Periodic Reporting for period 1 - R3DINBOW (Sustainable Design of 3D-printed Responsive Interfaces for Electrically Monitoring Bistable (Supra)Molecular Switches: Towards 3D-printed Logic Gates)
Reporting period: 2021-07-01 to 2023-06-30
The ability of electronic devices to act as switches makes digital information processing possible. The current silicon-based semiconductor processors are fabricated according to a top-down principle. However, the need to scale down in the size of such electronic devices has prompted the search for molecule-based information processing components (Molecular Electronics), such as switching memories, sensors and logic gates. Concretely, within the past two decades, developments in Nanotechnology have shown the capabilities of molecules to perform some of the computational logic functions -relating to the concept of logical zeros (0) and ones (1) binary code- achieved in mainstream semiconductor technology. Molecular logic gates differ from the currently used semiconductor elements by small size, multifunctional nature and variability of input and output signals. Nonetheless, the transition of logic elements from mostly optical means for reading output signals to electronic transduction tools would be beneficial for developing many novel logic elements for information processing, (bio)sensing and actuation. Accordingly, the design, construction and miniaturization of molecular electronic systems capable of performing complex logic functions is a current challenge. Herein, 3D printing technology is presented as a promising tool to open up new horizons in the field of electronic devices in general, and molecular logic gates in particular. For this goal, a sustainable bottom-up approach has been devised for the development of the next generation of “intelligent” 3D-printed electronic devices —3D-printed responsive interfaces—, where bistable (supra)molecular switches will be electrically read out on carbon-based 3D-printed conductive substrates as the proof. This goal is in strong agreement with the EU’s digital strategy, while helping to achieve its target of a climate-neutral Europe by 2050. Accordingly, R3DINBOW entails the challenging design of a library of “intelligent” 3D-printed responsive interfaces by the incorporation of molecular and supramolecular components upon conductive carbon-based 3D-printed substrates (like 3D-nGEs) via a sustainable bottom-up approach. The discernible molecular properties between well-known bistable switchable states (0, 1) have been exploited to electrically read out the system as an EIS output signal. To this end, an innovative combination of 1) 3D printing technology, 2) Molecular Engineering Engineering, 3) Electrochemistry and 4) Green Chemistry, has been devised in order to tackle three specific research objectives (RO):
• RO1. Application of eco-friendly approaches for the fabrication of 3D-printed responsive interfaces (Months: 1–6).
• RO2. Testing & optimization of bistable (supra)molecular switches on 3D-printed responsive interfaces by EIS (Months: 5–9).
• RO3. Development of a sustainable approach for engineering metal-based 3D-printed responsive interfaces (Months: 9–13).
Consequently, R3DINBOW rises with the aim of building up the basis towards the yet undisclosed concept of molecular 3D-printed logic gates, a challenge in the Molecular Electronics field that would respond to the current needs of our Society.
• RO1. Application of eco-friendly approaches for the fabrication of 3D-printed responsive interfaces (Months: 1–6).
• RO2. Testing & optimization of bistable (supra)molecular switches on 3D-printed responsive interfaces by EIS (Months: 5–9).
• RO3. Development of a sustainable approach for engineering metal-based 3D-printed responsive interfaces (Months: 9–13).
Consequently, R3DINBOW rises with the aim of building up the basis towards the yet undisclosed concept of molecular 3D-printed logic gates, a challenge in the Molecular Electronics field that would respond to the current needs of our Society.
5 articles published in high IF journals have derived from the R3DINBOW project:
• RO1. A robust synthetic strategy was devised for in situ functionalizing 3D-printed nanocomposite graphene-based electrodes (3D-nGEs) with different functional inorganic nanoparticles (FINPs), which not only improved the electrochemical features of electronic transducers, but also acted as nanotemplates for further functionalization. This goal was successfully achieved by employing the well-known Intermatrix Synthesis (IMS) method. The excellent findings were reported ACS Applied Energy Materials (IF: 6.96) and Angewandte Chemie (IF: 16.82 HOT PAPER).
• RO2. Active biomolecular and supramolecular components were successfully anchored upon 3D-nGEs, resulting in the first prototypes of 3D-printed responsive interfaces, were electrochemical methods were utilized to readout the system. Further, 3D-nGEs were also functionalized with a responsive 2D material as 2D-Ti3C2Tx MXene carrying a photo-active molecule for electrically monitoring a light-driven molecular switch. The results of this work have been published in the Journal of Materials Chemistry A (IF: 14.51).
• RO3. Motivated by the excellent results obtained when using carbon-based 3D-printed electronics, alternative metal-based filaments were explored. A general functionalization approach was devised to modify copper-based 3D-printed electronics with active noble metals via galvanic exchange. It is important to point out that it was the first time that metal-based 3D-printed electronics were functionalized and applied for energy and biosensing approaches, demonstrating the innovation of the action with two publications in high IF journals (Applied Materials Today, IF: 10.04; and Applied Catalysis B: Environmental, IF: 24.32).
• RO1. A robust synthetic strategy was devised for in situ functionalizing 3D-printed nanocomposite graphene-based electrodes (3D-nGEs) with different functional inorganic nanoparticles (FINPs), which not only improved the electrochemical features of electronic transducers, but also acted as nanotemplates for further functionalization. This goal was successfully achieved by employing the well-known Intermatrix Synthesis (IMS) method. The excellent findings were reported ACS Applied Energy Materials (IF: 6.96) and Angewandte Chemie (IF: 16.82 HOT PAPER).
• RO2. Active biomolecular and supramolecular components were successfully anchored upon 3D-nGEs, resulting in the first prototypes of 3D-printed responsive interfaces, were electrochemical methods were utilized to readout the system. Further, 3D-nGEs were also functionalized with a responsive 2D material as 2D-Ti3C2Tx MXene carrying a photo-active molecule for electrically monitoring a light-driven molecular switch. The results of this work have been published in the Journal of Materials Chemistry A (IF: 14.51).
• RO3. Motivated by the excellent results obtained when using carbon-based 3D-printed electronics, alternative metal-based filaments were explored. A general functionalization approach was devised to modify copper-based 3D-printed electronics with active noble metals via galvanic exchange. It is important to point out that it was the first time that metal-based 3D-printed electronics were functionalized and applied for energy and biosensing approaches, demonstrating the innovation of the action with two publications in high IF journals (Applied Materials Today, IF: 10.04; and Applied Catalysis B: Environmental, IF: 24.32).
R3DINBOW has explored 3D printing technology to revolutionize the traditional manufacturing process of Molecular Electronics. The use of 3D-printed electronic devices as platforms to harbour active molecules to apply binary logic at the molecular level has been considered for the first time. This gap has been successfully filled through the innovative action of combining the synergistic properties of active molecules with the advantage of 3D-printed conducting substrates to design unprecedented 3D-printed responsive interfaces. The transition from conventional semiconductor silicon systems to unconventional molecular carbon ones for information processing implies a bottom-up migration in the Periodic Table. Thus, R3DINBOW has been devised as a novel, facile, versatile and generic environmentally friendly bottom-up approach (from its activation to their functionalization and integration with active molecules), where tailored carbon-based 3D-printed electronic devices carrying active molecules are pursued. The main advancement achieved beyond the state-of-the-art is the following:
• State-of-the-art: Mainstream ‘top-down’ silicon systems using tedious tools; Advancement: Novel ‘bottom-up’ carbon-based 3D-printed responsive interfaces via sustainable Surface Engineering.
• State-of-the-art: Activation of 3D-nGEs with toxic DMF; Advancement: Activation of 3D-nGES with aqueous solutions containing reducing agents.
• State-of-the-art: Functionalization of 3D-nGEs with FINs via weak physisorption; Advancement: Robust and cost-effective in situ functionalization of 3D-nGEs with FINPs via IMS.
• State-of-the-art: General optical readout of (supra)molecular switches; Advancement: Electrical readout of (supra)molecular switches via EIS (utilizing FMNs to amplify the output signals).
• State-of-the-art: General synthesis of the specific (supra)molecular components; Advancement: All the utilized materials are commercially available.
• State-of-the-art: Use of conventional carbon/polymer filaments for 3D printing; Advancement: Use of alternative metal/polymer filaments for 3D printing.
Therefore, this project has represented a nucleus for future studies towards the design, fabrication and customization of “intelligent” 3D-printed electronic devices, generating new knowledge in 3D-printed-based Molecular Electronics, which will have a transformative impact on modern science and technology.
• State-of-the-art: Mainstream ‘top-down’ silicon systems using tedious tools; Advancement: Novel ‘bottom-up’ carbon-based 3D-printed responsive interfaces via sustainable Surface Engineering.
• State-of-the-art: Activation of 3D-nGEs with toxic DMF; Advancement: Activation of 3D-nGES with aqueous solutions containing reducing agents.
• State-of-the-art: Functionalization of 3D-nGEs with FINs via weak physisorption; Advancement: Robust and cost-effective in situ functionalization of 3D-nGEs with FINPs via IMS.
• State-of-the-art: General optical readout of (supra)molecular switches; Advancement: Electrical readout of (supra)molecular switches via EIS (utilizing FMNs to amplify the output signals).
• State-of-the-art: General synthesis of the specific (supra)molecular components; Advancement: All the utilized materials are commercially available.
• State-of-the-art: Use of conventional carbon/polymer filaments for 3D printing; Advancement: Use of alternative metal/polymer filaments for 3D printing.
Therefore, this project has represented a nucleus for future studies towards the design, fabrication and customization of “intelligent” 3D-printed electronic devices, generating new knowledge in 3D-printed-based Molecular Electronics, which will have a transformative impact on modern science and technology.