Formation Mechanism of Porous Silicon Layer by

Anodization in ?HF? Solution

Takashi Unagami

J. Electrochem. Soc. 1980, Volume 127, Issue 2, Pages 476-483.

doi: 10.1149/1.2129690

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 Formation Mechanism of Porous Silicon Layer
by Anodization in HF Solution
Takashi Unagami
Nippon Telegraph and Telephone Public Corporation,
Musashino Electrical Communication Laboratory, Musashino-shi, Tokyo, 180, Japan

ABSTRACT
The mechanism of formation of porous silicon layer (PSL) has been studied
according to the following e x p e r i m e n t a l results. PSL is formed by the local
dissolution of silicon which occurs only at the base of the pores. The HF
concentration of the electrolyte in the pores of PSL is constant during anodiza-
tion and the anodic reaction i n the pores proceeds u n i f o r m l y in the thickness
direction. The dissolution of silicon i n the pores is the results of the d i v a l e n t
and the t e t r a v a t e n t reactions of silicon with HF, without the disproportionation
reaction. The insoluble surface porous film (SPF) exists at the surface of PSL
and the silicic acid is formed in PSL. A model of forming PSL is proposed, with
emphasis being placed on the anodic reaction and the local dissolution of silicon
which is initiated by S P F and is promoted by the h i n d r a n c e layers composed
of the sJ_licic acid.

The anodization of silicon in hydrofluoric acid solu-
tion has been studied by m a n y investigators. These
investigations are almost always related to the electro-
polishing of silicon to process silicon wafers for the
electronic device fabrication. On the other hand, Uhlir
(1) found in 1936 that anodic film is formed on a
silicon wafer b y the anodization u n d e r certain condi-
tions. This anodic f i l m is the porous silicon layer
(PSL) which consists m a i n l y of silicon (2). PSL is
oxidized very rapidly at low temperature, so thick
oxide layers can be formed b y short time oxidation.
These thick oxide layers can be applied in the
fabrication of integrated circuits (3).
T u r n e r (4), and s u b s e q u e n t l y M e m m i n g and
S c h w a n d t (5), investigated the formation condition
of PSL and proposed that PSL is formed by the dis-
proportionation reaction of silicon difluoride. On the
other hand, in an investigation of the structure of
PSL, Arita and S u n o h a r a (6), and U n a g a m i and Seki
(7), postulated that the anodic dissolution of silicon
occurs at local points on atomic scale to form PSL
from the observation that PSL has a single crystal
structure. No detailed investigations have been re-
ported with respect to the formation mecilanism of
PSL, p a r t i c u l a r l y with respect to the mechanism of
the progress of the local silicon dissolution.
I n this paper the author studied the anode potential-
c u r r e n t characteristics for various HF concentration,
the HF concentration of the electrolyte in PSL, the
dissolution of silicon b y the anodization, the structure
Of PSL, the infrared spectra of PSL, and the electric
resistivity of PSL. Based on these results, the forma-
tion mechanism of PSL is discussed.
Experimental Procedures
Wafer preparations.--Silicon wafers were (111) p-
type single crystals (boron-doped) made by the
Czochralski method. Before the anodization, wafers
were cleaned b y boiling in the solution (1 NH~OH
1 H202 § 4 H20). After that, the thin oxide layer was
removed in dilute HF solution and the wafers were
rinsed in deionized water.
PSL formation.--The electrolytic cell for PSL form-
ation by the anodization has been given in a previous
paper (7). I n the case of high resistivity silicon wafers,
a l u m i n u m alloy layers were formed before the ano-
dization on the back surface of the silicon wafers in
order to make the anodic c u r r e n t distribution uniform.
Key words: porous silicon layer, anodization, formation mech-
anism.
The silicon wafers were covered with acid-proof wax
(Apiezon wax) to perform the anodic reaction selec-
tively in the wafer. Gas bubbles b r e a k out from the
silicon wafer surface during anodizing, so the u l t r a -
sonic oscillator was used to p r e v e n t gas bubbles from
sticking on the surface. A constant c u r r e n t source
was supplied as the electric power.
The measurement of the anode potential-current
characteristics.--The anode potential was measured
against a saturated calomel electrode (SCE). The
anode p o t e n t i a l - c u r r e n t characteristics were recorded
with a X - Y recorder. The SCE capillary tip end was
dipped in HF solution positioned near the silicon
wafer surface and the opposite electrode was con-
nected with the anode electrode.
The measurement of weight change.--The weight
change was measured with a n electric microbalance
made by Mettler. After the anodization and immersion
in H F solution, the samples were dried by blowing
dry N2 gas on them without rinsing i n water.
Infrared spectra measurement.--Infrared transmis-
sion spectra were measured with a double beam type
infrared spectrometer (a Model IR-27G) made by
Shimadzu Seisakusho, Limited. The wafers were 4 ,~
7 ~ - c m in resistivity. I n order to p r e v e n t the influence
of the absorption of a substrate, a wafer which has
the same thickness and the same resistivity was pre-
pared as the reference. The transmission spectra were
m e a s u r e d in the wavelength range from 2.5 to 25 ~m.
Experimental Results
The anode potential-current characteristics.--The
characteristics of the anodization in various HF con-
centration solution were measured. The results are
shown in Fig. 1. The potentials, obtained at the end
of a 30 sec period of supplying the constant anodic
current, are plotted. I n the region of the low anodic
c u r r e n t density, the characteristics obey Tafel's law
and the dependence on HF concentration does not
appear. On the other hand, in the high c u r r e n t density
region, Tafel's law is not satisfied and the character-
istics depend strongly on HF concentration. The anode
potential becomes high with decreasing HF concentra-
tion at the same anodic c u r r e n t density.
The anode potential is shown in Fig. 2 u n d e r the
condition of the constant c u r r e n t density anodization.
HF concentration is 50% in weight percent (w/o).
The growth rate of PSL is 8.45 ~m/min, 4.50 ~m/min,
and 0.95 # m / m i n at 100 m A / c m 2, 50 m A / c m 2, a n d l0

476
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VaT. 127, No. 2 POROUS SILICON LAYER 477

i02 A
>
E I00
LU
L~
o3 0
I0 (D

g- _J |
15 % HF
..oE I--
<z 5%HF z
E 5%HF
v

>- 1.0 I f P-type (111) O.O04~O.Ol~-cm <~ - 2 0 0 ~) 15 % H F

(3.
~) 5 0 % HF
UJ
Z
uJ
E3
?, -300 P-type (111) 0 . 0 0 4 ~ 0 . 0 1 a - c m
z
F-
<Z
z16' - 400 p P J ~ ~ p , ~ i I p I i
r
rr
0 30 60 90 120

ANODIC REACTION T I M E (SEC)

o Fig. 3. Relationship between anode potential and onodic reaction
o
z<t IO 2 time under various HF concentrations. Anodic current density is
10 mA/cm s.

the anode potential is constant. However, i n a low

I(~3-- i i i i i r i i I I q i i [ i concentrated (5%, 10%) HF solution, some increase
- 4 0 0 - 200 0 200 400 600 800 I000 1200 (a few mV) in the anode potential appears after two
minutes. When the H F concentration is low, a change
ANODE POTENTIAL vs SCE (mV) in electrolyte concentration appears to occur.
Fig. 1. Anode potential-current characteristics under various HF The analysis of the electrolyte in the pores.--The
concentrations. weight and the HF concentration of the electrolyte
i n the pores were e x a m i n e d by the m e a s u r e m e n t s of
the weight change and fluoride ions concentration.
Th e weight was measured before the anodization, just
after the anodization, and after the h e a t - t r e a t m e n t .
IA= I00 mA/cm 2 The weight and fluoride ions concentration just after
3 0 0 ;--
the anodization were m e a s u r e d w i t h o u t r e m o v i n g the
wax, in order to p r e v e n t the electrolyte in the pores
> from coming out into a solvent (trichloroethylene).
E 200
T?ae h e a t - t r e a t m e n t was done in dried N2 gas or a
50 mA/cm 2 v a c u u m at 100 ~ -.- 150~ for two hours. The result
I.tJ
(..) of the weight change is shown in Fig. 4. a w l is the
o3 I00
change b e t w e e n the weight before and that after the
~0
> anodization. On the other hand, aW2 is the change
._i b e t w e e n the weight before the anodization and that
<~ 0
after the h e a t - t r e a t m e n t . So, the weight change be-
t- t w e e n these two values, WE, is the a m o u n t of the
z I O mA/cm ~
uJ - I 0 0 electrolyte in the pores. The electrolyte in the pores
}-- can be released by the h e a t - t r e a t m e n t . Figure 5 shows
0 this effect. The weight changes, caused by i m m e r s i n g
ft.
the h e a t - t r e a t e d PSL in 50% HF solution and by the
uJ
E3 -200 I A : Anodic current density
h e a t - t r e a t m e n t of i m m e r s e d PSL, are shown. The
0 sample has the same weight after the h e a t - t r e a t m e n t
Z P- type (111) flO04~O.OI a - c m as before immersion in 50% HF solution. That is, the
- 300
h e a t - t r e a t m e n t can release all the solution in the
pores. F r o m the result shown in Fig. 4, W~.~ is given
- 400 I , I , I / I I I , I I I in Fig. 6. WE increases l i n e a r l y with the anodic reac-
0 30 60 90 120 tion time. W~, given in Fig. 6, is the weight correspond-
ing to the solution with which the volume of the
ANODIC REACTION T I M E (SEC) pores in PSL are filled. The total volume of the pores
Fig. 2. Relationship between anode potential and anodic reaction in PSL is calculated from ~W2 and the specific gravity
time. HF concentration is 50 w/o. of 50% HF solution is 1.12 g/cm '~ at the room t e m p e r a -
ture. As shown in Fig. 6, WE corresponds to about
57% weight of W~. That is, about 57% of the pore
m A / c m 2 i n the anodic c u r r e n t density, respectively. volume in PSL seems to be filled with HF solution
A t all anodic c u r r e n t density, the anode potential shows at the time of the anodization. Because of the gas
no change, that is, the anode potential is constant generation at the time of the anodization, the pores
in spite of f o r m i n g thick PSL. F r o m these results, the are partially filled with the generated gas.
H F concentration of the electrolyte in PSL is pre- The HF concentration of the electrolyte in the pores
sumed to be constant d u r i n g the anodization. was measured with a fluoride electrode. The samples
F i g u r e 3 shows the relationship b e t w e e n the anode of PSL formed in 50% HF solution were i m m e d i a t e l y
potential and the anodic reaction time u n d e r the i m m e r g e d in 10 cm s deionized water. These experi-
various H F concentration. The anodic c u r r e n t density m e n t a l solutions were measured after PSL had soaked
is 10 m A / c m 2. I n a highly concentrated H F solution, for two hours. A pH m e t e r was used to m e a s u r e the
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4?8 ft. EZectrochem. Soc.: S O L I D - S T A T E S C I E N C E AND T E C H N O L O G Y February I980

2.0 r
A
1.0
'o
E 0.9 /
/
/
E O.8 /
/

Ws /

3
0.7

0.6
//
1.5 AWz / 0 0.5
//

E"
'E / ? 0.4

0.3

E 0.2 / / / J
AWl ~0.1
w 1.0 U.i I I I
Z 0 I 2 5
I
CD ANODIC REACTIONTIME (MIN)
I Fig. 6. Relationship between weight of HF solution and anodic
reaction time.
w 0.5 P- type (111) solutions is d e t e r m i n e d according to the result shown
in Fig. 7. The results are shown i n Table I. The H F
0.02~0.055 n-cm weight percent of the electrolyte in the pores is Wt
which is obtained from Wt' X 10/WE. As a result, the
HF concentration of the electrolyte i n pores is consid-
ered to be constant and the same as that of the outer
HF solution of the pores. This result is consistent with
the result that the anode potential is constant during
the constant c u r r e n t anodization, as shown i n Fig. 2.
If" I I t
0 I 2 3
Figure 8 shows the weight of H F solution p e n e t r a t e d
into the pores w h e n the i m m e r s i o n time i n 50% H F
solution is changed. The pores i n P S L were emptied
ANODIC REACTION TIME (MIN) beforehand by the h e a t - t r e a t m e n t . It is obvious that
HF solution of 50 ~ 60% of WE can penetrate into the
Fig. 4. Relationship between weight change and anodic reaction pores w i t h i n a few seconds. F r o m the results that HF
time. Anodic current density and HF concentration are 100 mA/cm ~ concentration of the electrolyte i n the pores is con-
and 50%, respectively.
stant and HF solution can penetrate into the pores
rapidly, it can be thought that the reactants and the
products of the anodic reaction can be supplied and
0.5 released rapidly in the pores, respectively.
P- type (111) Dissolution of silicon by anodization.--Uhlir (1) and
' • 0.4 o 0.02~0.035fi -cm T u r n e r (2) have reported that silicon dissolution is
/% >
E 0.5
E
LLI ~J
e-%
0,2
T"
I--
I-" O. 210
0
w
hi 200
121
190
-0.1 I I I o
180
3
IMMERSIONIN 50 % HF.'f HEAT TREATMENTIN "1 170
(FORONE MINUTES) DRY N2 AT 150"0
0 160
_J
Fig. 5. Weight change by immersion in 50% HF solution and
heat-treatment in dry N2 at 150~ PSL was formed at 100 mA/ 150
z
cm2 for 3 min. IJJ 140
I I I

potential of the fluoride electrode with respect to iO- 4 10-3 i0-a

SCE connected to the e x p e r i m e n t a l solution in the
Teflon beaker. PSL was formed in a p - t y p e silicon WEIGHT % OF HF
substrate (0.02 ,~ 0.035 n - c m ) . The potential of fluoride
electrode as a function of HF weight percent is shown Fig. 7. Relationship between potential of fluoride electrode and
in Fig. 7. The HF weight percent of the e x p e r i m e n t a l HF weight percent.
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Vol. 127, No. 2 POROUS SILICON LAYER 479
Table I. Determination of weight percent of HF solution in PSL
'E
.o
WaferNo! Anodizafi=OIn(S
C~176
z) Ex (mY) Wt I (%) WE (g) Wt (%) E
C) ,oo%~ ,mi. 18,.4 9.2~,o-' ,.s ~,o-" ~5, .-. 25
E
(~ * 2rain 170.6 1,75 xl(~ 3 3.5S xlO-4 ~49

C~ ~ 3rain 161.8 2.8 x I(3:3 S.3 x I()" ~53 I 1"~20

2r
_J
Ex--- Potential of the experimental solution with fluorine electrode /
s
Wt'---Weight % of H F i n the experimental solution (see F i g . 7 ) t't
WE -- Weight of HF solution in P S L (see Fig. 6 ) h 15
Wt ---Weight % of HF solution in PSL >,
W
d i v a l e n t i n the condition of f o r m i n g PSL while t e t r a -
v a l e n t in the condition of electropolishing. I n order bLJ 10 co
to study the m e c h a n i s m of silicon dissolution, the
results of the detailed investigation are reported. The
substrates of 0.02 ~ - c m i n resistivity were used. Figure .~_
9 shows the relationship b e t w e e n the anodic reaction ~_ 5
time a n d both the PSL thickness (TD) and the a m o u n t
of dissolved silicon (AW). The a m o u n t of dissolved
silicon per u n i t area is derived from • as shown
i n Fig. 4. PSL was formed in 50% H F solution and
the anodic c u r r e n t density was 100 m A / c m 2. T~ and 0 0
AW increase with increasing the anodic reaction time.
The silicon density of PSL (p) is denoted as the ANO01C REACTIONTIME (MIN)
equation
Fig. 9. Thickness of PSL and amount of dissolved silicon vs. anodic
AW reaction time for p-type (0.02 D,-cm) silicon substrate.
P = Po - - ~ [1]
Tp
4
w h e r e po is the silicon density of a b u l k silicon wafer
(2.329 g/cm3). As the values of AW a n d Tp, which are f . . ~ ELECTROPOLS
I HN
IG
3
obtained from Fig. 9, are substituted into Eq. [1], p is
constant to be about 1.5 g / c m 3. That is, PSL, which
~ P O R O U S SILICONLAYER
has a u n i f o r m silicon density in the thickness direc- FORMAT
O
IN
tion, is formed. So, it is clear that the dissolution of A'-'~ 0.5%HF
silicon b y the anodization is u n i f o r m in the thickness I o~o 5 %HF
direction. 9~o 50~176HF
On the other hand, the effective dissolution valence i f i i
(Zi) is given as Zi = Ne/Nsi where Nsi is the n u m b e r i0-~ 'I I(3 I'02 I0~
of dissolved silicons which is obtained from AW and ANODIC CURRENT DENSITY (mA/cm 2)
Ne is the n u m b e r of flowed e l e m e n t a r y charges. That
is, Zi corresponds to a n average n u m b e r of e l e m e n t a r y Fig. I0. Relationship between Zi and anodic current density
charges which is needed for dissolving one atom of
silicon. F i g u r e 10 shows the relationship between Zi has the value from 2 to about 2.8 u n d e r the condition
a n d the anodic c u r r e n t density as the HF concentra- of forming PSL.
tion is varied. Zi is charged b e t w e e n 2-4 according to
the condition of the anodization. It is clear that Zi Structure of P S L . - - P S L is a single crystal according
to the analysis of x - r a y diffraction, b u t only on the
surface of PSL, polycrystalline silicon can be seen
b y electron diffraction (3, 6, 7). The pores of PSL
distribute at random, and the pore diameter at the
0.6 surface is smaller t h a n some 10A a n d that of the
WE i n n e r part of PSL is some 10 ~ 300A. (3). Moreover,
A
the pores are not formed straight; that is, the pores
,~0.5 are formed zigzag in the thickness direction of PSL (7).
r
On the other hand, a n insoluble t h i n porous film i n
E 0.4 H F solution is formed at the surface of PSL (8). This
insoluble thin porous film is left even after PSL is
ILl soaked in HF solution for a m o n t h while the m a j o r i t y
O~ of PSL except this insoluble thin film is active and
<~ 0.3
I.JJ LUTION has dissolved already in HF solution. This insoluble
(.) thin film is n a m e d as surface porous film (SPF) and
02 is distinguished from the active PSL formed u n d e r
I-- SPF. That is, PSL can be divided into two layers of
-r
P- type (III) SPF and the active PSL, as shown in Fig. 11.
~o.~ F i g u r e 12 shows the thickness of both SPF (Ts)
O.02,,, 0.035..0.- cm
and PSL (Tp) vs. the anodic reaction time. Substrates
of 0.02 a - c m in resistivity and 50% HF solution were
0 used to form PSL. Ts is saturated w i t h i n one m i n u t e
I 5 I0 50 I00
while T;) increases with increasing the anodic reaction
IMMERSION TIME (SEC) time and grows to be thick (some 10 ~,m). S P F is
formed from the b e g i n n i n g w h e n forming PSL, so
Fig. 8. Weight increase of PSL vs. immersion time. PSL was formed the growth of PSL, that is, the dissolution of silicon
at 100 mA/cm 2 for 3 min. i n a silicon substrate, is done through SPF.
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480 J. EIect-rochem. S'oc.: S O L I D - S T A T E S C I E N C E AND T E C H N O L O G Y February 1980

stain film formed in HNOa-HF solution (9). But the

i ~ SPF dependence of Tp on substrate resistivity differs from
.". " , 9
-7-- that of Ts and that of the stain film. According to the
"~
ACTIVE POROUS observation of the PSL surface with electron beam
diffraction, there are polycrystalline silicon as well as
9 . . -~ SILICON LAYER single-crystalline silicon at the surface of PSL (7).
,. . 9 9 .' o . 9 . , Therefore, S P F consists of polycrystalline and single-
crystalline silicon. That is, the crystalline structure
of S P F agrees with that of the stain film. Moreover,
S P F is insoluble in HF solution but is rapidly dis-
solved by silicon etches. These chemical properties of
SUBSTRATE SPF agree precisely with those of the stain film.
Considering m a n y similar points b e t w e e n S P F and
the stain film, SPF can be thought to be formed b y
the same anodic reaction as the stain film. As Archer
has reported in his pauer (9), the disproportionation
reaction proposed b y T u r n e r occurs at the surface of
a substrate. That is
Fig. 11. Structure of PSL
Si + 2HF + (2 -- n ) e + ~ SiF2 + 2H + + h e - [2]
~25 2 SiF~-> Si~ + SiF4
E

,.o
o"--o" }I00
30
mA/cm z /
2O
v
E
=k ~ 2HF
H2 SiY6
[3]

i_.c~-
where n < 2, e+ and e - represent hole and electron.
S P F is formed by the deposition of e l e m e n t a r y silicons
_.J (Si ~ produced by the disproportionation reaction [3]
~)5 15 09
o- on the surface of a substrate. Considering that the
growth of SPF can occur only at first as shown in
u- Tp u.. Fig. 12, the disproportionation reaction [3] seems to
0 0
occur only at the early step of forming PSL a n d at
u')05 10 ~ the surface of PSL. So no disproportionation reaction
i.iJ takes place after the growth of S P F is stopped. The
z reaction of forming thick PSL u n d e r S P F can be
thought to differ from that of forming SPF, because
of the differences in reactivity to HF solution, the
I--. ~.--~-- I.-- growth progress (Fig. 12) and the dependence on
substrate resistivity (Fig. 13).
J Infrared spectra of P S L . - - T h e dependence of the
0 I 2 3 0
absorbance on PSL thickness was examined by i n f r a -
red spectroscopy. The absorption bands appear at
4.7 ~m (vt), 9.5 #m (re), 11.1 #m (vs), 12.2 /~m (v4),
ANO01C REACTION TIME (MIN) 16 #m (vs), and 21 #m (v6) (10). vl and v~ are due to
Fig. 12. Thickness of SPF and PSL vs. anodic reaction time, as a the Si-H bond. vs is due to the Si-Si bond, re, v4, and
function of anodic current density. v6 are due to the a n t i s y m m e t r i c stretching, symmetric
stretching, and b e n d i n g of the Si-O bond, respectively.
The relationship b e t w e e n the absorbance ( , . t ) of
The dependence of T~ and T, on substrate resistivity these bonds and PSL thickness is shown in Fig. 14.
is shown in Fig. 13. The anodization was performed and t are the extinction coefficient and PSL thick-
for two minutes in 50% HF solution and the anodic ness, respectively. The anodization was done in 50%
c u r r e n t density was 100 m A / c m 2. The a m o u n t of HF solution at a constant c u r r e n t density of 100 m A /
dissolved silicon was constant for the various resis- cm2. The absorbance increases with increasing PSL
tivity of substrates. T~ is strongly dependent on sub- thickness. When PSL is etched in a F r e o n (CF4) gas
strate resistivity and the m a x i m u m of Ts appears at plasma, ~.t decreases as the PSL thickness decreases.
about 0.02 s in resistivity. Ts has the same depen- This shows that the Si-H, Si-Si, and Si-O bonds are
dence on substrate resistivity as the thickness of the

E 02 20 E
e Si-Si bonds
~o &O
W
(.)
a- 0,15
n 15 .._1 Z
09 CO

0 I.L ~" 2.0 e

O9 0 10o
m ;.t Si-H bonds (4.7pm,ll.lum)
Z <
V Z
o o~ 5 "~ I.O / o = J , - - bending
I-- I/ o / . ~ / ~ : - - symmetric stretching
I-- /~ ~ -o~/ _~_J_~.._/ ~_ _~_' '~~j _
- ~zS
_ zi -.O
: bonds
- ~ ~o- ontisymmetric stretching
[---~A~* . . . . i i [ = I I i
tO-3 I0-2 I0-[ i I0 0 2 4 6 8 I0 12 14 16 18
SUBSTRATE RESiSTiVITY (D~-crn) THICKNESS OF POROUS SILICON LAYER (pm)
Fig. 13. Dependence of thickness of SPF and PSL on substrate Fig. 14. Relationship between absorbance and thickness of PSL.
resistivity. Resistivity of p-type substrate is 4 ,~ 7 O,-cm.
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VoL 127, No. 2 POROUS SILICON LAYER 481

d i s t r i b u t e d u n i f o r m l y in the thickness direction of of magnitude. This o r d e r is different f r o m t h a t of

PSL.
The changes of i n f r a r e d a b s o r p t i o n spectra caused
b y i m m e r s i o n in 50% H F solution are shown in Fig.
15. The a b s o r p t i o n s t r e n g t h of S i - O bonds decreases
w i t h increasing the t i m e of immersion. A f t e r i m m e r -
sion for a b o u t 20 hr, the absorption due to S i - O bonds
is still observable. This result means that the product,
which is o b s e r v e d as S i - O bonds at 9.5, 12.2, and 21
~m has a small dissolution r a t e into H F solution. This
insoluble p r o d u c t is changed b y the h e a t - t r e a t m e n t
a b o v e about 300~ in a v a c u u m as shown in Fig. 16.
The a b s o r p t i o n at 10.2 ~m due to SiO (11), is i n -
creased b y the h e a t - t r e a t m e n t . The w e i g h t is not in-
creased b y the h e a t - t r e a t m e n t , so o x i d a t i o n of P S L
has not occurred. The increased a m o u n t of the a b s o r p -
tion at 10.2 ~m has v a n i s h e d i m m e d i a t e l y b y i m m e r -
sion in H F solution. The insoluble p r o d u c t is changed
to silicon oxide soluble in H F solution by the h e a t -
t r e a t m e n t . As results, it is clear t h a t the insoluble
p r o d u c t f o r m e d d u r i n g anodization has the following
t h r e e characteristics. (i) The a b s o r b a n c e (,.t),,2,
(a't)v4, and (a.t),, 6 at v2, ~4, and ~6, respectively,
a r e r a n k e d as (~'t)v4 > (~'t)~6 > (a't)v2 in o r d e r
WAVELENGTH(pm)
6 7 8 9 I0 II 12131415
i i i i i i
l i n c r e a s e d as P S L thickness increases. This m e a n s t h a t
Z takes place o n l y at the base of the pores in PSL.
0
CO
U3
CO
Z e l e m e n t a r y silicons, which a r e p r o d u c e d b y the dis-
Si- H
or"
!.-- AFTER ANODIZATION
.... IMMERSION FOR 5h
16h
20h
silicon dioxide l a y e r s f o r m e d b y high t e m p e r a t u r e
o x i d a t i o n of b u l k silicon. In the case of silicon dioxide
l a y e r of b u l k silicon, the o r d e r is (~'t)v2 > (a't)t,6 >
(a't)v4. (ii) I n s o l u b i l i t y in H F solution. (iii) The
conversion into SiO occurs b y h e a t - t r e a t m e n t .
On the o t h e r hand, SiF2 or SiF4 is p r o d u c e d b y the
anodic reaction, as m e n t i o n e d l a t e r in detail. So it
is possible that SiF2 and SiF4 react w i t h H20 in H F
solution. W h e n SiF2 or SiF4 reacts w i t h H20, silicic
acid (12) or fluorodisiloxane (13) is considered to be
produced. In the i n f r a r e d spectra of fluorodisiloxane,
the strong absorption due to S i - F bonds a p p e a r s (13).
But no absorption due to S i - F bonds a p p e a r s in the
i n f r a r e d absorption spectra of PSL, so the p r o d u c t o b -
served as Si-O bonds seems to be silicic acid.
The resistivity of PSL.--The resistivity of P S L in
the thickness direction was m e a s u r e d b y f o r m i n g an
a l u m i n u m electrode on the surface of PSL. A l u m i n u m
was e v a p o r a t e d in a vacuum. The v o l t a g e - c u r r e n t
characteristics w e r e m e a s u r e d with a curve t r a c e r
w i t h o u t any h e a t - t r e a t m e n t a f t e r f o r m i n g PSL. A
S c h o t t k y j u n c t i o n is f o r m e d on the surface of PSL.
The i-V characteristic gives essentially a s t r a i g h t line
in the high c u r r e n t region in the f o r w a r d direction.
The resistivity of P S L in the thickness direction is
o b t a i n e d f r o m the slope of the {-V characteristic.
20 25 F i g u r e 17 shows the r e s i s t i v i t y of P S L f o r m e d in the
i i i I |
silicon substrates with the various resistivity. P S L was
f o r m e d in 50% H F solution and the anodic c u r r e n t
density was 100 m A / c m 2. It is clear that the resistivity
i='-.- of P S L has the high resistivity of 104 -- l0 s ~ - c m ,
As shown in Fig. 2, the anode p o t e n t i a l is not
the anodic c u r r e n t is passed not t h r o u g h the r e s i d u a l
silicon l a y e r in P S L b u t t h r o u g h the pores in PSL.
That is, the anodic reaction (the dissolution of silicon)
Discussion
As a l r e a d y m e n t i o n e d above, the insoluble surface
porous film ( S P F ) exists at t h e surface of P S L and
is f o r m e d b y the d i s p r o p o r t i o n a t i o n reaction. T h a t is,
p r o p o r t i o n a t i o n reaction, deposit on the surface and
form SPF. This d i s p r o p o r t i o n a t i o n reaction takes place
o n l y at the e a r l y step of the anodization, because
the g r o w t h of S P F becomes saturated. Considering
t h a t S P F is f o r m e d at the surface of P S L f r o m t h e
b e g i n n i n g of the anodization and S P F is insoluble

Si- $i
Fig. 15. Change of absorption spectra of PSL by immersion in
50% HF solution.

WAVELENGTH (JJm)
2.5 5 4 5 6 7 8 9 I0 II 12 1:51415 2O 25
%

V J
(/)
t2.
U_
O
)-
Z I-
0 ~>
I--
I/) I P-type (111)
co - - AFTER ANODIZATION (lOOm~/cm2,1min)^

..... 300 ~ 2h IN VACUUM uJ

or" ----- AFTER IMMERSION IN 50% HF (30sec)

F-

Oi I p , , I I , ,
0 -3 10.2 lO-i I I0
SUBSTRATE RESISTIVITY (#...-crn)
Fig. 16. Absorption spectra of PSL after anodizatlon, heat-treat-
ment atDownloaded
300~ in a onvacuum, and immersion in 50% HF solution. Fig. 17. Resistivity of PSL formed in various resistivity substral~es
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482 J. Electrochem. Soc.: S O L I D I S T A T E S C I E N C E A N D T E C H N O L O G Y
i n H F solution, it can be thought that the place of
dissolving silicon in the substrate is restricted by SPF,
so that local corrosion occurs.
The anodic reaction of forming thick PSL u n d e r
S P F differs from that of forming SPF, as discussed
above. Therefore, a n o t h e r anodic reaction which does
not consist of the disproportionation reaction m u s t be
considered i n the case of forming PSL u n d e r SPF.
As for the reaction of dissolving silicon difluoride in
HF solution without the disproportionation reaction,
two possibilities proposed b y M e m m i n g and Schwadt
are replaced by the disproportionation reaction as
follows
.SiF~ 3-. 2HF -~ SiF4 3-. H2
2HF [4]
or
L~ H2 SiF6
SiF2 3-. 2H20 ~ SiO2 + 2HF 3" H2
I -I-6HF
) H2 SiF6 3-. 2H20
[5]
The r e m a r k a b l e difference b e t w e e n reaction [4] and
[5] is that SiO2 is formed a n d dissolved in HF solu-
tion i n the case of reaction [5], but not in the case
of reaction [4]. For the formation of PSL, the disso-
lution of silicon difluoride is performed by reaction
[4] from the following result. As shown in Fig. 10,
the growth rate of PSL is 7.5 # m / m i n at an anodic cur-
rent density of 100 m A / c m 2 in 50% H F solution. On
the other hand, the dissolution rate of SiO.~ in 50% HF
solution is 1.4 # m / m i n . Therefore, in the case of
reaction [5], the reaction rate is equal to or smaller
t h a n 1.4 # m / c m '~. That is, the reaction rate of reaction
[5] is much smaller t h a n the growth rate of PSL.
Consequently, as the reaction of dissolving silicon
difluoride in HF solution occurs, reaction [4] can
take place.
According to investigation about the effective dis-
solution valence (see Fig. 10), the valence has the
value b e t w e e n 2 to about 2.8 u n d e r the condition
of forming PSL. Silicon is thought to be dissolved
b y the anodization in the divalent state or in the
t e t r a v a l e n t state (1, 2, 5), so the effective dissolution
valence more t h a n 2 means that the dissolution in
the t e t r a v a l e n t state.as well as divalent state occurs.
F r o m the same reason about the reaction rate as
the divalent reaction, the tetrava]ent dissolution reac-
tion which consists of n e i t h e r the formation nor
the dissolution of SiO2 must be considered. That is,
the reaction b e t w e e n silicon and HF can occur, b u t
that between silicon and H20 cannot. The following
anodic reaction seems to be the most probable for
the t e t r a v a l e n t dissolution reaction of silicon
Si -1- 4HF -t- (4 -- %)e + .--> SiF4 3-. 4H+ 3-. %e-
~ 2HF
H2 SiF6
[61
(where X<4)
At the larger value of the effective dissolution valence,
the t e t r a v a l e n t reaction [6] seems to increase in ratio
between the divalent reaction and the t e t r a v a l e n t
reaction.
PSL is formed b y the local anodization of generating
pores. D u r i n g anodization, the H F concentration of
the electrolyte i n the pores is constant and the same
as that of the outer HF solution of the pores. HF
solution can penetrate into the pores rapidly. There-
fore, it can be thought that the reactants and the
products of the anodic reaction can be supplied and
released rapidly i n the pores, respectively. On the
other hand, d u r i n g anodization, the anodic potential
is constant in a high concentrated HF solution as
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February 1980
shown in Fig. 2. These results show that the anodic
reactions in the pores (reaction [2], [4], and [6])
proceed u n i f o r m l y in the thickness direction of PSL.
This agrees with the result of infrared spectra mea-
s u r e m e n t that Si-H, Si-O, and Si-Si bonds formed by
the anodization are distributed u n i f o r m l y in the thick-
ness direction of PSL.
The resistivity of PSL is very high. So if the anodic
c u r r e n t passes through the residual silicon layer in
PSL d u r i n g anodization, the anode potential must
increase significantly with increasing PSL thickness.
F r o m the fact that the anode potential is constant
d u r i n g the constant c u r r e n t density anodization, it can
be considered that the anodic reaction occurs only
at the base of pores in PSL.
According to i n f r a r e d spectra measurement, silicic
acid is formed in the process of PSL formation. More-
over, this silicic acid has a small dissolution rate in
concentrated H F solution. The silicic acid is thought
to be produced by the reaction of H20 with a part
of Si, SiF2, or SiF4. SiF2 and SiF~ are produced b y
reaction [2], ]4[, a n d [6]. The silicic acid is left i n
PSL d u r i n g anodization and seems to act as a h i n d r a n c e
layer to the following anodization. That is, the ano-
dization of dissolving silicon can progress only at places
where the si]icic acid is not formed, and not at places
where the silicic acid is formed. It can be said that
the local dissolution is promoted by the hindrance
layers composed by the silicic acid.
Proposed Formation Mechanism of PSI.
The mechanism proposed to form PSL is required
to initiate and sustain the local dissolution of silicon
in a silicon substrate. At the surface of PSL, the
insoluble surface porous film (SPF) is formed from
the b e g i n n i n g of the anodization. SPF restricts the
place of dissolving silicon, so that the local anodization
can be initiated. The following anodic reaction takes
place only at the base of the pores in PSL. The silicic
acid is produced in PSL d u r i n g anodization. The local
dissolution of silicon is promoted by the h i n d r a n c e
layers composed of the silicic acid. The anodic reac-
tion in the pores is u n i f o r m in the thickness direction
of PSL and contains no disproportionation reaction.
From these results, the mechanism of formation of
PSL is proposed as shown in Fig. 18.
Conclusions
F r o m the result of e x p e r i m e n t a l investigations and
discussions, the following are obtained.
1. The insoluble surface porous film (SPF) exists
at the surface of PSL and is formed by the deposition
of e l e m e n t a r y silicon. The deposition of e l e m e n t a r y
silicon takes place only at the early step of the ano-
dization.
SUPPLY OF Hz RELEASE
HF SOLUT~N SPF(SURFACE POROUS FILM)
-o
0
o
'ZIHZHIIH
co
F
~ ~ HINDRANCELAYER
" COMPOSED OF SILICIC
0
Z
X~ ACID
r--
m ~-~HF SOLUTION
co HOLES SUPPLY ANODIC REACTION
C Si-I-2HF+(2-n) e t - SiFz +2H++ne -
-H [~HF
SiF4 -+H 2
m
Si +4HF + (4-.X.)e+-- SiF4,4H§ -
Fig. 18. Proposed formation mechanism of PSL
VoW. I27, No. 2 POROUS SILICON LAYER 483

2. In the pores of PSL, the dissolution of silicon M a n u s c r i p t s u b m i t t e d M a r c h 27, !979; r e v i s e d m a n u -

is the r e s u l t of the d i v a l e n t a n d the t e t r a v a l e n t r e a c -
tions w i t h o u t the d i s p r o p o r t i o n a t i o n reaction. The
d i v a l e n t anodic reaction is given as
Si ~ 2HF ~- (2 -- n)e + --> SiF2 ~ 2H + ~- n e -
SiF2 ~ 2HF--> SiF4 -~ H2
script received Sept. 20, 1979.
A n y discussion of this p a p e r will a p p e a r in a Dis-
cussion Section to be p u b l i s h e d in the D e c e m b e r 1980
JOURNAL. A l l discussions for the D e c e m b e r 1980 Dis-
cussion Section should be s u b m i t t e d b y Aug. 1, 1980.

[_~ 2HF
H2 SiFe
Publication costs of this article were assisted by
Nippon Telegraph and Telephone Public Corporation.

REFERENCES
(n < 2, e + and e - are hole and electron, r e s p e c t i v e l y ) .
The t e t r a v a l e n t anodic reaction is given as 1. A. Uhlir, Bell Syst. Tech. J., 35, 333 (1956).
Si + 4HF + (4 -- ~)e+ --> SiF4 + 4H+ -~ k e - 2. D. R. Turner, This Journal, 105, 402 (1958).

~_~
3. Y. Watanabe, Y. Arita, T. Yokoyama, a n d Y. I g a -
2HF rashi, ibid., 122, 1351 (1975).
4. D. R. Turner, in "The Surface C h e m i s t r y of Metals
H2 SiF6 and Semiconductors," H. C. Gatos, Editor, p. 285,
J o h n W i l e y and Sons, N e w Y o r k (1960).
(k < 4) 5. R. M e m m i n g and G. Schwandt, Surf. Sci., 4, 109
(1966).
3. The e l e c t r o l y t e in the pores of P S L has the con- 6. Y. A r i t a and Y. Sunohara, This Journal, 124, 285
stant H F concentration d u r i n g anodization in con- (1977).
c e n t r a t e d H F solution. 7. T. U n a g a m i and M. Seki, ibid., 125, 1339 (1978).
4. The anodic reaction in the pores proceeds u n i - 8. T. U n a g a m i and K. Kato, Trans. IEE Jpn., 98-A,
f o r m l y in the thickness direction and takes place No. 10, 15 (1978).
o n l y at the base of the pores. 9. R. J. Archer, J. Phys. Chem. Solids, 14, 104 (1960).
10. K. H. Beckmann, Surf. Sci., 3, 314 (1965).
5. P S L is f o r m e d by the local dissolution of silicon.
The local dissolution of silicon is initiated b y S P F 11. K. Sato, This Journal, 117, 1065 (1970).
and is p r o m o t e d b y the h i n d r a n c e l a y e r s composed 12. F o r instance: M. Cannon S n e e d and R o b e r t C.
of the silicic acid. Brasted, " C o m p r e h e n s i v e Inorganic Chemistry,"
Vol. 7, p. 95, D. Van N o s t r a n d Company, Inc.,
Acknowledgment Princeton, New Jersey.
The a u t h o r wou]d like to t h a n k Mr. H. I k a w a for 13. J. L. Margrave, K. G. Sharp, and P. W. Wilson, J.
h e l p f u l guidance and discussions. Am. Chem. Soc., 92, 1530 (1970).

Electronic Properties of As-and P-Implanted

Cadmium Telluride
Muren Chu and Richard H. Bube
Department of Materials Science and Engineering, StanSord University, Stanford, California 94305
and James F. Gibbons
Department of Electrical Engineering, Stanford University, Stanford, California 94305

ABSTRACT
I m p l a n t a t i o n of As and P into p r e a n n e a l e d n - t y p e CdTe crystals p r o d u c e d
conversion f r o m n - to p - t y p e for the w h o l e range of Cd pressures used for
p o s t i m p l a n t a t i o n annealing. Since A r - i m p l a n t e d samples showed t y p e con-
version o n l y for the lower Cd pressures, it is concluded t h a t As and P cause
chemical doping in CdTe. Defect e q u i l i b r i u m b e h a v i o r and diffusion in the
i m p l a n t e d samples as a function of the p o s t i m p l a n t a t i o n Cd p r e s s u r e used for
annealing w e r e i n v e s t i g a t e d by chemical s t r i p p i n g of the i m p l a n t e d surface.
The defect e q u i l i b r i u m b e h a v i o r is consistent w i t h a m o d e l p r o p o s e d b y S e l i m
and K r S g e r on the basis of their investigation of P i m p u r i t y in CdTe, in w h i c h
the shallow acceptors i n t r o d u c e d b y i m p l a n t a t i o n a r e c o m p e n s a t e d b y i n t e r -
stitial Cd for h i g h e r p o s t i m p l a n t a t i o n a n n e a l i n g Cd pressures, and b y As or P
at Cd sites at lower Cd pressures. Two fast diffusion mechanisms w e r e o b -
served in A s - i m p l a n t e d samples, b u t o n l y one of these in P - i m p l a n t e d samples.

O n l y a few i m p l a n t a t i o n investigations h a v e been that As c h e m i c a l l y dopes the CdTe. Doping efficiency

c a r r i e d out w i t h CdTe. K a c h u r i n et al. (1) first i n -
v e s t i g a t e d the i m p l a n t a t i o n of A g a n d Ga in CdTe
thin films, b u t the doping effects w e r e unclear. Don-
n e l l y (2) i m p l a n t e d As + ions into n - t y p e CdTe c r y s -
tals and r e p o r t e d conversion to p - t y p e a f t e r p o s t i m -
p l a n t a t i o n annealing; s i m i l a r results w e r e r e p o r t e d
b y A g r i n s k a y a et at. (3), who c o m p a r e d the results
of i m p l a n t i n g Ne a n d As ions in CdTe and concluded
Key words: implantation, p-n junctions, defects, diffusion.
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has been increased b y c o i m p l a n t a t i o n of As + a n d Cd +,
as well as P+ a n d Cd +, to produce p - t y p e CdTe (4).
Gettings and Stephens (5) r e p o r t e d conversion of a
p - t y p e CdTe s u b s t r a t e to n - t y p e u n d e r i m p l a n t a t i o n
of n - t y p e dopants such as Bi a n d In. A n i m p l a n t a t i o n
efficiency of 30% was m e a s u r e d for a dose of 1014
cm -2 In ions. A l t h o u g h m o r e a c t i v i t y was g e n e r a t e d
by Bi ions, Te and A r ions p r o d u c e d no m e a s u r a b l e
electrical changes. A n o b s e r v e d increase in lattice