Electronic Structure of Materials

Teerakiat Kerdcharoen
Capability Building Center for Nanoscience & Nanotechnology Faculty of Science Mahidol University

http://nanotech.sc.mahidol.ac.th

Objectives of this Lecture

New tools that help scientists understand materials at the bottom To understand how electronic structure determine atomic structure (nanoscopic structure) and finally macroscopic properties of materials How materials function from the nanoscale point of view Basic of nanotechnology

State of Matter/Materials
Solid Liquid Gas Plasma
Many materials have unclear boundary between each state, and may have some phases in between. Examples: Polymers have transition between plastic and glass phases

State of Matter/Materials

Understanding Scale

Structure of Materials
Macroscopic structure
- shape, roughness, hardness, flexibility, strength etc.
(process engineering and manufacturing)

Mesoscopic structure
- morphology, grain or particle size, phase
(materials engineering)

Nanoscopic (~Microscopic) structure

- molecular geometry, electronic structure
(nanotechnology)

Structure Characterization
Macroscopic structure
- Mechanical properties (hardness, strength etc)

Mesoscopic structure
- SEM, TEM, Optical microscope, XRD

Nanoscopic structure
- STM, AFM, SNOM, X-Ray Crystallography

Mesoscopic Structure
Morphology of the surface
(grain, domain, phase)

Pictures from R. W. Siegel Rensselaer Polytechnic Institute (left and middle) Picture from NASA Ames Lab (right)

Nanoscopic Structure
Atomic resolution

Pictures from NASA Ames Lab

Nanoscopic Structure
Atomic resolution

Pictures from NASA Ames Lab (left), Nature magazine (right)

How small is nanometer ?

micrometer millimeter
1 nm= 1/1,000,000,000 meter

1.74 meter

nanometer

Why Study Electronic Structure

Electronic structure Chemical force Geometry of molecule, nanostructure Electronic properties Thermodynamic properties Mechanical properties

Electronic Structure

Materials Properties

Atomic Orbital
Home of electron = orbital Probability defines shape & size of orbital

1s

Pictures from http://www.chemguide.co.uk/

2s

2p

Chemical Bonding
A bond is the force that connect 2 atoms together

H-F (hydrogen fluoride)

Molecular Orbital
Example: The case of Hydrogen Fluoride (H-F)

Molecular orbitals are homes of electrons in a molecule.

Molecular Orbital
Example: The case of Hydrogen Fluoride (H-F)

Electrons condense into some region making chemical bond

Molecular Orbital
Example: The case of Hydrogen Fluoride (H-F)

Some homes span only over a limited space or only on one atom. The electrons in such orbitals are localized.

Theory of Electronic Structure

Electron is represented by wave function

Electron density is the probability to find electron at a location

Theory of Electronic Structure

To find the wave function and other properties, one must solve the Schroedinger equation 1-D

3-D

Electrons in Metal
The model: Electron gas (particle in a box) Each atom donates one electron and the free electrons can go wherever they want

Energy is discrete (Quantum State)

Fermi Level
Empty states

Fermi level

Filled states

When we fill up the states by electrons the most top level is called Fermi level.

Band Theory

Band Theory

Band Theory

Electronic Structure Calculation

Electrons are described by wave function.
To know the properties of these electrons, we probe the wave function with appropriate operator.

Hamiltonian Operator

QM: Born-Oppenheimer Approximation

Electron is 1800 times lighter than protron/neutron

Hartree Approximation
Wavefunction can be expanded by a set of functions.

Total wavefunction is a product of one-electron wavefunctions (molecular orbitals).

Slater determinant preserves antisymmetry principle and introduces orthonormality of the wavefunction.

Construction of MO
Molecular Orbital is a linear combination of Atomic Orbitals. Atomic Orbital Molecular Orbital Atomic Orbital is based on radial function and spherical harmonic.

Nowadays, atomic orbital is usually based on Gaussian Type Orbitals.

Construction of AO
Quality of atomic orbitals can be controlled by mathematical functions
STO-3G 3-21G 6-31G* 6-31G**

Examples: H-F

How accurate is the calculation

Chem. Phys. Lett. 321 (2000) pp. 78-82

STM Experiment

DFT Calculation

Frontier States
The frontier states involve in electronics and optoelectronics.

LUMO (Lowest Unoccupied)

HOMO (Highest Occupied)

Luminescence
When electron steps down from higher energy level to Lower energy level, it release photon.

1) 2) 3)

Transition due to defect Interband transition Intraband transition

Chemical structure from electronic structure

Molecule as we know, is a soup of electrons and nuclei. Bonding is only interpretation or explanation of this soup.

Molecular Mechanics (MM)

Molecular Mechanics consider a molecule as system of rigid balls connected via springs

- depend strongly on concepts of bonding - neglect the electronic degrees of freedom - follows the Newtonian laws

MM: Energy Terms

Energy of a system is a sum of all interactions within and between the springs

MM: Valence Terms

Valence term is the relative energy of a spring.

MM: Valence Term

Valence terms are interactions within the springs. A spring wants to relax to its original shape.

MM: Valence Terms

Picture from: Peter J. Steinbach, Introduction to Macromolecular Simulation.

MM: Cross Terms

Cross term is due to coupling between 2 springs. It is a correction to independent spring model.

MM: Cross Terms

Cross terms are interactions between 2 or more springs. Cross terms are corrections to the independent spring model.

MM: Non-Bond Terms

Non-Bonded term is interaction between two balls.

MM: Non-Bond Terms

Non-bond terms are interactions between the balls. Non-bond terms are long-range interactions. Repulsion

Attraction

MM: Non-Bond Terms

Non-bond terms are interactions between the balls. Non-bond terms are long-range interactions.
3

Repulsion

V(r)
0

-3 0.8 1.0 1.2 1.4 1.6 1.8

r, nm
2.0

Attraction

MM: Sum of Energy

E=

Stretching(C-H1)+Stretching(C-H2)+... + Bend(H1-C-H2) + Bend (H1-C-H3) + + Bend(H1-C-C) + + Bend (C-C=O) + . + Torsion (H1-C-C=O) + ... + + Torsion (O1=C-O2-H4) + vdW(H1-H4) + + Elec (H1-H4) +

We can design nanoscale devices

We can model the machinery

We can simulate nanoscale phenomena

Introduction to Nanotechnology

What is Nanotechnology ?
Capability to manipulate, control, assemble, produce and manufacture things at atomic precision

Richard Feynman
There is plenty of room at the bottom
-- Special Lecture in 1959 -The principles of physics, as far as I can see, do not speak against the possibility of maneuvering things atom by atom. It is not an attempt to violate any laws; it is something, in principle, that can be done; but in practice, it has not been done because we are too big The problems of chemistry and biology can be greatly helped if our ability to see what we are doing, and to do things on an atomic level, is ultimately developed---a development which I think cannot be avoided.

Nobel Prize in Physics, 1965

Nanotechnology is the Future ?

1800-1900: 1900-1950: 1950-2000: 2000-2050: 2050-2100: 1st Industrial Revolution Automation Age Quantum Revolution Atomic Age IT Revolution Electronic Age Biotech Revolution Genomic Age nd Industrial Revolution 2 Nano Age

The Law of S-Curve

Nanotechnology in Nature

Moores Law
Gordon Moore Co-Founder of Intel Corp.

CPU is doubled in performance every 18 months The feature size for device in a semiconductor chip is decreasing by a factor of 2 every one and a half year The number of transistors the industry would be able to place on a computer chip would double every 1.5 years

Cost of constructing a new Fabs will double every 3 years

Moores Curve

Nanocomputer
Mechanical Nanocomputer Electronic Nanocomputer Chemical / Biochemical Nanocomputer Quantum Computer

Mechanical Nanocomputer
The first mechanical computer was designed by Charles Babbage (Cambridge University) in 1837 called Difference Engine No. 1 K. Eric Drexler proposed a design of mechanical nanocomputer based on rods and gears made of molecules in 1988.

Pictures from Acc. Chem. Res. 34 (2001) 445.

Electronic Nanocomputer
Continue a miniaturization of current electronic computer Elementary components are based on soft materials, i.e. organic molecules, semiconducting polymers or carbon nanotubes, instead of inorganic solid-state materials Use only 1 or few electrons instead of billion electrons Use self assembly or other patterning techniques instead of photolithography

Chemical Nanocomputer
Computing is based on chemical reactions (bond breaking and forming) Inputs are encoded in the molecular structure of the reactants and outputs can be extracted from the structure of the products Adleman proposed DNA computing in 1994 for solving Hamiltons path problem

Picture from http://www.englib.cornell.edu/scitech/w96/DNA.html

Quantum Computer
Based on proposals by Bennett, Deutsch and Feynman in 1980s Use quantum bit (qubit) from the physical properties of materials, i.e. spin state, polarization. Parallelism in Nature

Hybrid System
Integration between Silicon and Carbon systems Life and Non-Life Integration Mechanical, Electronic, Chemical and Quantum Integration

Aviram & Ratners Molecular Diode

1974 : Aviran & Ratner proposed a model of molecular rectifier

Discovery of Conductive Polymers

1977 : Shirakawa and MacDiarmid (Nobel Prize 2000) accidentally found that doped conjugated polymers can conduct electricity

Discovery of OLED
1987 : Kodaks scientist developed organic light emitting diode (OLED)

Picture from Kodak and from Richard Friends group

Single Molecules Conduction

1996 : Tour and Weiss demonstrated electrical conduction in molecular wire

Discovery of Molecular Diode

1997 : Metzger discovered first D-pi-A molecular rectifier

Organic IC
1998 : de Leeuw succeed to fabricate organic IC made of 326 allpolymer transistors

Single-Molecule Switch
1999 : Tour and Reed demonstrate negative differential resistance behavior in molecule

Picture from Mark Reed

Invention of Dip-Pen Nanolithography

2000 : Mirkin invented Dip-Pen Nanolithography

Picture from Mirkins Group

Scanning Probe Microscope

Scanning Probe Microscope