S o l a r Cells, 31 (1991) 181-196 181

Is a solar cell an endoreversible engine?

Alexis De Vos
Labor(~to~gum voor e l e k t r o n i k a e n m e e l t e c h n i e k (LEM), R i j k s u n i v e v s i t e i t te Gent,
S i n t Pieters~nieuwstraat 41, B-9000 Gent ( B e l g i u m )

(Received July 17, 1990; in final form September 7, 1990)

Abstract

Endoreversible processes are a special class of irreversible processes: the irreversibilities

are all located m the transport of heat from the heat sources to the heat engine and
from the heat engine to the heat sinks. It has been demonstrated before that photothermal
solar energy conversion can be modeled as an endoreversible process. In the present
paper, we investigate if a solar cell can equally be considered as an endoreversible engine.
We will demonstrate that in fact a photovoltaic converter is somewhat more complicated
than a photothermal converter. This forces us to introduce a more general model of
endoreversible engines, where thermodynamic reservoirs are not only characterized by
a temperature, but also by a chemical potential, and where not only energy, but also
matter is exchanged between reservoirs.

1. I n t r o d u c t i o n

I n 1 9 7 9 , R u b i n [1] d e f i n e d a c l a s s o f i r r e v e r s i b l e h e a t e n g i n e s : t h e
"endoreversible engines". The working fluid of such an engine only undergoes
r e v e r s i b l e t r a n s f o r m a t i o n s , b u t is c o u p l e d t o t h e e x t e r n a l w o r l d b y i r r e v e r s i b l e
p r o c e s s e s . T h u s all l o s s e s a r e a s s o c i a t e d w i t h t h e t r a n s f e r o f h e a t t o a n d
from the engine.
T h e a b o v e d e f i n i t i o n w a s a d o p t e d b y A n d r e s e n e t a l . [2] a n d b y D e V o s
[3]. E v e n t u a l l y it f o u n d its w a y i n t o t h e r m o d y n a m i c s t e x t b o o k s [4, 5].
T h e s i m p l e s t e n d o r e v e r s i b l e p r o c e s s is t h e t r a n s f o r m a t i o n o f h e a t i n t o
w o r k b y t h e e n g i n e o f C u r z o n a n d A h l b o r n [6]. T h e C u r z o n a n d A h l b o r n
e n g i n e is a n e n d o r e v e r s i b l e e n g i n e a v a n t l a l e t t r e , a s C u r z o n a n d A h l b o r n
d e s c r i b e d t h e i r m o d e l in 1 9 7 5 , i . e . f o u r y e a r s b e f o r e R u b i n i n t r o d u c e d
e n d o r e v e r s i b i l i t y . T h e e f f i c i e n c y o f t h e C u r z o n - A h l b o r n e n g i n e is l i m i t e d b y
the rate at which heat can be exchanged between the working fluid and the
two heat reservoirs. The hot and the cold heat reservoirs are connected to
a reversible Carnot engine by means of thermal resistances (see Fig. l(a)).
E n t r o p y is c r e a t e d in t h o s e t w o r e s i s t o r s a n d t h e r e f o r e t h e o v e r a l l e n g i n e
( i . e . C a r n o t e n g i n e p l u s t w o r e s i s t o r s ) is i r r e v e r s i b l e , o r m o r e p r e c i s e l y ,
endoreversible.
In 1 9 5 7 , M t i s e r [7] d e s c r i b e d a m o d e l f o r t h e c o n v e r s i o n o f s o l a r e n e r g y
i n t o w o r k b y m e a n s o f s o l a r p a n e l s . D e V o s [3, 8] d e m o n s t r a t e d t h a t t h i s
model of solar energy conversion was in fact also an endoreversible engine

0379-6779/91/$3.50 © Elsevier Sequoia/Printed in The Netherlands

 182

V-C
QIt gl

(>z

~2

@ @
Fig. 1. Two thermodynamic configurations: (a) two resistors and an engine; (b) one resistor
and an engine,

a v a n t l a l e t t r e . I n d e e d Mtiser's engine c a n be derived f r o m the C u r z o n - A h l b o r n

engine b y omitting o n e of the two linear t h e r m a l r e s i s t o r s a n d b y r e p l a c i n g
the o t h e r one by a non-linear resistor.
If p h o t o t h e r m a l c o n v e r s i o n of solar energy, i . e . c o n v e r s i o n of s o l a r
e n e r g y into heat by collection in a solar a b s o r b e r and s u b s e q u e n t c o n v e r s i o n
into w o r k b y m e a n s of a C a r n o t engine, is an e n d o r e v e r s i b l e p r o c e s s , t h e n
the q u e s t i o n arises if p h o t o v o l t a i c c o n v e r s i o n , i . e . direct c o n v e r s i o n of solar
energT into electrical work, is also an e n d o r e v e r s i b l e p r o c e s s . The p r e s e n t
p a p e r tries to a n s w e r this question.

2. The C u r z o n - A h l b o r n engine

Figure l ( b ) s h o w s two h e a t reservoirs, one at the high t e m p e r a t u r e T1

a n d one at the low t e m p e r a t u r e T2. It f u r t h e r displays a n irreversible c o m p o n e n t :
a t h e r m a l r e s i s t o r w h i c h limits the h e a t flow Q1, a n d c a u s e s a t e m p e r a t u r e
d r o p f r o m T1 to an i n t e r m e d i a t e t e m p e r a t u r e T3. Finally, t h e r e is a r e v e r s i b l e
C a r n o t engine b e t w e e n the i n t e r m e d i a t e h e a t r e s e r v o i r at t e m p e r a t u r e T3
a n d the cold r e s e r v o i r at t e m p e r a t u r e Tz. In o r d e r to d e t e r m i n e the p r o p e r t i e s
of the structure, we only h a v e to i m p l e m e n t the two laws of t h e r m o d y n a m i c s :
A x i o m 1. C o n s e r v a t i o n of energy:

EQ + E w = 0
w h e r e Q are the h e a t flows, W the w o r k flows a n d £ d e n o t e s a s u m m a t i o n
o v e r a closed surface.
A x i o m 2. C o n s e r v a t i o n of e n t r o p y in the r e v e r s i b l e parts:
 183

~ Q =0
T
w h e r e we take into a c c o u n t that a heat c u r r e n t Q is a c c o m p a n i e d by an
enLropy c u r r e n t Q / T , w h e r e a s a w o r k c u r r e n t W is n o t a c c o m p a n i e d by any
e n t r o p y current.
B e c a u s e o f A x i o m 1 we have

Q1 =W+Q2 (1)
B e c a u s e of A x i o m 2 we have

Q1 IT3 = Q2/T2 (2)

Finally we n e e d a constitutive law for the t h e r m a l c o n d u c t o r . After C u r z o n
and Ahlborn, we use a linear law, i . e . a so-called F o u r i e r law:
QI = g ( T ~ - 7"3) (3)
We will call g the c o n d u c t a n c e . As Q1 is e x p r e s s e d in J s -1, the d i m e n s i o n
o f g is J s - ' K -1.
The first step in the m a t h e m a t i c a l m a n i p u l a t i o n consists o f solving (2)
for Q2, w h i c h leads to Q 2 = Q 1 T 2 / T 3 and of substituting this result into (1),
w h i c h we t h e n solve for W. This yields
W = (1 -- T 2 / T 3 ) Q ~ (4)
If we i n t r o d u c e the following definition of the c o n v e r s i o n efficiency -q:
= WIQ,
we t h e n obtain
V = 1 - T2/T3 (5)
w h i c h is n o t h i n g else but the classical p r o o f of C a r n o t ' s formula, for a
reversible engine w o r k i n g b e t w e e n the t e m p e r a t u r e s T3 a n d 7'2.
The s e c o n d step in the m a t h e m a t i c s consists o f the substitution of t h e
value (3) of Q~ in (4), s u c h that
W=g(T1 - T~)(1 - T2/T~) (6)
Besides the given t e m p e r a t u r e s T1 and T2, a n d the given c o n d u c t a n c e g,
this f o r m u l a c o n t a i n s also the quantity T3, w h i c h is n o t a p r e m i s e of the
problem. T h e r e f o r e we have the value o f the latter p a r a m e t e r freely at o u r
disposal.
Figure 2(a) s h o w s us the delivered p o w e r W as a f u n c t i o n o f the
i n t e r m e d i a t e t e m p e r a t u r e 7'3. W e see that for 7'3 = T1 the delivered p o w e r W
is zero. This is easily u n d e r s t o o d , as T a = T1 implies Q1 to be equal to zero,
after eqn. (3), and if t h e r e is no heat supplied, no h e a t c a n be c o n v e r t e d
into work. F u r t h e r we see that W is also zero for 7"3 = T2. N o w t h e r e is a
definite heat flow, but the latter is c o n v e r t e d into w o r k with a zero efficiency
1 - T2/T3.
 184

Q
m,

~q

@ 05

.q
/ 0
0
I I I I I
05
I I I I E
1

Fig. 2. Dclivcred work rate W, (a) as a function of the intermediate temperature T~; (b) as
a function of the conversion efficiency ~?= 1 - T 2 / T ~.

Fig. 3. Energy conversion efficiency ~? as a function of temperature ratio T2/T,, (a) according
to Carnot; (b) according to Curzon and Ahlborn.

In b e t w e e n its two zeros, the f u n c t i o n W(T3) s h o w s a m a x i m u m . The

c o o r d i n a t e s of this e x t r e m u m are f o u n d b y solving dW/dT3 = O. The r e a d e r
will easily verify t h a t this leads to T3 = ~ T2, which, a f t e r s u b s t i t u t i o n into
(5), i m m e d i a t e l y leads to
v = 1 - ~T2/T1

W e h a v e thus derived the Curzon a n d A h l b o r n formula, w h i c h e x p r e s s e s the

efficiency of the engine in m a x i m u m - p o w e r condition. F i g u r e 3 s h o w s the
relation b e t w e e n ~? a n d the t e m p e r a t u r e ratio Te/T1. W e see t h a t the C u r z o n
& Ahlborn c u r v e lies substantially b e l o w the s t r a i g h t line ~?= 1 - T2/T1, w h i c h
e x p r e s s e s the C a r n o t efficiency Vc for the s a m e engine, b u t w o r k i n g in
r e v e r s i b l e conditions. This c o n f i r m s the g e n e r a l rule: efficiency u n d e r irre-
versible conditions is l o w e r t h a n u n d e r r e v e r s i b l e conditions. The Curzon &
Ahlborn efficiency ~?c~ n o t only h o l d s for linear t h e r m a l c o n d u c t o r s in
c o m b i n a t i o n with a C a r n o t engine, b u t it t u r n s out to b e also a v e r y g o o d
a p p r o x i m a t i o n for linear c o n d u c t o r s c o m b i n e d with o t h e r cyclic engines,
s u c h as Otto, J o u l e a n d Diesel e n g i n e s [ 9 - 1 1 ] .
Figure 2(b) s h o w s the delivered p o w e r W, not as a f u n c t i o n of T3 as
in Fig. 2(a), b u t r a t h e r as a f u n c t i o n of 1 - T e / T 3 , i.e. the efficiency ~? of
the C a r n o t engine. The a d v a n t a g e of this abscissa, c o m p a r e d with the a b s c i s s a
T:~, h a s b e e n d e m o n s t r a t e d in r e f e r e n c e [3]. A p a r t f r o m W('q), Fig. 4 also
displays the h e a t flux Q,(~?) a n d the e n t r o p y c r e a t i o n r a t e S ( ~ ) . The m a t h -
cmatical f o r m s of the t h r e e curves can easily be found. Indeed, elimination
of T:3 f r o m (3) a n d (5) i m m e d i a t e l y yields
 185

tW A I

t
• I

I J
© I\ 1/
q

Fig. 4. Thermodynamic quantities as a function of the conversion efficiency 77= 1 - Tu/T3 of

a Curzon-Ahlborn engine: (a) heat consumption rate QI; (b) work production rate W; (c)
entropy creation rate S.

T1 - T2 - T1
Q, = g (7)
1-~?
Multiplication by ~ t h e n gives
v(T1 - T~ - T1 ~?)
W=g (8)
1-~?
Finally, substitution of (7) and (8) into S = Q2/T2 - Q1/T1 = ( Q1 - g O / T 2 - Q1 /
T1 yields:

S=g (71-T2-T1~?) ~
T~ T2(1 - v )
We see that u n d e r reversible conditions, i.e. ~? equal to its C a r n o t value
~ ? c = I - T 2 / T 1 , b o t h Q1 a n d W are zero. This r e m i n d s us of the g e n e r a l
principle that u n d e r reversible c o n d i t i o n s c o n v e r s i o n h a p p e n s infinitely slowly.
We see further that for this s a m e value of ~? the e n t r o p y creation rate S is
b o t h m i n i m u m and zero. This r e m i n d s us o f the fact that in a reversible
s y s t e m e n t r o p y is constant, w h e r e a s in an irreversible s y s t e m e n t r o p y is
increasing.
U n d e r m a x i m u m - p o w e r conditions, i.e. -q equal to its C&A value
~?c~A= 1 - Te~-~l, the quantities Q~, W and S take n o n - z e r o values:

V~ = g v ~ ( ~ - ~ - ~ )

and
 186

For sake of c o m p l e t e n e s s , it s h o u l d be r e m e m b e r e d that C u r z o n and

Ahlborn derived their f o r m u l a for a model, m o r e general t h a n the one in
Fig. ](b). Indeed, they c o n s i d e r e d the m o d e l of Fig. l(a), w h e r e also the
heat flow Q2 is limited by a finite heat c o n d u c t a n c e . W e did omit the latter
(i.e. g2 = + o~), b e c a u s e it is irrelevant in the next sections, w h e r e we treat
solar energbz conversion. This will allow us, f r o m n o w on, to simplify notations,
by using Q instead of Q~ and W - Q instead of Q2 (see Fig. l(b)).

3. The Miiser e n g i n e

The Mtiser m o d e l differs f r o m the C u r z o n - A h l b o r n m o d e l of Fig. l ( a )

by one feature: heat does not flow by c o n d u c t i o n , but by radiation. T h e r e f o r e
the linear Fourier law is r e p l a c e d by the non-linear S t e f a n - B o l t z m a n n law:
Q=g(T~ - T ~ ) (9)
w h e r e g n o w has the units J s - 1 K-4. W h e n we n o w c o n s i d e r the set of
eqns. (1), (2) and (9) instead of the set (1), (2) and (3), t h e n we do n o t
end up with eqn. (6), but with
W = g( T'~ - 7~)(1 - 7'2/T~)
Again a p p l y i n g dW/dT3 = 0 for m a x i m u m - p o w e r operation, n o w yields a fifth
degree e q u a t i o n for T3:
4 T ~ - 3T2 T ~ - T~ T2=O
This equation was d i s c o v e r e d by Mtiser [7] in 1957, and afterwards redis-
c o v e r e d i n d e p e n d e n t l y by Castafis [12], by J e t e r [13] and b y De Vos and
Pauwels [14]. A generalization, involving a c o n d u c t i o n law ~ --~ .,(T ~1 _ T"~ 3J,
was d i s c u s s e d by De Vos [3, 8].
Figure 5 s h o w s the quantities Q, W and S for the Mtiser model. The
curves are similar to the c o r r e s p o n d i n g curves on Fig. 4 for the C u r z o n and
Ahlborn model. But we see that the curve Q0?) is m o r e " r e c t a n g u l a r " in
the Mtiser case t h a n in the C&A case. In p h o t o v o l t a i c specialists' t e r m i n o l o g y ,
one would say that the Mfiser engine has a better "fill f a c t o r " t h a n the C&A
engine.
W h e r e a s the curve Q(~?) is a simple h y p e r b o l a in the C&A case, it is a
fifth d e g r e e curve in the Mtiser case. It is t h e r e f o r e no surprise that m a x i m u m -
p o w e r values of ~7, Q, W and S c a n n o t be e x p r e s s e d in c l o s e d form. But
we still find the simple p r o p e r t y that Q, W and ~: all b e c o m e zero at ~7= ~?c.

4. The Miiser e n g i n e w i t h b a n d g a p

In our theoretical walk f r o m the C&A engine t o w a r d s the solar cell, we

n o w m o v e a further step: w e give Mtiser's solar a b s o r b e r a b a n d g a p . This
 187

®
j.

I
Iw / % 1
®

~c ' o I 2 Eg Eev]
F i g . 5. T h e r m o d y n a m i c quantities as a f u n c t i o n of the conversion efficiency -I7 = 1 - T~/T.a of
a Miiser engine: (a) heat consumption rate Q; (b) work production rate W; (c) entropy creation
rate 3.
Fig. 6. Work produced per unit time by a photothermal solar energy convertor as a function
of bandgap: (a) with fully concentrated sunlight; (b) with non-concentrated sunlight.

m e a n s we u s e a selective coating, t h a t only a b s o r b s s o l a r p h o t o n s with

e n e r g y h~ l a r g e r t h a n the b a n d g a p Eg o f the c o a t i n g material.
F o r s a k e of c o m p l e t e n e s s , it is n e c e s s a r y to s t r e s s that, f r o m an e c o n o m i c a l
p o i n t of view, the a b o v e decision is n o t a wise one, as it will l o w e r the
p o w e r o u t p u t of the s o l a r installation. Indeed, in t h e a b o v e Mtiser m o d e l
w e implicitly a s s u m e d t h a t the s u n at t e m p e r a t u r e T1 a n d the s o l a r a b s o r b e r
at t e m p e r a t u r e 7"3 " s u r r o u n d " e a c h o t h e r c o m p l e t e l y , i.e. all r a d i a t i o n e m i t t e d
b y the s u n r e a c h e s the c o l l e c t o r a n d v i c e v e r s a . This s u p p o s e s t h e u s e of
an ideal light c o n c e n t r a t o r . H o w e v e r , in the c a s e of fully c o n c e n t r a t e d sunlight,
the ideal b a n d g a p is Eg = 0. This is illustrated in Fig. 6(a). Only in the c a s e
of n a t u r a l sunlight or m o d e r a t e c o n c e n t r a t i o n , will the u s e of a selective
a b s o r b e r be profitable (see Fig. 6Co)). This w a s e x t e n s i v e l y d i s c u s s e d b y
Castafis [12] a n d o t h e r s [ 1 5 - 1 8 ] . If w e i n t r o d u c e a finite b a n d g a p in o u r
m o d e l with ideal s o l a r r a d i a t i o n c o n c e n t r a t i o n , t h e n it is only for p e d a g o g i c a l
r e a s o n s , as a t h o u g h t e x p e r i m e n t .
T h e i n t r o d u c t i o n o f the b a n d g a p m a k e s the c o n s t i t u t i v e law o f the t h e r m a l
conductor more complicated. We now have

[E~h hvv 2 dv hvv 2 dv

(10)
Q =g exp(h~/kT1)- 1 - exp(h~/kT3) - 1
Eg/h

w h e r e k d e n o t e s the B o l t z m a n n c o n s t a n t . T h e r e a d e r will easily verify t h a t

for Eg--*0, eqn. (10) b e c o m e s eqn. (9), a f t e r redefining ( ~ 4 k 4 / 1 5 h ~ ) g as g.
 188

Written as a function of the f u n d a m e n t a l p a r a m e t e r ~?= 1 - T2/T3, e q u a t i o n

(10) b e c o m e s :

Q('q) = g exp(hu/kT~) - 1 - exp[hv(1 - ~)/kT2] - 1

Eg ~It Eg/h

The c o r r e s p o n d i n g curves Q0?), W 0 ? ) and S(~?) are very similar to t h o s e

of the Mtiser engine with zero b a n d g a p (Fig. 5). Again m a x i m u m - p o w e r
values of V, Q, W and 3 have to be calculated numerically. Again Q = 0,
W = O and S = O at V = ~ c .

5. T h e s o l a r cell

In an ideal solar cell, e a c h p h o t o n a b s o r b e d gives rise to the creation

of an e l e c t r o n - h o l e pair and thus to a c u r r e n t pulse equal to q, the e l e m e n t a r y
charge. Equally, each r e c o m b i n a t i o n of an e l e c t r o n - h o l e pair gives rise to
the emission of a photon. In such an idealized cell, any non-radiative
r e c o m b i n a t i o n m e c h a n i s m is absent. The c u r r e n t I t h r o u g h this cell is given
by
I=qN,
where N is the net particle flux, a b s o r b e d by the cell. F o r a single h o m o j u n c t i o n
solar cell at t e m p e r a t u r e 7'2, the latter is given [14, 19] by

[E~J v 2 d~ v 2 dv
N(V) =g exp(h~,/kT,)- 1 - exp[(hv-qV)/kT2]- 1
•, ~ Zg/h

where V is the voltage over the solar cell. This equation is very similar to
the Q0?) characteristic (11) of the heat engine d i s c u s s e d in the p r e v i o u s
section. W h e r e a s in the latter, lira n ~ 1Q = - ~ , we have n o w limv-,s~/qN = -- ~ .
It is therefore no surprise that in p h o t o v o l t a i c s the dimensionless n u m b e r
5 = q V / E g plays the same role as -q = 1 - T2/T3 in p h o t o t h e r m a l conversion.
We n o w r e m a r k that the electrical p o w e r W = V I can be written as
W = ~EgN(~), w h e r e the function N(~) is given by

If v2dv v2dv
N(~) = g exp(hv/kTl) - 1 - e x p [ ( h v - .~,Eg)/kT2] -- 1
Eg/h Eg/h

For the e n e r g y e x c h a n g e with the sun, we have

U=g
[E~J hvv 2 dv
exp(h~,/kT1)- 1 -
h v v 2 dv
exp[ ( h v - qV) /kT2 ] - 1
]
Eg/h

[E~J hvv 2 dv h v v 2 dv ]
~ g
exp(hv/kT1) - 1 e x p [ ( h v - (;Eg) /kT2 ] - 1
Eg/h
 189

T h e c o r r e s p o n d i n g c u r v e s N(O, U(O a n d W(O a r e s h o w n in F i g . 7.

T h e c u r v e N ( ~ ) d i s p l a y s a n o p e n - c i r c u i t p o i n t a t ¢ = ¢oc, w h e r e ¢o¢ is
given by the equation

~f v2 dv - ~f v2 dv =0
Eg/h
exp(hv/kT1) - 1
Eg/h
exp[(hv- ~ocEg)/kT2] - 1
This expression cannot be simplified, and therefore cannot be solved ana-
l y t i c a l l y f o r ¢oc. W e c a n , h o w e v e r , p r o v e t h a t
~?c< ~oc< 1
An alarming feature now appears. From Fig. 7 we see that, at this
p a r t i c u l a r v a l u e ¢oc o f ¢, t h e e n e r g y e x c h a n g e U(¢o~) is n o t z e r o ! I n d e e d ,
U ( 0 b e c o m e s z e r o f o r a n o t h e r v a l u e o f ¢, s a y Ceq. T h i s e q u i l i b r i u m v a l u e
o f ¢ is g i v e n b y t h e e q u a t i o n

~f hvv2 dv ~f hvv2 dv
Eg/h
exp(hv/kT1) - 1 -
Eg/h
exp[(hv- ~'eqEg)/kT2 ]- 1 = 0

®
o

wo•
®
I ,,
r I I I
I 2 3 h')//Eg
Fig. 7. Thermodynamic quantities as a function of dimensionless electrical voltage ~'= qV/Eg
of a solar cell: (a) particle consumption rate N; (b) energy consumption rate U; (c) work
production rate W; (d) entropy creation rate ~.
Fig. 8. Absorbed and emitted spectra of a solar energy converter in open-circuit condition:
(a) incoming spectrum, which is also the outgoing spectrum in the photothermal case; (b)
outgoing spectrum in the photovoltaic case.
190

Also this e q u a t i o n c a n n o t be simplified a n d has to be solved numerically.

One finds, however, that

71C < ~oc "( ~eq < 1

In the p h o t o t h e r m a l case, the open-circuit condition ~?oc= 1 - T 2 / T 1 n o t

only implied balance of the i n c o m i n g e n e r g y with the o u t g o i n g energy,

~f hvv2 d~, = ~f hvv2 dv

exp(hv/kTl) - 1 exp[hv(1 - ~?o¢)/kT2] - 1
Eg/h Eg lh

g u a r a n t e e i n g U= O, but we had m o r e : detailed balance. A b s o r b e d and emitted

radiation were in b a l a n c e at every f r e q u e n c y interval of the two spectra:
v 2 dv v 2 dv
exp(hv/kT1) - 1 exp[hv(1 -~?oc)/kT2] - 1
This is not the case in the p r e s e n t p h o t o v o l t a i c conversion. U n d e r o p e n -
circuit conditions, we have here an overall particle balance,

v2 dv = f v'2 dv
exp(hv/kTl) - 1 exp[(hv- (,ocEg)/kT2] - 1
Eg/h Eg/h

but no detailed balance. This is illustrated b y the s p e c t r a l c u r v e s

/2 2 /22
and
exp(hv/kT~) - 1 exp[(hv- ~ocEg)/kT2] - 1
in Fig. 8.
Now we calculate the e n t r o p y p r o d u c t i o n rate. W e have

S(~)= u ( ~ ) - w ( ~ ) u(~) (12)

T2 T1
(see Fig. 7(d)). The f u n c t i o n S s h o w s a n o n - z e r o m i n i m u m at a value of
the a b s c i s s a ~, different f r o m b o t h ~o~ and ~q.
F r o m (12) we have

and
1

Neither of the quantities 3(~oc) and S(~eq) is zero. B e c a u s e T2 < T1 and ~oc < ~eq,
one can easily verify that b o t h are positive.
Thus, for ~=-~q we have a n o n - z e r o e n t r o p y c r e a t i o n rate S(~q). This
e n t r o p y creation is n o t c a u s e d b y the existence o f a n y e n e r g y t r a n s p o r t , as
 191

U(~eq) = 0. W e can associate it with the particle t r a n s p o r t N. Equally, for

( = {oc we have a n o n - z e r o e n t r o p y c r e a t i o n rate S(~'o¢). This e n t r o p y c r e a t i o n
is not c a u s e d b y the e x i s t e n c e of any particle t r a n s p o r t , as N ( ( o ¢ ) = 0. W e
can associate it with the e n e r g y t r a n s p o r t U. It is thus clear that a m o d e l
is n e c e s s a r y w h e r e U and N are t r e a t e d on an equal basis. T h e r e f o r e , in the
n e x t section we will r e m o d e l endoreversibility, taking into a c c o u n t b o t h
e n e r g y and mass t r a n s p o r t s .

6. A u n i f i e d m o d e l

F r o m the a b o v e sections, it is clear that the " d r i v i n g " p a r a m e t e r s ~7 of

p h o t o t h e r m a l c o n v e r s i o n and ( of p h o t o v o l t a i c c o n v e r s i o n play similar roles.
T h e r e f o r e it is interesting to i n c o r p o r a t e t h e m in a single solar e n e r g y
c o n v e r s i o n model.
F o r this p u r p o s e , we c o n s i d e r t h e r m o d y n a m i c reservoirs, n o t defined
m e r e l y b y a t e m p e r a t u r e T, but by two p a r a m e t e r s : their t e m p e r a t u r e T and
their " c h e m i c a l p o t e n t i a l " ~. The " e n e r g y " and " m a t t e r " fluxes U and N
b e t w e e n r e s e r v o i r (Ta, ~a) and r e s e r v o i r (Ta, l%) o b e y the following laws:

[E~J huu 2 dv huu 2 du

U=g exp[(hu-p,~)/kT1]- i - exp[(hv-p,a)/kT3]-i
• ~ Eg/k

N=g e x p [ ( h v - I%)/kTa ] - 1 - exp[(hv-I.~)/kTa] - lJ (13)

Eg/h Eg/h

(see Fig. 9(b)). The reversibility of the engine b e t w e e n the r e s e r v o i r s (Ta,

1~3) and (T2, ~2) is e x p r e s s e d by the generalized f o r m of A x i o m 2:

U-pJV 0. (14)
T
See e.g. references [20, 21]. Besides we have, for any closed volume, that
Axiom 1 is fullfilled, Z U + ' Z W = 0, as well as an Axiom 0, ~ N = O . Taking
Axioms 0 and 1 into account, eqn. (14) b e c o m e s
U-- W - p.2N U - ~3 N
-- ~0

which leads to
_72

If we postulate
W = ~?U+ (.EgN
192

we obtain a " v e c t o r i a l " efficiency (~7, O, with

72 T2 ~ ~,~
7,7=1--- ~'=
Ta ' Ta Eg Eg
If n o t only the engine part b e t w e e n reservoir (Ta, /~a) and reservoir (Tz, /~2)
is reversible, but the whole engine is reversible, i.e. w h e n T3 = T1 and/~a =/*a,
then r7 and ( take their reversible or C a r n o t values, given by

7"._, Te ILl ~L2

tic = 1 T1 ' ( c - T1 Eg Eg

W e r e m a r k that (Vc, (c) is not only the point in the (7, 0 - p l a n e w h e r e S = 0,

but is also the (only) intersection of the two curves U(~, 0 = 0 and N(r/,
0=0.
In non-reversible conditions, the e n t r o p y creation rate is given by

(U-W)-1~2N U-I~I N
s(n, 0 =
7"2 T1
U - ~TU- (,EgN-1.z2N U - I.xaN
T2 T1

Simple r e g r o u p i n g of t e r m s leads to

T, rl ~ \ T , p'' - p'z - ~:Eg

=(~c-~) ~U + ( ~ - ~ ) -E- ~g N

Let us n o w c o n s i d e r the physical m e a n i n g of the quantities /~,, t~2 and

t~a. The chemical potential 1~1 of the p h o t o n s o u r c e m i g h t be i n t e r p r e t e d as
q times the bias voltage VI of a light emitting diode, serving as e n e r g y
source. The potential t~a is q times the voltage V3 = V of the c o n v e r t e r diode.
It s h o u l d be n o t e d that diodes 1 and 3 form a p h o t o c o u p l e r pair, used to
c o n v e r t the e n e r g y emitted by diode 1. The e n e r g y and m a t t e r e x c h a n g e
rates U and N can t h e r e f o r e be visualized as in Fig. 10. Finally, the chemical
potential t~2 can be i n t e r p r e t e d as q times the bias V2 of s o m e diode f u n c t i o n i n g
as sink.
In solar e n e r g y conversion, there is of c o u r s e no diode 1 and no diode
2. Neither the s o u r c e 1 n o r the sink 2 can be biased by any voltage V, or
V.~. The s o u r c e is the sun, i.e. a black body. Thus ~1 = 0. The sink is our
earthly e n v i r o n m e n t , i.e. also a black body. Thus /z2 = 0. T h e r e f o r e only t~a
c a n be different f r o m zero. The solar e n e r g y c o n v e r s i o n is d e p i c t e d in Fig.
9(c). W e n o w replace the p a r a m e t e r s Ts and ~a by the dimensionless driving
p a r a m e t e r s ~7= 1 - T2/T~ and ~= T2~a/T3Es=T2qV/T3Es. This c h a n g e s eqns.
(13) into
 193

"i"1,0
r-~ i T7"~'1 i •

T
T3"P3 r3 ,qV

W W I=qN
u_ UUw~N D

U-
rz.o U i
r2.~2

@ ® © T
Fig. 9. Three thermodynamic configurations: (a) Curzon and Ahlborn or Miiser configuration;
(b) generalized configuration; (c) solar energy configuration, becoming Mtiser's configuration,
if V = O, or the solar cell configuration, if T 3 = 7'2.
Fig. 10. Photocoupler pair.

N(~?, ~) ~ g
IfEg/h e x p ( h vv2dv
/kT1) - 1
Eg/h
exp[(h~l v2d
- 7 ) - (.Eg)/kT2] - 1

g(v, ~) ~ g
exp(hv/kr,) - 1 exp[(h~l - rl)-.~g)/kT2l - 1
Eg/h Eg/h

It s h o u l d b e n o t e d t h a t (for a n y ~ 0) t h e B o s e f a c t o r
1
e x p [ ( h v ( 1 - ~?) - ~ g ) / k T 2 ] - 1
c a n n o t b e fitted t o a n y B o s e f a c t o r o f t h e f a m i l i a r f o r m

1
exp(hv/kT3)- 1
because

hv(1 - ~?) - ~Eg a n d h___v

T2 7"3
c a n n o t b e e q u a l f o r all h v r a n g i n g f r o m E g t o + ~ .
F r o m t h e f u n c t i o n s U(~?, ~) a n d N(~?, ~ ) w e c a n d e d u c e t h e f u n c t i o n s
W(~?, ~) = z l U + ~ E g N
U-W U
T2 T1
w h i c h a r e p l o t t e d in Fig. 11. W e s e e t h a t W d i s p l a y s a m a x i m u m , n o t l o c a t e d
o n t h e ~?-axis o r 6-axis, a n d t h a t ~ d i s p l a y s a z e r o m i n i m u m o n t h e ~?-axis.
 194

pv-M,~,~ \\

0 ~ ~=0~:÷~,
Fig. 11. Lines of constant thermodynamic quantities in the (~7, ~)-plane: (a) work production
rate W (A-MPP, absolute maximum-power point; PT-MPP, photothermal maximum-power point;
PV-MPP, photovoltaie maximum-power point; RP, reversible point); (b) entropy creation rate
S.

F o r the s a k e of c o m p l e t e n e s s , it is n e c e s s a r y to s t r e s s t h a t the quantity

" c o n v e r s i o n efficiency" as defined b y s o l a r e n e r g y c o n v e r s i o n specialists is
not to be c o n f u s e d with the efficiency f a c t o r 7. In f a c t the s o l a r e n e r g y
c o n v e r s i o n efficiency is s i m p l y given b y the ratio
W
(~-4k4/15h~)gT~
i.e. by
15 h ~3
~.4k4gT~ O?U + ~EgN)

7. C o n c l u s i o n

W e h a v e s t r e s s e d t h a t the c u r r e n t - v o l t a g e c h a r a c t e r i s t i c I(V) of a single

j u n c t i o n s o l a r cell is v e r y similar to the heat-efficiency c h a r a c t e r i s t i c QO?)
of a single selective a b s o r b e r Mtiser h e a t engine. N e v e r t h e l e s s s o m e differences
a p p e a r . In the p h o t o t h e r m a l c o n v e r s i o n , t h e r e exists o n e v a l u e o f the " d r i v i n g
p a r a m e t e r " , i.e. the efficiency ~7, w h e r e the p r o c e s s is c o m p l e t e l y reversible:
h e a t t r a n s p o r t and w o r k p r o d u c t i o n r u n infinitely slowly ( Q = W = 0 ) a n d no
e n t r o p y is c r e a t e d ( S = 0). In the p h o t o v o l t a i c c o n v e r s i o n , t h e r e is no s u c h
p a r t i c u l a r value of the " d r i v i n g p a r a m e t e r " , i.e. the d i m e n s i o n l e s s v o l t a g e
 195

~: energT t r a n s p o r t and w o r k p r o d u c t i o n r u n infinitely slowly for two different

values of ~ a n d e n t r o p y is c r e a t e d ( S > 0) for a n y value of ~.
A g e n e r a l i z e d e n d o r e v e r s i b l e engine enables us to describe b o t h the
p h o t o t h e r m a l a n d the p h o t o v o l t a i c c o n v e r t e r s b y one and the s a m e model.
Here two p a r a m e t e r s , n a m e l y ~? and ~, are present. There is one single
reversible o p e r a t i n g point: (~?, ~) = (~?c, ~c)- The a p p a r e n t a s y m m e t r y b e t w e e n
p h o t o t h e r m a l and p h o t o v o l t a i c solar e n e r g y c o n v e r s i o n is c a u s e d b y the fact
that in this particular case Vc ¢ 0 a n d ~c = 0, w h i c h in its t u r n is a c o n s e q u e n c e
of the fact that b o t h t~l, the c h e m i c a l potential of the sun, and 1~2, the
c h e m i c a l potential of the e n v i r o n m e n t , are zero.
If we n o w c o m e b a c k to the q u e s t i o n p o s e d in the title of the p r e s e n t
paper, we can w i t h o u t d o u b t a n s w e r " y e s " . The original definition of en-
doreversible engines, i n t r o d u c e d by Rubin, i . e . "irreversible engines w h e r e
all irreversibilities are r e s t r i c t e d to the c o u p l i n g of the engine to the external
w o r l d " can still be handled. However, in the t e r m i n o l o g y u s e d b y C u r z o n
a n d Ahlborn, i . e . "irreversible engines w h e r e all irreversibilities are c a u s e d
by the heat e x c h a n g e b e t w e e n the engine and the external w o r l d " we have
to replace " h e a t e x c h a n g e " b y " e n e r g y or m a t t e r e x c h a n g e " . Alternatively
one c o u l d r e p l a c e " h e a t e x c h a n g e " b y " h e a t or m a t t e r e x c h a n g e " . In the
first case we c o n s i d e r as p e r m i t t e d s o u r c e s of irreversibilities the two flux
t y p e s U a n d N; in the s e c o n d case we c o n s i d e r the two flux t y p e s Q a n d
N, as i n t r o d u c e d by Callen [20]. However, w h e r e a s the fluxes U and N are
n o n - d i v e r g e n t within a t h e r m a l c o n d u c t o r g, this is n o t always the case for
fluxes Q. This m a k e s m o d e l s b a s e d on the two i n d e p e n d e n t fluxes Q and
N s o m e w h a t m o r e c o m p l i c a t e d t h a n m o d e l s b a s e d on the two i n d e p e n d e n t
fluxes U and N. This p h e n o m e n o n will be t r e a t e d m o r e extensively in a
s e p a r a t e p a p e r [22].

Acknowledgments

Alexis De Vos is r e s e a r c h e n g i n e e r in the f r a m e w o r k of I m e c v.z.w.

(Leuven). The p r e s e n t r e s e a r c h was s u p p o r t e d by the C o m m i s s i o n of E u r o p e a n
C o m m u n i t i e s , in the f r a m e w o r k of the " J o u l e " p r o g r a m m e .

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