Journal of the Korean Physical Society, Vol. 46, No. 5, May 2005, pp.

1152∼1156

Anisotropic Etching Characteristics of Si in Tetramethylammonium Hydroxide

: Isopropyl Alcohol : Pyrazine Solutions

Gwiy-Sang Chung∗
School of Electrical Engineering, University of Ulsan, Ulsan 680-749

(Received 28 October 2004, in final form 3 December 2004)

This paper describes the anisotropic etching characteristics of single-crystal Si in tetramethylam-

monium hydroxide (TMAH) : isopropyl alcohol (IPA) : pyrazine solutions. With the addition of
IPA to the TMAH solution, an improvement in the flatness on the etching front and a reduction
in undercutting were observed, but the etch rate on (100) Si was decreased. However, the (100) Si
etch rate was improved by the addition of pyrazine. An etch rate of 0.8 µm/min on (100) Si, which
was faster by 13 % than the etch rate for a 20-wt.% solution of pure TMAH, was obtained using
20-wt.% TMAH : 0.005-g/ml pyrazine solutions, but the etch rate on (100) Si was decreased when
more pyrazine was added to the solution. With the addition of pyrazine to a 25-wt.% TMAH solu-
tion, no significant variations in flatness on the etching front were observed, and the undercutting
ratio was reduced by 30 ∼ 50 %. These results indicate that anisotropic etching of Si using TMAH :
IPA : pyrazine solutions provides a powerful and versatile method for realizing of intelligent micro-
electro-mechanical systems (MEMS) integrated with signal-processing and compensation circuits.

PACS numbers: 73.61.Cw

Keywords: Anisotropic etching, TMAH : IPA : pyrazine solutions, Etching rate, Flatness, Undercutting

I. INTRODUCTION will be disturbed. This causes significant variations in

Recently, there has been increasing interest in the de-
velopment of micro-electro-mechanical systems (MEMS)
using Si micromachining technology [1,2]. Owing to its
superior electrical and mechanical properties [3], single-
crystal Si has been applied to various MEMS. Among
various micromachining technologies, bulk Si microma-
chining technology is a very important technique. In
particular, making three-dimensional microstructures by
anisotropic wet etching of single-crystal Si is of even
greater importance in MEMS applications. If intelli-
gent micro-sensors and micro-actuators integrated with
signal-processing and compensation circuits are to be re-
alized, it is necessary to use an anisotropic etching tech-
nique for Si in a conventional fabrication line and Si
foundry [4]. The flatness of the etched surface is a crit-
ical factor in determining the characteristics of devices.
Especially, fabricating micro-diaphragms on Si require
a uniform thickness over the entire etched surface [5].
Since undercutting is revealed only after deep etching
has been done, it is very difficult to make the desired
structures [6]. In the case of micro-diaphragms formed
by anisotropic wet etching, in particular, a significant
irregularity or nonuniformity exists on the etched micro-
diaphragm surface, the stress in the micro-diaphragm
∗ E-mail:
gschung@ulsan.ac.kr; Fax: +82-52-259-1686
-1152-
the sensitivity, the offset, and the dynamic range of the
resulting devices [7].
Anisotropic etchants frequently used for single-crystal
Si include KOH [7], NaOH [3], ethylenediamine-
pyrocatechol (EDP) [8], hydrazine-water [9], and tetram-
ethylammonium hydroxide (TMAH) [4]. EDP and
hydrazine-water are toxic, unstable and, therefore, not
easy to handle. KOH and NaOH have excellent
anisotropic etching properties, but the use of KOH is
usually restricted to post-processing, as it is contaminat-
ing and, therefore, banned in clean rooms. For considera-
tions of process compatibility, the etchant must be com-
patible with the CMOS manufacturing process. Since
TMAH has no alkaline-ion contaminants, it can be used
in integrated circuit processing. The anisotropic etching
characteristics of TMAH are similar to those of KOH
in term of etching characteristics. TMAH is also used
to remove positive photoresists. Due to its low etching
rate on thermal oxides, satisfactory results can be ob-
tained [10–12]. However, rough etched surfaces at low
concentration and serious undercuttings at high concen-
tration are drawbacks. To overcome these drawbacks,
works on TMAH : IPA (isopropyl alcohol) solutions have
recently been done. Although addition of IPA improves
the smoothness of the surface and reduces undercuttings,
it reduces the etch rate of Si in TMAH [13,14]. To keep
the good etching characteristics, to enhance the etch rate
of Si in TMAH : IPA solutions and the flatness of the
Anisotropic Etching Characteristics of Si in Tetramethylammonium· · · – Gwiy-Sang Chung -1153-

etched-surfaces, and to compensate for undercutting, in

this study we investigated the anisotropic etching char-
acteristics of single-crystal Si when solutions of pyrazine
(C3 H4 N2 ) were added into TMAH : IPA solutions at vari-
ous concentrations and at different etch-solution temper-
atures.

II. EXPERIMENTS

The starting materials consisted of 550-µm-thick,

<100>-oriented 5-inch p- and n-type Si wafers. The elec-
trical resistivities were 13 ∼ 18 Ω·cm and 4 ∼ 6 Ω·cm,
respectively. RCA cleaning was performed before start-
ing the experiments. The native oxide was removed with
a buffered oxide-etchant solution for 10 sec.
To observe the variation in the etch rate with the ad-
dition of IPA and pyrazine, we used TMAH solutions at
concentrations of 10- 15- 20- and 25-wt.%. The effect
of adding 8.5- and 17-vol.% solutions of IPA was evalu-
ated. The effect of adding 0.001- to 0.003-g/ml solutions
of pyrazine was also studied. The temperature of the
etchant was adjusted to 80, 85, 90, or 95 ◦ C. The ef-
fect of temperature and the effect of adding of IPA and
pyrazine were then analyzed. To enhance the flatness
of the etched surfaces and to compensate for the under-
cutting of convex corners, we added both IPA at 8.5- Fig. 1. (a) Variations of the etch rate on a (100) single-
crystal Si plane as a function of the addition of IPA and
and 17-vol.% and pyrazine at 0.001- to 0.005-g/ml to
pyrazine to 20- and 25-wt.% TMAH solutions at 80 ◦ C. (b)
TMAH solutions. The temperature of the etchant was Variations of the etch rate on a (100) single-crystal Si plane as
maintained at 80 ◦ C in our work. functions of the temperature of the etchant and the addition
To prevent variations in the etchants composition, we of pyrazine to 20-wt.% TMAH solution.
used a Pyrex etch-bath equipped with a reflux condenser.
Samples were placed in the bath vertically so that hydro-
gen bubbles could easily escape from the samples. The
etching depth, the flatness of the etched surface, and (100) Si in 20-wt.% TMAH and 25-wt.% TMAH solu-
the undercutting were measured and examined using a tions with the addition of 8.5-and 17-vol.% IPA and of
profilometer, scanning electron microscopy (SEM), and 0.001- 0.003- 0.005- 0.01- and 0.03-g/ml pyrazine. The
atomic force microscopy (AFM), respectively. highest etch rate of (100) Si was obtained in the 20-
wt.% TMAH : 0.005-g/ml pyrazine solution. When the
amount of pyrazine exceeded 0.005-g/ml, the etch rate
decreased. Fig 1(b) shows the effects of temperature and
III. RESULTS AND DISCUSSION
of the addition of pyrazine on the etch rate. As the figure
shows, the etch rate increased significantly with increas-
The etch rate of (100) Si in TMAH solutions is 0.3 ∼ ing temperature in a 20-wt.% TMAH solution. An etch
1.28 µm/min depending on the concentration and tem- rate of 1.79 µm/min was obtained in 20- wt.% TMAH :
perature of TMAH, and the etch rate of (111) Si in 0.005-g/ml pyrazine solutions at 95 ◦ C. However, adding
TMAH solutions is 0.013 ∼ 0.061 µm/min. The higher pyrazine did not significantly influence the etch rate.
the concentration of TMAH, the lower the etch rate. The The mechanism of anisotropic etching of Si is as fol-
higher the temperature of the etchant, the higher the lows: Two hydroxide ions can bind with two dangling
etch rate because the chemical reaction rate increases bonds of a Si atom on a (100) surface, injecting two elec-
with increasing temperature. trons into the conduction band as in Eq. (1). Next the
The selectivity of (111) and (100) Si is about 0.03 ∼ Si-Si backbones of the Si(OH)2 neighboring lattice atoms
0.05. When IPA at 8.5 and 17 vol.% is added to the must be broken to obtain a soluble Si complex, which is
TMAH solution, the etch rates of (111) and (100) Si de- positively charged, as in Eq. (2). The Si-hydroxide com-
creases by about 7 ∼ 8 % and 10 ∼ 15 %, respectively. plex reacts further with two more hydroxide ions to give
Moreover, the addition of IPA does not affect the selec- orthosilicic acid, Eq. (3). The Si(OH)4 can leave the
tivity. Fig 1(a) shows the variations in the etch rate for solid surface by diffusion, but in the bulk electrolyte, it
-1154- Journal of the Korean Physical Society, Vol. 46, No. 5, May 2005

is unstable due to the high pH valve of the solution. In reaction products and on an observation that hydrogen
this environment, a complex can be formed as in Eq. evolves during etching at a stoichiometric ratio of ap-
(4). Excess electrons in the conduction band can be proximately 2 H2 /Si, we propose an oxidation-reduction
transferred to water molecules as in Eqs. (5) and (6), step with hydroxide ions and water reacting with the Si
producing hydroxide ions and hydrogen as in Eq. (7). surface, followed by a chelation stage involving pyrazine:
The over-all reaction is represented in Eq. (8).
Si(OH)6−− + C4 H4 N2 → SiO3 C4 H4 N2 + 3H2 O. (10)
S S OH We assumed the chelation to be slow, unless pyrazine
Si: 2OH− → S +2e− was added at a concentration of 5 g per liter. In that
S S OH (1) case, we consider the oxidation reaction to be rate limit-
ing. Pyrazine was assumed to act mainly as an agent to
++ increase the solubility of the Si compound, thus increas-
S OH S OH
ing the reaction rate and finally leading to an increased
S → S + 2e− etch rate.
S OH S OH (2) The density of hillocks decreased with increasing con-
centration of the TMAH solutions. In a 25-wt.% TMAH
S OH ++ solution, the etched surfaces appeared to be very clean.
However, when the concentration of the TMAH solution
S + 2OH− → Si(OH)4 + Sisolid was lower than 15-wt.%, the etched surfaces showed poor
S OH (3) characteristics in terms of roughness.
− Fig 2 shows SEM micrographs of etched surfaces in a
Si(OH)4 → SiO2 (OH)2 + 2H+ (4) 10-wt.% TMAH solution as a function of the addition of
IPA. In an IPA-free 10-wt.% TMAH solution, a very high
2H+ + 2OH− → 2H2 O (5)
density of hillocks was observed. However, as IPA was
4H2 O + 4e− → 4H2 O− (6)
− −
4H2 O− → 4(OH) + 4H → 4(OH) + 2H2 (7)
−
Si + 2OH− + 2H2 O → SiO2 (OH)2 + 2H2 (8)

In the structural formula of the TMAH molecular used

in this work, Eq. (9), owing to weak bonding of the
OH(CH3 )4 N+ molecular and the OH- ion, OH- ions are
separated, and finally, OH- radicals are supplied to the
etching reaction:
+
CH3
CH3 − −N − −CH3 OH−
CH3 (9)
When the TMAH is doped with Si, its pH value de-
creases. This corresponds to a decrease in the bulk so-
lution. Hydroxl ions from the bulk solution probably do
not contribute significantly to the Si etching mechanism
since an increase in the <100> etch rate was observed
for concentrated TMAH solutions doped with Si. The
pH value could decrease through dissociation of the Si
etching reaction product, which acts as a weak acid as
shown in Eqs. (4) and (5). The hydroxyl ions necessary
to dissolve of Si must be produced on the Si surfaces,
and has been proposed that water dissociates to form
the OH- ions.
When using TMAH-pyrazine (C4 H4 N2 )-based solu-
tion, the primary role of the pyrazine is thought to be to
convert Si(OH)4 into a more complex anion, increasing
the solubility of the etch product. However, this effect Fig. 2. SEM micrographs of variations in the flatness of
nearly saturates at a concentration of 5 g of pyrazine the etched surface of single-crystal Si in a 10- wt.% TMAH
per liter of TMAH. Based on a chemical analysis of the solution for additions of (a) 0-, (b) 8.5- and (c) 17-vol.% IPA.
Anisotropic Etching Characteristics of Si in Tetramethylammonium· · · – Gwiy-Sang Chung -1155-

Fig. 4. AFM image of the etched Si surface for a 20-wt.%

TMAH : 8.5-vol.% IPA : 0.005-g/ml pyrazine solution

20-wt.% TMAH : 8.5-vol.% IPA : 0.005-g/ml pyrazine

solution. A very good flatness was achieved for the Si
surface etched in a TMAH : IPA : pyrazine in compar-
ison the surface etched in a TMA solution. Therefore,
anisotropic etching in a TMAH : IPA : pyrazine solution
shows great promise due to its capability to provide Si
microstructures with very flat and highly uniform sur-
faces.
When etching is performed for a long time, a defor-
mation convex corners, occurs. To obtain the desired
etched structures, this deformation, called undercutting
must be compensated for. We examined the compen-
Fig. 3. SEM pictures of variations in the flatness of the sation effects of both IPA and pyrazine on a 1 × 0.25
etched surface of single-crystal Si for (a) 25- wt.% TMAH, mm2 rectangular pattern. The undercutting ratio (UR )
(b) 25-wt.% TMAH : 17 vol.% IPA, and (c) 25-wt.% TMAH is defined by UR = l/h, where l is the distance from the
: 17-vol.% IPA : 0.005-g/ml pyrazine. edge of the pattern to an etched section and h is etched
depth. Fig 5 shows the variation in the undercutting ra-
tio as a function of the addition of IPA and pyrazine. For
added to 10-wt.% TMAH solution, the density of hillocks a pure 25-wt.% TMAH solution, UR was 9.8. As IPA was
was considerably reduced, and a high-quality the etched added to the 25-wt.% TMAH solution, UR decreased to
surface was achieved. Merlos et al. [13] reported that
the etch rate of Si decreased when IPA was added to
a 25-wt.% TMAH solution. In our experiment, we also
identified that the higher etch rate of Si in a 10-wt.%
TMAH solution was higher than it was in a 25-wt.%
TMAH solution.
Fig 3 shows SEM micrographs of Si surfaces etched in a
25-wt.% TMAH solution with variation of additives. The
surface quality was very good in a 25-wt.% TMAH so-
lution. Adding IPA to the 25-wt.% TMAH solution did
not significantly deteriorate the flatness of etched sur-
face. Adding pyrazine to the 25-wt.% TMAH solution,
enhanced the etch rate. However, adding pyrazine de-
teriorated the quality of the etched surface, the purpose
of adding the pyrazine to TMAH solutions would not be
achieved. This was not case; the addition of pyrazine did
not significantly affect the quality of the etched surfaces.
Accordingly, we increased the etch rate while maintain-
ing good quality of the etched surface by adding pyrazine
to a 25-wt.% TMAH solution. Fig. 5. Variations of undercutting as a function of the ad-
Fig 4 shows an AFM image of Si surface etched in a dition of pyrazine to both TMAH and TMAH : IPA solutions.
-1156-
6.8. The value of UR decreased down to 3.7 and 2.1 as
0.001- and of 0.005-g/ml of pyrazine, respectively, were
added. The addition of IPA to the 25-wt % solution
decreased the UR by about 30 %, but the addition of
pyrazine to the 25-wt % TMAH solution decreased UR
more than the addition of IPA alone.
IV. CONCLUSION
If TMAH is used as an anisotropic etchant of single-
crystal Si, very good etching characteristics are achieved.
The etch rate of (100) Si is increased by the addition of
pyrazine to TMAH and TMAH : IPA solutions. When
0.005-g/ml of pyrazine was added to a 20-wt.% TMAH
solution, the etch rate of (100) Si was highest. How-
ever, addition of more pyrazine decreased the etch rate
of (100) Si. The temperature of the etchants affected the
etch rate of (100) Si very severely. An etch rate of 1.79
µm/min was obtained in a 20-wt.% TMAH : 0.005-g/ml
pyrazine solution at 95 ◦ C. The quality of the etched sur-
face at lower concentrations of TMAH was very rough,
but the etch rate was very high. If IPA was added to
10-wt.% TMAH, a very smooth surface was obtained for
the sample etched in a 10-wt.% TMAH : 17-vol.% IPA
solution. The addition of pyrazine to the TMAH and the
TMAH : IPA solutions did not decrease the quality of the
etched surface. Next, we evaluated the effect of adding
pyrazine in compensating for the undercutting in TMAH
solutions. The additon of IPA and pyrazine to TMAH
solutions compensated very well for the undercutting at
convex corners. From these results, anisotropic etching
using TMAH : IPA : pyrazine solutions clearly provides
a powerful and versatile process for realizing many types
of integrated micro-sensors, micro-actuators, and micro-
structures.
Journal of the Korean Physical Society, Vol. 46, No. 5, May 2005
ACKNOWLEDGMENTS
This work was supported by 2005 Research Fund of
University of Ulsan.
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