B23-Circular Dichroism
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Jessica
Wade
,
Francesco
Salerno
,
Rachel C.
Kilbride
,
Dong Kuk
Kim
,
Julia A.
Schmidt
,
Joel A.
Smith
,
Luc M.
Leblanc
,
Emma H.
Wolpert
,
Adebayo A.
Adeleke
,
Erin R.
Johnston
,
Jenny
Nelson
,
Tadashi
Mori
,
Kim E.
Jelfs
,
Sandrine
Heutz
,
Matthew J.
Fuchter
Diamond Proposal Number(s):
[29151]
Abstract: Chiral π-conjugated molecules bring new functionality to technological applications and represent an exciting, rapidly expanding area of research. Their functional properties, such as the absorption and emission of circularly polarized light or the transport of spin-polarized electrons, are highly anisotropic. As a result, the orientation of chiral molecules critically determines the functionality and efficiency of chiral devices. Here we present a strategy to control the orientation of a small chiral molecule (2,2′-dicyano[6]helicene) by the use of organic and inorganic templating layers. Such templating layers can either force 2,2′-dicyano[6]helicene to adopt a face-on orientation and self-assemble into upright supramolecular columns oriented with their helical axis perpendicular to the substrate, or an edge-on orientation with parallel-lying supramolecular columns. Through such control, we show that low- and high-energy chiroptical responses can be independently ‘turned on’ or ‘turned off’. The templating methodologies described here provide a simple way to engineer orientational control and, by association, anisotropic functional properties of chiral molecular systems for a range of emerging technologies.
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Oct 2022
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I03-Macromolecular Crystallography
I04-1-Macromolecular Crystallography (fixed wavelength)
I04-Macromolecular Crystallography
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Elizabeth L.
Bell
,
Ross
Smithson
,
Siobhan
Kilbride
,
Jake
Foster
,
Florence J.
Hardy
,
Saranarayanan
Ramachandran
,
Aleksander A.
Tedstone
,
Sarah J.
Haigh
,
Arthur A.
Garforth
,
Philip J. R.
Day
,
Colin
Levy
,
Michael P.
Shaver
,
Anthony P.
Green
Diamond Proposal Number(s):
[12788, 17773]
Abstract: The recent discovery of IsPETase, a hydrolytic enzyme that can deconstruct poly(ethylene terephthalate) (PET), has sparked great interest in biocatalytic approaches to recycle plastics. Realization of commercial use will require the development of robust engineered enzymes that meet the demands of industrial processes. Although rationally engineered PETases have been described, enzymes that have been experimentally optimized via directed evolution have not previously been reported. Here, we describe an automated, high-throughput directed evolution platform for engineering polymer degrading enzymes. Applying catalytic activity at elevated temperatures as a primary selection pressure, a thermostable IsPETase variant (HotPETase, Tm = 82.5 °C) was engineered that can operate at the glass transition temperature of PET. HotPETase can depolymerize semicrystalline PET more rapidly than previously reported PETases and can selectively deconstruct the PET component of a laminated multimaterial. Structural analysis of HotPETase reveals interesting features that have emerged to improve thermotolerance and catalytic performance. Our study establishes laboratory evolution as a platform for engineering useful plastic degrading enzymes.
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Aug 2022
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[18563]
Open Access
Abstract: The addition of alkali metal halides to hybrid perovskite materials can significantly impact their crystallisation and hence their performance when used in solar cell devices. Previous work on the use of potassium iodide (KI) in active layers to passivate defects in triple-cation mixed-halide perovskites has been shown to enhance their luminescence efficiency and reduce current–voltage hysteresis. However, the operational stability of KI passivated perovskite solar cells under ambient conditions remains largely unexplored. By investigating perovskite solar cell performance with SnO2 or TiO2 electron transport layers (ETL), we propose that defect passivation using KI is highly sensitive to the composition of the perovskite–ETL interface. We reconfirm findings from previous reports that KI preferentially interacts with bromide ions in mixed-halide perovskites, and – at concentrations >5 mol% in the precursor solution – modifies the primary absorber composition as well as leading to the phase segregation of an undesirable secondary non-perovskite phase (KBr) at high KI concentration. Importantly, by studying both material and device stability under continuous illumination and bias under ambient/high-humidity conditions, we show that this secondary phase becomes a favourable degradation product, and that devices incorporating KI have reduced stability.
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Nov 2020
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I07-Surface & interface diffraction
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Donghui
Li
,
Xiaolong
Chen
,
Jinglong
Cai
,
Wei
Li
,
Mengxue
Chen
,
Yuchao
Mao
,
Baocai
Du
,
Joel A.
Smith
,
Rachel C.
Kilbride
,
Mary E.
O'Kane
,
Xue
Zhang
,
Yuan
Zhuang
,
Pang
Wang
,
Hui
Wang
,
Dan
Liu
,
Richard A. L.
Jones
,
David G.
Lidzey
,
Tao
Wang
Diamond Proposal Number(s):
[22651]
Abstract: Optimizing the components and morphology within the photoactive layer of organic solar cells (OSCs) can significantly enhance their power conversion efficiency (PCE). A new A-D-A type non-fullerene acceptor IDMIC-4F is designed and synthesized in this work, and is employed as the third component to prepare high performance ternary solar cells. IDMIC-4F can form fibrils after solution casting, and the presence of this fibrillar structure in the PBDB-T-2F:BTP-4F host confines the growth of donors and acceptors into fine domains, as well as acting as transport channels to enhance electron mobility. Single junction ternary devices incorporating 10 wt% IDMIC-4F exhibit enhanced light absorption and balanced carrier mobility, and achieve a maximum PCE of 16.6% compared to 15.7% for the binary device, which is a remarkable efficiency for OSCs reported in literature. This non-fullerene acceptor fibril network strategy is a promising method to improve the photovoltaic performance of ternary OSCs.
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Feb 2020
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I07-Surface & interface diffraction
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Wei
Li
,
Zuo
Xiao
,
Joel As.
Smith
,
Jinlong
Cai
,
Donghui
Li
,
Rachel C.
Kilbride
,
Emma L. K.
Spooner
,
Onkar S.
Game
,
Xianyi
Meng
,
Dan
Liu
,
Richard A. L.
Jones
,
David G.
Lidzey
,
Liming
Ding
,
Tao
Wang
Diamond Proposal Number(s):
[20419]
Abstract: Traditional single-junction binary organic solar cells suffer from narrow absorption windows, limiting their ability to harvest photons. One promising approach to avoid this issue is through the construction of a ternary system to enhance the spectral response and efficiency. However, the complex morphology and photophysical processes within ternary blends leave the criteria of an effective third component unclear, and so they remain a challenge. In this work, we report on the fabrication of PTB7-Th:COi8DFIC-based ternary solar cells with enhanced efficiency by employing either a polymer donor or a nonfullerene acceptor as the third component. We demonstrate that the third component is highly associated with the condensed state of the host acceptor and is the primary factor in determining efficiency improvement. The π-π stacking molecular packing of COi8DFIC helps to maintain the optimal phase separation within the ternary blends and improves both the hole and electron charge mobilities, resulting in enhanced power conversion efficiency of over 14%, compared to 13.1% in binary devices. We also found an excessive amount of polymer donor or nonfullerene acceptor increases the phase separation and encourages lamellar crystallization with the host acceptor domain, resulting in reduced light-harvesting and external quantum efficiencies at long wavelengths. Our results provide a rational guide to selecting the third component to fabricate high-performance nonfullerene-based ternary solar cells.
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Dec 2019
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I07-Surface & interface diffraction
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Mengxue
Chen
,
Zhuohan
Zhang
,
Wei
Li
,
Jinlong
Cai
,
Jiangsheng
Yu
,
Emma L. K.
Spooner
,
Rachel C.
Kilbride
,
Donghui
Li
,
Baocai
Du
,
Robert S.
Gurney
,
Dan
Liu
,
Weihua
Tang
,
David G.
Lidzey
,
Tao
Wang
Diamond Proposal Number(s):
[20419]
Abstract: Fluorinated non-fullerene acceptors (NFAs) usually have planar backbone and a higher tendency to crystallize compared to their non-fluorinated counterparts, which leads to enhanced charge mobility in organic solar cells (OSCs). However, this self-organization behavior may result in excessive phase separation with electron donors and thereby deteriorate device efficiency. Herein, we demonstrate an effective approach to tune the molecular organization of a fluorinated NFA (INPIC-4F), and its phase separation with the donor PBDB-T, by varying the casting solvent. A prolonged film drying time encourages the crystallization of INPIC-4F into spherulites and consequently results in excessive phase separation, leading to a low device power conversion efficiency (PCE) of 8.1%. Contrarily, a drying time leads to fine mixed domains with inefficient charge transport properties, resulting in a moderate device PCE of 11.4%. An intermediate film drying time results in the formation of face-on π-π stacked PBDB-T and INPIC-4F domains with continuous phase-separated networks, which facilitates light absorption, exciton dissociation as well as balanced charge transport towards the electrode, and achieves a remarkable PCE of 13.1%. This work provides a rational guide for optimizing the molecular ordering of NFAs and electron donors for high device efficiency.
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Sep 2019
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I07-Surface & interface diffraction
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Baocai
Du
,
Renyong
Geng
,
Wei
Li
,
Donghui
Li
,
Yuchao
Mao
,
Mengxue
Chen
,
Xue
Zhang
,
Joel A.
Smith
,
Rachel C.
Kilbride
,
Mary E.
O'Kane
,
Dan
Liu
,
David G.
Lidzey
,
Weihua
Tang
,
Tao
Wang
Diamond Proposal Number(s):
[22651]
Abstract: The insufficient phase separation between polymer donors and non-fullerene acceptors (NFAs) featuring with low-structural orders disrupts efficient charge transport and increases charge recombination, consequently limits the maximum achievable power conversion efficiency (PCE) of organic solar cells (OSCs). Herein, an NFA IT-M has been added as the third component into the PBDB-T:m-INPOIC OSCs, and is shown to effectively tune the phase separation between donor and acceptor molecules, although all components in the ternary system exhibit low degrees of structural orders. The incorporation of 10 wt% IT-M into a PBDB-T:m-INPOIC binary host blend appreciably increases the length scale of phase separation, creating continuous pathways which increase and balance charge transport. This leads to an enhanced photovoltaic performance from 12.8% in the binary cell to 13.9% for the ternary cell with simultaneously improved open-circuit voltage, short-circuit current and fill factor. This work highlights the beneficial role of ternary components in controlling the morphology of the active layer for high performance OSCs.
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Sep 2019
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I07-Surface & interface diffraction
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Wei
Li
,
Zuo
Xiao
,
Jinlong
Cai
,
Joel A.
Smith
,
Emma L. K.
Spooner
,
Rachel C.
Kilbride
,
Onkar S.
Game
,
Xianyi
Meng
,
Donghui
Li
,
Huijun
Zhang
,
Mengxue
Chen
,
Robert S.
Gurney
,
Dan
Liu
,
Richard A. L.
Jones
,
David
Lidzey
,
Liming
Ding
,
Tao
Wang
Diamond Proposal Number(s):
[120419]
Abstract: The chemical structure of non-fullerene acceptors (NFAs) affects their light-harvesting capabilities, energy levels and molecular orders, all of which play a crucial role in determining the efficiency of organic solar cells (OSCs). In this work, we have systematically investigated a series of ladder-type NFAs having different carbon-oxygen-bridged electron-donating cores, and revealed the effects of core structures and film casting conditions on molecular ordering and performance of OSCs. We found that NFAs containing the thieno [3,2-b]thiophene centered, 6 or 8 fused rings (i.e. COi6DFIC, COi8DFIC) exhibit narrower optical band gaps than NFAs containing the benzene centered, 5 or 7 fused rings (i.e. COi5DFIC, COi7DFIC). NFAs containing less fused rings in the carbon-oxygen-bridged core (i.e. COi5DFIC and COi6DFIC) exhibit edge-on molecular orientation in the blends with face-on oriented PTB7-Th donor, and result in low device efficiency. Although NFAs containing more fused rings (i.e. COi7DFIC and COi8DFIC) possess a pronounced flat-on lamellar crystalline structure in the pure state, the crystallization can be reduced when blending with PTB7-Th and under hot-substrate casting, while the lamella in COi8DFIC can be effectively suppressed to form face-on H- and J-type aggregates, leading to enhanced efficiency.
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Jul 2019
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I07-Surface & interface diffraction
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Mengxue
Chen
,
Dan
Liu
,
Wei
Liu
,
Robert S.
Gurney
,
Donghui
Li
,
Jinlong
Cai
,
Emma L. K.
Spooner
,
Rachel C.
Kilbride
,
James D.
Mcgettrick
,
Trystan M.
Watson
,
Zhe
Li
,
Richard A. L.
Jones
,
David G.
Lidzey
,
Tao
Wang
Diamond Proposal Number(s):
[20419]
Abstract: Fluorination of conjugated molecules has been established as an effective structural modification strategy to influence properties, and has attracted extensive attention in organic solar cells (OSCs). Here, we have investigated optoelectronic and photovoltaic property changes of OSCs made of polymer donors with the non-fullerene acceptors (NFAs) ITIC and IEICO and their fluorinated counterparts IT-4F and IEICO-4F. Device studies show that fluorinated NFAs lead to reduced Voc but increased Jsc and FF, and therefore the ultimate influence to efficiency depends on the compensation of Voc loss and gains of Jsc and FF. Fluorination lowers energy levels of NFAs, reduces their electronic bandgaps and red-shifts the absorption spectra. The impact of fluorination on the molecular order depends on the specific NFA, with the conversion of ITIC to IT-4F reduces structural order, which can be reversed after blending with the donor PBDB-T. Contrastingly, IEICO-4F presents stronger π−π stacking after fluorination from IEICO, and this is further strengthened after blending with the donor PTB7-Th. The photovoltaic blends universally present a donor-rich surface region which can promote charge transport and collection towards anode in inverted OSCs. The fluorination of NFAs, however, reduces the fraction of donors in this donor-rich region, consequently encourage the intermixing of donor/acceptor for efficient charge generation.
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Jun 2019
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