Hole Hopping Research Articles

Quasi-Planar Core Based Spiro-Type Hole-Transporting Material for Dopant-Free Perovskite Solar Cells.

Hole-transporting material (HTMs) are crucial for obtaining the stability and high efficiency of perovskite solar cells (PSCs). However, the current state-of-the-art n-i-p PSCs relied on the use of 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) exhibit inferior intrinsic and ambient stability due to the p-dopant and hydrophilic Li-TFSI additive. In this study, a new spiro-type HTM with a critical quasi-planar core (Z-W-03) is developed to improve both the thermal and ambient stability of PSCs. The results suggest that the planar carbazole structure effectively passivates the trap states compared to the triphenylamine with a propeller-like conformation in spiro-OMeTAD. This passivation effect leads to the shallower trap states when the quasi-planar HTMs interact with the Pb-dimer. Consequently, the device using Z-W-03 achieves a higher Voc of 1.178 V compared to the spiro-OMeTAD's 1.155 V, resulting in an enhanced efficiency of 24.02 %. In addition, the double-column π-π stacking of Z-W-03 results in high hole mobility (~10-4 cm2 V-1 s-1) even without p-dopant. Moreover, when the surface interface is modified, the undoped Z-W-03 device can achieve an efficiency of nearly 23 %. Compared to the PSCs using spiro-OMeTAD, those with Z-W-03 exhibit enhanced stability under N2 and ambient conditions. This superior performance is attributed to the quasi-planar core structure and the presence of multiple CH/π and π-π intermolecular stacking in Z-W-03. The multiple CH/π and π-π intermolecular contacts of HTMs can improve the hole hopping transport. Therefore, it is imperative to focus on further molecular structure design and optimization of spiro-type HTMs incorporating quasi-planar cores and carbazole moieties for the commercialization of PSCs.

Quasi‐Planar Core Based Spiro‐Type Hole‐Transporting Material for Dopant‐Free Perovskite Solar Cells

AbstractHole‐transporting material (HTMs) are crucial for obtaining the stability and high efficiency of perovskite solar cells (PSCs). However, the current state‐of‐the‐art n‐i‐p PSCs relied on the use of 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐OMeTAD) exhibit inferior intrinsic and ambient stability due to the p‐dopant and hydrophilic Li‐TFSI additive. In this study, a new spiro‐type HTM with a critical quasi‐planar core (Z‐W‐03) is developed to improve both the thermal and ambient stability of PSCs. The results suggest that the planar carbazole structure effectively passivates the trap states compared to the triphenylamine with a propeller‐like conformation in spiro‐OMeTAD. This passivation effect leads to the shallower trap states when the quasi‐planar HTMs interact with the Pb‐dimer. Consequently, the device using Z‐W‐03 achieves a higher Voc of 1.178 V compared to the spiro‐OMeTAD's 1.155 V, resulting in an enhanced efficiency of 24.02 %. In addition, the double‐column π–π stacking of Z‐W‐03 results in high hole mobility (~10−4 cm2 V−1 s−1) even without p‐dopant. Moreover, when the surface interface is modified, the undoped Z‐W‐03 device can achieve an efficiency of nearly 23 %. Compared to the PSCs using spiro‐OMeTAD, those with Z‐W‐03 exhibit enhanced stability under N2 and ambient conditions. This superior performance is attributed to the quasi‐planar core structure and the presence of multiple CH/π and π–π intermolecular stacking in Z‐W‐03. The multiple CH/π and π–π intermolecular contacts of HTMs can improve the hole hopping transport. Therefore, it is imperative to focus on further molecular structure design and optimization of spiro‐type HTMs incorporating quasi‐planar cores and carbazole moieties for the commercialization of PSCs.

Functionalized porphyrin as a carrier bridge and a passivator for perovskite solar cells

Interfacial modification becomes one of the most emerging strategies in the state-of-the-art perovskite solar cells (PSCs). Here, two porphyrin derivatives (p-MeOTPP, m-DMeOTPP) with different methoxy groups are employed as the modifiers between perovskite and the hole transporting layer (HTL). The interaction at both of perovskite/modifier and modifier/HTL interfaces, and the hole-transfer ability of the modifier molecule are comprehensively studied, which are jointly responsible for the significant improvement in the optoelectronic properties of the device. More importantly, discussion on a molecular level reveals the distinct roles of modifiers with highly similar structures. A highest power conversion efficiency (PCE) of 24.56% is achieved for m-DMeOTPP modified PSCs, which is attributed to a synergy of efficient passivation effect at perovskite/modifier interface, sufficient built-in potential at modifier/HTL interface and minimal reorganization energy of hole hopping process. p-MeOTPP has a stronger passivation ability, but causes unfavorable interfacial dipole at modifier/HTL interface and a large energy barrier when hole’s hopping, only resulting in a smaller enhancement. Additionally, both modifers improve the device stability by strongly suppress the immigration of iodine species and moisture penetration. This work presents a synergy mechanism for interfacial engineering to pursue PSCs with high efficiency and stability, and provides practical guidelines at a molecular level to design a modifier not only as an efficient passivator but also as a high-speed carrier bridge.

Molecular engineering push-pull structural versatility in the triphenylamine-thienodioxine-based hole transporting materials for high-performance organic and perovskite solar cells

This study proposes a push-pull molecular engineering approach to fabricate versatile hole-transporting materials (HTMs) for photovoltaic cells. Herein, we introduce a D-π-A strategy for fabricating four highly functional small molecules of thienodioxine core-based HTMs (CJ06C1 to CJ06C4), via core functionalization with diversified electron-withdrawing acceptor moieties. The engineered HTMs are evaluated by employing quantum calculations to analyze the structure-property relationships from optoelectronic, electrochemical, and solvability attributes. The findings reveal that acceptor-integrated HTMs unveil excellent band alignment with active perovskite layer with deeper HOMO energy levels (-4.96 eV to 5.02 eV), transparency in the visible portion λmaxabs<521, which entail appropriate photophysical attributes. In comparison to the reference HTM (CJ06), the acceptor-integrated HTMs have exhibited potentially higher hole mobility rate, accredited to smaller hole reorganization energies (0.15 eV to 0.21 eV), greater transfer integral values (0.26 eV to 0.31 eV) and greater hole hopping rates (1.08×1028 S−1 to 3.70×1028 S−1). The electron-excitation investigation exhibited stronger electronic coupling, smaller hole-electron spatial overlapping, and higher charge transference length (19.42 Å to 21.14 Å) in the fabricated HTMs. Thus ensued a significant upsurge in intrinsic charge transference (74.22–99.74 %) and lower exciton binding energies, leading to easy charge dissociation and low recombination chances compared to the parent HTM (CJ06C1). Moreover, the findings from dipole moments (12.56 D to 13.05 D) and solvation-free energy (-91.08 kJ/mol) to −108.1 kJ/mol),imply easier processability and aptness for film formation. Overall, this study ensures the efficiency of thienodioxine core functionalization with acceptor moieties for fabricating state-of-the-art HTMs. The promising attributes of fabricated HTMs pave the way for forthcoming perovskite solar cells.

Design and study of novel benzodithiazole-based hole transport materials for improved performance of perovskite solar cells: A DFT approach

The present research used end-capped molecular engineering to fabricate novel hole transport materials based on the benzodithiazole (BBT) core, designated as BBT-M1 to BBT-M5 HTMs. The computational techniques such as DFT and TD-DFT were employed to characterize the effect of terminal acceptors in designed molecules. Their results were compared with parent (BBT-R) and Spiro (MeOTAD) HTMs. Under TD-DFT investigation, absorption peaks of designed molecules were identified within the range of 380–559 nm, indicating their operation near UV and near/mid visible region. It was observed that designed materials have more compatible and deeper HOMO levels ranging from −5.242 to −5.161 eV, which leads to high open circuit voltage. They also exhibit better planarity, increased solubility and reactivity, moderate stability, and a narrow band gap ranging from 1.93 to 2.36 eV. Furthermore, the reorganization energy of holes (0.145–0.205 eV) is significantly lower than that of electrons (0.221–0.376 eV), indicating an overall tendency towards hole transport material. In BBT-M1 to BBT-M5 HTMs, the charge transfer integral of hole (0.229–0.353 eV), hole hopping rate (5.218×1014–6.969×1014 s–1), open circuit voltage (1.311–1.392 V) and fill factor (90.50–90.93 %) are remarkably better than BBT-R and Spiro (MeOTAD). Based on these outstanding attributes, it is proposed that BBT-M1 to BBT-M5 molecules are potential HTM candidates to replace conventional HTMs such as spiro (MeOTAD).

Porphyrin-Based Hole-Transporting Materials for Perovskite Solar Cells: Boosting Performance with Smart Synthesis.

Perovskite solar cells (PSCs) are becoming a promising and revolutionary advancement within the photovoltaic field globally. Continuous improvement in efficiency, straightforward processing methods, and use of lightweight and cost-effective materials represent superior features, among other notable aspects. Still, long-term stability and durability are issues to address to facilitate widespread commercial adoption and practical application prospects. Research has focused on overcoming these challenges, and charge transport materials play a critical role in determining charge dynamics, photovoltaic performance, and device stability. Conventional hole-transporting materials (HTMs), spiro-OMeTAD and PTAA, contribute to remarkable power conversion efficiencies owing to high thin-film quality and matched energy alignment. However, they often show a high material cost, low carrier mobility, and poor stability, which greatly limit their practical applications. Now, this review outlines recent advances in synthetic approaches to porphyrin-based HTMs to tune the charge dynamics by optimizing their molecular structures and properties. The main structural features comprise porphyrins of A4-type, trans A2B2-type, and photosynthetic pigment analogues. Strategies include well-established routes to provide the required macrocycles, such as condensation of pyrrole or dipyrromethanes with suitable aldehydes, metalation of the porphyrin inner core, and postfunctionalization of peripheral positions. These functionalizations involve conventional procedures (e.g., halogenation, esterification, transesterification, nucleophilic oxidation, reduction, and nucleophilic substitution) as well as metal-catalyzed ones such as Suzuki-Miyaura, Sonogashira, Buchwald-Hartwig, and Ullmann cross-coupling reactions. As HTMs can also protect the perovskite layer from the external environment, porphyrin structures play a pivotal role in chemical, mechanical, and environmental stability, with their high hydrophobicity ability as the most significant parameter. The impact of porphyrins on the hole hopping of other HTMs while acting as an additive or an interlayer, passivating defects, and improving charge transport is also highlighted to provide real insights into ways to develop efficient and stable porphyrin-based materials for PSCs. This perspective aims to guide the scientific community in the design of new porphyrin molecules to place PSCs as an outperformer in photovoltaic technologies.

Mutational dissection of a hole hopping route in a lytic polysaccharide monooxygenase (LPMO)

Oxidoreductases have evolved tyrosine/tryptophan pathways that channel highly oxidizing holes away from the active site to avoid damage. Here we dissect such a pathway in a bacterial LPMO, member of a widespread family of C-H bond activating enzymes with outstanding industrial potential. We show that a strictly conserved tryptophan is critical for radical formation and hole transference and that holes traverse the protein to reach a tyrosine-histidine pair in the protein’s surface. Real-time monitoring of radical formation reveals a clear correlation between the efficiency of hole transference and enzyme performance under oxidative stress. Residues involved in this pathway vary considerably between natural LPMOs, which could reflect adaptation to different ecological niches. Importantly, we show that enzyme activity is increased in a variant with slower radical transference, providing experimental evidence for a previously postulated trade-off between activity and redox robustness.

Influence of cationic vacancy diffusion on the aging behavior of low-temperature SrCo1-xRuxO3 thermosensitive ceramics

The thermosensitive ceramics of negative temperature coefficient (NTC), SrCo1-xRuxO3 (0 ≤ x ≤ 0.8), were synthesized using the solid-phase method. The research systematically explored the phase structure, microstructure, elemental chemical states, electrical properties, and aging performance. X-ray diffraction (XRD) data indicates that with the increase of Ru content, the lattice parameter increases. Scanning electron microscopy (SEM) images reveal a dense and uniform microstructure. X-ray photoelectron spectroscopy (XPS) data indicates the presence of Co2+/Co3+ and Ru4+/Ru5+ ion pairs. Resistive temperature data indicates its potential use as a low-temperature thermosensitive resistance material in the range of 2–300 K. Fitting the resistance-temperature curve using the thermally activated band conduction model and Mott's 3D variable range hopping model. Proposed the Ru–O2--Co hopping model, elucidating the hole hopping transport mechanism in NTC ceramics. Impedance spectroscopy analysis indicates that grain boundary resistance dominates the overall resistance of the sample. After aging at 77 K for 864 h, the maximum aging drift rate of the ceramic material is 1.55 %. Proposed a novel cationic vacancy diffusion model to explain aging phenomena, offering a new perspective for designing high-stability low-temperature NTC thermistors.

Mechanistic Aspects of Photodegradation of Deoxynucleosides Induced by Triplet State of Effluent Organic Matter.

Excited triplet states of wastewater effluent organic matter (3EfOM*) are known as important photo-oxidants in the degradation of extracellular antibiotic resistance genes (eArGs) in sunlit waters. In this work, we further found that 3EfOM* showed highly selective reactivity toward 2'-deoxyguanosine (dG) sites within eArGs in irradiated EfOM solutions at pH 7.0, while it showed no photosensitizing capacity toward 2'-deoxyadenosine, 2'-deoxythymidine, and 2'-deoxycytidine (the basic structures of eArGs). The 3EfOM* contributed to the photooxidation of dG primarily via one-electron transfer mechanism, with second-order reaction rate constants of (1.58-1.74) × 108 M-1 s-1, forming the oxidation intermediates of dG (dG(-H)•). The formed dG(-H)• could play a significant role in hole hopping and damage throughout eArGs. Using the four deoxynucleosides as probes, the upper limit for the reduction potential of 3EfOM* is estimated to be between 1.47 and 1.94 VNHE. Compared to EfOM, the role of the triplet state of terrestrially natural organic matter (3NOM*) in dG photooxidation was minor (∼15%) mainly due to the rapid reverse reactions of dG(-H)• by the antioxidant moieties of NOM. This study advances our understanding of the difference in the photosensitizing capacity and electron donating capacity between NOM and EfOM and the photodegradation mechanism of eArGs induced by 3EfOM*.

Resistive Avalanches in La1-xSrxCoO3-δ (x = 0, 0.3) Thin Films and Their Reversible Evolution by Tuning Lattice Oxygen Vacancies (δ).

Strong correlations are often manifested by exotic electronic phases and phase transitions. LaCoO3-δ (LCO) is a system that exhibits such strong electronic correlations with lattice-spin-charge-orbital degrees of freedom. Here, we show that mesoscopic oxygen-deficient LCO films show resistive avalanches of about 2 orders of magnitude due to the metal-insulator transition (MIT) of the film at about 372 K for the 25 W RF power-deposited LCO film on the Si/SiO2 substrate. In bulk, this transition is otherwise gradual and occurs over a very large temperature range. In thin films of LCO, the oxygen deficiency (0 < δ < 0.5) is more easily reversibly tuned, resulting in avalanches. The avalanches disappear after vacuum annealing, and the films behave like normal insulators (δ ∼0.5) with Co2+ in charge ordering alternatively with Co3+. This oxidation state change induces spin state crossovers that result in a spin blockade in the insulating phase, while the conductivity arises from hole hopping among the allowed cobalt Co4+ ion spin states at high temperature. The chemical pressure (strain) of 30% Sr2+ doping at the La3+ site results in reduction in the avalanche magnitude as well as their retention in subsequent heating cycles. The charge nonstoichiometry arising due to Sr2+ doping is found to contribute toward hole doping (i.e., Co3+ oxidation to Co4+) and thereby the retention of the hole percolation pathway. This is also manifested in energies of crossover from the 3D variable range hopping (VRH) type transport observed in the temperature range of 300-425 K, while small polaron hopping (SPH) is observed in the temperature range of 600-725 K for LCO. On the other hand, Sr-doped LCO does not show any crossover and only the VRH type of transport. The strain due to Sr2+ doping refrains the lattice from complete conversion of δ going to 0.5, retaining the avalanches.

Effect of substituting donors on the hole mobility of hole transporting materials in perovskite solar cells: a DFT study.

Several hole-transporting materials (HTMs) have been designed by incorporating different types of π-conjugation group such as long chain aliphatic alkenes and condensed aromatic rings of benzene and thiophene and their derivatives on both sides between the planar core and donor of a reference HTM. Various electronic, optical, and dynamic properties have been calculated by using DFT, TDDFT, and Marcus theory. In this study, all the designed HTMs show a lower HOMO energy level and match well with the perovskite absorbers. Inserting condensed rings results in better hole mobility compared to aliphatic double bonds. It is found that the charge transfer integral is the dominant factor which mainly influences the hole mobility in our studied HTMs. Other factors such as hole reorganization energy, hole hopping rate, and centroid distance have a minor effect on hole mobility. Thus, this study is expected to provide guidance for the design and synthesis of new HTMs with increased hole mobility.

Tryptophan to Tryptophan Hole Hopping in an Azurin Construct.

Electron transfer (ET) between neutral and cationic tryptophan residues in the azurin construct [ReI(H126)(CO)3(dmp)](W124)(W122)CuI (dmp = 4,7-Me2-1,10-phenanthroline) was investigated by Born-Oppenheimer quantum-mechanics/molecular mechanics/molecular dynamics (QM/MM/MD) simulations. We focused on W124•+ ← W122 ET, which is the middle step of the photochemical hole-hopping process *ReII(CO)3(dmp•-) ← W124 ← W122 ← CuI, where sequential hopping amounts to nearly 10,000-fold acceleration over single-step tunneling (ACS Cent. Sci. 2019, 5, 192-200). In accordance with experiments, UKS-DFT QM/MM/MD simulations identified forward and reverse steps of W124•+ ↔ W122 ET equilibrium, as well as back ET ReI(CO)3(dmp•-) → W124•+ that restores *ReII(CO)3(dmp•-). Strong electronic coupling between the two indoles (≥40 meV in the crossing region) makes the productive W124•+ ← W122 ET adiabatic. Energies of the two redox states are driven to degeneracy by fluctuations of the electrostatic potential at the two indoles, mainly caused by water solvation, with contributions from the protein dynamics in the W122 vicinity. ET probability depends on the orientation of Re(CO)3(dmp) relative to W124 and its rotation diminishes the hopping yield. Comparison with hole hopping in natural systems reveals structural and dynamics factors that are important for designing efficient hole-hopping processes.

Dipoles and defects caused by CO2 plasma improve carrier transport of silicon solar cells

AbstractCarrier‐selective contact is a fundamental issue for solar cells. For silicon heterojunction (SHJ) solar cells, it is important to improve hole transport because of the low doping efficiency of boron in amorphous silicon and the barrier stemming from valence band offset. Here, we develop a carbon dioxide (CO2) plasma treatment (PT) process to form dipoles and defect states. We find a dipole moment caused by longitudinal distribution of H and O atoms. It improves hole transport and blocks electron transport and thus suppresses carrier recombination. In the meantime, the CO2 PT process also results in defect states, which reduce passivation performance but improve hole hopping in the intrinsic amorphous layer. As a balance, an appropriate CO2 PT process at the i/p interface increases fill factor and power conversion efficiency of SHJ solar cells. We emphasize, based on sufficient evidences, this work finds a distinct role of the CO2 plasma in SHJ solar cells opposed to reported mechanisms.

Synthesis and study of structural and electrical transport properties of Ni and Zr doped Y-type Ba-Co hexa-ferrite

In present study, Co2 Y-type barium hexaferrite samples of Ba2Co2NixZrxFe12-2xO22 (with x =0.5 and 1.0) were synthesized using the solid-state reaction method with sintering temperatures of 900°C and 1200°C. To examine the effects of Ni-Zr doping on the crystal structure and dielectric properties of Y-type barium cobalt hexaferrite, samples were characterized using EDS, XRD and SEM techniques. The XRD results confirmed the formation of pure Y-type hexagonal ferrites at 1200°C sintering temperatures. EDS analysis confirmed elemental compositions and SEM provided morphology of the materials. The dielectric properties were measured using Impedance analyzer. At normal frequencies, the x = 1.0 doped sample showed significant increase in dielectric value which came to be of the order of 2500. This might be attributed to electron hopping between Fe2+ and Fe3+ ions and hole hopping between Ni2+ and Ni3+ ions, which could enhance dielectric properties in ferrites under applied electric fields. Furthermore, electrons transferred between Fe2+/Fe3+ ions and holes transferred between Ni2+/Ni3+ ions explain the pronounced improvement in electrical properties observed for x = 1.0 samples.

Intramolecular Electron Transfer in Multi-Redox Systems Based on Cyclic [3]Spirobifluorenylene Compound.

Cyclic [3]spirobifluorenylene with bulky alkyl groups at the ends (1) was designed and synthesized to investigate the electron transfer phenomena in a π-conjugated system including orthogonal π-conjugated chains. The three bifluorenyl units in 1 are conjugated to each other via spiro-conjugation, resulting in the splitting of the HOMO levels to a small extent. Therefore, the SOMO-HOMO gap of the radical cation species is small, which is considered to allow the facile intramolecular electron transfer. In the TD-DFT calculations for the radical cation species of 1, the geometry-featured interchain electronic transitions were visualized by NTO calculations. The radical cation species of 1 generated by chemical oxidation with SbCl5 exhibited a broadened and lower-energy shifted NIR absorption band compared to those of its partial structures. Considering the results of the TD-DFT calculations, the NIR band of the radical cation of 1 was attributed to the intramolecular electron transfer processes among the bifluorenyl units in the macrocycle. ESR experiments also indicated the delocalization of a spin of 1·+ in the whole molecule via hole hopping in the ESR time scale at room temperature. This work demonstrates the usefulness of spiro-conjugation as a bridging unit in molecular wires to facilitate smooth electron transfer.

Photo-Programmable Processes in Bithiophene–Azobenzene Monolayers on Gold Probed via Simulations

In this study, we investigate the structural changes, electronic properties, and charge redistribution within azo-bithiophene (Azo-BT)-chemisorbed monolayers under different light stimuli using the density functional theory and molecular dynamics simulations. We consider two types of switches, Azo-BT and BT-Azo, with different arrangements of the Azo and BT blocks counting from the anchor thiol group. The chemisorbed monolayers of pure cis- and trans-isomers with a surface concentration of approximately 2.7 molecules per nm2 are modeled on a gold surface using the classical all-atom molecular dynamics. Our results reveal a significant shrinkage of the BT-Azo layer under UV illumination, whereas the thicknesses of the Azo-BT layer remain comparable for both isomers. This difference in behavior is attributed to the ordering of the trans-molecules in the layers, which is more pronounced for Azo-BT, leading to a narrow distribution of the inclination angle to the gold surface. Conversely, both layers consisting of cis-switches exhibit disorder, resulting in similar brush heights. To study charge transfer within the immobilized layers, we analyze each snapshot of the layer and calculate the mean charge transfer integrals using Nelsen’s algorithm for a number of interacting neighboring molecules. Combining these integrals with reorganization energies defined for the isolated molecules, we evaluate the charge transfer rates and mobilities for electron and hole hopping within the layers at room temperature based on Marcus’ theory. This research offers new perspectives for the innovative design of electrode surface modifications and provides insights into controlling charge transfer within immobilized layers using light triggers. Additionally, we identify molecular properties that are enhanced via specific molecular design, which contributes to the development of more efficient molecular switches for various electronic applications.

Impact of Molecular Orientation on Lateral and Interfacial Electron Transfer at Oxide Interfaces.

Molecular dyes, called sensitizers, with a cis-[Ru(LL)(dcb)(NCS)2] structure, where dcb is 4,4'-(CO2H)2-2,2'-bipyridine and LL is dcb or a different diimine ligand, are among the most optimal for application in dye-sensitized solar cells (DSSCs). Herein, a series of five sensitizers, three bearing two dcb ligands and two bearing one dcb ligand, were anchored to mesoporous thin films of conducting tin-doped indium oxide (ITO) or semiconducting TiO2 nanocrystallites. The number of dcb ligands impacts the surface orientation of the sensitizer; density functional theory (DFT) calculations revealed an ∼1.6 Å smaller distance between the oxide surface and the Ru metal center for sensitizers with two dcb ligands. Interfacial electron transfer kinetics from the oxide material to the oxidized sensitizer were measured as a function of the thermodynamic driving force. Analysis of the kinetic data with Marcus-Gerischer theory indicated that the electron coupling matrix element, Hab, was sensitive to distance and ranged from Hab = 0.23 to 0.70 cm-1, indicative of nonadiabatic electron transfer. The reorganization energies, λ, were also sensitive to the sensitizer location within the electric double layer and were smaller, with one exception, for sensitizers bearing two dcb ligands λ = 0.40-0.55 eV relative to those with one λ = 0.63-0.66 eV, in agreement with dielectric continuum theory. Electron transfer from the oxide to the photoexcited sensitizer was observed when the diimine ligand was more easily reduced than the dcb ligand. Lateral self-exchange "hole hopping" electron transfer between surface-anchored sensitizers was found to be absent for sensitizers with two dcb ligands, while those with only one were found to hop with rates similar to those previously reported in the literature, khh = 47-89 μs-1. Collectively, the kinetic data and analysis reveal that interfacial kinetics are highly sensitive to the surface orientation and sensitizers bearing two dcb ligands are most optimal for practical applications of DSSCs.

Lateral Electron and Hole Hopping between Dyes on Mesoporous ZrO2: Unexpected Influence of Solvents with a Low Dielectric Constant

Lateral intermolecular charge transfer between photosensitizers on metal oxide substrates is important for the understanding on the overall working principles of dye-sensitized systems. Such studies usually concentrate on either hole or electron transfer separately and are conducted in solvents with a high dielectric constant (εs) that are known, however, to show a drastic decrease of the local dielectric constant close to the metal oxide surface. In the present study, both hole and electron hopping between organic donor-acceptor photosensitizers was experimentally investigated on PB6 dye-sensitized mesoporous ZrO2 films. The donor (close to the surface) and acceptor (away from surface) subunit of the PB6 dye were observed to be involved in hole and electron hopping, respectively. Hole and electron transfer kinetics were found to differ remarkably in high-εs solvents, but similar in solvents with εs < 12. This finding indicates that low-εs solvents maintain similar local dielectric constant values close to, and further away from, the semiconductor surface, which is different from the previously observed behavior of high dielectric constant solvents at a metal oxide interface.

Effect of morphology and particle size on the electrical properties of nano-nickel ferrite

Four powder samples of Nickel ferrite (NiFe2O4) with different morphology and nanoparticle size have been synthesized by various methods: electrospinning, hydrothermal, green, and sol-gel. Through the use of XRD, FT-IR, SEM, TEM, and BET techniques, the prepared powders were characterized. The produced ferrite displayed a cubic spinel phase with various nanofiber, nanotube, nanorod, and nanosphere morphological structures. The electrical conductivity values for each sample increased with increasing temperature indicating the semiconducting behavior of all samples. The conductivity values were found to be dependent on each nanoparticle's size and morphology. The variation of dielectric constant (ε′), dielectric loss (ε′′), and ac conductivity for the investigated samples at different temperatures and frequencies has been studied. Both dielectric constant (ε′) and dielectric loss (ε′′) were decreased with the increase of frequency while A.C. conductivity increased. Knop's phenomenological theory explains the frequency variation of (ε′ and ε′′). The hopping of electrons and holes is suggested to be the electrical conduction mechanism.

New insights into controlling radical migration pathways in heme enzymes gained from the study of a dye-decolorising peroxidase.

In heme enzymes, such as members of the dye-decolorising peroxidase (DyP) family, the formation of the highly oxidising catalytic Fe(iv)-oxo intermediates following reaction with hydrogen peroxide can lead to free radical migration (hole hopping) from the heme to form cationic tyrosine and/or tryptophan radicals. These species are highly oxidising (∼1 V vs. NHE) and under certain circumstances can catalyse the oxidation of organic substrates. Factors that govern which specific tyrosine or tryptophan the free radical migrates to in heme enzymes are not well understood, although in the case of tyrosyl radical formation the nearby proximity of a proton acceptor is a recognised facilitating factor. By using an A-type member of the DyP family (DtpAa) as an exemplar, we combine protein engineering, X-ray crystallography, hole-hopping calculations, EPR spectroscopy and kinetic modelling to provide compelling new insights into the control of radical migration pathways following reaction of the heme with hydrogen peroxide. We demonstrate that the presence of a tryptophan/tyrosine dyad motif displaying a T-shaped orientation of aromatic rings on the proximal side of the heme dominates the radical migration landscape in wild-type DtpAa and continues to do so following the rational engineering into DtpAa of a previously identified radical migration pathway in an A-type homolog on the distal side of the heme. Only on disrupting the proximal dyad, through removal of an oxygen atom, does the radical migration pathway then switch to the engineered distal pathway to form the desired tyrosyl radical. Implications for protein design and biocatalysis are discussed.