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Web Date: June 25, 2013

Using Force To Pattern Organic Compounds On Graphene

Materials Science: Polymer tips push cyclopentadiene-containing inks into graphene, creating covalent linkages between the ink and the two-dimensional material
Department: Science & Technology
News Channels: Materials SCENE, Nano SCENE, Organic SCENE, JACS In C&EN
Keywords: graphene, atomic force microscopy, AFM, cyclopentadiene, Diels Alder reaction, graphene functionalization
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Forced Patterns
An array of polymer tips attached to an atomic force microscope created this pattern of dye dots (orange) on a graphene surface. Researchers coated the tips with an ink containing the dye cyanine3 linked to cyclopentadiene. The inset image shows a magnification of one of these patterns.
Credit: J. Am. Chem. Soc.
Micrograph of graphene surface functionalized with the dye cyanine3.
 
Forced Patterns
An array of polymer tips attached to an atomic force microscope created this pattern of dye dots (orange) on a graphene surface. Researchers coated the tips with an ink containing the dye cyanine3 linked to cyclopentadiene. The inset image shows a magnification of one of these patterns.
Credit: J. Am. Chem. Soc.
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Under Pressure
When a polymer-tip array (over reaction arrow) pushes a cyclopentadiene ink (under reaction arrow) into a graphene surface (left), the force accelerates a Diels-Alder reaction between the ink and the surface. The ink attaches covalently to the graphene (right).
Credit: J. Am. Chem. Soc.
Reaction scheme for Diels-Alder reactions that modify a graphene surface.
 
Under Pressure
When a polymer-tip array (over reaction arrow) pushes a cyclopentadiene ink (under reaction arrow) into a graphene surface (left), the force accelerates a Diels-Alder reaction between the ink and the surface. The ink attaches covalently to the graphene (right).
Credit: J. Am. Chem. Soc.

To fabricate electronic devices that take advantage of graphene’s conductivity and strength, materials scientists first need to chemically modify the material to tweak its other properties. Attaching biomolecules, for instance, could enable new types of sensors, and patterning graphene with impurities would make the material behave like a semiconductor, needed for many electronic devices.

Unfortunately, graphene often resists such functionalization. Now chemists report that a little force does the trick (J. Am. Chem. Soc. 2013, DOI: 10.1021/ja4042077).

A team led by Adam B. Braunschweig at the University of Miami and Kendall N. Houk at the University of California, Los Angeles, attached molecules in patterns on graphene’s surface via Diels-Alder reactions accelerated by pressure. Other researchers had shown that graphene can participate in Diels-Alder reactions either as the diene or the dienophile, the two types of reactants in the ring-forming reaction (J. Am. Chem. Soc. 2011, DOI: 10.1021/ja200118b). It’s also well known that pressure accelerates the Diels-Alder reaction.

So the chemists coated an array of 80-nm-wide polymer tips with inks containing various molecules linked to cyclopentadiene, a classic Diels-Alder reactant. For one of the inks, they attached the dye cyanine3 to cyclopentadiene. The researchers mounted the tip array onto an atomic force microscope and gently pushed the tips into the surface of graphene. The cyclopentadienes reacted with the graphene, resulting in 20 µm by 40 µm patches of graphene decorated with patterns of dye dots.

The technique works at ambient temperatures and pressures, the chemists note. They are now trying to use the method to functionalize graphene with carbohydrates to make biological sensors.

 
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