L3 Electronic Material basics

• Materials Science and Engineering: An Introduction, by William D. Callister and David G. Rethwisch,
Wiley, 2013, 9rd Ed.
• Physics of Semiconductor Devices, by Simon. M. Sze, Wiley, 2006, 3rd Ed.
• Electronic Properties of Materials, by Rolf E. Hummel, Springer, 2001, 3rd Ed.

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Electrical properties

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 PRIMARY INTERATOMIC BONDS

Ionic Bonding Covalent Bonding Metallic Bonding

sharing of electrons among all
bonding forces coulombic sharing of electrons between two atoms atoms
metals and their alloys
ceramic materials nonmetallic elemental molecules (H2, O2) nondirectional
3~8 eV/atom elemental solids (C, Si, Ge) Weak (Hg 0.7 eV/atom)
high melting temperatures Some solid compounds (GaAs, InSb, SiC) or strong (W 8.8eV/atom)
Strong (diamond) or weak (bismuth) good conductors
hard and brittle of both electricity and heat,
Good plasticity

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 SECONDARY BONDING OR
VAN DER WAALS BONDING, physical bonds
• Dipole (van der Waals bonding between two dipoles)

Fluctuating Induced Dipole Bonds Polar Molecule-Induced Dipole Bonds

• hydrogen bond, (a special case of polar molecule bonding, bare proton unscreened by any electrons)

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 Application example: Water

expansion contraction expansion

-LT 0 oC 4 oC HT

Each H2O has 4.5 neighbors by H bond

Each H2O has 4 neighbors by H bond Denser structure (9% denser)
More open structure - Lower density

Imagine what happens if ice is denser than water?

Good things: no water pipe burst

Bad: all the fish would have died.

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Polarization speed for different polarization origins

H2O

NaCl

Si

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Melting temperature is closely related to bonding energy

• Higher bonding energies, higher melting temperatures;

• Secondary bonds are much weaker than the primary bonds.

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Determination of atomic distance

+
-

r
-
+

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Band splitting depending on atomic distance
Closer atoms –
stronger intact-
energy level
widening and
overlapping

Electrons only
bound to its
nucleus –
Discrete levels

continuum discrete energy level

From atomic orbitals

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Possible electron band structures in solids at 0 K

1s22s22p63s2

(a) The electron band structure found in metals such as copper, in which there are available electron states above and
adjacent to filled states, in the same band. (b) The electron band structure of metals such as magnesium, wherein there is an
overlap of filled and empty outer bands. (c) The electron band structure characteristic of insulators; the filled valence band
is separated from the empty conduction band by a relatively large band gap ( eV). (d) The electron band structure found in
the semiconductors, which is the same as for insulators except that the band gap is relatively narrow.

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 Application examples: Band structure and electrical properties

Mg: Al:
1s22s22p63s2 1s22s22p63s23p1

Full shells? Unfilled sp band

Not really- Close to free electron
3s3p overlap Great conductivity

Unfilled sp band No d or f electrons,

Good conductivity nonmagnetic

Fe: Ar? Si?, NaCl?

1s22s22p63s23p64s23d6
Cu:
d electrons – 1s22s22p63s23p63d104s1
transition metal, Filled d band-
nonmagnetic,
OK conductivity, 1s electron- free e like
- exceptional
With unfilled d or f conductivity
electrons, magnetic,

Flexiable d band –
valence changing
capability

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A few intermediate elements play important roles

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Electron configurations are the key
Explain properties of Ar? Si?, NaCl? TiO2? TiO?

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Typical energy band structures for two important
semiconductors
Indirect bandgap direct bandgap

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Fermi-Dirac Distributions

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 Fermi-Dirac Distributions of doped semiconductor

Physics of Semiconductor Devices, by

Simon. M. Sze, Wiley, 2006, 3rd Ed.

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Electrical conduction

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 Classification based on conductance

>1010Ω-cm insulators 1-100 μΩ-cm metals

105 Ω-cm Si

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 Matthiessen’s Rule and TCR
the various electron scattering processes that contribute to the total resistivity (ρ) of a metal do so independently and
additively. The individual thermal, impurity, and defect resistivities are rth, rimp and rdef, respectively.

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Temperature coefficient of resistivity (TCR)

α: Temperature coefficient
of resistivity

Metal:
TCR > 0

Semiconductor and insulator:

TCR < 0

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 Application examples: how to determine the nano-
conduction channel composition using TCR?!
(composition of nanofilament?!)

TCR>0 TCR<0
(TCR vs composition of thin films)

(TCR of nanofilament)

(Composition)

(TCR)
Advanced Materials, Volume 23, Issue 47, pages 5633–5640, December 15, 2011

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 Other scattering: grain boundary and
interface at nanoscale

Figure The resistance of interconnects increases with decreasing conductor width in high aspect ratio lines due to increased sidewall and grain boundary
scattering [(a) From footnote a, (b) based on reference 9]

below 22nm, carrier scattering from the boundaries of individual copper crystal grains and the
interfaces with barrier layers that separate the conductor from the dielectric is rapidly pushing up
interconnect resistivity and, with it, the resistance of individual wires.

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 The Wiedemann-Franz Law
Good electrical conductors are often good thermal conductors:
similar mechanism for conduction of electric current and heat.
Ktotal = Kphonon + Kelectron
Only electrons are responsible for both; free electrons behave like ideal gas

Then at a constant temperature, the ratio of the electrical and thermal conductivities should be
constant for metal conductors.

• Metals with good conductivity generally obey the Wiedemann-Franz law: Al 2.18, Cu 2.3, Mg 2.38, Ni 2.15…
• Some alloys with relatively low electrical conductivities have a larger L than calculated: heat conduction by
electrons and phonons (high vibration of atoms): 55Cu-45Ni 3.56
• Non-metals does not obey the Wiedemann-Franz law due to different thermal conducting mechanisms.

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 Hall Effect
Hall voltage
Electron mobility and carrier type can be determined.

Hall coefficient

Positive and/or negative charge carriers that are part

of the current are deflected by the magnetic field and give rise to the
Hall voltage, VH.

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Determining the direction of magnetic force
The right hand rule states that: to determine the direction of the magnetic force on a positive
moving charge, ƒ, point the thumb of the right hand in the direction of v (velocity), the fingers in
the direction of B, and a perpendicular to the palm points in the direction of F.
Negative charge will have the opposite direction.

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Sheet Resistance

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Sheet Resistance

S S S

S>5t
S<<W, L
Current probes outside

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 Van der Pauw measurements

1. The contacts are on the edge of the sample

2. The contacts are sufficiently small
3. The sample is homogeneous in thickness

The values of the correction function f

are tabulated for any value of the
resistance ratio R12,34/R23,41

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ELECTRON TRANSPORT MECHANISMS

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 MIS (metal-insulator-semiconductor)

Energy-band diagrams showing conduction mechanisms of (a) direct tunneling, (b) Fowler-Nordheim tunneling, (c) thermionic emission, and (d) Frenkel-Poole emission.

Physics of Semiconductor Devices, by

Simon. M. Sze, Wiley, 2006, 3rd Ed.

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Tunneling

Physics of Semiconductor Devices, by

Simon. M. Sze, Wiley, 2006, 3rd Ed.

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Thermal Emission

A is the Richardson constant

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 Space charge limited current
What is space charge:
• Charge is not considered as point charge but as charge distributed over a volume inside the
dielectric;
How is it formed:
• Ionization of species within the dielectric (depletion region – slightly doped);
• Charge injection from electrodes (trapping)
• the rate of carrier injection from the contact exceeds the rate at which charge
can be transported through the film.
The consequences:
• Modify the electric field profile
• Limit further current injection, resulting in nonlinear conduction.

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 Ohmic contact: metal/n-type

Separate In contact Current-voltage

A metal-semiconductor junction will therefore form a barrier for electrons and holes if the Fermi energy of the
metal as drawn on the flatband diagram is somewhere between the conduction and valence band edge.

ΦM < Φs for n type

ΦM > Φs for p type

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Application example: ohmic contact for Si

Criteria for ohmic contact

ΦM < Φs for n type
ΦM > Φs for p type
Al / Si
At interface, Al dope Sià p-type Si

ΦAl > Φsi

Therefore, Al/Si good ohmic contact after annealing
about 550 oC

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Common equations for conduction processes
determination in insulators
Basic Conduction Processes in Insulators

Very Strong V dep, no T dep

Strong T dep

Trapped elections
Thermally activated,
hopping b/w isolated states

Current decreases over

time due to ionic charge
build-up
Strong V dep, no T dep

Physics of Semiconductor
Devices, by Simon. M. Sze,
Wiley, 2006, 3rd Ed.

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 In most of the real cases in the post-CMOS devices:
Localized states within bandgap for amorphous insulators
Most insulating films are amorphous: oxides, nitrides etc.
Extra states in bandgap due to structural imperfections;
Thermal activated conduction: variable range hoping.

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 Real example: possible conductions in memristors

(1) Schottky emission: thermally activated electrons injected over the barrier into the conduction band. (2) Fowler–
Nordheim tunnelling: electrons tunnel from the cathode into the conduction band; usually occurs at high electric field. (3)
Direct tunnelling: electrons tunnel from cathode to anode directly; only when the oxide is thin enough. When the insulator
has localized states (traps) caused by disorder, off-stoichiometry or impurities, trap-assisted transport contributes to
additional conduction, including the following steps: (4) tunnelling from cathode to traps; (5) emission from traps to the
conduction band (Poole–Frenkel emission); (6) tunnelling from trap to conduction band; (7) trap-to-trap hopping or
tunnelling, ranging from Mott hopping between localized states to metallic conduction through extended states; and (8)
tunnelling from traps to anode. EF, Fermi energy level; Ev, valence band; Ec, conduction band; Eb, Schottky barrier height; Et,
trap barrier height.

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Metal/Insulator contacts

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Band diagrams of metal-semiconductor contacts

Decreasing contact gap

Contact potential/built-in potential

Barrier height (n-type)

Barrier height (p-type)
Physics of Semiconductor Devices, by
Simon. M. Sze, Wiley, 2006, 3rd Ed.

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Band diagrams of metal-semiconductor contacts

As the electrons leave the semiconductor, a positive charge, due to the ionized donor atoms,
stays behind (depletion region). This charge creates a negative field and lowers the band edges of
the semiconductor.

Electrons flow into the metal until equilibrium is reached between the diffusion of electrons from the
semiconductor into the metal and the drift of electrons caused by the field created by the ionized impurity
atoms.
Physics of Semiconductor Devices, by
Simon. M. Sze, Wiley, 2006, 3rd Ed.

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Band diagrams of metal-semiconductor contacts

Barrier height Is the potential difference between the Fermi energy of the metal and the band edge where the
majority carriers reside

Barrier height (n-type)

Barrier height (p-type)
Physics of Semiconductor Devices, by
Simon. M. Sze, Wiley, 2006, 3rd Ed.

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 Reverse and Forward biasing conditions
N-type P-type
Thermal equilibrium

Forward bias
+V -V

• Positive bias applied to the metal. (Metal/n-type Semiconductor)

• Fermi energy of the metal is lowered with respect to the Fermi energy in the semiconductor.
• This results in a smaller potential drop across the semiconductor.
•The balance between diffusion and drift is disturbed and more electrons will diffuse towards
the metal than the number drifting into the semiconductor.
•This leads to a positive current through the junction at a voltage comparable to the built-in
potential.
•A large current exists under forward bias.

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Reverse and Forward biasing conditions

+V -V
Reverse bias

•Negative voltage is applied to the metal side. (Metal/n-type Semiconductor)

• Fermi energy of the metal is raised with respect to the Fermi energy in the semiconductor.
• The potential across the semiconductor now increases, yielding a larger depletion region and a
larger electric field at the interface.
• The barrier, which restricts the electrons to the metal, is unchanged so that that barrier, independent of the
applied voltage, limits the flow of electrons.
• The metal-semiconductor junction with positive barrier height has therefore a pronounced rectifying behavior.
• Almost no current exists under reverse bias.

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Barrier height in reality: not that simple

(1) an unavoidable interface layer,

(2) the presence of interface states.
(3) the barrier height can be modified due to
image-force lowering.

Detailed energy-band diagram of a metal-n-semiconductor

contact with an interfacial
Physics of Semiconductor Devices, by
layer (vacuum) of the order of atomic distance.
Simon. M. Sze, Wiley, 2006, 3rd Ed.

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 Case discussion

Strange electrode materials dependence of memristors

•Barrier height on n-type semiconductors

increases for metals with a higher work
Function;

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Barrier height/Resistance does not increases with work functions

Applied Physics A 102 (4), 785-789 (2011)

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Instead decreases with Oxygen affinity

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Metal/semiconductor interface in Reality

•barrier heights reported in the literature to vary widely due to

different surface cleaning procedures.
• Experimental barrier heights often differ from the ones calculated.
•This is due to the detailed behavior of the metal-semiconductor interface.
•The ideal metal-semiconductor theory assumes both materials are pure, that
there is no interaction between the two materials and no
unwanted interfacial layer.
•Chemical reactions between the metal and the semiconductor alter the barrier
height as do interface states at the surface of the semiconductor and interfacial
layers.
•Another typical example is GaAs, which is known to have a large density of
surface states so that the barrier height becomes virtually independent of the
metal.

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