Measuring Boltzmann’s Constant and Absolute Zero by

considering the energy distribution of electrons in a

semi-conducting diode

Murray Purves

School of Physics and Astronomy

The University of Manchester

First Year Laboratory Report

April 2008

Abstract

In this investigation, the voltage a semiconductor diode was measured as the supply voltage
was changed, whilst the diode was kept at a temperature of 1º C. This data was used to obtain
values for the current through the diode as a function of supply voltage, and then was
analysed numerically to obtain a value of . The experiment was then repeated at a
temperature of 100 º C and another value of obtained. These two results were then used
to find a value for , and the value of absolute zero on the Celsius scale. The results found
were: C s2 K m-2 kg-1, and ºC. These compare well
with the preferred values of these constants, at C s2 K m-2 kg-1, and
ºC.
Introduction

Ludwig Boltzmann (1844-1906) was an Austrian physicist, most famous for his invention of
statistical mechanics, which is now used in almost all areas of modern physics, from quantum
physics to thermodynamics[1]. Statistical mechanics is the application of probability theory to
physical systems, using average microscopic properties (behaviour of individual particles) to
determine the macroscopic (large-scale) properties of the system. Statistical mechanics
follows one fundamental postulate: ‘All quantum states of a system that are consistent with
the macroscopic description are equally likely’; that is to say, all of the particles within a
system are equally likely to be in any state that fits in with how the system behaves as a
whole[2]. At the heart of this system is Boltzmann’s constant, k, which has units of
m2 kg s-2 K-1, and the value of which was the subject of this investigation.
The other focus of this experiment was determining the value of absolute zero on the Celsius
scale. Absolute zero is the temperature at which the energy, other than rest-mass energy, of
particles is the lowest it can possibly be, and is defined as 0 K.

Theory

Consider a sealed box filled with a gas. The temperature of this gas can easily be measured,
and in controlled conditions will remain constant. The temperature of the gas is a property
governed by the kinetic energy of the particles in the gas; however, measuring the kinetic
energy of any individual particle in this gas would be impossible. This is because the kinetic
energy of each individual particle is constantly changing, as it exchanges energy with its
neighbours through collision with them. However, the average energy of the particles remains
constant, as energy is neither created nor lost throughout the system. The energy of the
individual particles can be thought of as a probability distribution, with the precise form of
this distribution depending on the system under consideration. However, the relationship
between energy and temperature for any system is always proportional to the Boltzmann
factor, , where k is Boltzmann’s constant, and T is the temperature of the system. For a
system where this is the only term in the energy- temperature relationship, the probability that
a particle has an energy greater than E is equal to the Boltzmann factor.

This energy- temperature relation applies to a great many physical systems, not only the
kinetic motion of particles in a gas. Other examples include the distribution of particles at
different heights in the atmosphere, and the subject of this investigation, the movement of
charges in a semiconductor diode.

A proportion of the electrons in a semiconductor are free to move about, in a fashion

analogous to the molecules in a gas. These are known as free electrons. A semiconductor
diode is an electronic component in which there is a junction between two different
semiconducting materials, with different densities of free electrons. These free electrons are
able to cross this junction, and move from one material to another. At first, electrons will
flow from the side of highest density to the low density side, to reach equilibrium. However,
this is not entirely possible, as the movement of charges from one material to another changes
the total charge density of the materials (including bound electrons), and a potential
difference Vd builds up between the materials. This hinders the movement of electrons, as
each electron now needs an energy of eVd (as , Q being the charge of an object) to
overcome the barrier created by the potential difference. The number of electrons with a high
enough energy to cross the potential barrier is proportional to the Boltzmann factor, with the
energy in this case being eVd. The current I0 created by the flow of electrons is thus
proportional to . The potential barrier increases as current flows increases, until an
equilibrium state is reached, in which there is no net flow of electrons from one side of the
junction to another.

This potential barrier can be altered by the addition of an external voltage Vs, reducing the
magnitude of the barrier to e(Vd-Vs). This alteration then changes the expression for current
flow across the diode to

The relationship between voltage and current for a semiconductor diode is thus determined
[3]
by the Boltzmann factor . The aims of this investigation are to verify that this form for
the relationship is correct, and then to determine the values of and absolute zero on the
Celsius scale.

Procedure

In this investigation, the semiconductor diode used was actually a transistor with two of its
legs fused together. This form of diode functions exactly as a normal diode would, but has the
property that I0 is very small, enabling us to neglect the second term in the diode equation
above, simplifying it to

which makes further calculations based on this formula easier to handle.

The diode was immersed in a beaker of first ice, and then boiling water for the two halves of
the experiment. The water was boiled through the use of a small electrical heater upon which
the beaker was placed, and the ice provided from an ice maker in the laboratory. A lid was
placed on the beaker to minimise changes in diode temperature caused by the surroundings.
This lid was also fitted with a steam outlet pipe to allow steam from the boiling water to flow
out of the system into another beaker, preventing a build-up of pressure. A thermometer was
placed in the beaker next to the diode, to further facilitate keeping the diode temperature
constant throughout the experiment. Connected to the diode were the electronic components
needed to make the necessary measurements for the investigation, as outlined in Fig. 1:
 +Vs

R
V
s V
D

0V
Fig.1: Diagram of the circuit used in the investigation

Once the apparatus was set up as in Fig. 1, the beaker was filled in ice, and the diode
temperature recorded at 1ºC. Originally, the plan was to carry out the experiment at 0ºC,
however, this value was unattainable. A resistor of 10kΩ was then attached to the circuit, at
the position labelled R in Fig. 1. The supply voltage Vs was then varied in steps of ≈2V, from
2 to 24V, and the voltage across the diode VD measured at each interval. This procedure was
then repeated using resistances of 100kΩ and 1000kΩ, and again at each resistance using
boiling water, at a temperature of 100ºC. Using these two values, the voltage across the
resistor VR and the current through the diode I can be inferred, using the following formulae
derived from basic principles of electric circuits:
and
The following table shows an example of the results obtained by following this method:

R (Ω) T (°C) Vsupply (V) Vdiode (V) Vresistor (V) I (A)

10000 1 2.02 0.642 1.378 0.0001378
10000 1 4.02 0.664 3.356 0.0003356
10000 1 6.05 0.675 5.375 0.0005375
10000 1 8.06 0.683 7.377 0.0007377
10000 1 10.05 0.689 9.361 0.0009361
10000 1 11.96 0.693 11.267 0.0011267
10000 1 14.05 0.697 13.353 0.0013353
10000 1 16.02 0.701 15.319 0.0015319
10000 1 18.02 0.704 17.316 0.0017316
10000 1 20.05 0.706 19.344 0.0019344
10000 1 22.11 0.709 21.401 0.0021401
10000 1 23.99 0.711 23.279 0.0023279

Fig. 2: Example results from investigation

Discussion and Analysis of Results

Looking at the original equation for the voltage-current relationship for a semiconductor
diode, , it is apparent that it can be reduced to a linear equation by taking the
natural logarithm of both sides:
Plotting V against ln I will produce a straight- line graph of gradient . Fig. 3 shows the two
lines formed by data from experiments at 1ºC and 100ºC:

Fig.3: Graph showing results from both experiments; results from 1ºC are shown in dark
blue, those from 100ºC are in pink. The error bars are barely visible (see later discussion).

These two values for can be equated, and used to find a value for absolute zero on the
Celsius scale. If we consider 1ºC to be T0, we can express 100ºC as (T0+99). The two values
for can then be considered as the constants a and b:
, and
These equations can then be manipulated to give a value for T0 (1ºC) on the Absolute, or
Kelvin scale:

Using this result, a value for 0 K can be calculated:

which is 7.8% above the preferred value of -273.15 ºC.

Now that the value of absolute zero is known, the temperatures used in the experiment (1ºC
and 100ºC) can be converted into Kelvin, and the Kelvin values used to calculate :

Using 1 ºC = 297.4 K
 Using 100 ºC = 396.4 K

So, to 2 significant figures, C s2 K m-2 kg-1.

Calculation of Error in Results Obtained

The error in the final value for is attributable largely to the accuracies of the electronic
meters used; the only chance for human error to take effect was the manual measurement of
temperature. Estimations of this error, based on instrument accuracy, were as follows:

As , the fractional errors in these must be added in quadrature to produce a value

for the fractional error in . Since all errors are close to each other in terms of magnitude,
none can be neglected in the calculation. Using this method, a value for the error in is
produced at:

giving a final value of C s2 K m-2 kg-1.

Summary

The results from this experiment compare very favourably with the preferred values of the
constants measured. The value of absolute zero was calculated to within 10% of the preferred
value, and the result obtained for was excellent, falling just outside one error bound from
the standard result. This leads me to the conclusion that the experiment was a success, and
was conducted in an accurate and efficient manner. It also shows that the exponential
relationship between voltage and current for a semiconductor diode holds true, to a high
degree of confidence.
References

[1]- http://www-groups.dcs.st-and.ac.uk/~history/Biographies/Boltzmann.html
- University of St. Andrews, 1998

[2]- http://www.physics.sfsu.edu/~gmarcy/smgraphical.html -Geoffrey Marcy

[3]- ‘The Boltzmann Constant’, Physics Department, University of Manchester

All results for preferred values of constants taken from the Google calculator:
http://www.google.com/help/calculator.html.