Electrical Conductivity Boost: In Situ Polypyrrole Polymerization in Monolithically Integrated Surface-Supported Metal-Organic Framework Templates

Author(s)

Vello, Tatiana Parra ; Albano, Luiz Gustavo Simao ; dos Santos, Thamiris Cescon ; Colletti, Julia Cantovitz ; Santos Batista, Carlos Vinicius ; Leme, Vitoria Fernandes Cintra ; dos Santos, Thamiris Costa ; Miguel, Maria Paula Dias Carneiro ; de Camargo, Davi Henrique Starnini ; Bof Bufon, Carlos Cesar

• Document type: Journal article
• Source: SMALL; v. N/A, p. 14-pg., 2023-09-26.

Abstract

Recent progress in synthesizing and integrating surface-supported metal-organic frameworks (SURMOFs) has highlighted their potential in developing hybrid electronic devices with exceptional mechanical flexibility, film processability, and cost-effectiveness. However, the low electrical conductivity of SURMOFs has limited their use in devices. To address this, researchers have utilized the porosity of SURMOFs to enhance electrical conductivity by incorporating conductive materials. This study introduces a method to improve the electrical conductivity of HKUST-1 templates by in situ polymerization of conductive polypyrrole (PPy) chains within the SURMOF pores (named as PPy@HKUST-1). Nanomembrane-origami technology is employed for integration, allowing a rolled-up metallic nanomembrane to contact the HKUST-1 films without causing damage. After a 24 h loading period, the electrical conductivity at room temperature reaches approximately 5.10-6 S m-1. The nanomembrane-based contact enables reliable electrical characterization even at low temperatures. Key parameters of PPy@HKUST-1 films, such as trap barrier height, dielectric constant, and tunneling barrier height, are determined using established conduction mechanisms. These findings represent a significant advancement in real-time control of SURMOF conductivity, opening pathways for innovative electronic-optoelectronic device development. This study demonstrates the potential of SURMOFs to revolutionize hybrid electronic devices by enhancing electrical conductivity through intelligent integration strategies. A significant enhancement in electrical conductivity and a comprehensive electrical characterization at low temperatures of surface-supported metal-organic frameworks (SURMOFs) are detailed in this study. By employing in situ polymerization of polypyrrole (PPy), this work successfully integrates an HKUST-1 SURMOF thin-film into a solid-state device using an innovative nanomembrane-origami technology concept. This integration allows for damage-free and self-adjusting contact. The electrical characterization conducted at low temperatures exhibits remarkable consistency with well-established electrical conduction mechanisms. Most notably, the achieved electrical conductivity reaches an impressive value of 5.10-6 S m-1, representing a remarkable improvement of seven orders of magnitude when compared to the initial pristine film. This groundbreaking outcome underscores the substantial potential of this approach in enhancing the electrical properties of SURMOFs, paving the way for exciting prospects in the development of advanced hybrid electronic devices.image (AU)

• FAPESP's process: 17/02317-2 - Interfaces in materials: electronic, magnetic, structural and transport properties
• Grantee: Adalberto Fazzio
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 14/50906-9 - INCT 2014: in Functional Complex Materials
• Grantee: Fernando Galembeck
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 16/25346-5 - Capacitive devices for hybrid nanostructures characterization: study of electrical properties of surface metal-organic frameworks -SURMOFs- and metallophthalocyanines
• Grantee: Tatiana Parra Vello
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 19/01561-2 - Study of Surface-Mounted Metal-Organic Frameworks (SURMOFs) growth mechanisms to application on electrical devices
• Grantee: Tatiana Parra Vello
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate
• FAPESP's process: 14/25979-2 - Fabrication and characterization of devices and systems based on hybrid nanomembranes
• Grantee: Carlos César Bof Bufon
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 17/25553-3 - Fabrication and characterization of self-rolled up nanomembranes of surface-supported metal-organic frameworks (SURMOFs) for applications in ultracompact electronic devices
• Grantee: Luíz Gustavo Simão Albano
• Support Opportunities: Scholarships in Brazil - Post-Doctoral