Mikhail E. Itkis

Chemical Modification of Epitaxial Graphene: Spontaneous Grafting of Aryl Groups

The addition of nitrophenyl groups to the surface of few-layer epitaxial graphene (EG) by the formation of covalent carbon-carbon bonds changed the electronic structure and transport properties of the EG from near-metallic to semiconducting.

Spectroscopy of Covalently Functionalized Graphene

In order to engineer a band gap into graphene, covalent bond-forming reactions can be used to change the hybridization of the graphitic atoms from sp(2) to sp(3), thereby modifying the conjugation length of the delocalized carbon lattice; similar side-wall chemistry has been shown to introduce a band gap into metallic single-walled carbon nanotubes. Here we demonstrate that the application of such covalent bond-forming chemistry modifies the periodicity of the graphene network thereby introducing a band gap (∼0.4 eV), which is observable in the angle-resolved photoelectron spectroscopy of aryl-functionalized graphene. We further show that the chemically-induced changes can be detected by Raman spectroscopy; the in-plane vibrations of the conjugated π-bonds exhibit characteristic Raman spectra and we find that the changes in D, G, and 2D-bands as a result of chemical functionalization of the graphene basal plane are quite distinct from that due to localized, physical defects in sp(2)-conjugated carbon.

Bolometric Infrared Photoresponse of Suspended Single-Walled Carbon Nanotube Films

The photoresponse in the electrical conductivity of a single-walled carbon nanotube (SWNT) film is dramatically enhanced when the nanotube film is suspended in vacuum. We show here that the change in conductivity is bolometric (caused by heating of the SWNT network). Electron-phonon interactions lead to ultrafast relaxation of the photoexcited carriers, and the energy of the incident infrared (IR) radiation is efficiently transferred to the crystal lattice. It is not the presence of photoexcited holes and electrons, but a rise in temperature, that results in a change in resistance; thus, photoconductivity experiments cannot be used to support the band picture over the exciton model of excited states in carbon nanotubes. The photoresponse of suspended SWNT films is sufficiently high that they may function as the sensitive element of an IR bolometric detector.

Determination of the acidic sites of purified single-walled carbon nanotubes by acid–base titration

We report the measurement of the acidic sites in three different samples of commercially available full-length purified single-walled carbon nanotubes (SWNTs) – as obtained from CarboLex (CLI), Carbon Solutions (CSI) and Tubes@Rice (TAR) – by simple acid–base titration methods. Titration of the purified SWNTs with NaOH and NaHCO3 solutions was used to determine the total percentage of acidic sites and carboxylic acid groups, respectively. The total percentage of acidic sites in full length purified SWNTs from TAR, CLI and CSI are about 1–3%.

END-GROUP AND DEFECT ANALYSIS OF SOLUBLE SINGLE-WALLED CARBON NANOTUBES

By use of solution phase mid-IR spectroscopy we are able to obtain an estimate for the ratio of the carbon atoms in the single-walled carbon nanotube (SWNT) backbone to the carbon atoms in the end-groups and at defect sites of the octadecylamido (ODA) functionalized soluble SWNTs (s-SWNT-CONH(CH2)17CH3). This analysis shows that the weight percentage of the octadecylamido functionality in the s-SWNTs is about 50%.

Effect of Covalent Chemistry on the Electronic Structure and Properties of Carbon Nanotubes and Graphene

In this Account, we discuss the chemistry of graphitic materials with particular reference to three reactions studied by our research group: (1) aryl radical addition, from diazonium precursors, (2) Diels-Alder pericyclic reactions, and (3) organometallic complexation with transition metals. We provide a unified treatment of these reactions in terms of the degenerate valence and conduction bands of graphene at the Dirac point and the relationship of their orbital coefficients to the HOMO and LUMO of benzene and to the Clar structures of graphene. In the case of the aryl radical addition and the Diels-Alder reactions, there is full rehybridization of the derivatized carbon atoms in graphene from sp(2) to sp(3), which removes these carbon atoms from conjugation and from the electronic band structure of graphene (referred to as destructive rehybridization). The radical addition process requires an electron transfer step followed by the formation of a σ-bond and the creation of a π-radical in the graphene lattice, and thus, there is the potential for unequal degrees of functionalization in the A and B sublattices and the possibility of ferromagnetism and superparamagnetism in the reaction products. With regard to metal functionalization, we distinguish four limiting cases: (a) weak physisorption, (b) ionic chemisorption, in which there is charge transfer to the graphitic structure and preservation of the conjugation and band structure, (c) covalent chemisorption, in which there is strong rehybridization of the graphitic band structure, and (d) covalent chemisorption with formation of an organometallic hexahapto-metal bond that largely preserves the graphitic band structure (constructive rehybridization). The constructive rehybridization that accompanies the formation of bis-hexahapto-metal bonds, such as those in (η(6)-SWNT)Cr(η(6)-SWNT), interconnects adjacent graphitic surfaces and significantly reduces the internanotube junction resistance in single-walled carbon nanotube (SWNT) networks. The conversion of sp(2) hybridized carbon atoms to sp(3) can introduce a band gap into graphene, influence the electronic scattering, and create dielectric regions in a graphene wafer. However, the organometallic hexahapto (η(6)) functionalization of the two-dimensional (2D) graphene π-surface with transition metals provides a new way to modify graphitic structures that does not saturate the functionalized carbon atoms and, by preserving their structural integrity, maintains the delocalization in these extended periodic π-electron systems and offers the possibility of three-dimensional (3D) interconnections between adjacent graphene sheets. These structures may find applications in interconnects, 3D-electronics, organometallic catalysis, atomic spintronics and in the fabrication of new electronic materials.

Effect of single-walled carbon nanotube purity on the thermal conductivity of carbon nanotube-based composites

Raw [as-prepared (AP)] and purified single-walled carbon nanotubes (SWNTs) were utilized for the preparation of SWNT-epoxy composites. Purified functionalized SWNTs provide a significantly greater enhancement of the thermal conductivity, whereas AP-SWNTs allow the best electrical properties because of their ability to form efficient percolating network. A series of SWNT samples of varying purity but identical chemical functionality was prepared to delineate the effect of SWNT purity on the thermal conductivity of SWNT-epoxy composites. The authors found that purified SWNTs provide approximately five times greater enhancement of the thermal conductivity than the impure SWNT fraction demonstrating the significance of SWNT quality for thermal management.

Anisotropic Thermal and Electrical Properties of Thin Thermal Interface Layers of Graphite Nanoplatelet-Based Composites

Thermal interface materials (TIMs) are crucial components of high density electronics and the high thermal conductivity of graphite makes this material an attractive candidate for such applications. We report an investigation of the in-plane and through-plane electrical and thermal conductivities of thin thermal interface layers of graphite nanoplatelet (GNP) based composites. The in-plane electrical conductivity exceeds its through-plane counterpart by three orders of magnitude, whereas the ratio of the thermal conductivities is about 5. Scanning electron microscopy reveals that the anisotropy in the transport properties is due to the in-plane alignment of the GNPs which occurs during the formation of the thermal interface layer. Because the alignment in the thermal interface layer suppresses the through-plane component of the thermal conductivity, the anisotropy strongly degrades the performance of GNP-based composites in the geometry required for typical thermal management applications and must be taken into account in the development of GNP-based TIMs.

Advances in the chemical modification of epitaxial graphene

Chemistry will play an increasingly important role in the realization of graphene applications. The chemical formation of covalent carbon–carbon bonds involving the basal plane carbon atoms offers an alternative approach to the control of the electronic properties of graphene, and potentially allows the generation of insulating and semiconducting regions in graphene wafers. This review summarizes recent progress in the covalent modification of epitaxial graphene and the effect that chemistry has on the electronic and magnetic properties of the material.

Effect of nitrophenyl functionalization on the magnetic properties of epitaxial graphene.

Graphene displays unprecedented electronic properties including room-temperature ballistic transport and quantum conductance, and because of its small spin-orbit interaction, graphene has the potential to function as the building block of future spintronic devices. Theoretical calculations indicate that a defective graphene sheet will be simultaneously semiconducting and magnetic; thus it would act as a room-temperature magnetic semiconductor. Recently, ferromagnetic ordering at room temperature has been observed by magnetometry measurements on bulk samples of reduced graphene oxide.