History of graphene

Konstantin Novoselov (left) and Andre Geim (right) at a 2010 Nobel Prize press conference A lump of graphite, a graphene transistor, and a tape dispenser, a tool that was used for the exfolitation of single-layer graphene from graphite in 2004. Donated to the Nobel Museum in Stockholm by Andre Geim and Konstantin Novoselov in 2010.

Single-layer graphene was explored theoretically by P. R. Wallace in 1947. It was first unambiguously produced and identified in 2004, by the group of Andre Geim and Konstantin Novoselov, though they credit Hanns-Peter Boehm and his co-workers for the experimental discovery of graphene in 1962.[1][2] Boehm et al. introduced the term graphene in 1986.[3][4]

## Contents

* 1 Early history
* 2 Naming
* 3 Discovery
* 4 Commercialization
* 5 References

## Early history

In 1859 Benjamin Collins Brodie became aware of the highly lamellar structure of thermally reduced graphite oxide.[5][6]

The structure of graphite was identified in 1916[7] by the related method of powder diffraction.[8] It was studied in detail by Kohlschütter and Haenni in 1918, who described the properties of graphite oxide paper.Cite error: Closing `</ref>` missing for `<ref>` tag[9] The emergent massless Dirac equation was first pointed out by Gordon W. Semenoff, David DiVincenzo and Eugene J. Mele.[10] Semenoff emphasized the occurrence in a magnetic field of an electronic Landau level precisely at the Dirac point. This level is responsible for the anomalous integer quantum Hall effect.[11][12][13]

The earliest TEM images of few-layer graphite were published by G. Ruess and F. Vogt in 1948.[14] Later, single graphene layers were observed directly by electron microscopy.[15] Before 2004 intercalated graphite compounds were studied under a transmission electron microscope (TEM). Researchers occasionally observed thin graphitic flakes ("few-layer graphene") and possibly even individual layers. An early, detailed study on few-layer graphite dates to 1962 when Boehm reported producing monolayer flakes of reduced graphene oxide.[16][17][18][19]

Starting in the 1970s single layers of graphite were grown epitaxially on top of other materials.[20] This "epitaxial graphene" consists of a single-atom-thick hexagonal lattice of sp2-bonded carbon atoms, as in free-standing graphene. However, significant charge transfers from the substrate to the epitaxial graphene, and in some cases, the d-orbitals of the substrate atoms hybridize with the π orbitals of graphene, which significantly alters the electronic structure of epitaxial graphene.

Single layers of graphite were observed by TEM within bulk materials, in particular inside soot obtained by chemical exfoliation. Efforts to make thin films of graphite by mechanical exfoliation started in 1990,[21] but nothing thinner than 50 to 100 layers was produced before 2004.

## Naming

The term graphene was introduced in 1986 by chemists Hanns-Peter Boehm, Ralph Setton and Eberhard Stumpp. It is a combination of the word graphite and the suffix -ene, referring to polycyclic aromatic hydrocarbons.[3][4]

## Discovery

Initial attempts to make atomically thin graphitic films employed exfoliation techniques similar to the drawing method. Multilayer samples down to 10 nm in thickness were obtained. Earlier researchers tried to isolate graphene starting with intercalated compounds, producing very thin graphitic fragments (possibly monolayers).[18] Neither of the earlier observations was sufficient to launch the "graphene gold rush" that awaited macroscopic samples of extracted atomic planes.

One of the first patents pertaining to the production of graphene was filed in October 2002 and granted in 2006.[22] It detailed one of the first large scale graphene production processes. Two years later, in 2004 Geim and Novoselov extracted single-atom-thick crystallites from bulk graphite.[23] They pulled graphene layers from graphite and transferred them onto thin silicon dioxide (SiO2) on a silicon wafer in a process called either micromechanical cleavage or the Scotch tape technique.[24] The SiO2 electrically isolated the graphene and weakly interacted with it, providing nearly charge-neutral graphene layers. The silicon beneath the SiO2 could be used as a "back gate" electrode to vary the charge density in the graphene over a wide range. US patent patent 6667100, filed in 2002, describes how to process expanded graphite to achieve a graphite thickness of one hundred-thousandth of an inch (0.25 nm). The key to success was high-throughput visual recognition of graphene on a properly chosen substrate that provides a small but noticeable optical contrast.

The cleavage technique led directly to the first observation of the anomalous quantum Hall effect in graphene,[11][13] which provided direct evidence of graphene's theoretically predicted Berry's phase of massless Dirac fermions. The effect was reported by Geim's group and by Kim and Zhang, whose papers[11][13] appeared in Nature in 2005. Before these experiments other researchers had looked for the quantum Hall effect[25] and Dirac fermions[26] in bulk graphite.

Geim and Novoselov received awards for their pioneering research on graphene, notably the 2010 Nobel Prize in Physics.[27]

## Commercialization

In 2014, the National Graphene Institute was announced to support applied research and development in partnership with other research organizations and industry.[28]

Commercialization of graphene proceeded rapidly once commercial scale production was demonstrated. In 2014 two North East England commercial manufacturers, Applied Graphene Materials[29] and Thomas Swan Limited[30] (with Trinity College, Dublin researchers),[31] began manufacturing. In East Anglia Cambridge Nanosystems[32][33][34] operates a graphene powder production facility. By 2017, 13 years after creation of the first laboratory graphene electronic device, an integrated graphene electronics chip was produced commercially and marketed to pharmaceutical researchers by Nanomedical Diagnostics in San Diego.[35]

## References

1. ↑ 1.0 1.1 Geim, A K (2012). "Graphene prehistory". Physica Scripta 146: 014003. doi:10.1088/0031-8949/2012/T146/014003. Bibcode: 2012PhST..146a4003G.
2. ↑ Boehm, H. P.; Clauss, A.; Fischer, G. O.; Hofmann, U. (1 July 1962). "Das Adsorptionsverhalten sehr dünner Kohlenstoff-Folien". Zeitschrift für Anorganische und Allgemeine Chemie 316 (3–4): 119–127. doi:10.1002/zaac.19623160303. ISSN 1521-3749. }
3. ↑ 3.0 3.1 Cite error: Invalid `<ref>` tag; no text was provided for refs named `brit`
4. ↑ 4.0 4.1 Boehm, H.P; Setton, R; Stumpp, E (1986). "Nomenclature and terminology of graphite intercalation compounds". Carbon 24 (2): 241. doi:10.1016/0008-6223(86)90126-0.
5. ↑ Geim, A. K. (2012). "Graphene Prehistory". Physica Scripta T146: 014003. doi:10.1088/0031-8949/2012/T146/014003. Bibcode: 2012PhST..146a4003G.
6. ↑ Brodie, B. C. (1859). "On the Atomic Weight of Graphite". Philosophical Transactions of the Royal Society of London 149: 249–259. doi:10.1098/rstl.1859.0013. Bibcode: 1859RSPT..149..249B.
7. ↑ Debije, P; Scherrer, P (1916). "Interferenz an regellos orientierten Teilchen im Röntgenlicht I" (in de). Physikalische Zeitschrift 17: 277. http://resolver.sub.uni-goettingen.de/purl?PPN252457811_1916/dmdlog4.
8. ↑ Friedrich, W (1913). "Eine neue Interferenzerscheinung bei Röntgenstrahlen" (in de). Physikalische Zeitschrift 14: 317.
Hull, AW (1917). "A New Method of X-ray Crystal Analysis". Phys. Rev. 10 (6): 661–696. doi:10.1103/PhysRev.10.661. Bibcode: 1917PhRv...10..661H.
9. ↑ Wallace, P. R. (1947). "The Band Theory of Graphite". Physical Review 71 (9): 622–634. doi:10.1103/PhysRev.71.622. Bibcode: 1947PhRv...71..622W.
10. ↑ DiVincenzo, D. P.; Mele, E. J. (1984). "Self-Consistent Effective Mass Theory for Intralayer Screening in Graphite Intercalation Compounds". Physical Review B 295 (4): 1685–1694. doi:10.1103/PhysRevB.29.1685. Bibcode: 1984PhRvB..29.1685D.
11. ↑ 11.0 11.1 11.2 Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Katsnelson, M. I.; Grigorieva, I. V.; Dubonos, S. V.; Firsov, A. A. (2005). "Two-dimensional gas of massless Dirac fermions in graphene". Nature 438 (7065): 197–200. doi:10.1038/nature04233. PMID 16281030. Bibcode: 2005Natur.438..197N.
12. ↑ Gusynin, V. P.; Sharapov, S. G. (2005). "Unconventional Integer Quantum Hall Effect in Graphene". Physical Review Letters 95 (14): 146801. doi:10.1103/PhysRevLett.95.146801. PMID 16241680. Bibcode: 2005PhRvL..95n6801G.
13. ↑ 13.0 13.1 13.2 Zhang, Y.; Tan, Y. W.; Stormer, H. L.; Kim, P. (2005). "Experimental observation of the quantum Hall effect and Berry's phase in graphene". Nature 438 (7065): 201–204. doi:10.1038/nature04235. PMID 16281031. Bibcode: 2005Natur.438..201Z.
14. ↑ Ruess, G.; Vogt, F. (1948). "Höchstlamellarer Kohlenstoff aus Graphitoxyhydroxyd" (in de). Monatshefte für Chemie 78 (3–4): 222–242. doi:10.1007/BF01141527.
15. ↑ 15.0 15.1 Meyer, J.; Geim, A. K.; Katsnelson, M. I.; Novoselov, K. S.; Booth, T. J.; Roth, S. (2007). "The structure of suspended graphene sheets". Nature 446 (7131): 60–63. doi:10.1038/nature05545. PMID 17330039. Bibcode: 2007Natur.446...60M.
16. ↑ "Discussion on graphene's early history and Boehm's 1962 isolation of graphene". Graphene-Info. 16 March 2017. http://www.graphene-info.com/graphene-history-controversy-and-nobel-prize.
17. ↑ "Many Pioneers in Graphene Discovery". Letters to the Editor. Aps.org. January 2010. http://www.aps.org/publications/apsnews/201001/letters.cfm.
18. ↑ 18.0 18.1 Boehm, H. P.; Clauss, A.; Fischer, G.; Hofmann, U. (1962). "Surface Properties of Extremely Thin Graphite Lamellae". Proceedings of the Fifth Conference on Carbon. Pergamon Press. http://www.americancarbonsociety.org/sites/default/files/conference/1961/1961_V1_73.PDF.
19. ↑ This paper reports graphitic flakes that give an additional contrast equivalent of down to ≈0.4 nm or 3 atomic layers of amorphous carbon. This was the best possible resolution for 1960 TEMs. However, neither then nor today it is possible to argue how many layers were in those flakes. Now we know that the TEM contrast of graphene most strongly depends on focusing conditions.[15] For example, it is impossible to distinguish between suspended monolayer and multilayer graphene by their TEM contrasts, and the only known way is to analyse relative intensities of various diffraction spots.[1]
20. ↑ Oshima, C.; Nagashima, A. (1997). "Ultra-thin epitaxial films of graphite and hexagonal boron nitride on solid surfaces". J. Phys.: Condens. Matter 9 (1): 1–20. doi:10.1088/0953-8984/9/1/004. Bibcode: 1997JPCM....9....1O.
21. ↑ Geim, A. K.; Kim, P. (April 2008). "Carbon Wonderland". Scientific American. http://www.scientificamerican.com/article.cfm?id=carbon-wonderland. "... bits of graphene are undoubtedly present in every pencil mark"
22. ↑ "United States Patent: 7071258". US Patent Office. http://patft.uspto.gov/netacgi/nph-Parser?Sect2=PTO1&Sect2=HITOFF&p=1&u=/netahtml/PTO/search-bool.html&r=1&f=G&l=50&d=PALL&RefSrch=yes&Query=PN/7071258.
23. ↑ Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. (22 October 2004). "Electric Field Effect in Atomically Thin Carbon Films". Science 306 (5696): 666–669. doi:10.1126/science.1102896. ISSN 0036-8075. PMID 15499015. Bibcode: 2004Sci...306..666N.
24. ↑ "The Story of Graphene". October 2014. http://www.graphene.manchester.ac.uk/explore/the-story-of-graphene/a-discovery-at-manchester/. "Following discussions with colleagues, Andre and Kostya adopted a method that researchers in surface science were using –using simple Sellotape to peel away layers of graphite to expose a clean surface for study under the microscope."
25. ↑ Kopelevich, Y.; Torres, J.; Da Silva, R.; Mrowka, F.; Kempa, H.; Esquinazi, P. (2003). "Reentrant Metallic Behavior of Graphite in the Quantum Limit". Physical Review Letters 90 (15): 156402. doi:10.1103/PhysRevLett.90.156402. PMID 12732058. Bibcode: 2003PhRvL..90o6402K.
26. ↑ Luk'yanchuk, Igor A.; Kopelevich, Yakov (2004). "Phase Analysis of Quantum Oscillations in Graphite". Physical Review Letters 93 (16): 166402. doi:10.1103/PhysRevLett.93.166402. PMID 15525015. Bibcode: 2004PhRvL..93p6402L.
27. ↑ "Graphene pioneers bag Nobel prize". Institute of Physics, UK. 5 October 2010. http://physicsworld.com/cws/article/news/43939.
28. ↑ "New £60m Engineering Innovation Centre to be based in Manchester". The University of Manchester. 10 September 2014. http://www.graphene.manchester.ac.uk/latest.php.
29. ↑ Burn-Callander, Rebecca (1 July 2014). "Graphene maker aims to build British, billion-pound venture". Daily Telegraph. https://www.telegraph.co.uk/finance/businessclub/10936423/Graphene-maker-aims-to-build-British-billion-pound-venture.html.
30. ↑ Gibson, Robert (10 June 2014). "Consett firm Thomas Swan sees export success with grapheme". The Journal. http://www.thejournal.co.uk/business/business-news/consett-firm-thomas-swan-sees-7243084.
31. ↑ "Global breakthrough: Irish scientists discover how to mass produce 'wonder material' graphene". The Journal.ie. 20 April 2014. http://www.thejournal.ie/graphene-irish-researchers-major-breakdown-mass-production-1424843-Apr2014/.
32. ↑ Hope, Katie (24 March 2014). "Next Silicon Valleys: Why Cambridge is a start-up city". BBC News. https://www.bbc.co.uk/news/technology-26668034.
33. ↑ "Meet the first lady of graphene, turning harmful gases into the wonder stuff". Telegraph.co.uk. 6 December 2014. https://www.telegraph.co.uk/finance/newsbysector/industry/11273843/Meet-the-first-lady-of-graphene-turning-harmful-gases-into-the-wonder-stuff.html.
34. ↑ "Cambridge Nanosystems opens new factory for commercial graphene production". Cambridge News. 16 June 2015. http://www.cambridge-news.co.uk/Cambridge-Nanosystems-opens-new-factory/story-26705678-detail/story.html.
35. ↑ "Graphene biosensors – finally a commercial reality". http://www.newelectronics.co.uk/electronics-technology/graphene-biosensors-finally-a-commercial-reality/153805/.

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