Feihu Wang

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.

Functionalized Single-Walled Carbon Nanotube-Based Fuel Cell Benchmarked Against US DOE 2017 Technical Targets

Chemically modified single-walled carbon nanotubes (SWNTs) with varying degrees of functionalization were utilized for the fabrication of SWNT thin film catalyst support layers (CSLs) in polymer electrolyte membrane fuel cells (PEMFCs), which were suitable for benchmarking against the US DOE 2017 targets. Use of the optimum level of SWNT -COOH functionality allowed the construction of a prototype SWNT-based PEMFC with total Pt loading of 0.06u2005mgPt/cm2 - well below the value of 0.125u2005mgPt/cm2 set as the US DOE 2017 technical target for total Pt group metals (PGM) loading. This prototype PEMFC also approaches the technical target for the total Pt content per kW of power (<0.125u2005gPGM/kW) at cell potential 0.65u2005V: a value of 0.15u2005gPt/kW was achieved at 80°C/22u2005psig testing conditions, which was further reduced to 0.12u2005gPt/kW at 35u2005psig back pressure.

Electro-oxidized Epitaxial Graphene Channel Field-Effect Transistors with Single-Walled Carbon Nanotube Thin Film Gate Electrode

We report the effect of electrochemical oxidation in nitric acid on the electronic properties of epitaxial graphene (EG) grown on silicon carbide substrates; we demonstrate the availability of an additional reaction channel in EG, which is not present in graphite but which facilitates the introduction of the reaction medium into the graphene galleries during electro-oxidation. The device performance of the chemically processed graphene was studied by patterning the EG wafers with two geometrically identical macroscopic channels; the electro-oxidized channel showed a logarithmic increase of resistance with decreasing temperature, which is ascribed to the scattering of charge carriers in a two-dimensional electronic gas, rather than the presence of an energy gap at the Fermi level. Field-effect transistors were fabricated on the electro-oxidized and pristine graphene channels using single-walled carbon nanotube thin film top gate electrodes, thereby allowing the study of the effect of oxidative chemistry on the transistor performance of EG. The electro-oxidized channel showed higher values for the on-off ratio and the mobility of the graphene field-effect transistor, which we ascribe to the availability of high-quality internal graphene layers after electro-oxidation of the more defective top layers. Thus, the present oxidative process provides a clear contrast with previously demonstrated covalent chemistry in which sp(3) hybridized carbon atoms are introduced into the graphitic transport layer of the lattice by carbon-carbon bond formation, thereby opening an energy gap.

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

We demonstrate the ability of first row transition metals to form electrically conducting interconnects between semiconducting single-walled carbon nanotubes (SWNTs) by constructive rehybridization between sidewall benzene rings as a result of the formation of bis-hexahapto-metal-bonds [(η6-SWNT)M(η6-SWNT)], which bridge adjacent SWNTs. Metal deposition on SWNT films enhances the conductivity by three distinct mechanisms: physisorption of gold leads to the formation of a non-interacting gold film and a monotonic conductivity increase; ionic chemisorption of lithium strongly increases the conductivity due to charge transfer to the SWNTs; covalent chemisorption of first row transition metals leads to an abrupt change in conductivity due to formation of (η6-SWNT)M(η6-SWNT) interconnects.

Enhanced electromodulation of infrared transmittance in semitransparent films of large diameter semiconducting single-walled carbon nanotubes

We report a comprehensive study of the gate-induced electromodulated transmittance of infrared light by single-walled carbon nanotube (SWNT) thin films. The observed electromodulation is significantly enhanced by utilizing large diameter SWNTs, increasing the ratio of semiconducting to metal SWNTs, and by decreasing the SWNT film thickness. The amplitude of the effect reported herein ( approximately 7%) is more than an order of magnitude larger than in previous SWNT thin film solid state devices.

Enhanced photosensitivity of electro-oxidized epitaxial graphene

We report the enhanced photosensitivity of epitaxial graphene (EG) after electrochemical oxidation in nitric acid. The onset of photoconductivity appears at a photon energy of ∼1.7u2002eV while the responsivity reaches 2.5 A/W at a wavelength of 470 nm (blue light, energy 2.64 eV) and further increases to 200 A/W in the UV spectral range (3.5 eV, 350 nm). The observed photoresponse is attributed to the formation of deep traps at the electro-oxidized EG interface, which release charge carriers under illumination and prolong the life time of the photocarriers. Potential applications of electro-oxidized EG in ultraviolet photodetection are discussed.