Periodic Reporting for period 4 - TEMPORE (Self-Regulating Porous Nano-Oscillators: from Nanoscale Homeostasis to Time-Programmable Devices)
Berichtszeitraum: 2023-04-01 bis 2024-12-31
While the concepts of biomimicking and bioinspiration have been widely explored, the field of material science is still very far from the kind of autonomy characterizing living systems. Developing artificial devices with life-like autonomy is a scientific dream in chemistry and material science. One of the keys for autonomous behavior is the ability to integrate internal self-regulation and to program dynamic actions in the time-domain. Translating the concepts of self-regulation from (bio) chemical to physical, non-reacting systems would represent a major breakthrough in terms of applications enabling the design of all-solid autonomous devices and the emergence of devices in domains such as robotics, optics or sensing. In the TEMPORE project, we aim at developing autonomous and self-regulating nanomaterials that are able to adapt to the environment (homeostasis, phototropism) and are programmed to change states with time (such as oscillations). To do so, we couple the responsiveness of optically active nanoporous materials (sol-gel and MOF based materials) and nanoparticles. The main objectives of the project are: (i) fabricating the autonomous nanomaterials, (ii) understanding and control their dynamic behaviour, (iii) demonstrating proof-of-concept of autonomous devices.
The goal of the ERC TEMPORE project was to develop examples of nanomaterials and devices capable of autonomous and dynamic responses. To achieve this, we leveraged adsorption/desorption in porous nanomaterials integrated into optical nanostructures (plasmonic or photonic) to achieve:
- self-regulation, homeostasis
- program temporal events (oscillations, self-decay…)
- self-organization, phototropism
The main achievement of the project for each work package is summarized below.
WP1
The objective of this part is the fabrication, optimization and assembly of the porous nanocomposites that includes photonic/plasmonic nanoparticles and nanostructures and/or nanoporous films/nanoparticles including sol-gel-based oxides and MOFs. Two main approaches have been explored:
a) chemical synthesis:
We have prepared a range of noble metal nanoparticles with tunable size and thermo-optical properties: gold nanorods, nanospheres, nanobipyramids by nucleation growth approaches and other porous metals such as Rh, Ru and High Entropy alloys prepared by spray-drying process (ACS Nano 2022, Materials Horizons 2020, Analytical Chemistry 2025). In parallel, we worked on the synthesis of the nanoporous materials. Concerning the sol-gel porous oxides we first focused on the dielectric SiO2 and TiO2. Notably, the thermo-optical properties of core-shell Au nanorods@mesoporous silica composite films in presence of vapors were studied by in-situ ellipsometry (Nanoscale 2020). We also explored the viability of photonic and/or plasmonic sol-gel porous materials with very different optical properties such as conductive Sn, Mo, and Ir oxides and dielectric/conductive VO2. Notably, those materials also exhibited interesting sensing and electrocatalytic performances (Nature Communications 2021), additional functionalities that can be coupled with optical thermoregulation. Metal Organic Frameworks nanoparticles (ZIF-8, ZIF-67, MIL-101, MOF-5) were also prepared and self-assembled to fabricate several plasmonic/photonic composite materials with tunable optical/thermal properties.
b) patterned films
We mainly focused on the fabrication of microporous and mesoporous components shaped as thin films. We succeed in developing fabrication methods at low temperatures compatibles with the integration in photonic and plasmonic nanostructures (Journal of Sol-Gel Science and Technology, 2020). In parallel, the nanoimprint lithography process have been greatly improved in terms of resist materials. We developed a resist formulation allowing direct imprint of several noble metals and porous materials at the sub-200 nm scale (Small, 2022). In addition we implemented an original crack patterning method to pattern porous oxides and metals (Advanced Materials 2022, Advanced Materials Technologies 2024) that has been patented.
WP2
The objective of this part is the characterization of the thermo-optical properties of the objects. We investigated extensively the thermo-optical properties and the response kinetics of the films by buinding a new environmental UV-vis and IR ellipsometric experiment (Chemical Communications 2024, Journal of Sol-Gel Science and Technology, 2023). We built the microscopy set-up equipped with a thermal and environmental chamber and compatible with a light excitation and spectroscopic imaging with high temporal resolution. . As a case study, a single-object analysis of photonic MOF structures was carried out to investigate the spatio-temporal evolution as function of the temperature (Advanced Materials 2021). In parallel thermo-optical numerical simulations were carried out in collaboration with colleagues from the Institut d’Optique Graduate School (IOGS).This tool allows the simulation of the optical properties of the composites and of the local temperature gradients (article submitted).
WP3
The objective of this part is to fabricate proof-of-concept of bio-inspired dynamic devices. Several life-like devices have been proposed including:
- self-regulating photonic porous pigments (Chemistry of Materials 2023),
- plant inspired homeostatic photonic porous devices with multiple feedbacks (Advanced Functional Materials 2025)
- spatiotemporal self-organization in colloidal films inspired by phototropism (Nature Communications 2024)
- self-regulating and self-oscillating porous metasurfaces (article submitted)
- self-organized anti-fogging and anti-reflective metasurfaces (Advanced Optical Materials 2025)
- dissipative,reconfigurable and self-oscillating photonic sensors (patent application)
- self-regulation, homeostasis
- program temporal events (oscillations, self-decay…)
- self-organization, phototropism
The main achievement of the project for each work package is summarized below.
WP1
The objective of this part is the fabrication, optimization and assembly of the porous nanocomposites that includes photonic/plasmonic nanoparticles and nanostructures and/or nanoporous films/nanoparticles including sol-gel-based oxides and MOFs. Two main approaches have been explored:
a) chemical synthesis:
We have prepared a range of noble metal nanoparticles with tunable size and thermo-optical properties: gold nanorods, nanospheres, nanobipyramids by nucleation growth approaches and other porous metals such as Rh, Ru and High Entropy alloys prepared by spray-drying process (ACS Nano 2022, Materials Horizons 2020, Analytical Chemistry 2025). In parallel, we worked on the synthesis of the nanoporous materials. Concerning the sol-gel porous oxides we first focused on the dielectric SiO2 and TiO2. Notably, the thermo-optical properties of core-shell Au nanorods@mesoporous silica composite films in presence of vapors were studied by in-situ ellipsometry (Nanoscale 2020). We also explored the viability of photonic and/or plasmonic sol-gel porous materials with very different optical properties such as conductive Sn, Mo, and Ir oxides and dielectric/conductive VO2. Notably, those materials also exhibited interesting sensing and electrocatalytic performances (Nature Communications 2021), additional functionalities that can be coupled with optical thermoregulation. Metal Organic Frameworks nanoparticles (ZIF-8, ZIF-67, MIL-101, MOF-5) were also prepared and self-assembled to fabricate several plasmonic/photonic composite materials with tunable optical/thermal properties.
b) patterned films
We mainly focused on the fabrication of microporous and mesoporous components shaped as thin films. We succeed in developing fabrication methods at low temperatures compatibles with the integration in photonic and plasmonic nanostructures (Journal of Sol-Gel Science and Technology, 2020). In parallel, the nanoimprint lithography process have been greatly improved in terms of resist materials. We developed a resist formulation allowing direct imprint of several noble metals and porous materials at the sub-200 nm scale (Small, 2022). In addition we implemented an original crack patterning method to pattern porous oxides and metals (Advanced Materials 2022, Advanced Materials Technologies 2024) that has been patented.
WP2
The objective of this part is the characterization of the thermo-optical properties of the objects. We investigated extensively the thermo-optical properties and the response kinetics of the films by buinding a new environmental UV-vis and IR ellipsometric experiment (Chemical Communications 2024, Journal of Sol-Gel Science and Technology, 2023). We built the microscopy set-up equipped with a thermal and environmental chamber and compatible with a light excitation and spectroscopic imaging with high temporal resolution. . As a case study, a single-object analysis of photonic MOF structures was carried out to investigate the spatio-temporal evolution as function of the temperature (Advanced Materials 2021). In parallel thermo-optical numerical simulations were carried out in collaboration with colleagues from the Institut d’Optique Graduate School (IOGS).This tool allows the simulation of the optical properties of the composites and of the local temperature gradients (article submitted).
WP3
The objective of this part is to fabricate proof-of-concept of bio-inspired dynamic devices. Several life-like devices have been proposed including:
- self-regulating photonic porous pigments (Chemistry of Materials 2023),
- plant inspired homeostatic photonic porous devices with multiple feedbacks (Advanced Functional Materials 2025)
- spatiotemporal self-organization in colloidal films inspired by phototropism (Nature Communications 2024)
- self-regulating and self-oscillating porous metasurfaces (article submitted)
- self-organized anti-fogging and anti-reflective metasurfaces (Advanced Optical Materials 2025)
- dissipative,reconfigurable and self-oscillating photonic sensors (patent application)
Because our project is at the cross-over between materials sciences and physics some new methodologies were developed including (i) new synthetic method based on spray-drying to prepare and assemble porous hollow noble metals, oxides and composites; (ii) new optical characterization methods to probe the thermo-optical properties at the nanoscale; (iii) new concept of label-free thermal sensing using vapors condensed in nanoporous materials; (iv) new patterning method based on crack self-assembly
Several life-like devices have been proposed including self-regulating photonic pigments, plant inspired homeostatic photonic devices with multiple feedbacks, spatiotemporal self-organization inspired by phototropism, self-regulating metasurfaces, self-oscillating nano systems, anti-fogging and anti-reflective metasurface and dissipative photonic liquids.
Several life-like devices have been proposed including self-regulating photonic pigments, plant inspired homeostatic photonic devices with multiple feedbacks, spatiotemporal self-organization inspired by phototropism, self-regulating metasurfaces, self-oscillating nano systems, anti-fogging and anti-reflective metasurface and dissipative photonic liquids.