Article

Dynamic Wet Etching of Silicon through Isopropanol

Alcohol Evaporation
Tiago S. Monteiro 1,2 , Pamakštys Kastytis 1 , Luís M. Gonçalves 2 , Graça Minas 2, * and
Susana Cardoso 1,3
Received: 1 August 2015 ; Accepted: 9 October 2015 ; Published: 15 October 2015
Academic Editor: Joost Lötters
1 Instituto de Engenharia de Sistemas de Computadores–Microsystems and Nanotechnology (INESC–MN),
Rua Alves Redol, Lisboa 1000-029, Portugal; tmonteiro@inesc-mn.pt (T.S.M.);
kastytismail@gmail.com (P.K.); scardoso@inesc-mn.pt (S.C.)
2 Microelectromechanical Systems Research Unit (CMEMS-UMinho), Universidade do Minho,
Campus de Azurem, Guimarães 4800-058, Portugal; lgoncalves@dei.uminho.pt
3 Departamento de Física–Instituto Superior Técnico–Universidade de Lisboa, Av. Rovisco Pais,
Lisboa 1000, Portugal
* Correspondence: gminas@dei.uminho.pt; Tel.: +351-253-510190; Fax: +351-253-510189

Abstract: In this paper, Isopropanol (IPA) availability during the anisotropic etching of silicon in
Potassium Hydroxide (KOH) solutions was investigated. Squares of 8 to 40 µm were patterned
to (100) oriented silicon wafers through DWL (Direct Writing Laser) photolithography. The
wet etching process was performed inside an open HDPE (High Density Polyethylene) flask
with ultrasonic agitation. IPA volume and evaporation was studied in a dynamic etching
process, and subsequent influence on the silicon etching was inspected. For the tested conditions,
evaporation rates for water vapor and IPA were determined as approximately 0.0417 mL/min
and 0.175 mL/min, respectively. Results demonstrate that IPA availability, and not concentration,
plays an important role in the definition of the final structure. Transversal SEM (Scanning Electron
Microscopy) analysis demonstrates a correlation between microloading effects (as a consequence of
structure spacing) and the angle formed towards the (100) plane.

Keywords: isopropanol evaporation; isopropanol availability; silicon wet etching;

microloading effect

1. Introduction
Surface texturing of crystalline silicon wafers is a widely used process in different areas of
application. From the solar cell industry [1,2] to MEMS (Microelectromechanical Systems) device
fabrication [3–5] and biological applications [6,7], silicon wet etching profile has been studied and
improved in order to address the specific requirements that each of these technological fields require.
The silicon wet etching process is a common manufacture process that involves the use of liquid
etchants in the removal of exposed areas of the sample. Isotropic or anisotropic profiles can be
achieved, depending on the crystalline orientation of the silicon wafer and the etchants used in
the process. Regarding anisotropic wet etching, KOH (potassium hydroxide) is the most popular
inorganic etchant conventionally used [8]. Although other etchants succeed in achieving a better
smoothness, such as the organic compound TMAH (tetramethyl ammonium hydroxide), these are
considerably more costly and in most cases neurotoxic, thus presenting a huge health risk that
requires the appropriate safety measurements [9–11].
The process at which KOH removes silicon atoms is well described in the literature. Etch rates
vary with different crystallographic orientations due to the atomic bonds formed at the surface silicon

Micromachines 2015, 6, 1534–1545; doi:10.3390/mi6101437 www.mdpi.com/journal/micromachines

Micromachines 2015, 6, 1534–1545

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atoms. Wafers with a (100) orientation present superficial atoms with two backbonds, connecting to
two underlying silicon atoms, and two dangling bonds, capable of suffering a nucleophilic reaction
connecting to two underlying silicon atoms, and two dangling bonds, capable of suffering a
with nucleophilic
OH radicals, as shown
reaction withinOHFigure 1a.asThrough
radicals, shown inthe thermal
Figure excitation
1a. Through and injection
the thermal of electrons
excitation and
from injection of electrons from the backbond into the conduction band, energy is applied in breaking
the backbond into the conduction band, energy is applied in breaking these bonds and releasing
these bonds and releasing
the silicon–hydroxide complex the[8].
silicon–hydroxide complex [8].

Si Si OH
-
Si + 2 OH Si + 2 e-cond
Si Si OH
(a)

Si Si
-
Si Si + OH Si Si OH + e-cond
Si Si
(b)
Figure 1. Schematic diagram representing the chemical structure of: surface and respective binding
Figure 1. Schematic diagram representing the chemical structure of: surface and respective binding
of hydroxide ions during a wet etch process for (a) (100) and (b) (111) silicon wafers.
of hydroxide ions during a wet etch process for (a) (100) and (b) (111) silicon wafers.
Anisotropy is achieved in different crystalline orientations since structural variations are
present at the
Anisotropy superficialinatoms.
is achieved For crystalline
different a (111) oriented plane, as
orientations depicted
since in Figure
structural 1b, only
variations areonepresent
dangling bond exists for each superficial atom, thus making it harder to
at the superficial atoms. For a (111) oriented plane, as depicted in Figure 1b, only one dangling bondbe etched when comparing
existswith
for aeach
(100)superficial
oriented plane, atom,as in Figure
thus 1a [8].it harder to be etched when comparing with a (100)
making
Different chemicals can be used to interact with the surface and compete with OH radicals.
oriented plane, as in Figure 1a [8].
Isopropyl Alcohol (IPA) is a widely known molecule that modulates the etching rate of specific
Different chemicals can be used to interact with the surface and compete with OH radicals.
crystallographic planes in KOH wet etching processes. Various authors have suggested that IPA acts
Isopropyl Alcohol
as a mask, (IPA)
limiting the is a widely
access of KOHknown
particlesmolecule that ofmodulates
to the surface the etching
the Silicon sample [12,13].rate of specific
However,
crystallographic planes in KOH wet etching processes. Various authors
no chemical reaction seems to be formed between IPA and silicon atoms, thus acting as a mere have suggested that IPA
modulation
acts as a mask, agent,
limitingratherthethan an etching
access of KOH stopparticles
agent [14]. to the surface of the Silicon sample [12,13].
However,These models reaction
no chemical for the behavior
seems to of be IPA
formed molecules
between at IPA
different concentrations
and silicon atoms, thus take acting
into as
consideration that, for a saturated concentration,
a mere modulation agent, rather than an etching stop agent [14]. a layer of IPA molecules is formed at the surface of
the solution, rather than being diluted. From the proposed models,
These models for the behavior of IPA molecules at different concentrations take into this abundance of IPA affects the
formation that,
consideration of a linear
for amonolayer
saturatedofconcentration,
alcohol molecules at theof
a layer surface of the sample
IPA molecules [12,13]. at the surface
is formed
Therefore, the final structure at which a silicon wafer is etched is intrinsically dependent on
of the solution, rather than being diluted. From the proposed models, this abundance of IPA affects
both the crystallographic orientation of the wafer and the type of chemicals used in the etching
the formation of a linear monolayer of alcohol molecules at the surface of the sample [12,13].
solution. Precisely controlling the concentration of IPA at any given time is a crucial step in order to
Therefore, the final structure
achieve a homogeneous etchingat which a silicon wafer is etched is intrinsically dependent on both
process.
the crystallographic
The silicon wet orientation of the originates
etching reaction wafer andbyproducts
the type of chemicals
in the used in Si(OH)
form of silicates, the etching
4 [8]. Ifsolution.
not
dispersed from the surface of the sample, these silicates will prevent the continuous etching and act
Precisely controlling the concentration of IPA at any given time is a crucial step in order to achieve a
as pseudo-masks,
homogeneous etching promoting
process. a very rough and heterogeneous etching. Assuring a constant flow
between
The these
silicon wetsilicates
etching andreaction
fresh OHoriginates
radicals allows for a better
byproducts in thecontrol
formofofthesilicates,
process, Si(OH)
improving 4 [8]. If
both smoothness
not dispersed from the andsurface
homogeneity
of the across
sample, thethese
entiresilicates
sample [15].
will prevent the continuous etching and
Conventional promoting
act as pseudo-masks, KOH wet aetch veryprocess
rough isand usually performedetching.
heterogeneous inside aAssuring
large, closed quartz flow
a constant
container with external temperature control. Magnetic stirring of the etching solution allows for a
between these silicates and fresh OH radicals allows for a better control of the process, improving
considerable increase in etching homogeneity, creating an internal spiral flow that dilutes the
both smoothness and homogeneity across the entire sample [15].
etching byproducts and allows for continuous access to the silicon substrate. However, studies
Conventional
performed by Yang KOH wet
et al. [15]etch
have process is usually
demonstrated performed
that, even with magnetic insidestirring,
a large, closed
defects appear quartz
container
on the surface of the sample as a result of silicates adherence and incomplete hydrogen for a
with external temperature control. Magnetic stirring of the etching solution allows
bubbles detachment.
considerable increase in etching homogeneity, creating an internal spiral flow that dilutes the etching
byproducts and allows for continuous access to the silicon substrate. However, studies performed by
Yang et al. [15] have demonstrated that, even with magnetic stirring, defects appear on the surface of
the sample as a result of silicates adherence and incomplete 2 hydrogen bubbles detachment.

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Ultrasonic agitation plays a great importance in this process, distributing the same amount of
vibrational energy throughout the entire solution. This allows for an increase in the efficiency at
which particles are interacting with the sample surface and hydrogen bubbles detach [15].
Since both ultrasonic agitation and wet etching are exothermic processes, a minimum working
temperature is always established. This temperature varies with the power applied through the
agitation and the area of silicon molecules exposed to the etching process. Therefore, samples with
considerable larger areas origin higher etching temperatures, and by consequence, higher etching and
evaporation rates.
In this study, we present a dynamic wet etching process that allows for a constant control and
modulation of two important etching variables: temperature and additives. Through the use of an
open container, in which solvent evaporation plays an important role, it is possible to control the
impact of specific additives on the etching profile. Therefore, we demonstrate a method combining
low temperature (~40 ˝ C) and ultrasounds that provides etching uniformity and control on a low
volume experiment (20 mL). It is competitive with conventional high temperature processes. This
method has a final impact on the production scale, reducing the energetic and reagents costs.
The experiments have demonstrated that, for the same sample, it is possible to obtain different
pyramidal profiles due to microloading effects and additive influence. A wide array of applications
is expected for this type of technology in the fields of solar cell industry and MEMS microfabrication.
This work was performed to study the etching profile and angles of pyramidal structures to be used
in biological cell penetration. Surface topography plays a crucial role, as these structures must be
further processed through microfabrication methods.

2. Experimental Details
Experiments were carried out on 0.01–0.03 Ωcm, n-doped, 500 ˘ 25 µm-thick polished silicon
wafers with a monocrystalline (100) orientation (Sil’tronix, Silicon Technologies, Archamps, France).
After surface cleaning, with Alconox (Sigma Aldrich 242985 Alconoxr detergent, St. Louis, MO, USA)
and IPA, a 300 nm thick Chromium layer was deposited by Magnetron Sputtering (Alcatel SCM
450: 3.07 mTorr, 20 sccm Argon, 20 WDC, 51 min [16]). Using Direct Writing Laser photolithography
(Lasarray DWL2.0: positive resist PFR 7790 G 1.5 µm-thick [16]), square structures (8 to 40 µm) were
defined to study the effect of KOH wet etching and IPA influence over the different crystallographic
planes. Profile alignment was performed using the wafers flat and the DWL2.0 software, to a
maximum deviation of 0.02 rad. The wafer was then diced in 9 mm ˆ 9 mm individual dies. The
resist pattern was transferred to the Cr film by wet etch (Sigma Aldrich 651826 Chromium Etchant,
St. Louis, MO, USA). Finally, the Silicon surface is ready to be etched. Notice that any native oxide
will be also etched during this process. Because silicon structures to be etched are less than 20 µm
thick, the backside of the silicon wafer was left unprotected, with minor impact on the total wafer
thickness. The schematic description of the process can be seen in Figure 2.
Twenty-two percent (22 wt %) KOH solutions were prepared by dissolving 70 g of KOH pellets
(85% pure, Sigma Aldrich) into approximately 200 mL of distilled water. Since the dissolution of KOH
in water is an exothermic process, the solutions were left to cool down overnight before using.
In order to provide a steady and gradual solvent evaporation, low temperatures were aimed for
this work. A minimum temperature of 43 ˝ C inside the ultrasonic bath (stabilization temperature
achieved after 30 min) was obtained as a consequence of ultrasound agitation. In this work, we
demonstrate that even for low temperatures, the quality/uniformity of the etching is competitive
with the one obtained with higher temperatures for conventional processes.
Afterwards, the KOH solution was inserted inside a 250 mL HDPE (High Density Polyethylene)
flask with a surface area of 28.27 cm2 and placed inside an ultrasonic bath (Fisher Scientific FB15047,
37 kHz, 30/90 W, Waltham, MA, USA).
A stabilization temperature of about 39 ˝ C, inside the KOH solution, was achieved before the
process could continue. At this stage, IPA was added as needed and the sample was placed inside

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the wet etching solution. The temperature was measured inside the KOH solution every 5 min
using aa mercury
mercury thermometer.
thermometer.AllAllexperiments
experiments were conducted
were inside
conducted a clean
inside room
a clean at an
room at average
an average
temperature
temperature of 40ofC40˘°C1.5
˝ ± 1.5
˝ C.°C.
After After the process
the process waswas completed,
completed, thethefinal
finalvolume
volume was
was measured
measuredusing
usinga graduated
a graduatedHDPEHDPE
cylinder,
cylinder, for analysis
for analysis of solvent
of solvent evaporation.
evaporation.

FigureFigure 2. Schematic
2. Schematic diagram
diagram forforthe
themanufacture
manufacture process
processofofstructures
structuresthrough Si wet
through Si etch
wetusing
etch ausing
Cr a
mask.
Cr mask. AAperfect
perfect pyramid
pyramid isisobtained
obtained after the the
after top top
mesamesa
maskmaskis released.The instant when
is released.The thiswhen
instant ocurs this
is defined
ocurs is definedasasoptimal
optimaletch time.
etch time.

The samples were then rinsed with distilled water and observed under a microscope to access
the samples
The progress of the Si
were etching.
then rinsed with distilled water and observed under a microscope to access
the progressTooffully characterize
the Si etching. the etching process, the chromium mask layer was removed with
Tochromium etchant, asthe
fully characterize described
etchingbefore. The
process, thesamples were mask
chromium then coated withremoved
layer was a 5 nm gold
withlayer for
chromium
SEM
etchant, as (scanning
describedelectron
before.microscopy)
The samplesanalysis.
were then coated with a 5 nm gold layer for SEM (scanning
electron microscopy) analysis.
3. Results and Discussion
3. Results and Discussion
3.1. Evaporation of Solvents
Since processes
3.1. Evaporation of Solventsrun in an open system, the evaporation rate of solvents (IPA and water) should
be considered. The final volume of the etching solution was measured and compared to the initial
Since processes run in an open system, the evaporation rate of solvents (IPA and water) should
volumes of dissolved KOH and IPA, to evaluate the evaporation rate of water and IPA.
be considered. The final volume of the etching solution was measured and compared to the initial
Each experiment started with an initial volume of 20 mL of 22 wt % KOH solution. A control
volumes of dissolved
sample, containing KOH and IPA,
no added IPA, to
and evaluate the evaporation
three samples containing 1,rate of 5water
3 and mL ofand IPA.added IPA,
initially
respectively, Sample B, C and D in Figure 3, underwent a 120 min etching process under theAsame
Each experiment started with an initial volume of 20 mL of 22 wt % KOH solution. control
sample,conditions.
containingFigure 3 summarizes
no added thethree
IPA, and initialsamples
and finalcontaining
volumes of 1, solution,
3 and 5upon
mL of process completion.
initially added IPA,
Regardless
respectively, of the
Sample B, amount
C and DofinIPAFigureinitially added, given
3, underwent enough
a 120 time (120
min etching min here)
process underallthe
IPAsame
evaporates
conditions. Figureand3 the final solution
summarizes the isinitial
only composed of dissolved
and final volumes KOH. Theupon
of solution, same process
final volume was
completion.
achieved
Regardless with
of the the reference
amount of IPAsample
initially(Sample
added,A,given
without addition
enough timeof(120
IPA),min
when applying
here) all IPAthe same
evaporates
process. From here it can be determined an approximate evaporation rate of 0.0417 mL/min for
and the final solution is only composed of dissolved KOH. The same final volume was achieved with
water vapor, and it can be concluded that the final volume is independent of the IPA content, if
the reference sample (Sample A, without addition of IPA), when applying the same process. From
sufficient time is given to evaporate all IPA.
here it can Four
be determined
experimentsan approximate
were conducted evaporation rate
to further study of influence,
IPA 0.0417 mL/min for water
as described vapor,
in Table and it
1. For
can beexample,
concluded in Sample 4, from an initial volume of 40 mL (20 mL of KOH dissolved in water and to
that the final volume is independent of the IPA content, if sufficient time is given
evaporate all IPA.
Four experiments were conducted to further 4study IPA influence, as described in Table 1. For
example, in Sample 4, from an initial volume of 40 mL (20 mL of KOH dissolved in water and

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Micromachines 2015, 6, 1534–1545

20 mLMicromachines 27 volume,
of IPA),2015, mL of page–page
etchant were available after 60 min. Approximately 2.5 mL of water
were evaporated, considering the evaporation rate of 0.0417 mL/min described. Consequently, the
20 mL of IPA), 27 mL of etchant were available after 60 min. Approximately 2.5 mL of water were
remaining difference of 10.5 mL can be attributed to IPA evaporation, thus resulting in an evaporation
evaporated, considering the evaporation rate of 0.0417 mL/min described. Consequently, the
rate of 0.175 mL/min. The errors in measuring the final volume (some droplets remained inside the
remaining difference of 10.5 mL can be attributed to IPA evaporation, thus resulting in an
HDPE flask) are rate
evaporation estimated
of 0.175 as mL/min.
a few hundred µL. Table
The errors 1 showsthe
in measuring thefinal
initial KOH (some
volume and IPA content in
droplets
solution for each
remained Si wet
inside etch process.
the HDPE flask) areThe optimal
estimated as aetch
few time
hundredwasμL.inferred
Table 1after
shows periodic microscopic
the initial KOH
and IPA content in solution for each Si wet etch process. The optimal etch time was inferred structure.
inspections, analyzing whenever the top mesa (Figure 2) would detach from the remaining after
This periodic microscopic
corresponds to a fullinspections,
patternedanalyzing
pyramid, whenever
with the top mesa
sharp (Figure
vertices. 2) would
This optimaldetach
etchfrom
time is
the remaining
dependent not onlystructure. This corresponds
of the nominal size of eachto aprofile,
full patterned
but alsopyramid, with sharp
of temperature, KOHvertices. This
concentration
optimal
and IPA etch timeIn
availability. is this
dependent
work, notIPAonly of the nominal
availability in the size of each
solution wasprofile, butthus
tested, alsopresenting
of temperature,
different
KOH concentration and IPA availability. In this work, IPA availability in the
optimal etch times, with a time error estimated bellow 5 min, as a consequence of the initial volumesolution was tested,
thus presenting different optimal etch times, with a time error estimated bellow 5 min, as a
of IPA added to the etching solution. At the optimal etch time, the final volume of solution was
consequence of the initial volume of IPA added to the etching solution. At the optimal etch time, the
measured and the dissolved KOH and IPA volumes calculated. Considering initial volumes and
final volume of solution was measured and the dissolved KOH and IPA volumes calculated.
evaporation rates,
Considering the volumes
initial IPA availability can be calculated
and evaporation rates, the IPA(Table 1), representing
availability the amount
can be calculated of time
(Table 1),
necessary to evaporate all IPA in the etching solution.
representing the amount of time necessary to evaporate all IPA in the etching solution.

25

IPA
20
KOH
15
Volume (mL)

10

0
A B C D
Solvent evaporation conditions
Figure 3. Graphical representation of the total initial volume (blue), as sum of initial KOH volume
Figure 3. Graphical representation of the total initial volume (blue), as sum of initial KOH volume
(20 mL) and IPA volume (0 to 5 mL), versus the final volume (red) after a total etching time of
(20 mL) and IPA volume (0 to 5 mL), versus the final volume (red) after a total etching time of 120 min.
120 min.

Table 1. Experimental conditions used in the definition of 10 μm × 10 μm wide pyramid structures

Table 1. Experimental conditions used in the definition of 10 µm ˆ 10 µm wide pyramid structures
through wet etching. IPA availability represents the predicted time at when all IPA would evaporate.
through wet etching. IPA availability represents the predicted time at when all IPA would evaporate.
If the “IPA availability” is greater than the “Etch time”, the etch process occurs entirely in the
If thepresence
“IPA availability” is greater than the “Etch time”, the etch process occurs entirely in the presence
of IPA. Otherwise, a two phase process would occur (first with dissolved KOH and IPA,
of IPA. Otherwise,
followed a two phase
by dissolved process would occur (first with dissolved KOH and IPA, followed by
KOH only).
dissolved KOH only).
Sample VKOH (mL) VIPA (mL) Etch Time (min) Final Volume (mL) IPA Availability (min)
1 20 0 40 18 0
Sample VKOH (mL) VIPA (mL) Etch Time (min) Final Volume (mL) IPA Availability (min)
2 20 3 50 18 17
1 3 20 20 0 5 60
40 1718 29 0
2 4 20 20 3 20 60
50 2718 114 17
3 20 5 60 17 29
4 Sample20 1 was used as20a control sample,60where IPA was never
27added. For Samples 2114and 3, the
optimal etch time (50 and 60 min, respectively) was reached after the entire evaporation of IPA from
the solution
Sample (achieved
1 was used asata17control
and 29sample,
min, respectively).
where IPASample 4 wasadded.
was never etched in theSamples
For presence2ofand
IPA3, the
during the entire process.
optimal etch time (50 and 60 min, respectively) was reached after the entire evaporation of IPA from
the solution (achieved at 17 and 29 min, respectively).
5 Sample 4 was etched in the presence of IPA
during the entire process.

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Therefore, IPAIPA
Therefore, influence
influenceover
overthe
thewet
wet etching processofofsilicon
etching process siliconcancan
be be measured
measured in terms
in terms of of
availability, rather than concentration. Assuming that IPA is still in the solution, at any
availability, rather than concentration. Assuming that IPA is still in the solution, at any given time, given time,
and
and at a at a macroscopic
macroscopic level,
level, variationsininits
variations its concentration
concentration would
wouldnot notinfluence its its
influence effect. Figure
effect. 4
Figure 4
further
further demonstrates
demonstrates thethe time
time evolutionofofthis
evolution this process.
process.

Figure
Figure 4. Evolution
4. Evolution of of solutionvolumes
solution volumesas as aa consequence
consequence ofofsolvent
solventevaporation.
evaporation.The The
mainmain
chartchart
represents the volume of the whole solution (water and IPA) and the inset chart representsIPA
represents the volume of the whole solution (water and IPA) and the inset chart represents the the IPA
volume evolution, during the etch process. Sample 1 (green); Sample 2 (black); Sample 3 (red); and
volume evolution, during the etch process. Sample 1 (green); Sample 2 (black); Sample 3 (red); and
Sample 4 (blue).
Sample 4 (blue).
The IPA availability effect is reinforced by results of a parallel etching process, containing an
initialIPA
The volume of 20 mLeffect
availability dissolved KOH and 2by
is reinforced mLresults
IPA, and
of then addingetching
a parallel 2 mL IPA every 10containing
process, min,
an initial volume of 20 mL dissolved KOH and 2 mL IPA, and then adding 2 mL IPAofevery
ensuring that IPA is always available during the entire etching process (evaporation rate
0.175ensuring
10 min, mL/min that
was observed, as previously
IPA is always described).
available Theentire
during the macroscopic
etchingetching
processresults from this rate
(evaporation
of 0.175 mL/min was observed, as previously described). The macroscopic etching resultsother
experiment are quite similar from those obtained in Sample 4, and distinguishable from every from this
sample. The same etching profile can be achieved either with an initial saturated solution, or with a
experiment are quite similar from those obtained in Sample 4, and distinguishable from every other
lower, but continuously assured, concentration of IPA.
sample. The same etching profile can be achieved either with an initial saturated solution, or with a
We can support that, after the expected evaporation time has been achieved, the wet etching
lower, but
process continuously
will continueassured, concentration
in the same of Sample
conditions as IPA. 1 (without IPA). Therefore, we have two
We
specific moments that are particularly relevant to the etchingtime
can support that, after the expected evaporation haswhen
process: beenIPA
achieved, the wet
is still present etching
in the
solution and when all IPA evaporates.
process will continue in the same conditions as Sample 1 (without IPA). Therefore, we have two
specific moments that are particularly relevant to the etching process: when IPA is still present in the
3.2. Influence
solution and when of IPA in theevaporates.
all IPA Wet Etch of Silicon
The etch rate for the (110) and (331) planes can be 2× and 1.5× larger than the etch rate for the
3.2. Influence of IPA
(100) plane, in the WetinEtch
respectively, KOH of etching
Silicon solutions [12]. This results in a very sharp, but irregular
structure
The etch with
rate afor
very
themarked underetching
(110) and profile.
(331) planes canThe
be obtained structures
2ˆ and 1.5ˆ largerpresent an octagon
than the etch ratebase
for the
with a basal diameter up to 1/3 and height up to 1/4 of the profile nominal size (mask size), thus
(100) plane, respectively, in KOH etching solutions [12]. This results in a very sharp, but irregular
illustrating a severe underetch. However, the etching rate of specific planes in silicon KOH etching
structure with a very marked underetching profile. The obtained structures present an octagon base
can be modulated through IPA. The addition of IPA to the etching solution greatly reduces the etch
with rate
a basal diameter
in these planesup to 1/3
down and
to 8× height
lower [12].up
In to 1/4conditions,
these of the profile nominal
the (110) planesize (mask size), thus
is predominantly
illustrating
protected, thus significantly increasing the base diameter of the structure and reorienting itKOH
a severe underetch. However, the etching rate of specific planes in silicon towardsetching
can bethemodulated
(100) axis. As the etching
through IPA.undergoes in saturated
The addition of IPA conditions (where
to the etching IPA is thoroughly
solution presentthe
greatly reduces in etch
thethese
rate in process), the down
planes structures maintain
to 8ˆ lowera[12].
squareInshape
thesealigned with the
conditions, theaxis,
(110)whilst
planeincreasing base
is predominantly
width thus
protected, (Figure 5). Due toincreasing
significantly this progressive
the baseincrease and of
diameter profile spacing, and
the structure the structures
reorienting end up
it towards
colliding upon their edges. Therefore, spacing between adjacent profiles needs
the (100) axis. As the etching undergoes in saturated conditions (where IPA is thoroughly present to be carefully
in theplanned to prevent
process), grouping.
the structures maintain a square shape aligned with the axis, whilst increasing base
width (Figure 5). Due to this progressive increase and 6 profile spacing, the structures end up colliding
upon their edges. Therefore, spacing between adjacent profiles needs to be carefully planned to
prevent grouping.

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Micromachines 2015, volume, page–page

Figure
Figure 5. 5.Evolution
Evolution of
of base
base width,
width,along
alongthethe
wetwet
etchetch
process, obtained
process, from from
obtained a 8 μma ×88µmμm ˆ square
8 µm
Figure
square 5. Evolution
maskmask
with ofofbase
a spacing
with a spacing width,
16 μm, along
under
of 16 µm, IPAthe wet etch
saturated
under IPA process,conditions,
obtained
conditions,
saturated from
as described adescribed
as for8sample
μm × 8 4for
μm square1. 4
in sample
Table
in mask
Top with
Table view a microscope
1. Top spacing of 16images
μm, under
view microscope show
imagesIPA saturated
how
show conditions,
the individual
how the as described
square
individual for sample
patterns
square patternsareare 4enlarged
in Tableand
enlarged 1.
and
Top view microscope
merged together.
merged together. images show how the individual square patterns are enlarged and
merged together.
The structure base width starts to recede after complete evaporation of IPA, as a more
TheThe structure
structure base
baseiswidth
width starts
startsintototherecede
recede after complete
after complete evaporation
evaporationofofIPA, IPA, asa amore more
pronounced (110) etch performed absence of IPA. Moreover, the increase etchasrate of the
pronounced
pronounced (110) etchthe
(110)
(331) plane promotes
etch isis performed
performed in thea square
in
transition from
the absenceshaped
absence of IPA.toMoreover,
of IPA. Moreover,
an octagonal the shaped
theincreasestructure,
increase etch rate as
etch rateof seen
thethe
of
(331)
(331) plane6.promotes
plane
in Figure
promotes thethe transition
At this stage,
transition from occurs
from
this transition
a a square
square shaped to anand
shaped to
progressively,
an octagonal
octagonal shaped structure,
shaped
is independent
structure, as seen in
as seen
of the overlaying
in
Figure Figure
6. At 6.
mask, sinceAt this
this stage,
the stage, this transition
this transition
structure width
occurs
has grown occurs progressively,
progressively,
beyond and
and is
the nominal issize,
independent
independent ofoverlaying
of the
and therefore, theisoverlaying
mask,
no longer
mask,
since the since the
structure structure
width haswidthgrown has grown
beyond beyond
the the
nominal nominal
size, and size, and
therefore, therefore, is
is no longer
defined by it. As observed in the images representative for the etching process after 80 and 100 min, no longer
defined by
it. defined
within by it. As
As observed
Figure 6, observed
in the imagesin the
the reorientation images
of therepresentative
representative for the
structure foroccurs
the process
etching
shape etching
whilstprocess
after 80after
the initialand 80100
mask, and 100 min,
min,
shown within
as a
within
Figure 6, Figure
the 6, the reorientation
reorientation of the of the
structure structure
bright square, remains overlaid to the dark structure. shape shape
occurs occurs
whilst whilst
the the
initial initial
mask, mask,
shown shown
as a as a
bright
brightremains
square, square, overlaid
remains overlaid to the
to the dark dark structure.
structure.

Figure 6. Top view microscopic images demonstrating the evolution of base width, upon the wet
Figure
Figure 6. Top
Top view
etch6.process, view microscopic
microscopic
obtained a 8images
from images × demonstrating
μmdemonstrating
8 μm square the
themask evolution
evolution of base
with aof spacing
base width,
width, upon
of 40upon
μm, thethe
wet
after wet
etch
IPA
etch
process,process,
obtained obtained
from a 8from
µm a 8
8 μm
µm × 8
squareμm square
mask with mask
a with
spacing a spacing
of 40 µm, of 40
after μm,
IPA
evaporation. This process occurred first as described in Figure 5 (up to 80 min), but with an increased
ˆ after IPA
evaporation.
evaporation.
This process
spacing toThis
asoccurredprocess
preventfirst occurred
as firstinasFigure
described
merging, followed described
by into
5 (up
etching in Figure 5 without
(upbut
80 min),
solution to 80
withmin),
IPA an but with
increased
(after 80 anspacing
min). increasedas to
spacing
prevent as to prevent
merging, merging,
followed followed
by etching by etching
in solution in solution
without without
IPA (after 80 IPA
min).(after 80 min).
7
7

1540
Micromachines 2015, 6, 1534–1545

Micromachines 2015, volume, page–page

Therefore, modulating the availability of IPA at any given time during the wet etch process
allows forTherefore,
a more precise control
modulating of the finalofstructure.
the availability IPA at any Thegiveninitial
time IPA
duringvolume
the wetnecessary to keep
etch process
allows for a more
IPA availability until precise
the etchcontrol of the
process final structure.
depends not only The
oninitial IPA volume
exposed necessary
silicon area to keep
and the IPA etch
desired
availability
depth, until
but also on thethe etch process
volume depends
and surface notofonly
area on exposed
the etching silicon area and the desired etch
solution.
depth,sample
Each but alsowas
on the volume and
patterned withsurface
threearea
mask of the etching
profiles assolution.
depicted in Figure 7: (a) 200 µm wide
Each sample was patterned with three mask profiles
rectangular mask; (b) 10 µm square mask with a spacing of 20 µm, as depicted in Figure 7: (a) 200
for v-grove μm wide and
patterning;
rectangular mask; (b) 10 μm square mask with a spacing of 20 μm, for
(c) 10 µm square mask with a spacing of 20 µm. SEM imaging was used in the determination v-grove patterning; and of
(c) 10 μm square mask with a spacing of 20 μm. SEM imaging was used in the determination of
pyramid lateral angles. All samples reveal a consistency towards each angles, and by consequence,
pyramid lateral angles. All samples reveal a consistency towards each angles, and by consequence,
towards each planes. Three profiles were obtained at same time instants (for each sample, in the same
towards each planes. Three profiles were obtained at same time instants (for each sample, in the
etch solution), and by consequence,
same etch solution), with the
and by consequence, same
with the IPA
sameavailability.
IPA availability.

Figure 7. Evolution of measured patterns angle in different IPA availability conditions, obtained
Figure 7. Evolution of measured patterns angle in different IPA availability conditions, obtained from:
from: (a) 200 μm wide rectangular mask (black); (b) 10 μm v-grove from a square mask with a
(a) 200 µm wide rectangular mask (black); (b) 10 µm v-grove from a square mask with a spacing of
spacing of 20 μm (blue); and (c) 10 μm square mask with a spacing of 20 μm (red).
20 µm (blue); and (c) 10 µm square mask with a spacing of 20 µm (red).
As seen in Figure 7a,b, the 200 μm wide pattern and the v-groves present a 54.7° ± 2° angle,
characteristic
As of the (111)
seen in Figure 7a,b,plane.
the 200 Thisµmresult
widewaspattern
obtainedand independently
the v-groves of the IPA volume
present a 54.7˝added
˘ 2˝toangle,
the etch solution,
characteristic and isplane.
of the (111) in accordance with the
This result wasexpected
obtained results. When defining
independently grooves,
of the the etched
IPA volume added
structure always orientates to align with the wafer flat, forming squared
to the etch solution, and is in accordance with the expected results. When defining grooves, the pyramids with (111) planes.
IPA influence on the final profile is negligible, either on the base width or profile topography.
etched structure always orientates to align with the wafer flat, forming squared pyramids with (111)
Typically, the end result is a uniform etch, as in Figure 7b. However, dense structures are deeply
planes. IPA influence on the final profile is negligible, either on the base width or profile topography.
influenced by the neighboring topography, which can be seen by the angle decrease to 46.5°. IPA
Typically, the endplays
concentration result is influence
little a uniform etch,
in the as patterning
final in Figureresult,
7b. However, dense
but its absence structures
originates are deeply
a structure
influenced by the
with a rough etch.neighboring topography, which can be seen, in Figure 7c, by the angle decrease to
46.5 . IPAThe
˝
discrepancy plays
concentration between theinfluence
little results from Figure
in the final7a,c is focused
patterning onlybut
result, on its
theabsence
adjacentoriginates
area
aroundwith
a structure each aofrough
the structures.
etch hardly While the first portrays
quantifiable by SEM a long line that was patterned 200 μm apart
analysis.
fromdiscrepancy
The any other structure,
between thethe
latter depicts
results fromstructures patterned
Figure 7a,c in a dense
is focused only array.
on theThe difference
adjacent areacan
around
be attributed to microloading effect, in which etchants and byproducts
each of the structures. While the first portrays a long line that was patterned 200 µm apart from of the reaction have more
difficulty
any other diffusingthe
structure, through
lattersmaller
depictsareas [17]. Therefore,
structures in dense
patterned in arrays
a denseof structures,
array. The as soon as the can
difference
wet etch begins, the (100) plane is less accessible than the (110) plane. In order to modulate this
be attributed to microloading effect, in which etchants and byproducts of the reaction have more
scenario, the desired structures may be patterned further apart, or additives can be incorporated in
difficulty diffusing through smaller areas [17]. Therefore, in dense arrays of structures, as soon as
the etching solution in order to increase the wettability of the silicon wafer. On the contrary,
the wet etch begins, the (100) plane is less accessible than the (110) plane. In order to modulate this
scenario, the desired structures may be patterned further apart, or additives can be incorporated in
8
the etching solution in order to increase the wettability of the silicon wafer. On the contrary, v-groves

1541
Micromachines 2015, 6, 1534–1545

Micromachines 2015, volume, page–page

are not affected by the microloading effect, and denser arrays of pyramidal structures with sharper
Micromachines
v-groves are 2015,
notvolume, page–page
affected by the microloading effect, and denser arrays of pyramidal structures with
edges can be patterned. All the v-grove structures are formed with a square base, independently
sharper edges can be patterned. All the v-grove structures are formed with a square base,
v-groves
of the nominal are profile
independently not ofaffected
shapeby (mask)
the nominalthe microloading
profile shape effect,
or orientation. and denser
Figure arrays of pyramidal
8 demonstrates
(mask) or orientation. Figure structures
in detail
in with
the result
8 demonstrates detail
of the
sharper
microloading edges
effect can be
depictedpatterned.
in FigureAll the
7c. v-grove
the result of the microloading effect depicted in Figure 7c. structures are formed with a square base,
independently of the nominal profile shape (mask) or orientation. Figure 8 demonstrates in detail
the result of the microloading effect depicted in Figure 7c.

Figure 8. SEM cross-section image of the structure obtained with a 10 μm × 10 μm square mask,
Figure 8. SEM cross-section image of the structure obtained with a 10 µm ˆ 10 µm square mask,
spaced 20 μm from the next square, in a 22 wt % KOH wet etch process (Sample 2 in Table 1).
Figure
spaced 8. SEM
20 µm fromcross-section image in
the next square, ofathe
22 structure
wt % KOH obtained with
wet etch a 10 μm
process × 10 μm
(Sample square
2 in Tablemask,
1).
spaced 20 μm from takes
IPA availability the next
ansquare,
importantin a 22 wt defining
role % KOH wettheetch process
etched (Samplein2 top
structure in Table
view1).SEM images.
Near the optimal volume of IPA, the influence on the number
IPA availability takes an important role defining the etched structure in top view of etched planes is maximized.
SEM images.
IPA availability
Squares aligned withtakes
the an important
wafer flat will role defining
have the etched
reorientation, structure
initially to a in top view SEM
dodecahedron, images.to
and finally
NearNear
the optimal
the volume
optimal volumeof IPA,
of the
IPA, influence
the influenceon the
on number
the numberof etched
of planes
etched is
planes maximized.
is maximized.Squares
an octagon profile, as seen in Figure 9a. This will result in an octagonal pyramid with faces oriented
aligned with the wafer
Squares flatwafer
willflat
have
willreorientation, initially to to
a adodecahedron, andfinally
finally
to to an
towardsaligned with
the (331) the
plane. have reorientation, initially dodecahedron, and
an octagon profile, as seen in Figure 9a. This will result in an octagonal pyramid with faces oriented
octagon profile, as seen in Figure 9a. This will result in an octagonal pyramid with faces oriented
towards
towards the the (331)
(331) plane.
plane.

Figure 9. Microscopic inspection of a 22 wt % KOH wet etch process, (Sample 2, in Table 1) after
20 min. Initial profile: (left) 40 μm and (right) 20 μm; square: (a) aligned with the wafer flat; and
Figure
Figure 9. Microscopic
9. Microscopic
(b) misaligned inspection
the wafer aflat.
inspection
22.5° with
of a 22
22 wt
wt%%KOHKOHwet etch
wet process,
etch (Sample
process, 2, in 2,
(Sample Table 1) after
in Table 1) after
20 min.
20 min. Initial
Initial profile:(left)
profile: (left) 40
40 µm
μm and
and (right)
(right)2020μm;
µm;square: (a) (a)
square: aligned withwith
aligned the wafer flat; and
the wafer flat; and
(b) misaligned
(b) misaligned 22.5°
22.5 withthe
˝ with thewafer
wafer flat.
flat.

9 ˝ , to the same etching conditions, the result are

When exposing a squared profile, tilted 22.5
9
squared pyramids with no reorientation, as shown in Figure 9b. In fact, this is the same etching

1542
 Micromachines 2015, volume, page–page
Micromachines2015,
Micromachines 2015,6,volume, page–page
1534–1545
When exposing a squared profile, tilted 22.5°, to the same etching conditions, the result are
When
squared exposing
pyramids a squared
with profile, tilted
no reorientation, as shown22.5°,
in to the same
Figure 9b. In etching
fact, thisconditions,
is the same the result
etching are
plane
plane thatpyramids
squared is replicated
with bi-dimensionally
no reorientation, inshown
as structures aligned
inaligned
Figure 9b. with
In the the
fact, wafer
this is theflat, such as those in
that is replicated bi-dimensionally in structures with wafer flat,same
suchetching plane
as those in
Figure
that
Figure 9a.
is 9a. A predominance
replicated to etch
bi-dimensionally
A predominance in
to etch in these
in these planes,
structures forming
planes,aligned
forming withthe structural
the the pyramids
wafer pyramids
structural described
flat, such described
as those in in
Figure 6,
Figure 6, protects
9a.protects those
A predominancein Figure 9b
to etch
those in Figure from
9b in any
these
from reorientation.
anyplanes, formingAn
reorientation. An equal
theequal result
structural can
resultpyramids be obtained
described
can be obtained when
in
when
rotating the same misaligned profile by 45 ˝ . This way, it is possible to exactly define the desired
Figure
rotating6,the
protects
same those in Figure
misaligned 9b from
profile anyThis
by 45°. reorientation.
way, it is An equal to
possible result can define
exactly be obtained when
the desired
rotating
structure,the
structure, same amisaligned
between
between asquared
squaredand profile
and by 45°.
octagonal
octagonal Thisprofile,
shape
shape way, itonly
profile, is possible
only to exactly
by modifying
by modifying define
thealignment
the alignmentthe towards
desired
towards
structure,
the
thewafer between a squared and octagonal shape profile, only by modifying the alignment towards
waferflat.
flat.
the wafer flat.
Alternatively,
Alternatively, higher
highervolumes
volumesofofIPAIPAwill
willform
formstructures
structureswithwithrounder
rounder shapes,
shapes, independently
independentlyof
profileAlternatively,
of profile
orientation, higher
orientation,
as volumes of
as demonstrated
demonstrated in IPA inwill
Figure form
Figure
10. The structures
10. with topography,
The surface
surface rounder
topography, shapes,
however, isindependently
however,
muchisrougher
much
inof profile orientation, as demonstrated in Figure 10. The
rougher in these conditions and structural uniformity is hard to achieve.
these conditions and structural uniformity is hard to surface
achieve. topography, however, is much
rougher in these conditions and structural uniformity is hard to achieve.

Figure 10. Microscopic inspection of a 22 wt % KOH, saturated with IPA, wet etch process,
Figure 10. Microscopic inspection of a 22 wt % KOH, saturated with IPA, wet etch process, (Sample 4
Figure
(Sample10.
4 inMicroscopic
Table 1) afterinspection of a profile:
50 min. Initial 22 wt 10 % μm
KOH, saturated
squares with IPA,
(left) aligned and wet etch
(right) process,
misaligned
in Table 1) after 50 min. Initial profile: 10 µm squares (left) aligned and (right) misaligned 22.5˝ with
(Sample 4 in
22.5° with theTable
wafer1)flat.
after 50 min. Initial profile: 10 μm squares (left) aligned and (right) misaligned
the wafer flat.
22.5° with the wafer flat.
An evolution of this process can be observed in Figure 11. As demonstrated previously, in the
Anevolution
absence
An evolution
of IPA, the ofKOH
of this process
this process can(110)
etches the
can be observed
be observed in Figure
Figure 11.
plane predominantly,
in 11. As demonstrated
which
As causes thepreviously,
demonstrated ininthe
visible undercut
previously, the
absence
absence ofofIPA,
etch seen inIPA, the
Figure
the KOHKOH
11a. A etchesthethe
17 min
etches (110) plane
availability
(110) plane of predominantly,
IPA in the beginning
predominantly, which
which ofcauses
thethe
causes the
process visible undercut
isundercut
visible sufficient to
etch
etch
seen seenthe
stabilize
in in Figure
Figure etching11a.
11a. A 17 A for
rates
min 17 min availability
the (110)
availability of IPA of IPA
and (331)
in the in the
planes,
beginningbeginning
thus allowingofthe
of the theformation
process process is of
is sufficient
sufficient octagonal
to to
stabilize
stabilize
structure
the etchingthe etching
(Figure
rates rates
for11b).
the for and
(110) the (110)
However, withand
(331) the(331)
planes, planes,
increase
thus ofthus
IPAallowing
allowing the formation
availability,
the formation the of octagonal
square
of octagonal profile
structureis
structure
maintained
(Figure 11b).(Figure
with 11b). with
rounder
However, However,
edges,
theas with the
observed
increase of in increase
IPAFigure of IPAtheavailability,
11c,d.
availability, the issquare
square profile profilewith
maintained is
maintained
rounder edges,with
as rounder
observededges, as observed
in Figure 11c,d. in Figure 11c,d.

Figure 11. Microscopic inspection of a 22 wt % KOH wet etch process after 20 min. Initial profile:
Figure
Figure 11.
40 μm11. Microscopic
squares inspection
aligned inspection
Microscopic of aa 22
with the wafer
of 22 wtConditions
flat.
wt % KOH
% KOH wet areetch
wet process
processinafter
described
etch 20
Table
after min.
201: (a) Initial
min. Initialprofile:
Sample 1; (b)
profile:
40 µm squares aligned with the wafer flat. Conditions are described in Table 1: (a) Sample(b)1;
40 μm
Sample squares
2; (c) aligned
Sample 3; with
and the
(d) wafer
Sample flat.
4. Conditions are described in Table 1: (a) Sample 1;
Sample
(b) 2; (c)
Sample Sample
2; (c) 3; and
Sample (d)(d)
3; and Sample
Sample4. 4.
Once IPA evaporates, these profiles tend to revert to a situation as in Figure 11a, given the
width Once IPAstructure
of the evaporates, these profiles
is enough to allowtend
for to revert toprofile
a gradual a situation as in Figure
reorientation, 11a,the
before given the
etching
widthOnce IPA evaporates, these profiles tendfor
to revert to a situation as in Figure 11a, given the width
reachesofthethe structure
mesa release is enough
stage. to allow
For the experimentala gradual profile
conditions reorientation,
tested, a thresholdbefore
is heldthe etching
for the IPA
ofreaches
the structure
the mesaisrelease
enoughstage.
to allow the
for experimental
a gradual profile reorientation, abefore the etching reaches the
availability between 17 and 29For min. However, sinceconditions tested,
the structures threshold
observed is held11
in Figure for thewide
are IPA
mesa release
availability stage.
between For the
17to
andexperimental
29 min. conditions
However, tested,
sincecould, a threshold
the structures is held
observed for the
inthe
FigureIPA availability
11 are of wide
enough for the etching proceed, a longer etching eventually, allow for correction the
between
enough 17
forand
etched planes 29a min.
theasetching However,
to of since
proceed,
consequence the
a longer
KOH structures
etching(110)
increasing observed
could, in etch
Figure
eventually,
and (331) allow 11 for
rate. are the
wide enough of
correction forthe
the
etching to proceed, a longer etching could, eventually, allow for
etched planes as a consequence of KOH increasing (110) and (331) etch rate. the correction of the etched planes as
a consequence of KOH increasing (110) and (331) etch rate.
10
10
1543
Micromachines 2015, 6, 1534–1545
Micromachines 2015, volume, page–page

As
As aa summary,
summary, Figure
Figure 1212 presents
presents aa diagram
diagram relating
relating the
the etching
etching profiles
profiles obtained
obtained along
along the
the
etching evolution time,
etching evolution time,with
withthe
the
IPA IPA availability.
availability. In general,
In general, squaresquare patterns
patterns are transferred
are transferred to
to silicon
silicon
under aunder a squared-based
squared-based pyramidpyramid (transition
(transition from region
from region A to B)A to B) whenever
whenever a minimum
a minimum levellevel
of IPAof
IPA is maintained
is maintained in solution.
in solution. Oncontrary,
On the the contrary,
square square
basedbased pyramids
pyramids (region(region
A) may A)rearrange
may rearrange
along
along
etchingetching time
time into into polygons
n-side n-side polygons
(region (region C) if meanwhile
C) if meanwhile there is there
no IPAis available
no IPA available in the
in the solution.
solution. This transition
This transition is gradual is gradual
and, at any and,
givenattime,
any the
given time, shape
structure the structure shapeon
is dependent is profile
dependent
size andon
profile sizeContinuing
etch rate. and etch rate. Continuing
the etching untilthe
theetching
top mesa until the top mesa
is released is released
(optimal (optimal
etch time) etch time)
can stabilize the
can stabilize
octagonal thepyramidal
base octagonalshape
base pyramidal
(region D).shape (region D).

Figure
Figure 12.
12. Schematic
Schematic diagram
diagram of
of the
the evolution
evolution of
of silicon
silicon wet
wet etch
etch structures,
structures, under
under IPA
IPA influence,
influence, for
for
aa 10
10 μm
µm square mask and
square mask and the
the conditions
conditions depicted
depicted in
in Table
Table 1.
1.

4.
4. Conclusions
Conclusions
Results
Results demonstrate
demonstrate thatthatIPA
IPAavailability,
availability,and
andnotnotconcentration,
concentration, plays
playsan an
important
importantrolerole
in the
in
definition of the final structure. When working in an open system, where
the definition of the final structure. When working in an open system, where evaporation affects evaporation affects the
chemical
the chemical balance of the
balance etching
of the etching solution,
solution, weweshould
shouldtake takeinto
intoaccount
account volumes
volumes rather
rather than
than
concentrations. IPA directly reduces the etch rate for the (110) plane, comparatively
concentrations. IPA directly reduces the etch rate for the (110) plane, comparatively to the (100) to the (100)
plane.
plane. Therefore,
Therefore, longer
longer availability
availability of of IPA
IPA during
during aa reaction
reaction will
will originate
originate structures
structures with
with aa wider
wider
base. However, for a long enough etch, the complete evaporation of IPA will
base. However, for a long enough etch, the complete evaporation of IPA will allow the increase etchallow the increase etch
of
of the (110) plane, thus receding the base width, and (331) plane, converting
the (110) plane, thus receding the base width, and (331) plane, converting square shaped to octagonal square shaped to
octagonal shaped structures.
shaped structures. Nonetheless,Nonetheless,
if a steady if a steady
supply supply
of IPA of IPA isadded,
is constantly constantly added,
to assure itsto assure its
availability,
availability,
the same resultsthe same results are
are obtained as ifobtained as ifconcentration
a saturated a saturated concentration of IPApresent.
of IPA was always was always present.
An
An optimal volume of IPA is desired in order to obtain reproducible structures with
optimal volume of IPA is desired in order to obtain reproducible structures with the
the desired
desired
size and surface
size and surface smoothness.
smoothness.In Inananopen
opensystem,
system,IPAIPAcancanbe be added
added to the
to the solution
solution at any
at any moment
moment and
and its availability calculated from the evaporation rate. This fine tailoring of the
its availability calculated from the evaporation rate. This fine tailoring of the etching conditions in aetching conditions
in a dynamic
dynamic process
process maymay openopen up new
up new possibilities
possibilities forprecise
for the the precise control
control ofdesired
of the the desired structures.
structures.
Acknowledgments: This work was supported by FCT (Fundação para a Ciência e Tecnologia) in the scope of
Acknowledgments: This work was supported by FCT (Fundação para a Ciência e Tecnologia) in the scope of
the project PTDC/EBB-EBI/120334/2010 and by FEDER funds through the “Eixo I do Programa Operacional
the project PTDC/EBB-EBI/120334/2010 and by FEDER funds through the “Eixo I do Programa Operacional
Fatores
Fatores de
de Competitividade”
Competitividade” (POFC)
(POFC) QREN,
QREN, project
project reference
reference COMPETE:
COMPETE: FCOMP-01-0124-FEDER-020241.
FCOMP-01-0124-FEDER-020241.
First author thanks
First author thanks FCT
FCT for
for scholarship
scholarshipgrant
grantSFRH/BD/74975/2010.
SFRH/BD/74975/2010. INESC-MN
INESC-MN and
and acknowledges
acknowledges
Pest-OE/CTM/LA0024/2011
Pest-OE/CTM/LA0024/2011 project.
project.

1544
11
Micromachines 2015, 6, 1534–1545

Author Contributions: Tiago Monteiro and Susana Cardoso performed the main work of the dynamic wet
etching of silicon. Pamakštys Kastytis helped with the etching angles analysis. Luis Gonçalves, Graça Minas
and Susana Cardoso supervised the presented work. All authors have analyzed the results and findings.
Tiago Monteiro and Susana Cardoso have written the main manuscript and all authors reviewed the manuscript.
Conflicts of Interest: The authors declare no conflict of interest.

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