Graphene 101 An Inventor's Guide to Making Graphene

Graphene 101 - An Inventors Guide To Making Graphene

by

Robert Murray-Smith

Copyright 2013 Robert Murray-Smith

Smashwords Edition

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The front cover image was provided by http://graphite.com.co/with kind permission for use with this edition. However, copyright is retained by the company.

Contents

Introduction

History

The Uses of Graphene

What Is Graphene

The Properties of Graphene

Routes To Graphene

Methods of Preparing Graphene at Home

Summary

Short Glossary

FAQs

Sources of Materials

Introduction.

Graphene is a two dimensional material consisting of a single layer of carbon atoms arranged in a honeycomb or chicken wire structure. It is the thinnest material known to man and yet is also one of the strongest materials there is. It conducts electricity as well as copper and is better than all other materials as a conductor of heat. Graphene is almost completely transparent, yet so dense that even the smallest of atoms cannot pass through it.

Being such a fascinating material lots of people are interested in it and it has become something of a mystery that is generally thought of as being something only an expensive lab can produce. This is far from the truth. This book grew out of a series of youtube videos i created to show how graphene could be made in your own home with a minimum of materials and tools. So many people asked me to write it down that I have done just that and the result is here in these pages. If you read the book and watch the videos you too can be making graphene at home and experimenting until your heart is content. I have tried to be as full as possible in my descriptions and videos but inevitably I will have missed something - so please - feel free to contact me via my youtube channel with any question you may have and I will do my best to answer them. My channel is

http://www.youtube.com/user/RobertMurraySmith

see you there.

History.

The creation of graphene is already the stuff of scientific and media legend. It stands alongside the accidental discovery of penicillin by Alexander Fleming – and it it is hoped that it will prove just as valuable.

Two scientists at the University of Manchester, Andrei Geim and Kostya Novoselov, are generally credited with the discovery. The story goes that they were playing about with flakes of carbon graphite in an attempt to investigate its electrical properties when they decided to see if they could make thinner flakes with the help of sticky tape. While all credit must go to Geim and Novoselov for what they did the unusual properties of graphite, it's oxide and graphene predates them by some years.

The earliest reports of graphene oxide (GO) and graphite intercalated compounds (GICs) can be traced back to the 1840s, when the German scientist Schafhaeutl reported the intercalation (that is, insertion of a small molecules, such as an acid or alkali metal, in between the carbon layers of a graphite sample) and then exfoliation of this graphite material with sulphuric and nitric acids.

A wide range of intercalants and exfoliants have been used since that time, including potassium (as well as other alkali metals), fluoride salts of various types, transition metals (iron, nickel, and many others), and various organic compounds like acetic and formic acid.

Intercalation retains the stacked structure of graphite, but the interlayer spacing is widened, often by several angstroms or more, which results in the electronic decoupling of the individual layers. This electronic decoupling leads, in some cases, to intriguing superconductivity effects: a harbinger of the extraordinary electronic properties later demonstrated in freestanding graphene of Geim and Novoselov. The term graphene grew out of the chemistry of GICs as the need for the language to describe the decoupled layers became apparent. (the term graphene was first coined by Boehmetal in 1986.) It was later argued that if the interlayer spacing of GICs could be extended throughout the entire structure, and the small molecule spacers removed, pristine graphene may be obtained.

It was back in 1859, that the British chemist Brodie used what may be recognized as modifications of the methods described by Schafhaeutl in an effort to characterize the molecular weight of graphite by using strong acids (sulphuric and nitric), as well as oxidants, such as KClO. The use of these conditions resulted not only in the intercalation of the layers of graphite, but also in chemical oxidation of its surface, and ultimately in the formation of GO. Chemical modification of the surface of graphite in this manner has proven to be a valuable method for a variety of purposes, including the preparation of GICs, GO, and other similar materials; the preparation of single layer reduced graphene oxide (r-GO); and the use of GO or graphene oxide as chemical oxidants in synthetic reactions.

Fictionalisation of the surface of graphite in this manner lessens the interplanar forces that cause lamellar stacking; thus, these oxidized layers can be readily exfoliated under ultrasonic, thermal, or other energetic conditions. Nearly 40 years later, Staudenmaier reported a slightly different version of the oxidation method used by Brodie for the preparation of GO by adding the chlorate salt in multiple aliquots over the course of the reaction instead of in a single portion.

These intercalation and oxidation experiments are the first examples of the delamination of graphite into single graphene sheets. More over, many of these methods, or modifications of them, are still used today for the preparation of r-GO and other chemically modified graphites (CMGs).

Nearly a century after the studies reported by Brodie, in 1962, Boehm et al. found that the chemical reduction of dispersions of GO in dilute alkaline media with hydrazine,

hydrogen sulfide, or iron(II) salts produced thin sheet carbon that contained only small amounts of hydrogen and oxygen.

The crucial task of determining the number of layers present in the thin sheets was accomplished by densitometry against a set of standardized films of known thickness by using transmission electron microscopy (TEM). The carbon material was found to exhibit a minimum thickness of 4.6 angstroms, which deviates only slightly from the thickness, observed in recent studies (ca. 4 angstroms).

However, electron-micrograph densitometry measurements suffered from a relatively high degree of experimental error associated with variations in the thickness of the calibration standards used as well as unevenness in the photographic emulsions.

Regardless, Boehm concluded that, this observation confirms the assumption that the thinnest of the lamellae really consisted of single carbon layers

In the same 1962 study, similar products were obtained by the thermal deflagration (i.e., exfoliation) of GO. On the basis of the IUPAC definition, it seems that Boehm and his friends isolated r-GO, rather than pristine graphene (i.e., without heteroatomic contamination).

Nevertheless, similar methods are still widely used for the thermal reduction of GO. In a separate study, Morgan and Somorjai used low-energy electron diffraction (LEED) to investigate the adsorption of various gaseous organic molecules (e.g., CO, C2H4,C2H2) onto a platinum surface at high temperature.

After analysing these LEED data, May postulated in 1969 that single, as well as multiple, layers of a material that features a graphitic structure were present as a result of these adsorption processes. He also deduced that the first monolayer of graphite minimizes its energy of placement on each of the studied faces of platinum.

In 1975, van Bommel and his colleagues described the epitaxial sublimation of silicon from single crystals of silicon carbide at elevated temperatures under ultrahigh vacuum (UHV; <10 to minus 10 Torr), monolayered flakes of carbon consistent with the structure of graphene were obtained, as determined by LEED and Auger electron spectroscopy.

Multilayered carbon materials were also found, with the number of layers formed dependent on the experimental conditions employed: at temperatures below 800 degrees C, the SiC largely retained its native structure, whereas an increase in the temperature resulted in the appearance of graphite rings in the LEED pattern.

Moreover, the disappearance of the carbide peak in the Auger spectrum was reported to be coupled to the appearance of a graphite peak. The authors highlighted a graphitisation mechanism proposed by Badami in which three layers of residual carbon collapse onto one another upon sublimation of the silicon to effectively form graphitic sheets.

In the studies that supported this model, Badami determined by X-ray diffraction analysis that when only one or two layers of carbon collapsed, the C-C distance was approximately 1.85. However, upon the collapse of the third layer, the C-C distance decreased to 1.42. This process is consistent with both the predicted and experimentally determined bond lengths in graphene (ca.1.41–1.43 angstroms).

Recent results have shown that it is possible to perform the aforementioned sublimation experiments under much higher pressures than the ultrahigh-vacuum

conditions used by van Bommel.

Under higher pressures, layers of graphene with dimensions of 3–50 micrometers may be obtained, as opposed to dimensions of tens of nanometers when the experiments are carried out under high vacuum.

Aside from epitaxial growth and the chemical/thermal reduction of GO, a unique, recently described method for the isolation of graphene, reduced graphene oxide, or CMGs is micromechanical exfoliation. There are several carbon sources available for this method, including natural graphite, kish graphite (precipitated from molten iron), and highly ordered pyrolytic graphite (HOPG). HOPG is often chosen because of its high atomic purity and smooth surface, which enables the easy delamination of carbon layers as a result of the weak van der Waals forces that hold the layers together.

In 1999, a micromechanical approach was used to obtain thin sheets comprising multiple graphene layers, although these sheets were not fully exfoliated into their respective monolayers.

In this method, lithographic patterning of