Urea-assisted N-type conversion of laser-induced graphene for thermoelectric applications
Source abstract
Abstract
Abstract Thermoelectric materials enable direct heat-to-electricity conversion. They have gained increasing interest in sustainable and wearable energy-harvesting systems. However, progress in flexible thermoelectric devices remains limited by the shortage of high-performance n-type organic materials, hindering the development of efficient p–n complementary modules. Laser-induced graphene (LIG) has attracted considerable attention for thermoelectric applications due to its high electrical conductivity, scalable fabrication, and compatibility with flexible substrates. However, LIG produced from polyimide typically exhibits p-type behavior, which limits its applicability in thermoelectric modules requiring complementary n-type materials. In this study, we address this limitation by introducing a simple and scalable urea-assisted strategy to convert p-type LIG into n-type LIG through nitrogen doping during the laser-induced graphitization process. First, we have fabricated LIG by direct laser writing on polyimide and subsequently treated with 5 and 10 wt% urea solutions, followed by mild annealing. Subsequent structural and chemical characterizations confirmed effective nitrogen incorporation, dominated by graphitic-N species, while preserving the porous 3D LIG network. Thermoelectric measurements revealed enhanced electrical conductivity (up to 1120 S/m) and a clear p-to-n transition, as evidenced by negative Seebeck coefficients in urea-treated films. The optimized LIG-10 N sample delivered the highest thermoelectric performance, reaching a power factor of 0.136 µW m⁻¹ K⁻² at 60 °C. Overall, this work provides a practical route for engineering n-type LIG, supporting the development of flexible thermoelectric modules for wearable and low-power energy-harvesting applications. Graphical Abstract
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Graphene research and applications · Advanced Sensor and Energy Harvesting Materials · Nanomaterials and Printing Technologies
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (58)
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1. Agusu L, Ahmad LO, Alimin et al (2018) Hydrothermal Synthesis of Reduced Graphene Oxide Using Urea as Reduction Agent: Excellent X-band Electromagnetic Absorption Properties. IOP Conf Ser Mater Sci Eng 367. https://doi.org/10.1088/1757-899X/367/1/01200210.1088/1757-899X/367/1/012002 ↗
2. Anadkat D, Pandya A, Jaiswal A et al (2024) Experimental comparison between graphene and reduced graphene oxide along with significant conversion of rGO from n-to p-type. J Mater Sci Mater Electron 35:1–12. https://doi.org/10.1007/s10854-024-12591-810.1007/s10854-024-12591-8 ↗
3. Bayat F, Nazeri M, Grau G, Pisana S (2025) Encapsulating laser-induced graphene to preserve its electrical properties and enhance its mechanical robustness. Adv Eng Mater. https://doi.org/10.1002/adem.20250168610.1002/adem.202501686 ↗
4. Boran F, Çeti̇Nkaya Gürer S (2019) The effect of starting material types on the structure of graphene oxide and graphene. Turk J Chem 43:1322–1335. https://doi.org/10.3906/kim-1901-4710.3906/kim-1901-47 ↗
5. Bubnova O, Crispin X (2012) Towards polymer-based organic thermoelectric generators. Energy Environ Sci 5:9345–9362. https://doi.org/10.1039/c2ee22777k10.1039/c2ee22777k ↗
6. Cao J, Zheng J, Liu H et al (2022) Flexible elemental thermoelectrics with ultra-high power density. Mater Today Energy 25:100964. https://doi.org/10.1016/j.mtener.2022.10096410.1016/j.mtener.2022.100964 ↗
7. Cheng L, Yeung CS, Huang L et al (2024) Flash healing of laser-induced graphene. Nat Commun 15:1–11. https://doi.org/10.1038/s41467-024-47341-110.1038/s41467-024-47341-1 ↗
8. Coros M, Varodi C, Pogacean F et al (2020) Nitrogen-doped graphene: the influence of doping level on the charge-transfer resistance and apparent heterogeneous electron transfer rate. Sensors Basel. https://doi.org/10.3390/s2007181510.3390/s20071815 ↗
9. Du Y, Xu J, Paul B, Eklund P (2018) Flexible thermoelectric materials and devices. Appl Mater Today 12:366–388. https://doi.org/10.1016/j.apmt.2018.07.00410.1016/j.apmt.2018.07.004 ↗
10. Elsabawy KM, Fallatah AM, Owidah ZO (2021) Ultrahigh-energy laser-assisted exfoliation for fast eco-synthesis of reduced graphene oxide with structure quality. J Electron Mater 50:3814–3818. https://doi.org/10.1007/s11664-021-08906-810.1007/s11664-021-08906-8 ↗
11. Factorovich M, Guz L, Candal R (2011) N-TiO 2: chemical synthesis and photocatalysis. Adv Phys Chem. https://doi.org/10.1155/2011/82120410.1155/2011/821204 ↗
12. Farooq U, Ali B, Bidsorkhi HC et al (2023) Graphene-based Flexible Thermoelectric Generators for Heat Recovery Systems. 2023 IEEE Nanotechnol Mater Devices Conf NMDC 2023 152–156. https://doi.org/10.1109/NMDC57951.2023.1034407910.1109/NMDC57951.2023.10344079 ↗
13. Gadhavi PM, Sivalertporn K, Poopanya P, Talati M (2024) Effect of dual nitrogen doping on the electronic, thermodynamic, transport and thermoelectric properties of graphene. Comput Condens Matter 38:e00875. https://doi.org/10.1016/j.cocom.2023.e0087510.1016/j.cocom.2023.e00875 ↗
14. Gautam NK, Alshoaibi A, Lavania S et al (2025) Fabrication and characterization of MWCNT/MXene nanocomposites as an electrode material for supercapacitor applications. Diamond Relat Mater. https://doi.org/10.1016/j.diamond.2025.11304610.1016/j.diamond.2025.113046 ↗
15. Grossman JC, Getachew BA, Bergsman DS (2020) Laser-induced graphene from polyimide and polyethersulfone precursors as a sensing electrode in anodic stripping voltammetry. ACS Appl Mater Interfaces 12:48511–48517. https://doi.org/10.1021/acsami.0c1172510.1021/acsami.0c11725 ↗
16. Guo HL, Su P, Kang X, Ning SK (2013) Synthesis and characterization of nitrogen-doped graphene hydrogels by hydrothermal route with urea as reducing-doping agents. J Mater Chem A 1:2248–2255. https://doi.org/10.1039/c2ta00887d10.1039/c2ta00887d ↗
17. Hong CT, Yoo Y, Kang YH et al (2015) Effect of film thickness and crystallinity on the thermoelectric properties of doped P3HT films. RSC Adv 5:11385–11391. https://doi.org/10.1039/c4ra15681a10.1039/c4ra15681a ↗
18. Huang Y, Xiao G, Chen J et al (2025) n-Type polymer semiconductors based on conformation-locked π-extended bithieno[3,4-c]pyrrole-4,6-dione (BTPD) acceptor units for organic thermoelectrics. J Mater Chem C. https://doi.org/10.1039/d5tc02503f10.1039/d5tc02503f ↗
19. Hwang HJ, Kim SY, Lee SK, Lee BH (2023) Large scale graphene thermoelectric device with high power factor using gradient doping profile. Carbon N Y 201:467–472. https://doi.org/10.1016/j.carbon.2022.09.04810.1016/j.carbon.2022.09.048 ↗
20. Islamova VR, Rybin MG, Tonkikh AA et al (2022) Quantitative Estimation of p- and n-Doping Effects on Electrophysical and Optical Properties of CVD Graphene. J Phys Chem C 126:4620–4629. https://doi.org/10.1021/acs.jpcc.1c0998210.1021/acs.jpcc.1c09982 ↗
21. Jaafar E, Kashif M, Sahari SK, Ngaini Z (2018) Study on morphological, optical and electrical properties of graphene oxide (GO) and reduced graphene oxide (rGO). Mater Sci Forum 917 MSF:112–116. https://doi.org/10.4028/www.scientific.net/MSF.917.11210.4028/www.scientific.net/MSF.917.112 ↗
22. Jiang H, Liu L, Zhao K et al (2020) Effect of pyridinic- and pyrrolic-nitrogen on electrochemical performance of Pd for formic acid electrooxidation. Electrochim Acta 337:135758. https://doi.org/10.1016/j.electacta.2020.13575810.1016/j.electacta.2020.135758 ↗
23. Kang MH, Prieto López LO, Chen B et al (2016) Mechanical Robustness of Graphene on Flexible Transparent Substrates. ACS Appl Mater Interfaces 8:22506–22515. https://doi.org/10.1021/acsami.6b0655710.1021/acsami.6b06557 ↗
24. Kincal C, Solak N (2024) Controlling thermoelectric properties of laser-induced graphene on polyimide. Nanomaterials Basel. https://doi.org/10.3390/nano1410087910.3390/nano14100879 ↗
25. Kocaman Kabi̇l F, Kol S, Aydemi̇r N, Oral AY (2025) Scalable fabrication of Polyethylenimine (PEI) doped laser-induced graphene (LIG) inks. ACS Omega 10:42826–42836. https://doi.org/10.1021/acsomega.5c0525910.1021/acsomega.5c05259 ↗
26. Kondapalli VKR, Akinboye OI, Zhang Y et al (2024) Three-dimensional graphene sheet-carbon veil thermoelectric composite with microinterfaces for energy applications. ACS Appl Mater Interfaces 16:13150–13160. https://doi.org/10.1021/acsami.3c1960510.1021/acsami.3c19605 ↗
27. Lavania S, Aljaafari A, Dhiman G et al (2026) Fabrication of nitrogen-doped laser-induced graphene-based electrodes: evaluation of electrochemical energy storage performance of symmetric supercapacitor devices. J Phys Chem Solids 209:113296. https://doi.org/10.1016/j.jpcs.2025.11329610.1016/j.jpcs.2025.113296 ↗
28. Le TSD, Phan HP, Kwon S et al (2022) Recent advances in laser-induced graphene: mechanism, fabrication, properties, and applications in flexible electronics. Adv Funct Mater. https://doi.org/10.1002/adfm.20220515810.1002/adfm.202205158 ↗
29. Lee SP, Chong KF, Lim EH et al (2025) engineered by laser crafting. 290–302. https://doi.org/10.1002/flm2.7000110.1002/flm2.70001 ↗
30. Liang X, Zhong J, Shi Y et al (2015) Hydrothermal synthesis of highly nitrogen-doped few-layer graphene via solid-gas reaction. Mater Res Bull 61:252–258. https://doi.org/10.1016/j.materresbull.2014.09.08810.1016/j.materresbull.2014.09.088 ↗
31. Liu H, Chen K, Wu R et al (2023) Laser-induced graphene-based flexible substrate with photothermal conversion and photoresponse performance on Polyimide film. ACS Appl Mater Interfaces 15:46550–46558. https://doi.org/10.1021/acsami.3c1072910.1021/acsami.3c10729 ↗
32. Lu Y, Wang JY, Pei J (2019) Strategies to enhance the conductivity of n-Type polymer thermoelectric materials. Chem Mater 31:6412–6423. https://doi.org/10.1021/acs.chemmater.9b0142210.1021/acs.chemmater.9b01422 ↗
33. Luo Z, Lim S, Tian Z et al (2011) Pyridinic N doped graphene: synthesis, electronic structure, and electrocatalytic property. J Mater Chem 21:8038–8044. https://doi.org/10.1039/c1jm10845j10.1039/c1jm10845j ↗
34. Mahmoud HA, AlJafari A, Bahabri M et al (2025) Processing-controlled Seebeck modulation in laser-induced graphene for flexible temperature sensors. ACS Appl Electron Mater 7:6384–6393. https://doi.org/10.1021/acsaelm.5c0056210.1021/acsaelm.5c00562 ↗
35. Matsoso BJ, Ranganathan K, Mutuma BK et al (2016) Time-dependent evolution of the nitrogen configurations in N-doped graphene films. RSC Adv 6:106914–106920. https://doi.org/10.1039/c6ra24094a10.1039/c6ra24094a ↗
36. Naftaly M, Das S, Gallop J et al (2021) Sheet resistance measurements of conductive thin films: a comparison of techniques. Electronics. https://doi.org/10.3390/electronics1008096010.3390/electronics10080960 ↗
37. Novak TG, Kim J, Kim J et al (2020) Complementary n-type and p-type graphene films for high power factor thermoelectric generators. Adv Funct Mater 30:1–7. https://doi.org/10.1002/adfm.20200176010.1002/adfm.202001760 ↗
38. Pavithra A, Rakkesh RA, Durgalakshmi D, Balakumar S (2017) Room temperature detection of hydrogen gas using graphene based conductometric gas sensor. J Nanosci Nanotechnol 17:3449–3453. https://doi.org/10.1166/jnn.2017.1305410.1166/jnn.2017.13054 ↗
39. Rajab SE, Abud MM, Azzawi MM (2025) Laser-induced graphene-based temperature sensors on polyimide substrates. J Opt. https://doi.org/10.1007/s12596-025-02773-w10.1007/s12596-025-02773-w ↗
40. Rao Y, Bechtold T, Hohlfeld D (2025) Design of packaged thermoelectric generators for implantable medical devices: a comprehensive parameter study. Energy 320:134932. https://doi.org/10.1016/j.energy.2025.13493210.1016/j.energy.2025.134932 ↗
41. Robert Bigras G, Glad X, Vandsburger L et al (2019) Low-damage nitrogen incorporation in graphene films by nitrogen plasma treatment: effect of airborne contaminants. Carbon 144:532–539. https://doi.org/10.1016/j.carbon.2018.12.09510.1016/j.carbon.2018.12.095 ↗
42. Ruciński A, Gronek W (2025) Organic Semiconductors for Thermoelectric Modules: Potential, Limitations and Engineering Perspectives. 4:21–28
43. Siburian R, Sihotang H, Lumban Raja S et al (2018) New route to synthesize of graphene nano sheets. Orient J Chem 34:182–187. https://doi.org/10.13005/ojc/34012010.13005/ojc/340120 ↗
44. Smits FM (1958) Measurement of sheet resistivities with the four-point probe. Bell Syst Tech J 37:711–718. https://doi.org/10.1002/j.1538-7305.1958.tb03883.x10.1002/j.1538-7305.1958.tb03883.x ↗
45. Suemori K, Hoshino S, Kamata T (2013) Flexible and lightweight thermoelectric generators composed of carbon nanotube-polystyrene composites printed on film substrate. Appl Phys Lett. https://doi.org/10.1063/1.482464810.1063/1.4824648 ↗
46. Sun L, Wang L, Tian C et al (2012) Nitrogen-doped graphene with high nitrogen level via a one-step hydrothermal reaction of graphene oxide with urea for superior capacitive energy storage. RSC Adv 2:4498–4506. https://doi.org/10.1039/c2ra01367c10.1039/c2ra01367c ↗
47. Tam T, Van, Trung NB, Kim HR et al (2014) One-pot synthesis of N-doped graphene quantum dots as a fluorescent sensing platform for Fe3 + ions detection. Sens Actuators B Chem 202:568–573. https://doi.org/10.1016/j.snb.2014.05.04510.1016/j.snb.2014.05.045 ↗
48. Wang L, Yao Q, Bi H et al (2014a) Large thermoelectric power factor in polyaniline/ graphene nanocomposite films prepared by solution. https://doi.org/10.1039/c4ta01541j. -assistant dispersing method10.1039/c4ta01541j ↗
49. Wang X, Sun G, Routh P et al (2014b) Heteroatom-doped graphene materials: syntheses, properties and applications. Chem Soc Rev 43:7067–7098. https://doi.org/10.1039/c4cs00141a10.1039/c4cs00141a ↗
50. Wang X, Wang H, Liu B (2018) Carbon Nanotube -Based Organic Thermoelectric Materials for Energy Harvesting. https://doi.org/10.3390/polym1011119610.3390/polym10111196 ↗
51. Wang Y, Ishihara M, Kirihara K et al (2024) Controlled n-type doping in graphene using a photobase generator and polyethylene oxide blends. Diamond Relat Mater 147:111306. https://doi.org/10.1016/j.diamond.2024.11130610.1016/j.diamond.2024.111306 ↗
52. Witjaksono G, Junaid M, Khir MH et al (2021) Effect of nitrogen doping on the optical bandgap and electrical conductivity of nitrogen-doped reduced graphene oxide. Molecules. https://doi.org/10.3390/molecules2621642410.3390/molecules26216424 ↗
53. Xu S, Hong M, Shi XL et al (2019) High-performance PEDOT:PSS flexible thermoelectric materials and their devices by triple post-treatments. Chem Mater 31:5238–5244. https://doi.org/10.1021/acs.chemmater.9b0150010.1021/acs.chemmater.9b01500 ↗
54. Yang CR, Tseng SF, Chen YT (2018) Characteristics of graphene oxide films reduced by using an atmospheric plasma system. Nanomaterials 8:1–12. https://doi.org/10.3390/nano810080210.3390/nano8100802 ↗
55. Zhang CK, Lin WY, Zhao ZJ et al (2015) CVD synthesis of nitrogen-doped graphene using urea. Sci China Phys Mech Astron 58:0–5. https://doi.org/10.1007/s11433-015-5717-010.1007/s11433-015-5717-0 ↗
56. Zhang X, Liu Y, Lu P, Zhang M (2020) Preparation and properties of hydrogel based on sawdust cellulose for environmentally friendly slow release fertilizers. Green Process Synth 9:139–152. https://doi.org/10.1515/gps-2020-001510.1515/gps-2020-0015 ↗
57. Zhu X, Yu Y, Li F (2019) A review on thermoelectric energy harvesting from asphalt pavement: configuration, performance and future. Constr Build Mater 228:116818. https://doi.org/10.1016/j.conbuildmat.2019.11681810.1016/j.conbuildmat.2019.116818 ↗
58. Zhu Y, Yan L, Xu M et al (2021) Difference between ammonia and urea on nitrogen doping of graphene quantum dots. Colloids Surf A Physicochem Eng Asp 610:125703. https://doi.org/10.1016/j.colsurfa.2020.12570310.1016/j.colsurfa.2020.125703 ↗