Hole Transfer Dynamics Research Articles

Ultrafast Electron Injection, Hole Transfer, and Charge Recombination Dynamics in CdSe QD Super-Sensitized Re(I)–Polypyridyl Complexes with Catechol and Resorcinol Moiety: Effect of Coupling

Ultrafast charge-transfer dynamics have been demonstrated in CdSe quantum dots (QD) using two Re(I)–polypyridyl complexes having pendent catechol (Re1,2) and resorcinol (Re1,3) as the sensitizer molecules. The energy level diagram of CdSe QD and Re1,2 and Re1,3 sensitizer reveals that photoexcited hole of CdSe QD can be transferred to both Re1,2 and Re1,3 molecule, and photoexcited Re1,2 and Re1,3 can inject electron in the conduction band, which has been confirmed by steady-state and time-resolved photoluminescence studies with selective photoexcitation. Femtosecond transient absorption studies have been carried out to monitor charge-transfer dynamics in early time scale. Transient absorption spectra show formation of cation radicals for both Re1,2 and Re1,3 in the 550–650 nm region with a peak at 590 nm region and broad absorption in the 650–1000 nm region, which can be attributed to photoexcited electron in the conduction band of CdSe QD. Charge recombination was determined by monitoring the decay of cation radicals as well as decay of an electron and found to be slower in the Re1,3/CdSe system as compared to that of the Re1,2/CdSe system, which is due to weaker electronic coupling in the former system.

Hot-hole extraction from quantum dot to molecular adsorbate.

Ultrafast thermalized and hot-hole-transfer processes have been investigated in CdSe quantum dot (QD)/catechol composite systems in which hole transfer from photoexcited QDs to the catechols is thermodynamically favorable. A series of catechol derivatives were selected with different electron-donating and -withdrawing groups, and the effect of these groups on hole transfer and charge recombination (CR) dynamics has been investigated. The hole-transfer time was determined using the fluorescence upconversion technique and found to be 2-10 ps depending on the molecular structure of the catechol derivatives. The hot-hole-transfer process was followed after monitoring 2S luminescence of CdSe QDs. Interestingly, hot-hole extraction was observed only in the CdSe/3-methoxycatechol (3-OCH3) composite system owing to the higher electron-donating property of the 3-methoxy group. To confirm the extraction of the hot hole and to monitor the CR reaction in CdSe QD/catechol composite systems, ultrafast transient absorption studies have been carried out. Ultrafast transient-absorption studies show that the bleach recovery kinetics of CdSe QD at the 2S excitonic position is much faster in the presence of 3-OCH3. This faster bleach recovery at the 2S position in CdSe/3-OCH3 suggests hot-hole transfer from CdSe QD to 3-OCH3. CR dynamics in CdSe QD/catechol composite systems was followed by monitoring the excitonic bleach at the 1S position and was found to decrease with free energy of the CR reaction.

Cascading electron and hole transfer dynamics in a CdS/CdTe core-shell sensitized with bromo-pyrogallol red (Br-PGR): slow charge recombination in type II regime.

Ultrafast cascading hole and electron transfer dynamics have been demonstrated in a CdS/CdTe type II core-shell sensitized with Br-PGR using transient absorption spectroscopy and the charge recombination dynamics have been compared with those of CdS/Br-PGR composite materials. Steady state optical absorption studies suggest that Br-PGR forms strong charge transfer (CT) complexes with both the CdS QD and CdS/CdTe core-shell. Hole transfer from the photo-excited QD and QD core-shell to Br-PGR was confirmed by both steady state and time-resolved emission spectroscopy. Charge separation was also confirmed by detecting electrons in the conduction band of the QD and the cation radical of Br-PGR as measured from femtosecond transient absorption spectroscopy. Charge separation in the CdS/Br-PGR composite materials was found to take place in three different pathways, by transferring the photo-excited hole of CdS to Br-PGR, electron injection from the photo-excited Br-PGR to the CdS QD, and direct electron transfer from the HOMO of Br-PGR to the conduction band of the CdS QD. However, in the CdS/CdTe/Br-PGR system hole transfer from the photo-excited CdS to Br-PGR and electron injection from the photo-excited Br-PGR to CdS take place after cascading through the CdTe shell QD. Charge separation also takes place via direct electron transfer from the Br-PGR HOMO to the conduction band of CdS/CdTe. Charge recombination (CR) dynamics between the electron in the conduction band of the CdS QD and the Br-PGR cation radical were determined by monitoring the bleach recovery kinetics. The CR dynamics were found to be much slower in the CdS/CdTe/Br-PGR system than in the CdS/Br-PGR system. The formation of the strong CT complex and the separation of charges cascading through the CdTe shell help to slow down charge recombination in the type II regime.

Electron Trap to Electron Storage Center in Specially Aligned Mn-Doped CdSe d-Dot: A Step Forward in the Design of Higher Efficient Quantum-Dot Solar Cell.

Specially aligned surface-accumulated Mn-doped CdSe (MnCdSe) quantum dots (QDs) have been synthesized to study the effect of dopant atom on charge-carrier dynamics in QD materials. EPR studies suggest that the (4)T1 state of Mn(2+) lies above the conduction band of CdSe, and as a result no Mn-luminescence was observed from MnCdSe. Femtosecond transient absorption studies suggest that Mn atom introduces structural defects in surface-doped CdSe, which acts as electron trap center in doped QD for the photoexcited electron. Bromo-pyrogallol red (Br-PGR) were found to form strong charge-trasfer complex with both CdSe and MnCdSe QDs. Charge separation in both the CdSe/Br-PGR and MnCdSe/Br-PGR composites was found to take place in three different pathways by transferring the photoexcited hole of CdSe/MnCdSe QDs to Br-PGR, electron injection from photoexcited Br-PGR to the QDs, and direct electron transfer from the HOMO of Br-PGR to the conduction band of both the QDs. Hole-transfer dynamics are found to be quite similar (∼1.1 to 1.3 ps) for both of the systems and found to be independent of Mn doping. However, charge recombination dynamics was found to be much slower in the MnCdSe/Br-PGR system as compared with that in the CdSe/Br-PGR system, which confirms that the Mn dopant act as the electron storage center. As a consequence, the MnCdSe/Br-PGR system can be used as a better super sensitizer in quantum-dot-sensitized solar cell to increase efficiency further.

Hole Transfer Dynamics from a CdSe/CdS Quantum Rod to a Tethered Ferrocene Derivative

Hole transfer between a CdSe/CdS core/shell semiconductor nanorod and a surface-ligated alkyl ferrocene is investigated by a combination of ab initio quantum chemistry calculations and electrochemical and time-resolved photoluminescence measurements. The calculated driving force for hole transfer corresponds well with electrochemical measurements of nanorods partially ligated by 6-ferrocenylhexanethiolate. The calculations and the experiments suggest that single step hole transfer from the valence band to ferrocene is in the Marcus inverted region. Additionally, time-resolved photoluminescence data suggest that two-step hole transfer to ferrocene mediated by a deep trap state is unlikely. However, the calculations also suggest that shallow surface states of the CdS shell could play a significant role in mediating hole transfer as long as their energies are close enough to the nanorod highest occupied molecular orbital energy. Regardless of the detailed mechanism of hole transfer, our results suggest that holes may be extracted more efficiently from well-passivated nanocrystals by reducing the energetic driving force for hole transfer, thus minimizing energetic losses.

Ultrafast Charge- and Energy-Transfer Dynamics in Conjugated Polymer: Cadmium Selenide Nanocrystal Blends

Hybrid nanocrystal–polymer systems are promising candidates for photovoltaic applications, but the processes controlling charge generation are poorly understood. Here, we disentangle the energy- and charge-transfer processes occurring in a model system based on blends of cadmium selenide nanocrystals (CdSe-NC) with poly[2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) using a combination of time-resolved absorption and luminescence measurements. The use of different capping ligands (n-butylamine, oleic acid) as well as thermal annealing allows tuning of the polymer–nanocrystal interaction. We demonstrate that energy transfer from MDMO-PPV to CdSe-NCs is the dominant exciton quenching mechanism in nonannealed blends and occurs on ultrafast time scales (<1 ps). Upon thermal annealing electron transfer becomes competitive with energy transfer, with a transfer rate of 800 fs independent of the choice of the ligand. Interestingly, we find hole transfer to be much less efficient than electron transfer and to extend over several nanoseconds. Our results emphasize the importance of tuning the organic–nanocrystal interaction to achieve efficient charge separation and highlight the unfavorable hole-transfer dynamics in these blends.

Electron and hole transfer dynamics of a triarylamine-based dye with peripheral hole acceptors on TiO2 in the absence and presence of solvent

We investigated photoinduced primary charge transfer processes of the sensitizer E6 on TiO2 without solvent and in contact with the organic solvent acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium tetracyanoborate [C2mim](+)[B(CN)4](-) using transient absorption spectroscopy, spectroelectrochemistry, and DFT/TDDFT calculations. E6, which belongs to a family of triarylamine dyes for solar cell applications, features two peripheral triarylamine units which are connected via diether spacer groups to the core chromophore and are designed to act as hole traps. This function was confirmed by spectroelectrochemistry, where the E6˙(+) radical cation shows a considerably blue-shifted absorption compared to dyes without these two substituents. This indicates that one of the terminal triarylamine units must carry the positive charge. After photoexcitation of E6 at 520 nm (S0 → S1 band), electrons are injected into TiO2 predominantly within the cross-correlation time (<80 fs), with some subsequent delayed electron injection (τ ca. 250 fs). Importantly, a transient Stark shift (electrochromism) is observed (time constants ca. 0.8 and 12 ps) which is related to a changing electric field generated by the E6˙(+) radical cations and injected electrons. This field induces absorption shifts of the dye species on the surface. Interestingly, these dynamics are largely unaffected by solvent molecules. However, pronounced differences are observed on longer timescales. In contact with solvent, one observes an increase in the E6˙(+) absorption band above 600 nm with a time constant of 75 ps. This is assigned to hole transfer from the core chromophore to one of the peripheral triarylamine substituents. Electron-cation recombination occurs on much longer timescales and is multiexponential, with time constants of ca. 100 μs, 1 ms and 15 ms. Because of hole trapping, it is slower than for similar dyes lacking the peripheral triarylamines. Additional experiments were performed for E6 attached to the wide band gap semiconductor ZrO2. Here, electron injection occurs into surface trap states with subsequent recombination. Another fraction of non-injecting E6 molecules in S1 quickly decays to S0 (time constants 1 and 35 ps).

Trap and Transfer. Two-Step Hole Injection Across the Sb2S3/CuSCN Interface in Solid-State Solar Cells

In solid-state semiconductor-sensitized solar cells, commonly known as extremely thin absorber (ETA) or solid-state quantum-dot-sensitized solar cells (QDSCs), transfer of photogenerated holes from the absorber species to the p-type hole conductor plays a critical role in the charge separation process. Using Sb2S3 (absorber) and CuSCN (hole conductor), we have constructed ETA solar cells exhibiting a power conversion efficiency of 3.3%. The hole transfer from excited Sb2S3 into CuSCN, which limits the overall power conversion efficiency of these solar cells, is now independently studied using transient absorption spectroscopy. In the Sb2S3 absorber layer, photogenerated holes are rapidly localized on the sulfur atoms of the crystal lattice, forming a sulfide radical (S(-•)) species. This trapped hole is transferred from the Sb2S3 absorber to the CuSCN hole conductor with an exponential time constant of 1680 ps. This process was monitored through the spectroscopic signal seen for the S(-•) species in Sb2S3, providing direct evidence for the hole transfer dynamics in ETA solar cells. Elucidation of the hole transfer mechanism from Sb2S3 to CuSCN represents a significant step toward understanding charge separation in Sb2S3 solar cells and provides insight into the design of new architectures for higher efficiency devices.

Exciton and Hole-Transfer Dynamics in Polymer: Fullerene Blends

Ultrafast hole transfer dynamics from fullerene derivative to polymer in bulk heterojunction blends are studied with visible-pump - IR-probe spectroscopy. The hole transfer process is found to occur in 50/300 fs next to the interface, while a longer 15-ps time is attributed to exciton diffusion towards interface in PC71 BM domains. High polaron generation efficiency in P3HT blends indicates excellent intercalation between the polymer and the fullerene even at highest PC71 BM concentration thereby yielding a valuable information on the blend morphology.

Shell Thickness Dependent Photoinduced Hole Transfer in Hybrid Conjugated Polymer/Quantum Dot Nanocomposites: From Ensemble to Single Hybrid Level

Photoinduced hole transfer is investigated in inorganic/organic hybrid nanocomposites of colloidal CdSe/ZnS quantum dots and a cationic conjugated polymer, poly(9,9'-bis(6-N,N,N-trimethylammoniumhexyl)fluorene-alt-phenylene, in solution and in solid thin film, and down to the single hybrid level and is assessed to be a dynamic quenching process. We demonstrate control of hole transfer rate in these quantum dot/conjugated polymer hybrids by using a series of core/shell quantum dots with varying shell thickness, for which a clear exponential dependency of the hole transfer rate vs shell thickness is observed, for both solution and thin-film situations. Furthermore, we observe an increase of hole-transfer rate from solution to film and correlate this with changes in quantum dot/polymer interfacial morphology affecting the hole transfer rate, namely, the donor-acceptor distance. Single particle spectroscopy experiments reveal fluctuating dynamics of hole transfer at the single conjugated polymer/quantum dot interface and an increased heterogeneity in the hole-transfer rate with the increase of the quantum dot's shell thickness. Although hole transfer quenches the photoluminescence intensity of quantum dots, it causes little or no effect on their blinking behavior over the time scales probed here.

Hole transfer dynamics from dye molecules to p-type NiO nanoparticles: effects of processing conditions

Hole transfer dynamics of Atto647N sensitized p-type NiO nanoparticle (NP) thin films is investigated using both ensemble-averaged and single-molecule spectroscopy techniques. The rate of hole transfer is dependent on the processing conditions and is enhanced when the NiO is pre-annealed in air as compared to vacuum. This is possibly due to an upward shift of the valence band of the semiconductor and an increase in the free energy for hole transfer as more Ni(2)O(3) are formed in the presence of air. The stretched exponential fluorescence decay profile of Atto647N on NiO NP suggests the presence of a distribution of hole transfer rates. This is in agreement with the observed emission lifetime and intensity fluctuations and non-monoexponential fluorescence decays for individual Atto647N molecules on NiO NP films. A plausible explanation for the heterogeneous hole transfer rates is an inhomogeneous distribution of (defect) sites on the metal oxide due to the processing conditions and a fluctuation in the intermolecular interaction.

Hole and excess electron transfer dynamics in DNA

Charge transfer in DNA attracts substantial attention from researchers in a wide group of fields such as bioscience, nanotechnology and physical chemistry. It is well known that both positive and negative charges, which are holes and excess electrons, respectively, contribute to the charge transfer in DNA. In the case of hole transfer in DNA, detailed mechanisms and dynamical parameters have been estimated by means of time-resolved spectroscopic methods and product analysis. On the other hand, detailed dynamics of excess electron transfer have not been established yet, although several aspects have been revealed by the continuous efforts of various research groups. In the present Perspective, studies on the charge transfer dynamics in DNA are summarized.

Hole Transfer from Single Quantum Dots

Photoinduced hole transfer dynamics from single CdSe/CdS(3ML)/CdZnS(2ML)/ZnS(2ML) core/multishell quantum dots (QDs) to phenothiazine (PTZ) molecules were studied by single QD fluorescence spectroscopy to investigate the static and dynamic heterogeneities of the hole transfer process as well as its effect on the blinking dynamics of QDs. Ensemble-averaged transient absorption and fluorescence decay measurements show that excitons in QDs dissociate by transferring the valence band hole to PTZ with a time constant of 50 ns for the 1:1 PTZ-QD complex, and the subsequent charge recombination process (i.e., electron transfer from the conduction band of the reduced QD to oxidized PTZ to regenerate the complex in the ground state) occurs mainly on the 100 to 1000 ns time scale. Single QD-PTZ complexes show pronounced correlated fluctuations of fluorescence intensity and lifetime with time. In addition to the dynamic fluctuation, there are considerable heterogeneities of average hole transfer rate among different QD-PTZ complexes. The hole transfer process has little effect on the statistics of the off-states, which is often believed to be positively charged QDs with a valence band hole. Instead, it increases the probability of weakly emissive or "gray" states.

Effect of Electrostatic Interactions and Dynamic Disorder on the Distance Dependence of Charge Transfer in Donor−Bridge−Acceptor Systems

Using a tight-binding model of charge transport in systems with static and dynamic disorder, we present a theoretical study of the positive charge transfer in molecular assemblies that involve a hole donor and an acceptor connected by fluorene and phenyl bridges. Two parameters that determine the rate of charge transfer within the proposed model are the charge transfer integral between neighboring units and the site energies. Fluctuations in the values of the charge transfer integral and the energy landscape for hole transport were calculated by taking into account variations of the dihedral angle between neighboring units and electrostatic interaction of positive charge moving along the bridge and the negative charge that remains on the hole donor. Analysis of the dynamics of hole transfer and the distribution of the positive charge during this process allows the conclusion that the rapid fall of the hole transfer rate coefficient observed in experiments with short bridges (three and four structural units for systems with fluorene and phenyl bridges, respectively) can be attributed to the electrostatic interaction. This interaction is responsible for the formation of the effective barrier between donor and acceptor with the height that increases as the number of structural bridge units remains less than 3 (fluorene bridge) or 4 (phenyl bridge). For longer bridges, however, the effective barrier changes only weakly and now the charge transport is mostly dominated by the fluctuation-assisted incoherent hole migration along the bridge. The latter mechanism exhibits much weaker dependence of the rate coefficient on the bridge length in agreement with the available experimental results.

Shell-dependent hole transport in highly luminescent CdSe-core CdS/ZnCdS/ZnS multi-shell nanocrystals

The photoinduced hole transfer dynamics from CdSe quantum dots (QDs), shelled with ZnS or CdS/CdZnS/ZnS layers, to organic hole transporting materials (HTMs) is investigated by absorption, steady-state and time-resolved photoluminescence (PL) spectroscopy. The PL intensity and lifetime of the QDs are dramatically quenched when HTMs are added into the dilute QD solution. The quenching efficiency of the QDs significantly decreases with increasing the shell thickness and increases with decreasing the oxidation potential of the HTMs. These facts are correlated with the photoinduced hole transfer from the QDs to the HTMs. The above results are helpful in understanding the photoexcitation dynamics-related phenomena of organic molecule conjugated nano-object.

Energy- and Hole-Transfer Dynamics in Oxidized Porphyrin Dyads

The mechanisms and dynamics of quenching of a photoexcited free base porphyrin (Fb*) covalently linked to a nearby oxidized zinc porphyrin (Zn(+)) have been investigated in a set of five dyads using time-resolved absorption spectroscopy. The dyads include porphyrins joined at the meso-positions by a diphenylethyne linker or a diarylethyne linker with 2,6-dimethyl substitution on either one or both of the aryl rings. Another dyad is linked at the beta-pyrrole positions of the porphyrins via a diphenylethyne linker. The type of linker and attachment site modulate the interporphyrin through-bond electronic coupling via steric hindrance (porphyrin-linker orbital overlap) and attachment motif (porphyrin electron density at the connection site). For each ZnFb dyad, the zinc porphyrin is selectively electrochemically oxidized (to produce Zn(+)Fb), the free base porphyrin is selectively excited with a 130 fs flash (to produce Zn(+)Fb*), and the subsequent dynamics monitored. The Zn(+)Fb* excited state has a lifetime of approximately 3 to approximately 30 ps (depending on the linker steric hindrance and attachment site) and decays by parallel excited-state energy- and hole-transfer pathways. The relative yields of the two channels depend on a number of factors including the linker-mediated through-bond electronic coupling and a modest (< or =20%) Forster through-space contribution for the energy-transfer route. One product of Zn(+)Fb* decay is the metastable ground-state ZnFb(+), which decays to the Zn(+)Fb preflash state by ground-state hole transfer with a linker-dependent rate constant of (20 ps)(-1) to (150 ps)(-1). Collectively, these results provide a detailed understanding of the mechanism and dynamics of quenching of excited porphyrins by nearby oxidized sites, as well as the dynamics of ground-state hole transfer between nonequivalent porphyrins (Zn and Fb). The findings also lay the foundation for the study of ground-state hole transfer between identical porphyrins (e.g., Zn/Zn, Fb/Fb) in larger multiporphyrin arrays wherein a hole is selectively placed via electrochemical oxidation.

Energy Landscape of an Electron Hole in Hydrated DNA

First-principles/molecular mechanics, force-field, and 1-D lattice model schemes are used to address the energy landscape of an electron hole in hydrated DNA. Force-field calculations are used to derive a statistical description of the electrostatic fluctuations in DNA yielded by the polar environment, and a periodic first-principles/molecular mechanics scheme is employed to calculate the hole energy at uniform DNA segments embedded in hydrated DNA double helices. The results are then mapped onto 1-D lattice models to address issues relevant to charge transfer in hydrated DNA. It is shown that the polar environment generates an intense dynamical energy disorder along the DNA strands, exhibiting exponential spatio-temporal correlations. The fluctuations of the polar environment lead to hole states localized over a few DNA bases and compete evenly with the DNA sequence to define the hole energy landscape. The spatial correlations of the environment-induced fluctuations are also shown to influence strongly the hole transfer dynamics in DNA.

Picosecond electron transfer dynamics in polymer systems in solutions: cellulose tris(9-ethylcarbazolyl-3-carbamate) and amylose tris(9-ethylcarbazolyl-3-carbamate)

Photoinduced electron transfer (ET) dynamics, such as charge separation (CS), charge recombination (CR), and hole transfer (HT) processes in cellulose tris(9-ethylcarbazolyl-3-carbamate) (CTCz) and amylose tris(9-ethylcarbazolyl-3-carbamate) (ATCz) with a guest electron acceptor in solutions were investigated by means of picosecond transient absorption spectroscopy. Each glucoside unit of these polymer chains has three carbazolyl (Cz) units in such a configuration that two of them are in a close proximity and the other stays apart. Hole transfer dynamics in these systems in the early stage following the excitation were analyzed on the basis of one-dimensional random walk model where cationic state migrates along the polymer chain. On the other hand, the deviation of the experimental results from the calculated curve based on the above model was observed in nanosecond time region. By integrating the kinetic profiles with the temporal evolution of the absorption spectra of the charge-separated state, the trapping process of the cation at the dimer site was found to be responsible for this deviation. By comparing the present results with those in the monomer and dimer model systems as well as in other Cz containing polymer systems, the role of dimer cation in the HT process was discussed.

Picosecond laser photolysis studies on photoinduced electron transfer processes in poly(1-vinylpyrene) in solutions

The primary processes of photoinduced electron transfer (ET) dynamics in poly(1-vinylpyrene) (PVPy) doped with electron acceptors were investigated by means of picosecond transient absorption measurement in solutions with different polarities. The simple scheme (Scheme 1) based on a one-dimensional random walk model that the cation radical continuously migrates along pendant aromatic moieties in the polymer chain interprets the hole transfer (HT) dynamics in the longer delay time after the excitation. However, in the early stage, the deviation observed due to the dimer cation formation, which acts as a trap site for the cation and a very slow HT process occurred as a result of a detrapping process. By integrating the present results with the previous investigation on other aromatic vinyl polymers, the role of the dimer cation on the hole migration process along the polymer chain were discussed.

Symmetry-Forbidden vs Symmetry-Allowed Electron and Hole Transfer in Medium Sized Intramolecular Organic Donor−Acceptor Radical Ions. A Trajectory Surface Hopping Study

This paper presents a quasi-classical molecular dynamics study of symmetry effects on the dynamics of intramolecular electron transfer and hole transfer in a series of rigid organic donor−acceptor radical ions derived from 3 − 8, in which pairs of identical chromophores (double bonds, cyclopentadiene groups, or fulvene units) are attached to opposite ends of either an adamantane bridge or a bishomocubane bridge. The charge-shift process taking place by the most symmetrical transition structure in the mono-radical ions of these species may be either formally symmetry-allowed or symmetry-forbidden, depending on the sign of the migrating charge, the nature of the chromophore pair, and the identity of the connecting bridge. The degree to which symmetry breaking molecular vibrations affect the dynamics of charge-shift in these systems was explored using a recently developed Landau−Zener trajectory surface hopping (LZ-TSH) model. Reaction trajectories, which may hop between the ground state and the first excite...