on the Side: Comparison of meso and 2-Substituted Donor-Acceptor Difluoroborondipyrromethene (Bodipy) DyadsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2010Andrew C. Benniston Abstract The preparation of several difluoroborondipyrromethene (Bodipy) dyads is described incorporating covalently attached hydroquinone/quinone groups at the 2-position (BD-SHQ, BD-SQ, BD-SPHQ, BD-SPQ). The compounds, currently under investigation as chemical sensors for reactive oxygen species, show various levels of fluorescence depending on the oxidation state of the appended group. The 19F NMR spectrum for BD-SHQ in CDCl3 at room temperature reveals the two fluorines are inequivalent on the NMR timescale. In contrast, the 19F NMR spectrum for the counterpart quinone compound, BD-SQ, is consistent with two equivalent fluorine atoms. The two results are interpreted as the quinone is free to rotate around the connector bond, whereas this motion is restricted for the hydroquinone group and makes the fluorines chemically inequivalent. Cyclic voltammograms recorded for all derivatives in CH2Cl2 electrolyte solution are consistent with typical Bodipy-based redox chemistry; the potentials of which depend on factors such as presence of the phenylene spacer and oxidation state of the appended group. A comparison of the electrochemical behaviour with the counterpart meso derivatives reveals some interesting trends which are associated with the location of the HOMO/LUMOs. The absorption profiles for the compounds in CH3CN are again consistent with Bodipy-based derivatives, though there are some subtle differences in the band-shapes of the closely-coupled systems. In particular, the absorption spectra for the dyad, BD-SQ, in a wide range of solvents are appreciably broader than for BD-SHQ. Femtosecond transient absorption spectroscopy performed on the hydroquinone derivatives, BD-SHQ and its meso analogue is interpreted as electron transfer occurs from the hydroquinone unit to the first-excited singlet (S1) state of the Bodipy center, followed by ultrafast charge recombination to reinstate the ground state. The coupling of OH vibrations to the return electron transfer process is invoked to explain the lack of clear identification of the charge-separated state in the transient records. [source] Solar Cells by Design: Photoelectrochemistry of TiO2 Nanorod Arrays Decorated with CdSeADVANCED FUNCTIONAL MATERIALS, Issue 12 2010Jin Ho Bang Abstract One-dimensional (1D) nanostructures of TiO2 are grown directly on transparent, conductive glass substrate using hydrothermal/solvothermal methods. When employed as a photoanode in photoelectrochemical cells, the vertically aligned TiO2 nanorod array exhibits slower charge recombination at electrolyte interface as compared to mesoscopic TiO2 particulate film. Electrochemical deposition of CdSe onto TiO2 nanorod array is carried out to extend absorption into visible light region. The role of CdSe-sensitized, 1D rutile TiO2 architecture in the solar cell design is discussed. [source] Enhanced-Light-Harvesting Amphiphilic Ruthenium Dye for Efficient Solid-State Dye-Sensitized Solar CellsADVANCED FUNCTIONAL MATERIALS, Issue 11 2010Mingkui Wang Abstract A ruthenium sensitizer (coded C101, NaRu (4,4,-bis(5-hexylthiophen-2-yl)-2,2,-bipyridine) (4-carboxylic acid-4,-caboxylate-2,2,-bipyridine) (NCS)2) containing a hexylthiophene-conjugated bipyridyl group as an ancillary ligand is presented for use in solid-state dye-sensitized solar cells (SSDSCs). The high molar-extinction coefficient of this dye is advantageous compared to the widely used Z907 dye, (NaRu (4-carboxylic acid-4,-carboxylate) (4,4,-dinonyl-2,2,-bipyridine) (NCS)2). In combination with an organic hole-transporting material (spiro-MeOTAD, 2,2,,7,7,-tetrakis-(N,N -di- p -methoxyphenylamine) 9, 9,-spirobifluorene), the C101 sensitizer exhibits an excellent power-conversion efficiency of 4.5% under AM 1.5 solar (100 mW cm,2) irradiation in a SSDSC. From electronic-absorption, transient-photovoltage-decay, and impedance measurements it is inferred that extending the ,-conjugation of spectator ligands induces an enhanced light harvesting and retards the charge recombination, thus favoring the photovoltaic performance of a SSDSC. [source] Surface Design in Solid-State Dye Sensitized Solar Cells: Effects of Zwitterionic Co-adsorbents on Photovoltaic PerformanceADVANCED FUNCTIONAL MATERIALS, Issue 13 2009Mingkui Wang Abstract In solid-state dye sensitized solar cells (SSDSCs) charge recombination at the dye-hole transporting material interface plays a critical role in the cell efficiency. For the first time we report on the influence of dipolar co-adsorbents on the photovoltaic performance of sensitized hetero-junction solar cells. In the present study, we investigated the effect of two zwitterionic butyric acid derivatives differing only in the polar moiety attached to their common 4 carbon-chain acid, i.e., 4-guanidinobutyric acid (GBA) and 4-aminobutyric acid (ABA). These two molecules were implemented as co-adsorbents in conjunction with Z907Na dye on the SSDSC. It was found that a Z907Na/GBA dye/co-adsorbent combination increases both the open circuit voltage (Voc) and short-circuit current density (Jsc) as compared to using Z907Na dye alone. The Z907Na/ABA dye/co-adsorbent combination increases the Jsc. Impedance and transient photovoltage investigations elucidate the cause of these remarkable observations. [source] The Energy of Charge-Transfer States in Electron Donor,Acceptor Blends: Insight into the Energy Losses in Organic Solar CellsADVANCED FUNCTIONAL MATERIALS, Issue 12 2009Dirk Veldman Abstract Here, a general experimental method to determine the energy ECT of intermolecular charge-transfer (CT) states in electron donor,acceptor (D,A) blends from ground state absorption and electrochemical measurements is proposed. This CT energy is calibrated against the photon energy of maximum CT luminescence from selected D,A blends to correct for a constant Coulombic term. It is shown that ECT correlates linearly with the open-circuit voltage (Voc) of photovoltaic devices in D,A blends via eVoc,=,ECT,,,0.5,eV. Using the CT energy, it is found that photoinduced electron transfer (PET) from the lowest singlet excited state (S1 with energy Eg) in the blend to the CT state (S1,,,CT) occurs when Eg,,,ECT,>,0.1,eV. Additionally, it is shown that subsequent charge recombination from the CT state to the lowest triplet excited state (ET) of D or A (CT,,,T1) can occur when ECT,,,ET,>,0.1,eV. From these relations, it is concluded that in D,A blends optimized for photovoltaic action: i) the maximum attainable Voc is ultimately set by the optical band gap (eVoc,=,Eg,,,0.6,eV) and ii) the singlet,triplet energy gap should be ,EST,<,0.2,eV to prevent recombination to the triplet state. These favorable conditions have not yet been met in conjugated materials and set the stage for further developments in this area. [source] Integration of a Rib Waveguide Distributed Feedback Structure into a Light-Emitting Polymer Field-Effect TransistorADVANCED FUNCTIONAL MATERIALS, Issue 9 2009Michael C. Gwinner Abstract Ambipolar light-emitting organic field-effect transistors (LEFETs) possess the ability to efficiently emit light due to charge recombination in the channel. Since the emission can be made to occur far from the metal electrodes, the LEFET structure has been proposed as a potential architecture for electrically pumped organic lasers. Here, a rib waveguide distributed feedback structure consisting of tantalum pentoxide (Ta2O5) integrated within the channel of a top gate/bottom contact LEFET based on poly(9,9-dioctylfluorene- alt -benzothiadiazole) (F8BT) is demonstrated. The emitted light is coupled efficiently into the resonant mode of the DFB waveguide when the recombination zone of the LEFET is placed directly above the waveguide ridge. This architecture provides strong mode confinement in two dimensions. Mode simulations are used to optimize the dielectric thickness and gate electrode material. It is shown that electrode absorption losses within the device can be eliminated and that the lasing threshold for optical pumping of the LEFET structure with all electrodes (4.5,µJ cm,2) is as low as that of reference devices without electrodes. These results enable quantitative judgement of the prospects for realizing an electrically pumped organic laser based on ambipolar LEFETs. The proposed device provides a powerful, low-loss architecture for integrating high-performance ambipolar organic semiconductor materials into electrically pumped lasing structures. [source] Nanorod-Based Dye-Sensitized Solar Cells with Improved Charge Collection Efficiency,ADVANCED MATERIALS, Issue 1 2008H. Kang Dye-sensitized solar cells (DSSCs) comprising chemically synthesized nanorods and nanoparticles are investigated. In identical circumstances, except for the charge-collection efficiency, nanorod-based DSSCs show improved photovoltaic properties (6.2 % versus 4.3 % for NP-based DSSCs) owing to the characteristics of slightly enhanced electron transport and predominantly degraded charge recombination, compared with nanoparticle-based DSSC. [source] Theoretical investigation of charge transfer excitation and charge recombination in acenaphthylene,tetracyanoethylene complexINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 1 2003Hai-Bo Yi Abstract Ab initio calculations were performed to investigate the charge separation and charge recombination processes in the photoinduced electron transfer reaction between tetracyanoethylene and acenaphthylene. The excited states of the charge-balanced electron donor,acceptor complex and the singlet state of ion pair complex were studied by employing configuration interaction singles method. The equilibrium geometry of electron donor,acceptor complex was obtained by the second-order Møller,Plesset method, with the interaction energy corrected by the counterpoise method. The theoretical study of ground state and excited states of electron donor,acceptor complex in this work reveals that the S1 and S2 states of the electron donor,acceptor complexes are excited charge transfer states, and charge transfer absorptions that corresponds to the S0 , S1 and S0 , S2 transitions arise from ,,,* excitations. The charge recombination in the ion pair complex will produce the charge-balanced ground state or excited triplet state. According to the generalized Mulliken,Hush model, the electron coupling matrix elements of the charge separation process and the charge recombination process were obtained. Based on the continuum model, charge transfer absorption and charge transfer emission in the polar solvent of 1,2-dichloroethane were investigated. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem 94: 23,35, 2003 [source] Donor/Spacer/Acceptor Block Copolymer Containing Poly(2,7-carbazole) and Perylenetetracarboxydiimide SubunitsMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 13 2010Changduk Yang Abstract A straightforward synthesis of a conjugated rod/spacer/rod-type block copolymer containing PCz electron-donor and PDI electron-acceptor blocks is described. Two chromophores are covalently connected through sebacate units as saturated spacer. The resulting donor/spacer/acceptor-type block copolymer (PCz-S-PDI) can be applied to limit charge recombination between donor/acceptor interfaces and to control the scale length of nanostructure formation. PCz-S-PDI was used to produce a solar cell with the power conversion efficiency of 0.004%. [source] Mesoscopic Modelling of Polymer-Based Optoelectronic DevicesPLASMA PROCESSES AND POLYMERS, Issue S1 2007Hélder M. C. Barbosa Abstract Substantial progress has been made in fabricating optoelectronic devices using polymers as an active material. In polymer light emitting diodes (PLEDs), a balanced injection of electrons and holes from the electrodes is fundamental to increase their performance. Using a mesoscopic model based on a generalized Monte-Carlo method, we studied the influence of changing zero-field barrier heights at both electrode,polymer interfaces in the performance of a PLED with an active layer of poly(para -phenylenevinylene) (PPV). Our results show that by controlling the electrodes work functions it is possible to tune the region inside the device where charge recombination preferentially takes place. [source] Interface-tailored and nanoengineered polymeric materials for (opto)electronic devicesPOLYMER INTERNATIONAL, Issue 6 2009Hong Ma Abstract For plastic (opto)electronic devices such as light-emitting diodes (LEDs), photovoltaic (PV) cells and field-effect transistors (FETs), the processes of charge (hole/electron) injection, charge transport, charge recombination (exciton formation), charge separation (exciton diffusion and dissociation) and charge collection are critical to enhance their performance. Most of these processes are relevant to nanoscale and interfacial phenomena. In this review, we highlight the state-of-the-art developments of interface-tailored and nanoengineered polymeric materials to optimize the performance of (opto)electronic devices. These include (1) interfacial engineering of anode and cathode for polymer LEDs; (2) nanoengineered (C60 and inorganic semiconductor nanoparticles) ,-conjugated polymeric materials for PV cells; and (3) polymer and monolayer dielectrics/interfaces for FETs and light-emitting and nano-FETs. Copyright © 2009 Society of Chemical Industry [source] The Effect of Heavy Atoms on Photoinduced Electron Injection from Nonthermalized and Thermalized Donor States of MII,Polypyridyl (M=Ru/Os) Complexes to Nanoparticulate TiO2 Surfaces: An Ultrafast Time-Resolved Absorption StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 2 2010Sandeep Verma Abstract We have synthesized ruthenium(II), and osmium(II),polypyridyl complexes ([M(bpy)2L]2+, in which M=OsII or RuII, bpy=2,2,-bipyridyl, and L=4-(2,2,-bipyridinyl-4-yl)benzene-1,2-diol) and studied the interfacial electron-transfer process on a TiO2 nanoparticle surface using femtosecond transient-absorption spectroscopy. Ruthenium(II)- and osmium(II)-based dyes have a similar molecular structure; nevertheless, we have observed quite different interfacial electron-transfer dynamics (both forward and backward). In the case of the RuII/TiO2 system, single-exponential electron injection takes place from photoexcited nonthermalized metal-to-ligand charge transfer (MLCT) states. However, in the case of the OsII/TiO2 system, electron injection takes place biexponentially from both nonthermalized and thermalized MLCT states (mainly 3MLCT states). Larger spin,orbit coupling for the heavier transition-metal osmium, relative to that of ruthenium, accounts for the more efficient population of the 3MLCT states in the OsII -based dye during the electron-injection process that yields biexponential dynamics. Our results tend to suggest that appropriately designed OsII,polypyridyl dye can be a better sensitizer molecule relative to its RuII analogue not only due to much broader absorption in the visible region of the solar-emission spectrum, but also on account of slower charge recombination. [source] Mechanism of Charge Separation in DNA by Hole Transfer through Consecutive AdeninesCHEMISTRY - A EUROPEAN JOURNAL, Issue 12 2008Kiyohiko Kawai Prof. Abstract To investigate the mechanism of charge separation in DNA with consecutive adenines adjacent to a photosensitizer (Sens), a series of naphthalimide (NI) and 5-bromouracil (brU)-modified DNAs were prepared, and the quantum yields of formation of the charge-separated states (,) upon photo-excitation of the Sens NI in DNA were measured. The , was modulated by the incorporation site of brU, which changes the oxidation potential of its complementary A through hydrogen bonding and the hole-transfer rates between adenines. The results were interpreted as charge separation by means of the initial charge transfer between NI in the singlet excited state and the second- and third-nearest adenine to the NI. In addition, the oxidation of the A nearest to NI leads to the rapid charge recombination within a contact ion pair. This suggests that the charge-separation process can be refined to maximize the , by putting a redox-inactive spacer base pair between a photosensitizer and an A,T stretch. [source] Selective Inclusion of Electron-Donating Molecules into Porphyrin Nanochannels Derived from the Self-Assembly of Saddle-Distorted, Protonated Porphyrins and Photoinduced Electron Transfer from Guest Molecules to Porphyrin DicationsCHEMISTRY - A EUROPEAN JOURNAL, Issue 31 2007Takahiko Kojima Prof. Abstract A doubly protonated hydrochloride salt of a saddle-distorted dodecaphenylporphyrin (H2DPP), [H4DPPP]Cl2, forms a porphyrin nanochannel (PNC). X-ray crystallography was used to determine the structure of the molecule, which revealed the inclusion of guest molecules within the PNC. Electron-donating molecules, such as p -hydroquinone and p -xylene, were selectively included within the PNC in sharp contrast to electron acceptors, such as the corresponding quinones, which were not encapsulated. This result indicates that the PNC can recognize the electronic character and steric hindrance of the guest molecules during the course of inclusion. ESR measurements (photoirradiation at ,>340,nm at room temperature) of the PNC that contains p -hydroquinone, catechol, and tetrafluorohydroquinone guest molecules gave well-resolved signals, which were assigned to cation radicals formed without deprotonation based on results from computer simulations of the ESR spectra and density functional theory (DFT) calculations. The radicals are derived from photoinduced electron transfer from the guest molecules to the singlet state of H4DPP2+. Transient absorption spectroscopy by femtosecond laser flash photolysis allowed us to observe the formation of 1(H4DPP2+)*, which is converted to H4DPP+. by electron transfer from the guest molecules to 1(H4DPP2+)*, followed by fast disproportionation of H4DPP+., and charge recombination to give diamagnetic species and the triplet excited state 3(H4DPP2+)*, respectively. [source] The Influence of Charge Transport and Recombination on the Performance of Dye-Sensitized Solar CellsCHEMPHYSCHEM, Issue 1 2009Mingkui Wang Dr. Abstract Electrochemical impedance spectroscopy (EIS) and transient voltage decay measurements are applied to compare the performance of dye sensitized solar cells (DSCs) using organic electrolytes, ionic liquids and organic-hole conductors as hole transport materials (HTM). Nano-crystalline titania films sensitized by the same heteroleptic ruthenium complex NaRu(4-carboxylic acid-4,-carboxylate) (4,4,-dinonyl-2,2,-bipyridyl)(NCS)2,, coded Z-907Na are employed as working electrodes. The influence of the nature of the HTM on the photovoltaic figures of merit, that is, the open circuit voltage, short circuit photocurrent and fill factor is evaluated. In order to derive the electron lifetime, as well as the electron diffusion coefficient and charge collection efficiency, EIS measurements are performed in the dark and under illumination corresponding to realistic photovoltaic operating conditions of these mesoscopic solar cells. A theoretical model is established to interpret the frequency response off the impedance under open circuit conditions, which is conceptually similar to photovoltage transient decay measurements. Important information on factors that govern the dynamics of electron transport within the nanocrystalline TiO2 film and charge recombination across the dye sensitized heterojunction is obtained. [source] | |||||||||||||||||||||||||