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1963 Russ. Chem. Rev. 32 207

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Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

4. D.Hadzi and N.Sheppard, Proc.Roy.Soc, 216A, 247 (1953). 42. V.Moreno, K.Dimetter, and J.V.Quagliano, Spectrochim.
5. M.S.C.Flett, Trans.Faraday Soc, 44, 767(1948). Acta, 16, 1368 (1960).
6. W.J.Potts and W.Wright, Analyt.Chem., 28_, 1255 (1956). 43. R.Neeb, Z.analyt.Chem., 161, 161(1958).
7. L.J.Bellamy, "The Infrared Spectra of Complex Molecules" 44. D.Mucke, G.Geppert, and L.Kipke, J.prakt.Chem., £, 16
(Translated into Russian), Moscow, 1957, p. 196. (1959).
8. R.C.Gore, R.B.Barnes, and E.Petersen, Analyt.Chem., 45. S.Kirschner and R.Kisling, J.Amer.Chem.Soc, 82, 4171
21, 382 (1949). (I960).
9. G.F.Svatos, C.Curran, and J.V.Quagliano, J.Amer.Chem. 46. M.P.Bernard, Compt.rend., 25£, 1830 (1960).
Soc, 77, 6159 (1955). 47. W.R.Jencks and J.Carrinolo, Nature, 182, 598 (1958).
10. D.Segnini, C.Curran, and J.V.Quagliano, Spectrochim.Acta, 48. D.A.Long and W.O.George, ProcChem.Soc, 242(1960).
16_, 540 (1960). 49. D.A.Long and W.O.George, Trans.Faraday Soc, 56, 1570
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12. Y.Kuroda and M.Kubo, J.Phys.Chem., 64, 759 (1960). 51. J.D.S.Goulden, Spectrochim.Acta, 16, 715(1960).
13. M.J.Schmelz, T.Miyazawa, S.Mizuschima, T.J.Lane, and 52. J.D.S.Goulden, Chem.and Ind., 721(1960).
J.V.Quagliano, Spectrochim.Acta, j), 51 (1957). 53. F.S.Parker, Appl.Spectroscopy, 12, 163 (1958).
14. S. Fronaeus and R.Larsson, Acta Chem. Scand.,l£, 1364 54. A.E.Martin, Nature, 166, 474 (1950).
(1960). 55. J.M.Hunsberger, J.Amer.Chem.Soc, 72, 5626 (1950).
15. E.Childers and G.W.Struthers, Analyt.Chem., 27, 737 56. R. S. Rassmussen and R. R. Brattain, J . Amer. Chem. Soc.,
(1955). 71, 1053 (1949).
16. F.Cappelina, V.Carossiti, andG.Fabbri, Ann.Chim.(Italy), 57. R.S.Rassmussen, D.D.Tuncliff, and R.R.Brattain,
50, 615 (1960). J.Amer.Chem.Soc, 71, 1068 (1949).
17. J.M.Hunt, M.P.Wisherd, andL.C.Bonham, Analyt.Chem., 58. H.Yamada, Bull.Chem.Soc.Japan, 32, 1051(1959).
22, 1478 (1950). 59. A.Yamamote and Sh.Kambara, J.Chem.Soc.Japan, Pure
18. T.Shimanoushi, M.Tsuboi, T.Takenischi, and N.Iwata, Chem. Sec, 80, 97A, 1239 (1959).
Spectrochim.Acta, 16, 1328 (1960). 60. L.J.Bellamy and R.F.Branch, J.Chem.Soc, 4491(1954).
19. A.A.Glagolevaand A.A.Ferkhmin, Zhur.Obshch.Khim., 29, 61. B.E.Bryant, J.Pariaud, and W.C.Fernelius, J.Org.Chem.
1715 (1959). 19, 1889 (1954).
20. W.H.T.Davison, Chem.and Ind., 408(1953). 62. O.E.Ayers and J.E.Land, J.Phys.Chem., 65, 145 (1961).
21. J.L.Hales, J.I.Jones, and A.S.Lindsey, J.Chem.Soc., 63. R.Cardinaud, Bull. Soc chim. France, 634(1960).
3145 (1954). 64. B.L.Shaw and T.H.Simpson, J.Chem.Soc, 5027(1952);
22. D.T.Sawyer and P.J.Paulsen, J.Amer.Chem.Soc, 81, 816 655 (1955).
(1959).
23. D.T.Sawyer and J.M.McKinnie, J.Amer.Chem.Soc, jJ2, Institute of General and
4191 (1960). Inorganic Chemistry,
24. D.T.Sawyer, Ann.New York, Acad.Sci., 88, 307(1960). Academy of Sciences
25. D.H.Busch and J.C.Bailar, J.Amer Chem.Soc, 75, 4574 of the Ukrainian SSR
(1953).
26. J.V.Quagliano, G.F.Svatos, and B.C.Curran, Analyt.
Chem., 26, 429 (1954).
27. B.C.Curran, D.N.Sen, S.Mizuschima, and J.V.Quagliano,
Analyt.Chem., 26, 429 (1954).
28. C.Duval and J.Lecomte, Bull. Soc chim. France, 1£, 180 THE ELECTROCHEMISTRY OF SEMI-
(1943). CONDUCTORS
29. S.Mizuschima, D.N.Sen, B.C.Curran, and J.V.Quagliano,
J.Amer.Chem.Soc, 77, 211 (1955). V . A . M y a m l i n and Y u . V . P l e s k o v
30. S.Kirschner, J.Amer.Chem.Soc, 78_, 2372(1956).
31. R.H.Gillette, J.Amer.Chem.Soc, 58, 1143 (1936).
32. N.Fuson, M.L.Josien, E.A.Jones, and J.R.Lowson, CONTENTS
J.Chem.Phys., 20, 1627 (1952).
33. J.Bellanato and J.R.Barcelo, Spectrochim. Acta, 16, 1333 I. Introduction 208
(1960).
34. D.T.Sawyer and P.J.Paulsen, J.Amer.Chem.Soc, 8£, II. The semiconductor—electrolyte system at equilibrium 208
1597 (1958). 1. Potential distribution at the phase boundary 208
35. H.A.Weakliem and J.L.Hoard, J.Amer.Chem.Soc, 81,
549 (1959). 2. Differential capacity 210
36. M.L.Morris and D.H.Buseh, J.Amer.Chem.Soc.» 78, ΠΙ. Kinetics of electrode reactions 212
5178 (1956).
37. D.H.Busch and J.C.Bailar, J.Amer.Chem.Soc, 78, 716 1. Rate limitation by the electrochemical stage 212
(1956). 2. Rate limitation by minority carrier diffusion 214
38. E.J.Kyuno, J.Chem.Soc.Japan, Pure Chem.Sec, 81, 232
(1960). 3. Generation of minority carriers in the space-
39. D.Mucke, G.Geppert, and L.Kipke, J.prakt.Chem., 12, -charge region 216
161 (1961). 4. The role of free and valence electrons in
40. D.M.Sweeny, C.Curran, and J.V.Quagliano, J.Amer. electrochemical reactions 217
Chem.Soc., 77, 5508 (1955).
41. A.J.Saraceno, J.Nakagawa, S.Mizuschima, C.Curran, and 5. Formation of oxide layers on the electrode
J.V.Quagliano, J.Amer.Chem.Soc, 80, 5018 (1958). surface 218

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 Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

IV. Chemical etching 218 in potential within the semiconductor. We shall also calcu-
late the thickness of the space-charge layer in the semi-
V. Application of electrochemical methods of surface
conductor.
treatment in physicochemical research and in semi-
conductor technology 220 Consider first Poisson's equation in the form

(1)
dx*
I. INTRODUCTION
where φ (χ) is the potential at the point χ, ρ(ΛΓ) is the space-
Recent advances in semiconductor physics, and the wide -charge density at the same point, and e is the dielectric
application of semiconductor devices in radio circuits have permittivity of the medium. The χ axis is chosen normal
created a new branch of electrochemistry: the electro- to the phase boundary. Let the semiconductor occupy the
chemistry of semiconductors. Over 200 papers primarily region χ > 0, and the electrolyte occupy the region χ < -d0,
concerned with the electrochemical properties of silicon where d0 is the thickness of the Helmholtz layer (of the
and germanium have been published since 1955. In more 8
order of 10" cm).
recent years, electrochemists have become interested in
new semiconducting materials, such as intermetallic com- In an η -type semiconductor with fully ionised donor
pounds, silicon carbide, and various oxides and sulphides. levels the space-charge density is given by the expression
p{x) = e[— n(x) + p(x) + ND],
The development of semiconductor electrochemistry
owes its origin to the experiments of Brattain and Garrett. where n, p, and ND are the concentrations of electrons,
In the Soviet Union, Efimov and Erusalimchik were the first positive holes, and donors respectively, and e is the abso-
to study semiconductor electrochemistry, but it was not lute value of the electronic charge. At equilibrium, the
long before the researches of workers at the Institute of concentrations of free current carriers in the presence of
Electrochemistry and the Institute of Physical Chemistry an electric field in the semiconductor are given by Boltz-
of the Academy of Sciences of the USSR, and at the Karpov mann expressions:
Physicochemical Institute began to show an awareness of
semiconductor problems. Theoretical studies of semi- «[φ(χ)-φ Β ]
conductor electrochemistry in the USSR were started under i= pc
kT
(2)
the initiative of V.G.Levich.
Gerischer, Green, and Dewald are among those who The symbols «»> />»> and φ Β refer to the electron concen-
have made significant contribution to the development of tration, the hole concentration, and the potential at a point
far removed from the space-charge region (x —* «>). An
basic ideas in semiconductor electrochemistry.
adequate, though qualitative, description of the system can
be obtained by considering only small changes in potential.
We shall assume, in other words, that βφ/kT is much less
II. THE SEMICONDUCTOR-ELECTROLYTE SYSTEM
than unity everywhere in the semiconductor. This enables
AT EQUILIBRIUM
us to neglect higher terms in the series expansions of the
exponentials of Eqn. (2), and to express the space-charge
1, Potential Distribution at the Phase Boundary
density in the form
The equilibrium potential of a semiconductor is the
potential differencet in the equilibrium system:
metal Μ | semiconductor I electrolyte I metal M. At a point well inside the semiconductor there is no space
This potential does not depend on the position of the Fermi charge, and -n« + p» + ND = 0. In an w-type semiconduc
level in the semiconductor 1 » 2 . tor η» » Ρco' Under these conditions Eqn. (3) takes the
form
The Galvani potential which appears at the phase bound- . . ΙΦΜ-ΦΙ
ary between semiconductor and electrolyte is distributed P(*) = —
over three separate regions: the diffuse part of the double
layer in the electrolyte, the Helmholtz double layer, and Poisson's equation [Eqn. (1)] can now be written in the form
the semiconductor%. Its magnitude is a function of the αίφ 4πβ« [φ (χ) — <pB] nm . .
position of the Fermi level in the semiconductor 1 ' 2 » 8 . It dx* ~~ ΓΤΪ · w
can be shown (see below) that in the absence of surface
states§ the potential drop across the first two regions where e^s the dielectric constant of the semiconductor.
can be made negligibly small in comparison with the change
Integration of Eqn. (4) gives
t Equilibrium potentials for reactions at germanium and
silicon electrodes in aqueous solutions have been calculateds ~ 5 .
[More recent values can be found in Holmes160 [Ed. of Trans-
lation) .] The electric field intensity Ε is related to άφ/dx by the
$ Contributions to the Galvani potential arising from adsorption expression Ε = -άφ/dx. The field at the semiconductor
of polar molecules of the solvent (or solute) on the electrode will surface (x = 0) is therefore given by
not be considered.
§ The term surface state T»8 refers to an electronic energy (5)
level localised at the semiconductor surface. These levels «1

appear when the crystal lattice is cleaved to generate a surface

(Tamm states), when impurities are adsorbed on the surface, and The quantity d1 has the dimension of length and is called
so on. the Debye length. Expression (5) can be interpreted as

208
 Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

follows: the potential drop φ1 in the semiconductor is con- The thickness of the Helmholtz layer is approximately
centrated in a region of thickness d1 (the Debye length) such 10"8 cm. Therefore, using Eqns. (9), (10), and (11), we
that the ratio of φ1 to dx measures the intensity of the elec- conclude that in sufficiently concentrated solutions the
tric field at the surface of the semiconductor, EJ. major part of the Galvani potential drop occurs in the semi-
conductor. Thus we are justified in considering the semi-
As stated above, the value of the Galvani potential can conductor-solution interface as a capacitor in which the two
be considered a s the sum of three t e r m s : φ = φ0 + φγ + ψ', layers of charge have a diffuse structure. The properties
where φ0, ψι} and ψ' denote the potential drop in the Helm- of the interface are determined mainly by the distributed
holtz layer, in the semiconductor, and in the diffuse part of space charge in the semiconductor.
the electrolyte double layer respectively.
The importance of the assumed absence of surface states
The charge density in a uni-univalent electrolyte is given
on the semiconductor needs to be stressed. In the pre-
by sence of a large density of surface states the potential dif-
(6) ference across the Helmholtz layer can account for a large
where c + and c_ denote the number of cations and of anions fraction of the drop in Galvani potential. We shall calcu-
per cm 3 . By simultaneously solving Poisson's equation (1) late the potential drop in the Helmholtz region for the case
and Eqn. (6) for the electrolyte we obtain an expression of of a density of surface states Ns = 1014 cm" 2 , assuming a
the same form a s Eqn. (5) for the ψ' -potential 1 0 . Hence degree of ionisation of 0.1. From the formula for a plane
we conclude that the diffuse charge distributions in the parallel-plate condenser, the electric field in the Helm-
semiconductor and in the electrolyte a r e very similar. holtz layer is given by the following expression (in which
€o = 3 ) :
Since the electric field in the Helmholtz double layer is
assumed to be constant, i.e.
zz. IO7 V cm .

we can express the Galvani potential in the form

In this case the potential drop in the Helmholtz double layer
φ = Exdy. + £„<*<> + ΕΛ, (7) accounts for a few tenths of a voltf.
Experimentally it is found that, as in the case of metal-
where E2 is the electric field in the solution at χ = -d0. If lic electrodes, the potential drop across the diffuse part of
we now assume that the semiconductor surface is free from the double layer in the electrolyte (ψ') is appreciable only
surface states we can use Gauss' theorem and state that in extremely dilute solutions. Recent work 11 » 12 has shown
the electrostatic induction does not show a discontinuity at that the ψ' -potential of a germanium electrode in dilute
the interface: aqueous solutions is of the order of 20-40 mV and de-
creases rapidly with increase in concentration.
0
8 £
0 (8)
The difference in potential across the space-charge
where e 0 , e x , and €2 denote the permittivities of the Helm- region of the semiconductor (φ^ can be deduced from
holtz layer, the semiconductor, and the electrolyte respec- measurements of the surface conductivity (σ) of the semi-
tively. The ratio of the potential drops can now be found conductor in contact with the solution. Garrett and Brat-
from Eqns. (5) and (8): tain 13 have calculated an expression relating σ to φχ for a
"dry" semiconductor surface^. Harten 1 5 concluded, from
φ» _ d et
<Pi __ <k e« t
(9) a detailed study of the experimental and theoretical curves
for a silicon electrode, that a potential applied to the sili-
Thus we see that, provided a correction for the difference con-electrolyte interface will appear almost exclusively
in permittivity of the two media is made, the ratio of the within the semiconductor. Krotova showed16, by the same
potential drop in the semiconductor to that in the electrolyte procedure, that some 15 to 50% of the potential of a ger-
is equal to the ratio of the corresponding Debye lengths. manium electrode close to its steady-state potential appears
The Debye length of a semiconductor of not too high carrier across the Helmholtz layer. The inference is that ger-
density usually differs from the thickness of the diffuse layer manium surfaces, as normally prepared, contain an appre-
in an electrolyte by several powers of ten. Thus, in a semi- ciable density of surface states; adsorption of traces of
conductor of the germanium type with a density of donor copper from the solution can account for some of them " .
levels ND = «« = 1014 cm" 3 , €1 = 16, kT= 4 Χ 10" 14 erg at In the zinc oxide electrode, on the other hand, practic-
room temperature, and we obtain ally the whole of the charge is concentrated within the
semiconductor;1 8 in other words, this material is free from
CxlO* cm. (10) surface states ' 2 1 .
The thickness of the diffuse layer in an electrolyte, d2, Illumination of a semiconductor electrode affects the
decreases with increase in concentration, and becomes potential drop (<px) within the semiconductor, and therefore
infinitesimally small in21very concentrated solutions. In a also the electrode potential. Garrett and Brattain 1 3
normal solution (c = 10 ions cm" 3 , e 2 = 80) the thickness point out that the photopotential (i .e. the change in electrode
d2 is approximately potential upon illumination) must vanish when there is no
=10'cm. (11)
t The Helmholtz potential drop can also become appreciable if
J We have adopted the terminology of semiconductor physics the space charge in the semiconductor is very large 2
.
in calling the quantity rfj the Debye length. The charge9 density in J Myamlin14 has derived an expression for σ at the semicon-
a double layer was first calculated, however, by Gouy . ductor-electrolyte boundary.

209
 Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

space charge in the semiconductor. The electrode potential 2. Differential Capacity

(measured against some reference electrode) which corre-
sponds to this state of affairs is called the "flat band poten- We shall now calculate the capacity of a semiconductor
tial" because there is no electric field to distort the edges electrode. The differential capacity is defined as
of the energy bands near the semiconductor surface. C = \dQ/d<p\} where Q is the total charge and φ is the total
Measurements of photopotential are therefore a very con- potential drop. We can write Q = Q1 + Qs, where Qa is the
venient way of obtaining the value of the flat band poten- space charge in the semiconductor and Qs th e charge in the
tial 21 » 22 . The influence of free electron concentration on surface states. Allowing for the charge in the donor and
the flat band potential of germanium provides further sup- the acceptor levels, and making use of Eqn. (2), we write
port for the conclusion that in this material the potential Poisson's equation [Eqn. (1)] in the form
drop in the space-charge region of the semiconductor is
comparable in magnitude with the potential drop in the ά?φ __ 4JI # / κι KT \ \ (Λ Ο\

Helmholtz layer 2 3 §.
The flat band potential of germanium is affected by the where Ν A is the concentration of acceptor levels.
method of surface preparation and also by the nature of the The potential φ ρ, deep within the semiconductor and far
electrolyte 23 . In germanium with intrinsic conductivity, from the space-charge region, is given by the expression
for example, the flat band potential is 0.5 V in 1 Ν ΚΟΗ and
0.13 V in IN H2SO4, showing that even in the absence of ND — NA = ΙΠι sinh , \io)
space charge within the semiconductor, the Helmholtz
potential drop (and therefore also the surface charge) is where ni is the free electron concentration in the pure
quite appreciable. (intrinsic) semiconductor.
The appearance of surface charge on germanium has The last equation is readily integrated and leads to an
been discussed 2 3 · 2 5 in terms of oxidation of the surface. expression for the total charge in the semiconductor, Q1#
Measurements of charging curves have shown 26 - 30 that ger- The final result is 5 1
manium surfaces are normally covered with a monolayer
of oxide in non-oxidising solutions. Evidently the surface Qi=± V~2^-( e l|) lsinhUB(UB-Us)-(coshUB-coBhUs))l/', (14)
oxide partly dissociates (e.g. by forming GeOOH" groups in
an alkaline medium), the degree of dissociation depending where
on the pH of the solution. The surface charge thus gener-
ated is retained even when there is no space charge in the
semiconductor (i.e. at the flat band potential) and is balanced In these expressions <ps is the potential at the semiconduc-
by the charge of the ions electrostatically adsorbed from tor surface, i.e. at χ = 0. Eqn. (14) gives the total space
the solution. The double layer present on a germanium charge in the semiconductor, Qlt as a function of the poten-
electrode at its flat band potential has an obvious similarity tial difference φλ = φ5-ψΒ within the semiconductor, and
to the structure of a mercury surface at the point of zero of the number of donor and acceptor levels.
charge under conditions of specific adsorption of, say,
bromide ionsiF. The flat band potential should not be con- The next step is to allow for the charge trapped in any
fused, however, with the zero-charge potential: the latter surface states which may be present on the semiconductor
corresponds to a situation such that both the space charge surface. We shall consider a concrete case and assume
and the surface charge must vanish. that donor levels are present on the surface (i.e. levels
which are positively charged when empty and neutral when
The surface recombination velocityt, an important pro- occupied by an electron). Let Ns be the number of sur-
perty of semiconductor surfaces, is related to the potential face states per unit area. The electronic occupancy of
7
drop across the Debye region of the semiconductor . It these states is governed by the Fermi distribution:
has been shown that the surface recombination velocity at a
semiconductor-electrolyte interface is a function of poten-
tial 3 9 " 4 3 , solution composition 44 " 46 , and surface prepara- l+exp- kT
tion. A characteristic, bell-shaped curve is obtained when where Es is the energy level of the surface states and EF
the surface recombination velocity is plotted against poten- is the Fermi level. The energy difference Es - Ε F is a
tial: the situation is therefore analogous to the semicon- function of the potential drop in the space-charge region of
ductor-gas interface 4 7 . The parameters of the curve can the semiconductor. The actual energy of an electron in a
be used to characterise the recombination centres by evaluat- surface state is given by
ing the ratio of the capture cross-sections for electrons
and for holes 3 9 . Mild anodic etching of the germanium
reduces the rate of surface recombination; strong cathodic
polarisation, on the other hand, sharply increases it39»48»49. where E°s is the energy level of the surface states in the
It would appear that additional recombination centres are absence of space charge in the semiconductor. The charge
created, under these conditions, as a result of adsorption in the surface states is given by the expression
of the evolved hydrogen or penetration of the hydrogen into η _ -/χ/ - \ _ eN
S
(15)
the germanium crystal lattice}:. l + exp. kT
It is convenient to evaluate the quantity l/C,
§ See also Refs.16 and 24.
IF The adsorption of various ions on germanium and silicon has
been investigated 31 " 38 . dQ
t See p.215.
t It has been suggested50 that adsorbed hydrogen can give rise
to acceptor levels as well as recombination centres. | - 4 + ί- + Α:. (16)

210
Vol.32 Ν α 4 RUSSIAN CHEMICAL REVIEWS April 1963

where Cv C o , and C 2 are the capacities of the semiconduc-

tor (with allowance for surface states), of the Helmholtz
layer, and of the diffuse part of the double layer in the
electrolyte, respectively. The capacity of the semiconduc-
tor, C,= \dQ/d(<pc -<PB) I, can be calculated 2 by means of
Eqns. (12) and (15): V

4n }T2LD [sinh UBWB - I/s)-(cosh Ug - cosh £/s)]%

aoi
-β; ο o.i fl2>t.v
exp Fig. 1. Variation of differential
(17)
kT {l+exp[£F-E» + «(<ps· capacity with potential drop in the
The electric field in the Helmholtz part of the double layer space-charge region of the semi-
is constant, and therefore the capacity Co of the Helmholtz conductor, calculated for rt-type
region can be calculated from the formula for a parallel- germanium by Eqn. (17).
-plate condenser:
C« = — ^ - — 1 0 7 cm"1
«πα,,

The capacity of the diffuse layer in the electrolyte is given

by 1 0 : more positive potentials, and in />-type semiconductors at
more negative potentials, than the flat band potential.
8, 1
(18) Bohnenkamp and Engell's measurements 52 » 53 of the capa-
city of the germanium electrode support the ideas outlined
We have seen that the total capacity of the semiconductor - above. The capacity vs. potential curve shows a minimum,
electrolyte system is determined by the diffuse and the at which, in agreement with theoretical calculations, the
surface charges in the semiconductor, by the Helmholtz capacity is only a few hundredths of a microfarad per cm 2 ,
layer, and by the diffuse charge in the electrolyte. We i.e. 2-3 orders of magnitude less than the capacity of a
shall proceed to evaluate the various contributions to the metal electrode. The experimentally observed relation-
total capacity for the specific case of an η-type semicon- ship between capacity and electrode potential fits the theo-
ductor (ni/ND « 1 ) free from surface charge. Under these retical expression for the effect of the potential drop in the
conditions Eqn. (17) simplifies to space-charge region (cpj) on the capacity of the electrode,
see Eqn. (17)§, whence it can be concluded that changes in
«φ.
φ1 account for the major part of any change in electrode
(19) potential.
•«•-1- The potential of minimum capacity of intrinsic german-
ium (i.e. the flat band potential) varies smoothly with the
Terms proportional to ni/ND (i.e. « 1) are ignored in the pH of the solution 5 2 " 5 4 . This confirms our previous con-
above formula. Green 2 has derived expressions in which clusions as to the effect of the surface condition on the
these terms are retained. At potentials of the order of potential drop in the Helmholtz layer. The capacity mini-
φ " kT/e the capacities of the semiconductor (Cx) and of the mum of intrinsic germanium lies at 0.5 V (in 1 Ν ΚΟΗ solu-
electrolyte (C2) are found from Eqns. (18) and (19) to be in- tion) and at 0.2-0.3 V (in 1 Ν H2SO4).
versely proportional to the appropriate Debye length. Bohnenkamp and Engell's observation of the effect of
Introducing the approximate numerical values of the Debye frequency (between 1 and 160 kc/s) on the capacity and on
lengths, and using Eqn. (16), the final result is that the the potential of minimum capacity is still unexplained^.
total capacity of the system is controlled by the capacity of The effect may indicate the presence of a frequency-
the diffuse part of the semiconductor double layer. -dependent capacity of the type associated with electrode
Under conditions of appreciable surface charge on the reactions, or alternatively it may be ascribed to surface
semiconductor {e.g. with a density Ns = 1014 cm" 2 of sur- states with different relaxation times being present on ger-
2
face states, assumed to be 10% ionised) we have e Ns/kT ** manium B 5 .
<=* 107 cm" 1 = 10 μΈ cm" 2 . Applying Eqns. (17) and (18) we The capacity of the silicon electrode is somewhat lower
now find that the capacity of the semiconductor can become than that of the germanium electrode. The electrode capa-
comparable with the Helmholtz capacity. city is again determined by the space charge in the semi-
Let us now compute the capacity of a semiconductor conductor se-59. Illumination of the electrode increases the
electrode without surface states at the flat band potential, concentration of mobile charges (as a result of the photo-
i.e. with <ps = ΨΒ- Applying Eqn. (17), we obtain: -excitation of hole-electron pairs), and the capacity rises
towards the characteristic value of metal electrodes
(~ 10 μΈ cm" 2 ).
(20)
§ Eqn. (17) takes no account of the passage of current through
the semiconductor-electrolyte interface. It can, however, be
The variation of capacity with potential is shown in Fig. 1. applied to germanium because this electrode behaves as an ideally
It can be shown52 that for an intrinsic semiconductor the polarisable electrode over a certain range of potentials.
capacity minimum occurs at the flat band potential. In 1Γ The capacity of a ZnO electrode is independent of frequency18
«-type semiconductors the capacity minimum occurs at between 50 c/s and 100 kc/s.

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 Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

Efimov and Erusalimchik found a minimum in the capa- -whence

city of the germanium electrode at a quite different poten-
tial: 0.6 V in 0.1 Ν HC1. They call this potential the zero - dint ~
(26)
-charge potential of germanium 80 . Their high specific
capacity (10-20 μΈ" cm" 2 ), unaffected by the properties of If the reaction at the semiconductor surface is of the
the semiconductor, suggests that these workers were mea- second order with respect to electrons, Eqn. (22) is modi-
suring the capacity of the Helmholtz layer. Before each fied as follows:
measurement the electrodes were subjected to prolonged o f Αφ.
cathodic polarisation which, as stated above, can raise the «ι = * ι ^ + [ η ( * = 0)]«β «τ . (27)
surface recombination velocity very considerably. It
would appear that this treatment also makes the semicon- which leads to
ductor surface "metal-like". The full significance of
Efimov and Erusalimchik's measurements 8 0 , however, is (28)
dint 2F
far from clear. These remarks also apply to Efimov and
Erusalimchik's 8 1 anomalously high value for the capacity Note that Eqns. (26) and (28) give values of Βφ/d Ini
of a silicon electrode. similar to those obtained for metals, but for different
reasons.
At high surface charges Δφ 0 becomes greater than <pv
ΠΙ. KINETICS OF ELECTRODE REACTIONS
and the semiconductor electrode tends towards metallic
properties. Under these conditions the kinetics of an
1. Rate Limitation by the Electrochemical Stage electrochemical reaction at a semiconductor electrode will
be almost indistinguishable from those at a metal electrode.
To give a clearer understanding of the behaviour of the
We shall consider two examples: the anodic dissolution
semiconductor-electrolyte interface we shall discuss an
of a semiconductor and the cathodic evolution of hydrogen,
electrochemical redox reaction of the type
the electrochemical stage being assumed to be rate-deter-
A+ + <T5±A. (21) mining in both cases. Under these conditions the evolution
10 of hydrogen at a germanium electrode is described, irre-
By analogy with the slow-discharge theory we can write
spective of the conductivity type of the semiconductor, by a
expressions 2 » 8 2 for the currents carried by the reduction
(i x ) and the oxidation (i2) reactions: Tafel equation with a slope RT/aF of about 0.1-0.12, cor-
responding to a transfer coefficient of about 0.5. 63 ~ 67 The
aF &<t. stoichiometric number is ν = 1, the exchange current is
= ki CA+ η (JC = 0) e (22) i o = 10" e -10~ 8 Acm" 2 . Other workers 49 » 88 - 70 have reportedf
Ρ /''Αφ.
RT/aF = 0.16, a = 0.3, and i = 10"7 A cm" 2 .
(23) Green 2 suggests the following mechanism for the hydro-
gen evolution reaction by comparing experimental results
where kx and k2 are constants, cp* is the concentration of with RT/aF and ν values calculated for various assumed
A+ ions in the electrolyte, n(x = 0) is the electron concen- mechanisms. Hydrogen ion discharge,
tration at the plane separating the Helmholtz layer from the
semiconductor, F is the Faraday, a and β are constants
(ο? + β = 1), Αφ0 is the departure of the potential drop in the occurs relatively fast, and the rate-limiting stage is iden-
Helmholtz part of the double layer from its equilibrium tified with electrochemical desorption:
value, and R is the gas constant.
H + +Had 8 +<?--H 9 .
Eqns. (22) and (23) are applicable to reactions, like (21), The rate of evolution of hydrogen on an η-type silicon
in which free electrons take part. Eqn. (22) differs from cathode also increases exponentially with electrode poten-
10
the slow-discharge equation for metallic electrodes by tial: the value of the coefficient RT/aF appears to vary
the factor n{x = 0), introduced here because the concentra- 73
from 0.095 to 0.18.
81

tion of free electrons at the semiconductor-electrolyte

interface is not constant. This is the fundamental differ- Turning now to the anodic dissolution of germanium, we
ence between a metallic and a semiconducting electrode shall discuss a very characteristic feature of this reaction
surface. which stems from the semiconductor nature of germanium:
the participation of positive holes. In other words, when a
The electron concentration at the interface, n(x = 0), germanium atom goes into solution with a formal valency of
depends on φχ, the potential drop in the semiconductor, and +4$ it gives up some of its electrons to the valence band
obeys Boltzmann's distribution law. Applying Eqn. (2) we 78 78
(see p.215). Brattain and Garrett " demonstrated that
obtain a new expression for the current: the concentration of holes at the electrode surface depends
«φ» + (ΜΑφ. on the potential!, and that the expression for the reaction
*r (24) overvoltage should include the term (RT/F) In (p/p0), where
p and p0 are the actual and the equilibrium values of the
hole concentration at the surface. One method of varying
As we have already pointed out (see p.209) the potential p is to illuminate the electrode: in this way the authors
drop in the Helmholtz layer is usually much smaller than
the potential drop in the semiconductor. Therefore,
ignoring small terms, t The value Ri/aF = 0.23 has also been reported71·72.
t At very high current densities GeO
74 75
is formed as well as
quadrivalent germanium compounds ' .
79 80
* ι = ^l CA+ (25) § Other workers · later reached the same conclusion.

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Vol.32 No. 4 RUSSIAN CHEMICAL REVIEWS April 1963

were able to show78 that the current is proportional to the For i = 0, integration of Eqn. (29) leads to the Boltz-
intensity of illumination and therefore that the slow step is mann distribution. Even if i Φ 0, however, it is possible
kinetically of the first order with respect to holes. to have
The anodic oxidation of germanium in alkaline solutions
consumes hydroxide ions, as shown by the appearance of a eu_ En
dx
limiting current in the polarisation curves obtained in
dilute NaOH solutions. The value of the limiting current so that in Eqn. (29) i becomes negligible in comparison with
is determined 81 by the rate of diffusion of OH" ions to the the much larger terms on the right-hand side. Under
electrode surface. At still higher potentials the current these conditions, integration of Eqn. (29) again gives the
begins to rise again because a new reaction sets in: the Boltzmann distribution.
dissolution of germanium, which involves water molecules.
Beck and Gerischer 2 5 studied the effect of alkali concen- It follows that we can legitimately apply Boltzmann ex-
tration on the overvoltage (at currents well below the limit- pressions provided that the total current is much smaller
ing diffusion current of OH" ions) and concluded that the than both the drift and the diffusion currents.
slow step in the anodic dissolution of germanium is uni- But what is the magnitude of expressions of the type
molecular with respect to hydroxide ions. The current- eu.En? Consider, for example, an anodic process at a
potential relationship is described by a Tafel equation with germanium electrode. We shall assume that the pre-
β = 0.7-0.81Τ (Fig. 2, curve 1). sence of the electrolyte increases the steady-state concen-
Beck and Gerischer 2 5 have put forward a reaction mech- tration of holes at the surface, resulting in a Galvani
anism for the anodic dissolution of germanium which potential of 0.1 V.
accounts for these experimental facts. Germanium atoms The electric field is of the order of pjd±. Putting
at the electrode surface become oxidised with formation of dx = 10~4 cm, we find Ε = 103 V cm In germanium of
GeOOH" groups, a process requiring one hydroxide ion and
one positive hole. The slow stage is associated with the 1 Ω cm resistivity the concentration of free electrons, n«>,
passage of the GeOOH" into solution, to give H 2 Ge0 3 . is 2 x 1015 cm" 3 , and the concentration of holes, />«>, is
3 x 1011 cm" 3 . Under these conditions the drift current of
In the derivation of the kinetic equation (25) we used the holes takes the value
Boltzmann distribution to give the electron concentration in
the semiconductor during the passage of current. This eii+fp^lO-'Acin·1. (30)
distribution, however, is strictly applicable only to equili-
brium situations, i.e. in the absence of external currentf. Consequently, hole densities will be accurately described
We will now discuss the limitations of this procedure. by Boltzmann expressions as long as the anodic current is
Consider the expression for the current of electrons in an significantly smaller than the above valuet.
«-type semiconductor: These results sometimes prove incorrect when applied
to electrodes for which the surface density of carriers is
= eu_E(x) η (χ) -f eD- (29) very much less than the carrier density in the uniform bulk
of the semiconductor, far from the space-charge region.
Here M_ and D_ are the mobility and the diffusion coefficient The concentration of electrons at the interface is given by
of electrons respectively. The term euJEn describes the η = nooexpie^/fcT), and can be very small if the exponential
drift current of electrons due to the presence of an electric has a low enough value. The Boltzmann distribution ceases
field; the second term, eD_(dn/dx), is the diffusion current. to apply when the surface layer of the semiconductor is
depleted of free carriers. Two recently published papers
have dealt with the calculation of polarisation curves with
allowance for a non-equilibrium distribution of carriers.
82
One of these discusses the current-voltage character-
istic of the interface between an electrolyte and an η -type
semiconductor. Strong electron depletion at the equilibrium
potential is assumed. This produces a surface layer with
a low concentration of free carriers, of high electrical r e -
sistance, and having rectifying propertiest. When current
is passed through such a contact in the forward direction,
electrons are injected into it by the field and the resistance
decreases. Reverse current, on the other hand, further
depletes the contact of electrons and makes its resistance
tO1 1O'i,k cm*
still higher. The donor levels are assumed 8 2 to be weakly
ionised. The rectification at the contact is described by
Fig. 2. Polarisation curves for the anodic the ratio AF(+t)/AV(-t), where Δ7(+ί) and AF(-i) refer to
dissolution of germanium: l)P-type; 2)n-type.
% A rectification effect is observed also at metal-solution
contacts, e.g. when the anodic and the cathodic reaction have
widely different overvoltages, or when the rate of one of these
reactions is limited by concentration polarisation. We are not
26
f Turner finds ΕΤ/βΞ = 0.12, whence β = 0 . 5 . concerned here with this type of rectification (although it can occur
t We are not considering the case of very high charge on the at semiconducting as well as metallic electrodes), but only with
electrode, when the Boltzmann distribution ceases to apply even rectification effects specific to the semiconductor-electrolyte
under equilibrium conditions. interface.

213
 Vol.32 Ν α 4 RUSSIAN CHEMICAL REVIEWS April 1963

the total potential drop (in the semiconductor and in the where the term % includes constants and functions which
Helm holt ζ layer) under conditions of reverse and forward vary much more slowly than l n i . The value of iu m is given
bias respectively. Its value is given by by
(36)
(31)
β
where »/ is the concentration of free electrons in intrinsic
germanium, D+ is the hole diffusion constant, ρ is the r e -
where i0 is the exchange current of the reaction, I is the sistivity of the germanium, and L is the hole diffusion
thickness of the semiconductor. Inserting I = 10~3 cm, dx length.
(the Debye length) = 10"4 cm, d0 = 10"8 cm, and In (i/i0) =
Let us examine Eqn. (35) in detail. At currents
= 10, we find:
i « iiim the potential varies with current according to
A V ( + I)
.2x10». (32) RT, I
(37)
Clearly, this system has rectifying properties. and Tafel's law is obeyed. At currents close to the limiting
The above treatment 8 2 has been extended83 to the case current the third term of Eqn. (35) becomes predominant:
of an η -type semiconductor with current carriers of both
types. The authors consider a reaction of type (21), (38)
involving carriers of a single type (free electrons). The
equilibrium concentrations of electrons and holes in the When the potential is raised still further a sharply defined
surface layer are assumed to be much smaller than the limiting current is observed.
concentration of majority carriers (free electrons) in the
bulk of the semiconductor. The calculated current-volt- An analysis has been given85 of the distribution of
age characteristic shows an interesting feature: rectifica- carriers close to the surface. Fig. 3 shows the distribu-
tion is present only over a limited range of potentials (of tion of holes for currents not very different from the limit-
the order of the width of the energy gap) as long as the sur- ing current. In the Debye region (0 <x <dj) the hole den-
face remains depleted of electrons and holes. As soon as sity increases rapidly in response to the electric field.
the applied field raises the surface density of holes to the Beyond the Debye region there is no field, and the hole
level of the bulk electron density a distinctive breakdown concentration falls below its equilibrium value (/>«,) because
phenomenon sets in. holes are carried away, across the boundary, by the elec-
trochemical reaction. Under limiting current conditions
the hole concentration at the edge of the Debye region
effectively vanishes. At points well removed from the
2. Rate Limitation by Minority Carrier Diffusion boundary the hole density increases, and reaches its equi-
librium value (poo) at a depth of the order of L, the hole
We have so far considered systems in which the electro- diffusion length. We should note that this distribution is
chemical reaction is the slowest step. This happens at analogous to the distribution of cations in an electrolyte
low current densities (less than 10"* A cm" 2 on germanium) undergoing discharge, at a negatively charged electrode
or when majority carriers (holes in p-type semiconductors, surface under conditions of concentration polarisation:
electrons in η -type semiconductors) are involved in the dx is equivalent to the thickness of the electrical double
reaction. If the reaction, however, consumes minority layer and L to the thickness of the diffusion layer. The
carriers, which are present at low concentration, it is not limiting current can be readily evaluated by the following
surprising to find that the current is limited (beyond a cer- simple arguments. Since the whole of the region dx ^ χ < L
tain potential) by the rate of arrival of minority carriers at lies beyond the space-charge layer, the supply of holes to
the electrode surface. We shall discuss the kinetics of the interface occurs mainly by diffusion. The limiting
reactions of this type, taking the anodic dissolution of ger- diffusion current of holes will be
manium as a concrete example84»85.
As stated above, holes must be supplied to the interface (39)
from the bulk of the semiconductor in order that germanium
shall dissolve. Part of the reaction current is carried
where the concentration gradient is approximately
across the phase boundary by free electrons, however, and lim
we may write the ratio of hole to electron current in the
άρ
form (40)
!±£Ξ& = ±. (33)
Ignoring recombination in the space-charge region, and
where r and m are integers, The°total current of german- using Eqn. (33), we arrive at the total limiting current:
ium dissolution is given by
(41)
• 0) + L(x = 0) = kpa(i (34)
where α is a constant. The germanium surface at its Since the resistivity of the semiconductor is ρ at ΐ/βη^,Μ.,
equilibrium potential is assumed to have a high density of and pconoo= n\i Eqn. (36) follows at once. Thus the value
excess holes. The current-voltage curve for η-type ger- of the limiting current is independent of the parameters of
manium now takes the form the kinetic equation (34), and is also unaffected by any
assumptions as to the nature and charge of the surface
(35) states.
RT

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 Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

87
p-n junction located close to the electrode surface , and
also by raising the temperature (which raises the bulk con-
88
centration of holes in the semiconductor) .
Thus in the anodic dissolution of w-type germanium the
semiconductor-electrolyte boundary behaves very much
like a reverse-biased p-n junction when η-type german-
ium is subjected to anodic dissolution. Current is carried
across the boundary by minority carriers (holes), and the
rate at which holes can diffuse from the bulk to the surface
Fig. 3. Hole concentration profile near
of the semiconductor determines the value of the current.
the surface of η-type germanium dissolving
The blocking current is therefore diffusional, in contrast to
anodically under limiting current conditions.
the type of rectification discussed onp.213-214. Practically
the whole of the potential difference applied to the electrode
appears across the blocking layer of the semiconductor
when limiting current is flowing: only a very small fraction
of the potential is dropped across the Helmholtz layer.
Since the thickness of the blocking layer is very small (of
We will now reconsider our assumption that recombina- the same order as the Debye length), the field intensity
5 1
tion can be neglected, because the limiting dissolution within the blocking layer can exceed 10 V cm" for a poten-
current of germanium can be increased by hole generation tial of a few volts. Under these conditions hole-electron
in the Debye region. To allow for this effect we use the pair generation can occur by an avalanche process, which
concept of surface recombination velocity 7 , vg· We shall produces breakdown in this rectifier-like structure (see
not attempt to discuss the actual mechanism of hole gener- curve 2 of Fig. 2). The value of the breakdown voltage
ation at surface states or in the space-charge region. depends on the resistivity of the germanium, and can amount
Following Shockley, we assume a hole generation current to several tens of volts in the case of high-resistivity speci-
is proportional to the departure of the hole concentration mens.
at the edge of the space-charge region, plf from its equili-
It should be noted that free electrons (as well as holes)
brium value, poo'.
can take part in the anodic dissolution of germanium,
-Ρ»)· (42) making the limiting anodic dissolution current larger than
the limiting hole diffusion current [see Eqn. (36)]. The
Under limiting current conditions, px = 0 and
ratio (r + m)/r = a' is called the current multiplication
(43) coefficient by analogy with the current multiplication which
takes place a t a transistor collector. Brattain and Garrett 7 8
Therefore the limiting current of positive holes is given by
devised the following method of measuring a', which was
adopted in more recent work 87 » 89 . The electrode consists
(44)
of a germanium wafer which is made much thinner than the
hole diffusion length (Fig. 4). An annular ohmic contact
The hole diffusion length L and the hole lifetime τ are r e -
and a. p-n junction (prepared, for example, by the indium
lated by the expression L = (DT)*, SO that finally
alloy process) are placed on one side of the wafer; the
opposite side is immersed in the electrolyte and acts as
ί+lim = (45) the anode. During polarisation of the p-n junction in the
transmitting direction it serves as a source of holes, which
diffuse through the germanium plate and reach the german-
Vdovin et al.85 have discussed one particular generation
ium-solution interface, where they participate in the anodic
mechanism, and calculated current-voltage characteristics
dissolution reaction. The limiting dissolution and hole dif-
and limiting current densities on the assumption that hole
fusion currents can be measured simultaneously, and used
generation occurs entirely at surface states, and not within
to calculate ot'. Measurements by this (and by other)
the space-charge region.
methods all give 78 » 89 ot' values of the order of 1.65, pointing
A limiting current is not observed in the anodic dissolu- to the following stoichiometric equation for the anodic dis-
tion of />-type germanium, because the supply of holes to solution of germanium in alkaline solutions:
the surface cannot be diffusion-controlled when holes are
Ge + 2.4e+ + 6OH" -> GeOr + 1 -6e" + 3HaO.
the majority carriers.
where e* and e~ denote holes and electrons respectively.
Curve 2 of Fig. 2 shows an experimental polarisation
curve for the anodic dissolution of «-type germanium. For
current densities up to 10~* A cm* 2 the current-potential
relationship is of the Tafel form (as in the case of />-type
germanium). At higher potentials the current plateau II 0—ι
appears: Flynn 8 6 states that the value of the limiting cur-
rent is proportional to the resistivity of the germanium (p)
and inversely proportional to the hole diffusion length (L),
as required by Eqn. (36). It seems clear, therefore, that
the diffusion of holes from the bulk of the specimen to its Fig. 4. Electrode for studying the role of
surface constitutes the slow step, and that surface recom- free carriers in electrochemical reactions on
bination occurs at a negligible rate. The limiting current germanium:
can be increased by providing more holes at the surface, e.g. l)P-n junction; 2)n-type germanium, 3) solu-
by illumination of the electrode 7 8 , by hole injection from a tion.

215
 Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

The value of a' varies with dissolution conditions (for All the instances of diffusional control so far outlined
example, with the current of injected holes) 8 9 " 9 2 and cannot, apply to electrodes of thickness many times larger than the
therefore, be identified with any particular molecular minority carrier diffusion length, L. Calculations have
scheme for the reaction. It would appear that when ger- also been made 1 0 8 of the voltage-current characteristic and
manium goes into solution electrons have to enter both the of the limiting current value for the case of a germanium
valence band (a process which consumes holes) and the con- wafer of thickness W < L, in contact with the electrolyte
duction band: the ratio of hole current to electron current on one side and provided with an ohmic metal contact (which
is a statistical quantity depending on the concentration of determines the surface recombination velocity vs) on the
holes at the interface, and can be altered by photo-injection other side.
of holes or by other means 89 » 90 .
Under these conditions the limiting anodic dissolution
If the thickness of the electrode shown in Fig. 4 is not current takes the value
much greater than the thickness of the space-charge region
(~20μ, say), the latter can be made to grow and "flood" the
entire specimen if a sufficiently high reverse voltage is (46)
applied to the p-n junction 93 » 94 . Under these conditions the £>+ cosh— -f vsLsinh —
hole (and electron) concentrations fall much below their
equilibrium values, and the germanium ceases to dissolve Efimov and Erusalimchik 109 » 110 have observed, at least
anodically as soon as the edge of the depletion region comes qualitatively, a relationship of this type between the limit-
into contact with the germanium-electrolyte interfaced. 93 ing current and the resistivity and hole diffusion length of
The limiting currents reported in the anodic dissolution very thin germanium electrodes.
of selenium 98 and of η-type cadmium sulphide 9 9 " 1 0 2 suggest
that positive holes may be involved also in these reactions.
3. Generation of Minority Carriers in the Space-Charge
The exact mechanism whereby holes participate in the Region
anodic dissolution of the semiconductors is still not clear.
Possibly, the rupture of a covalent bond between lattice We will now discuss the anodic dissolution of «-type
atoms becomes easier when a hole is localised at a surface silicon. Eqn. (36) predicts a much smaller limiting disso-
atom. lution current for silicon than for germanium of comparable
The cathodic evolution of hydrogen at a £-type german- resistivity if the dissolution of silicon, like that of german-
ium surface also shows features indicative of minority ium, requires holes. The quantity «t- which appears in
carrier diffusion from the bulk to the surface of the semi- Eqn. (36) is related to the width of the energy gap, thus:
conductor. Brattain and Garrett 7 8 established that free
electrons take part in the reaction, which reaches a limit-
ing rate (~ 1 mA cm" 2 ) at a definite potential. This con-
clusion was subsequently confirmed by Green 2 , Gerischer 4 9 ,
and Dewald21. The limiting diffusion current of electrons It follows that ni, and therefore also the limiting diffusion
is usually less clearly defined than the limiting hole dif- current of minority carriers, must decrease very rapidly
fusion current: this is because the surface condition of the if the width of the forbidden band is increased. Experi-
mentally, however, the dissolution of silicon is found to
germanium electrode is gradually altered by the adsorption
support currents which are comparable in magnitude to
and penetration of atomic hydrogen into the germanium those of germanium anodes. Flynn 88 believes that genera-
lattice during the evolution. These phenomena are known tion in the space-charge region can provide the holes
(see p.210) to increase the rate of surface generation and needed for the dissolution of silicon. One of us m has
recombination of hole-electron pairs 48 > 8e > 103 » 104 . The exact derived a quantitative model for the anodic dissolution of
similarity, even at very high current densities, between silicon in which allowance is made for generation in the
the polarisation curves for hydrogen evolution from « - and Debye region. The theory of Shockley and Read 1 1 2 is used
/>-type germanium electrodes previously saturated with to describe the recombination process. The number of
hydrogen105 can be explained in the same way. Such elec- carriers recombining per unit volume and unit time works
trodes behave like metallic electrodes and effectively lose out to
their semiconductor properties. If the polarisation curve,
on the other hand, is determined rapidly, the hydrogen
overvoltage on «-type germanium is found to be smaller (47)
106
than on />-type .
where
The observation of Paleolog et al.107 that the rate of
hydrogen evolution on />-type germanium, though smaller B,-Et
than on «-type, decreases with increasing germanium = «/ exp
kT
Pi. = n, exp
kT
resistivity, cannot be reconciled with the views outlined
above, which require that the limiting electron current
should increase with increase in resistivity — see Eqn. (36). τρ0 and τ« 0 are, respectively, the hole lifetime in a strongly
The authors suggest 107 that valence electrons rather than «-type sample and the electron lifetime in a strongly/»-type
free electrons are concerned in the hydrogen evolution r e - sample containing the same recombination centres as the
action on />-type germanium. experimental material; Et is the energy level of the recom-
bination centres; Ει is the Fermi level of the intrinsic
semiconductor. The polarisation curve for silicon dissolu-
tion now has the form
§ A method of producing very thin germanium wafers 95> 9δ by
(48)
this technique has been described (see also Albers and Thomas 97 ).

216
 Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

where ψ0 is a constant, i0 is the exchange current of the 4. The Role of Free and Valence Electrons in Electro-
silicon dissolution reaction, and the current iy is given by chemical Reactions

(49) We have so far been concerned with reactions involving

participation of free carriers of a single kind. Thus,
dx being the Debye length of the semiconductor. Eqn. (22) refers to a reduction reaction in which electrons
are transferred from the conduction band to the ions or
At currents i < ix the second term in Eqn. (48) varies molecules undergoing reduction. The kinetic equation for
more slowly than the third, and the current-voltage curve an oxidation reaction in which holes are consumed has a
approximates to Tafel *s law: similar form. However, we have seen that even in the
case of anodic dissolution of germanium free carriers of
φ = — In — + const. both kinds may be involved. Dewald119, Gerischer 12°-123,
and also Dogonadze and Chizmadzhev124 have examined
When the currents i and ix are of similar magnitude the quantitatively the relative extents to which the conduction
parabolic relationship between current and potential becomes and the valence band can be expected to contribute to the
predominant, and the potential increases much faster than overall charge transfer between the semiconductor and the
with the logarithm of the current. The current ix charac- solution during an electrochemical reaction. We will
terises the transition to a region of strongly current- summarise some of the conclusions of the most recent 1 2 4
-dependent potential. From Eqn. (49), ix is proportional to of the above papers, dealing with the kinetics of redox
the Debye length, and therefore also to the square root of reactions in which there is no adsorption of reactants and
the silicon resistivity: no rupture or deformation of chemical bonds.
ii~V7 · (50) The value of the exchange current i0 (consisting of an
electronic component if and a hole component ίζ) was
Eqn. (49) can be obtained by the following semiquantita- calculated by a quantum mechanical method. The ratio of
tive argument. We seen from Eqn. (47) that effective the exchange currents between the solution and the conduc-
generation can occur where np «η?; η <ηχ; p <p1. tion and the valence band is largely controlled by the factor
Under these conditions the rate of hole generation per unit
volume will be

\u\ =
where φχ is the equilibrium potential drop in the semicon-
The total number of holes generated in the Debye region is ductor, which determines the amount of deformation of the
found by multiplying U by the thickness of the Debye region. energy bands in the surface region.
This product, multiplied by the electronic charge, gives The value of φχ depends on the redox potential of the
the corresponding electric current in the form of Eqn. (49). system. In strongly oxidising solutions the energy bands
Theoretical conclusions are in qualitative agreement are bent upwards at equilibrium (φχ < 0), the surface of the
with experiment. Polarisation curves for the anodic dis- semiconductor becomes richer in holes, and the hole com-
solution of η-type silicon, taken in hydrofluoric acid or in ponent of the exchange current predominates. In the pre-
hot alkaline solutions (when the silicon surface remains sence of strong reducing agents (φχ > 0) the conduction band
free from passivating films), show two distinct sections. plays the major part in the exchange process.
At low anodic polarisations (current density up to lO^A cm" 2 ) When the system departs from equilibrium, the anodic
the current-voltage curve is of the Tafel type (as in the current to the conduction band (ΐ%) and the cathodic current
case of p-type silicon). At more positive potentials the from the valence band (i£) are independent of the overvoltage,
current increases more slowly with voltage, and approaches η, and equal to their respective components of the exchange
3 2
a limiting value (~ 10 ~ A cm~ ). In this region the current current, if the potential drop in the Helmholtz layer can be
density increases with silicon resistivity, as expected from neglected:
Eqn. (50), and is quite independent of electrode thickness n V 1 4 .
The slower anodic dissolution of η-type silicon as compared /; = /·; ;? = , ? . (51)
with p-type is conclusive proof that holes take part in this
reaction. This result is not unexpected: the overvoltage across the
The value of the current, and its response to changes in Helmholtz layer, which can accelerate the purely electro-
115 116
temperature and in illumination » , support Flynn's ori- chemical stage of the process, is assumed negligible,
86
ginal hypothesis that the rate of anodic dissolution of whereas the concentration of charges taking part in the
η -type silicon is determined by field generation of holes in reaction (valency electrons in the valence band or unfilled
the space-charge region adjacent to the semiconductor sur- levels in the conduction band) is large and independent of
face, and not by the diffusional transport of holes from the the overvoltage. The same conclusion was also reached
bulk to the surface. elsewhere 1 2 5 .
Generation of hole-electron pairs in the space-charge The anodic current to the valence band and the cathodic
region also limits1 1the rate of anodic dissolution of η -type current from the conduction band are described by equa-
gallium arsenide 7 . tions similar to Eqn. (25):
The evolution of hydrogen from p-type silicon also £η FT,
61 73 118 116
appears to be hindered > > . Greger concludes that (52)
the rate of this reaction is determined by the generation of
free electrons in the space-charge region at the silicon- Thus the components of the current at a semiconductor
solution interface. electrode are formally given by Tafel expressions in which

217
 Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

133 134 135

the transfer coefficients a and β are either 1 — Eqn. (51) — ions , of oxalate ions, and probably also of iodide ions >
or 0 — Eqn. (52). The overall reaction current is the does not involve positive holes. The oxidation current of
127
sum of these partial currents: K4Fe(CN)e in acid solution and of ethylide ions in a Zieg-
138
Fr\
ler electrolyte , on the other hand, passes directly into
the valence band.

We are particularly interested in the ratio of hole current

to electron current, which can be measured experimentally. 5. Formation of Oxide Layers on the Electrode Surface
At not too high over voltages this ratio is given by:
If the products of anodic oxidation are insoluble (or
sparingly soluble) the anode surface becomes covered with
an adsorbed layer or with a relatively thick oxide film,
which often has a very high resistance. Silicon electrodes
The quantity η - φ1 is simply the potential of the electrode form an oxide film in most aqueous solutions (except HF
(except for an unknown additive constant). and KOH), and in some non-aqueous solutions such as
137 139
methylacetamide - , liquid ammonia, and sulphur
The more positive the potential, therefore, the higher is 140 141
dioxide ' .
the proportion of electrons from the valence band in r e -
duction reactions and the proportion of holes in oxidation Surface oxide can bring about passivation of the silicon
reactions. anode. Electrical breakdown of the film is observed at a
high enough potential (~ 15 V). Beyond this point the anodic
At very high overvoltages the concentration of free current is determined by the semiconductor properties of
carriers at the semiconductor surface becomes very large, silicon: thus, on a />-type anode the current increases
and the surface tends towards metallic properties. In exponentially with potential, whereas η-type anodes show a
particular, the potential drop at the interface becomes limiting current 7 3 . Under certain conditions a layer of
concentrated mostly in the Helmholtz layer, and the above amorphous silicon can form on the surface of a silicon
considerations cease to apply. Gerischer has discussed single crystal 1 4 2 .
this system 12°.
Germanium oxide is readily soluble in water, but oxide
In their study 126 of the anodic dissolution of η-type ger- layers can be produced on germanium anodes by using
manium in solutions of oxidants (alkaline K3Fe(CN)6; solutions of nitrates in methylacetamide 138 ' 143 . When in-
FeCl3), Gerischer and Beck found that the limiting german- dium antimonide is oxidised in KOH solutions, the rate of
ium dissolution current increases with the concentration formation and the properties of the oxide film depend 1on the
of the oxidising agent. They explain this phenomenon by crystallographic orientation of the electrode surface 4 4 " 1 4 7 .
postulating that the dissolution reaction is accompanied by
some reduction of the oxidising agent, in which electrons On the whole, the properties of oxide layers on silicon,
from the valence band are involved. Thus the reduction germanium, and indium antimonide are relatively unaffected
reaction injects holes into the valence band of the semicon- by the semiconducting properties of the underlying elec-
ductor which can be used by the 127 dissolution reaction. Hole trode material. The electrochemical behaviour of these
injection has also been observed in alkaline solutions of films (rectifying properties, photo-effect, etc.) is very
oxygen, in KMnO4, and in Ce(SO4)3. similar to that of anodic oxide film son aluminium, tantalum,
niobium, and other metals.
Direct experimental evidence 103 , and indirect evidence
based on polarisation curves 1 2 8 , 1 2 9 , favours the hypothesis
that valency electrons take part in a number of reductions. IV. CHEMICAL ETCHING
Even the formation of GeH4 on a germanium cathode has
130
been shown to involve electrons from the valence band. Chemical etching of semiconductor surfaces is a stan-
Direct measurements of the relative numbers of free dard operation in the radio industry and in laboratory prac-
and valence-band electrons 1taking part in reduction reac- tice (for metallographic, electronic, and other investiga-
tions have been carried out 3 1 with the electrode shown in tions). Etchants contain, as a rule, an oxidising agent,
Fig.4. The reverse-biased p-n junction was used as a and also a complexing agent whose function is to combine
hole collector. Any reduction reaction at the germanium - with the semiconductor ions in solution 148 . The view that
solution interface which interacts preferentially with the chemical etching involves chemical oxidation of the semi-
valence band will inject holes into the semiconductor. conductor followed by dissolution of the resulting oxides is
These are able to diffuse across the thin germanium wafer, widely held 1 4 9 " 1 5 2 . However, careful studies of the etching
and are collected by the p-n junction. The ratio of the behaviour of germanium and silicon in solutions of the most
increase in collector current to the reduction current is important oxidising agents (HNO3, H2O2, etc.) have demon-
effectively equal to γ, the fraction of valence-band elec- strated that the process is electrochemical in nature. Two
trons in the reduction current. complementary reactions take place on the semiconductor
surface at identical rates and at a common potential: an
The value of γ can vary from close to unity (KMnO4 anodic half-reaction (dissolution of the semiconductor) and
0.8-0.9, K3Fe(CN)6 0.6-0.8) to zero (K2Cr2O7 0.03-0.08, a cathodic half-reaction (reduction of the oxidising agent).
H2O2 0). KI3 and quinone occupy an intermediate position The parameters for these two reactions determine the
(y ~ 0.4). In qualitative agreement with the theoretical steady-state potential and the corrosion rate 1 1 9 » 1 5 3 " 1 5 6 .
calculation, the contribution of the valence band to the
reduction current is found 104 ' 132 to increase at more posi- In some cases {e.g. silicon in alkali solutions 7 3 ' 1 5 7 ' 1 5 9 )
tive electrode potentials. etching can take place by a purely chemical mechanismii.
Oxidation reactions at a germanium electrode have not IT Various aspects of chemical etching are discussed in a recent
been studied in detail. The oxidation of bivalent vanadium monograph 160 .

218
 Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

154 185
A more detailed discussion of the electrochemical mech- from polarisation curves > . It is possible that chemi-
anism of corrosion seems justified. We have already cal oxidation of germanium by hydrogen peroxide takes
stressed the fact that holes are required for the anodic dis- place in parallel with the electrochemical corrosion pro-
solution of semiconductors like silicon and germanium. cess.
These holes can be generated in the bulk or at the surface
of the semiconductor. It follows that the rate of corrosion When finished germanium devices, containing various
of an η-type semiconductor cannot exceed the limiting rate metallic components, are etched in H2O2, the anodic and
of diffusion (or generation) of holes. By the same argument, the cathodic reactions become localised in different parts of
if the cathodic reaction consumes free electrons the rate of the device: germanium functions as the anode, copper as
corrosion of a />-type semiconductor is determined by the the cathode. Indium and tin are usually strongly polarised
188
limiting rate of diffusion or generation of free electrons. and have very little effect on the rate of dissolution .
Under factory conditions, alkaline solutions of H2O2 are
However, an additional source of supply of holes is also used for etching germanium, and the etching rate depends
187
available to the anodic process. We have seen that many on the concentration of alkali .
oxidising agents are reduced at a semiconductor by elec- Germanium is corroded by solutions of electrolytes con-
trons from the valence band. Holes are thus injected into taining dissolved oxygen, the necessary cathodic reaction
the semiconductor by the cathodic reaction, and are imme- being provided by the reduction of O2. Oxygen concentra- 2
diately available to the anodic reaction. Under these con- tions are usually small, and the etching rate (1-10 μΑ cm" )
ditions the cathodic and the anodic reaction are no longer is less than the limiting current of minority carriers, and
independent: the rate of corrosion ceases to be a function unaffected by semiconductor properties. At low O2 con-
of the semiconductor properties of the sample and is centrations the etching rate is determined by the diffusion
limited by the diffusion of the oxidising agent in solution or of oxygen to the reacting surface; at higher concentrations
by the electrochemical step. In practice the rate of corro- the electrochemical step (reduction of adsorbed oxygen) is
sion of germanium in concentrated solutions of oxidising rate-limiting. It is important to note that the rate of cor-
agents is found to be higher than the limiting current of rosion depends on the concentration of indifferent electro-
holes to the electrode surface by several powers of ten. lyte, and reaches a maximum at a critical concentration
These ideas were first put forward by Gerischer and Beck 128 , (normally less than 0.01 N) which is characteristic of the
and were further developed by Dewald119 and Turner 1 B 3 . particular electrolyte. Harvey and Gatos have suggested
that the reduction of oxygen is catalysed by anions adsorbed
In this way, many oxidising agents can play a dual role on the germanium surface: when the adsorption of anions
in the corrosion of semiconductors: they undergo the becomes excessive, the oxygen coverage of the surface
cathodic reaction, and they also provide holes for the (and therefore also the reaction rate) must decrease 1 8 8 " 1 7 0 .
anodic reaction. When holes are generated faster than
the anodic dissolution can use them up, the excess holes Even in the absence of oxidising agents the steady-state
(accompanied by an equal number of electrons) diffuse potential of germanium and silicon is a corrosion poten-
from the surface into the bulk of the corroding specimen ^ , ^ 3 . tial 3>171»172. Measurements carried out under scrupulous
This hole current has been experimentally observed by the conditions of reagent purity have shown that the cathodic
method described on p.218 . «w»132 This process can raise process is hydrogen evolution, the anodic process is ger-
the bulk (as well as the surface) concentration of holes con- manium oxidation to give the brown modification of GeO
siderably, and in η-type and in weakly />-type specimens between pH 0 and pH 4 and the yellow modification between
well above the equilibrium value. Since holes are involved pH 6 and pH 12. GeOf" ions may be involved in the poten-
in the potential-deter mining step of the reaction, the steady- tial-determining reaction at pH > 12.5. The measured
-state potential (but not the corrosion rate) should be a steady-state potential is practically independent of the ger-
function of the initial hole concentration in the semiconduc- manium conductivity type 3 .
tor. 161This effect has been observed by Gerischer and
Beck [dissolution of germanium in alkaline K3Fe(CN)6] When the solution contains salts of metals more noble
and by Turner 1 5 3 and Dewald119 (dissolution of germanium than silicon or germanium, the cathodic reaction takes the
and silicon in HNO3). form of electrodeposition of these metals. The so-called
"electroless" nickel platingt (followed by heat-treatment)
The reduction of nitric acid on germanium consumes is used to provide ohmic contacts for silicon 1 7 3 .
electrons from the valence band 119 » 182 . In concentrated The corrosion behaviour of A m B v compounds is very
solutions of HNO3, therefore, germanium and silicon similar to that of germanium. Thus, GaAs corrodes by an
corrode at a high rate (up to 6 A cm" 2 ), independent of the electrochemical mechanism 174 in solutions containing dis-
semiconductor properties of these elements. The corro- solved oxygen or KAu(CN)2. In dilute solutions of oxidising
sion rate is determined by the cathodic reaction, and this agents the rate of corrosion of InSb is determined by dif-
is found to be autocatalytic. The slow step is the formation fusion of the oxidant 175 » 176 ; in concentrated solutions, on
of N2O4 (HNO3 + HNO2 ->N2O4 + H2O), which is further r e - the other hand, the electrochemical step is rate-deter min-
duced at the electrode. On raising the concentration of ing. The compounds of the A I H B V series become passive 1 7 7
HNO3 the rate of corrosion of germanium increases at first, in concentrated HNO3.
reaches a maximum for a 6 Ν solution, and finally de-
creases as a result of the formation of a thick, passivating
film of oxide in very concentrated solutions of HNO3.
Addition of HF destroys the passivity 183 » 184 .
The rate of corrosion of germanium in acid solutions of
hydrogen peroxide is decreased by both anodic and cathodic
polarisation, suggesting that an electrochemical process
is involved. Experimentally measured corrosion rates, t Chemical deposition of a nickel phosphide coating by reduction
however, are significantly higher than the values expected of a nickel salt with hypophosphate (Ed. of Translation).

219
 Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

V. APPLICATION OF ELECTROCHEMICAL METHODS Thick, non-porous oxide films have been grown on ger-
OF SURFACE TREATMENT IN PHYSICOCHEMICAL manium and silicon devices, to protect them from the effect
RESEARCH AND IN SEMICONDUCTOR TECHNOLOGY of their ambient surroundings, by anodising the semicon-
217
ductors in a solution of nitrates in methylacetamide .
No practical device based on a semiconductor-electro-
By taking advantage of the rectifying properties of p-n
lyte system has yet been developed. The Bell Telephone
junctions and of the dependence of the r a t e of dissolution of
Laboratories have described an internally powered t r a n s i s -
178 germanium on the type and magnitude of its conductivity,
tor , based on the cell
selective etching of the various p a r t s of a transistor
218 221
(emitter, base, collector) can be achieved - . Various
GelKOHiAg2O, Ag, techniques for revealing the presence of p-n junctions in
9 germanium single crystals a r e based on the same p r i n -
and a field triode " , in which the properties of the ZnO- 222 223
ciple » . If, for example, a reverse-biased p-n junc-
electrolyte interface a r e utilised, but neither device has
tion (n region connected to the positive terminal of the
yet been put to practical u s e } . Nevertheless, electro-
battery, p region connected to the negative terminal) is
chemical methods have found wide application in semicon-
immersed in a dilute solution of alkali, most of the applied
ductor device technology.
potential is dropped a c r o s s the junction itself and the two
Electrochemical (as well as chemical) etching techniques regions a r e at a very different potential. The η region,
a r e used to remove mechanically damaged layers from being anodic, will dissolve, whereas the p region will act
semiconductor surfaces. For silicon and silicon carbide a s a cathode. If, on the other hand, both sides of the junc-
the electrolyte is a solution of hydrofluoric acid » ; for
181 182
tion a r e at the same (anodic) potential, and an auxiliary
germanium, solutions of sodium or potassium hydroxide cathode is provided, the p region will dissolve preferen-
have been u s e d 1 8 3 , and other compounds 1 8 4 " 1 8 7 . Germanium tially because at a given overpotential />-type germanium
can be electropolished in aqueous alkali or in non-aqueous anodes dissolve faster than «-type. The method can also
s o l u t i o n s 1 8 8 " 1 9 0 . Mixed melts of alkali metal halides have be used to reveal boundaries between regions of the same
also been used for electropolishing germanium 1 9 1 . Silicon conductivity type, but of widely different donor (or acceptor)
is electropolished in solutions of hydrofluoric a c i d 1 9 2 " 1 9 4 , concentration: the so-called l-h j u n c t i o n s 2 2 4 " 2 2 6 .
gallium arsenide and indium antimonide in a mixture of It is also possible to delineate p-n junctions in german-
perchloric acid and acetic anhydride 1 9 5 . Current densities ium by electrodeposition of copper or gold. A r e v e r s e -
a r e usually between a few hundredths of an a m p e r e and a -biased p-n junction immersed in a solution of a copper
few a m p e r e s per cm 2 of specimen surface. A very smooth or gold salt will be electroplated on the p side, since this
surface, with a roughness of l e s s than 50 A, can be obtained region is at a cathodic p o t e n t i a l 2 2 7 * 2 3 1 . If a solution of the dye
by s t i r r i n g the electrolyte 1 9 6 » 1 9 7 . Methylene Blue is used instead of the salt solution, the dye,
Electrolytic polishing of germanium in KOH solutions, is reduced (and decolorised) on the p side of the junction 2 3 2 .
and also in solutions of SbOCl, produces surfaces of ex- Silicon junctions a r e not usually polarised from an external
tremely low surface recombination velocity (of the order battery, but a r e flooded with light i n s t e a d 2 3 3 : the injected
of 100-200 cm s e c " 1 ) 1 9 8 " 2 0 0 . hole-electron p a i r s a r e separated by the p-n junction
(which behaves in this case as a photodiode), charging the
The jet-etching m e t h o d 2 0 1 has been developed for the η region negatively and ensuring that metal (gold, copper,
production of shallow depressions a few tens of microns in or silver) is electrodeposited only on this r e g i o n 2 3 4 " 2 3 7 .
diameter on germanium wafers in the manufacture of
surfaces-barrier t r a n s i s t o r s . A thin jet of electrolyte is Electrodeposition is also used to p r e p a r e rectifying and
directed from a glass nozzle on to the sample, which is biased ohmic contacts on silicon and g e r m a n i u m 2 3 8 " 2 4 2 . Germanium
anodically. The cathode is sealed in the wall of the nozzle. coatings on other metals can be electrodeposited from non-
Under factory conditions two jets a r e used, one on each -aqueous e l e c t r o l y t e s 2 4 3 " 2 4 6 ; electrolysis of molten salts
side of the wafer. The electrolyte consists of potassium gives germanium dendrites suitable for use in semiconduc-
hydroxide 2 0 2 " 2 0 4 or a metallic salt 1 7 3 " 1 7 9 » 1 8 2 " 1 9 6 » 1 9 8 " 2 0 8 . The tor d e v i c e s 2 4 7 .
electrolyte should have a much higher resistivity than the
germanium. Etching is c a r r i e d out at a current density of
about 1 A c m " 2 , and the operation is stopped when the r e - 1. H.Gerischer, in "Semiconductor Electrode Reactions",
maining thickness of germanium (which is to form the base "Advances in Electrochemistry and Electrochemical
of the transistor) is no more than a few microns. The Engineering, Vol.1. Electrochemistry" (Edited by
method is also suitable for gallium a r s e n i d e 2 0 9 , but a solu- P.Delahay), Interscience, New York, 1961.
tion of Cd(CN) 2 must be used a s the electrolyte. 2. M.Green in "Modern Aspects of Electrochemistry. No. 2"
(Edited by J. O'M. Bockris) (Translated into Russian),
Germanium can also be jet-etched cathodically (forma-
Inostr.Lit., 1962.
tion of GeH 4 ), but very high current densities a r e needed
3. B.Lovrecek and J.O'M. Bockris, J. Phys.Chem., 63, 1368
(up to 160 A c m " 2 ) . 2 1 0 - 2 1 2
(1959).
Depressions of any desired shape can be etched into 4. N.de Zoubov, E.Deltombe, M.Pourbaix, Cebelcor, Rapp.
germanium by the use of microcathodes situated very close Techn., No.27, 1 (1955).
to the surface 2 1 3 » 2 1 4 . Sharp points, with a radius of curva- 5. J. Besson and W.Kunz, Ann.Univ.Saraviensis, T_, 163(1958).
ture of 1 μ and suitable for field emission experiments, can 6. M.Green, J. Chem. Phys., 3^, 200 (1959).
be prepared by etching germanium in NaOH. 2 1 5 Lastly, an 7. W.Shockley, "Electrons and Holes in Semiconductors with
electrolytic saw for germanium has been m a d e 2 1 6 in which Application to Transistor Electronics" (Translated into
the cathode is a moving, fine tungsten wire. Russian), Inostr.Lit., 1953.
8. W.C.Dunlap, Jnr., "An Introduction to Semiconductors"
% A recent communication180 claims that the Si-H2SO4 system (Translated into Russian), Inostr.Lit., 1959.
can form the basis of a radiation detector. 9. G.Gouy, in "The Coagulation of Colloids" (A.I.Rabinovich

220
 Vol.32 No.4 RUSSIAN CHEMICAL REVIEWS April 1963

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