Effect of first row transition metals on the conductivity of semiconducting single-walled carbon nanotube networks

Wang, Feihu; Itkis, Mikhail E.; Bekyarova, Elena; Tian, Xiaojuan; Sarkar, Santanu; Pekker, Áron; Калинина, И. В.; Moser, Matthew L.; Haddon, Robert C.

doi:10.1063/1.4723717

Cited by 29 publications

(113 citation statements)

References 35 publications

(33 reference statements)

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“…In contrast to destructive hybridization, the organometallic hexahapto (η 6 ) functionalization of CNTs [22][23][24], graphene [6,8] and other graphitic materials [57] allow the constructive rehybridization of the π-system of the carbon materials with the vacant d π -orbitals of appropriate transition metals.…”

Section: Constructive Hybridization: Metal Complexationmentioning

confidence: 99%

“…We have distinguished two limiting cases for the interaction between the addend and the graphitic surface, which are discussed below as 9.2.1 and 9.2.2 [9,24].…”

Section: Reactions Of Carbon Nanotubes and Graphenementioning

confidence: 99%

“…Destructive hybridization accompanies the standard addition reactions (Figure 9.1(a)) which typically lead to the formation of covalent C−X (X = H, C, N, O, F, Cl, Br) bonds to the basal plane carbon atoms with concomitant conversion of the carbon atoms at the sites of attachment from sp 2 to sp 3 hybridization and the removal of these atoms from conjugation [9,24]. This type of chemistry has been widely used as a means for bandgap engineering in graphene [29,30], and examples include hydrogenation [31,32], halogenation [29,33], oxidation (ozonolysis) [34], carboxylation [35], hydroxylation and epoxidation [36][37][38][39], radical additions [2,4,16,30,[40][41][42][43][44][45][46][47], carbene addition [48][49][50], nitrene addition [51,52], Diels-Alder reactions [17,53] including benzyne addition [54,55] and 1,3-dipolar cycloaddition [56] reactions.…”

Section: Destructive Hybridization: Covalent Bond Formation Involvingmentioning

confidence: 99%

“…(4) Organometallic hexahapto-complexation, a new mode of covalent chemisorption on graphitic surfaces, which is based on organometallic chemistry and makes use of the hexahapto-metal bond to electronically conjugate adjacent carbon surfaces, which contain the benzenoid ring system [6,9,[22][23][24]57].…”

Section: Reactivity and Bonding In Organometallic Complexesmentioning

confidence: 99%

“…In this chapter, we review in parallel the organometallic chemistry of fullerenes [13], CNTs [6,14,[21][22][23][24] and graphene [6,8]. Our main focus is on the organometallic chemistry of CNTs and graphene, while the fullerene chemistry provides a well-understood point of comparison.…”

Section: Introductionmentioning

confidence: 99%

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Organometallic Chemistry of Carbon Nanotubes and Graphene

Sarkar

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Haddon

2014

Carbon Nanotubes and Graphene

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Section: Constructive Hybridization: Metal Complexationmentioning

confidence: 99%

“…We have distinguished two limiting cases for the interaction between the addend and the graphitic surface, which are discussed below as 9.2.1 and 9.2.2 [9,24].…”

Section: Reactions Of Carbon Nanotubes and Graphenementioning

confidence: 99%

Section: Destructive Hybridization: Covalent Bond Formation Involvingmentioning

confidence: 99%

Section: Reactivity and Bonding In Organometallic Complexesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Organometallic Chemistry of Carbon Nanotubes and Graphene

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Synthesis and Characterization of Hexahapto‐Chromium Complexes of Single‐Walled Carbon Nanotubes

Калинина

Bekyarova

Sarkar

et al. 2016

Chemical Synthesis and Applications of Graphene and Carbon Materials

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Organometallic Hexahapto Functionalization of Single Layer Graphene as a Route to High Mobility Graphene Devices

et al. 2012

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Pristine single layer graphene (SLG) has exceedingly high mobility, which is ∼ 4,000-20,000 cm 2 /Vs for typical devices supported on Si/SiO 2 substrates, and may reach as high as 250,000 cm 2 /Vs in suspended devices at room temperature. [ 1 ] Such high mobilities make graphene an extremely attractive candidate for the next generation electronic materials. However, the absence of a band gap, which is necessary for digital electronics, presents a technological challenge. One effective approach to band gap engineering is the (partial) saturation of the valences of some of the conjugated carbon atoms. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] Nitrophenyl functionalization, in which a fully rehybridized sp 3 carbon atom is created in the lattice, dramatically modifi es the electronic and magnetic structure of graphene, with signifi cantly reduced fi eld effect mobility. [18][19][20][21][22] Since this type of functionalization scheme introduces resonant scatters [ 23 ] into the graphene lattice, we refer to this as destructive rehybridization. [ 24 ] Most approaches for chemical modifi cation of graphene involve the creation of sp 3 carbon centers at the cost of conjugated sp 2 carbon atoms in the graphene lattice. We have recently investigated the application of organometallic chemistry by studying the covalent hexahapto modifi cation of graphitic surfaces with zero-valent transition metals such as chromium. [ 12 , 25 ] The formation of the hexahapto ( η 6 )-arene − metal bond leads to very little structural reorganization of the π -system. In the reaction of the zero-valent chromium metal with graphene, the vacant d π orbital of the metal (chromium) constructively overlaps with the occupied π -orbitals of graphene, without removing any of the sp 2 carbon atoms from conjugation. [ 12 , 25 ] Previously we have shown that the formation of such bishexahapto transition metal bonds between the conjugated surfaces of the benzenoid ring systems present in the surfaces of graphene and carbon nanotubes can dramatically change their electrical properties. [ 12 , 24-27 ] These prior works focus on using the bis-hexahapto-metal bond as an interconnect for electrical transport between the conjugated surfaces, thereby increasing the dimensionality of the carbon nanotube and graphene materials and thus we were concerned with the use of the bishexahapto-metal bond as a conduit for electron transport between surfaces. In contrast, the goal of the present study is to investigate the effect of the hexahapto-bonded chromium atoms on the electronic properties of graphene itself (within the plane of a single layer), by using mono-hexahapto-metal bonds to the graphene surface.Single layer graphene (SLG) fl akes used in this study were extracted from bulk graphite using a standard mechanical exfoliation method and placed on a Si substrate with 300 nm SiO 2 . Contacts consisting of 10 nm of Cr and 150 nm of Au were deposited on SLG by e-beam lithography. The devices were then annealed in vacuum by passing a high current...

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Effect of first row transition metals on the conductivity of semiconducting single-walled carbon nanotube networks

Cited by 29 publications

References 35 publications

Organometallic Chemistry of Carbon Nanotubes and Graphene

Organometallic Chemistry of Carbon Nanotubes and Graphene

Synthesis and Characterization of Hexahapto‐Chromium Complexes of Single‐Walled Carbon Nanotubes

Organometallic Hexahapto Functionalization of Single Layer Graphene as a Route to High Mobility Graphene Devices

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