Laser-induced Graphene Electrodes Research Articles

Optimizing Carbon Structures in Laser-Induced Graphene Electrodes Using Design of Experiments for Enhanced Electrochemical Sensing Characteristics.

In this study, we explored the morphological and electrochemical properties of carbon-based electrodes derived from laser-induced graphene (LIG) and compared them to commercially available graphene-sheet screen-printed electrodes (GS-SPEs). By optimizing the laser parameters (average laser power, speed, and focus) using a design of experiments response surface (DoE-RS) approach, binder-free LIG electrodes were achieved in a single-step process. Traditional trial-and-error methods can be time-consuming and may not capture the interactions between all variables effectively. To address this, we focused on linear resistance and substrate delamination to streamline the DoE-RS optimization process. Two LIGs, designated LIG A and LIG B, were fabricated using distinct and optimized laser settings, which resulted in a sheet resistance of 25 ± 2 Ω/sq and 21 ± 1 Ω/sq, respectively. These LIGs, characterized by scanning electron microscopy, Raman spectroscopy, and contact angle analysis, exhibited a highly porous morphology with 13% pore coverage and a contact angle <50°, which significantly increased their hydrophilicity when compared to the GS-SPE. For the electrochemical studies, the oxidation of NO2- ion by the graphene-based working electrodes was investigated, as it allowed for the direct comparison of the LIGs to the GS-SPE. These included cyclic voltammetry, electrochemical impedance spectroscopy, and differential pulsed voltammetry studies, which revealed that LIG electrodes displayed a remarkable 500% increase in peak current during NO2- oxidation compared to the GS-SPE. The LIGs also demonstrated improved stability and sensitivity (420 ± 30 and 570 ± 10 nAμM-1 cm-2) compared to the GS-SPE (73 ± 4 nAμM-1 cm-2) in the oxidation of NO2- ions; however, LIG B was more susceptible to ionic interference than LIG A. These findings highlight the value of applying statistical approaches such as DoE-RS to systematically improve the LIG fabrication process, enabling the rapid production of optimized LIGs that outperform conventional carbon-based electrodes.

Optimization of Laser Induced Graphene Electrodes for Water Splitting Applications

Optimization of Laser Induced Graphene Electrodes for Water Splitting Applications

LIG-Based High-Sensitivity Multiplexed Sensing System for Simultaneous Monitoring of Metabolites and Electrolytes.

With improvements in medical environments and the widespread use of smartphones, interest in wearable biosensors for continuous body monitoring is growing. We developed a wearable multiplexed bio-sensing system that non-invasively monitors body fluids and integrates with a smartphone application. The system includes sensors, readout circuits, and a microcontroller unit (MCU) for signal processing and wireless communication. Potentiometric and amperometric measurement methods were used, with calibration capabilities added to ensure accurate readings of analyte concentrations and temperature. Laser-induced graphene (LIG)-based sensors for glucose, lactate, Na+, K+, and temperature were developed for fast, cost-effective production. The LIG electrode's 3D porous structure provided an active surface area 16 times larger than its apparent area, resulting in enhanced sensor performance. The glucose and lactate sensors exhibited high sensitivity (168.15 and 872.08 μAmM-1cm-2, respectively) and low detection limits (0.191 and 0.167 μM, respectively). The Na+ and K+ sensors demonstrated sensitivities of 65.26 and 62.19 mVdec-1, respectively, in a concentration range of 0.01-100 mM. Temperature sensors showed an average rate of resistance change per °C of 0.25%/°C, within a temperature range of 20-40 °C, providing accurate body temperature monitoring.

Electrochemical Immunosensors on Laser-Induced Graphene Platforms for Monitoring of Anti-RBD Antibodies After SARS-CoV-2 Infection

The COVID-19 pandemic, caused by the SARS-CoV-2 virus, has posed a major challenge to global health. The development of fast, accurate, and accessible diagnostic methods is essential in controlling the disease and mitigating its impacts. In this context, electrochemical biosensors present themselves as promising tools for the efficient monitoring of SARS-CoV-2 infection. We have developed a highly specific biosensor for the detection of anti-SARS-CoV-2 antibodies in patient sera. The use of the RBD-S region as an antigen, although purified to minimize cross-linking, poses a specific challenge. The structural similarity between SARS-CoV-2 and other respiratory viruses, as well as the complexity of the serum matrix, hinders robust analytical strategies to ensure diagnostic accuracy. This work presents a novel immunosensor for COVID-19 diagnosis using laser-induced graphene (LIG) electrodes subjected to electrochemical reduction with graphene (named rGraphene-LIG). In the present study, we chose an initial approach focused on demonstrating the concept and evaluating the feasibility of the rGraphene-LIG sensor for SARS-CoV-2 detection. The rGraphene-LIG electrodes presented a notable current increase for the redox probe in the aqueous solution of a mixture of 5 mmol L−1 potassium ferricyanide/ferrocyanide ([Fe(CN)6]3−/[Fe(CN)6]4−) in 0.1 mol L−1 KCl (pH set at 7.4). As a proof of concept, the rGraphene-LIG electrode was applied for antibody determination in real samples using cyclic voltammetry, and a limit of detection (LOD) of 0.032 μg L−1 was achieved. When determining antigens in commercial samples, we obtained an LOD of 560 ηg mL−1 and a limit of quantification of 1677 ηg mL−1. The results of the electrochemical experiments were in accordance with the surface roughness obtained from atomic force microscopy images. Based on these results, the rGraphene-LIG electrode is shown to be an excellent platform for immunoglobulin detection when present in individuals after antigenic exposure caused by SARS-CoV-2.

Smartphone-based electrochemical sensing of propyl gallate in food samples by employing NiFe-Oxide decorated flexible laser-induced graphene electrode

Flexible graphene electronics utilizing laser-induced graphene (LIG) technology offer an efficient, cost-effective, and mask-free approach to produce graphene in a single step. LIG can be directly patterned on polyimide films, impacting their surface properties, chemical composition, and electrical conductivity. However, the electrochemical performance of standalone LIG is limited. To address this, the study enhances LIG by synthesizing nickel-iron Prussian blue analogues through co-precipitation and calcination, forming porous NiFe-Oxide, which is subsequently deposited onto the LIG surface via a facile physical deposition method. The porous NiFe-Oxide@LIG electrode material demonstrates excellent electrochemical sensing capabilities due to its high conductivity, improved surface area, enhanced active sites, and superior electrocatalytic performance for detecting the antioxidant propyl gallate (PG). This porous NiFe-Oxide@LIG electrode material features a linear detection range (0.5–5 μM), low detection limit (0.01 μM), high sensitivity (17.12 μAμM−1cm−2), and strong selectivity for PG. Additionally, it offers high reproducibility and repeatability, evidenced by the low relative standard deviation values of 2.61 % and 1.96 %, respectively. The practicality of the proposed sensor was validated using food samples, integrated into a smartphone-based sensing device, achieving satisfactory recovery rates above 79.2 %. This smartphone-based sensor enables effective onsite food quality and safety monitoring.

β-Cyclodextrin-Modified Laser-Induced Graphene Electrode for Detection of N6-Methyladenosine in RNA.

Laser-induced graphene (LIG) possesses characteristics of easy handling, miniaturization, and unique electrical properties. We modified the surface of LIG by electropolymerizing β-cyclodextrin (β-CD), which was used to immobilize antibodies on the electrode surface for highly sensitive detection of targets. N6-methyladenosine (m6A) is the most prevalent reversible modification in mammalian messenger RNA and noncoding RNA, influencing the development of various cancers. Here, β-CD was electropolymerized to immobilize the anti-m6A antibody, which subsequently recognized the target m6A. This was integrated into the catalytic hydrogen peroxide-hydroquinone (H2O2-HQ) redox system using phos-tag-biotin to generate electrochemical signals from streptavidin-modified horseradish peroxidase (SA-HRP). Under optimal conditions, the biosensor exhibited a linear range from 0.1 to 100 nM with a minimum detection limit of 96 pM. The method was successfully applied to the recovery analysis of m6A from HeLa cells through spiking experiments and aims to inspire strategies for point-of-care testing (POCT).

Highly stable scalable production of porous graphene-polydopamine nanocomposites for drug molecule sensing

As atenolol overdosing can lead to severe health complications, the rapid detection of atenolol intake in point-of-care settings is highly desirable. The recent advancement of redox analytical methodologies has facilitated the efficacious quantification of these compounds for drug analysis, but their performance still presents challenges in practical applications. This study addresses these challenges by controlling the electropolymerization of polydopamine (PDA) on highly porous laser-induced graphene (LIG) electrodes with enhanced electrochemical redox activity for the detection of drug molecules such as atenolol, with minimized interference with the other active substances to induce variation of electrochemical behavior. The enhanced sensitivity of atenolol is attributed to the superhydrophilicity and increased number of active surface sites and -NH2 groups in the PDA polymer through a controlled polymerization process. Moreover, the simulation results further reveal that highly sensitive sensing of atenolol molecules relies on optimal adsorption of the atenolol molecule on dopamine or dopaminequinone structural units. The resulting sensors with high repeatability and reproducibility can achieve a low detection limit of 80 μM and a sensitivity of 0.020 ± 0.04 μA/μM within a linear range from 100 to 800 μM. The materials and surface chemistry in the electrode design based on highly porous LIG provide insights into the integration and application of future scalable and cost-effective electrochemical sensors for use in point-of-care or in-field applications.

Room temperature-based hydrogen gas sensing over Laser-Induced Graphene electrode supported Pt nanoparticles for low LOD

This study introduces a novel hydrogen sensor that operates efficiently at room temperature with high sensitivity and selectivity. This sensor was created by utilizing a platinum on laser-induced graphene (Pt/LIG) structure. The synthesis process involves the creation of highly crystalline graphene with a large surface area, which serves as an optimal support for nanosized pt catalysts. Post-synthesized Pt nanoparticles were dispersed on the surface of the LIG electrode and envisaged for the hydrogen gas sensing property under ambient conditions without a heating or sensor device. Analysis showed that the Pt nanoparticles are uniquely characterized by their narrow size distribution of less than 5 nm and their homogeneous deposition on the LIG substrate, which itself exhibits a substantial specific surface area of 187.4 m²/g. This configuration enables the sensor to achieve a very low limit for detection of hydrogen to 200 ppb. Moreover, the sensor demonstrates exceptional performance attributes, including high sensitivity, excellent linearity, and remarkable cycle stability over 50 cycles. The synergy between the high surface area of the LIG and the catalytic activity of the Pt nanoparticles facilitates the detection of hydrogen at room temperature. This study contributes significantly to the field of gas sensing technology, particularly in applications requiring accurate and reliable hydrogen detection at ambient conditions.

Electrografted Laser-Induced Graphene: Direct Detection of Neurodegenerative Disease Biomarker in Cerebrospinal Fluid.

There are more than 50 neurodegenerative disorders, and amyotrophic lateral sclerosis (ALS) is one of the most common disorders that poses diagnostic and treatment challenges. The poly glycine-proline (polyGP) dipeptide repeat is a toxic protein that has been recognized as a pharmacodynamic biomarker of C9orf72-associated (c9+) ALS, a subtype of ALS that originates from genetic mutation. Early detection of polyGP will help healthcare providers start timely gene therapy. Herein, we developed a label-free electrochemical immunoassay for the simple detection of polyGP in unprocessed cerebrospinal fluid (CSF) samples collected from ALS patients in the National ALS Biorepository. For the first time, an electrografted laser-induced graphene (E-LIG) electrode system was employed in a sandwich format to detect polyGP using a label-free electrochemical impedance technique. The results show that the E-LIG-modified surface exhibited high sensitivity and selectivity in buffer and CSF media with limit of detection values of 0.19 and 0.27 ng/mL, respectively. The precision of the calibration model was better in CSF than in the buffer. The E-LIG immunosensor can easily select polyGP targets in the presence of other dipeptide proteins translated from the c9 gene. Further study with CSF samples from ALS patients demonstrated that the label-free E-LIG-based immunosensor not only quantified polyGP in the complex CSF matrix but also distinguished between c9+ and non-c9- ALS patients.

Introducing phosphoric acid to fluorinated polyimide towards high performance laser induced graphene electrodes for high energy micro-supercapacitors

Micro-supercapacitors (MSCs) have wide application prospects in microelectronic fields such as wearable electronics due to merits of stable performance, high safety and easy integration. However, the relatively low energy density of MSCs limits their practical application. In this context, phosphorus and fluorine co-doped laser-induced graphene (FP-LIG) microelectrodes were fabricated from fluorinated polyimide containing phosphoric acid by laser direct writing (LDW) method. The introduced phosphoric acid slows down the decomposition of –CF3 during the LDW process, resulting in much more ordered and stable pores; meanwhile, phosphorus entered the graphene lattice to replace some carbon atoms, forming a C3PO structure, which not only stabilizes the interface between the electrode and the electrolyte and therefore achieves an enlarged working potential of 1.4 V, but also increases the wettability of the electrode. Using FP-3-LIG microelectrodes and PVA/H2SO4 as the gel electrolyte, the assembled FP-3-MSC demonstrates significantly enhanced energy density, delivering an energy density of 10.40 μWh cm−2 (@0.09 mA cm−2), 2.7 times that of F-MSC and 346.7 times that of MSC. FP-3-MSC has excellent cyclic stability, displaying an areal capacitance retention rate of above 90 % after 10,000 long cycles. In addition, FP-3-MSC demonstrates excellent flexibility, indicating promising potential in the field of flexible wearable electronics.

One‐Step Laser Synthesis of Copper Nanoparticles and Laser‐Induced Graphene in a Paper Substrate for Non‐Enzymatic Glucose Sensing

AbstractThe synergy resulting from the high conductivity of graphene and catalytic properties of metal nanoparticle has been a resource to improve the activity and functionality of electrochemical sensors. This work focuses on the simultaneous synthesis of copper nanoparticles (CuNPs) and laser‐induced graphene (LIG) derived from paper, through a one‐step laser processing approach. A chromatography paper substrate with drop‐casted copper sulfate is used for the fabrication of this hybrid material, characterized in terms of its morphological, chemical, and conductive properties. Appealing conductive properties are achieved, with sheet resistance of 170 Ω sq−1 being reached, while chemical characterization confirms the simultaneous synthesis of the conductive carbon electrode material and metallic copper nanostructures. Using optimized laser synthesis and patterning conditions, LIG/CuNPs‐based working electrodes are fabricated within a three‐electrode planar cell, and their electrochemical performance is assessed against pristine LIG electrodes, demonstrating good electron transfer kinetics appropriate for electrochemical sensing. The sensor's ability to detect glucose through a non‐enzymatic route is optimized, to assure good sensing performance in standard samples and in artificial sweat complex matrix.

Flexible electrochemical sensor with 2D-on-2D layered structure for real-time on-site intelligent detection of carbendazim residues on fresh tea leaves

Excessive use of carbendazim (CBZ) for controlling fungal disease may result in pesticide residues in growth environments. There is an urgent requirement for real-time detection of CBZ content to enable rapid assessment of pesticide residues. Herein, a novel electrochemical sensor was created, which utilizes a laser-induced graphene (LIG) electrode modified with two-dimensional (2D) tungsten disulfide (WS2) nanosheets and a poly(L-lysine) (PLL) film to construct a 2D-on-2D layered structure. The PLL/WS2/LIG electrode exhibits strong charge transfer, excellent electrocatalytic performance, and high CBZ adsorption capacity, thus leading to enhanced sensitivity. As a result, the sensor exhibits a low detection limit of 1.2 ng/mL (6.2 nM), high sensitivity up to 135.1 μA(μg/mL)−1cm−2, and a wide response range of 0.01 to 1.5 μg/mL. Moreover, an intelligent analysis system, consisting of a portable device that connects to an online cloud platform equipped with a machine learning model and visualization software, has been developed for the real-time detection of CBZ residues on tea leaves in tea plantations. This study demonstrates that the PLL/WS2/LIG sensor and the intelligent analysis system have great potential to monitor pesticide residues to guarantee food safety.

CuO nanoparticles embedded in laser-induced graphene for flexible planar micro-supercapacitors

Utilizing predefined electrode geometries, laser direct writing technology is employed to intricately inscribe flexible polyimide (PI) films, thereby inducing porous graphene patterned electrodes for flexible planar micro-supercapacitors (MSCs), which greatly facilitates the integration of MSCs into functional devices for power supply. Nevertheless, prevailing challenges confront current flexible MSCs relying on laser-induced graphene (LIG), including the constrained electrochemical functionality of pure LIG electrodes and the uneven incorporation of heterogeneous constituents within LIG electrodes. In light of these challenges, this study delves into the fundamental mechanism underlying the formation of polyimide (PI) films and introduces an innovative approach to uniformly integrate CuO nanoparticles into the poly (acrylic acid) (PAA) precursor solution. The subsequent imidization process culminates in the synthesis of a CuO-embedded PI film. The research progresses to the fabrication of shape-controllable CuO/LIG patterned electrodes utilizing a precision laser direct writing technique, and the subsequent construction of flexible planar MSCs. Harnessing the synergistic interactions between the dual components within the electrode, the resulting MSC possesses an impressive areal capacitance of 6.45 mF·cm-2, coupled with an energy density of 0.896 mWh·cm-2 and a power density of 0.081 mW·cm-2, thus illustrating the potential of this innovative material integration for high-performance flexible energy storage implementations.

Flexible Acetylcholine Neural Probe with a Hydrophobic Laser-Induced Graphene Electrode and a Fluorous-Phase Sensing Membrane.

This work develops the first laser-induced graphene (LIG)-based electrochemical sensor with a superhydrophobic fluorous membrane for a flexible acetylcholine (ACh) sensor. ACh regulates several physiological functions, including synaptic transmission and glandular secretion. The ACh sensing membrane is doped with a fluorophilic cation-exchanger that can selectively measure ACh based on the inherent selectivity of the fluorous phase for hydrophobic ions, such as ACh. The fluorous-phase sensor improves the selectivity for ACh over Na+ and K+ by 2 orders of magnitude (compared to traditional lipophilic membranes), thus lowering the detection limit in artificial cerebrospinal fluid (aCSF) from 331 to 0.38 μ M, thereby allowing measurement in physiologically relevant ranges of ACh. Engraving LIG under argon creates a hydrophobic surface with a 133.7° contact angle, which minimizes the formation of a water layer. The flexible solid-contact LIG fluorous sensor exhibited a slope of 59.3 mV/decade in aCSF and retained function after 20 bending cycles, thereby paving the way for studying ACh's role in memory and neurodegenerative diseases.

Laser Fabrication of Humidity Sensors on Ethanol-Soaked Polyimide for Fully Contactless Respiratory Monitoring.

Humidity-sensor-based fully contactless respiratory monitoring can eliminate the discomfort and infection risks associated with any wearable device. However, challenges in the facile fabrication of highly sensitive humidity sensors continue to hinder their widespread application for fully contactless respiratory monitoring. In this study, we introduce a simple method to fabricate highly sensitive humidity sensors. Our method employs laser-induced graphene (LIG) on an ethanol-soaked polyimide (PI) film as the electrode of the humidity sensor. The ethanol-soaked PI between adjacent LIG electrodes functions as the sensing material, enabling ion-conductive humidity sensing. Compared to the LIG humidity sensors fabricated on untreated PI films, LIG humidity sensors fabricated on ethanol-soaked PI films exhibit superior performance with higher linearity (R2 = 0.9936), reduced hysteresis (ΔH = 5.1% RH), and increased sensitivity (0.65%/RH). Notably, the LIG humidity sensor fabricated on the ethanol-soaked PI film can detect a person's breathing from a distance of 30 cm, a capability not achieved by sensors fabricated on untreated PI films. Moreover, incorporating these LIG humidity sensors into an array further enhances both the detection distance and the sensitivity for respiratory monitoring. Experimental results demonstrate that the LIG humidity sensor array can be employed for fully contactless on-bed respiration monitoring and for continuous, fully contactless monitoring of the respiratory rate during treadmill exercise. These results highlight the great potential of our LIG humidity sensors for various practical applications in medicine and sports.

Ruthenium Anchored Laser-Induced Graphene as Binder-Free and Free-Standing Electrode for Selective Electrosynthesis of Ammonia from Nitrate.

Developing effective electrocatalysts for the nitrate reduction reaction (NO3RR) is a promising alternative to conventional industrial ammonia (NH3) synthesis. Herein, starting from a flexible laser-induced graphene (LIG) film with hierarchical and interconnected macroporous architecture, a binder-free and free-standing Ru-modified LIG electrode (Ru-LIG) is fabricated for electrocatalytic NO3RR via a facile electrodeposition method. The relationship between the laser-scribing parameters and the NO3RR performance of Ru-LIG electrodes is studied in-depth. At -0.59 VRHE, the Ru-LIG electrode exhibited the optimal and stable NO3RR performance (NH3 yield rate of 655.9µgcm-2h-1 with NH3 Faradaic efficiency of up to 93.7%) under a laser defocus setting of +2mm and an applied laser power of 4.8W, outperforming most of the reported NO3RR electrodes operated under similar conditions. The optimized laser-scribing parameters promoted the surface properties of LIG with increased graphitization degree and decreased charge-transfer resistance, leading to synergistically improved Ru electrodeposition with more exposed NO3RR active sites. This work not only provides a new insight to enhance the electrocatalytic NO3RR performance of LIG-based electrodes via the coordination with metal electrocatalysts as well as identification of the critical laser-scribing parameters but also will inspire the rational design of future advanced laser-induced electrocatalysts for NO3RR.

Printed and Laser Induced Graphene Electrochemical Biosensors for Rapid Environmental and Biomedical Monitoring

This presentation will demonstrate how low-cost printed and flexible graphene circuits can overcome the challenges associated with conventional electrical circuits to open the door to a highly sensitive monitoring of biochemical threats and toxins including nerve agents/pesticides. The use of inkjet and aerosol printing; spin coating; and laser writing (i.e., laser induced graphene) can be used to create such circuits with high resolution (line widths as low as 20 µm). Moreover, the use of rapid-pulse laser annealing of the printed graphene and/or salt porogens added into graphene inks before printing can be used to further improve the electrical conductivity (< 10 ohms/sq.) and electroactive surface area (nano/micro structuring) of the graphene circuits as well as be used to tune the surface of the printed graphene from one that is hydrophilic (water contact angle (WCA) = 48°) to one that is superhydrophobic (WCA = 158°). More recently we demonstrate how graphene synthesis, patterning and surface wettability can all be controlled through a laser induced graphene (LIG) process that creates a high surface area graphene surface directly from polyimide. Such LIG circumvents the need to create solution-phase graphene inks for printing. These printing and laser fabrication techniques are also amenable for use on flexible and chemically/thermally sensitive surfaces including polymers and paper.Moreover, the laser etched printed graphene and LIG exhibits an inherent 3D morphology that significantly increases the electrode electroactive surface over traditional 2D planar graphene electrodes. This large increase in surface area significantly improves the loading of enzyme onto the electrode surface and subsequently increases the heterogenous charge transport during catalytic pesticide sensing. Such ion sensors displayed near-Nernstian sensitivities, wide sensing ranges over four orders of magnitude extending from the 10–2 M down to detection limits in the 10–6 M range or for fertilizer ions (nitrate, ammonium, potassium, calcium, and magnesium) reaching down to detection limits less than 1 ppm in some cases in soil and water samples. The pesticide sensing capability of the sensor is able to reach an extremely low picomolar detect limit for organophosphates (paraoxon) and to the nanomolar regime for neonicotinoids in surface waters. We also demonstrate how this flexible LIG electrodes can be coupled with polymeric microfluidics and adhered to the body for continuous monitoring of lactate, glucose, and sodium in the sweat. Finally, we demonstrate how such surface wettability patterning of the printed graphene and LIG itself through laser etching can be used to make hydrophilic LIG tracks surrounded by near superhydrophic sidewalls for open microfluidic fluid transport without the need for polymeric microfluidics. Such open microfluidic tracks enable the splitting and transport of fluid samples to distinct electrochemical sensors for multiplexed biosensing of both fertilizer ion and pesticide monitoring from water samples and assist in harvesting sprayed pesticides in the field. Figure 1

Laser-Induced Graphene for Electrochemical Analysis of Food and Agricultural Contaminants

Carbon-nanomaterial sensors offer promising routes toward low-cost, high-throughput electrochemical sensors. Carbon nanomaterials, such as graphene and carbon nanotube (CNT), have been studied with various fabrication methods to produce sensors, including high-quality thin film graphene and CNT by chemical vapor deposition. However, the complexity and cost associated with their fabrication have hindered their implementation into single-use test strip sensors. Even high-yield mechanical and/or chemical exfoliation of graphene from graphite followed by solution phase printing of electrodes can be costly due to the complexity of ink formulation and the need for post-print annealing requirements. However, laser-induced graphene (LIG) avoids the need to exfoliate graphene from graphite or to create a solution-phase graphene ink by converting sp3 carbon found in carbon-rich substrates into conductive sp2-hybridized carbon found in graphene through a laser scribing technique. The resulting LIG also exhibits a high surface area and is porous with a high density of edge plane sites, which are beneficial for biofunctionalization and heterogeneous charge transport during electrochemical sensing. Furthermore, we have demonstrated that the surface area and wettability of the LIG can be tuned to greatly improve the sensitivity of electrochemical enzymatic biosensors (detection limits down to the picomolar range) and reduce the water layer buildup between the ion-selective membrane and the electrode, which improves the accuracy of the sensor readings. The fabricated LIG electrodes have been used in a wide variety of electrochemical sensing applications, including in food safety (foodborne pathogens and other contaminants), environmental monitoring (agrochemicals), and health monitoring sensors (salivary potassium and lactate, and urinary potassium and ammonium). Different electroanalytical methods are used, including amperometric, potentiometric, coulometric, and impedimetric, to quantify the analytes. We demonstrate how the ISE (ion-selective electrodes) can be functionalized with PVC-based ion-selective membranes for potassium, nitrate, nitrite, ammonium, sodium, and pH in various biological solutions, including soil and water for nutrient/fertilizer monitoring in farm fields. Additionally, we demonstrate how the hydrophilic LIG graphene can be used to create other highly sensitive electrochemical biosensors including enzymatic pesticide biosensors and Salmonella spp. immunosensors. All these electroanalytical sensors were validated in real-world samples and demonstrated to have limits of detection and linear sensing ranges that are relevant to their sensing applications. Results demonstrate the utility of LIG-based sensors for rapid and sensitive electrochemical measurement of contaminants as a readily modified platform for scalable production of electroanalytical devices applied toward point-of-service environmental and food monitoring.

Fabrication of high-resolution, flexible, laser-induced graphene sensors via stencil masking

The advent of wearable sensing platforms capable of continuously monitoring physiological parameters indicative of health status have resulted in a paradigm shift for clinical medicine. The accessibility and adaptability of such portable, unobtrusive devices enables proactive, personalized care based on real-time physiological insights. While wearable sensing platforms exhibit powerful capabilities for continuously monitoring physiological parameters, device fabrication often requires specialized facilities and technical expertise, restricting deployment opportunities and innovation potential. The recent emergence of rapid prototyping approaches to sensor fabrication, such as laser-induced graphene (LIG), provides a pathway for circumventing these barriers through low-cost, scalable fabrication. However, inherent limitations in laser processing restrict the spatial resolution of LIG-based flexible electronic devices to the minimum laser spot size. For a CO2 laser–a commonly reported laser for device production–this corresponds to a feature size of ∼120 μm. Here, we demonstrate a facile, low-cost stencil-masking technique to reduce the minimum resolvable feature size of a LIG-based device from 120 ± 20 μm to 45 ± 3 μm when fabricated by CO2 laser. Characterization of device performance reveals this stencil-masked LIG (s-LIG) method yields a concomitant improvement in electrical properties, which we hypothesize is the result of changes in macrostructure of the patterned LIG. We showcase the performance of this fabrication method via production of common sensors including temperature and multi-electrode electrochemical sensors. We fabricate fine-line microarray electrodes not typically achievable via native CO2 laser processing, demonstrating the potential of the expanded design capabilities. Comparing microarray sensors made with and without the stencil to traditional macro LIG electrodes reveals the s-LIG sensors have significantly reduced capacitance for similar electroactive surface areas. Beyond improving sensor performance, the increased resolution enabled by this metal stencil technique expands capabilities for scalable fabrication of high-performance wearable sensors in low-resource settings without reliance on traditional fabrication pathways.

Smart wearable flexible sensor based on laser-induced graphene/gold nanoparticles/black phosphorus nanosheets for in situ quercetin detection

In situ detection of metabolic substances in plants is necessary for the development of smart agriculture. However, there is a mechanical mismatch between the traditional rigid sensing interfaces and the softness surface of plant leaves, which can reduce the reliability and accuracy of sensor. Stretchable and flexible sensors provide new solutions to this problem. Herein, using quercetin (Que) as a model, we developed a flexible electrochemical sensor for in situ monitoring of metabolite in plants. A light and thin laser-induced graphene (LIG) electrodes with good flexibility were obtained after polydimethylsiloxane (PDMS) transfer. Gold nanoparticles (AuNPs) and two-dimensional black phosphorus (BP) nanosheets were fabricated on the electrode to further improve the electrochemical performance. The sensor can detect Que concentrations in the range of 1–100 μM with a detection limit of 0.65 μM (S/N=3). The sensor can adapt well to the soft plant leaf surfaces, thus realizing the application of in situ and in vivo detection in the field. This innovative plant wearable biosensor is expected to be a next-generation electronic candidate for intelligent agriculture, paving the way for in-situ and in vivo detection, and facilitating the intelligentsias of modern agriculture.