Hierarchically assembled Organic Materials for ElectRonICs – HOMERIC

The self-assembly processes of matter give us exquisite tools to create materials with an extreme dimensional control of their constitutive elements, providing thus extra functionalities in the form of their macroscopic assemblies which most of the time differ and complement the ones of the individual constitutive elements. These bottom-up approaches allow us to produce periodic structures with multiple characteristic lengths (from the molecule (1 nm) to the object (1 mm)), which can be combined with subsequent top-down strategies for the realization of more complex functional systems.
Consequently the concept of hierarchical organization through (self-)assembly at different length scales developed in the “HOMERIC” project is used in order to address the current challenges and bottlenecks in organic electronics materials.

vi) Well-defined and precisely controlled functionalized semiconducting and classical oligomers, homo- and copolymers with different structures and architectures (e.g. rod-coil, rod-rod, and coil-coil for block copolymers; star-like and hyper-branched macromolecules, etc.) have been performed.
vii) The development of block copolymers as well as the associated processing methodologies for large area defectless patterns resulting in lithographic resins addressing the ultra high-resolution patterning targeting the sub 22 nm node associated to patterning methodologies have been pursued. The industrial impact was the materials supply and the introduction of these technologies to microelectronic end-users. In parallel new innovative materials, formulations and their evaluation at the laboratory scale are under development for the future nodes.
viii) New original conductive inks with their associate formulations and printing process technologies for transparent electrodes have been developed and integrated to OLED and OPV flexible devices.
ix) Bi-color electrophoretic inks have produced and tested by integration to elementary laboratory devices. Also a primitive demonstrator of self-powered bicolor switch has been developed using the piezoelectric phenomenon of fluoropolymers.
x) The synthesis of both fluorocopolymer and fluoroterpolymer has been performed at the industrial scale. Polymer composition has been optimized depending on the technology and application. Ink formulations have been optimized for various printing technologies (screen printing, slot die…) for both polymer families. The first investigation in using this new family of polymers for energy harvesting has been performed.

Globally we will continue the work already engaged for the development of the materials for organic electronics using the concepts and tools of self-assembly. The laboratory scale developments concerning the synthesis, formulation and process of the new materials for organic electronics will move towards the pilot scale integration to ease their introduction at the industrial scale production. For that the newly established ELORPrintTec platform will be used.
We plan also to go from the laboratory and pilot development of the new materials on to their integration to devices and systems together with end users. This latter action will require a possible new consideration of the design, synthesis, formulation and processing of the materials depending of the required properties and performances of end user’s devices and systems. To help us for that latter action we have already lined up several small and medium high tech enterprises.

Peer-reviewed articles in refereed journals:
- Sub-10nm features obtained from directed self-assembly of semicrystalline polycarbosilane-based block copolymer thin films
Adv. Mater. 2(52), 261-265 (2015)
- An alternative anionic polyelectrolyte for aqueous PEDOT dispersions: toward printable transparent electrodes
Angew. Chem. Int. Ed., 54, 8506-8510 (2015)
- Synthesis and structure-property relationship of carbazole-alt-benzothiadiazole copolymers
J. Polym. Sci.: Part A, Polym. Chem. 53, 2059-2068 (2015).
- Optimization of Magnetic Inks Made of L10-Ordered FePt Nanoparticles and Polystyrene-block-Poly(ethylene oxide) Copolymers
Langmuir, 31(24), 6675-6680 (2015);
- Low band gap semiconducting copolymer nanoparticles by Suzuki cross-coupling polymerization in alcoholic dispersed media
Macromol. Rapid Commun. (2015) accepted.

Patents :
- Method allowing the creation of nanometric structures by self-assembly of block copolymers
WO/2015/087005 - PCT/FR2014/053279
- Process for producing thick nanostructured films obtained from a block copolymer composition
WO/2015/032904 - PCT/EP2014/068957
- Process for controlling the period of a nanostructured assemblage comprising a blend of block copolymers
WO/2015/032890 - PCT/EP2014/068928
- Method for the perpendicular orientation of nanodomains of block copolymers, using statistical or gradient copolymers, the monomers of which differ at least in part from those present in each of the blocks of the block copolymer
- Procédé de contrôle de l’énergie de surface à l’interface entre un copolymère à blocs et un autre composé
0456-ARK62/ PRO1332
- Procédé de réduction de la défectivité d’un film de copolymère à blocs

+ 6 patents pending

Vulgarisation :
- Nouvelles électrodes transparentes souples, Green News Techno, N°171, 13 juillet 2015.

The HOMERIC project aims at the implementation of an integrated Research and Development program addressing the whole value chain of hierarchically structured organic electronic materials - from the molecular synthesis to the proof of concept - while making the link between the fundamental discovery and industrial innovation. This project will be developed on the fertile ground agglomerated around the principal investigator at the University of Bordeaux through the Arkema / Aquitaine Council Chair of Excellence and the “Investissement d’Avenir” calls with the LabEx “AMADEus” (Advanced Materials by Design) and the EquipEx “ELORPrintTec” (Bordeaux University Facility for the Printed Organic Electronics: from Molecules to Devices and System Architectures as well as their Commercialization). The HOMERIC project has the ambition to develop the use of carbon-based materials as a common supply for electronic technologies through a multilevel hierarchical self-assembling methodology in order to confer multiple and durable functionalities resulting in the amplification of the targeted properties. This concept will be applied to four specific scientific challenges inherent to Organic Electronics: i) for lithographic materials and processes methodologies for sub-22 nm circuits printing applications inherent to high resolution lithography by using the direct self-assembly of block copolymers; ii) for the development of conductive printable inks for transparent electrodes based on sp² carbon derived species / semiconducting (co)polymers with the main objective to offer an alternative solution to ITO and/or PEDOT:PSS dispersions; iii) for reflective electronic displays based on the motion of electrophoretic particles with the development of a universal strategy for the scalable synthesis of bicolor inks while pursuing the formulation of an electrophoretic ink inherent to a single quadricolor pixel; iv) for organic ferrotronics through the combination of semiconducting and ferroelectric polymers with applications in solar energy harvesting and lighting. These challenges will be tackled by developing in an integrated manner a deep understanding of the structure / properties relationships related to organic electronic materials; from the design and synthesis to the control of the (self)-assembling behavior through the understanding of the functionalities interactions (electronic/ferroelectric, electronic/ionic, electronic/optic…). Besides most activities in the field involved so far purely academic actors and the organic electronics technologies lack of maturity for subsequent industrial developments. In order to promote the industrial emergence of these technologies, the HOMERIC Industrial Chair will bridge a fundamental scientific approach focused on creativity and innovation with the industrial and commercial constraints. One step towards this goal will be pursued through the transfer of the scientific advances to educated human capital and value through patents, patents licensing and transfer to spin-offs and industrial partners. Consequently we aim at the implementation of a mutualized research environment with scale-up tools for organic electronic materials in which different partners can agglomerate and find the required expertise and tools to develop organic electronics applications while providing training and educational support to future technicians and engineers by transmitting the acquired knowledge and know-how through educational masters and engineers programs and dedicated summer schools.
In conclusion the “organic electronics” industry is very much imminent and the proposed Industrial Chair HOMERIC, through its strategy and objectives in addressing the organic electronic materials, is set to respond with assiduity, efficiency and precision to the challenges inherent to this emerging technology.