The Materials Science of Nanoelectronics

MAT 791Q, Fall Semester 2003 Oct. 31, 2003

Carbon Nanotubes (CNT)

CNT structure CNT synthesis CNT electronic properties

Carbon Nananotubes: What are they?

Carbon nanotubes (NT) are hollow elongated cylindrical arrangements of atoms, closed at the ends with hemispherical caps They can be a single-wall or a multiwall variety, when several cylinders (and the corresponding caps) form a nested Russian doll structure. A perfect wall of an NT is essentially a rolled up monoatomic layer of graphite, that is a hexagonal honeycomb lattice of covalent C-C bonds.
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CNT is a tubular form of carbon with diameter as small as 1 nm. Length: few nm to microns. CNT is configurationally equivalent to a two dimensional graphene sheet rolled into a tube.

CNT can be metallic or semiconducting, depending on chirality.

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Single-walled and Multi-walled CNT

There are two main types of Carbon Nanotubes, Multi-Walled Nanotubes and SingleWalled Nanotubes. MWNTs contain overlapping cylindrical tubes, like a coaxial cable. Their diameters range from a few nanometers to around 40nm, depending on the number of concentric tubes. SWNTs, on the other hand, consist of one tube with a diameter of approximately 1.4nm.

Multi-Walled CNT

Single-Walled CNT

Multi-Walled CNT

What are the major structural characteristics?

NT diameter ranges from 1 nm to 20-30 nm, and is much less than its length Interlayer separation in a multi-wall NT is close to 0.34 nm (like in graphite). A crucial property is the corkscrew symmetry of NT depending on the orientation of the hexagonal pattern of the wall with respect to the molecular axis, often called helicity and specified by the angle between the NT circumference and the zigzag atomic motif of the hexagonal wall. Another conventional way to identify the helicity is by the vector (c1,c2) on the graphene lattice corresponding to the NT perimeter. NTs with c2 = 0 ( = 0) are called zigzag, and those with c2 = c1 ( = /6) are armchair. These types are achiral, while any tubule with 0 < < /6 is chiral.

Fabrication of Carbon Nanotube Materials: Arc-discharge method

The process involves striking a plasma between two graphite electrodes in a vacuum chamber filled with He. Relatively large quantities (102 -103gram/day) of MWNTs can be produced when the system is optimized. Materials produced typically consist of 50-70% MWNTs with large variations in outer (5-50nm) and inner (2-10nm) shell diameters and length. The impurities are multi-walled nanotube particles and amorphous carbon structures. Fullerenes: P<100 Torr The method is commercialized (yield~75% of C60 in soot) MWNT: with or without catalyst, P >500Torr SWNT: Catalyst required
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He
ArcI

discharge

Fabrication of Carbon Nanotube Materials: Laser-ablation

SWNTs with relatively high purity (60-70%) and narrow diameter distribution (1.2-1.8nm) can be fabricated by ablating a graphite target mixed with metal catalysts at high temperature. Both metallic and semiconducting nanotubes are produced. The laser ablation method affords more experimental control but at a slower production rate compared to that of the arc-discharge method.
Laser ablation

Oven T~ 1200oC

SWNT: Catalyst required Yield in soot ~90% (with two lasers)

Fabrication of Carbon Nanotube Materials: Chemical Vapor Deposition

CVD provides a low temperature alternative to the two high temperature processes discussed above and can potentially lead to economical high volume production. MWNT: low quality Catalyst required ~60% yield of all carbon feed SWNT Catalyst required Yield 200% in excess of Catalyst weight

CVD CnHm catalyst

Oven T~ 500-1000oC

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CNT has been grown by laser ablation (pioneering at Rice) and carbon arc process (NEC, Japan) - early 90s. SWNT, high purity, purification methods CVD is ideal for patterned growth (electronics, sensor applications) - Well known technique from microelectronics - Hydrocarbon feedstock - Growth needs catalyst (transition metal) - Multiwall tubes at 500-800 deg. C. - Numerous parameters influence CNT growth

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CNT Molecular Network

Large scale computer simulations based on ab initio methods enable understanding nanotube characteristics and serve as design tool - Evaluation of mechanical properties - Evaluation of electronic properties - Electron transport in CNT devices - Functionalization of the nanotubes - Design of electrical and mechanical devices - Evaluation of storage potential (H2, Li)

CNT T and Y Junctions

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Representative images of CNT bundles

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Carbon nanothermometer containing gallium

YIHUA GAO AND YOSHIO BANDO

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Energy band structure of CNT

CNT can be either metallic or semiconducting, depending on the 1st Brillouin Zone. The 1st Brillouin Zone is the primitive cell of the lattice in reciprical space, and it exhibits the wavevectors of the lattice. From this, a simple relationship stating that if:

n-m is divisible by three, metallic n-m not divisible by three, semiconducting, with a gap of ~0.5 eV.

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How do NT conduct?
for the same elemental composition, the answer depends on helicity. Armchair NT are metallic, with zero gap and an estimated carrier density ~1022 cm-3 for equivalent bulk material; chiral tubes with c2 - c1 multiple of 3 have a very small (meV) curvature-induced gap ~1/d2, and other types are semiconductors with a gap ~1/d in the range of 1 eV. Conductivity can be vulnerable to minor deformations. Besides these elastic perturbations, any atomic disorder or doping with other elements can change the electronics significantly.

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High-resolution STM image of an individual nanotube, showing the chiral winding of the hexagon lattice along the tube axis (Dekker)

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Band gap measurements

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Energy band in metallic CNT (Lieber)

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Electrical Characterization of CNT

Individual single-wall nanotube deposited on 2 Pt electrodes (C. Dekker)

4-probe measurements (Schoenenberger)

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Electrical characteristics of CNT

Method

Author Song et al. De Heer et al. Frank et al. Dai et al.

De Pablo et al. Ebbesson et al. Bachtold et al.

Sample
Bundles of MWNT
Oriented film of MWNT

Min. effective resistivity at 300 K, cm

Currentcarrying capacity, A/cm2

2-t 2-t 2-t 2-t

(STM)

6.5x10-3 20x10-3 >107 8x10-4 1.5x10-5 5.1x10-6 3x10-5

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Individual MWNT Individual MWNT Individual MWNT Individual MWNT Individual MWNT

2-t
(planar)

2.4x108

4-t
(planar)

6x106

4-t
(planar)

Continuous Quantum Wire?

e 2e G=2 =4 h h
2 2

Rmin

1 h h = = 2 = 6.5k 2 2 2e 4e
L=200 nm

Liang et al.
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CNT/metal Schottky diodes

Dekker
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Bandgap modulation of CNT by encapsulated metallofullerenes

Lee et al Gd@C82

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H. Dai: Chemical Doping of CNT

pn junction diodes

Esaki tunnel diode

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CNT p-n-p structure

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Oxygen desorption/adsorption doping

(Avouris)

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P. Avouris: Engineering CNT and CNT circuits by electrical breakdown

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Emerging Technology Sequence

Defect Tolerant QCA 3D Integration RTD-FET Magnetic RAM FD SOI Strained Si Vertical Transistor FinFET SET RSFQ QCA Molecular CNN Quantum computing

Emerging Technology Vectors Architecture

Molecular

Logic

Phase Change Nano FG SET Molecular

Memory

Planar double gate

Nonclassical CMOS

Time

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Summary
Carbon nanotube potentially could be used as nanoelectronic components
Naturally structured Electronic properties can be controlled by geometry and surface adsorbates Ballistic conductance demonstrated at length up to 0.2 m

BUT
There are no methods allowing for reproducible synthesis of CNTs with desired properties (e.g. geometry) No methods for large scale integration of CNTs in useful devices and circuits
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