Graphene Art - ACS Applied Nano Materials (ACS Publications)

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Graphene Art Yieu Chyan, Joseph Cohen, Winston Wang, Chenhao Zhang, and James M. Tour ACS Appl. Nano Mater., Just Accepted Manuscript • DOI: 10.1021/acsanm.9b00391 • Publication Date (Web): 23 Apr 2019 Downloaded from http://pubs.acs.org on April 23, 2019

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ACS Applied Nano Materials

Graphene Art Yieu Chyan,† Joseph Cohen, † Winston Wang,† Chenhao Zhang,† and James M. Tour‡†§,* †

Department of Chemistry, ‡Smalley-Curl Institute and NanoCarbon Center, §Department of

Materials Science and NanoEngineering, Rice University, 6100 Main Street, Houston, Texas 77005, USA *Email: [email protected]

Abstract Though carbon materials have long been applied to paper to convey meaning through images, the carbon that constitutes the paper remains in the form of a carbohydrate. Here we transform the carbohydrate carbons of paper into graphene for symbolic production and we term this graphene art. By using a commercial CO2 laser scriber as found in most machine shops, laserinduced graphene is generated from the paper to provide the requisite pattern reproduction. The graphene on paper is electrically conductive, permitting paper-based electronics.

Keywords paper, laser-induced graphene, art, black pigments, paper LIG circuits

Carbon has a long history of being used as a black pigment such as in charcoal cave drawings dating back nearly 30,000 years.1 India ink, consisting of a colloidal suspension of carbon black, often derived from soot, is still used today in art. In fact, many different forms of carbon have been used in art to make dark traces on paper. This includes the amorphous carbon found in India inks, the graphite found in pencils, and most recently even carbon nanotubes as in Vantablack.2 We report here that by using a laser-induction process, rather than the carbon material

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being applied to the paper, the carbohydrate materials of the paper substrate itself is directly converted into black-colored graphene foam. For centuries, paper has served as a substrate for the carbon markings used to convey meaning from one person to another. Paper is a robust platform for written or printed letters, symbols, and images that can represent abstract concepts and ideas. Using commonly available CO2 laser cutters found in many machine shops, we developed the laser-induced graphene (LIG) process to generate graphene from a wide variety of substrates using the rapid laser patterning built into the ubiquitous scribing tools.3 These substrates upon which LIG can form include numerous polymer films, wood, cotton, cardboard, and paper. Here, many forms of carbon materials can be photothermalized in milliseconds, in air, into LIG. This has led to a proliferation of applications for graphene including in sensors,4 antibacterial surfaces,5 supercapacitors,6 catalysts,7,8 and more.9,10 Repeatedly exposing the carbon material to additional laser pulses causes it to be rapidly heated to >2000°C and rapidly cooled until it forms a nanomaterial with atomically thin sheet structures stacking into foams.9,10 At the same time, digital control via computerized rastering of the laser beam allows for patterns to be generated in one step. Here, we explore the use of laser production of graphene to afford an artistic pattern from paper. As we recently reported, paper that has been treated with fire retardant can be converted to graphene by exposure to laser irradiation in air.11 Typically, white paper consists primarily of cellulose and hemicellulose and will burn at a relatively low temperature (~230 °C) if it has not been treated with a fire retardant. Adding a fire retardant, such as a phosphate or boron-based compound, will reduce the ablation of the paper and allow for the formation of an amorphous carbon char that can be converted to graphene upon multiple lasing pulses, which occurs in milliseconds through overlapping of laser pulses.11 Phosphorylation or borylation of the cellulose


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by the fire retardants is known to catalyze the dehydration and oxygen-elimination reaction reactions of cellulose resulting in an amorphous char high in aromatic content.

Figure 1. Schematic of lasing fire-retardant treated paper vs cellulose pyrolysis. Cellulose treated with a fire-retardant result in an amorphous char whereas untreated cellulose is first typically converted to levoglucosan and then to various volatile products.

This method allows for large areas of a paper surface to be converted to graphene by the laser-induction process. This conversion and patterning of the paper into graphene can be achieved in one step without requiring time and labor-intensive patterning and transfer processes. Using this method, 30-cm portraits of the Nobel laureates Andre Geim and Konstantin Novoselov were generated by LIG on paper (Figure 2).



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Figure 2. Portraits of (a) Andre Geim and (b) Konstantin Novoselov in LIG on boric-acid-treated paper. The carbohydrates of the paper were converted into graphene foam in the darkened areas.

The structure of the LIG obtained is critical to its optical properties. Typically, color is generated chemically in which different pigments absorb different wavelengths of light based on the optical properties of the constituent materials. By contrast, the properties of nanomaterials derive part of their color not merely from the composition but also from their structure. While the chemical bonding of the carbon in graphite is the same as that in graphene, the sheets of sp2 carbon in pencil lead are arranged differently from that of LIG. Rather than being stacked on top of each other, LIG consists of flakes of few layer turbostratic graphene that is randomly oriented to obtain a porous structure. This yields the black color of the LIG as compared with the more grayish color of graphite pencil marks. The microstructure is shown in Figure 3, in which scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images of paper-derived LIG are found. Figure 3a depicts unlased art paper that was flame retarded with boric acid and Figure 3b4 ACS Paragon Plus Environment

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c depict the same paper after lasing. This shows the conversion of the cellulosic fibers into flakes of porous graphene. As with LIG-derived from polyimide, morphology of the LIG can vary depending on the lasing conditions.11

Figure 3. a) SEM image of unlased paper treated with boric acid; b) SEM image after lasing at 10% speed 7% duty cycle (see Experimental Section. c) TEM image of LIG derived from boricacid-treated paper.



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Raman spectroscopy (Figure 4) confirms that the material is indeed graphene with the characteristic 2D peaks at ~2700 cm-1. The D to G ratio of approximately 1 shows that the graphene derived from fire retardant treated paper is more defective than that obtained from lasing polyimide or a material with high lignin content such as cork.11 The relatively small 2D to G ratio is consistent with few-layer bent graphene sheets rather than with single-layer graphene.12 In accord with the Raman spectra, the resistance of LIG traces can be as low as ~40 ohms/sq.

Figure 4. Raman spectrum of LIG derived from boric-acid-treated paper lased twice at 10% speed and 3% duty cycle.11


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In addition to the portraits, other artwork has also been made using the LIG process. A work entitled “Where do I stand?” was made from patterning the formation of LIG on paper. This is a computer-generated work inspired by the hexagonal lattice of graphene (Figure 5). Of note is



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the size of the work (~3700 cm2) showing that it is possible to make a large artwork using this nanomaterial formation process.

Figure 5. (a) A geometrical pattern based on overlapping hexagons by co-author Joseph Cohen printed in LIG on paper pre-treated with commercial phosphate-based fire retardant, entitled 8 ACS Paragon Plus Environment

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“Where do I stand?” (Photo by Joseph Cohen) (b) Exhibition at the Bioscience Research Collaborative at Rice University with the LIG graphene work on the left and TEM (top) and SEM (bottom) micrographs on the right (TEM image by co-author Chenhao Zhang; SEM image by coauthor Yieu Chyan; photo of the exhibition by co-author Joseph Cohen).

LIG is conductive unlike other amorphous forms of carbon made by charring paper. By lasing FeCl3-treated paper, for example, it is possible to make circuitry on paper allowing for an LED to be lit (Figure 6). The starting FeCl3-treated paper did not have this conductive property with sheet resistances multiple orders of magnitude higher (megaohms/sq vs ~40 ohms/sq).11

Figure 6. A simple paper-based circuit consisting of an LIG trace on FeCl3-treated paper. Folding the paper over to contact the coin-cell battery closes the circuit and lights the green LED.

Conclusion LIG is a departure from the typical exogenous addition of black pigments to paper, or even the traditional combustion of paper to amorphous carbon. Here the paper cellulose is converted in milliseconds to graphene. Moreover, as the LIG patterns are conductive, additional new types of artwork integrating electronics on paper are possible. The application of the LIG process to paper



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substrates allows for an inexpensive and facile method to obtain nanomaterials, allowing for the application of this material in artistic endeavors as well as in paper-based electronic circuits.

Experimental Section LIG from Paper by Multiple Lasing. Arches 140-lb cold-pressed 100% cotton fiber watercolor paper was converted to graphene by lasing with a XLS10MWH (Universal Laser Systems) laser platform using the 10.6 µm CO2 pulsed laser (75 W). First, the paper was treated with a fire retardant. Initial works (including for “Where do I stand?) used a phosphate-based commercial fire retardant designed for fabrics (Force Field Fire Guard, Joann’s Fabrics, Houston, TX). Commercial fire-retardant solution was sprayed on the paper and then spread manually using a brush then dried with a hot air gun. Superior results were obtained with an aqueous solution of boric acid (50 g/L) that was prepared with water at 80 °C and brushed on the surface of the paper with either a brush or a gloved hand. Following application of a thin layer of boric acid solution, it is preferable to dry the substrates overnight in a vacuum oven at 60 °C. However, for larger surfaces that did not fit in the oven, a heat gun or hair dryer was used to dry the paper. Finally, paper can be fire-retarded by dipping in a 1 M solution of FeCl3 in acetone prior to lasing. Depending on the size of the work, typically a scan rate of 15 cm/s was used but scan rates of up to 30 cm/s were used to reduce the processing time. The laser was defocused 3.81 mm to obtain multiple lasing as per the method described in our previous report.11 Typically, a laser duty cycle of 1−3% was used during the fabrication of LIG at 15 cm/s whereas powers of between 510% were used at 30 cm/s. The average power of the exposure is determined by the duty cycle (percentage of time the laser is on) and is controlled by the commercial software supplied by Universal Laser Systems.


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Characterization. A 200 kV JEOL 2100F field emission gun TEM was used to obtain the TEM images after scraping the LIG off the paper and sonicating in methanol before being dropped on a lacey carbon TEM grid. Raman microscopy was performed on a Renishaw Raman microscope using 514 nm laser excitation at room temperature attachment. SEM images were taken with a FEI Quanta 400 ESEM FEG.

Acknowledgments We gratefully acknowledge the support of Universal Laser Systems for their generously providing the XLS10MWH laser system with Multiwave Hybrid™ technology that was used for this research. The Universal Laser Systems staff kindly provided helpful advice.

Conflicts. Rice University owns intellectual property on the LIG process. J.M.T. is a stockholder but not an officer or direct, in a company that has licensed rights to the LIG process. Conflicts of interest are mitigated by regular disclosures to the Rice University Office of Sponsored Programs and Research Compliance.

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(10) Ye, R.; James, D. K.; Tour, J. M. Laser-Induced Graphene. Acc. Chem. Res. 2018, 51, 16091620. (11) Chyan, Y.; Ye, R.; Li, Y.; Singh, S. P.; Arnusch, C. J.; Tour, J. M. Laser-Induced Graphene by Multiple Lasing: Toward Electronics on Cloth, Paper, and Food. ACS Nano 2018, 12, 2176–2183. (12) Dimiev, A. M.; Ceriotti, G.; Behabtu, N.; Zakhidov, D.; Pasquali, M.; Saito, R.; Tour, J. M.


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Graphene Art - ACS Applied Nano Materials (ACS Publications)

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