Laser Structuring of Graphene Oxide for PHOTOtronic SENSors and Nanoscale Characterization (PHOTOSENS)

• Applicants: Professorin Dr.-Ing. Olfa Kanoun; Professor Dr. Dietrich R. T. Zahn
• Subject Area: Synthesis and Properties of Functional Materials ; Electronic Semiconductors, Components and Circuits, Integrated Systems, Sensor Technology, Theoretical Electrical Engineering ; Microsystems
• Term: from 2020 to 2023
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 430426661

• Final Report Year: 2024

Final Report Abstract

This project explored the application of laser technology to fine-tune the properties of graphene oxide (GO) materials for enhanced sensing applications. The goal was to control the work function and bandgap of reduced graphene oxide (rGO) layers using precise laser and material settings. We also investigated electron transport and conduction mechanisms for different patterned films to improve sensitivity and explore how tuning dielectric properties in microstructures affects the adsorption of chemical species and their resulting properties. To measure the work function of laser-patterned rGO electrodes, Raman spectroscopy revealed that optimal reduction occurs at 30 mW IR fs laser power. X-ray photoemission spectroscopy (XPS) measurements indicated that varying the pattern speed at this fixed power shifts the work function between 4.95 and 5.05 eV. The work function can also be tuned by the cw laser power range (660-960 mW) in the range of 4.85 to 5.1 eV. The bandgap of GO films decreases from 3.4 to 1.6 eV with increasing laser power (660 – 960 mW) until it saturates. However, quantitative evaluation is challenging due to the complex material structure and ablation at higher laser intensity. The fluctuation-induced tunneling (FIT) model best explains the temperature dependence of the resistance in laser-reduced rGO. Miniaturized structures were also developed, including fully reduced GO sensors and interdigitated electrode (IDE) structures, with IDEs showing higher sensitivity for humidity and volatile organic compound sensing. The project further explored creating heterostructures like GO-rGOx and rGOx-rGOy junctions using different laser reduction parameters. These structures enhance photosensitivity and generate a broad spectral photoresponse. In addition, we examined the work functions and bandgap properties of symmetric and asymmetric electrodes and found that rGOx-rGOy heterostructures exhibit asymmetrical I-V characteristics with high photoresponsivity of >3 A/W at 650 nm (red) wavelength. A van der Waals barrier formed heterostructures with negative differential resistance, where the photothermoelectric effect dominated, generating significant current and voltage under laser light. Strain sensitivity tests revealed that the orientation of laser writing significantly affects the rGO gauge performance where a gauge factor (GF) of 16 was obtained. Increased piezophototronic sensitivity is correlated to the tuning of the optical properties.

Publications

• Potential of carbonaceous materials for the realization of high performance sensors. 2020 17th International Multi-Conference on Systems, Signals & Devices (SSD), 1-6. IEEE.
  Kanoun, Olfa; Ramalingame, R.; Al-Hamry, A.; Bouhamed, Ayda; Bautista-Quijano, Jose Roberto & Rejandran, Dhivakar
  
• A Review of Nanocomposite-Modified Electrochemical Sensors for Water Quality Monitoring. Sensors, 21(12), 4131.
  Kanoun, Olfa; Lazarević-Pašti, Tamara; Pašti, Igor; Nasraoui, Salem; Talbi, Malak; Brahem, Amina; Adiraju, Anurag; Sheremet, Evgeniya; Rodriguez, Raul D.; Ben, Ali Mounir & Al-Hamry, Ammar
  
• Electrochemical Sensor for 4-Aminophenol Based on Flexible Laser Induced Graphene. 2021 International Workshop on Impedance Spectroscopy (IWIS), 94-96. IEEE.
  Nasraoui, Salem; Al-Hamry, Ammar; Ameur, Sami; Ali, Mounir Ben & Kanoun, Olfa
  
• Electrochemical sensor for nitrite detection in water samples using flexible laser-induced graphene electrodes functionalized by CNT decorated by Au nanoparticles. Journal of Electroanalytical Chemistry, 880, 114893.
  Nasraoui, Salem; Al-Hamry, Ammar; Teixeira, Priscila Rios; Ameur, Sami; Paterno, Leonardo G.; Ben, Ali Mounir & Kanoun, Olfa
  
• Flexible Impedimetric Electronic Nose for High-Accurate Determination of Individual Volatile Organic Compounds by Tuning the Graphene Sensitive Properties. Chemosensors, 9(12), 360.
  Lu, Tianqi; Al-Hamry, Ammar; Rosolen, José Mauricio; Hu, Zheng; Hao, Junfeng; Wang, Yuchao; Adiraju, Anurag; Yu, Tengfei; Matsubara, Elaine Yoshiko & Kanoun, Olfa
  
• Functionalized PEDOT:PSS based sensor array for determination of metallic ions in smart agriculture. 2021 6th International Conference on Nanotechnology for Instrumentation and Measurement (NanofIM), 1-4. IEEE.
  Lu, Tianqi; Al-Hamry, Ammar; Talbi, Malak; Zhang, Jichen; Adiraju, Anurag; Hou, Mengfu & Kanoun, Olfa
  
• A mononuclear nickel(II) complex as a redox mediator for electrochemical sensors. 2022 19th International Multi-Conference on Systems, Signals & Devices (SSD), 1024-1027. IEEE.
  Weheabby, Saddam; Al-Hamry, Ammar; Nasraoui, Salem; Ruffer, Tobias & Kanoun, Olfa
  
• Controlling excitons in the quantum tunneling regime in a hybrid plasmonic/2D semiconductor interface. Applied Physics Reviews, 9(3).
  Ferrera, M.; Rahaman, M.; Sanders, S.; Pan, Y.; Milekhin, I.; Gemming, S.; Alabastri, A.; Bisio, F.; Canepa, M. & Zahn, D. R. T.
  
• Development of an Efficient Voltammetric Sensor for the Monitoring of 4-Aminophenol Based on Flexible Laser Induced Graphene Electrodes Modified with MWCNT-PANI. Sensors, 22(3), 833.
  Nasraoui, Salem; Ameur, Sami; Al-Hamry, Ammar; Ben, Ali Mounir & Kanoun, Olfa
  
• Enhanced Nitrite Detection by a Carbon Screen Printed Electrode Modified with Photochemically-Made AuNPs. Chemosensors, 10(2), 40.
  Talbi, Malak; Al-Hamry, Ammar; Teixeira, Priscila Rios; Paterno, Leonardo G.; Ali, Mounir Ben & Kanoun, Olfa
  
• Exciton tuning in monolayer WSe2viasubstrate induced electron doping. Nanoscale Advances, 4(23), 5102-5108.
  Pan, Yang; Rahaman, Mahfujur; He, Lu; Milekhin, Ilya; Manoharan, Gopinath; Aslam, Muhammad Awais; Blaudeck, Thomas; Willert, Andreas; Matković, Aleksandar; Madeira, Teresa I. & Zahn, Dietrich R. T.
  
• Gold Nanoparticles-MWCNT Based Aptasensor for Early Diagnosis of Prostate Cancer. Biosensors, 12(12), 1130.
  Alnaimi, Aseel; Al-Hamry, Ammar; Makableh, Yahia; Adiraju, Anurag & Kanoun, Olfa
  
• Machine Learning-Based Multi-Level Fusion Framework for a Hybrid Voltammetric and Impedimetric Metal Ions Electronic Tongue. Chemosensors, 10(11), 474.
  Lu, Tianqi; Al-Hamry, Ammar; Hao, Junfeng; Liu, Yang; Qu, Yunze & Kanoun, Olfa
  
• Optimized Reduction of a Graphene Oxide‐MWCNT Composite with Electrochemically Deposited Copper Nanoparticles on Screen Printed Electrodes for a Wide Range of Detection of Nitrate. ChemElectroChem, 10(3).
  Anurag, Adiraju; Al‐Hamry, Ammar; Attuluri, Yashwanth; Palaniyappan, Saravanan; Wagner, Guntram; Dentel, Doreen; Tegenkamp, Christoph & Kanoun, Olfa
  
• Raman Fingerprint of Interlayer Coupling in 2D TMDCs. Nanomaterials, 12(22), 3949.
  Pan, Yang & Zahn, Dietrich R. T.
  
• Signature of lattice dynamics in twisted 2D homo/hetero-bilayers. 2D Materials, 9(4), 045018.
  Pan, Yang; Li, Shutong; Rahaman, Mahfujur; Milekhin, Ilya & Zahn, Dietrich R. T.
  
• Stability Enhancement of Laser-Scribed Reduced Graphene Oxide Electrodes Functionalized by Iron Oxide/Reduced Graphene Oxide Nanocomposites for Nitrite Sensors. Journal of Composites Science, 6(8), 221.
  Brahem, Amina; Al-Hamry, Ammar; Gross, Marcos Andriola; Paterno, Leonardo G.; Ali, Mounir Ben & Kanoun, Olfa
  
• Competing mechanisms of local photoluminescence quenching and enhancement in the quantum tunneling regime at 2D TMDC/hBN/plasmonic interfaces. Applied Physics Letters, 122(23).
  Pan, Yang; He, Lu; Milekhin, Ilya; Milekhin, Alexander G. & Zahn, Dietrich R. T.
  
• Enhanced photoconductivity of hybrid 2D-QD MoS2–AgInS2 structures. The Journal of Chemical Physics, 159(4).
  Kondratenko, Serhiy; Datsenko, Oleksandr I.; Babich, Danylo; Dzhagan, Volodymyr; Pan, Yang; Rahaman, Mahfujur; Selyshchev, Oleksandr & Zahn, Dietrich R. T.
  
• Layer-by-Layer Deposited Multi-Modal PDAC/rGO Composite-Based Sensors. Foods, 12(2), 268.
  Al-Hamry, Ammar; Lu, Tianqi; Bai, Jing; Adiraju, Anurag; Ega, Tharun K.; Pašti, Igor A. & Kanoun, Olfa
  
• Local dielectric function of hBN-encapsulated WS2 flakes grown by chemical vapor deposition. Journal of Physics: Condensed Matter, 35(27), 274001.
  Ferrera, Marzia; Sharma, Apoorva; Milekhin, Ilya; Pan, Yang; Convertino, Domenica; Pace, Simona; Orlandini, Giorgio; Peci, Ermes; Ramò, Lorenzo; Magnozzi, Michele; Coletti, Camilla; Salvan, Georgeta; Zahn, Dietrich R. T.; Canepa, Maurizio & Bisio, Francesco
  
• Structural characterization and electrochemical performance of laser-induced graphene: Insights into electron transfer kinetics and 4-aminophenol sensing. Diamond and Related Materials, 138, 110207.
  Nasraoui, Salem; Al-Hamry, Ammar; Madeira, T.I.; Ameur, Sami; Zahn, D.R.T.; Ben, Ali Mounir & Kanoun, Olfa
  
• Towards Embedded Electrochemical Sensors for On-Site Nitrite Detection by Gold Nanoparticles Modified Screen Printed Carbon Electrodes. Sensors, 23(6), 2961.
  Adiraju, Anurag; Munjal, Rohan; Viehweger, Christian; Al-Hamry, Ammar; Brahem, Amina; Hussain, Jawaid; Kommisetty, Sanhith; Jalasutram, Aditya; Tegenkamp, Christoph & Kanoun, Olfa
  
• Ultra-Sensitive and Fast Humidity Sensors Based on Direct Laser-Scribed Graphene Oxide/Carbon Nanotubes Composites. Nanomaterials, 13(9), 1473.
  Al-Hamry, Ammar; Lu, Tianqi; Chen, Haoran; Adiraju, Anurag; Nasraoui, Salem; Brahem, Amina; Bajuk-Bogdanović, Danica; Weheabby, Saddam; Pašti, Igor A. & Kanoun, Olfa
  
• Versatile sensing capabilities of layer-by-layer deposited polyaniline-reduced graphene oxide composite-based sensors. Sensors and Actuators B: Chemical, 390, 133988.
  Al-Hamry, Ammar; Lu, Tianqi; Bai, Jing; Adiraju, Anurag; Ega, Tharun K.; Paterno, L.G.; Pašti, Igor A. & Kanoun, Olfa
  
• Detection of H. pylori outer membrane protein (HopQ) biomarker using electrochemical impedimetric immunosensor with polypyrrole nanotubes and carbon nanotubes nanocomposite on screen-printed carbon electrode. Biosensors and Bioelectronics, 249, 115937.
  Jaradat, Hussamaldeen; Hryniewicz, Bruna M.; Pašti, Igor A.; Valério, Tatiana L.; Al-Hamry, Ammar; Marchesi, Luís F.; Vidotti, Marcio & Kanoun, Olfa
  
• Laser-induced fibers and copper phthalocyanine modified laser-induced graphene electrodes for sensitive and selective electrochemical detection of nitrite. RSC Advances, 14(39), 28648-28658.
  Adiraju, Anurag; Jalasutram, Aditya; Al-Hamry, Ammar; Talbi, Malak; Wang, Junfei; Tegenkamp, Christoph & Kanoun, Olfa
  
• Multifaceted experiments and photothermal simulations based analysis of laser induced graphene and its fibers. Discover Nano, 19(1).
  Adiraju, Anurag; Al-Hamry, Ammar; Jalasutram, Aditya; Wang, Junfei & Kanoun, Olfa
  
• Toward Humidity-Independent Sensitive and Fast Response Temperature Sensors Based on Reduced Graphene Oxide/Poly(vinyl alcohol) Nanocomposites. ACS Applied Electronic Materials, 6(6), 4718-4734.
  Al-Hamry, Ammar; Pan, Yang; Rahaman, Mahfujur; Selyshchev, Oleksandr; Tegenkamp, Christoph; Zahn, Dietrich R. T.; Pašti, Igor A. & Kanoun, Olfa