4D-STEM and Eels Analysis of Complex C-Based Sensor Architectures

Abstract

Transforming high-carbon precursors into open-porous carbon foams and coatings via thermal processes is gaining attention as a sustainable method for various applications, including catalysis, energy utilization, and sensing [1]. In this research, we adopt a one-step laser patterning approach to selectively pyrolyze doctor-bladed ink coatings on flexible PET substrates, thereby producing highly porous, intricately designed CO2 sensor structures with a thickness of about 50 µm. Our ink formulation includes glucose as a pore-forming agent and adenine as a nitrogen source to enhance sensing capabilities. Laser processing in an oxygen-rich setting results in flexible, highly porous sensor heterostructures characterized by distinct areas enriched with nitrogen and oxygen functionalities. The laser intensity’s attenuation with depth leads to the development of a distinctly porous graphitic surface layer (serving as the electrical transducer layer) and a denser nitrogen-enriched lower sensor layer, linked by a narrow transitional region [2]. To understand the formation and functionality of these sensors, we conducted an in-depth TEM analysis of cross-sections of the complete device, prepared through ultramicrotomy cross-sectioning. STEM-EELS elemental distribution maps distinctly show the chemical composition differences between the upper and lower layers of the sensor. Principal component analysis was utilized to separate the complex sensor structures into their constituent crystalline and amorphous carbon and nitrogen-containing phases. 4D-STEM analysis exposed the arrangement of the crystalline graphitic phase and the orientation of graphite basal planes adjacent to the pores of the open-porous sensor. Analyzing these structural parameters is essential for understanding the electrical performance of the sensor, as depicted in Figure 1 [3]. Figure 1: A (top)) SEM micrograph of sensor embedded in epoxy, (bottom) depth-dependent thermal laser intensity attenuation; B (left)) HA ADF-STEM micrograph showing different sensor layers, (middle) STEM-EELS nitrogen distribution map, (right) PCA bond analysis, C) HRTEM images of sensor from transducer (top) and sensor (bottom) layers with SAED image of respective ROIs (inset); D) 4D-STEM analysis depicting misalignment angle between graphitic carbon basal plane normal relative to the pore surface normalReferences[1] M. Hepp, et al. npj Flexible Electronics 6, 1-9 (2022)[2] H. Wang, et al. Advanced Functional Materials 32, 2207406 (2022)[3] C. Ophus, et al. Microscopy and Microanalysis 28, 390-403 (2022) Acknowledgements: We acknowledge use of the DFG-funded Micro-and Nanoanalytics Facility (MNaF) at the University of Siegen (INST 221/131-1). Figure 1