E 45 Laboratory Manual

Laboratory 6
Electronic Properties of Materials
Objectives
1. To understand the nature of electrical conductivity in materials
2. To investigate the change of electrical resistivity with temperature in metals, semiconductors, and insulators
3. To determine the relationship between electrical resistivity and the presence of impurities in these materials

Overview
This lab is designed to illustrate how electrical conductivity is related to microstructure, temperature, and impurity
concentration in materials. In this laboratory, students (1) determine the concentration of impurities in metallic samples by measuring resistivity, (2) determine the energy gap of a germanium semiconductor, and (3) determine both the
formation energy and the migration energy of charged vacancies in an ionic solid (sodium chloride).

Equipment
Part A Conductors

1. Five binary copper alloys containing the same solute in a single-phase solid solution
2. Constant temperature baths
a. 77K (boiling N2)
b. 200K (crushed CO2)
c. 273K (ice-water)
d. 305K (room temperature)
e. 373K (boiling water).
3. Kelvin double-bridge apparatus
Part B Semiconductors

4. Sample of germanium, in holder with leads attached

5. Hotplate, beaker, mercury-in-glass thermometer (0C 100C), dewar flask for crushed CO2
Copyright 2014, Berkeley

Professor Lane W. Martin

Laboratory 6: Electronic Properties of Materials

6. Volt-ohm-milliammeter
Part C Insulators

8. Sample of NaCl with embedded thermocouple and accessible leads

9. Furnace, potentiometer, temperature controller
10. Resistance measuring bridge with AC signal source and null detector (range 103 - 107 )

Background
When an electric field is applied to a solid, free electrons are accelerated. These electrons suffer a loss of energy by
collisions with the atoms of the sample. The current that results is proportional to the average electron velocity, which
is determined by the intensity of the applied electric field and the collision frequency. Only electrons with energy
near the Fermi level may be accelerated, as the other electrons inhabit states that are surrounded by full (occupied)
states, and are consequently forbidden to accelerate (change state) by the Pauli Exclusion Principle.
If the valance band is full and does not overlap empty bands, the lack of adjacent empty states severely limits conduction. This is the accepted model for insulators and semiconductors.
Electrons may move through an ideal crystal without resistance, but in real crystals electrons collide with lattice impurities and lattice imperfections. The resistivity due to impurities and imperfections is called the residual resistivity
and is usually independent of temperature. However, the total resistivity is the sum of the residual resistivity and
thermal contributions.
Semiconducting materials are comparatively poor conductors of electricity. They are characterized by a nearly full
valance band that is separated from a nearly empty conduction band by an energy gap of 2 electron volts (eV) or less.
Thermal energy can promote electrons to the conduction band and leave vacant states, called holes, in the valance
band. Both conduction electrons and holes serve as charge carriers. When only valance and conduction states are
involved, the semiconductor is said to be intrinsic. Substitutional impurity atoms of higher or lower valance may
contribute electrons to the conduction band or holes to the valance band. If these carriers make a dominant contribution to the conductivity, the material is said to be an extrinsic semiconductor, either n-type or p-type, respectively.
If the gap is a few electron volts or more, very high fields are required to surmount it. At ordinary voltages, very little
current flows, so the material behaves as an insulator. There are, however, other ways for electrons to cross the energy
gap. The energy of thermal motion will allow a small fraction of the electrons in the valance band to enter the conduction band. This fraction increases with increasing temperature. In the case of extrinsic semiconductors, impurities
and imperfections contribute to the conductivity by creating new energy levels, which are dominant at low temperatures.
In ionic solids, where the energy gap is too large, the electrons do not participate in electrical conduction, and charge
transport occurs by ion diffusion.

page 2
" of 8
"

Laboratory 6: Electronic Properties of Materials

Electrical Resistivity of Conductors

The total resistivity of a conductor is given by the sum of the thermal component (th) and the residual component
(r) in an equation known as Matthiessens Rule

= th + r
Above the Debye temperature, the thermal component of the resistivity is approximately linear in conductors. A simple way to estimate the overall purity and perfection of a conductor is to therefore measure the ratio of the resistivities
at room temperature and at liquid helium temperature (4.2K), where = r at 4.2K, because the thermal component is
effectively zero at such low temperature. Likewise, for an ultrapure element, = th at all temperatures because the
residual resistivity is effectively zero due to the absence of appreciable impurity scattering.
To find r from measurements of resistance, R, at different temperatures write Matthiessen's rule at two temperatures,
say T1 and T2:

(T1 ) = th (T1 ) + r
(T2 ) = th (T2 ) + r
Define

R(T1 )
R(T2 )

and for a pure element,

(T1 )
th (T1 )
=
(T2 )
th (T2 )

where R is the measured resistance and th(T) can be obtained from the literature.
For pure copper: th(273K) = 1.55 micro-ohm-cm; th(77K) = 0.195 micro-ohm-cm; and
r =

th (T2 )
1

page 3
" of 8
"

Laboratory 6: Electronic Properties of Materials

Semiconductors

To determine the band gap (Eg) from measurements of R at various temperatures, note that the conductance G is
G=

1
=F
R

where F is a geometrical factor and is the conductivity

= C exp

Eg
2kT

Then
Eg
2kT

ln G = ln (F C)

ln G (ohm1

and the slope of a graph of ln G versus 1/T yields (Eg/2k) as illustrated in Fig. 1.

Slope = Eg/2k

1/T (K1)

Figure 1 Plot of ln(conductance) vs 1/T for an intrinsic semiconductor. The slope of the curve gives the
band gap Eg.

page 4
" of 8
"

Laboratory 6: Electronic Properties of Materials

Note that this applies only when the semiconductor is in the intrinsic regime. If the germanium is not sufficiently
pure, it will be necessary to go to a temperature considerably above room temperature before the thermally-generated
carriers are numerous enough to dominate the carrier concentration. This type of behavior is most commonly seen in
extrinsic semiconductors, as shown in Fig. 2. If carriers from ionized impurities are dominant, the carrier concentration will be relatively independent of temperature.

slope = Eg/2k
exhaustion range

extrinsic
behavior

ln

(ohm1

intrinsic
behavior

slope = (EgEd) / k

1/T (K1)

Figure 2 Plot of ln(conductivity) vs 1/T for an extrinsic (n-type) semiconductor. In the extrinsic, the slope
of the curve also contains the energy Ed of the donor level below the conduction band edge.

Insulators

Electrical conductivity in ionic solids arises from the migration of ions under the influence of an electric field. In alkali halides the positive ions are much more mobile than the negative ions. Consequently, most of the current is carried by positive ions and we will neglect the contribution of the negative ions.
The mobility of ions in a perfect lattice is extremely low. This is because of the high energy barrier preventing interchange of atoms. Consequently the presence of some lattice defects is essential for the occurrence of ionic conductivity. The concentration of a pair of positive and negative ion vacancies is given by
n = c exp

W
2kT

where n is the number of anion-cation vacancy pairs (Schottky defects), W is the formation energy of such a pair,
and c is a constant depending upon the material.

page 5
" of 8
"

Laboratory 6: Electronic Properties of Materials

The positive ions surrounding a positive ion vacancy will have a finite probability of jumping into the vacant site. As
a result, the vacancy will move through the crystal by a positive ion - vacancy exchange, and diffusion becomes possible. The expression of the conductivity, , derived on this basis has the following form:

= A exp

Em +
kT

W
2

where A is a constant for a particular crystal, and Em is the activation energy for vacancy migration. Therefore, from a
plot of ln() versus (1/T) you can calculate the value of (Em+ W/2). Plots of this sort for real alkali halides typically
have the form of Fig. 3.

ln

(ohm1

slope = (Em+ [W/2]) / k

slope = Em/ k

1/T (K1)

Figure 3 Schematic ionic conductivity vs temperature curve for NaCl. The change to a steeper slope at
higher temperatures (lower 1/T) comes from the creation of more Schottky defects, which contribute to the
conductivity.

There is a break observed somewhere in the temperature range between 400C and 700C depending upon the purity
of the crystal. Below a critical temperature essentially all the vacancies arise because of impurities, and the number of
vacancies becomes temperature independent. In that case the temperature dependence of the conductivity is controlled only by the migration energy Em. Above the critical temperature the number of thermally produced vacancies
predominates over the number due to the impurity atoms and consequently the conductivity depends on the energy W,
specifically on (Em + W/2). This means that the slope in Fig. 2 should be Em and (Em + W/2) respectively in the two
ranges of temperature. By determining these two slopes, the values of Em and W can be calculated.

page 6
" of 8
"

Laboratory 6: Electronic Properties of Materials

Experimental Procedures
Part A

1. Measure R at all five (5) temperatures for all copper alloy samples (varying impurity levels).
Part B

2. Zero the ohmmeter on the scale you are using for each measurement, check to be sure that all electrical contacts
are ohmic, and use only de-ionized water as a cooling medium.
3. Measure the resistance of the germanium sample at 200K, 273K, 373K, and seven (7) more temperatures between
273K and 373K.
4. Measure sample cross-sectional area and length.
5. Do not measure at 77K (liquid nitrogen) as the samples are likely to fracture at this temperature.
Part C

6. Place crucible with polycrystalline NaCl and embedded electrodes into furnace, and turn ON the furnace.
7. Connect the electrodes to the measuring terminals of the bridge and determine the temperature from thermocouple
readings.
8. The NaCl sample must reach 300500C before measurement can begin. The lowest temperature of measurement
will be that below which R is too large to be measured.
9. Measure the resistance of the specimen in the temperature range of approximately 400C to 770C at intervals of
about 50C. The highest temperature of measurement should be 750775C. Do not exceed 790C as the melting
point of NaCl is 801C.

!
Lab Report
Part A
Question 1

Rank the five (5) specimens in order of purity, and specify r for each specimen in micro-ohm-cm.
Question 2

To what precision can you verify Matthiessen's rule?

To answer this question, consider how the resistivity

changes with temperature for a fixed concentration of impurities, then how the resistivity changes with impurity
concentration when the temperature is fixed.

page 7
" of 8
"

Laboratory 6: Electronic Properties of Materials

Question 3

Would you expect to increase or decrease as T is increased through the melting point? Why?
Question 4

If you dope a metal A with another metal B where B < A, do you expect the resistivity of the alloy to increase or
decrease? Why?

!
Part B
Question 5

Plot ln (G) versus 1/T for the semiconducting sample studied in this lab.
Question 6

Over what temperature range, if any, does your sample behave as an intrinsic semiconductor?
Question 7

What is the energy gap for your sample? Compare with published literature values and cite your sources.
Question 8

Predict the resistance at 150C of your sample.

!
Part C
Question 9

Plot ln (G) versus 1/T for the insulator sample studied in this lab.
Question 10

What is the temperature corresponding to the change in slope of the ln (G) vs 1/T plot? If you don't observe any
change in slope, what does that mean?
Question 11

From your plot determine both Em and W in eV.

Question 12

Do you think that conductivity measurements could be used as an index of purity in ionic crystals? Discuss.

page 8
" of 8
"