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Molecular Photonic Breadboards

Lead Research Organisation: University of Sheffield
Department Name: Chemistry

Abstract

New manufacturing methods are required if we are to live sustainably on the earth. In the electronics industry there is enormous interest in the possibility of manufacturing devices using organic materials: they can be manufactured sustainably from earth-abundant resources at energy costs that are typically significantly less than those associated with the production of equivalent inorganic materials. Electronic devices based on organic components are now readily available in the high street. For example, organic light-emitting diodes are used to produce the displays used in some high-end TV sets and in smartphones (e.g. iPhone X). However, a fundamental problem prevents the realisation of the full potential of organic materials in electronic devices. When light is absorbed by molecular semiconductors, it causes the creation of excitons - pairs of opposite charges - that carry excitation through the device. However, the excitons in organic materials recombine and cancel themselves out extremely rapidly - they can only move short distances through the material. This fundamental obstacle limits the application of organic materials in consumer electronics and also in many other areas of technology - in quantum communications, photocatalysis and sensor technologies.

We propose an entirely new approach to solving this problem that is based on combining molecular designs inspired by photosynthetic mechanisms with nanostructured materials to produce surprising and intriguing quantum optical effects that mix the properties of light and matter.

On breadboards, threaded mounts hold optical components relative to one another so that rays of light can be directed through an optical system. This proposal also aims to design breadboards, but of a very different kind. The smallest components will be single chromophores (light absorbing molecules), held at fixed arrangements in space by minimal building blocks called antenna complexes, whose structures are inspired by those of proteins involved in photosynthesis. Antenna complexes are designed and made from scratch using synthetic biology and chemistry so that transfer of energy can be controlled by programming the antenna structure. Instead of using threaded mounts, we will organise these components by attachment to reactive chemical groups formed on solid surfaces by nanolithography. In these excitonic films, we will develop design rules for efficient long-range transport.

In conventional breadboards, light travels in straight lines between components. However, we will use the phenomenon of strong light-matter coupling to achieve entirely different types of energy transfer. In strong coupling, a localised plasmon resonance (an light mode confined to the surface of a nanoparticle) is hybridised with molecular excitons to create new states called plexcitons that combine the properties of light and matter. We will create plexcitonic complexes, in each of which an array of as many as a thousand chromophores is strongly coupled to a plasmon mode. In these plexcitonic complexes, the coupling is collective - all the chromophores couple to the plasmon simultaneously, and so the rules of energy transfer are completely re-written. Energy is no longer transferred via a series of linear hopping steps (as it is in organic semiconductors), but is delocalised instantaneously across the entire structure - many orders of magnitude further than is possible in conventional organic semiconductors. By designing these plexcitonic complexes from scratch we aim to create entirely new properties. The resulting materials are fully programmable from the scale of single chromophores to macroscopic structures.

By combining biologically-inspired design with strong light-matter coupling we will create many new kinds of functional structures, including new medical sensors, 'plexcitonic circuits', and quantum optical films suitable for many applications, using low-cost, environmentally benign methods.

Planned Impact

Wealth creation

Much of the work described in this proposal is fundamental in nature: it aims to establish a new field of investigation based on the use of synthetic biological approaches to control quantum optical phenomena. However, it is firmly directed towards possible applications and molecular photonic breadboards (MPB) are a generic approach to the control of optical energy transfer that may be used to address many technological problems.

One important area of application is in optoelectronics. The short exciton diffusion lengths (10 nm) of polymer semiconductors are a fundamental barrier to their commercial exploitation. If we succeed in achieving efficient long-range transport of excitons in our molecular photonic breadboards, this will be transformational for many areas. Thus it will be important to explore the utility of MPB for device design. In particular, we will examine their suitability for solar energy capture. To this end we have made the design of polymer scaffolds an integral element of our programme. Although biomolecules give precise structural control, polymers are a much more suitable scaffold for large-scale device production. The approaches we will develop will be based on inexpensive synthesis carried out in aqueous conditions. There is extensive expertise in Sheffield to help us design prototypical solar cells. These measurements will be carried out in the lifetime of the project to explore the potential for early translation.

Society

The work described here may have significant impact on healthcare. A key element of the programme is the design of membrane systems for the measurement of exciton dynamics. These membranes offer enormous potential for the measurement of membrane processes (currently membrane proteins are the target for ca. 50% of drugs). The integration of strong plasmon-exciton coupling into optical biosensors is potentially transformative, offering fast quantitative analysis on a simple, inexpensive platform suitable for adoption in clinical chemistry laboratories with minimal infrastructure. We will explore the clinical utility of such approaches for cancer diagnosis with collaborators in the Sheffield Dental Hospital.

Energy supply problems are of economic significance because they impact the UK's international competitiveness, and they also impact on quality of life. The development of cost-effective renewable energy sources is vital to the UK economy, to the well-being of its citizens, and to the reduction of long-term harm caused by climate change. The goal of this proposal is to provide design principles to facilitate the development of improved, low-cost polymer photovoltaic devices. Achieving this goal would impact in a positive way on quality of life in the UK. For very similar reasons, it would also impact positively on international development: in the world's poorest nations the need for inexpensive sources of renewable energy is even greater, and often, the need to mitigate the effects of climate change is the greatest there too.

People

We will train 10 PDRAs in cross-disciplinary fields relevant to important emerging technologies. We will build an exciting, vibrant programme of research designed to attract the most able young scientists, and will help them to stretch themselves. They will form an enthusiastic multi-disciplinary team working to meet highly ambitious technical goals and targets. There will necessarily be a strong emphasis on collaboration and team-work. The multidisciplinary nature of this project will ensure that all hired personnel will become 'multi-lingual' in various branches of science. This rare and enriching experience will broaden their horizons, whether they choose to take up employment within industry or follow an academic career path. We will build a programme of outreach activities to take our excitement, and insights from the programme, into the wider community to inspire others.

Publications

10 25 50
 
Description The aim of this project was to develop a new approach to the production of molecular materials for applications in optoelectronics that was inspired by biological photosynthetic mechanisms and integrated the physics of strong light-matter coupling. We have been developing an entirely new approach to the design of molecular photonic materials that could extend excitation transfer distances from nm to cm. At the core of our proposal is the construction of programmable molecular photonic breadboards, a modular approach to the design of photonic materials that is inspired by natural photosynthetic membranes. In optics, breadboards are used to organise optical components precisely in space. In molecular photonic breadboards, minimal units - synthetic antenna complexes - are designed from scratch to organise molecular components precisely in space. These building blocks are assembled to form nanostructured films in which energy transfer pathways are controlled from the nm to the cm scale. At the heart of our strategy is the combination of biologically-inspired design principles with the exciting new physics of strong light-matter coupling, in which, under certain conditions, the properties of excitons are mixed with those of localised surface plasmon resonances to yield new hybrid states that combine the properties of light and matter.
This is a very complex project that addresses a complex challenge. However, it is now beginning to bear fruit in exciting ways.
We have developed new synthetic peptides and proteins that are capable of binding dye molecules and orienting them in a precise fashion relative to a metal surface, thus allowing us to optimise coupling between a surface plasmon polariton and the dye molecules. We have begun attempting to develop a new biomimetic approach to photonic materials that is based on the layer-by-layer assembly of multiple component assemblies of such synthetic peptide- and protein-based antenna complexes.
We have also successfully designed a variety of pigment-polymer antenna complexes, which are inspired by biological pigment-protein antenna complexes, but in which the peptide scaffold that organises the pigment molecules is replaced by a surface-grafted polymer scaffold. We find that we can achieve very high dye loadings (chlorophyll loadings higher than those found in biological light-harvesting complexes), and that we can achieve strong plasmon-exciton coupling, with coupling energies approximately twice as large as those measured for biological light-harvesting complexes. We find that the poly base poly(2-(dimethylamino) ethyl metacrylate) (PDMA) binds the cyanine dye strongly, and surprisingly, it strongly templates the formation of J-aggregates that display oreintational anisotropy. The bound TDBC molecules are almost exclusively in the form of J-aggregates when bound within PDMA scaffolds. Spectroscopic linewidths are small, indicative of a comparatively well-controlled aggregation mechanism. Dispersion measurements in silver surfaces indicate coupling strengths twice those observed for biological light-harvesting complexes. In films of dye-functionalised polymers, excited-state lifetimes are slightly smaller than, but similar to, excited state lifetimes of dye molecules in solution, and significantly longer than excited-state lifetimes of the same dyes in spin-cast films of the same dyes. Thus, it appears that biomimetic pigment-polymer antenna complexes are programmable, and offer a high degree of control of the organisation and aggregation states of dye molecules in films.
Exploitation Route It is too early to be able to say for certain. However, we hope that our demonstration that programmable films of pigment-polymer antenna complexes can be produced using environmentally benign, water-based synthetic processes will open the way to potential applications in a variety of areas, including solar energy capture, optoelectronics and sensors.
Sectors Chemicals

Energy

Environment

Healthcare

Manufacturing

including Industrial Biotechology

 
Title Alumina nanoparticles enable optimal spray-coated perovskite thin film growth on self-assembled monolayers for efficient and reproducible photovoltaics 
Description The power conversion efficiencies of metal halide perovskite photovoltaics have increased rapidly over the past decade attracting significant academic and industrial interest. The ease with which high performance perovskite photovoltaics can be fabricated through solution processing routes has opened up significant possibilities for fabrication through existing, industrially mature high-throughput solution coating techniques such as spray-coating. The power conversion efficiencies of spray-coated metal halide perovskite photovoltaics are limited by non-radiative recombination at the interfaces with charge transport layers necessitating the implementation of new charge transport layers. The self-assembled monolayer (SAM) charge transport layers have resulted in record perovskite photovoltaic device performances, due to reduced non-radiative recombination. However, poor wettability associated with some SAMs significantly limits their applicability, this is exaggerated for droplet-based scalable technologies like spray-coating. Here we report an optimised aluminium oxide nanoparticle interlayer which enables spray-coating of triple cation metal halide perovskite thin films and devices onto Me-4PACz (([4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid). Our interlayer results in improved structural and optoelectronic properties of spray-coated perovskite thin films, compared to those fabricated through spin-coating. These improved properties enable the fabrication of p-i-n photovoltaic devices with efficiencies over 20 % - some of the highest reported for both spray-coated devices in p-i-n architecture, and devices having a spray-coated "triple cation" perovskite active layer. 
Type Of Material Database/Collection of data 
Year Produced 2024 
Provided To Others? Yes  
URL https://orda.shef.ac.uk/articles/dataset/Alumina_nanoparticles_enable_optimal_spray-coated_perovskit...
 
Title Alumina nanoparticles enable optimal spray-coated perovskite thin film growth on self-assembled monolayers for efficient and reproducible photovoltaics 
Description The power conversion efficiencies of metal halide perovskite photovoltaics have increased rapidly over the past decade attracting significant academic and industrial interest. The ease with which high performance perovskite photovoltaics can be fabricated through solution processing routes has opened up significant possibilities for fabrication through existing, industrially mature high-throughput solution coating techniques such as spray-coating. The power conversion efficiencies of spray-coated metal halide perovskite photovoltaics are limited by non-radiative recombination at the interfaces with charge transport layers necessitating the implementation of new charge transport layers. The self-assembled monolayer (SAM) charge transport layers have resulted in record perovskite photovoltaic device performances, due to reduced non-radiative recombination. However, poor wettability associated with some SAMs significantly limits their applicability, this is exaggerated for droplet-based scalable technologies like spray-coating. Here we report an optimised aluminium oxide nanoparticle interlayer which enables spray-coating of triple cation metal halide perovskite thin films and devices onto Me-4PACz (([4-(3,6-dimethyl-9H-carbazol-9-yl)butyl]phosphonic acid). Our interlayer results in improved structural and optoelectronic properties of spray-coated perovskite thin films, compared to those fabricated through spin-coating. These improved properties enable the fabrication of p-i-n photovoltaic devices with efficiencies over 20 % - some of the highest reported for both spray-coated devices in p-i-n architecture, and devices having a spray-coated "triple cation" perovskite active layer. 
Type Of Material Database/Collection of data 
Year Produced 2024 
Provided To Others? Yes  
URL https://orda.shef.ac.uk/articles/dataset/Alumina_nanoparticles_enable_optimal_spray-coated_perovskit...
 
Title Data for 'Twisted Carotenoids Do Not Support Efficient Intramolecular Singlet Fission in the Orange Carotenoid Protein' 
Description This dataset contains the data shown in the article 'Twisted Carotenoids Do Not Support Efficient Intramolecular Singlet Fission in the Orange Carotenoid Protein' (J. Phys. Chem. Lett., 2023, DOI: 10.1021/acs.jpclett.3c01139). The dataset is provided as a zip file ('Data.zip'). To access the contained data and folders, please download the zip file, and extract it using a file archiver program. Where possible, both raw and analysed data have been included, along with the finalised versions of the figures. Please refer to the README files for further details (including an index specifying the contents). We recommend opening 'README.html' in a web browser to view with HTML formatting, or if not available, opening 'README.md' within a text editor. 
Type Of Material Database/Collection of data 
Year Produced 2023 
Provided To Others? Yes  
Impact n/a 
URL https://figshare.shef.ac.uk/articles/dataset/Data_for_Twisted_Carotenoids_Do_Not_Support_Efficient_I...
 
Title Data for 'Twisted Carotenoids Do Not Support Efficient Intramolecular Singlet Fission in the Orange Carotenoid Protein' 
Description This dataset contains the data shown in the article 'Twisted Carotenoids Do Not Support Efficient Intramolecular Singlet Fission in the Orange Carotenoid Protein' (J. Phys. Chem. Lett., 2023, DOI: 10.1021/acs.jpclett.3c01139). The dataset is provided as a zip file ('Data.zip'). To access the contained data, please download the zip file, and extract it using a file archiver program. Where possible, both raw and analysed data have been included, along with the finalised versions of the figures. Please refer to the README files for further details (including an index specifying the contents). We recommend opening 'README.html' in a web browser to view with HTML formatting, or if not available, opening 'README.md' in a text editor. 
Type Of Material Database/Collection of data 
Year Produced 2023 
Provided To Others? Yes  
URL https://figshare.shef.ac.uk/articles/dataset/Data_for_Twisted_Carotenoids_Do_Not_Support_Efficient_I...
 
Title Plexcitonic Antenna Complexes 
Description Spreadsheets containing the original data used to plot the figures in Lishchuk et al, "Active control of strong plasmon-exciton coupling in biomimetic pigment-polymer antenna complexes grown by surface-initiated polymerisation from gold nanostructures" 
Type Of Material Database/Collection of data 
Year Produced 2022 
Provided To Others? Yes  
Impact n/a 
URL https://figshare.shef.ac.uk/articles/dataset/Plexcitonic_Antenna_Complexes/19125446
 
Title Plexcitonic Antenna Complexes 
Description Spreadsheets containing the original data used to plot the figures in Lishchuk et al, "Active control of strong plasmon-exciton coupling in biomimetic pigment-polymer antenna complexes grown by surface-initiated polymerisation from gold nanostructures" 
Type Of Material Database/Collection of data 
Year Produced 2022 
Provided To Others? Yes  
URL https://figshare.shef.ac.uk/articles/dataset/Plexcitonic_Antenna_Complexes/19125446/1
 
Title The role of the organic cation in developing efficient green perovskite LEDs based on 2D/3D perovskite heterostructures 
Description Characterisation data for perovskite LED study. Atomic force microscopy data have file type .ibw, these can be opened using Gwyddion an open source AFM image analysis software. File naming system code can be found in attached naming system.txt file. Other data is presented as .csv files and comprises device characterisation data, grazing incidence x-ray scattering, photoluminescence spectroscopy, UV-vis spectroscopy, ultraviolet photoelectron spectroscopy. 
Type Of Material Database/Collection of data 
Year Produced 2023 
Provided To Others? Yes  
URL https://orda.shef.ac.uk/articles/dataset/The_role_of_the_organic_cation_in_developing_efficient_gree...
 
Description Collaboration with Milan Delor, Columbia University 
Organisation Columbia University
Country United States 
Sector Academic/University 
PI Contribution James Pidgeon, a post-doc working on this project, visited Prof Delor's laboratory in January 2024 to carry out experiments.
Collaborator Contribution Prof Delor has provided access to state of the art instrumentation and researchers in his lab have provided training to Dr James Pidgeon
Impact No outputs yet - the collaboration is at an early stage
Start Year 2024
 
Description Molecular Photonic Breadboards - Public Engagement Video 
Form Of Engagement Activity A broadcast e.g. TV/radio/film/podcast (other than news/press)
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Public/other audiences
Results and Impact A short video was recorded giving the background to the grant, and explaining in accessible terms the research that has been funded by UKRI. The video has not been available for long so it is too early to assess the scope of the impacts. This can be updated in future returns to ResearchFish.
Year(s) Of Engagement Activity 2024
URL https://player.sheffield.ac.uk/events/molecular-photonic-breadboards