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Discovery of graphene

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30: 45: 2285: 287: 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. 231:
One of the first patents pertaining to the production of graphene was filed in October 2002 and granted in 2006. 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. They pulled
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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
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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
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know that the TEM contrast of graphene most strongly depends on focusing conditions. 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.
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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.
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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, but nothing thinner than 50 to 100 layers was produced before 2004.
164:(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. 159:
The earliest TEM images of few-layer graphite were published by G. Ruess and F. Vogt in 1948. Later, single graphene layers were observed directly by electron microscopy. Before 2004 intercalated graphite compounds were studied under a
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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
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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".
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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".
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fragments (possibly monolayers). Neither of the earlier observations was sufficient to launch the "graphene gold rush" that awaited macroscopic samples of extracted atomic planes.
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Starting in the 1970s single layers of graphite were grown epitaxially on top of other materials. This "epitaxial graphene" consists of a single-atom-thick hexagonal lattice of
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carbon atoms, as in free-standing graphene. However, significant charge transfers from the substrate to the epitaxial graphene, and in some cases, the
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Kopelevich, Y.; Torres, J.; Da Silva, R.; Mrowka, F.; Kempa, H.; Esquinazi, P. (2003). "Reentrant Metallic Behavior of Graphite in the Quantum Limit".
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in 1947 as a starting point for understanding the electronic properties of 3D graphite. The emergent massless Dirac equation was first pointed out by
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commercial manufacturers, Applied Graphene Materials and Thomas Swan Limited (with Trinity College, Dublin researchers), began manufacturing. In
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DiVincenzo, D. P.; Mele, E. J. (1984). "Self-Consistent Effective Mass Theory for Intralayer Screening in Graphite Intercalation Compounds".
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Zhang, Y.; Tan, Y. W.; Stormer, H. L.; Kim, P. (2005). "Experimental observation of the quantum Hall effect and Berry's phase in graphene".
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electrically isolated the graphene and weakly interacted with it, providing nearly charge-neutral graphene layers. The silicon beneath the
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Meyer, J.; Geim, A. K.; Katsnelson, M. I.; Novoselov, K. S.; Booth, T. J.; Roth, S. (2007). "The structure of suspended graphene sheets".
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Boehm, H. P.; Clauss, A.; Fischer, G. O.; Hofmann, U. (1 July 1962). "Das Adsorptionsverhalten sehr dünner Kohlenstoff-Folien".
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in 2005. Before these experiments other researchers had looked for the quantum Hall effect and Dirac fermions in bulk graphite.
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Oshima, C.; Nagashima, A. (1997). "Ultra-thin epitaxial films of graphite and hexagonal boron nitride on solid surfaces".
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was announced to support applied research and development in partnership with other research organizations and industry.
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and his co-workers for the experimental discovery of graphene in 1962; while it had been explored theoretically by
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Commercialization of graphene proceeded rapidly once commercial scale production was demonstrated. In 2014 two
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Boehm, H.P; Setton, R; Stumpp, E (1986). "Nomenclature and terminology of graphite intercalation compounds".
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could be used as a "back gate" electrode to vary the charge density in the graphene over a wide range.
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Luk'yanchuk, Igor A.; Kopelevich, Yakov (2004). "Phase Analysis of Quantum Oscillations in Graphite".
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Gusynin, V. P.; Sharapov, S. G. (2005). "Unconventional Integer Quantum Hall Effect in Graphene".
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Geim and Novoselov received awards for their pioneering research on graphene, notably the 2010
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of graphene, which significantly alters the electronic structure of epitaxial graphene.
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Ruess, G.; Vogt, F. (1948). "Höchstlamellarer Kohlenstoff aus Graphitoxyhydroxyd".
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in graphene, which provided direct evidence of graphene's theoretically predicted
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precisely at the Dirac point. This level is responsible for the anomalous integer
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The cleavage technique led directly to the first observation of the anomalous
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Friedrich, W (1913). "Eine neue Interferenzerscheinung bei Röntgenstrahlen".
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The structure of graphite was identified in 1916 by the related method of
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was first unambiguously produced and identified in 2004, by the group of
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Hassel, O; Mack, H (1924). "Über die Kristallstruktur des Graphits".
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graphene layers from graphite and transferred them onto thin
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in 1947. Boehm et al. introduced the term graphene in 1986.
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Boehm, H. P.; Clauss, A.; Fischer, G.; Hofmann, U. (1962).
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Philosophical Transactions of the Royal Society of London
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Wallace, P. R. (1947). "The Band Theory of Graphite".
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The 244: 241: 240: 239: 237: 234:silicon dioxide 225: 215:, referring to 211:and the suffix 205:Eberhard Stumpp 189: 104: 23: 22: 15: 12: 11: 5: 2323: 2321: 2313: 2312: 2302: 2301: 2295: 2294: 2292: 2291: 2280: 2277: 2276: 2274: 2273: 2268: 2267: 2266: 2261: 2253: 2251:Shapley–Curtis 2248: 2243: 2241:Leibniz–Newton 2238: 2236:Galileo affair 2233: 2228: 2222: 2220: 2216: 2215: 2213: 2212: 2207: 2202: 2197: 2192: 2186: 2184: 2180: 2179: 2177: 2176: 2171: 2170: 2169: 2159: 2154: 2149: 2143: 2141: 2137: 2136: 2134: 2133: 2131:Speed of light 2128: 2127: 2126: 2121: 2116: 2108: 2103: 2098: 2092: 2090: 2086: 2085: 2083: 2082: 2077: 2075:Nanotechnology 2072: 2067: 2066: 2065: 2056: 2054: 2050: 2049: 2047: 2046: 2045: 2044: 2039: 2034: 2024: 2023: 2022: 2012: 2011: 2010: 2005: 2000: 1995: 1985: 1984: 1983: 1978: 1973: 1968: 1960: 1955: 1954: 1953: 1943: 1942: 1941: 1936: 1928: 1927: 1926: 1921: 1913: 1912: 1911: 1902: 1900: 1898:Modern physics 1894: 1893: 1891: 1890: 1889: 1888: 1883: 1878: 1873: 1866:Thermodynamics 1863: 1862: 1861: 1851: 1850: 1849: 1844: 1834: 1833: 1832: 1827: 1817: 1816: 1815: 1805: 1804: 1803: 1798: 1788: 1787: 1786: 1781: 1776: 1771: 1761: 1760: 1759: 1748: 1746: 1740: 1739: 1729: 1727: 1726: 1719: 1712: 1704: 1697: 1696: 1671: 1662:Cambridge News 1649: 1631: 1612: 1590: 1563: 1540: 1510: 1480: 1443:(16): 166402. 1427: 1390:(15): 156402. 1374: 1356: 1287: 1265: 1241: 1206: 1196: 1176:Pergamon Press 1152: 1134: 1116: 1060: 1031: 965: 920:(14): 146801. 904: 846: 811: 792:(9): 622–634. 776: 749:(1): 317–337. 688: 677:(1): 121–144. 655: 636:(6): 661–696. 605: 579: 528: 485: 455: 438: 402: 357: 355: 352: 328: 325: 300:Dirac fermions 270: 258: 242: 224: 221: 188: 185: 146:Eugene J. Mele 116:graphite oxide 103: 100: 58:tape dispenser 24: 14: 13: 10: 9: 6: 4: 3: 2: 2322: 2311: 2308: 2307: 2305: 2290: 2282: 2281: 2278: 2272: 2269: 2265: 2262: 2260: 2257: 2256: 2254: 2252: 2249: 2247: 2244: 2242: 2239: 2237: 2234: 2232: 2229: 2227: 2226:Bohr–Einstein 2224: 2223: 2221: 2217: 2211: 2208: 2206: 2203: 2201: 2198: 2196: 2193: 2191: 2188: 2187: 2185: 2181: 2175: 2172: 2168: 2165: 2164: 2163: 2160: 2158: 2155: 2153: 2150: 2148: 2145: 2144: 2142: 2138: 2132: 2129: 2125: 2122: 2120: 2117: 2115: 2112: 2111: 2109: 2107: 2104: 2102: 2099: 2097: 2094: 2093: 2091: 2087: 2081: 2080:String theory 2078: 2076: 2073: 2071: 2068: 2064: 2061: 2060: 2058: 2057: 2055: 2051: 2043: 2040: 2038: 2035: 2033: 2030: 2029: 2028: 2025: 2021: 2018: 2017: 2016: 2013: 2009: 2006: 2004: 2001: 1999: 1996: 1994: 1991: 1990: 1989: 1986: 1982: 1979: 1977: 1974: 1972: 1969: 1967: 1964: 1963: 1961: 1959: 1956: 1952: 1949: 1948: 1947: 1944: 1940: 1937: 1935: 1932: 1931: 1929: 1925: 1922: 1920: 1917: 1916: 1914: 1910: 1907: 1906: 1904: 1903: 1901: 1899: 1895: 1887: 1884: 1882: 1879: 1877: 1874: 1872: 1869: 1868: 1867: 1864: 1860: 1857: 1856: 1855: 1852: 1848: 1845: 1843: 1840: 1839: 1838: 1835: 1831: 1830:Metamaterials 1828: 1826: 1823: 1822: 1821: 1818: 1814: 1811: 1810: 1809: 1806: 1802: 1799: 1797: 1794: 1793: 1792: 1789: 1785: 1782: 1780: 1777: 1775: 1772: 1770: 1767: 1766: 1765: 1762: 1758: 1755: 1754: 1753: 1750: 1749: 1747: 1745: 1741: 1736: 1732: 1725: 1720: 1718: 1713: 1711: 1706: 1705: 1702: 1685: 1681: 1675: 1672: 1667: 1663: 1659: 1653: 1650: 1645: 1641: 1635: 1632: 1627: 1623: 1616: 1613: 1600: 1594: 1591: 1578: 1574: 1567: 1564: 1551: 1544: 1541: 1528: 1524: 1520: 1514: 1511: 1498: 1494: 1490: 1484: 1481: 1476: 1472: 1468: 1464: 1460: 1456: 1451: 1446: 1442: 1438: 1431: 1428: 1423: 1419: 1415: 1411: 1407: 1403: 1398: 1393: 1389: 1385: 1378: 1375: 1371: 1366: 1360: 1357: 1352: 1348: 1344: 1340: 1336: 1332: 1328: 1324: 1320: 1316: 1311: 1306: 1302: 1298: 1291: 1288: 1275: 1269: 1266: 1262: 1258: 1257: 1252: 1245: 1242: 1237: 1233: 1229: 1225: 1221: 1217: 1210: 1207: 1200: 1197: 1181: 1177: 1173: 1166: 1159: 1157: 1153: 1148: 1144: 1138: 1135: 1130: 1129:Graphene-Info 1126: 1120: 1117: 1112: 1108: 1104: 1100: 1096: 1092: 1087: 1082: 1078: 1074: 1067: 1065: 1061: 1056: 1052: 1048: 1045:(in German). 1044: 1043: 1035: 1032: 1027: 1023: 1019: 1015: 1011: 1007: 1003: 999: 994: 989: 985: 981: 974: 972: 970: 966: 961: 957: 953: 949: 945: 941: 937: 933: 928: 923: 919: 915: 908: 905: 900: 896: 892: 888: 884: 880: 875: 870: 866: 862: 855: 853: 851: 847: 842: 838: 834: 830: 826: 822: 815: 812: 807: 803: 799: 795: 791: 787: 780: 777: 772: 768: 764: 760: 756: 752: 748: 745:(in German). 744: 736: 732: 727: 722: 718: 714: 710: 706: 702: 698: 692: 689: 684: 680: 676: 673:(in German). 672: 671: 666: 659: 656: 651: 647: 643: 639: 635: 631: 627: 620: 617:(in German). 616: 609: 606: 601: 598:(in German). 597: 593: 589: 583: 580: 575: 571: 566: 561: 557: 553: 549: 545: 544: 539: 532: 529: 523: 518: 514: 510: 506: 502: 501: 496: 489: 486: 481: 477: 473: 469: 462: 460: 456: 452: 447: 445: 443: 439: 433: 429: 425: 421: 417: 413: 406: 403: 397: 392: 388: 384: 380: 376: 372: 365: 363: 359: 353: 351: 348: 345: 341: 336: 334: 331:In 2014, the 326: 324: 322: 317: 315: 314: 309: 305: 301: 297: 296:Berry's phase 293: 288: 280: 251: 235: 229: 222: 220: 218: 214: 210: 206: 202: 198: 194: 186: 184: 180: 178: 174: 170: 165: 163: 157: 155: 151: 147: 143: 139: 135: 134:P. R. Wallace 130: 128: 124: 119: 117: 113: 109: 102:Early history 101: 99: 97: 96:P. R. Wallace 93: 89: 85: 81: 80: 76:Single-layer 71: 67: 63: 59: 55: 52:, a graphene 51: 46: 39: 35: 31: 27: 19: 2195:The Martians 2100: 1859:Spectroscopy 1801:Aerodynamics 1779:Field theory 1687:. Retrieved 1683: 1674: 1666:the original 1661: 1652: 1643: 1634: 1625: 1615: 1603:. Retrieved 1593: 1581:. Retrieved 1577:the original 1566: 1554:. Retrieved 1543: 1531:. Retrieved 1527:the original 1522: 1513: 1503:17 September 1501:. Retrieved 1497:the original 1483: 1440: 1436: 1430: 1387: 1383: 1377: 1368: 1359: 1300: 1296: 1290: 1278:. Retrieved 1268: 1260: 1254: 1244: 1219: 1215: 1209: 1199: 1189:17 September 1187:. Retrieved 1180:the original 1171: 1146: 1137: 1128: 1119: 1076: 1072: 1046: 1040: 1034: 983: 979: 917: 913: 907: 864: 860: 824: 820: 814: 789: 785: 779: 746: 742: 708: 704: 691: 674: 668: 658: 633: 629: 618: 614: 608: 599: 595: 582: 547: 541: 531: 504: 498: 488: 471: 467: 415: 411: 405: 378: 374: 337: 330: 318: 311: 298:of massless 289: 230: 226: 212: 208: 201:Ralph Setton 192: 190: 181: 166: 158: 150:Landau level 131: 120: 105: 77: 75: 62:Nobel Museum 26: 2119:Higgs boson 1605:20 December 1370:microscope. 1222:(1): 1–20. 550:: 249–259. 344:East Anglia 250:Scotch tape 36:(left) and 2140:By periods 1958:Geophysics 1930:Cosmology 1280:12 January 697:Bernal, JD 507:: 014003. 474:(2): 241. 381:: 014003. 354:References 177:π orbitals 173:d-orbitals 84:Andre Geim 66:Andre Geim 54:transistor 48:A lump of 38:Andre Geim 2183:By groups 2167:Astronomy 2003:Molecules 1837:Mechanics 1752:Astronomy 1533:9 October 1335:0036-8075 771:121157442 630:Phys. Rev 588:Debije, P 432:1521-3749 279:US patent 223:Discovery 191:The term 169:sp-bonded 106:In 1859, 2310:Graphene 2304:Category 2289:Category 2114:timeline 2101:Graphene 2063:timeline 2032:timeline 2020:timeline 1993:timeline 1934:timeline 1919:timeline 1909:timeline 1871:timeline 1842:timeline 1825:timeline 1813:timeline 1796:timeline 1769:timeline 1757:timeline 1735:timeline 1689:9 August 1626:BBC News 1475:15525015 1422:12732058 1343:15499015 1111:17330039 1018:16281031 960:37267733 952:16241680 899:16281030 699:(1924). 626:Hull, AW 451:Graphene 209:graphite 193:graphene 112:lamellar 79:graphene 72:in 2010. 56:, and a 50:graphite 2124:Neutron 1981:Weapons 1966:Fission 1881:Entropy 1583:23 July 1556:24 July 1455:Bibcode 1402:Bibcode 1351:5729649 1315:Bibcode 1297:Science 1224:Bibcode 1091:Bibcode 1026:4424714 998:Bibcode 932:Bibcode 879:Bibcode 829:Bibcode 794:Bibcode 751:Bibcode 713:Bibcode 638:Bibcode 552:Bibcode 509:Bibcode 383:Bibcode 1971:Fusion 1876:Energy 1854:Optics 1473:  1420:  1349:  1341:  1333:  1109:  1073:Nature 1024:  1016:  980:Nature 958:  950:  897:  861:Nature 769:  733:  621:: 317. 602:: 277. 574:108699 572:  468:Carbon 430:  313:Nature 284:  187:Naming 2042:tests 1998:Atoms 1976:Power 1951:tests 1445:arXiv 1392:arXiv 1347:S2CID 1305:arXiv 1183:(PDF) 1168:(PDF) 1081:arXiv 1022:S2CID 988:arXiv 956:S2CID 922:arXiv 869:arXiv 767:S2CID 735:94336 731:JSTOR 570:JSTOR 308:Zhang 1691:2017 1607:2014 1585:2014 1558:2014 1535:2014 1505:2017 1471:PMID 1418:PMID 1339:PMID 1331:ISSN 1282:2014 1191:2017 1107:PMID 1014:PMID 948:PMID 895:PMID 709:A106 505:T146 428:ISSN 306:and 213:-ene 203:and 144:and 86:and 68:and 1463:doi 1410:doi 1323:doi 1301:306 1232:doi 1099:doi 1077:446 1051:doi 1006:doi 984:438 940:doi 887:doi 865:438 837:doi 825:295 802:doi 759:doi 721:doi 679:doi 675:105 646:doi 560:doi 548:149 517:doi 476:doi 420:doi 416:316 391:doi 379:146 304:Kim 266:SiO 254:SiO 238:SiO 2306:: 1682:. 1660:. 1642:. 1624:. 1521:. 1491:. 1469:. 1461:. 1453:. 1441:93 1439:. 1416:. 1408:. 1400:. 1388:90 1386:. 1345:. 1337:. 1329:. 1321:. 1313:. 1299:. 1259:. 1253:. 1230:. 1218:. 1174:. 1170:. 1155:^ 1145:. 1127:. 1105:. 1097:. 1089:. 1075:. 1063:^ 1047:78 1020:. 1012:. 1004:. 996:. 982:. 968:^ 954:. 946:. 938:. 930:. 918:95 916:. 893:. 885:. 877:. 863:. 849:^ 835:. 823:. 800:. 790:71 788:. 765:. 757:. 747:25 729:. 719:. 707:. 703:. 667:. 644:. 634:10 632:. 619:14 600:17 594:. 568:. 558:. 546:. 540:. 515:. 503:. 497:. 472:24 470:. 458:^ 441:^ 426:. 414:. 389:. 377:. 373:. 361:^ 323:. 219:. 199:, 156:. 140:, 118:. 1737:) 1733:( 1723:e 1716:t 1709:v 1693:. 1628:. 1609:. 1587:. 1560:. 1537:. 1507:. 1477:. 1465:: 1457:: 1447:: 1424:. 1412:: 1404:: 1394:: 1353:. 1325:: 1317:: 1307:: 1284:. 1238:. 1234:: 1226:: 1220:9 1193:. 1113:. 1101:: 1093:: 1083:: 1057:. 1053:: 1028:. 1008:: 1000:: 990:: 962:. 942:: 934:: 924:: 901:. 889:: 881:: 871:: 843:. 839:: 831:: 808:. 804:: 796:: 773:. 761:: 753:: 737:. 723:: 715:: 685:. 681:: 652:. 648:: 640:: 576:. 562:: 554:: 525:. 519:: 511:: 482:. 478:: 436:} 434:. 422:: 399:. 393:: 385:: 271:2 259:2 243:2 236:( 20:)

Index

History of graphene

Konstantin Novoselov
Andre Geim

graphite
transistor
tape dispenser
Nobel Museum
Andre Geim
Konstantin Novoselov
graphene
Andre Geim
Konstantin Novoselov
Hanns-Peter Boehm
P. R. Wallace
Benjamin Collins Brodie
lamellar
graphite oxide
powder diffraction
graphite oxide paper
P. R. Wallace
Gordon W. Semenoff
David DiVincenzo
Eugene J. Mele
Landau level
quantum Hall effect
transmission electron microscope
sp-bonded
d-orbitals

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