Imperial College London

Professor James Durrant, CBE, FRS

Faculty of Natural SciencesDepartment of Chemistry

Professor of Photochemistry
 
 
 
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Contact

 

+44 (0)20 7594 5321j.durrant Website

 
 
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Assistant

 

Miss Lisa Benbow +44 (0)20 7594 5883

 
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Location

 

G22CMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Publication Type
Year
to

661 results found

Mohapatra AA, Dong Y, Boregowda P, Mohanty A, Sadhanala A, Narayan A, McNeill C, Durrant JR, Patil S, Jiao X, Chakkingal Parambil Pet al., 2020, Rational Design of Donor Acceptor Based Semiconducting Copolymers with High Dielectric Constant

<jats:p>&lt;div&gt; &lt;div&gt; &lt;div&gt; &lt;p&gt;An efficient photogeneration of free charge carriers has long been recognized as theparamount challenge in organic photovoltaic (OPV) devices. The low dielectric constantorganic semiconductors fall short to reduce strong Coulombic interaction of tightly boundexciton and hence lead to a loss mechanism in OPVs due to charge-carrier recombination. Tocircumvent this problem, we adopt a strategy to enhance the dielectric constant of organicsemiconductors by incorporating tetraethyleneglycol (TEG) side-chains. We report synthesisof three new semiconducting copolymers by combining thiophene substituteddiketopyrrolopyrrole (TDPP) monomer with three other monomeric units with varyingelectron donating strength: benzodithiophene (BBT-3TEG-TDPP), TDPP (TDPP-3TEG-TDPP)and naphthalene diimide (PNDITEG-TDPP). BBT-3TEG-TDPP and PNDITEG-TDPP showedhighest dielectric constants (~ 5) at 1MHz frequency suggesting efficient contribution ofdipolar polarization from TEG side-chains. To understand the electronic contribution of thepolymer backbone and the polarity of TEG side-chains, and the resulting enhancement of thedielectric constant, we further performed first-principles density functional theorycalculations. Single-component organic solar cells (OSC) fabricated utilizing these polymersresulted in poor performance which is attributed to the absence of free charge generation.Furthermore, transient absorption spectroscopy studies show low exciton diffusion length asobserved in donor-acceptor type conjugated polymers. Our results suggest that, the strategyof enhancing dielectric constant with polar side-chains is not sufficient to reduce Coulombicinteraction between hole and electron in OSCs.&lt;/p&gt; &lt;/div&gt; &lt;/div&gt; &lt;/div&gt;</jats:p>

Working paper

Mesa CA, Steier L, Moss B, Francàs L, Thorne JE, Grätzel M, Durrant JRet al., 2020, Impact Of Synthesis Route on the Water Oxidation Kinetics of Hematite Photoanodes

<jats:p><jats:italic>Operando</jats:italic> spectroelectrochemical analysis is used to determine the water oxidation reaction kinetics for hematite photoanodes prepared using four different synthetic procedures. Whilst these photoanodes exhibit very different current / voltage performance, their underlying water oxidation kinetics are found to be almost invariant. Lower photoanode performance was found to correlate with the observation of optical signals indicative of charge accumulation in mid-gap oxygen vacancy states, indicating these states do not contribute directly to water oxidation.</jats:p>

Working paper

Mesa CA, Steier L, Moss B, Francàs L, Thorne JE, Grätzel M, Durrant JRet al., 2020, Impact Of Synthesis Route on the Water Oxidation Kinetics of Hematite Photoanodes

<jats:p>&lt;p&gt;&lt;i&gt;Operando&lt;/i&gt; spectroelectrochemical analysis is used to determine the water oxidation reaction kinetics for hematite photoanodes prepared using four different synthetic procedures. Whilst these photoanodes exhibit very different current / voltage performance, their underlying water oxidation kinetics are found to be almost invariant. Lower photoanode performance was found to correlate with the observation of optical signals indicative of charge accumulation in mid-gap oxygen vacancy states, indicating these states do not contribute directly to water oxidation.&lt;/p&gt;</jats:p>

Working paper

Daboczi M, Kim J, Lee J, Kang H, Hamilton I, Lin C-T, Dimitrov SD, McLachlan MA, Lee K, Durrant JR, Kim J-Set al., 2020, Towards efficient integrated perovskite/organic bulk heterojunction solar cells: interfacial energetic requirement to reduce charge carrier recombination losses, Advanced Functional Materials, Vol: 30, Pages: 1-8, ISSN: 1616-301X

Integrated perovskite/organic bulk heterojunction (BHJ) solar cells have the potential to enhance the efficiency of perovskite solar cells by a simple one‐step deposition of an organic BHJ blend photoactive layer on top of the perovskite absorber. It is found that inverted structure integrated solar cells show significantly increased short‐circuit current (J sc) gained from the complementary absorption of the organic BHJ layer compared to the reference perovskite‐only devices. However, this increase in J sc is not directly reflected as an increase in power conversion efficiency of the devices due to a loss of fill factor. Herein, the origin of this efficiency loss is investigated. It is found that a significant energetic barrier (≈250 meV) exists at the perovskite/organic BHJ interface. This interfacial barrier prevents efficient transport of photogenerated charge carriers (holes) from the BHJ layer to the perovskite layer, leading to charge accumulation at the perovskite/BHJ interface. Such accumulation is found to cause undesirable recombination of charge carriers, lowering surface photovoltage of the photoactive layers and device efficiency via fill factor loss. The results highlight a critical role of the interfacial energetics in such integrated cells and provide useful guidelines for photoactive materials (both perovskite and organic semiconductors) required for high‐performance devices.

Journal article

Wang Y, Liu X, Han X, Godin R, Chen J, Zhou W, Jiang C, Thompson JF, Bayazit MK, Shevlin SA, Durrant JR, Guo Z, Tang Jet al., 2020, Unique hole-accepting carbon-dots promoting selective carbon dioxide reduction nearly 100% to methanol by pure water, NATURE COMMUNICATIONS, Vol: 11

Journal article

Lin C-T, Ngiam J, Xu S, Chang Y-H, Du T, Macdonald TJ, Durrant J, McLachlan Met al., 2020, Enhancing the operational stability of unencapsulated perovskite solar cells through Cu-Ag bilayer electrode incorporation, Journal of Materials Chemistry A, Vol: 8, Pages: 8684-8691, ISSN: 2050-7488

We identify a facile strategy that significantly reduces electrode corrosion and device degradation in unencapsulated perovskite solar cells (PSCs) operating in ambient air. By employing Cu-Ag bilayer top electrodes PSCs, we show enhanced operational lifetime compared with devices prepared from single metal (Al, Ag and Cu) analogues. Time-of-flight secondary ion mass spectrometry depth profiles indicate that the insertion of the thin layer of Cu (10nm) below the Ag (100nm) electrode significantly reduces diffusion of species originating in the perovskite active layer into the electron transport layer and electrode. X-ray diffraction (XRD) analysis reveals the mutually beneficial relationship between the bilayer metals, whereby the thermally evaporated Ag inhibits Cu oxidation and the Cu prevents interfacial reactions between the perovskite and Ag. The results here not only demonstrate a simple approach to prevent the electrode and device degradation that enhance lifetime and stability but also give an insight into ageing related ion migration and structural reorganisation.

Journal article

Woods DJ, Hillman S, Pearce D, Wilbraham L, Flagg L, Duffy W, Mcculloch I, Durrant J, Guilbert A, Zwijnenburg M, Sprick RS, Nelson J, Cooper Aet al., 2020, Side-chain tuning in conjugated polymer photocatalysts for improved hydrogen production from water, Energy & Environmental Science, Vol: 13, Pages: 1843-1855, ISSN: 1754-5692

Structure–property–activity relationships in solution processable polymer photocatalysts for hydrogen production from water were probed by varying the chemical structure of both the polymer side-chains and the polymer backbone. In both cases, the photocatalytic performance depends strongly on the inclusion of more polar groups, such as dibenzo[b,d]thiophene sulfone backbone units or oligo(ethylene glycol) side-chains. We used optical, spectroscopic, and structural characterisation techniques to understand the different catalytic activities of these systems. We find that although polar groups improve the wettability of the material with water in all cases, backbone and side-chain modifications affect photocatalytic performance in different ways: the inclusion of dibenzo[b,d]thiophene sulfone backbone units improves the thermodynamic driving force for hole transfer to the sacrificial donor, while the inclusion of oligo ethylene glycol side-chains aids the degree of polymer swelling and also extends the electron polaron lifetime. The best performing material, FS-TEG, exhibits a HER of 72.5 μmol h−1 for 25 mg photocatalyst (2.9 mmol g−1 h−1) when dispersed in the presence of a sacrificial donor and illuminated with λ > 420 nm light, corresponding to a hydrogen evolution EQE of 10% at 420 nm. When cast as a thin film, this HER was further boosted to 13.9 mmol g−1 h−1 (3.0 mmol m−2 h−1), which is among the highest rates in this field.

Journal article

Durrant J, 2020, Outstanding Reviewers for <i>Sustainable Energy & Fuels</i> in 2019, SUSTAINABLE ENERGY & FUELS, Vol: 4, Pages: 2086-2086, ISSN: 2398-4902

Journal article

Kosco J, Bidwell M, Cha H, Martin T, Howells CT, Sachs M, Anjum DH, Gonzalez Lopez S, Zou L, Wadsworth A, Zhang W, Zhang L, Tellam J, Sougrat R, Laquai F, DeLongchamp DM, Durrant JR, McCulloch Iet al., 2020, Enhanced photocatalytic hydrogen evolution from organic semiconductor heterojunction nanoparticles, Nature Materials, Vol: 19, Pages: 559-565, ISSN: 1476-1122

Photocatalysts formed from a single organic semiconductor typically suffer from inefficient intrinsic charge generation, which leads to low photocatalytic activities. We demonstrate that incorporating a heterojunction between a donor polymer (PTB7-Th) and non-fullerene acceptor (EH-IDTBR) in organic nanoparticles (NPs) can result in hydrogen evolution photocatalysts with greatly enhanced photocatalytic activity. Control of the nanomorphology of these NPs was achieved by varying the stabilizing surfactant employed during NP fabrication, converting it from a core–shell structure to an intermixed donor/acceptor blend and increasing H2 evolution by an order of magnitude. The resulting photocatalysts display an unprecedentedly high H2 evolution rate of over 60,000 µmol h−1 g−1 under 350 to 800 nm illumination, and external quantum efficiencies over 6% in the region of maximum solar photon flux.

Journal article

Lee J, Lee J-H, Yao H, Cha H, Hong S, Lee S, Kim J, Durrant JR, Hou J, Lee Ket al., 2020, Efficient and photostable ternary organic solar cells with a narrow band gap non-fullerene acceptor and fullerene additive, JOURNAL OF MATERIALS CHEMISTRY A, Vol: 8, Pages: 6682-6691, ISSN: 2050-7488

Journal article

Hong DP, Jain SM, Li M, Wang Z-K, Manzhos S, Feron K, Pitchaimuthu S, Liu Z, Motta N, Durrant JR, Sonar Pet al., 2020, All-Rounder Low-Cost Dopant-Free D-A-D Hole-Transporting Materials for Efficient Indoor and Outdoor Performance of Perovskite Solar Cells, ADVANCED ELECTRONIC MATERIALS, Vol: 6, ISSN: 2199-160X

Journal article

Spitler MT, Modestino MA, Deutsch TG, Xiang CX, Durrant JR, Esposito DV, Haussener S, Maldonado S, Sharp ID, Parkinson BA, Ginley DS, Houle FA, Hannappel T, Neale NR, Nocera DG, McIntyre PCet al., 2020, Practical challenges in the development of photoelectrochemical solar fuels production, SUSTAINABLE ENERGY & FUELS, Vol: 4, Pages: 985-995, ISSN: 2398-4902

Journal article

Back H, Kim G, Kim H, Nam C-Y, Kim J, Kim YR, Kim T, Park B, Durrant JR, Lee Ket al., 2020, Highly stable inverted methylammonium lead tri-iodide perovskite solar cells achieved by surface re-crystallization, ENERGY & ENVIRONMENTAL SCIENCE, Vol: 13, Pages: 840-847, ISSN: 1754-5692

Journal article

Corby S, Francàs L, Kafizas A, Durrant JRet al., 2020, Determining the role of oxygen vacancies in the photoelectrocatalytic performance of WO3 for water oxidation, Chemical Science, Vol: 11, Pages: 2907-2914, ISSN: 2041-6520

Oxygen vacancies are common to most metal oxides, whether intentionally incorporated or otherwise, and the study of these defects is of increasing interest for solar water splitting. In this work, we examine nanostructured WO3 photoanodes of varying oxygen content to determine how the concentration of bulk oxygen-vacancy states affects the photocatalytic performance for water oxidation. Using transient optical spectroscopy, we follow the charge carrier recombination kinetics in these samples, from picoseconds to seconds, and examine how differing oxygen vacancy concentrations impact upon these kinetics. We find that samples with an intermediate concentration of vacancies (∼2% of oxygen atoms) afford the greatest photoinduced charge carrier densities, and the slowest recombination kinetics across all timescales studied. This increased yield of photogenerated charges correlates with improved photocurrent densities under simulated sunlight, with both greater and lesser oxygen vacancy concentrations resulting in enhanced recombination losses and poorer J–V performances. Our conclusion, that an optimal – neither too high nor too low – concentration of oxygen vacancies is required for optimum photoelectrochemical performance, is discussed in terms of the competing beneficial and detrimental impact these defects have on charge separation and transport, as well as the implications held for other highly doped materials for photoelectrochemical water oxidation.

Journal article

Lin C-T, Lee J, Kim J, Macdonald TJ, Ngiam J, Xu B, Daboczi M, Xu W, Pont S, Park B, Kang H, Kim J-S, Payne DJ, Lee K, Durrant JR, McLachlan MAet al., 2020, Origin of open-circuit voltage enhancements in planar Perovskite solar cells induced by addition of bulky organic cations, Advanced Functional Materials, Vol: 30, ISSN: 1616-301X

The origin of performance enhancements in p‐i‐n perovskite solar cells (PSCs) when incorporating low concentrations of the bulky cation 1‐naphthylmethylamine (NMA) are discussed. A 0.25 vol % addition of NMA increases the open circuit voltage (Voc) of methylammonium lead iodide (MAPbI3) PSCs from 1.06 to 1.16 V and their power conversion efficiency (PCE) from 18.7% to 20.1%. X‐ray photoelectron spectroscopy and low energy ion scattering data show NMA is located at grain surfaces, not the bulk. Scanning electron microscopy shows combining NMA addition with solvent assisted annealing creates large grains that span the active layer. Steady state and transient photoluminescence data show NMA suppresses non‐radiative recombination resulting from charge trapping, consistent with passivation of grain surfaces. Increasing the NMA concentration reduces device short‐circuit current density and PCE, also suppressing photoluminescence quenching at charge transport layers. Both Voc and PCE enhancements are observed when bulky cations (phenyl(ethyl/methyl)ammonium) are incorporated, but not smaller cations (Cs/MA)—indicating size is a key parameter. Finally, it demonstrates that NMA also enhances mixed iodide/bromide wide bandgap PSCs (Voc of 1.22 V with a 1.68 eV bandgap). The results demonstrate a facile approach to maximizing Voc and provide insights into morphological control and charge carrier dynamics induced by bulky cations in PSCs.

Journal article

Hamid Z, Wadsworth A, Rezasoltani E, Holliday S, Azzouzi M, Neophytou M, Guilbert AAY, Dong Y, Little MS, Mukherjee S, Herzing AA, Bristow H, Kline RJ, DeLongchamp DM, Bakulin AA, Durrant JR, Nelson J, McCulloch Iet al., 2020, Influence of Polymer Aggregation and Liquid Immiscibility on Morphology Tuning by Varying Composition in PffBT4T-2DT/Nonfullerene Organic Solar Cells, ADVANCED ENERGY MATERIALS, Vol: 10, ISSN: 1614-6832

Journal article

Francas L, Corby S, Selim S, Lee D, Mesa CA, Godin R, Pastor E, Stephens IEL, Choi K-S, Durrant JRet al., 2020, Spectroelectrochemical study of water oxidation on nickel and iron oxyhydroxide electrocatalysts (vol 10, 5208, 2019), NATURE COMMUNICATIONS, Vol: 11, ISSN: 2041-1723

Journal article

Durrant J, 2020, Foreword, ISBN: 9780128178362

Book

Achilleos DS, Yang W, Kasap H, Savateev A, Markushyna Y, Durrant JR, Reisner Eet al., 2020, Solar Reforming of Biomass with Homogeneous Carbon Dots, Angewandte Chemie, ISSN: 0044-8249

© 2020 The Authors. Published by Wiley-VCH GmbH A sunlight-powered process is reported that employs carbon dots (CDs) as light absorbers for the conversion of lignocellulose into sustainable H2 fuel and organics. This photocatalytic system operates in pure and untreated sea water at benign pH (2–8) and ambient temperature and pressure. The CDs can be produced in a scalable synthesis directly from biomass itself and their solubility allows for good interactions with the insoluble biomass substrates. They also display excellent photophysical properties with a high fraction of long-lived charge carriers and the availability of a reductive and an oxidative quenching pathway. The presented CD-based biomass photoconversion system opens new avenues for sustainable, practical, and renewable fuel production through biomass valorization.

Journal article

Mesa Zamora C, Francas Forcada L, Yang KR, Garrido-Barros P, Pastor Hernandez E, Ma Y, Kafizas A, Rosser TE, Mayer MT, Reisner E, Grätzel M, Batista VS, Durrant Jet al., 2020, Multihole water oxidation catalysis on hematite photoanodes revealed by operando spectroelectrochemistry and DFT, Nature Chemistry, Vol: 12, Pages: 82-89, ISSN: 1755-4330

Water oxidation is the key kinetic bottle neck of photoelectrochemical devices for fuel synthesis. Despite advances in the identification of intermediates, elucidating the catalytic mechanism of this multi-redox reactionon metal-oxidephotoanodes remains a significant experimental and theoretical challenge. Here we report an experimental analysis of water oxidation kinetics on four widely studied metal oxides, focusing particularly upon hematite.We observe that hematite is able toaccess a reaction mechanism third order in surface hole density, assigned to equilibration between three surface holes and M(OH)-O-M(OH) sites. This reaction exhibits a remarkably low activation energy (Ea~ 60 meV). Density functional theory is employedto determine the energetics of charge accumulation and O-O bond formation on a modelhematite 110 surface. The proposed mechanism shows parallels with the function of oxygen evolving complex of photosystem II,and provides new insights to the mechanism of heterogeneous water oxidation on a metal oxide surface.

Journal article

Selim S, Pastor E, García-Tecedor M, Morris MR, Francas L, Sachs M, Moss B, Corby S, Mesa CA, Gimenez S, Kafizas A, Bakulin AA, Durrant JRet al., 2019, Impact of oxygen vacancy occupancy on charge carrier dynamics in BiVO4 photoanodes, Journal of the American Chemical Society, Vol: 141, Pages: 18791-18798, ISSN: 0002-7863

Oxygen vacancies are ubiquitous in metal oxides and critical to performance, yet the impact of these states upon charge carrier dynamics important for photoelectrochemical and photocatalytic applications, remains contentious and poorly understood. A key challenge is the unambiguous identification of spectroscopic fingerprints which can be used to track their function. Herein, we employ five complementary techniques to modulate the electronic occupancy of states associated with oxygen vacancies in situ in BiVO4 photoanodes, allowing us to identify a spectral signature for the ionisation of these states. We obtain an activation energy of ̴ 0.2 eV for this ionisation process, with thermally activated electron de-trapping from these states determining the kinetics of electron extraction, consistent with improved photoelectrochemical performance at higher temperatures. Bulk, un-ionised states however, function as deep hole traps, with such trapped holes being energetically unable to drive water oxidation. These observations help address recent controversies in the literature over oxygen vacancy function, providing new insights into their impact upon photoelectrochemical performance.

Journal article

Ambroz F, Xu W, Gadipelli S, Brett DJL, Lin C-T, Contini C, McLachlan MA, Durrant JR, Parkin IP, Macdonald TJet al., 2019, Room Temperature Synthesis of Phosphine-Capped Lead Bromide Perovskite Nanocrystals without Coordinating Solvents, PARTICLE & PARTICLE SYSTEMS CHARACTERIZATION, Vol: 37, ISSN: 0934-0866

Journal article

Daboczi M, Hamilton I, Xu S, Luke J, Limbu S, Lee J, McLachlan MA, Lee K, Durrant JR, Baikie I, Kim J-Set al., 2019, The origin of open-circuit voltage losses in perovskite solar cells investigated by surface photovoltage measurement, ACS Applied Materials & Interfaces, Vol: 11, Pages: 46808-46817, ISSN: 1944-8244

Increasing the open circuit voltage (Voc) is one of the key strategies for further improvement of the efficiency of perovskite solar cells. It requires fundamental understanding of the complex optoelectronic processes related to charge carrier generation, transport, extraction and their loss mechanisms inside a device upon illumination. Herein we report the important origin of Voc losses in methylammonium lead iodide perovskite (MAPI) based solar cells, which results from undesirable positive charge (hole) accumulation at the interface between the perovskite photoactive layer and the PEDOT:PSS hole transport layer. We show strong correlation between the thickness-dependent surface photovoltage and device performance, unraveling that the interfacial charge accumulation leads to charge carrier recombination and results in a large decrease in Voc for the PEDOT:PSS/MAPI inverted devices (180 mV reduction in 50-nm-thick device compared to 230-nm-thick one). In contrast, accumulated positive charges at the TiO2/MAPI interface modify interfacial energy band bending, which leads to an increase in Voc for the TiO2/MAPI conventional devices (70 mV increase in 50-nm-thick device compared to 230-nm-thick one). Our results provide an important guideline for better control of interfaces in perovskite solar cells to improve device performance further.

Journal article

Francàs L, Corby S, Selim S, Lee D, Mesa C, Godin R, Pastor E, Stephens I, Choi K-S, Durrant Jet al., 2019, Spectroelectrochemical study of water oxidation on nickel and iron oxyhydroxide electrocatalysts, Nature Communications, Vol: 10, ISSN: 2041-1723

Ni/Fe oxyhydroxides are the best performing Earth-abundant electrocatalysts for water oxidation. However, the origin of their remarkable performance is not well understood. Herein, we employ spectroelectrochemical techniques to analyse the kinetics of water oxidation on a series of Ni/Fe oxyhydroxide films: FeOOH, FeOOHNiOOH, and Ni(Fe)OOH (5% Fe). The concentrations and reaction rates of the oxidised states accumulated during catalysis are determined. Ni(Fe)OOH is found to exhibit the fastest reaction kinetics but accumulates fewer states, resulting in a similar performance to FeOOHNiOOH. The later catalytic onset in FeOOH is attributed to an anodic shift in the accumulation of oxidised states. Rate law analyses reveal that the rate limiting step for each catalyst involves the accumulation of four oxidised states, Ni-centred for Ni(Fe)OOH but Fe-centred for FeOOH and FeOOHNiOOH. We conclude by highlighting the importance of equilibria between these accumulated species and reactive intermediates in determining the activity of these materials.

Journal article

Wu J, Luke J, Lee HKH, Tuladhar PS, Cha H, Jang S-Y, Tsoi WC, Heeney M, Kang H, Lee K, Kirchartz T, Kim J-S, Durrant JRet al., 2019, Tail state limited photocurrent collection of thick photoactive layers in organic solar cells, Nature Communications, Vol: 10, ISSN: 2041-1723

Weanalyseorganic solar cells with four differentphotoactive blends exhibiting differing dependencies ofshort-circuit current upon photoactive layer thickness.These blends and devices are analysedbytransient optoelectronic techniques ofcarrier kinetics and densities, airphotoemission spectroscopyof material energetics, Kelvin probe measurements of work function, Mott-Schottky analyses of apparent doping density and by device modelling. We concludethat,for the device series studied, the photocurrent losswith thick active layersis primarilyassociatedwith the accumulation of photo-generated charge carriers in intra-bandgap tail states.This charge accumulation screens the device internal electricalfield, preventing efficient charge collection. Purification of one studied donor polymer is observed to reduce tail statedistribution anddensity and increase the maximal photoactive thickness forefficient operation. Ourwork suggests that selectingorganic photoactive layerswith a narrow distribution of tail states isa keyrequirement for the fabrication of efficient, high photocurrent, thick organic solar cells.

Journal article

Corby S, Francàs L, Kafizas A, Durrant JRet al., 2019, Determining the Role of Oxygen Vacancies in the Photocatalytic Performance of WO3 for Water Oxidation

<jats:p>Oxygen vacancies are common to most metal oxides, whether intentionally incorporated or otherwise, and the study of these defects is of increasing interest for solar water splitting. In this work, we examine nanostructured WO&lt;sub&gt;3&lt;/sub&gt; photoanodes of varying oxygen content to determine how the concentration of bulk oxygen-vacancy states affects the photocatalytic performance for water oxidation. Using transient optical spectroscopy, we follow the charge carrier recombination kinetics in these samples, from picoseconds to seconds, and examine how differing oxygen vacancy concentrations impact upon these kinetics. We find that samples with an intermediate concentration of vacancies (~2% of oxygen atoms) afford the greatest photoinduced charge carrier densities, and the slowest recombination kinetics across all timescales studied. This increased yield of photogenerated charges correlates with improved photocurrent densities under simulated sunlight, with both greater and lesser oxygen vacancy concentrations resulting in enhanced recombination losses and poorer J-V performances. Our conclusion, that an optimal – neither too high nor too low – concentration of oxygen vacancies is required for optimum photoelectrochemical performance, is discussed in terms of the impact of these defects on charge separation and transport, as well as the implications held for other highly doped materials for photoelectrochemical water oxidation.</jats:p>

Journal article

Corby S, Francàs L, Kafizas A, Durrant JRet al., 2019, Determining the Role of Oxygen Vacancies in the Photocatalytic Performance of WO3 for Water Oxidation

<jats:p>Oxygen vacancies are common to most metal oxides, whether intentionally incorporated or otherwise, and the study of these defects is of increasing interest for solar water splitting. In this work, we examine nanostructured WO<jats:sub>3</jats:sub> photoanodes of varying oxygen content to determine how the concentration of bulk oxygen-vacancy states affects the photocatalytic performance for water oxidation. Using transient optical spectroscopy, we follow the charge carrier recombination kinetics in these samples, from picoseconds to seconds, and examine how differing oxygen vacancy concentrations impact upon these kinetics. We find that samples with an intermediate concentration of vacancies (~2% of oxygen atoms) afford the greatest photoinduced charge carrier densities, and the slowest recombination kinetics across all timescales studied. This increased yield of photogenerated charges correlates with improved photocurrent densities under simulated sunlight, with both greater and lesser oxygen vacancy concentrations resulting in enhanced recombination losses and poorer J-V performances. Our conclusion, that an optimal – neither too high nor too low – concentration of oxygen vacancies is required for optimum photoelectrochemical performance, is discussed in terms of the impact of these defects on charge separation and transport, as well as the implications held for other highly doped materials for photoelectrochemical water oxidation.</jats:p>

Journal article

Luo H, Papaioannou N, Salvadori E, Roessler MM, Ploenes G, van Eck ERH, Tanase LC, Feng J, Sun Y, Yang Y, Danaie M, Jorge AB, Sapelkin A, Durrant J, Dimitrov SD, Titirici M-Met al., 2019, Manipulating the Optical Properties of Carbon Dots by Fine-Tuning their Structural Features, CHEMSUSCHEM, Vol: 12, Pages: 4432-4441, ISSN: 1864-5631

Journal article

He Q, Shahid M, Wu J, Jiao X, Eisner FD, Hodsden T, Fei Z, Anthopoulos TD, McNeill CR, Durrant JR, Heeney Met al., 2019, Fused Cyclopentadithienothiophene acceptor enables ultrahigh short‐circuit current and high efficiency >11% in as‐cast organic solar cells, Advanced Functional Materials, Vol: 29, Pages: 1-7, ISSN: 1616-301X

A new method to synthesize an electron‐rich building block cyclopentadithienothiophene (9H‐thieno‐[3,2‐b]thieno[2″,3″:4′,5′]thieno[2′,3′:3,4]cyclopenta[1,2‐d]thiophene, CDTT) via a facile aromatic extension strategy is reported. By combining CDTT with 1,1‐dicyanomethylene‐3‐indanone endgroups, a promising nonfullerene small molecule acceptor (CDTTIC) is prepared. As‐cast, single‐junction nonfullerene organic solar cells based on PFBDB‐T: CDTTIC blends exhibit very high short‐circuit currents up to 26.2 mA cm−2 in combination with power conversion efficiencies over 11% without any additional processing treatments. The high photocurrent results from the near‐infrared absorption of the CDTTIC acceptor and the well‐intermixed blend morphology of polymer donor PFBDB‐T and CDTTIC. This work demonstrates a useful fused ring extension strategy and promising solar cell results, indicating the great potential of the CDTT derivatives as electron‐rich building blocks for constructing high‐performance small molecule acceptors in organic solar cells.

Journal article

Macdonald TJ, Batmunkh M, Lin C-T, Kim J, Tune DD, Ambroz F, Li X, Xu S, Sol C, Papakonstantinou I, McLachlan MA, Parkin IP, Shapter JG, Durrant JRet al., 2019, Origin of performance enhancement in TiO2-carbon nanotube composite perovskite solar cells, Small Methods, Vol: 3, Pages: 1-10, ISSN: 2366-9608

Carbon nanotubes are shown to be beneficial additives to perovskite solar cells, and the inclusion of such nanomaterials will continue to play a crucial role in the push toward developing efficient and stable device architectures. Herein, titanium dioxide/carbon nanotube composite perovskite solar cells are fabricated, and device performance parameters are correlated with spectroscopic signatures of the materials to understand the origin of performance enhancement. By probing the charge carrier dynamics with photoluminescence and femtosecond transient absorption spectroscopy, the results indicate that charge transfer is not improved by the presence of the carbon nanotubes. Instead, carbon nanotubes are shown to passivate the electronic defect states within the titanium dioxide, which can lead to stronger radiative recombination in the titanium dioxide/carbon nanotube films. The defect passivation allows the perovskite solar cells made using an optimized titanium dioxide/carbon nanotube composite to achieve a peak power conversion efficiency of 20.4% (19% stabilized), which is one of the highest values reported for perovskite solar cells not incorporating a mixed cation light absorbing layer. The results discuss new fundamental understandings for the role of carbon nanomaterials in perovskite solar cells and present a significant step forward in advancing the field of high‐performance photovoltaics.

Journal article

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