Eco-Friendly Synthesis of Wrinkle-Free Ultra-Flat Multi-Layer Graphene by Femtosecond Laser Irradiation of Graphite Under Ambient Conditions

Here, we report a single-step, high-yield technique for producing planar sheets of wrinkle-free multi-layer graphene (MLG) under ambient conditions by ablation of graphite powder dispersed in ethanol using a femtosecond laser. The parameters for the synthesis of MLG have been optimized and established. The number of layers and quality of MLG produced at several laser fluences (39.4 J/cm2, 98.72 J/cm2, 197.45 J/cm2, 296.16 J/cm2) was established based on detailed characterization using field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM) with selected area electron diffraction (SAED), atomic force microscopy (AFM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). Wrinkle-free, ultra-flat crystalline MLG sheets with 2-12 layers were produced in each case with an average lateral dimension of ∼1--3 μm. The associated oxy- functional groups were characterized and quantified using FTIR and XPS. The highest percentage of sp2 C atoms and C/O ratio for MLG was achieved at the lowest laser fluence. The higher the laser fluence higher the defects produced in the MLG sheets. The technique produces zero chemical waste, has a very high yield of ∼ 95%, and is promising for bulk-scale production of MLG.

[1]  R. Savu,et al.  In situ growth of laser-induced graphene micro-patterns on arbitrary substrates. , 2022, Nanoscale.

[2]  K. Kar,et al.  Laser processing of graphene and related materials for energy storage: State of the art and future prospects , 2022, Progress in Energy and Combustion Science.

[3]  Pei Lay Yap,et al.  Thermogravimetric Analysis (TGA) of Graphene Materials: Effect of Particle Size of Graphene, Graphene Oxide and Graphite on Thermal Parameters , 2021, C.

[4]  Pei Lay Yap,et al.  Unlocking thermogravimetric analysis (TGA) in the fight against “Fake graphene” materials , 2021, Carbon.

[5]  Fuqian Yang,et al.  Effects of laser power and substrate on the Raman shift of carbon-nanotube papers , 2020, Carbon Trends.

[6]  A. G. Bannov,et al.  Thermal analysis of carbon nanomaterials: advantages and problems of interpretation , 2020, Journal of Thermal Analysis and Calorimetry.

[7]  D. Dorranian,et al.  Producing graphene nanosheets by pulsed laser ablation: Effects of liquid environment , 2019 .

[8]  R. Singh,et al.  Fabrication and electrochemical evaluation of micro-supercapacitors prepared by direct laser writing on free-standing graphite oxide paper , 2019, Energy.

[9]  D. Dorranian,et al.  Effect of Laser Fluence on the Characteristics of Graphene Nanosheets Produced by Pulsed Laser Ablation in Water , 2019, Journal of Applied Spectroscopy.

[10]  Ki Jun Yu,et al.  Electronic and Thermal Properties of Graphene and Recent Advances in Graphene Based Electronics Applications , 2019, Nanomaterials.

[11]  R. Malekfar,et al.  High-quality liquid phase-pulsed laser ablation graphene synthesis by flexible graphite exfoliation , 2019, Journal of Materials Science & Technology.

[12]  M. Lobino,et al.  Laser‐Reduced Graphene: Synthesis, Properties, and Applications , 2018 .

[13]  Lan Jiang,et al.  Quantitative detection of oxygen in reduced graphene oxide by femtosecond laser-induced breakdown spectroscopy. , 2018, Applied optics.

[14]  R. Young,et al.  Mechanical properties of graphene and graphene-based nanocomposites , 2017 .

[15]  S. Homaeigohar,et al.  Graphene membranes for water desalination , 2017 .

[16]  Zhen Zhen,et al.  Graphene: Fundamental research and potential applications , 2017 .

[17]  Morsy,et al.  Thermally Reduced Graphene Oxide: Synthesis, Structural and Electrical Properties , 2017 .

[18]  Lei Li,et al.  Graphitic materials: Intrinsic hydrophilicity and its implications , 2017 .

[19]  R. Singh,et al.  Laser-assisted synthesis, reduction and micro-patterning of graphene: Recent progress and applications , 2017 .

[20]  Marc P. Coons,et al.  The Hydrated Electron. , 2017, Annual review of physical chemistry.

[21]  V. Srikanth,et al.  One-step synthesis of bulk quantities of graphene from graphite by femtosecond laser ablation under ambient conditions , 2017 .

[22]  T. Derrien,et al.  Fundamentals of ultrafast laser–material interaction , 2016 .

[23]  Abubaker Hassan Hamad,et al.  Effects of Different Laser Pulse Regimes (Nanosecond, Picosecond and Femtosecond) on the Ablation of Materials for Production of Nanoparticles in Liquid Solution , 2016 .

[24]  Stanislav A. Moshkalev,et al.  Fabrication of interdigitated micro-supercapacitor devices by direct laser writing onto ultra-thin, flexible and free-standing graphite oxide films , 2016 .

[25]  M. Hong,et al.  Fabrication of Laser-reduced Graphene Oxide in Liquid Nitrogen Environment , 2016, Scientific Reports.

[26]  Alina Matei,et al.  FTIR Spectroscopy for Carbon Family Study , 2016, Critical reviews in analytical chemistry.

[27]  E. Toyserkani,et al.  Single-step synthesis of graphene quantum dots by femtosecond laser ablation of graphene oxide dispersions. , 2016, Nanoscale.

[28]  John Robertson,et al.  The mechanism of direct laser writing of graphene features into graphene oxide films involves photoreduction and thermally assisted structural rearrangement , 2016 .

[29]  X. Ren,et al.  Morphology selective preparation and formation mechanism of graphene nanoribbons from graphite by liquid-phase pulsed laser ablation , 2016 .

[30]  S. M. Arakelyan,et al.  Laser ablation of carbon targets placed in a liquid , 2015 .

[31]  B. Scrosati,et al.  The role of graphene for electrochemical energy storage. , 2015, Nature materials.

[32]  J. L. Shen,et al.  Laser-ablation production of graphene oxide nanostructures: from ribbons to quantum dots. , 2015, Nanoscale.

[33]  Zhong Yan,et al.  Thermal properties of graphene and few-layer graphene: applications in electronics , 2015, IET Circuits Devices Syst..

[34]  M. Ibrahim,et al.  Preparation and Characterization of Microwave Reduced Graphite Oxide for High-Performance Supercapacitors , 2014 .

[35]  Woo-Gwang Jung,et al.  Facile and safe graphene preparation on solution based platform , 2014 .

[36]  C. S. Chen,et al.  Direct synthesis of graphene on any nonmetallic substrate based on KrF laser ablation of ordered pyrolytic graphite , 2014 .

[37]  W. Duley,et al.  Femtosecond laser ablation of highly oriented pyrolytic graphite: a green route for large-scale production of porous graphene and graphene quantum dots. , 2014, Nanoscale.

[38]  Robert H. Hurt,et al.  All in the graphene family - A recommended nomenclature for two-dimensional carbon materials , 2013 .

[39]  Bowen Yao,et al.  An improved Hummers method for eco-friendly synthesis of graphene oxide , 2013 .

[40]  Yingyan Zhang,et al.  Mechanical properties of graphene : effects of layer number, temperature and isotope , 2013 .

[41]  S. Adachi,et al.  Photoelectron spectra of solvated electrons in bulk water, methanol, and ethanol , 2012 .

[42]  Minhao Shi,et al.  One-step solid state preparation of reduced graphene oxide , 2012 .

[43]  Yong‐Lai Zhang,et al.  Bandgap Tailoring and Synchronous Microdevices Patterning of Graphene Oxides , 2012 .

[44]  Yang Liu,et al.  Pulsed laser assisted reduction of graphene oxide , 2011 .

[45]  T. Feng,et al.  Formation of graphene sheets through laser exfoliation of highly ordered pyrolytic graphite , 2011 .

[46]  J. Park,et al.  Fast growth of graphene patterns by laser direct writing , 2011 .

[47]  Tarek Lutz,et al.  Nanoscale mapping of electrical resistivity and connectivity in graphene strips and networks. , 2011, Nano letters.

[48]  M. Dresselhaus,et al.  Perspectives on carbon nanotubes and graphene Raman spectroscopy. , 2010, Nano letters.

[49]  R. Palmer,et al.  Ultrafast laser ablation of graphite , 2009 .

[50]  Jian‐Hao Chen,et al.  Defect scattering in graphene. , 2009, Physical review letters.

[51]  Ying Ying Wang,et al.  Uniaxial strain on graphene: Raman spectroscopy study and band-gap opening. , 2008, ACS nano.

[52]  A. Ferrari,et al.  Raman spectroscopy of graphene and graphite: Disorder, electron phonon coupling, doping and nonadiabatic effects , 2007 .

[53]  M. I. Katsnelson,et al.  On the roughness of single- and bi-layer graphene membranes , 2007, cond-mat/0703033.

[54]  J. Coates Interpretation of Infrared Spectra, A Practical Approach , 2006 .

[55]  G. Sulaiman,et al.  Preparation and characterization of graphene sheet prepared by laser ablation in liquid , 2020, Materials Today: Proceedings.

[56]  D. Kochuev,et al.  Mechanisms of graphene exfoliation under the action of femtosecond laser radiation in liquid nitrogen , 2018 .

[57]  Y. Nishina,et al.  Chemical surface modification of graphene oxide by femtosecond laser pulse irradiation in aqueous suspensions , 2016, Journal of Materials Science.

[58]  Yuan Zhang,et al.  Study of reduced graphene oxide preparation by hummers’ method and related characterization , 2015 .

[59]  Jannik C. Meyer Transmission electron microscopy (TEM) of graphene , 2014 .

[60]  M. Wall The Raman Spectroscopy of Graphene and the Determination of Layer Thickness , 2011 .

[61]  B. Fultz,et al.  Transmission electron microscopy and diffractometry of materials , 2001 .

[62]  S. Akhtar,et al.  $gamma$ RADIOLYSIS OF LIQUID ETHANOL. YIELDS OF HYDROGEN AND FREE IONS. SOLVATED ELECTRON RATE CONSTANTS. , 1971 .