Let be equal-length primitive translation vectors of the graphene lattice, separated by . The carbon nanotube chiral vector
identifies the two points joined when the sheet is rolled: is the circumference, not the tube axis. The right-hand panel of the preceding original diagram shows and .
The periodic boundary condition is , with an integer. Applying it at either Dirac valley gives the nanotube zone folding criterion
for a metallic tube. Thus is an armchair metallic example, whereas is a zigzag semiconducting example. Other choices with also give a semiconducting carbon nanotube.
This criterion is the ideal flat-sheet approximation. Curvature can open a small gap in nominally metallic non-armchair tubes; ideal armchair tubes remain gapless in that approximation. The property is determined by the wrapping vector, not simply by calling a tube “chiral” or by its diameter alone.
A single-walled carbon nanotube confines the electron around its circumference while allowing motion along its axis. Nanotube zone folding therefore turns the graphene bands into one-dimensional subbands. A semiconducting carbon nanotube has no allowed circumferential wave vector through a Dirac valley; a metallic tube has a band crossing at the Fermi energy in the ideal model. Each massive subband edge gives a one-dimensional van Hove singularity in the density of states, and corresponding peaks appear in the joint density of states.
For light polarized along the tube, the main electric-dipole selection rule conserves circumferential angular momentum: transitions connect matching valence and conduction subbands. These finite-energy transitions are conventionally in a semiconducting carbon nanotube and in a metallic tube. A metallic band crossing does not make its first strong interband peak have zero energy. Perpendicular polarization admits different angular-momentum channels, often much weaker because of depolarization. Excitons, dielectric screening and trigonal warping modify the simple band-edge transition energies.
Figure 1.
Nanotube optical transitions and two example roll-up vectors
. Original band and lattice schematics. Arrows indicate matching-subband transitions; the metallic crossing is separate from its finite-energy interband resonance. Lattice points represent graphene unit cells rather than individual atoms. Source. Details.
Experimentally, measure absorption versus photon energy; Raman spectroscopy becomes resonantly enhanced when the excitation matches an optical transition. A photoluminescence excitation spectrum of dispersed semiconducting tubes correlates excitation near with emission near after relaxation. Metallic tubes generally lack comparable bright emission because nonradiative relaxation is efficient. Combining optical energies with radial-breathing-mode Raman spectroscopy or electron diffraction assigns tube diameter and roll-up indices; a Kataura plot organizes those assignments.[ref]
In catalytic chemical vapor deposition, a metal nanoparticle activates a carbon-containing feedstock and supplies mobile carbon to the growing rim. Carbon can diffuse over the particle surface and, depending on the catalyst state, through its bulk. Once a curved carbon cap nucleates, continued incorporation extends the tube. Strong catalyst-support adhesion favors base growth; weaker adhesion can allow the particle to lift with the tube tip. A liquid catalyst is not universally required.
Particle size constrains tube diameter, but semiconducting character requires a particular wrapping family: . Merely making particles smaller does not select that congruence class. Routes toward predominantly semiconducting carbon nanotubes include controlling catalyst composition, exposed facets and size distribution to bias cap/rim nucleation and growth, or adjusting carbon chemical potential and growth/etching conditions so that metallic tubes are less likely to survive.
These are mechanistic strategies rather than a universal recipe. Experiments with catalyst conditioning found that high semiconducting selectivity depended sensitively on oxidizing/reducing gas conditions and came with a strong yield penalty, motivating a catalyst-deactivation model.[ref]
The useful distinction is between selecting a structure at nucleation, selecting its growth rate, and selectively terminating or removing unwanted tubes. Each can enrich the semiconducting fraction, but they do not establish the same growth mechanism.
graphene is a two-dimensional honeycomb lattice with two sublattices. Nearest-neighbour hopping gives two bands . They touch at two inequivalent valleys. Expanding near valley gives
The two-component spinor describes sublattice amplitudes, not real spin. This is a massless two-dimensional Dirac Hamiltonian with material velocity in place of . The emergent band quasiparticles are relativistic in this mathematical sense; the electron's vacuum rest mass is not set to zero. Real spin and valley each contribute a degeneracy of two in the ideal low-energy model.
A single-walled carbon nanotube is a rolled graphene sheet with carbon nanotube chiral vector . Periodicity requires , selecting lines through graphene momentum space and producing one-dimensional transverse electronic modes. Near a valley,
A quantization line through one of the Dirac valleys in graphene gives a metallic branch; ideal nanotube zone folding gives the criterion . Otherwise the nearest line misses the valley and opens . The transverse momentum gives a carbon-nanotube Dirac mass, with . For a large-radius ideal semiconducting tube, and , showing the inverse-diameter gap. Curvature, strain, spin-orbit coupling and interactions can change the simple classification; nominally metallic non-armchair tubes can acquire small gaps. One-dimensional transverse electronic mode thresholds give Van Hove singularities, unlike graphene's low-energy density of states proportional to .
A gate changes occupation and the Fermi level in both systems. Ideal monolayer graphene can be tuned through charge neutrality from holes to electrons, but an ordinary scalar gate does not open a bulk band gap. Including spin and valley,
The gate relation includes geometric and quantum capacitances, so one should not equate gate voltage to Fermi energy without the capacitance model. A semiconducting carbon nanotube can instead be depleted when its Fermi level lies in a gap and turned on in electron or hole bands. Contact Schottky barriers can strongly influence the observed nanotube field effect. A truly gapless ideal metallic tube cannot be switched off simply by moving the Fermi level through its band crossing. These gate responses reflect band structure and contacts, not a change of wrapping indices.
Figure 1.
Original low-energy graphene cut and metallic or gapped nanotube subbands
. Details.
A measured emission intensity as excitation photon energy is varied, with emitted energy also selected or resolved. Excitation-emission maps can separate transitions belonging to different semiconducting carbon nanotubes.