Solid State Communications, Vol. 51, No. 10, pp. 829-832, 1984. Printed in Great Britain.

0038-1098/84 $3.00 + .00 Pergamon Press Ltd.

A SIMPLE THEORETICAL MODEL FOR PHOTOELECTROCHEMICAL SOLAR CELL S. Chandra, D.P. Singh and S.N. Sahu Department of Physics, Banaras Hindu University, Varanasi 221005, India

(Received 5 March 1984; in revised form 15 May 1984 by R. Fieschi)

An expression is derived for the quantum efficiency of a photoelectrochemical solar cell considering the space charge recombination, charge transfer velocity and the dark current. The theory is applied to explain the quantum efficiency vs band bending curve for n-CdSe]S2-, S]- junction solar cell for different light intensity and electrolyte concentration. 1. INTRODUCTION PHOTOELECTROCHEMICAL solar cells (PESCs) using semiconductor/electrolyte junction (instead of a p - n junction) are of growing interest for solar energy conversion and storage [1-4]. It essentially consists of a semiconductor photoelectrode dipped in an electroltye and a metallic counter electrode dipped in the same electrolyte. Charge transfer at the semiconductor/ electrolyte interface produces a band bending (Vb) or space charge layer (SCL). In spite of a large amount of experimental work, the theoretical situation is far from being satisfactory. Most of the models of PESC end up in mathematical complexity or else recourse to oversimplification is adopted. The first attempt was made by Butler [5] based on Gartner's [6] approach developed for p - n junction solar cell. All the photogenerated carriers are assumed to contribute to the photocurrent across the junction neglecting all loss mechanisms. Butler's theory failed for semiconductor/electrolyte junction solar cell because the space charge recombination at the interface during the charge transfer cannot be neglected. Wilson's model [7] takes into account the recombination at the interface but the space charge recombination and the dark current contribution have been omitted. On the contrary Reichmann and Russak [8] did not consider the surface recombination while the space charge recombination was considered. More complete models taking into account of dark current contribution, space charge and surface recombination have been given by Haneman and McCann [9] using curvilinear quasi-Fermi-level as used by Panayotatos and Card [10] and E1 Guibaly et al. [11, 12] using "fiat" quasi-Fermi-level concept. The energy level diagram of an electrolyte near the illuminated interface under forward bias V is shown in Fig. 1 (El Guibaly [11, 12]. All the potential drop has been considered across the space charge layer. At the semiconductorelectrolyte interface, in actual practice, double layers also exist on the electrolyte side (termed as Helmholtz and Gouy layer) apart from the space charge layer in the semiconductor side. The Helmholtz layer is due to the formation of a dipolar structure at the interface and adsorption of ions from the electrolyte on the electrode surface [13]. For highly concentrated electrolyte, we can neglect the potential drop across the Helmholtz layer [14] but in general this is not true. Under forward bias, the quasi-Fermi-level for electrons (Ern) and for holes (E~) in the depletion region (DR) of the semiconductor are assumed to be flat. The separation between them is q V under dark and qU under illumination where U > V. This assumption represents the fact that the minority carrier concentration under illumination is larger than its value in the dark. In the present paper we have tried to develop a mathematically simple theory for a PESC by including space charge recombination and opposing dark current based on E1 Guibaly's approach [11, 12]. In E1 Guibaly's derivation for photocurrent under bias, an expression based on Fig. 1, the total current is

J=(S't/S)~-~{exp(qV/kT)+Bexp[q(v--U)/T]} -- (S~/S)Io{1 -- [exp (-- aW)/(1 + aLp)]} = Jd--Jz

(1 a) (ab)

where S~ = normalized surface charge transfer velocity; S r = normalized surface recombination velocity; B = a space charge recombination parameter and S = S~ + Sr + exp [--q(Vb -- lO/kT] + B exp [--q(V b -- V-U/2)/kT]. The second term in equation (1) has been identified as the photocurrent because of the occurrence of photon flux term, Io. The first term has been identified as the dark current, Ja. This is erroneous since the presence of U in the first term also implicitly makes it light intensity dependent. A correct approach would be to arrive at a detailed expression for current under illumination and

829

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THEORETICAL MODEL FOR PHOTOELECTROCHEMICAL SOLAR CELL

Vol. 51,No. 10

[ Semiconductor

] [,Etectrotyte I J

Metal

~{Fp(x)} = V(x)-R(x),

(5)

Ee

;:

Efn i

where G(x) and R (x) are generation and recombination rates. Integrating equation (5) within the limit x = 0 to x = W we obtain the hole flux at the surface, Fp(0),

[f,reaDz Irv.................. '~"-,.-..t~

X I=W I--0

Fp(O) = Fp(W)--Io(1--r)
where
Fp(W) =

l~_Lp]

f R ( x ) dx (6)

-- D dpn
P dx x=W

DpPn (eqU/kT-- 1)
Lp

Fig. 1. Schematic of the energy band diagram of a n-type semiconductor/electrolyte interface (see text). then subtract the standard dark current contribution. This is what has been attempted in this paper. Further, a simple derivation is given here for calculating the hole density at the edge of the space charge region. The final expression for quantum efficiency of a PESC is in a simple calculable form and explains the experimental results of the n-CdSe/S 2-, S~- electrolyte system. 2. THEORY Consider a semiconductor/electrolyte junction as shown in Fig. 1. The density of holes (minority carriers) in dark (P.o) and under illumination (Pn) in the neutral region are related as [15].

~Lp/o(1 -- r) e -~w aLp+ 1

(7)

It is very difficult to exactly evaluate the integral appearing in equation (6) because of ill-defined general nature of R(x). However, under the assumption of flat quasiFermi-levels of electrons and holes separated by qU, the expressions given by Sah et al. [17] and Grove [16] can be written as
W J R (X) dx = 2OVth~Vt,,i IA/.~qU/2kT 1.~ A/ ~ . . . 0 (8)

where a is the capture cross-section for electrons and holes assumed as equal, vth is the carrier thermal velocity, N t is the trap density near the intrinsic Fermilevel E i , and rt i is the intrinsic carrier concentration. From equations (6), (7) and (8) we get Fp(0) = Dpp.o ( e q U / k T 1)--Io(1 - - r )
+ B W e qU/zkT,

d2Pn Pn--Pno +G(x) = 0,

Dp dx 2 Tp

(2)

( e t
1

where Dp and rp are the diffusion coefficient and life time for holes. G(x) is the photogeneration rate given by [6]

(9)

G(x) = O d o ( 1 - r ) e - ~ ,

(3)

where a is the absorption coefficient, Io is the incident photon flux and r is the reflectance. Solving equation (2) under the boundary conditions (i) at x = 0% Pn = Pno, (ii) at x = W, Pn = Pn(W) = Pno eqU/kT [16]; the hole density at any point inside the semiconductor is obtained as:
P n ( X ) -- PnO = Pno [eqU/kT -+

where B = aVthNtni. Now we obtain an alternate epxression for Fp(0) in terms of surface recombination velocity (St) and surface transfer velocity (St) at the interface given below:

Fp(O) = -- (Sr + St)[Pn(O )-pdo(O)],

(10)

1] e ( W - x ) / L p
e-aX] (4)

eft0(1 -- r)rp

[eWO_o.Lp_x/W)/L p _

where Pdo(O) and Pn(O) are respectively the surface concentrations of holes in dark at equilibrium and in the presence of light and applied bias, V. In general Sr ~ S t. Hence, Sr can be neglected and (St + St) can be simply written as S. From Fig. 1 it is clear that
Pdo(O) =

where Lp = hole diffusion length = (Dprp) 1/2. p,(W) = hole density at the edge of depletion layer of width, W.

P.o e V b / k T

and

p,(O) = Pno eaV#kT [ eq(v- V)/kT].

Then from equations (10) and (11) Fp(0) = --SPnoeqVb/kT[e q(U-v)/kT- 1)].

(11)

W = (2eseo/qND)ln(Vb- V) 1/2.
Further, the hole flux at any point in the depletion region is given by following continuity equation [15]

(12)

Vol. 51, No. 10

10

THEORETICAL MODEL FOR PHOTOELECTROCHEMICAL SOLAR CELL

(a) . .,~ =__,~: : :
10

831

08

b~ 0.5

0.6

.g"

,'"

.~ 0.6

.2

04

zf"

b)

~ 04 E ~

E ~ 02 o I
O~ 02 Band 03 Oa 05 0.6 bending ~ V b - V (volts)

I
0.7

I
0.8

01

0.2

03 Band

O z.

0.5

06

Or7

08

bending ,Vb-V ( v o t t s )

Fig. 2. Theoretical (solid line) and experimental (dotted line) quantum efficiency at different intensity of illumination as a function of band bending. The adjustableparameters: S = 1 1 0 3 c m s e c - l , B = 2.6 1014 cm-a-sec -1. Intensity of illumination is: (i) for curve a, 7.1 mW cm -2 (equivalent to Io = 3.7 mA cm-=) and (ii) for curve b, 0.71 mW cm -2 (equivalent to I0 = 0.37 mA cm-2).

Fig. 3. Theoretical (solid lines) and experimental (dotted line) quantum efficiency for different electrolyte concentrations at Io = 0.37 mA cm -~ (~ 0.71 mW cm-Z). The adjustable parameters a r e : B = 2.6 x 10 x4 cm -3 sec -1, S = 103 cm sec -1 for curve a corresponding to the electrolyte (2.5 M Na2S + 1 MS + 1 M KOH) and S = l0 s cm sec -x for curve b corresponding to the electrolyte (0.25 M NazS + 0.1 MS + 1M KOH).

Thus equating equations (9) and e qU/zkT w e get

eqU/2kT = X

(12) and

solving for

= _
I

Lp

1 + -d-Lpi])]

(13)

2 ~Dppn + SPn o e q(Vb- V)/kT

(L,,

)
3. RESULTS AND DISCUSSION (14) In order to check the validity of our theory we have applied our results to calculate the effect of (i) illumination intensity, and (ii) electrolyte concentration controlling the charge transfer velocity on the quantum effeiciency of n-CdSe photoanode and polysulfide electrolyte junction PESC. The values of constants are [8]: Carrier life time, rp = 10 -9 sec, intrinsic carrier concentration, n i = 107 cm -3, hole diffusion length, Lp -1 10 -4 cm, reflectance, r = 0.1, absorption coefficient, a = 5.2 104 cm -1, initial band bending, F~ (without applied bias) = 0.7 V, donor concentration, N D = 1.0 x 1017cm -3, diffusion coefficient, Dp = 10 cm2sec -I, wavelength of light, X = 650 nm. Figure 2 shows the effect o f intensity of light at (k = 650 nm) on quantum efficiency of PESC for different band bendings. For theoretical calculations, quantities S and B are treated as parameters while other constants are taken as above. It is clear that the agreement between our theory and experiment [8] is

Then introducing X in equation (12) we get

Fp(O) = - - S P n o e q ( V b - V ) / k T [ ~ - - e q V / k T ] .

The above flux is reaching at the surface in the presence of light. The hole flux reaching at the surface in the dark in presence o f applied bias F is given by [ 16]
Fff(O) = DpPno (eqV/kT _ 1) + B W e qv/2kT.

(15)

Lp Therefore, the net hole flux reaching the surface o f the semiconductor due to photoexcitation is given by

F~(O) = Fp(O)--Fap(O)
= _ {SPn eq(Vb - V)lhT (X 2 _ eqV/kT) + D p P n ( e q V / k T - - 1) + B W eqV/2~T}. Lp

(16)

The quantum efficiency is given by 77-

fF~(0)j
Io

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THEORETICAL MODEL FOR PHOTOELECTROCHEMICAL SOLAR CELL REFERENCES 1. 2.

Vol. 51, No. 10

reasonably good for low and higher values of band bending. But for moderate values of band bending the theoretical values are higher than experimental values. The discrepancy is attributed to the following reasons: (i) The surface recombination plays an important role in the moderate band bending region because of the competition between Sr and S t [18]. However we have neglected Sr in the present case. (ii) the charge transfer parameter 'S' is treated in our model as independent of applied bias and band bending which is not rigorously true in view of the above [ 11 ]. Another point which emerges from Fig. 2 is that as we lower the intensity, the efficiency also decreases. This is a consequence of the non-linear dependence of b~(O) on I0 as given in equation (16). Figure 3 shows the effect of charge transfer velocity on quantum efficiency for different band bending. The values of parameter S for different concentrations are assumed to be related as : S = kCredox, where k is a constant, and Creaox is the concentration of the electrolyte. For higher concentration of electrolyte, there is a reasonable agreement between the theory and experiment while it is not so at lower concentrations. The probable reasons for disagreement are: (i) Our assumption that S is independent of band bending, is not rigorously true as pointed out earlier. (ii) the potential drop across the Helmholtz layer cannot be neglected for the less concentrated electrolyte, and (iii) the series resistance can also not be neglected for less conducting electrolyte at lower concentrations. We have not considered the series resistance effect in our model which is known to be quite complicated for p - n junction solar cells.

3.
4. 5. 6. 7. 8. 9. 10. I 1. 12. 13. 14. 15. 16. 17. 18.

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