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2836 J. Electrochem. Soc., Vol. 140, No. 10, October 1993 9 The Electrochemical Society, Inc.

7. Y. Kunugi, T. Nonaka, Y.-B. Chong, and N. Watanabe, ganic Synthesis, p. 415, Okayama (1986).
ibid., In press. 10. S. Torii, Electroorganic Syntheses, Chap. 11, Kodan-
8. M. M. Letord-Quemere, E Coeuret, and J. Legrand, sha-VCH, Tokyo (1985).
Electrochim. Acta, 33, 881 (1988). 11. J. Kau'len and H.-J. Sch~fer, Synthesis, 513 (1979).
9. T. Isoya, K. Nakagawa, andA. Aoshima, in Proceedings 12. Y.-B. Chong and N. Watanabe, Kagaku Kogaku, 46,439
of the First International Symposium on Electroor- (1991).

The Physicsof Macropore Formation in


Low Doped n-Type Silicon
V. Lehmann
Siemens AG, 8000 Mi2nchen 83, Germany

ABSTRACT
Macropore formation in n-type silicon is a self-adjusting phenomenon characterized by a specific current density at
the pore tip. At this specific current density, the dissolution reaction changes from the charge-transfer-limited to the
mass-transfer-limited regime. The passivation of the pore walls in hydrofluoric acid is caused by a depletion of holes due
to the n-type doping of the substrate. Equations based on these findings are presented and allow us to precalculate the
dimensions of the pores. The validity of the model and its mathematical description is verified in experiments. Pores of a
depth up to the wafer thickness and aspect ratios of 250 were etched using this method.

Pore formation is a well-known feature of many metal The Hypothesesof Macropore Formation
and semiconductor electrodes under anodic conditions in in n-Type Silicon
different electrolytes. Common products, for example alu-
First, the physics of the macropore formation model is
minum capacitors, have been manufactured for decades
discussed. The validity of the presented model is verified in
using electrochemical pore formation to enhance the per-
formance of the devices. Nevertheless in most cases the experiments, which are described in the subsequent sec-
physics of pore formation is poorly understood. tions. Basically two conditions must be fulfilled for electro-
The formation of porous layers on silicon electrodes an- chemical pore growth in a homogeneous solid-state elec-
odized in hydrofluoric acid has been studied since 1956,1 trode: (i) the pore walls must be passivated against
and different formation mechanisms have been pro- dissolution; and (it) the pore tips must be in a condition
posed. 215 Recently microporous silicon layers that consist that promotes dissolution.
of nanometer-size pores have received much attention be- Dissolution of a silicon electrode proceeds in aqueous
cause in two independent publications quantum-size acidic HF-containing electrolytes if electron acceptors are
structures were proposed to be responsible for their sur- present. The electron acceptor can be a chemical species
prising optical properties: a blueshift of the absorption such as HNO3 or a silicon electrode under anodic bias. In
edge of about 0.5 eV compared to bulk silicon n and room the latter case the electron can be injected into the elec-
temperature photoluminescence. ~s But not only the proper- trode or can recombine with a defect electron (h § at the
ties, but also the electrochemical formation mechanism of electrode surface. Electron injection requires an energy
microporous silicon itself was explained as a self-adjusting that is 1.1 eV higher than the energy required for the re-
phenomenon due to hole (h § depletion by a quantum con- combination process and therefore is observed only as a
finement in the porous structure, n'l~ Significant quantum second step in the dissolution reaction. 17 Consequently a
effects require structural sizes below 5 nm; but sizes as hole (h +) is required to initiate the dissolution of a silicon
large as 10 ~m were found for pores in n-type silicon elec- atom.
trodes. Therefore a different formation mechanism must be The surface morphology produced by this dissolution
responsible for macropore formation. This work gives con- process depends critically on whether mass transport or
clusive evidence that macropore formation is a self-adjust- charge supply is the rate-limiting step. If diffusion of chem-
ing mechanism, too. But in contrast to depletion due to ical reactants in the electrolyte is rate limiting, a surface
quantum confinement, the pore walls become depleted of charge of holes builds up. Hills on the surface dissolve
charge carriers that promote dissolution due to the n-type faster than depressions because they are more exposed to
doping of the semiconductor. An essential feature of elec- the electrolyte. As a result the surface becomes smoother;
trochemical macropore formation is a steady-state condi- this effect is known as electropolishing. Electropolishing of
tion between mass transport in the electrolyte and charge the silicon anode is observed for current densities larger
supply from the electrode at the pore tip, which is not than a critical value Jps. 1 For current densities below JPs,
present during micropore formation. This steady state is pores form in the electrode surface. The pore walls become
characterized by a specific current density present at all depleted of holes and therefore are passivated against dis-
pore tips during anodization. The presented model enables solution, if either their size is small enough to confine
us to control all relevant parameters such as location, di- charge carriers or if the electrode is of n-type doping. The
ameter, depth, and growth rate of the pores. Equations are first effect was discussed,recently; 11,~7therefore, this work
given that enable us to precalculate the requested pore ge- focuses on macropore formation in n-type silicon elec-
ometry depending on a few formation parameters, such as trodes. But the micropore formation due to a quantum con-
doping density, applied bias, illumination intensity, HF finement effect must be kept in mind because a superposi-
concentration, and pore initiation pattern. Pores orthogo- tion of both effects is observed and is discussed later.
nal to the surface with depths up to the wafer thickness and Holes are minority carriers in n-type semiconductors,
aspect ratios as large as 250 were produced by this and that passivates them against dissolution in hydrofluo-
technique. ric acid under anodic bias. At room temperature the h u m - .

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J. Electrochem. Soc., Vol: 140, No. 10, October 1993 9 The Electrochemical Society, Inc. 2837

ber of thermally generated holes is very small, but hole between the pores and therefore the walls become passi-
generation can be enhanced if the n-type electrode is illu- vated. The maximum flow of holes a pore tip can absorb is
minated or if the applied bias is increased until the break- limited by the maximum mass-transfer rate in the elec-
down field strength is reached. Holes generated by this trolyte. This transfer is dependent on ionic concentrations,
mechanism are collected by the pore tips and they promote temperature, and diffusion coefficients. The steady-state
dissolution there. For both kinds of hole generation, pores condition between hole current and ionic transfer at the
of a specific morphology form. Since no passivating layer pore tip is the same as in the nonilluminated case. If more
of a different chemical composition is involved, which holes are offered than can be consumed at the tip, they start
protects the pore walls, the only decisive difference be- to penetrate into the walls between the pores and promote
tween pore tips and pore walls is their geometry and their dissolution there. If the hole current is increased further,
location. the wall thickness eventually becomes zero and electropol-
If the electrode is not illuminated, holes may be gener- ishing starts. We prove in the following sections that all
ated by electrical breakdown. Now the geometry of the pore tips are in the steady-state condition of maximum
pore tip becomes important. Breakdown in silicon occurs mass transfer specified by the critical current density Jes-
for an electric field strength in excess of 3 • 10~ V/cm. The Photogeneration of holes allows us to control the hole cur-
electric field strength is a function of bias, doping density, rent independently of the applied bias and therefore is fa-
and geometry. High doping density or sharp pore tips in the vorable for experiments. In the following the implications
anode surface lower the required bias for breakdown. 2 In of the presented pore-formation mechanism are discussed
devices with solid contacts, breakdown leads to high cur- and studied by experiments.
rent densities and finally destroys the device by thermal Terminology and Experimental Setup
heating. If the contact is realized by an electrolyte, the
maximum local current density is limited by mass transfer To avoid ambiguity, the following terminology is used:
of chemical reactants. This limitation leads to a steady- the word hole always is used to designate a defect electron
state condition between charge supply and mass transfer at (h ~) in the semiconductor. An etched opening in the semi-
the pore tip which is the key to understanding the pore-for- conductor surface is designated as a pore and isclassified
mation mechanism. according to the International Union of Pure and Applied
The condition at the pore tip in an illuminated n-type Chemistry (IUPAC) convention I~ according to size as mi-
electrode is different only insofar as the breakdown field cropore if <2 nm wide, as mesopore if 2 to 50 nm wide, and
strength is not necessary to generate charge carriers and as macropore if >50 nm wide.
The procedure of sample preparation and the experimen-
therefore the pore radius may increase beyond the value
tal setup used to produce maeropores is described in detail
necessary for breakdown. Now the location of the pore tips
elsewhere. ~ Therefore only a brief description is given here:
becomes important. If an array of pores as shown in Fig. 1
electrochemical pore etching was performed on <100>-ori-
and a flow of photogenerated holes from the bulk is as-
ented, n-type, single-c13zstalline silicon samples of differ-
sumed, then the pore tips are located closest to the source of
ent resistivities. During etching, the front side of the sam-
holes. If all holes are consumed in the dissolution reaction
ple was in contact with the HF electrolyte and kept in the
at the pore tips, no holes are left to penetrate into the walls
dark. To increase the flow of minority carriers (h § at the
front side, the back side was illuminated) ~ An optical high-
pass filter was used to prevent hole generation near or in
the porous region. An ohmic contact at the edge of the sam-
ple and a platinum wire in the electrolyte were used to
apply a bias. The described setup is sketched in the upper
right corner of Fig. 1. Applying this procedure to a polished
wafer surface results in the random pattern of pores shown
in Fig. 1. To produce the predetermined pattern of pores
shown in Fig. 2, etch pits in the sample surface are needed,
at which pore formation initiates. Oxidation of the sample,
a standard lithography, and subsequent alkaline etching
are sufficient procedures to generate a pattern of etch pits,
as shown in the upper right corner of Fig. 2. This pattern
was used in all subsequent experiments.
The Steady-State Condition at the Pore Tips
Since the steady-state condition of the pore tips is the
most impm~ant feature of the system, it is discussed in
detail first. The reaction at a solid-state electrode is limited
either by charge transfer or by mass transport. This reac-
tion gives rise to the existence of two distinct regimes in the
anodic part of the current-voltage plot. For low current
densities, the reaction is limited by charge supply from the
electrode and is characterized by an ohmic or linear Tafel
slope 2~of the I-V curve. For high current densities, the reac-
tion is limited by mass transport in the electrolyte near the
electrode surface (Nernst diffusion layer), 21 indicated by a
smaller slope of the I-V curve. Depending on electrolyte
and electrode material, a change of dissolution reaction or
growth of a passivating layer often is observed at the t r a n -
sition between these regimes. For a flat silicon anode, the
transition from the charge-supply-limited to the mass-
Fig. 1. Surface, cross section, and a 45 ~ bevel of an n-type silicon
sampie (1015/cm 13phosphorus doped) showing a random pattern of transport-limited case is characterized by a critical current
macropores. Pore initiation was enhanced by applying 10 V bias ,n density JPs, which is observable by a peak and a change of
the first minute of anodization followed by 149 min at 3 V. The slope in the current-voltage plot. At this current density,
current density was kept constant at 10 mA/cm 2 by adjusting the the dissolution morphology changes fundamentally. For J >
back-side illumination. A 6% aqueous solution of HF was used as an JPs, holes accumulate at the electrode surface, and HF is
electrolyte. The setup used for anodization is sketched in the upper depleted at the electrode surface. Consequently dissolution
right corner of the figure. is limited by the mass-transfer rate that is lower in depres-

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2838 J. Electrochem. Soc., Vol. 140, No. 10,October 1993 9 The Electrochemical Society, Inc.

crepancy is p r o b a b l y due to a microporous layer t h a t covers


the electrode in the l a t t e r case. In the first case the elec-
trode is electropolished, and therefore free of any layer,
before JPs is measured.
The current density at the electrode surface is a measure
of the rate of dissolution. C o n s e q u e n t l y the rate v of pore
g r o w t h can be calculated if the local current density at the
pore tip J~p is d i v i d e d by the dissolution valence n (number
of charge carriers p e r dissolved silicon atom), the elemen-
tary charge e (1.602 • 10 ~9 C), and the atomic density of
silicon Nsi (5 • 1022/cm 3)

v = J t j [ n ( - e)Nsi] [2]

The present m o d e l assumes t h a t for stable pore growth,


w h i c h occurs w h e n the current density is limited by hole
g e n e r a t i o n and not by the applied bias, Jt~p is e q u a l to the
critical current density JPs. If this is true, Jt~p can be substi-
t u t e d by JPs in Eq. 2. The dissolution valence n increases
w i t h current density from a value of 2 to 4.1 This increase
was m e a s u r e d g r a v i m e t r i c a l l y a n d was v e r y steep at JPs for
p - t y p e as w e l l as n - t y p e m a t e r i a l (Fig. 5). N o w v can be
calculated (using Eq. 1, 2, and Jtip = YPs) and c o m p a r e d w i t h
the e x p e r i m e n t a l l y observed values. The result is s h o w n in
Fig. 6: the e x p e r i m e n t a l l y observed g r o w t h rates p l o t t e d as
a f u n c t i o n of the H F c o n c e n t r a t i o n (squares in Fig. 6) fit
well w i t h the calculated values of v for n = 2 and n = 4 (lines
in Fig. 6). This result proves t h a t the condition Jtip = JPs is
valid w i t h a m a x i m u m error of a few percent. Figure 6 also
suggests t h a t n varies d e p e n d i n g on the f o r m a t i o n condi-
tions. This v a r i a t i o n was c o n f i r m e d by g r a v i m e t r i c meas-
Fig. 2. Surface, cross section, and a 45 ~ bevel of an n-type silicon u r e m e n t s in w h i c h 2.2 < n < 3 was f o u n d for most of the
sample (101S/cm 3 phosphorus doped) showing a predetermined pat- etched m a c r o p o r e structures (triangles in Fig. 7).
tern of macropores (3 V, 350 min, 2.5% HF). Pore growth was in-
duced by a regular pattern of pits produced by standard lithography A t this p o i n t we discuss a second-order effect t h a t even
and subsequent alkaline etching (inset upper right). To measure the reduces the growth rate v of a pore which is ahead of the
depth dependence of the growth rate, the current density was period- other pores in the array. This pore becomes more efficient in
ically kept at 5 mA/cm 2 for 45 min and then reduced to 3.3 mA/cm 2 hole collection which increases Jt~ slightly. Figure 5 shows
for 5 min. This reduction results in a periodic decrease of the pore that a slight increase of the current density Jt~p at values
diameter, as marked by white labels in the figure. close to JPs produces a large increase of the dissolution va-
lence n. Since the growth rate v is proportional to Jt~p/n ,2an
increase of Jtlp reduces v: a pore which is ahead grows
sions or pits, which results in electropolishing of the sur- slower than the other pores. This mechanism is responsible
face. For J < JPs, the reverse is true: holes are depleted at the for the remarkable homogeneity in depth for an array of
electrode, and HF accumulates at the electrode surface. pores (Fig. 2).
Therefore every depression or pit in the surface initiates The pore-tip c o n d i t i o n Jtip = JPs allows one to calculate
pore growth because it focuses the electric field lines of the the d i a m e t e r of the pores. All charge t r a n s f e r occurs via the
pore tips, and the tip current density is JPs; therefore, the
space-charge region and thereby enhances the local current
total etching current equals the sum of the cross-sectional
density. ~3 At J = JPs, ionic transfer and charge supply are in
areas of all pores Ap m u l t i p l i e d by JPs. The total etching
a steady-state condition. Typical current-voltage plots of
current divided by the initial sample surface a r e a A t (de-
p-type samples of different crystal orientation are shown in
fined by the sealing ring in the setup) gives the overall
Fig. 3. Since p- and n-type silicon substrates are different
current density J. Thus
in their electronic properties but not in their chemistry, the
current-voltage plots for illuminated n-type substrates A~ = AtJ/JFs [3]
(Fig. 8 center) are identical to one for p-type substrates
(Fig. 3), except for a shift of about 0.5 V. In both cases, the If a h o m o g e n e o u s orthogonal pattern, as shown in Fig. 2, is
critical current density is easily identified by the peak in used for pore initiation, the spacing of the pores p, the pore
the current-voltage plot. JPs is largest for silicon electrodes d i a m e t e r d, and the thickness of the r e m a i n i n g walls w are
of <i00> crystal orientation and is independent of the elec- the same for all pores. N o w At can be substituted by the
trolyte concentration Used (inset of Fig. 3). This independ- s q u a r e d p o r e spacing p 2, and Ap is substituted by the cross-
ence indicates that the dissolution process is of anisotropic sectional area of a single pore, w h i c h simply is a p p r o x i -
nature. m a t e d by a square d 2. By substitution and root extraction,
Since Jps is determined by mass transport, one expects a d is o b t a i n e d
dependence on the HF concentration c and the absolute
temperature T. To investigate this condition, JPs was meas- d = p (J/Jes) 1/2 [4]
ured for different c and T using the peak of the reverse scan
In an orthogonal pattern, the pore w a l l thickness w is given
of the voltammogram (cf. Fig. 3). If the results are plotted
by w = p - d, and therefore
vs. 1/T (Fig. 4), a typical Arrhenius behavior is found. The
activation energy E, = 345 meV can be calculated from the w = p [1 - (J/Jes) 1/2] [5]
slope of the curves in Fig. 4. JPs (in A/cm 2) as a function of
c [in weight percent (w/o) HF] and T (in K) is described by In reality the cross section of a m a c r o p o r e (Fig. 8, A-A) is
the equation (C = 3300 A/cm 2 (w/o HF) -312, E, = 0.345 eV) more complex; it m a y have all shapes b e t w e e n a circle and
a square. In a d d i t i o n the pore walls are covered w i t h a
Jes = Cc 312 exp ( - E J k T ) [1] m i c r o p o r o u s silicon layer w h i c h m a k e s the d e t e r m i n a t i o n
of the e x a c t pore area difficult. But e x p e r i m e n t s p r o v e d
If the forward scan in the v o l t a m m o g r a m is used for the that Eq. 4 is applicable: the d i a m e t e r s of macropores
calculation of the e x p o n e n t of c, it is a b o u t 1.3. This dis- (measured after r e m o v a l of the microporous layer) etched

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J. Electrochem. Soc., Vol. 140, No. 10, October 1993 9 The Electrochemical Society, Inc. 2839

[]
1.o d ~ & ~ l ~ ~

o.s
Ratio:
0.8- [] Jps(1lo)/Jps(loo) ~A~oojfi
9 Jps(11 1)/Jps(lO0)

Fig. 3. Cyclic voltammograms


of silicon anodes (101S/cms,
boron doped, vs. a Pt pseudorefi
6 ot =u
~.
s
Jps(100)
. . . . . . . . i . . .

1 HF-conc.(%) 1 0
. . . . .

erence electrode in 5% HF) with


different crystal orientations,
s0- //
showing the characteristic peak 9- // --.l." ~ _1_ ~
that indicates the critical current
density JPs. Jws was largest for
<100>-oriented samples inde-
pendent of the HF concentration
used (inset upper right).

o"-" ' -:: o ' ' 1' . . . .


Voltage (V) 2~

at different current densities J were a linear function of the is a function only of the critical current density Jes, and
square root of J/JPs (squares in Fig. 7). therefore a f u n c t i o n of c o n c e n t r a t i o n c and t e m p e r a t u r e T
The cross section of a pore orthogonal to the sample sur- (Eq. 2). The pore d i a m e t e r and w a l l thickness are deter-
face (lower right corner of Fig. 8) shows that the pore tip is
free of microporous silicon whereas the pore walls are cov-
ered with mieroporous silicon. This condition allows a
comment on the current density distribution at the pore tip,
because microporous Si is formed at a current density n
4 \\" __ = - - ~ - _ . : = - - 9
smaller than JPs, whereas for a current density larger or
equal to JPs its growth is suppressed:
The coexistence of two distinct pore sizes (macropores
9 p-type Si
covered with a microporous layer), which differ by three r n-type Si
orders of magnitude rather than a broad distribution of
pore sizes indicates that electrochemical pore formation in
silicon is not fractal in nature, as proposed recently. 6'1~
The presented equations express the self-adjusting prop-
erties of the formation mechanism. The rate of pore growth

~ 4 7%
5%
~e-3 3%

~ 2

I
2%

0
I J ps J(mA/cm2)
0 0,1 10 100
0.0028 0.0030 0.0032 0.0034 0.0036 Fig. 5. Dissolution valence n as a function of anodic current density
- - - ~ 1/T(K) (in 2.5% HF, at room temperature for a p-type and a (strongly illumi-
nated) n-type sample. For current densities below JPs,the samples
Fig. 4. Critical current density JPs(for <100>-oriented samples) for were measured with and without (chemically removed by an alkaline
different HF concentrations plotted vs. the inverse absolute tempera- dip) the microporous layer. This removal produces a minor difference
ture 1/T. Arrhenius type of behavior is observed. in n, indicated by two data points at certain current densities.

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2840 J. Electrochem. Soc., Vol. 140, No. 10, October 1993 9 The Electrochemical Society, Inc.

10 Bias Dependence of Macropore Formation


Since the current density J is adjusted by the intensity of
e- the back-side illumination, the influence of the applied
, m
bias can be studied independently of J. This influence is
E visualized in Fig. 8, which shows the formation conditions
E in t h e c u r r e n t density-voltage plot and the resulting pore
morphology. At - 0 . 4 V, the current density is constant over
the entire sample surface and only homogeneous micropo-
>1 rous silicon formation can be observed. At - 0 . 2 V, the cur-
rent density locally may reach the value indicated by the

t open circle in the center diagram; first macropores are


formed, but their depth is small compared to the thickness
of the microporous layer. For a bias 0.2 V more anodic, the
macropore formation is more pronounced, but not all pores
have the same depth, and the pore tips are still covered with
microporous silicon indicating that Jtip is still smaller than
JPs. At an applied bias of U = 2 V, the condition Jtip = Jes can
.1 be fulfilled, and stable pore growth is observed (Fig. 8,
1 ~ c (%HF) 10 lower right). A further increase of the bias does not result in
an increase of Jtlp to values significantly larger than JPs,
Fig. 6. Growth rates of macropares vcalculated from Eq. 1 and 2 because for Jtlp > Jes a surface charge of holes, which are not
planed for n = 2 and n = 4 (lines) and experimentally obtained instantly consumed in the dissolution reaction, accumulate
growth rates v (squares) vs. the HF-cancentratian c of the electrolyte. at the pore tip. These holes move into the wall region and
For all experiments, the ratio between the etching current density J promote dissolution there. The result is an increase in pore
and the critical current density JPs was kept constant: J/JPs = 0.25, diameter d, while the pore tip condition Yt~p= JPs and the
(101S/cm 3 phosphorus doped, room temperature, pattern shown in growth rate v are unchanged.
Fig. 2).
Stable macropore formation is obtained for an applied
bias which is sufficient to generate the critical current den-
sity Jvs (about 1 V in Fig. 8). An increase of the applied bias
mined by the ratio between the applied and the critical above this value does not change the morphology of the
current density J/JPs (Eq. 4 and 5), for a given initiation macropores significantly. Only the generation of mesopores
pattern. by the breakdown mechanism is enhanced for higher
voltages, as is discussed later.

Mass Transport in the Pores

e-
3.0 Mass transport in an electrolyte occurs either by convec-
tion or by diffusion. Convection in narrow pores is probable
/X only under the assumption of a stirring effect due to gas
bubbles. Hydrogen is a candidate for this effect because it
& is generated during anodic dissolution of silicon for J <
Z~ A Jps. 22 The pressure in a gas bubble is size dependent due to
T2.5 surface tension effects and is significantly higher than the
Z~ ambient pressure for bubble diameters of a few microme-
Z~ ters. Consequently any bubble at the pore tip immediately
increases its diameter up to the pore diameter. This increase
2.0 I I I
reduces the mass transport in the pore and reduces its
30 3
growth rate compared to neighboring pores. The formation
of pore arrays of a homogeneous depth (Fig. 2) is not con-
E E
ceivable under this assumption. It is more likely that hy-
drogen stays in solution in the pore because the solubility
-J o o of gases is increased under pressure and bubble formation
"O occurs at the initial surface of the sample. Since stable pore
formation was never observed for pore diameters in excess
of 20 ~m, it is assumed that this is the limit above which
bubbles are generated at the pore tip.
If mass transfer in the pores occurs by diffusion, one ex-
pects a parabolic growth law for the pores and linear de-
10 1 crease of HF concentration from Fick's first law. To investi-
gate this condition we must measure the growth rate as a
function of pore depth. The dependence of the pore radius
on the applied current density offers a perfect tool to set
markers during the growth of pores. This setup is visual-
0 . . . . . 0 ized in Fig. 2. During the total etching time (350 min), the
0.0 0.2 0.4 0.6 0.8 current density was periodically (every 50 min) decreased
(by 33%) for 5 min. The decrease in pore radius is clearly
(J/Jps) l/z visible. If the etching time t is plotted vs. the pore depth L,
Fig. 7. The dissolution valence n (triangles), the depth L (circles), it shows the expected parabolic curve (Fig. 9). The average
and the diameter d (squares) of macropares etched at different cur- electrolyte concentration at the pore tip during an etching
rent densities J (5 V, 3% HF, room temperature, 30 min, 1015/cm ~ period can be calculated using the data from Fig. 2 and
phosphorus doped) platted as a function of the square root of the equations 1 and 2. The depth profile of the HF concentra-
ratio J/JPs. J was adjusted by backside illumination (open symbols), tion from the bulk of the electrolyte c, to the pore tip con-
one sample was etched in the dark (solid symbols). Patterned sam- centration ct~p shows the expected linear dependence on
ples with a constant pore spacing p (cf. Fig. 2) were used. The thick- pore depth L (Fig 9). These findings confirm that mass
ness of the pore walls is given by w = p - d. transfer in the pore occurs by diffusion.

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J. Electrochem. Soc., Vol. 140, No. 10, October 1993 9 The Electrochemical Society, Inc. 2841

Fig. 8. The current density vs. voltage plot of a polished n-type silicon electrode in 5% aqueous HF using intense back-side illumination (solid
line) is shown in the center of the figure. N-Type silicon samples (10~5/cm 3 phosphorus doped, patterned as shown in Fig. 2) were anodized
at -0.4, -0.2, 0, and 2 V (vs. a Pt pseudoreference electrode) while the current density was adjusted to J by adjusting the illumination inten-
sity (solid circles in inset). The corresponding cross sections of the macropores (arthegonal to the sample surface) are shown in the micrographs
(broken arrows). The local pore-tip current density (open circles, solid arrows) is equal to or greater than J and limited by the critical value JPs.
The regions of electropolishing and microporous silicon formation at the pare tip are due to a decreases of the local current density toward the
pore walls. The cross section of a pore (parallel to the sample surface, A-A) is shown in the center bottom of the figure.

The data shown in Fig. 9 allow us to calculate the diffu- way that the concave surface regions become more efficient
sion coefficient DHF of HF in the electrolyte, if the flow Fm~ in collecting holes than the convex ones. Since hole transfer
of HF is known, using the first of Fick's laws from the electrode to the electrolyte dissolves the material,
D ~ = F H F L / ( c -- Ctip) [6] these regions are etched preferentially, and the pores start
to grow. Even a polished surface shows etch pits after a few
Since hydrofluoric acid is a weakly dissociated acid, it is
seconds of anodization. The pore initiation process on pol-
assumed that the HF molecule and not F- is the diffusing
ished silicon surfaces and its dependence on doping density
species. The final product of the dissolution process is
of the substrate was studied in detail e l s e w h e r e y and the
SiFt-. 22 But intermediate products which may account for
results therefore are reviewed only briefly. The number of
mass transfer in the pore are not known in detail. With
etch pits that form in the first seconds of anodization on a
participation of water, even SiF(OH)2 is conceivable.
polished n-type St-electrode is on the order of 101~ 2. But
Therefore the number of HF molecules per dissolved silicon
only a few (106/cm 2to 102/cm2) of these etch pits survive and
atom nm~ may have any value between 1 and 6. Under the
become pore tips. The density of resulting pore tips is deter-
assumptior/that n ~ equals the number of consumed charge
mined by the space-charge-region width and therefore the
carriers n, the flow of charge carriers J e s / - e at the pore tip
doping density. By using a predetermined pattern of pits,
equals the flow of HF molecules F ~ in the pore. Now
the density of pores can be varied more than one order of
the diffusion coefficient DnF is calculable and is about
magnitude for a given doping density and bias.
10 -2 cm2/s independently of the electrolyte concentration
The idea that thickness of the remaining silicon walls
used (experiments were performed for c = 2.5, 4, 6, and
between two pores has to be two times the space-charge-re-
10%). The value observed for DHF is comparable to known
gion width to be depleted is attractive, 12'14but Eq. 5 shows
diffusion coefficients in aqueous solutions at room temper-
that the thickness of the walls w is already determined by
ature (e.g., Na + = 1.33 • 10 -2 cm2/s)Y
the ratio J / J P s and the pore spacing p in the pattern. The
Passivation of Pore Walls validity of Eq. 5 was confirmed by experiments in which
Having discussed the steady-state condition at the pore the wall thickness was found to be up to a factor 10 smaller
tip in detail, we focus now on pore initiation and passiva- or wider than the space-charge-region width. The analysis
tion of the pore walls. Small pits in the n-type silicon anode of the minority-carrier diffusion profile in a sample under
bend the electric field lines of the space-charge region in a back-side illumination shows that the minority-carrier

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2842 J. Electrochem. Soc., Vol. 140, No. 10, October 1993 9 The Electrochemical Society, Inc.

concentration is zero at the electrolyte contact under the


assumption that no surface charge of minority charge car-
riers exists. A detailed mathematical modeling of the mi-
nority-carrier diffusion process is given in Ref. 19. In a
porous n-type electrode we can deduce that the hole con-
centration is zero at the pore tips and consequently that the
walls are depleted even for a space-charge-region width,
which is much smaller than the wall thickness. There are no
holes left which can penetrate into the wall region and
promote dissolution there. Only the order of magnitude of
obtainable pore spacings and the pore density for pore ini-
tiation at unpatterned surfaces is determined by the doping
density. 9
Pores Generated by Electrical Breakdown
Pore formation in n-type silicon due to breakdown of the
space-charge layer was first proposed by Theunissen. 2 In-
dependently of hole generation by light, charge carriers
also are generated if the breakdown field strength of silicon
(3 • 10 ~ V/cm) is reached. The strength of the electric field
in an anodized n-type silicon electrode is a function of dop-
ing density, applied bias, and geometry. If a polished n-type
sample is anodized in the dark at low bias, only a very small
initial current, due to thermal generation of carriers, is ob-
servable. But this current still promotes dissolution, and
etch pits form in the surface of the anode. If the curvature
of an etch pit becomes smaller than the critical radius, 23the
current that promotes further dissolution is generated by
the high electric field. This dissolution is the reason why
n-type electrodes kept in the dark show an increase of cur-
rent density with anodization time. 2 Pores generated by the
described effect were a few tens of nanometers in diameter
as shown in Fig. 10. Since every pore tip itself is the source
of hole generation, the position of a pore tip becomes inde-
pendent of the other pores. Now branching of the pores is
possible and fir-tree-shaped pore structures are observed.
But the steady-stat e condition Jt~p= JPs at the pore tip is still
valid for pore growth by breakdown. This condition was
concluded from the observation that the growth rate for
mesopores shows that same dependence on electrolyte con-
centration as observed for macropores. The absolute value
of v (for a constant HF concentration c) was somewhat
Fig. 10. Transmission electron micrographs of mesopores (cross
section parallel to the sample surface) produced by anodizing an
smaller than the one for macropores (solid circle in Fig. 7). n-lype silicon electrode in the dark (5 V, 3% HF, room temperature,
This value is due probably to the fact that HF is also con- 10~5/cm 3 phosphorus doped, patterned according to Fig. 2).
sumed in branched pores, which results in a more than
linear decrease in HF concentration in the main pore (cf.
Fig. 9). The probability for the formation of mesopores in- ately doped samples, anodization results in a layer with a
creases with doping density and applied bias. For degener- high density of homogeneously distributed mesopores of
about 10 nm in size. This is attributed to the fact that for
high doping the space-charge region becomes narrow
enough to allow tunneling of the charge carriers. ~
c (%HF) t(mJn)
Mesopores formed by the breakdown mechanism may be
found as a superposition on the larger macropores pro-
duced by back-side illumination. In this case some fine
branches orthogonal to the large center pore are observed
as shown in Fig. 11.
Dependence of Pore Formation on
Crystal Orientation
One striking property of macro- and mesopore formation
is its orientation dependence. This anisotropy can be un-
1 i 0

S :........ i1oo
I derstood in terms of the present model if one recalls that
the critical current density JPS was largest in <100> direc-
tion, as shown in Fig. 3. But this is no real explanation,
because it only shifts the problem to the question of why JPs
shows an anisotropy. To answer this question we must
0.0 ". . . . . . . . . . . . . . . . . . . I0 study the silicon surface on an atomistic scale. In the first
0 50 100 150 200 step of the dissolution process, 1~the surface Si-H bonds are
substituted by Si-F with consumption of one charge carrier
> L(pm) per bond. The bonded fluorine now induces a weakening of
Fig. 9. Using the depth markers shown in Fig. 2, the depth of the Si backbonds, so that they can be broken by HF or H20.
macropares L. was ploned vs. the anodization time t (squares). In This effect is strongest for {100} surfaces because two F
addition, the decrease of HF-concentration c in the pare was obtained atoms are polarizing two Si backbonds, whereas for (111}
using Eq. 1 and 2. The parabolic increase of pore depth and the surfaces only one F atom is polarizing three Si backbonds.
linear decrease of concentration indicate a difffusion-limited etching Consequently the attack of the backbonds is fastest on
process. {100} surfaces. This model is applicable to alkaline etching

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J. Electrochem. Soc., Vol. 140, No. 10, October 1993 9 The Electrochemical Society, Inc. 2843

(doping not specified24) and GaAs (n-type25) support this


idea. But even in systems with a different mechanism of
passivation the pore tip condition may be the same. For
example, in pore wall passivation in aluminum a hindrance
layer of a chemical composition which is different from the
one of the substrate is assumed. But the observed depend-
ence of pore diameter on formation current density26) sug-
gests that the tip current density is constant. This con-
stancy may be an indication that the observed steady-state
condition at the pore tip is not an exclusive feature of n-
type silicon electrodes.

Conclusion
Macropore formation in n-type silicon is characterized
by a critical current density at the pore tip. At this current
density, the transition between a charge-supply-limited re-
action and a mass-transfer-limited reaction occurs. The
pore walls become passivated due to a lack of holes, which
promote dissolution. The hole depletion is caused by the
n-type doping of the substrate. Pore morphology depends
on the hole generation mechanism; branched pores with
sharp tips form if holes are generated by breakdown,
whereas hole generation by illumination produces u n -
branched pores with larger tip radii. The possibility of pre-
determining the pore location with standard photolithog-
raphy offers a multitude of technological applications.

Acknowledgment
Helpful discussions with H. F611 and U. Gosele are great-
fully acknowledged.
Manuscript submitted Feb. 8, 1993; revised manuscript
received May 20, 1993.
Siemens AG assisted in meeting the publication cost of
this article.
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