Observation of Doping and Measurement of Bandgap in Germanium:

A Proof of Concept for Future Material Studies

J. Rable, R. Magee, and J. Schirmer
Pennsylvania State University, Department of Physics, 104 Davey Lab,
University Park, Pennsylvania 16802, USA
ABSTRACT
Germanium, as an intrinsic semiconductor available in highly purified
samples, enables the careful study of semiconductors under different
conditions and has a number of potential applications in fields ranging from
optics to high speed transistors [12]. In this study, we took a sample of
Germanium with an unknown purity and attempted to discover both its
bandgap and whether or not it contained dopants by using the Hall Effect,
originally discovered by Edwin Hall in the 19th century [1, 13]. In conductors,
where Hall discovered this effect, the overall dynamics are fairly simple one
type of charge carrier builds up along one edge of the material, achieving the
steady state by cancelling out the Lorentz force through a Hall Voltage.
However, in semiconductors like germanium, the presence of two types of
charge carriers, electrons and holes, creates a rich dynamical system
dependent on various material properties. By using these dependencies, we
found that our sample contained [PUT TYPE HERE] dopants with carrier
concentrations and mobilities of [VALUES]. Our sample also had a bandgap
of [BANDGAP], demonstrating a proof of concept in the determination of the
material properties of semiconductors. Moving forward, we expect this
technique to prove invaluable in the study of new and exotic materials.
1

I. INTRODUCTION
In an isolated atom, the nucleus tightly binds the electron to itself in
discrete energy levels [2, 4, 7, 8]. However, in crystals, where one has a
lattice of atoms bound together in close proximity, electrons feel multiple
potentials [4, 7, 8]. Though the electrons close to the nucleus continue to
remain in well-defined energy levels, the outer electrons, which experience
the potential from the other atoms more strongly, exist in structures called
bands [4, 7, 8]. In materials with high conductivity, where electrons flow
relatively freely, there exists a band called the conduction band through
which the outer, or valence, electrons of each atom can enter and flow
through [6-8]. Because electrons are fermions, they fill these bands
according to Fermi statistics, with thermal excitations being able to lift them
from the valence to conduction bands [7].
Conversely, insulators have a large energy gap, typically over 4eV,
between the valence and conduction bands, making it unlikely for electrons
to conduct; at low temperatures especially, thermal excitations cannot
overcome this gap, leading to a filled valence band at 0K [4, 6-8, 14].
However, in some materials, called semiconductors, the bandgap between
the valence and conduction bands is fairly small (approximately between
about 0.1 and 4eV), which allows electrons to thermally excited into the
conduction band, leaving behind an equal number of mobile quasiparticles

with charge e+ called holes [2, 6-8, 14]. Thus, in these materials, one would
expect conductivity to increase with temperature as more and more
electrons become able to enter the conduction band [7, 10, 11].
Intrinsic semiconductors, however, usually lack the conductivity to be
useful in most applications [6]. One solution around this is to dope the
semiconductor, or replace individual atoms in the lattice, with another type
of atom. By either donating an electron to the conduction band or a hole to
the valence band, they increase conductivity and make the new, extrinsic
semiconductor more useful [2, 6-8]. If they donate electrons, dopants
increase the ratio of negative to positive charge in the semiconductor,
making it n-type [2, 7, 13]. Conversely, if they steal electrons, producing
holes, dopants lead to a larger ratio of positive to negative charge, making
the semiconductor p-type [2, 7, 13].

In this study, we analyze the charge carriers in the semiconductor

germanium using the Hall Effect. The Hall Effect occurs when one applies a
magnetic field perpendicular to the flow of current through a material, which
causes the charge carriers to experience a Lorentz force [3, 7, 8, 13]. This
Lorentz force produces an additional charge gradient transverse to the field
and flow of current, creating a measureable voltage that allows us to
determine the charge carrier signs, densities, and mobilities [1, 3, 7, 8, 13].
Additionally, because the conductivity in semiconductors changes with
TABLE I. Properties of Germanium and Silicon
Germanium (Ge)

Silicon (Si)

Bandgap (eV)
0.67
1.11
Effective
0.55me
1.1me
electron mass
Effective hole
0.37me
0.54me
mass
Intrinsic carrier
2.0 * 1013
9.65*109
concentration
(cm-3)
Intrinsic
0.46
3.2 * 103
at measurements of charge vs. voltage to find the
temperature, weresistivity
can use our
bandgap of our sample [7, 10, 11].
II. BACKGROUND INFORMATION AND THEORY
The Hall Effect arises as a result of the Lorentz Force, given by:

v x B)

F=q(
E+

(1)

[3, 13]. In a material with many mobile charge carriers, one can apply the
Lorentz Force to a current, rather than a single charge, which is given by:
4

Referenc
es
[14,15]
[14]
[14]
[14, 15]

[15]

I =nwtq v

where

(2)

is the current, and q is the charge of the carriers, which move

with average velocity

through cross sectional area nw [1,3, 13]. The

Lorentz Force will produce a buildup of a charge gradient perpendicular to

the electric and magnetic field, which, in the steady state, will produce a
voltage that balances out the Lorentz Force. This voltage is the Hall Voltage,
given in a material with a single charge carrier by:

VH=

Bz I x Bz I x
=
RH
ntq
t

(3)

where B is the magnetic field (applied along the Z axis), I is the current
through the sample (applied along the X axis), n is the number of charge
carriers with charge q, t is the width of the sample in the z direction, and RH
is called the Hall Coefficient [FIG. 1] [1, 3, 6-8, 13]. Using this formula, one
can find the charge carrier density. It can also determine whether or not our
sample is doped in the event of doping, we will have an uneven ratio of
positive to negative charge carriers, which will give us a positive Hall Voltage
for a p-type semiconductor or a negative Hall Voltage for an n-type
semiconductor [6-8, 13].
Additionally, the Hall coefficient is related to the mobilities of the
charge carriers in the semiconductor by the formula:

=R H o

(4)

where is the carrier mobility of the holes or electrons (depending on

whether the sample is n or p type) and o is the intrinsic conductivity of the
sample at high temperatures [8].
Additionally, we can find the resistivity of our sample using the
equation:
=

wtR
s

(5)

with w being the sample width along y, s the sample width along x, t the
sample width along z, and R the resistance of the sample (given by the
quotient of longitudinal voltage divided by current) [Refer to FIG. 1] [3-8, 13].
We can then use this to find the conductivity, , which is the inverse of the
resistivity.
In an intrinsic semiconductor, one can find the hole and electron
concentrations using the equation:
E g
BT

3
k B T 32
ne =n p=2
(me me ) 4 e 2 k
2
2

( )

(6)

where T is the temperature, Eg is the band gap energy, me is the electron

effective mass, and mh is the hole effective mass [8,9].
However, in an extrinsic sample, the dopant-donated charge carrier
density is related to temperature by the equation:
6

3
4

ne xt T e

EI
2 kB T

(7)

where EI is the ionization energy of the donor atoms [8]. This relation gives
us two temperature regimes for our sample at high temperatures, our
doped sample will still behave like an intrinsic semiconductor, enabling us to
find the band gap using equation (6) [8]. Conversely, at low temperatures,
the extrinsic carrier density will begin to dominate. Thus, in the low
temperature regime, we can use (6) to find the ionization energy [8,9].
III. EXPERIMENTAL METHOD
First, we acquired a sample of Germanium in a bar shape (called a Hall
Bar). We selected Germanium because of both its properties as a
semiconductor and its potential applications. We also desired to find whether
or not our sample contained dopants, which would alter its carrier charge
densities. Next, we developed an apparatus to measure the Hall voltage
while varying the magnetic field, temperature, and current through the
sample [FIG. 2 and APPENDICES A, B, and C].
Because of the potential effect of the orientation of our magnetic field
and any possible misalignment of our apparatus, we took four voltage
measurements per datapoint. First, we took one measurement with the
magnetic field facing forward and one with it facing backwards. Next, we
measured with the current flowing forwards through the bar, and then with
the current backwards through the bar. By averaging over these four

measurements, we minimized any potential noise caused by imperfect

orientation of our applied voltage relative to the magnet and any
nonuniformity in our magnetic field. This also eliminated any voltage offset
produced by slight differences in voltage probe location between each side of
the Hall Bar.
We took our measurements in 10K temperature increments from room
temperature (~296K) down to 150K. Even though the Hall Effect should
theoretically become even more prominent as temperature decreases below
150K, at these temperatures our apparatus will begin to fail the sample will
begin to lose contact with the meters and our measurements will be ruined.
We also took our measurements in increments of 30V of power applied to our
magnet from 0 to 150V. We chose this value because our maximum power
rating on our magnet is 150V and because these increments should be
FIG. 2. A picture of the apparatus used to make measurements of the Hall
sufficient to show field dependence. Finally, we made measurements in
Voltage of our sample. The refrigerator (Janis refrigerator system with CTIcurrent increments of .1mA from 0 to 1mA. The decision to use these
Cryogenics 22-350 refrigerator and 8200 compressor) cools the sample
increments was made to find sufficient current dependence while avoiding
down via conductivity through the cold arm. At the end of the sample
sending too much power to our Hall bar (our current source cannot send
mount, the sample lies inside a magnetic field produced by the magnets
much more than 1mA through it).
(SpectroMagnetics 6-200), at a temperature produced by the refrigerator
IV. RESULTS
AND DISCUSSION
and sample mount system.
Additionally,
the vacuum pump keeps the
pressure around the sample at or below 20mTorr during the experiment.
In order to find the Hall Coefficient for our data at each temperature,
Near the sample, a magnetometer probe measures the strength of the
we plotted our measured Hall Voltages versus the product of our applied
applied field. For more details on the sample mount system, see
fields and currents, as suggested by equation (3). Additionally, we could use

the signs of our Hall Voltages, which were identical to the sign of the
magnetic field, to identify our sample as being p-type. Using our Hall
Coefficients, we could then find the carrier concentrations at each
temperature using the definition of the Hall Coefficient given by equation (3).
We then found our samples intrinsic conductivity using the values of the
applied current divided by the longitudinal voltage when there was no
applied field. Averaging over all temperatures and carrying through the error
from our measurement apparatus, we obtained an intrinsic conductivity of
1.5686 3.70 * 10-4 m. Using this value, we could then calculate the carrier
mobilities using equation (4). The results from this analysis at each
temperature are shown in Table II.
At high temperatures, our data suffered from our Hall Coefficient
beginning to approach zero, beyond the accuracy of our apparatus. For
example, because of this effect, we found a negative Hall Coefficient at
290K. Conversely, as the temperature approached 150K, we began to face a
different problem with our apparatus our sample, which is composed of
multiple materials with different coefficients of thermal expansion, began to
lose contact with our apparatus. This also altered our measurements and has
impacted our results.
In order to find the band gap and ionization energies of our sample, we
graphed ln(RH*T3/2) vs. the inverse of the temperature, as suggested by
equation (6). The slope of this graph at high temperatures gave us a band
gap energy of [VALUE], where our error comes from the R value of the fit and
9

our hall coefficient errors. Similarly, by graphing our lowest temperature

values in this manner, we obtained an ionization energy of [VALUE].

TABLE II. Results

FIG. 3. This figure shows graphs of our hall voltages versus our applied current
times the applied magnetic field. Each graph corresponds to data taken at 280K
and at varying field strengths, with the slope of the fit representing the hall
10
coefficient at that temperature [R. Magee, unpublished, (2016)].

FIG IV. These graphs show the spread of the Hall Voltage versus the applied
current across all of our applied magnetic field values at varying temperatures.
As the temperature decreases, the spread, and thus the dependence of the Hall

11

FIG V. These graphs of ln(RH*T3/2) vs. 1/T in the high and low temperature

regimes demonstrate how we obtained our band gap and ionization

energies. In the high temperature regime, the sample behaves like an
intrinsic semiconductor, allowing us to obtain the band gap energy using
the slope of the fit. Conversely, in the low temperature regime, the effects
of doping dominate, allowing us to obtain the ionization energy from the fit
[R. Magee, unpublished, (2016)].

V. CONCLUSION
In this study, we present a novel method of finding the carrier
concentration, carrier mobility, band gap, ionization energy, and doping type
of a semiconductor material using the Hall Effect. Though we utilized this
technique only on a single sample of Germanium, it can be used to analyze
any semiconducting material and should present a useful method of
characterizing novel materials.
12

Future experiments should focus on further refinement of this

technique in order to obtain more accurate measurements. Through the use
of more accurate multimeters, for example, one could eliminate a great deal
of error in the high temperature regime and thus obtain a better
measurement of the band gap energy. Similarly, through better prepared
samples that maintain electrical contact at more extreme temperatures, one
could obtain more accurate data in the temperature regime that we
explored. Additionally, a better prepared sample could be used to get data at
even lower temperatures than we measured at, which should give even
better results for the ionization energy. At all temperatures, a more sensitive
apparatus and better prepared sample will allow for more accurate Hall
coefficient, carrier density, and carrier mobility measurements in these
materials.
VI. ACKNOWLEDGEMENTS
The authors of this paper would like to thank M. Terrones and Z. Lin for
providing the material sample for this experiment and for their help with our
experimental setup, especially for their help with broken BNC cables and
network permissions.
VII. REFERENCES
[1] Z. Warren, academic, (2014)
[2] R. M. Eisberg, Fundamentals of Modern Physics, (Wiley, New York, 1961),
p. 515-517
13

[3] D. Griffiths, Introduction to Electrodynamics, 3rd Edition, (Prentice-Hall,

New Jersey, 1999), p. 204, 247
[4] N. Ashcroft, N. Mermin, Solid State Physics, (Harcourt College Publishers,
1976), p. 562-585
[5] T. R. Kuphaldt, Lessons in Electric Circuits, Volume I DC, 5th Edition,
(Design Science License, 2006), p. 282-288
[6] D. Bugg, Electronics: Circuits, Amplifiers, and Gates, 2nd Edition, (IOP
Publishing, London, 2005), p. 155-160
[7] R. A. Serway, C. J. Moses, and C. A. Moyer, Modern Physics, (Saunders
College Publishing, Philadelphia), p. 426-455
[8] C. Kittel, Introduction to Solid State Physics, Seventh Edition, (Wiley, New
York, 1996), p. 163-167, 232
[9] E. H. Putley, The Hall Effect and Semiconductor Physics, (Dover, New
York, 1968)
[10] Z. Xiao et al., J. Am. Chem. Soc., 136 (42), (2014)
[11] B. van Zeghbroek, Principles of Semiconductor Devices, (Academic,
2011)
[12] E. E. Haller, Germanium: From Its Discovery to High Speed Transistors,
(EECS Solid State Seminar, 3/18/2011)
[13] E. M. Purcell, Electricity and Magnetism, 2nd Edition, (McGraw-Hill, New
York, 1984), p. 241-245

14

[14] V. S Babu, Solid State Devices and Technology, 3rd Edition, (Pearson,
2010)
[15] B. G. Streetman and S. Banerjee, Solid State Electronic Devices (5th
ed.), (Prentice-Hall, New Jersey, 2010), pg. 524

15

VIII. APPENDIX A: SAMPLE MOUNT DESIGN

FIG. 3. This diagram shows the design of the sample mount. At the end,
the mount connects to the refrigerator. A high conductivity cold finger,
which allows the refrigerator to cool the sample, connects to the base of
the sample mount. Inside the base, a thermometer measures the
temperature and a heater heats the sample up to the proper temperature
as it drops below the desired temperature. On the mount itself, a cold
plate ensures good conductivity to the sample, which is mounted using a
chip carrier containing all the necessary wiring described in APPENDIX B.
Between the sample and the cold plate, a 20m thick Teflon film acts as
an insulator, preventing the plate from shorting our sample, while still
allowing good thermal contact. Apiezon grease coats the sample, Teflon
film, and cold plate to further ensure good thermal contact at low
temperatures. Additionally, dental floss, which maintains tension even at
low temperatures, wraps around the Hall bar, film, and cold plate to
maintain this contact, while a shield protects the wires from the floss. [M.
16

IX. APPENDIX B: WIRING

Designing the wiring of the apparatus required great care in ensuring
that all measurements were taken with the most accuracy possible. One of
the primary ways we ensured this was by using four-terminal sensing,
instead of the standard two-terminal sensing, to increase the accuracy of our
measurements [See FIG. 4 for theoretical diagram, FIG. 5 for bar diagram].
The
next step
was to
connect
our

FIG. 4. This shows a diagram of four terminal sensing. By measuring the

sample to

voltage across the subject, in this case our Hall Bar, directly, we eliminate

our

any added error created by the resistance of the other components of our
circuit. Even though the voltmeter lies far away from the actual sample,
the current carried along the wires to it is minimal compared to our applied

current, so the impact of these wires on the measurement will be fairly

voltmeters and current source properly while ensuring proper grounding and
shielding of the connections. We did this by utilizing a carefully labelled
junction box to act as an intermediary between our meters and our source
[See FIG. 5]. The junction box itself, as well as our current source sinks,
provided our only ground in the experiment to avoid looping them together.
BNC cables with shields isolated from the junction box ground connected the
box to our various devices. We isolated the shields of the cables in order to
17

avoid accidentally passing any additional currents through it, which would
impair our signal and lead to the production of a magnetic field.

FIG. 5. A diagram of our wiring to our sample. The junction box

connections are carefully labelled, and the only grounds lie at the junction
box casing and the current source sink. The sample itself is wired with a
current flowing vertically through it, with longitudinal voltage being
measured along this direction and Hall voltage being measured
horizontally across the center of the sample. [M. Terrones, Hall Effect,
(Pennsylvania State University, State College, 2016)]

18

X. APPENDIX C: APPARATUS PICTURES

(b)

FIG. 6. The above pictures show our experimental apparatus. One can see
the voltmeters, temperature controller (Lakeshore 331), current source
(Keithley 6220), Gaussmeter (FW Bell 5180), junction box, and magnet
power supply (Agilent N5770A). Two of the voltmeters (HP 34401A
multimeters) measured our longitudinal and hall voltages, as described in
APPENDIX B, while the third voltmeter (Keithley 2000 multimeter) received
data from the gaussmeter.

19

(a
(b

FIG. 7. These photographs show pictures of (a) our vacuum pump

apparatus (Edwards E2M2 rotary pump) and (b) our compressor. The
devices in (a) bring the pressure in the sample mount down to under
20mTorr or lower, while the compressor in (b) brings down the
temperature to the set point determined by our temperature controller,
shown in FIG. 6. The vacuum created by the pump is necessary because
the compressor requires low pressures to work properly.

20

FIG. 8. This picture shows our sample loaded into our mount. Dental floss
firmly secures the sample to the mount while the wire protector keeps the
wires from being put under pressure by the floss [Refer to APPENDIX A for
more details on sample mount]. [R. Magee, unpublished, (2016)

21