section 1 oms
DESCRIPTION
OMS1TRANSCRIPT
Organic Molecular Solids
Prof. Allen M. HermannProfessor of Physics Emeritus
University of ColoradoBoulder, Colorado USA
and
Vice-PresidentNanoTech Solutions, Inc.
Lexington, KY USA
Course Outline
Section I.. IntroductionMaterials, crystal structures
Prototypical Molecules, anthracene, naphthalene, etc.
Molecular Solids
Materials Preparation
Electronic Properties Measurements
II. Insulators
Charge Transport Theory, narrow bands
Delocalized (Bloch) Wave Functions
Localized Wave Functions
Excitons
Peirels Distortion (1D systems)
III. Transient and Steady-state Photoconductivity in Insulators, Theory and ExperimentSmall-signal limitDrift MobilityTrapping (shallow and deep)
IV. Effects of Finite Charge InjectionBoundary Conditions, Space Charge Limited CurrentsPulsed, Steady-state Electric Fields and Light ExcitationsDispersive transport
VI. Carbon-based nanostructures and SuperconductorsBuckyballs, Nanotubes, GrapheneOrganic Superconductors
V. Organic ConductorsCharge-transfer ComplexesQuasi-one-dimensional and two-dimensional materials, radical-ion saltsPolymers
VII. ApplicationsElectrostatic Imaging and Xerographic materialsOrganic Light-emitting diodes ) OLEDS and Active Matrix OLEDS (AMOLEDS) for Display and LightingSolar CellsField-effect transistorsBatteriesPhoto-detectorsLuminescence for Land-mine SniffingLasersSwitchesE-Ink
Section I.
. IntroductionMaterials, crystal structures
Prototypical Molecules, anthracene, naphthalene, etc.
Molecular SolidsMaterials PreparationElectronic Properties
Measurements
Conductivity Of Organic Materials
Bonds
Chapter 5 of Solymar
Introduction
• When two hydrogen atoms come close to each other
– They form a chemical bond, resulting in a hydrogen molecule (H2)
• When many silicon atoms come close– They form many chemical bonds, resulting in a crystal
• What brings them together?– The driving force is
To reduce the energy
Interactions between Atoms
• For atoms to come close and form bonds, there must be an attractive force– Na gives up its 3s electron and becomes Na+
– Cl receives the electron to close its n = 3 shell and becomes Cl-
– The Coulomb attractive force is proportional to r-2
• In the NaCl crystal, Na+ and Cl- ions are 0.28 nm apart– There must be a repulsive force when the ions are too close to
each other
– When ions are very close to overlap their electron orbitals and become distorted, a repulsive force arises to push ions apart and restore the original orbitals
– This is a short-range force
Equilibrium Separation
• There is a balance point, where the two forces cancel out (Fig. 5.1)– The energy goes to zero at infinite separation
– As separation decreases, the energy decreases, so the force is attractive
– At very small separation, the energy rises sharply, so the force is strongly repulsive
– The minimum energy point (Ec, or the zero force point) corresponds to the equilibrium separation ro
– The argument is true for both molecules in crystals
Mathematical
• Mathematically
– A and B are constants
– The first term represents the repulsion and the second attraction
• Minimum energy
– It must be negative, so m < n
mn r
B
r
A)r(E
)1n
m(
r
BE
m
o
C
Bond Types
• Four types in total
– Ionic
– Covalent
– Metallic
– van der Waals
Metallic Bonds
• Each atom in a metal donates one or more electrons and becomes a lattice ion
– The electrons move around and bounce back and forth
– They form an “electron sea”, whose electrostatic attraction holds together positive lattice ions
– The electrostatic attraction comes from all directions, so the bond is non-directional
– Metals are ductile and malleable
Covalent Bonds
• When two identical atoms come together, a covalent bond forms
• The hydrogen molecule– A hydrogen atom needs two electrons to fill its 1s shell
– When two hydrogen atoms meet, one tries to snatch the electron from the other and vice versa
– The compromise is they share the two electrons
• Both electrons orbit around both atoms and a hydrogen molecule forms
• The chlorine molecule– A chlorine atom has five 3p electrons and is eager to grab one more
– Two chlorine atoms share an electron pair and form a chlorine atom
Group IV
• Carbon 1s22s22p2; Si 1s22s22p63s23p2; Ge 1s22s22p63s23p63d104s24p2
• Each atom needs four extra electrons to fill the p-shell– They are tetravalent
• sp3 hybridization– s shell and p shell hybridize to form four equal-energy dangling
electrons
– Each of them pairs up with a dangling electron from a neighbor atom
– There are four neighbor atoms equally spaced
– Each atom is at the center of a tetrahedron
– Interbond angle 109.4
– Covalent bond is directional
Group IV
• At 0 K– All electrons are in bonds orbiting atoms– None can wander around to conduct electricity– They are insulators
• At elevated temperatures– Statistically, some electrons can have more enough energy to
escape through thermal vibrations and become free electrons– They are semiconductors
• The C–C bond is very strong, making diamond the hardest material known (Table 5.1)– Diamond has excellent thermal conductivity– It burns to CO2 at 700C
van der Waals Bonds
• Argon has outer shell completely filled
• When argon is cooled down to liquid helium temperature, it forms a solid– The electrons are sometimes here and sometimes there, so the
centers of the positive charge (nucleus) and negative charge (electrons) are not always coincident
– The argon atom is a fluctuating dipole (instantaneous dipole)
– It induces an opposite dipole moment on another argon atom, so they attract each other
– Such attraction is weak, so the materials have low melting and boiling temperatures
– They are often seen in organic crystals
Aromatic Hydrocarbon Bonds
Conducting Organic Materials
Extreme Case – Nearly Ionic Bonds in Highly Conducting Complexes
“Charge Transfer salts”
Discovery of Conducting Organic Crystals
Materials Preparation Techniques
S
S
S
S
S
S
S
S
Electronic Measurements
Conductivity (Resistivity)
Conductivity s = enm
n: number of carriers; m: mobility of the carriers
4-probe resistivity measurement
Van Der Pauw resistivity measurement
Hall effect
Drift Mobility from Time of Flight Measurements and TFT
Structures
Some references to this material