Introduction

Theory
Results

Electric Field Induced Deformations of Carbon

Nanotubes
On the way to the development of Nanoelectromechanical Systems

Zhao Wang

Institute UTINAM
University of Franche-Comté, France

April 12, 2007

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Basic definitions
Theory Application
Results Focus & Motivation

What is this?

First identification: S. Iijima, Nature, 354 56 (1991).

Very small diameter < 10 nm. 1 mm = 1000000 nm

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Basic definitions
Theory Application
Results Focus & Motivation

Atomic structure

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Basic definitions
Theory Application
Results Focus & Motivation

Atomic structure

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Basic definitions
Theory Application
Results Focus & Motivation

Atomic structure

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Basic definitions
Theory Application
Results Focus & Motivation

Atomic structure

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Basic definitions
Theory Application
Results Focus & Motivation

Electronic structure

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Basic definitions
Theory Application
Results Focus & Motivation

Overview

Unique properties:
Highest Young’s modulus, ≈ 1 TPa
Highest thermal conductivity, 4000 W/m.K
Highest current density 109 A/cm2
Ballistic electron transport
Electrode potential range/surface area
Sharp - large aspect ratio
Promising applications:
NEMS, field emission, electrical composites, Vias, FE, FETs,
composites, (bio-)sensors, supercapacitors, growth substrates
for bioengineering and ...

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Basic definitions
Theory Application
Results Focus & Motivation

Nanoelectromechanic systems(NEMS)

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Basic definitions
Theory Application
Results Focus & Motivation

Focus & Motivation

Focus:
The deformations of CNTs induced by external electric field:
electrostatic deflection
electrostriction

Objective:
giving a better theoretical understanding to the
electrostatic deformations of CNTs.
finding new properties of CNTs in the electric field.
developing the computational method concerning the
external field effects for carbon (particularly sp2 ) systems.
modeling recently designed NEMS and open the path to
some new designed nanodevices

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

2. Theory

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

History

Dipole-only model: Silberstein (1917) Phil. Mag., 33, 92.

Applequist (1972) JACS 94, 2952.
- A number of success in predicting molecular properties.
Charge-dipole model: Olson (1978)JCP 69, 5400.
- Adding the mobile charge for π bonded molecules.
Regularization of dipole interaction tensor: Thole
(1981)Chem. Phys. 59, 341.
- An extension to avoid the so-called ’polarizability catastrophe’.
Parametrization: Jensen (2002)JCP 116, 4001. Langlet
(2004)JCP 121, 9655. Mayer (2005)PRB 71, 235333.
- Adaptation to fullerenes and carbon nanotubes.

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

History

Dipole-only model: Silberstein (1917) Phil. Mag., 33, 92.

Applequist (1972) JACS 94, 2952.
- A number of success in predicting molecular properties.
Charge-dipole model: Olson (1978)JCP 69, 5400.
- Adding the mobile charge for π bonded molecules.
Regularization of dipole interaction tensor: Thole
(1981)Chem. Phys. 59, 341.
- An extension to avoid the so-called ’polarizability catastrophe’.
Parametrization: Jensen (2002)JCP 116, 4001. Langlet
(2004)JCP 121, 9655. Mayer (2005)PRB 71, 235333.
- Adaptation to fullerenes and carbon nanotubes.

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

History

Dipole-only model: Silberstein (1917) Phil. Mag., 33, 92.

Applequist (1972) JACS 94, 2952.
- A number of success in predicting molecular properties.
Charge-dipole model: Olson (1978)JCP 69, 5400.
- Adding the mobile charge for π bonded molecules.
Regularization of dipole interaction tensor: Thole
(1981)Chem. Phys. 59, 341.
- An extension to avoid the so-called ’polarizability catastrophe’.
Parametrization: Jensen (2002)JCP 116, 4001. Langlet
(2004)JCP 121, 9655. Mayer (2005)PRB 71, 235333.
- Adaptation to fullerenes and carbon nanotubes.

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

History

Dipole-only model: Silberstein (1917) Phil. Mag., 33, 92.

Applequist (1972) JACS 94, 2952.
- A number of success in predicting molecular properties.
Charge-dipole model: Olson (1978)JCP 69, 5400.
- Adding the mobile charge for π bonded molecules.
Regularization of dipole interaction tensor: Thole
(1981)Chem. Phys. 59, 341.
- An extension to avoid the so-called ’polarizability catastrophe’.
Parametrization: Jensen (2002)JCP 116, 4001. Langlet
(2004)JCP 121, 9655. Mayer (2005)PRB 71, 235333.
- Adaptation to fullerenes and carbon nanotubes.

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

polarization & dipole

Electric polarization:

An atomic dipole moment P:

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

polarization & dipole

Electric polarization:

An atomic dipole moment P:

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

polarization & dipole

Electric polarization:

An atomic dipole moment P:

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

polarization & dipole

Electric polarization:

An atomic dipole moment P:

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

polarization & dipole

Electric polarization:

An atomic dipole moment P:

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Dipole-only (PP) model

Atom i is modeled as a dipole p i .

U elec - electrostatic energy:

N is the total atom number.

E is the external(initial) electric field.
T stands for the tensor of vacuum electrostatic propagator
renormalized by a Gaussian distribution.
Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes
 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Dipole-only (PP) model

Atom i is modeled as a dipole p i .

U elec - electrostatic energy:

N is the total atom number.

E is the external(initial) electric field.
T stands for the tensor of vacuum electrostatic propagator
renormalized by a Gaussian distribution.
Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes
 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Charge-dipole (QP) model

Atom i is modeled as a dipole p i + a quantity of charge qi .

U elec - electrostatic energy

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Charge-dipole (QP) model

Atom i is modeled as a dipole p i + a quantity of charge qi .

U elec - electrostatic energy

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Regularized propagators (interaction tensors) T

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Regularized propagators (interaction tensors) T

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Regularized propagators (interaction tensors) T

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Regularized propagators (interaction tensors) T

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Atomic polarizabilities
Metallic CNTs * QP model with isotopic polarizability αiso =.
ᾱ = αiso
Semiconducting CNTs * PP model with anisotropic polarizabilities
α// = 2.47Å3 and α⊥ = 0.86Å3 .
ᾱ = 3/( α2 + 1
α⊥
)
//

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Self energies
i =j ?

Taking lim ri,j → 0, we obtained:

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Resolution for PP model:

The equilibrium state of the dipole distribution should correspond to

the minimum value of U elec . ⇒

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Resolution for PP model:

The equilibrium state of the dipole distribution should correspond to

the minimum value of U elec . ⇒

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Resolution for QP model:

The equilibrium state of the dipole and charge distribution should
correspond to the minimum value of U elec . ⇒

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Resolution for QP model:

The equilibrium state of the dipole and charge distribution should
correspond to the minimum value of U elec . ⇒

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Empirical potential
The total potential energy of system:

U tot = U elec + U p (1)

The interatomic potential U p * AIREBO

History of this empirical potential:
Empirical chemical pseudopotential theory - Abell(1985) PRB 31, 6184.
A many-body energy function for carbon - Tersoff (1988) PRL 61, 2879.
A step to conjugated hydrocarbons: REBO - Brenner (1990) PRB 42, 9458.
2nd generation - Brenner (2002) J. phys.: Condens. Matter 14, 783.
AIREBO = 2nd generation REBO + long-range + single bond torsional
- Stuart (2000) JCP 112, 6472

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Empirical potential
The total potential energy of system:

U tot = U elec + U p (1)

The interatomic potential U p * AIREBO

History of this empirical potential:
Empirical chemical pseudopotential theory - Abell(1985) PRB 31, 6184.
A many-body energy function for carbon - Tersoff (1988) PRL 61, 2879.
A step to conjugated hydrocarbons: REBO - Brenner (1990) PRB 42, 9458.
2nd generation - Brenner (2002) J. phys.: Condens. Matter 14, 783.
AIREBO = 2nd generation REBO + long-range + single bond torsional
- Stuart (2000) JCP 112, 6472

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Empirical potential
The total potential energy of system:

U tot = U elec + U p (1)

The interatomic potential U p * AIREBO

History of this empirical potential:
Empirical chemical pseudopotential theory - Abell(1985) PRB 31, 6184.
A many-body energy function for carbon - Tersoff (1988) PRL 61, 2879.
A step to conjugated hydrocarbons: REBO - Brenner (1990) PRB 42, 9458.
2nd generation - Brenner (2002) J. phys.: Condens. Matter 14, 783.
AIREBO = 2nd generation REBO + long-range + single bond torsional
- Stuart (2000) JCP 112, 6472

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Empirical potential
The total potential energy of system:

U tot = U elec + U p (1)

The interatomic potential U p * AIREBO

History of this empirical potential:
Empirical chemical pseudopotential theory - Abell(1985) PRB 31, 6184.
A many-body energy function for carbon - Tersoff (1988) PRL 61, 2879.
A step to conjugated hydrocarbons: REBO - Brenner (1990) PRB 42, 9458.
2nd generation - Brenner (2002) J. phys.: Condens. Matter 14, 783.
AIREBO = 2nd generation REBO + long-range + single bond torsional
- Stuart (2000) JCP 112, 6472

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Empirical potential
The total potential energy of system:

U tot = U elec + U p (1)

The interatomic potential U p * AIREBO

History of this empirical potential:
Empirical chemical pseudopotential theory - Abell(1985) PRB 31, 6184.
A many-body energy function for carbon - Tersoff (1988) PRL 61, 2879.
A step to conjugated hydrocarbons: REBO - Brenner (1990) PRB 42, 9458.
2nd generation - Brenner (2002) J. phys.: Condens. Matter 14, 783.
AIREBO = 2nd generation REBO + long-range + single bond torsional
- Stuart (2000) JCP 112, 6472

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

AIREBO

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

AIREBO

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

AIREBO

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Energy minimization

Energy minimization * searching for the optimized equilibrium

state of molecules.

Algorithm: Conjugated Gradient.

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction Electrostatic potential
Theory Interatomic energy
Results Structure optimization

Energy minimization

Energy minimization * searching for the optimized equilibrium

state of molecules.

Algorithm: Conjugated Gradient.

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

3. Results

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Electrostatic deflection of Cantilevered CNTs

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Electrostatic deflection of Cantilevered CNTs

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Electrostatic deflection of Cantilevered CNTs

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Electrostatic deflection of Cantilevered CNTs

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Electrostatic deflection of Cantilevered CNTs

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Charge and dipole

Induced dipoles and charges on ametallic (5,5) SWCNTs subjected to electric fields. The positive charges (red)

move along to the field direction and the negative ones (blue) move to opposite. The green vectors stand for the

dipoles. The maximal amplitudes of these charges and dipoles in the horizontal field are about 0.34 unit of e and

0.11 D, respectively. The middle of the tube remains neutral.

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Electrostatic force

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Electrostatic force

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Influence of field strength

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Influence of field direction

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Electrostriction

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Geometric effects - metallic tubes

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Geometric effects - semiconducting tubes

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Doubled-walled CNTs

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

5-7-7-5 defect

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

5-7-7-5 defect

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

5-7-7-5 defect

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Defective structure

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes

 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Electrocstatic deflection

Primary results show:

Electric field makes defective tuve straight.
Deflection is reduced by 5-7-7-5 defects.
Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes
 Introduction
Defect-free CNTs
Theory
Defective CNTs
Results

Thanks

Thanks!

Zhao Wang Electric Field Induced Deformations of Carbon Nanotubes