Sensors and Actuators A 102 (2002) 195–201

Electrochemical etching in HF solution for silicon micromachining

G. Barillaroa,*, A. Nanninia, M. Piottob
a
Dipartimento di Ingegneria dell’Informazione, Università di Pisa, Via Diotisalvi, 2, Pisa 56126, Italy
b
Centro di Studio per Metodi e Dispositivi per Radiotrasmissioni-CNR, Pisa, Italy
Received 17 April 2002; accepted 13 September 2002

Abstract

Electrochemical etching of silicon in hydrofluoric acid (HF) solution is employed as a micromachining technique. It is demonstrated that
the commonly accepted geometric constraints on the shape of electrochemically etched silicon structures can be significantly relaxed. Several
new structures etched on the same n-doped silicon wafer are reported. The fabricated structures include wall arrays, hole arrays, meander-
shaped structures, spiral-like walls, microtubes, micropillars, microtips and more. A simple model for the electrochemical etch process, which
describes the effect of the dimension of the initial seed, the current density, and also the KOH etching time of the initial pattern on the final
geometries, is detailed.
# 2002 Elsevier Science B.V. All rights reserved.

Keywords: Macroporous silicon; Silicon micromachining; Electrochemical etching; Pores formation

1. Introduction Our previous work [9] showed that the commonly

Electrochemical etching of silicon in hydrofluoric acid
(HF) electrolyte is a well-known technique for the formation
of porous silicon [1]. Depending on the doping of the
anodized silicon substrate, different pore morphologies
can be obtained, ranging from nanometric pores made from
p-type substrates, to micrometric pores obtained from illu-
minated n-type substrates. In the last case, by illuminating
the rear surface of the wafer with sufficiently energetic
photons, holes can be photogenerated in the bulk. Under
anodic bias, these holes move toward the front silicon–
electrolyte interface and silicon dissolution takes place.
Initially, the electric field concentrates at sharp defects on
the flat wafer surface. Surface defects therefore act as
seeding points for macropore formation. By pre-patterning
the wafer surface with defect sites, it is possible to determine
where macropores will form. KOH etching after a standard
photolithographic step can be used to create pyramidal
notches in the required positions which can act as an array
of defects. Both random [2] and pre-patterned [3] macropore
arrays with high aspect ratio (up to 250) were grown
throughout the wafer thickness [4] and on a whole wafer
[5]. Proposed applications range from IR filters [6] to
photonic crystals [7] and micromechanical systems [8].
*
Corresponding author. Tel.: þ39-050-568-657; fax: þ39-050-568-522.
E-mail address: g.barillaro@ing.unipi.it (G. Barillaro).
accepted geometric constraints on the dimensions of elec-
trochemically etched structures can be significantly relaxed.
Starting from this observation, in this paper, we demonstrate
that several different structures, whose geometries can be
more complex than the standard macropore arrays, can be
fabricated on the same silicon die. These geometries include
wall arrays, hole arrays, meander-shaped structures, spiral-
like walls, microtubes, micropillars, microtips and more. A
model which explains the feasibility of these structures and
also includes the effect of the KOH etching time on the final
geometry, is briefly exposed. The obtained results suggest
that the electrochemical etching of silicon in HF electrolyte
can be a valuable technique for silicon micromachining.
2. Fabrication process
The starting material was an n-doped silicon wafer,
h1 0 0i oriented, 2.4–4 O cm resistivity, 550 mm thick. A
silicon dioxide layer (5000 Å thick) was thermally grown on
the sample (Fig. 1a and b). A standard photolithographic
process was used to define the pattern of the initial seeds for
electrochemical etching. A BHF etch was then used to
transfer the pattern to the silicon dioxide (Fig. 1c). Initial
seeds were formed by KOH anisotropic etching through the
patterned silicon dioxide (Fig. 1d). When not explicitly
stated otherwise, the etch time was long enough to obtain
full pyramidal notches. On the same sample, several different

0924-4247/02/$ – see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 4 - 4 2 4 7 ( 0 2 ) 0 0 3 8 5 - 0
196 G. Barillaro et al. / Sensors and Actuators A 102 (2002) 195–201
Fig. 1. Schematic process fabrication of silicon microstructures (a–e)
using HF-based electrochemical etching.
patterns (straight lines, square dots and holes, spirals,
meander-shaped lines, and others), with different dimen-
sions and pitches were defined. Electrochemical etching in
HF was then used to fabricate regular structures in the
patterned substrate (Fig. 1e). The samples were rinsed in
deionized water and then dried in a convection oven at
95 8C for 10 min. The samples were finally cleaved to allow
scanning electron microscope (SEM) observation of the
cross-sections.
The experimental setup used for electrochemical etch is
described in detail elsewhere [9], and only briefly reported
here. The front side of the sample is exposed to the electro-
lyte in a polytetrafluoroethylene (PTFE) electrochemical
cell with a platinum cathode, which is about 5 mm from
the sample surface. The electrolyte (HF 48%: C2H5OH
99.9%: H2O, 1:2:17 by volume) is stirred to reduce hydrogen
bubble formation. The area of the sample exposed to the
electrolyte is about 0.6 cm2 and has a circular shape. Elec-
tron–hole pairs are generated by illuminating the back side
of the sample with a 300 W halogen lamp, 20 cm from the
sample, through a circular window in the metal sheet used to
provide the back electrical contact to the sample. The power
supply of the lamp can be varied to modulate the etching
photocurrent. An HP4145B parameter analyzer was used to
apply the anodization voltage and monitor the etching
current. All the experiments were executed at room tem-
perature using working current densities J < 30 mA/cm2
and constant anodization voltage of 2.5 V, as suggested in [4]
with respect to the measured electropolishing conditions
(Jps ¼ 30 mA/cm2, Vps ¼ 2 V).
3. Results and discussion
Fig. 2 shows a macropore array fabricated using the
described process. This is the commonly reported silicon
Fig. 2. Top view of a macropore array fabricated using the electrochemical
etching in HF.
structure fabricated by means of the electrochemical etching
in HF.
Though in the previous literature on the electrochemical
etching it is stated that severe limitation exists for regular
macropore array fabrication [3,4], in our recent work [9] we
demonstrated that the commonly accepted constraints on the
dimensions and shapes of macropore can be significantly
relaxed. In fact, in [9], several new features were reported:
(1) patterned pores with sides ranging from 2 to 15 mm were
fabricated starting from the aforementioned silicon substrate
(2.4–4 O cm); (2) macropore arrays with pitch variation up
to 100% (8 and 16 mm) were simultaneously grown on the
same silicon sample; (3) the porosity (P) was changed
between 25 and 90% starting with a fixed initial pattern
and only varying the etching current, according to the
relation P ¼ J/Jps; (4) branching of pores was observed
when the wall thickness between near pores was greater
than 4 mm, which is more than twice that of the space–charge
width.
As a consequence of the results reported in [9], we expect
that, differently from predictions of the previous literature, it
is possible to obtain on the same chip several geometries
with different pitch and dimension simply selecting a proper
initial pattern and then adjusting the etching current, once
the silicon substrate is given.
In fact, in this paper, we demonstrate that is possible to
fabricate holes, walls, spirals, meander-shaped structures,
microtubes, etc. on the same silicon die, with different pitch
and dimension, simply by using a proper initial seed for HF
electrochemical etching. In particular, we found that if
the pre-patterned defects were square holes, a standard
macropore array resulted, but if the KOH defect was con-
stituted by straight lines, a wall array was obtained (Fig. 3).
Moreover by properly arranging several walls, it is possible
to fabricate more complex geometries as meander-shaped
structures (Fig. 4), spiral-like walls (Fig. 5), and microtubes
 G. Barillaro et al. / Sensors and Actuators A 102 (2002) 195–201 197

Fig. 3. Cross-section of a wall array fabricate by means of the

electrochemical etching in HF.

(Fig. 6). Fig. 4 shows the top view of meander-shaped

structures with different dimension and pitch. We would
like to point out that random macropores are present in Fig. 4
where silicon substrate is not opportunely patterned. In fact,
once the doping of substrate is fixed, a maximum dimension
exists on the pores-free silicon material [3,9]: for smaller
dimension, only few holes can penetrate into the patterned
silicon giving rise to silicon dissolution, so that crystalline
silicon auto-protects itself against the electrochemical etch-
ing; for greater dimension, more holes can penetrate and
reach the silicon–electrolyte interface through the patterned
silicon so producing pores formation. Fig. 5 shows respec-
tively the top view of a spiral array (top image) and the cross-
section of such a spiral (bottom image). Fig. 6 shows the top
view (top image) and the cross-section (bottom image) of a
microtube array. It is evident from Fig. 6 (bottom) that an
Fig. 4. Top view of a meander-shaped structure array. In the darker areas,
the silicon has been etched away.
Fig. 5. Top view (top image) and cross-section (bottom image) of a spiral
array.
internal straight channel runs up to the end of each tube.
Arrays of micropillars were also fabricated using a square
dots array as initial pattern (Fig. 7). Fig. 7 shows the top view
(top image) and a 458 view (bottom image) of such an array.
It is evident from Fig. 7 that the silicon between adjacent
pillars was completely removed by electrochemical etching
so creating isolated silicon pillars. By combining the initial
patterns for pillars and macropores, an array of microtips can
be fabricated (Fig. 8). Fig. 8 shows the top view (top image)
and a 458 view of a microtips array.
Moreover, we found that once the geometrical shape of
the seed and the etching current are chosen, the final
structure obtained through electrochemical etching also
depends on the KOH etching time. For instance, using a
pattern constituted by incompletely etched squares (trun-
cated pyramids) and incompletely etched straight lines
(trapezoidal prisms), it is possible to obtain microtip and
microknife arrays, respectively [10], in a different way from
the one described in the previous paragraph. In fact, if the
pyramidal notches are not complete (truncated) and their
198 G. Barillaro et al. / Sensors and Actuators A 102 (2002) 195–201
Fig. 6. Top view (top image) and cross-section (bottom image) of a
microtube array.
dimensions are properly chosen, four macropores grow at
the corners of each notch and join, leaving a crystalline
silicon tip in the center, as clarified later.
The experimental results reported in Figs. 3–8 demon-
strate that it is possible to use the electrochemical etching
technique earlier described with much more freedom than
previously thought, although limitations exist depending on
the constraints of the macropore growth process due to the
substrate resistivity, as discussed in [9].
The fabricated structures show the possibility of using the
electrochemical etching in HF solution as an alternative tool
for silicon micromachining. The main properties of the
described process are: (1) high lateral (parallel to the wafer
surface) and vertical (perpendicular to the wafer surface)
uniformity of fabricated structures (see Figs. 3–8), as a
consequence of pores formation mechanism [4]; (2) good
reproducibility, once parameters of etching (voltage, current
density, HF concentration, etc.) are fixed; (3) high aspect
ratio and then high integration density capability; (4) good
flexibility about the structure shape. Furthermore, using
Fig. 7. Top view (top image) and 458 view (bottom image) of a micropillar
array. The pillars have a constant circular section apart from the foot that
has a more complicated shape (not simple square as it could appear in the
top image).
reactive ion etching (RIE) or isotropic etching to produce
the initial seeds [11] as an alternative to KOH, it is not more
necessary to align the initial pattern to h1 1 0i crystal
directions. Moreover, we would like to mention that lateral
and vertical dimensions of etched structures are controlled
by independent parameters: lateral etching strongly depends
on the etching density current, that establishes the overall
dimension of the resulting structure, once the initial defect is
fixed; vertical dimension only depends on the etching time.
Drawbacks of the proposed process can be ascribed to (1) the
presence of the HF, which is a corrosive agent, especially for
metals; and (2) the constraint on the maximum transversal
dimension of crystalline walls, which mainly depends on the
substrate resistivity. As far as the use of the HF is concerned,
a proper area can be protect using an Si3N4 layer, as reported
in literature [12]; while the doping of the silicon substrate
can be opportunely chosen in order to achieve the desired
transversal dimension [3].
 G. Barillaro et al. / Sensors and Actuators A 102 (2002) 195–201
Fig. 8. Top view (top image) and 458 view (bottom image) of a microtip
array.
In order to explain the feasibility of the previously pre-
sented structures and to state the limits of the detailed
technique, we refer to the model of regular macropore array
growth that we proposed in [9] and which can be completed
including the new experimental data reported in this paper.
The evolution model for HF electrochemical silicon etching
is schematically shown in Fig. 9. In the first time, shallow
random macropores are formed in correspondence of pre-
existing defect sites (Fig. 9a and b). The surface density of
the shallow random macropores could be relatively high,
about the defect density of a polished silicon surface
(106 defects/cm2). Due to the fact that most of the holes
coming from the substrate are collected by pores growing
into the nucleation seeds, any initial dissolution reaction out
of the pre-determined defects can not further proceed, if the
defects pattern is correctly chosen, and only few holes are
available for dissolution of the flat silicon surface. It is known
that an equilibrium density for stable random macropores
growth exists, which depends on silicon substrate resisti-
vity and anodization parameters (voltage, current density).
199
Fig. 9. Evolution model for electrochemical etching of silicon (a–e) in HF
solution.
A redistribution phase starts, then, as soon as the nucleation
process terminate, because the density of the macropores
growing is greater than the equilibrium density. In this
phase, some pores stop growing and terminate, whereas
other pores, collecting more holes, continue to grow increas-
ing their diameter. Thus, the diameter of the growing pores
increases to reach a proper value (Fig. 9c and d). As soon as
the redistribution phase terminate, a stable pore growth
regime starts yielding an arrangement of pores that does
not significantly change anymore (Fig. 9e). Stable growing
pores have a fixed diameter, which value depends on the
substrate resistivity in agreement with the diameter of stable
random pores (about 2 mm for the used substrate). In this
phase, the overall structure grows deep without further
modification of dimension and shape.
Interestingly, the number of pores growing in the pre-
determined notch depends on its dimensions. If the typical
dimension of the notch is approaching the diameter of stable
random pores, only one pore grows in correspondence of the
single defect, as reported by the commonly accepted model
for macropore array formation [3]. When the dimension of
the defect is much greater than the diameter of the random
pores, more pores grow in the defect site and coalesce,
creating a structure with a greater dimension than the single
pore diameter (Fig. 10a). Again, we found that the number of
stable pores growing into a single pre-patterned defect also
200 G. Barillaro et al. / Sensors and Actuators A 102 (2002) 195–201
Fig. 10. Effect of the defect dimension (a), current density (b) and KOH time (c) on the electrochemical etching of the silicon in HF.
depends on the etching current, once the dimension of the
defect is fixed. This is directly related to the dimension of the
obtained structure. In fact, rising the etching current is a
feasible way to increase the dimension of the overall result-
ing structures, by reducing dimensions of silicon walls
(Fig. 10b). Once the dimension of the initial defects and
the etching current are chosen, we found that the overall
structure depends on the KOH etching time. For instance, if
KOH etching of initial pattern is not complete (trapezoidal
prism or truncated pyramid), pores grow at the corners of
each defect, where most of holes coming from the substrate
are collected due to the higher electric field and, in depen-
dence of its dimensions and on the etching current, they
grow independently or coalesce leaving a silicon knife or
pillar in the center of the structure (Fig. 10c). The latter
effect is due to the depletion of holes in the pillar: in fact, the
space charge region of HF–silicon interface of growing
pores extends into the pillar, so protecting it against silicon
dissolution.
4. Conclusions
In this paper, we demonstrate that the commonly pro-
posed geometric constraints on the shape of electrochemi-
cally etched silicon structures can be significantly relaxed.
As a matter of fact, we fabricated several new structures on
the same n-doped silicon wafer, including wall arrays, hole
arrays, meander-shaped structures, spiral-like walls, micro-
tubes, micropillars, microtips and more. A simple model for
the etch, which includes the effect of the dimension of the
initial pattern, the current density, and the KOH etching time
of the initial pattern on the final geometries, is discussed.
The fabricated structures enable us to consider the electro-
chemical etching in HF as a useful tool for silicon micro-
machining, alternative to the commonly used techniques.
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Biographies
G. Barillaro received his laurea degree in electronic engineering and his
PhD degree in information engineering from the University of Pisa, Italy,
in 1998 and 2001, respectively. Since November 2001, he has a post-doc
position at the Information Department of University of Pisa. His main
research interests concern porous silicon applications and technologies,
silicon micromachining, solid state sensors, microelectronic devices and
technologies.
A. Nannini received his laurea degree in electronic engineering from the
University of Pisa, Italy, in 1982. He received his PhD degree in
electronics and information engineering in 1987 at the end of the first
Italian PhD course held by the University of Padova, Italy. From 1988 to
1992, he was a University Researcher at the ‘‘Scuola Superiore di Studi
 G. Barillaro et al. / Sensors and Actuators A 102 (2002) 195–201
Universitari e Perfezionamento S. Anna’’, Pisa. Since 1992, he worked in the
Department of Information Engineering of the University of Pisa as an
associate professor. Since November 2000, he is a full professor of ‘‘Electron
Devices’’. He is also holding the course: ‘‘Sensors and Detectors’’. He is
currently a member of the Council of the Inter-dipartimental Center ‘‘E.
Piaggio’’, he is a member of the Central Library Council of the Engineering
faculty and the vice-president of the Council of the Course of Studies in
Electronic Engineering. His main research interests concern solid state
sensors, microelectronic devices and technologies and MEMS.
201
M. Piotto received his laurea degree in electronic engineering from the
University of Pisa, Italy, in 1996 and his PhD degree in information
engineering in 2000. From 2000 to 2001, he worked at the Department of
Information Engineering of the University of Pisa as a graduated
technician. Since December 2001, he is researcher of the ‘‘Centro di
Studio per Metodi e Dispositivi per Radiotrasmissioni—National
Research Council’’ of Pisa. His main research interests concern
micromachining, MEMS, microelectronic and nanoelectronic devices
and technologies.