This material is based upon work supported by a start-up fund at the University of Minnesota, Twin Cities and an NSF CAREER Award (CMMI-1454293). Parts of this work were carried out in the Characterization Facility at the University of Minnesota, a member of the NSF-funded Materials Research Facilities Network (via the MRSEC program. Portions of this work were conducted in the Minnesota Nano Center, which is supported by the National Science Foundation through the National Nano Coordinated Infrastructure Network (NNCI) under Award Number ECCS-1542202. C. D. acknowledges support from the 3M Science and Technology Fellowship.

CAUTION: Several of the chemicals used in these syntheses are toxic and may cause irritation and severe organ damage when touched or inhaled. Please use appropriate safety equipment and wear personal protective equipment when handling the chemicals.
1. Preparation of Aluminum Oxide and Chromium Protection Layers on a Copper Sacrificial Layer
<ol>
	<li>Using an electron-beam evaporator, deposit 10 nm thick chromium (Cr) and 300 nm thick copper (Cu) layers (sacrificial layer) on the silicon (S...

<ol>
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S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electromechanical+resonators+from+graphene+sheets.">Electromechanical resonators from graphene sheets.</a> Science. 315 (5811), 490-493 (2007).</li><li>Menaa, F., Abdelghani, A., Menaa, B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Graphene+nanomaterials+as+biocompatible+and+conductive+scaffolds+for+stem+cells:+impact+for+tissue+engineering+and+regenerative+medicine.">Graphene nanomaterials as biocompatible and conductive scaffolds for stem cells: impact for tissue engineering and regenerative medicine.</a> Journal of Tissue Engineering and Regenerative. 9 (12), 1321-1338 (2015).</li><li>Han, M. Y., &#214;zyilmaz, B., Zhang, Y., Kim, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Energy+band-gap+engineering+of+graphene+nanoribbons.">Energy band-gap engineering of graphene nanoribbons.</a> Physical Review Letters. 98 (20), 206805 (2007).</li><li>Son, Y. W., Cohen, M. L., Louie, S. 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K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Graphene+kirigami.">Graphene kirigami.</a> Nature. 524 (7564), 204-207 (2015).</li><li>Michael Cai, W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanical+instability+driven+self-assembly+and+architecturing+of+2D+materials.">Mechanical instability driven self-assembly and architecturing of 2D materials.</a> 2D Materials. 4 (2), 022002 (2017).</li><li>Shenoy, V. B., Gracias, D. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Self-folding+thin-film+materials:+From+nanopolyhedra+to+graphene+origami.">Self-folding thin-film materials: From nanopolyhedra to graphene origami.</a> MRS Bulletin. 37 (9), 847-854 (2012).</li><li>Zhu, S., Li, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hydrogenation-Assisted+Graphene+Origami+and+Its+Application+in+Programmable+Molecular+Mass+Uptake,+Storage,+and+Release.">Hydrogenation-Assisted Graphene Origami and Its Application in Programmable Molecular Mass Uptake, Storage, and Release.</a> ACS Nano. 8 (3), 2864-2872 (2014).</li><li>Zhang, L., Zeng, X., Wang, X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Programmable+hydrogenation+of+graphene+for+novel+nanocages.">Programmable hydrogenation of graphene for novel nanocages.</a> Scientific Reports. 3, 3162 (2013).</li><li>Vickery, J. L., Patil, A. J., Mann, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fabrication+of+Graphene-Polymer+Nanocomposites+With+Higher-Order+Three-Dimensional+Architectures.">Fabrication of Graphene-Polymer Nanocomposites With Higher-Order Three-Dimensional Architectures.</a> Advanced Materials. 21 (21), 2180-2184 (2009).</li><li>Yang, X., Zhu, J., Qiu, L., Li, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Bioinspired+effective+prevention+of+restacking+in+multilayered+graphene+films:+towards+the+next+generation+of+high-performance+supercapacitors.">Bioinspired effective prevention of restacking in multilayered graphene films: towards the next generation of high-performance supercapacitors.</a> Advanced Materials. 23 (25), 2833-2838 (2011).</li><li>Choi, B. G., Yang, M., Hong, W. H., Choi, J. W., Huh, Y. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=3D+macroporous+graphene+frameworks+for+supercapacitors+with+high+energy+and+power+densities.">3D macroporous graphene frameworks for supercapacitors with high energy and power densities.</a> ACS Nano. 6 (5), 4020-4028 (2012).</li><li>Niu, Z., Chen, J., Hng, H. H., Ma, J., Chen, X. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=A+leavening+strategy+to+prepare+reduced+graphene+oxide+foams.">A leavening strategy to prepare reduced graphene oxide foams.</a> Advanced Materials. 24 (30), 4144-4150 (2012).</li><li>Li, Y., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Growth+of+conformal+graphene+cages+on+micrometre-sized+silicon+particles+as+stable+battery+anodes.">Growth of conformal graphene cages on micrometre-sized silicon particles as stable battery anodes.</a> Nature Energy. 1 (2), (2016).</li><li>Cho, J. H., Gracias, D. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Self-Assembly+of+Lithographically+Patterned+Nanoparticles.">Self-Assembly of Lithographically Patterned Nanoparticles.</a> Nano Letters. 9 (12), 4049-4052 (2009).</li><li>Cho, J. H., Azam, A., Gracias, D. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Three+Dimensional+Nanofabrication+Using+Surface+Forces.">Three Dimensional Nanofabrication Using Surface Forces.</a> Langmuir. 26 (21), 16534-16539 (2010).</li><li>Dai, C., Cho, J. 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G., Liu, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Thermal+stability+of+SU-8+fabricated+microstructures+as+a+function+of+photo+initiator+and+exposure+doses.">Thermal stability of SU-8 fabricated microstructures as a function of photo initiator and exposure doses.</a> Proceedings of SPIE. 4980, 209 (2003).</li><li>Winterstein, T., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=SU-8+electrothermal+actuators:+Optimization+of+fabrication+and+excitation+for+long-term+use.">SU-8 electrothermal actuators: Optimization of fabrication and excitation for long-term use.</a> Micromachines. 5 (4), 1310-1322 (2014).</li><li>Syms, R. R. A., Yeatman, E. M., Bright, V. M., Whitesides, G. 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For the cubes fabricated with CVD graphene, because each face of a given cube is designed with an outer frame surrounding a ~160 &#215; 160 &#181;m2 area of free-standing graphene, a single sheet of monolayer graphene does not have the necessary strength to permit parallel processing of the cubes. For this reason, graphene membranes consisting of three layers of CVD graphene monolayer sheets are produced via three separate graphene transfers using multiple PMMA coating/removal steps. On the other hand...

Two-dimensional (2D) graphene sheets possess extraordinary optical, electronic, and mechanical properties, making them model systems for the observation of novel quantum phenomena for next-generation electronic, optoelectronic, electrochemical, electromechanical, and biomedical applications1,2,3,4,5,6. Apart from the as-produced 2D layered structure of graphene, recently, various modification approaches have been investigated to observe new functionalities of graphene and seek new application opportunities. For example, modulating (or tuning) its physical properties (i.e.,&#160;doping level and/or band gap) by tailoring the shapes or patterning of the 2D structure to a one-dimensional (1D) or zero-dimensional (0D) structure (e.g., graphene nanoribbon or graphene quantum dots) has been studied to obtain new physical phenomena including quantum confinement effects, localized plasmonic modes, localized electron distribution, and spin-polarized edge states7,8,9,10,11,12. In addition, varying the texture of 2D graphene by crumpling (often called kirigami), delamination, buckling, twisting, or stacking of multiple layers, or changing the graphene surface shape by transferring 2D graphene on top of a 3D feature (substrate) has been shown to change the graphene&#39;s wettability, mechanical characteristics, and optical properties13,14.
Beyond changing the surface morphology and layered structure of 2D graphene, assembly of 2D graphene into functionalized, well-defined, three-dimensional (3D) polyhedrons has been of great interest recently in the graphene community to obtain new physical and chemical phenomena15. In theory, the elastic, electrostatic, and van der Waals energies of 2D graphene-based structures can be leveraged to transform the 2D graphene into various 3D graphene-origami configurations16,17. Based on this concept, theoretical modeling studies have investigated 3D graphene structure designs, formed from nanoscale 2D graphene membranes, with possible uses in drug delivery and general molecular storage16,17.&#160;Yet, the experimental progress of this approach is still far from realizing these applications. On the other hand, a number of chemical synthetic methods have been developed to achieve 3D structures via template-assisted assembly, flow-directed assembly, leavening assembly, and conformal growth methods18,19,20,21,22. However, these methods are currently limited in that they cannot produce a 3D, hollow, enclosed structure without losing the intrinsic properties of the graphene sheets.
Here, a strategy for building 3D, hollow, graphene-based microcubes (overall dimension of ~200 &#181;m) by using origami-like self-folding is outlined; overcoming the foremost challenges in the construction of free-standing, hollow, 3D, polyhedral, graphene-based materials. In origami-like, hands-free self-folding techniques, 2D lithographically patterned planar features (i.e.,&#160;graphene-based membranes) are connected with hinges (i.e.,&#160;thermal-sensitive polymer, photoresist) at various joints, thereby forming 2D nets which fold up when the hinges are heated to melting temperature23,24,25,26. The graphene-based cubes are realized with window membrane components composed of a few layers of chemical vapor deposition (CVD) grown graphene or graphene oxide (GO) membranes; both with the use of polymer frames and hinges. The fabrication of the 3D graphene-based cubes involves: (i) preparation of protection layers, (ii) graphene-membrane transfer and patterning, (iii) metal surface patterning on graphene-membranes, (iv) frame and hinges patterning and deposition, (v) self-folding, and (vi) removal of the protection layers (Figure 1). This article focuses mostly on the self-folding aspects of the 3D graphene-based cubes fabrication. Details on physical and optical properties of the 3D graphene-based cubes can be found in our other recent publications27,28.

<table border="0" cellpadding="0" cellspacing="0" style="width:1315px;" width="1313">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Acetone</td>
			<td style="width:295px;">Fisher Chemical</td>
			<td style="width:199px;">A18P-4</td>
			<td style="width:511px;">N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Aluminium oxide</td>
			<td style="width:295px;">Kurt J. Lesker Company</td>
			<td style="width:199px;">EVMALO-1-2.5</td>
			<td>99.99% Pure</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">APS Copper Etchant 100</td>
			<td style="width:295px;">Transene Company, Inc.</td>
			<td style="width:199px;">N/A</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Camera (for 3D image)</td>
			<td style="width:295px;">Nikon</td>
			<td style="width:199px;">D5100</td>
			<td>1080p Full HD, Effective pixels: 16.2 million, Sensorsize: 23.6 mm x 15.6 mm</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">CE-5 M Chromium Mask Etchant</td>
			<td style="width:295px;">Transene Company, Inc.</td>
			<td style="width:199px;">N/A</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Chemical deposition growth (CVD) system</td>
			<td style="width:295px;">Customized</td>
			<td style="width:199px;">N/A</td>
			<td>Lindberg/Blue Tube Furnace</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Chromium</td>
			<td style="width:295px;">Kurt J. Lesker Company</td>
			<td style="width:199px;">EVMCR35J</td>
			<td>99.95% pure</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Chromium Etchant 473</td>
			<td style="width:295px;">Transene Company, Inc.</td>
			<td style="width:199px;">N/A</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Copper</td>
			<td style="width:295px;">Kurt J. Lesker Company</td>
			<td style="width:199px;">EVMCU40QXQJ</td>
			<td>99.99% pure</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Developer-1 (MF319 developer)</td>
			<td style="width:295px;">Microposit</td>
			<td style="width:199px;">10018042</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Developer-2 (AZ developer)</td>
			<td style="width:295px;">Merck performance Materials Corp.</td>
			<td style="width:199px;">1005422496</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Developer-3 (SU-8 developer)</td>
			<td>MicroChem</td>
			<td style="width:199px;">NC9901158</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Digital Hot Plate</td>
			<td style="width:295px;">Thermo Scientific</td>
			<td style="width:199px;">HP131725</td>
			<td>Super-Nuvoa series, maximum temperature: 370 &#176;C</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">E-Beam Evaporator System</td>
			<td style="width:295px;">Rocky Mountain Vacuum Tech.</td>
			<td style="width:199px;">N/A</td>
			<td>RME-2000</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Graphene oxide</td>
			<td style="width:295px;">Goographene</td>
			<td style="width:199px;">N/A</td>
			<td>Purity: ~ 99%; Single layer ratio: ~99%;&#160; 0.7-1.2 nm in thickness.</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Isopropyl Alcohol</td>
			<td style="width:295px;">Fisher Chemical</td>
			<td style="width:199px;">A416-4</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Mask Aligner</td>
			<td style="width:295px;">Midas</td>
			<td style="width:199px;">MDA-400LJ</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Microscope</td>
			<td style="width:295px;">Omax</td>
			<td style="width:199px;">NJF-120A</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">multiple polymethyl methacrylate (PMMA)</td>
			<td style="width:295px;">MicroChem</td>
			<td style="width:199px;">950 PMMA A9</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Oxygen plasma&#160;</td>
			<td style="width:295px;">Technics Inc.</td>
			<td style="width:199px;">SERIES 800</td>
			<td>Microscale reactive ion etching (RIE)</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Photoresist-1 (S1813 Photoresist)</td>
			<td style="width:295px;">Microposit</td>
			<td style="width:199px;">10018348</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Photoresist-2 (SPR220 Photoresist)</td>
			<td style="width:295px;">MicroChem</td>
			<td style="width:199px;">SPR00220-7G</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Photoresist-3 (SU-8 Photoresist)</td>
			<td>MicroChem</td>
			<td style="width:199px;">SU-8-2010</td>
			<td>N/A</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Profilometer</td>
			<td style="width:295px;">Tencor Instruments</td>
			<td style="width:199px;">N/A</td>
			<td>Alpha-Step 200</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Raman</td>
			<td style="width:295px;">WITec Instruments Corp.</td>
			<td style="width:199px;">Alpha300R</td>
			<td>Confocal Raman Microscope</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Silicon Wafer</td>
			<td style="width:295px;">Siltronic AG</td>
			<td style="width:199px;">N/A</td>
			<td>100mm diameter, N-type, one-side polish, resitivity: 560-840 &#937;&#8226;cm</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Spinner</td>
			<td style="width:295px;">Best Tools</td>
			<td style="width:199px;">S0114031123</td>
			<td>SMART COATER 100</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Titanium</td>
			<td style="width:295px;">Kurt J. Lesker Company</td>
			<td>EVMTI45QXQA</td>
			<td>99.99% Pure</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:311px;">Ultrasonic Cleaner</td>
			<td style="width:295px;">Crest Ultrasonics</td>
			<td style="width:199px;">N/A</td>
			<td>Powersonic series</td>
		</tr>
	</tbody>
</table>

fabrication of three-dimensional graphene-based polyhedrons via origami-like self-folding

The assembly of two-dimensional (2D) graphene into three-dimensional (3D) polyhedral structures while preserving the graphene's excellent inherent properties has been of great interest for the development of novel device applications. Here, fabrication of 3D, microscale, hollow polyhedrons (cubes) consisting of a few layers of 2D graphene or graphene oxide sheets via an origami-like self-folding process is described. This method involves the use of polymer frames and hinges, and aluminum oxide/chromium protection layers that reduce tensile, spatial, and surface tension stresses on the graphene-based membranes when the 2D nets are transformed into 3D cubes. The process offers control of the size and shape of the structures as well as parallel production. In addition, this approach allows the creation of surface modifications by metal patterning on each face of the 3D cubes. Raman spectroscopy studies show the method allows the preservation of the intrinsic properties of the graphene-based membranes, demonstrating the robustness of our method.

Figure 2&#160;displays optical images of the lithographic processes of the 2D graphene and GO net structures and subsequent self-folding process. The self-folding process is monitored in real-time via a high-resolution microscope. Both types of 3D graphene-based cubes are folded at ~80 &#176;C. Figure 3 lays out video captured sequences showing the self-folding of 3D graphene-based cubes in a parallel manner. Under an op...

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Fabrication of Three-Dimensional Graphene-Based Polyhedrons via Origami-Like Self-Folding

Here, we present a protocol for fabrication of 3D graphene-based polyhedrons via origami-like self-folding.

Fabrication of Three-Dimensional Graphene-Based Polyhedrons via Origami-Like Self-Folding

The assembly of two-dimensional (2D) graphene into three-dimensional (3D) polyhedral structures while preserving the graphene's excellent inherent ...

This protocol uses origami-like self-folding methods to create 3D graphene-based polyhedrons. Two-dimensional graphene sheets possess extraordinary optical, electronic, and mechanical properties. By tailoring the shape of two-dimensional graphene, its physical, chemical, and optical properties can be tuned, which can introduce new material behaviors, allowing new application opportunities.In this regard, integrating 2D graphene into the structures of functionalized, well-defined, three-dimensional polyhedrons has been of great interest recently in the graphene community. 3D graphene polyhedrons may be beneficial for many applications. Examples include gas and water-protected containers, molecular storage, delivery systems, encapsulation of liquid-based materials, for easy to observation in electron microscopy, functional optoelectronic devices, and matter materials.A number of chemical routes for the production of 3D graphene-based structures have been introduced. However, these methods typically require strong chemical reactions, which affect the intrinsic properties of the graphene and present challenges in the construction of free-standing, hollow, 3D graphene polyhedrons. To overcome these limitations, this study shows a methodology for realizing multi-faced 3D microcubes with 2D graphene and graphene oxide by using origami-like self-folding.To help give context to the overall fabrication process of the 3D graphene-based cubes, a simplified six-step overview will now be introduced prior to the detailed protocol. First, prepare the protection layers. Then, perform graphene-membrane transfer in patterning onto the protection layers.Then, create metal surface patterning on the graphene membranes. Next, define polymer frames and hinges. Then, transform the 2D nets into 3D cubes via self-folding.Lastly, remove the protection layers. Using an electron beam evaporator, deposit 10 nanometer-thick chromium and 300 nanometer-thick copper layers on the silicon substrate. Spin coat photoresist at 2500 RPM followed by baking at 115 degrees Celsius for 60 seconds.Expose the designed 2D net areas to UV light on a contact mask aligner for 15 seconds and then develop for 60 seconds in developer. Rinse the sample with deionized water and blow-dry with an air gun. Deposit a 10 nanometer-thick chromium layer and lift off the remaining photoresist in acetone.Rinse the sample with deionized water and blow-dry with an air gun. To pattern 2D nets with six-square aluminum oxide and chromium protection layers on the nets, spin coat photoresist at 2, 500 RPM followed by baking at 115 degrees Celsius for 60 seconds. Expose the designed six-square protection layers to UV light on a contact mask aligner for 15 seconds and develop for 60 seconds in developer.Rinse the sample with deionized water and blow-dry with an airgun. Deposit a 100 nanometer-thick aluminum oxide layer in a 10 nanometer-thick chromium layer. Remove the remaining photoresist in acetone.Rinse the sample with deionized water and blow-dry with an airgun. Starting with the 15 millimeter square piece of graphene adhered on copper foil, spin coat a thin PMMA layer at 3000 RPM on the surface of the graphene. Bake at 180 degrees Celsius for 10 minutes.Place the PMMA graphene in copper foil-layered sheet, floating copper-side down in copper etchant for 24 hours to etch away the copper foil. After the copper foil is completely dissolved, leaving PMMA in graphene, transfer the floating PMMA-coated graphene onto the surface of a pool of deionized water using a microscope slide glass to remove any copper etchant residue. Repeat the transfer of the PMMA-coated graphene onto new deionized water pools several times to adequately rinse.Transfer the floating PMMA-coated graphene onto another piece of graphene adhered on copper foil to obtain a bilayer graphene membrane. Thermally treat the double-layer graphene on copper foil on a hot plate at 100 degrees Celsius for 10 minutes. Remove the PMMA on top of the double-layer graphene on the copper foil in an acetone bath, leaving a graphene, graphene, and copper foil layer stack, followed by transferring to deionized water.Repeat the graphene transfer one more time to get three stacked layers of graphene membranes. Place the PMMA, graphene, graphene, graphene, and copper foil layered sheet, floating copper side down in copper etchant for 24 hours to etch away the copper foil. Transfer the PMMA-coated three layers of graphene membranes onto the pre-fabricated aluminum oxide and chromium protection layers.After transfer of the graphene, remove the PMMA with acetone. Then, dip the sample in deionized water and dry in air. Thermally treat the multi-layer graphene on the substrate on a hot plate at 100 degrees Celsius for one hour.Spin coat photoresist at 2500 RPM and bake at 115 degrees Celsius for 60 seconds. UV expose the regions of photoresist directly above the square protection layer areas using a contact mask aligner for 15 seconds. Then develop for 60 seconds.Remove the newly-uncovered unwanted graphene areas via an oxygen plasma treatment for 15 seconds. Remove the leftover photoresist in acetone. Rinse the sample with deionized water and dry in air.Spin coat photoresist at 1700 RPM for 60 seconds on top of the previously fabricated aluminum oxide and chromium protection layers to obtain a 10 micrometer thick layer. Bake the photoresist at 115 degrees Celsius for 60 seconds and then wait for three hours. With the same mask used for patterning the aluminum oxide and chromium layers, UV expose the sample on a contact mask aligner for 80 seconds and develop for 90 seconds.Rinse the sample with deionized water and blow-dry with an air gun. Perform a UV flood exposure of the entire sample without a mask for 80 seconds. Spin coat the prepared graphene oxide and water mixture on the sample at 1000 RPM for 60 seconds.Perform the spin coating a total of three times. Dip the sample in developer to allow lift-off of unwanted graphene oxide. The lift-off process under a microscope is shown here with the footage accelerated.Rinse the sample with deionized water and carefully blow-dry the sample with an air gun. Thermally treat the sample on a hot plate at 100 degrees Celsius for one hour. Create 20 nanometer-thick titanium patterns on top of the patterned graphene-based membranes.Thermally treat the sample on a hot plate at 100 degrees Celsius for one hour. On top of the graphene-based membranes with titanium surface patterns, spin coat photoresist at 2500 RPM for 60 seconds to form a five micrometer-thick layer and bake at 90 degrees Celsius for two minutes. UV-expose the samples for 20 seconds, bake at 90 degrees Celsius for three minutes, and develop for 90 seconds.Rinse the sample with deionized water and isopropyl alcohol, and carefully blow-dry the sample with an air gun. Post-bake the samples at 200 degrees Celsius for 15 minutes to enhance the mechanical stiffness of frames. To make the hinge pattern, spin coat photoresist at 1000 RPM for 60 seconds to form a 10 micrometer-thick film on top of the prefabricated substrate.Bake at 115 degrees Celsius for 60 seconds and wait for three hours. UV-expose the sample on a contact mask aligner for 80 seconds and develop for 90 seconds. Rinse the sample with deionized water and carefully blow-dry the sample with an air gun.To release the 2D structures, dissolve the copper sacrificial layer under the 2D nets in a copper etchant. Carefully transfer the released structures into a deionized water bath by using a pipette and rinse a few times to remove the residual copper etchant. Place the 2D structures in deionized water, heated above the melting point of the polymer hinges.Monitor the self-folding in real time via optical microscopy and remove from the heat source upon successful assembly into closed cubes. After self-folding, remove the aluminum oxide and chromium protection layers with chromium etchant. Gently transfer the cubes into a deionized water bath and carefully rinse.The optical images show the lithographic processes of the 2D graphene and graphene oxide net structures and the subsequent self-folding process. The self-folding process is monitored in real time via a high-resolution microscope. Both types of 3D graphene-based cubes are folded at about 80 degrees Celsius.The figures lay out video-captured sequences showing the self-folding of 3D graphene-based cubes in a parallel manner. Under an optimized process, this approach shows a highest yield of approximately 90 percent. The figures show optical images of the 3D assembled graphene and graphene oxide-based cubes with and without surface patterns.The overall size of the self-folded cubes is 200 micrometers wide by 200 micrometers long by 200 micrometers high. 20 nanometer-thick titanium-patterned features and UMN lettering are defined on each face of the 3D graphene-based cubes. The figures include Raman spectroscopy of 2D graphene-based nets and 3D graphene-based cubes.The results show no noticeable changes in Raman peak position and intensity for both graphene and graphene oxide membranes after the self-folding. However, when protection layers are not used, noticeable changes in relative peak intensities were observed, indicating changes or damage to the properties of the graphene during the self-folding. This method allows the development of biomedical, electronic, and optical devices, including sensors and electric circuits using the numerous advantages of 3D configurations.Furthermore, since the process uses an early image to only graphene-based materials, this method may be applied to other two-dimensional material, such as tren-ja-men-a ai chai-hus knives and black passports, thereby allowing this opportunity to be used in developing next-generation 3D configurations of 2D materials.

fabrication-three-dimensional-graphene-based-polyhedrons-via-origami

Research

JoVE Journal

Engineering

8.8K vistas.  University of Minnesota, Minneapolis, United States. Este protocolo utiliza métodos de plegado automático similares al origami para crear poliedros basados en grafeno 3D. Las láminas bidimensionales de grafeno poseen extraordinarias propiedades ópticas, electrónicas y mecánicas. Al adaptar la forma del grafeno bidimensional, se pueden ajustar sus propiedades físicas, químicas y ópticas, lo que puede introducir nuevos comportamientos de materiales, lo que permite nuevas oportunidades de aplicación.En este sentido, la integració...