Report: PHYS 515, Spring 2012
Chemical potential of photons: theory and application
Mohammad Ryyan Khan
khan23@purdue.edu
Introduction
Photons are bosons characterized by the
chemical potential and temperature of the
system. Although photons are widely
characterized by zero chemical potential, they
can also have non-zero chemical potential. We
present a simple analysis for the calculation of
chemical potential of photons.
An example of non-zero chemical potential is
the case of the radiation from a semiconductor
diode. We derive the diode equation form a
thermodynamics perspective.
Chemical potential of photons
A. Zero chemical potential
Photons are bosons and they have the following
occupation probability:
1
f ( ) = ( )/ kT
e 1
The chemical potential of radiated photons are
usually taken to be zero ( = 0) which is also
practically observed. For example, in Plancks
radiation formula, the energy density is,
3 1
u = (2)
c e
2 3 ( )/ kT
1
The zero value of is thought to be because of
the non-conservation of number of
photons[1][2]. The change in energy in a system
radiating photons can be written as,
dU = pdV + TdS + dN (3)
Here p, V, T, S and N are the pressure, volume,
temperature, entropy and the number of
photons respectively. For constant entropy and
volume at equilibrium the energy of the system
reaches a minimum and thus dN = 0 . As the
number of photons are not conserved ( dN 0) ,
we must have = 0 . As explained in [2], the
above argument is not always true. The
incapability of photons to interact among each
other restricts them to reach equilibrium only
by themselves. Photons interact with other
particles to reach the equilibrium. Thus the
combined system of photons and the other
particles would dictate the value of the
chemical potential.
Temperature, T
(1)
Absorption and
re-emission
Figure 1: Blackbody radiation experiment.
A physical understanding of the above
statement can be obtained from a simple
blackbody radiation experiment. Say, we have a
closed box with dark inner walls. Now as we
heat up the box to a temperature T, the
radiation inside the box should have a
blackbody radiation spectrum governed by
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Report: PHYS 515, Spring 2012

Plancks Law. By making a small hole we can 3 1

u = 2 3 ( )/ kT
characterize the radiation that leaks out. c e 1
Measurements would show that this blackbody 3
1
radiation is described by a temperature T and = 2 3 ( qV )/ kT (7)
c e 1
chemical potential = 0 . As explained in [1], The effect of and T are shown in Fig. 2. The
the number of photons inside the box is defined peak of the spectral radiance shifts down to
by the interaction of photons with the walls of lower frequencies (energies) as the temperature
the box. Photons continuously get absorbed and is decreased. Change in temperature scales the
re-emitted from the walls so the number of spectrum in the energy scale. Of course the
photons is fixed at a certain temperature T. We peak value also varies.
cannot fix the number of photons (as it depends
on T). Thus, the only way to get dN = 0 is to
-16 -16
x 10 x 10
3 3
T=3000K =0

set = 0 .
T=4000K =-0.25eV
2.5 2.5
T=5000K =-0.5eV
T=6000K =-0.75eV
2 2

u (W/m2/J)

u (W/m2/J)
We can make similar arguments for large 1.5 1.5

bodies such as the sun, where photons can go

1 1
through multiple scattering, absorption and re-
0.5 0.5
emission so that = 0 . A large fraction (~90%)
0 0
of the photons of the sun with = 0 has
0 2 4 6 0 2 4 6
E (eV) E (eV)

(a) (b)
diffusive flow due to a temperature gradient
[3]. Figure 2: Effect of temperature (a) and negative chemical
potential (b) in the blackbody radiation energy density.
B. Non-zero chemical potential
The chemical potential only scales the spectrum
Consider a light emitting diode (LED) which leaving the peak approximately at the same
emits photons ( ) by the radiative position (Fig. 2(b)). This can be explained using
recombination of an electron hole pair: the following approximation:

e+h (4) 3 1
u =
The chemical potentials will be related as, c e
2 3 ( )/ kT
1
3
1
= e + h (5) = 2 3 ( )/ kT
The sum of the chemical potentials of the
c e
3 1
electron and hole is equal to the quasi Fermi = 2 3 e / kT ( )/ kT (8)
level splitting which in turn is proportional to c e
the applied voltage: The expression has been reduced to Weins Law
by neglecting the -1 term in the denominator.
= e + h Observe that e / kT appears in expression as a
= FC FV scaling factor. Thus the chemical potential only
= qV (6) changes the peak value, not its position in the
In this case, the Plancks formula shown in (2) spectrum.
will be modified as follows:

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Report: PHYS 515, Spring 2012

In textbooks [4], we mostly encounter negative factor of e / kT = e qV / kT 5 1016 . Chemical

chemical potential for bosons with zero ground potential being greater than the bandgap results
state energy. Photons can have positive in a negative energy density. That is why
chemical potential as explained below. chemical potential of the LED is
thermodynamically bounded by the bandgap
value.

1
Critical angle of
refraction, C
a(E)

0.5

0
0 1 2 3 4 5 6
E (eV)

(a) Mirror
-15
x 10
1.5
standard
Figure 4: Scattering of radiated photon from the diode.
Eg=1.5eV, =0
u (W/m2/J)

1 Eg=1.5eV, =0.75eV

0.5

The Diode equation

0
0 1 2 3 4 5 6 Shockleys diode equation is widely used in
E (eV)
semiconductor physics. The classical diode
(b)
equation is given by,

Figure 3: Radiation energy density for a material with certain
bandgap.
Assume an LED having material of bandgap
E g = 1.5eV . For illustrative purpose, say, the
temperature is T = 6000 K . The idealized
absorptivity (or emissivity) of the LED would
be:
E < Eg
0;
a( E ) =
1; E > Eg
This means that there will be no emission from
the LED for E < E g . This is shown in Fig. 3. The
photons above the bandgap follow the standard
blackbody spectrum. The intensity of the
radiation increases exponentially as an applied
voltage is increased. For example, if V = 1V
(i.e., = 1eV ) then the increase in intensity is a
J = J 0 ( e qV / kT 1)
(10)
Here J 0 is the reverse saturation current. This
J-V relation predicts practical Si-diodes to a
very good approximation. But this relationship
does not consider the effect of radiative
recombination and re-absorption which occurs
for direct bandgap semiconductors (such as
GaAs).
(9)
The radiative recombination followed by the re-
absorption of a fraction of these radiated
photons in the material is called photon
recycling. Effective recombination is reduced in
presence of photon recycling. Thus the classical
diode approximation overestimates J 0 if there
is a strong photon recycling process.

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Report: PHYS 515, Spring 2012

Let us derive the J-V relationship for a diode standard form of reverse saturation current is
with photon recycling (following the work in [5]:
[5]). By dividing the energy density in (7) by
energy, we can find the rate of photons emitted J 0 = qni2 BW (16)
per energy per solid angle: where,

(17)
n ph ( E , , T ) =
u ni2 B = 4 nr2 ( E ) n ph ( E , = 0, T ) dE
Eg
E
2E 2 1
= (11)
c 2 h3 e( )/ kT 1
Each photon is related to an electron-hole pair. -6
10
Thus the corresponding electric current density Standard
with photon recycling
(current per unit area) is given as follows: -8
10

J ( , T ) = q aF ( E , )n ph ( E , , T ) cos d dE
-10
10

J0 (A/m2)
Eg

(12) -12
10
Here is the solid angle and aF ( E , ) is the
absorptivity. The photon energy flux flowing
-14
10 (1 cos C )
normal to the surface is required; thus the cos -16
10 -2 0 2
factor in the expression. The absorptivity of the 10 10 10
W
structure shown in Fig. 4 is related to the
absorption coefficient ( E ) , width of the diode Figure 5: Comparison of the reverse saturation current
calculated using the standard model and the model including
W , refractive index of the material nr : photon recycling.

2 ( E )W (13) A comparison of the conventional ( J 0 ) and

aF ( E , ) = 1 exp
cos i derived ( J 0* ) saturation currents are shown in
Fig. 5 for various W product. We assume that
where, the absorption coefficient is not dispersive. We
(14) choose nr = 3 , E g = 1.1eV and T = 300 K . As
sin 2
cos i = 1 2 expected,
nr
W 0
J 0* qni2 BW (1 cos C ) (18)

Finally, the J-V characteristics can be written as, = J 0 (1 cos C )

J * = J ( = qV , T ) J ( = 0, T ) (15) Here C is the critical angle of refraction of the

semiconductor. The factor (1 cos C ) is due to
Here, the reverse saturation current is
the restriction on the escaping photons by the
J 0* = J ( = 0, T ) . Also for comparison, the critical angle.

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Report: PHYS 515, Spring 2012

Also note that from Fig. 5, the standard Let us now focus back to (15). We can rearrange
saturation current increases with diode width it to form an expression in the form of (10). We
W , whereas the current according to photon can neglect the -1 term in (11) to obtain:
recycling model saturates at high W . At high
2E 2 1
diode width, the re-absorption of the radiated n ph ( E , , T ) = 2 3 ( )/ kT
photons saturates and that is reflected into J 0* .
ch e
/ kT 2 E 1
2

-3
=e c 2 h3 e( )/ kT
W=10
10
= e n ph ( E , = 0, T )
/ kT
standard (19)
8 with photon recycling
Thus we can approximate (12) as,
6
J (A/m2)

J ( , T ) = e / kT J ( = 0, T )
4
= e / kT J 0* (20)
2 Using this value in (15) we get,

0
0 0.2 0.4 0.6 0.8 1 J * = e qV / kT J ( = 0, T ) J ( = 0, T )
V (V)
= J 0* (e qV / kT 1) (21)
(a)
3
W=10
10
Conclusions
8 standard
with photon recycling We have shown here that photons can have
zero and non-zero chemical potential.
6
J (A/m2)

Application of this concept in the case of

4 photon recycling in diode operation has been
demonstrated.
2

0
0 0.2 0.4
V (V)
(b)
Figure 6: J-V characteristics of a diode.
Because the standard model of (16)
overestimates the saturation current, the diode
current will always be overestimated in the case
where photon recycling process exists. This
statement is also verified in the numerical
results shown in Fig. 6.
0.6 0.8 References
[1] G. Cook, Understanding the chemical potential,
American Journal of Physics, vol. 63, no. 8, p. 737, 1995.
[2] P. Wurfel, The chemical potential of radiation,
Journal of Physics C: Solid State Physics, vol. 15, no. 18,
pp. 39673985, Jun. 1982.
[3] F. Herrmann and P. Wu rfel, Light with nonzero
chemical potential, American Journal of Physics, vol.
73, no. 8, p. 717, 2005.
[4] C. Kittel and H. Kroemer, Thermal physics. San
Francisco: W. H. Freeman, 1980.
[5] A. Mart, J. L. Balenzategui, and R. F. Reyna, Photon
recycling and Shockleys diode equation, Journal of
Applied Physics, vol. 82, no. 8, pp. 40674075, Oct.
1997.

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Report: PHYS 515, Spring 2012

Matlab codes: uw plot

clc
clear
close all

%%
ev=1.6e-19;
h=6.626e-34; hcut=1.054571596e-34;
c=3e8;
kB=1.38e-23;

N_E=1e3;
E_all=linspace(1e-10,6,N_E)*ev; % joules (for P_in)
w_all=E_all/hcut;

T=6000;
mu=0*ev;
Eg=0*ev;
a=(E_all/ev>=(Eg/ev));
%%

u_w=a.*hcut.*w_all.^3/pi^2/c^3 ./(exp((E_all-mu)/kB/T) -1 );

figure;
% subplot(211)
% plot(E_all/ev,a)
% subplot(212)
plot(E_all/ev,u_w)

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Report: PHYS 515, Spring 2012

Matlab codes: Diode J0 and J0* vs W

clc
clear
close all

%%
ev=1.6e-19;
h=6.626e-34; hcut=1.054571596e-34;
c=3e8;
kB=1.38e-23;

N_E=1e3;
E_all=linspace(1e-10,6,N_E)*ev; % joules (for P_in)

T=300;
mu=0*ev;
Eg=1.1*ev;
a=(E_all/ev>=(Eg/ev));
%%
theta_all=linspace(0,pi/2,1000);
nr=3;
cos_th_i=sqrt(1-(sin(theta_all).^2)/nr^2);

%%

aW_mat=logspace(-3,3,1e3);

for k=1:length(aW_mat)
aW=aW_mat(k);

%%

aF2=1-exp(-2*aW./cos_th_i);
dS_angle=2*pi*aF2.*cos(theta_all).*sin(theta_all);
S_angle=trapz(theta_all,dS_angle);

dS_angle_std=2*pi*aW.*cos(theta_all).*sin(theta_all);
S_angle_std=trapz(theta_all,dS_angle_std);

%%
n_ph=a* 2.*E_all.^2./(c^2*h^3) ./(exp((E_all-mu)/kB/T) -1 );
N_total=trapz(E_all,n_ph);

J0(k)=ev*N_total*S_angle;
J0_std(k)=ev*(4*pi*nr^2*aW)*N_total;

end

%%

figure
loglog(aW_mat,J0_std,'--')
hold on
loglog(aW_mat,J0)

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Report: PHYS 515, Spring 2012

Matlab codes: Diode J-V

clc
clear
close all

%%
ev=1.6e-19;
h=6.626e-34; hcut=1.054571596e-34;
c=3e8;
kB=1.38e-23;

N_E=1e3;
E_all=linspace(1e-10,6,N_E)*ev; % joules (for P_in)

T=300;
mu_mat=linspace(0,1,1e3)*ev;
Eg=1.1*ev;
a=(E_all/ev>=(Eg/ev));
%%
theta_all=linspace(0,pi/2,1000);
nr=3;
cos_th_i=sqrt(1-(sin(theta_all).^2)/nr^2);

%%

aW=1e-3;

for k=1:length(mu_mat)
mu=mu_mat(k);

%%

aF2=1-exp(-2*aW./cos_th_i);
dS_angle=2*pi*aF2.*cos(theta_all).*sin(theta_all);
S_angle=trapz(theta_all,dS_angle);

dS_angle_std=2*pi*aW.*cos(theta_all).*sin(theta_all);
S_angle_std=trapz(theta_all,dS_angle_std);

%%
n_ph0=a* 2.*E_all.^2./(c^2*h^3) ./(exp((E_all)/kB/T) -1 );
N_total0=trapz(E_all,n_ph0);

n_ph=a* 2.*E_all.^2./(c^2*h^3) ./(exp((E_all-mu)/kB/T) -1 );

N_total=trapz(E_all,n_ph);

J_mu(k)=ev*N_total*S_angle;
J_mu_std(k)=ev*(4*pi*nr^2*aW)*N_total;

J0(k)=ev*N_total0*S_angle;
J0_std(k)=ev*(4*pi*nr^2*aW)*N_total0;

end

J=J_mu-J0;
J_std=J_mu_std-J0_std;

%%

figure
plot(mu_mat/ev,J_std,'--')
hold on
plot(mu_mat/ev,J)
ylim([0 10])