Journal of Micromechanics and Microengineering

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 Journal of Micromechanics and Microengineering

J. Micromech. Microeng. 31 (2021) 095002 (9pp) https://doi.org/10.1088/1361-6439/ac12a3

Nanoscale directional etching features

and mechanism of HF/HNO3 etchant
Biyou Peng1,∗, Hongbo Wang2,∗ and Haifeng Huang1
1
School of Materials Science and Engineering, Xihua University, Chengdu 610039, Sichuan,
People’s Republic of China
2
State Key Laboratory of Electronic Thin Films and Integrated Devices, University of Electronic Science
and Technology of China, Chengdu 610054, Sichuan, People’s Republic of China

E-mail: pby@mail.xhu.edu.cn, hongbowang@uestc.edu.cn and hongbowang@swjtu.edu.cn

Received 1 April 2021, revised 21 June 2021

Accepted for publication 8 July 2021
Published 22 July 2021

Abstract
Large-scale and periodic silicon nanostructure arrays are an essential component for various
functional devices. However, the conventional selective etching mechanism of specific crystal
faces for monocrystalline silicon generally achieves slope or vertical morphology, which greatly
limits the preparation of other morphology of silicon nanostructures. In this work, the
conventional isotropic etchant HF/HNO3 has successfully achieved nanoscale directional
etching and cambered morphology on monocrystalline silicon surface for the first time by
changing the synchronous process of oxidation and dissolution into an asynchronous process.
Based on the self-assembled monolayer colloidal crystal templates, large-area and high-quality
nanopore arrays are prepared on the monocrystalline silicon surface. Particularly, the directional
etching ability of HF/HNO3 etchant is further confirmed by combining with electron beam
lithography and scanning probe lithography technologies. Hence, this nanoscale directional
etching mechanism and etchants provide a promising strategy to achieve cambered morphology
nanopores on the monocrystalline silicon surface.
Keywords: nanofabrication, HF/HNO3 etchant, directional etching, nanostructure array,
self-assembly

(Some figures may appear in colour only in the online journal)

1. Introduction lithography (SPL) [16–18], colloidal lithography [19, 20],

self-assembly [21], nano-imprinting [22], and electrochemical
Large-scale and various silicon nanostructure arrays are etching [23]. In fact, most of them need further wet or dry
playing an irreplaceable role in many fields, including energy etching to form useable nanostructure arrays on bulk silicon
conversion and storage [1–3], photo-/electro-catalysis [4–6], materials [24]. Among them, dry etching, such as reactive ion
biochemical sensing [7–9], photoelectric devices [10], etc. etching (RIE) and plasma etching, are highly dependent on
Among them, the cambered nanopore arrays show signific- expensive equipment and poisonous reactant gas [25]. These
ant advantages in improving the light extraction and engin- unfavorable characteristics go against their extensive commer-
eering far-field pattern radiation in these functional devices cial application and laboratory investigation. Particularly, the
[11–13]. To achieve thses regular nanostructure arrays, various poor surface smoothness fabricated by these high energy beam
fabrication techniques have been developed, including optical machining and other material microremoving processes are
lithography, high energy beam machining (femtosecond laser, not suitable for practical application [13]. Hence, process eco-
focused ion beam, electron beam) [14, 15], scanning probe nomy and smooth surface are quite desirable in the fabrication
of cambered nanopore arrays for commercial applications.
Wet etching is regarded as a promising alternative approach
∗
Authors to whom any correspondence should be addressed. due to its simple, flexible and low-cost features. However, the

1361-6439/21/095002+9$33.00 1 © 2021 IOP Publishing Ltd Printed in the UK

J. Micromech. Microeng. 31 (2021) 095002 B Peng et al

directional etchants used in silicon etching, including alkali 2. Experimental materials and methods
metal hydroxides (NaOH, KOH), [17, 26] amino hydrox-
ide (NH4 OH, (CH3 )4 NOH) [27], and ethylenediamine/cat- 2.1. Experimental materials
echol/water mixtures (called EDP or EPW) [28], are based on
All the etching samples were performed on p-type Si(100) sub-
the selective etching for specific crystal faces (such as Si(100)
strates (1 × 1 cm, all cut from a 6 inches Si(100) wafer) with
and Si(110)). Namely, the etching rate in one crystal face is
a thickness of 0.5 mm and resistivities of 1–10 Ω cm (MEMC
much faster than that in other directions (such as Si(111) is the
Electronic Materials, Inc., USA). The polystyrene (PS) col-
so-called etching ‘stop plane’) [29]. Those corrosion-resistant
loidal spheres with a diameter of 500 nm were all purchased
Si(111) crystal faces should gradually be exposed due to their
from BaseLine ChromTech Research Centre (Tianjin, China).
slowest etching rate with the extension of etching time. As a
All the self-assembled PS MCC samples were performed on
result, the sidewall of obtained nanostructures usually presents
Si(100) surface. Analytical grade nitric acid (HNO3 , 68%
a slope or vertical morphology due to the Si(111) plane is at
(w/w)) and hydrofluoric acid (HF, 40% (w/w)) purchased from
an angle of 54.74◦ with the Si(100) plane and 90◦ with the
Sinopharm Chemical Reagent Co., Ltd. All the solution pre-
Si(110) plane, respectively [30]. Hence, these conventional
paration and etching processes are operated in a polyethylene
directional etchants are difficult to fabricate cambered nano-
beaker under 25 ◦ C (the temperature was controlled by water
pore arrays on monocrystalline silicon surface. In this regard,
bath heater) and without any agitation.
it is highly desired to develop a new etching mechanism and
corresponding directional etchants rather than still employ
the common selective etching mechanism of specific crystal 2.2. Characterization
faces.
HF/HNO3 solution is a typical isotropic etchant, which All the SEM images were characterized using a field-emission
does not have the selective etching effect on the specific scanning electron microscope (SEM, FEI, Nova NanoSEM
crystal surface of silicon [31, 32]. Hence, they are always 450, Netherlands). The AFM image is scanned in a vacuum
used to remove contaminants, lattice damage, process dam- by using silicon nitride tips (MLCT, Veeco Instruments Inc.,
age, or improve the surface roughness of monocrystal silicon Plainview, NY, USA) with a spring constant of 0.1 N m−1
in the semiconductor industry due to its obvious advantages in contact mode. The microscopic crystal structures of the
of being simple, fast, and compatible with integrated cir- as-fabricated nanopores on the silicon surface were detected
cuits manufacturing processes [33–35]. In the past 60 years, by cross-sectional transmission electron microscope (XTEM)
many researchers successfully fabricated various microstruc- (Tecnai G2 F20, FEI, USA). The XTEM samples of the fab-
tures with HF/HNO3 etchant [36–39]. However, when the size ricated area were prepared using a FIB (NanoLab 400, FEI,
of functional structures is reduced to the nanoscale, the inher- USA) miller. Before FIB cutting, an epoxy polymer passiva-
ent isotropic etching property of HF/HNO3 etchants seriously tion layer was deposited on the sample surface to protect the
affects the etching morphology, which leads to few nanostruc- surface from damage in the subsequent FIB cutting process.
tures can be fabricated with HF/HNO3 etchants [31, 40]. Until
recently, Qian et al find that the HNO3 -rich HF/HNO3 solution 2.3. Nanofabrication method of HF/HNO3 etchant
exhibits an obvious and controllable selective etching effect
for the amorphous silicon and deformation silicon [40]. How- Periodic nanopore arrays are critical components for the fun-
ever, the nanoscale directional etching of HF/HNO3 etchant on damental and applied studies in various functional devices
original monocrystalline silicon is still not achieved due to its [41, 42]. Here, we employ the unconventional HF/HNO3
ultrafast etching rate (350–610 µm min−1 ) and intrinsic iso- etchant to prepare the periodic nanopore array on silicon
tropic etching feature [40]. This is because the mask layer on surface with the assist of MCC templates for the first time
the silicon surface can be quickly removed and loses its pro- (figures 1(a)–(e)). The main reason for using MCCs as the
tective ability. As a result, these adverse features greatly limit template for the directional etching investigation of HF/HNO3
its nanofabrication applications. etchant is that the preparation and subsequent nanofabrica-
In this work, we achieve the directional etching of tion of MCCs are simple, low-cost, and flexible for large-
HF/HNO3 etchant on intact monocrystalline silicon by max- scale practical application [21]. Particularly, the materials
imizing the asynchronization of the oxidation and dissolution of colloidal particles can be chosen from polymer (poly-
process HF/HNO3 etchant. Combing with the self-assembled methyl methacrylate, polystyrene), metal (Au, Ag), dielectric
large-scale monolayer colloidal crystal (MCC) templates [21], materials (SiO2 ). Furthermore, the morphology of colloidal
high-quality nanopore arrays are successfully fabricated on the particles is also multifarious, including spherical, triangle,
monocrystalline silicon surface. The detailed directional etch- stellate, tetragonal, and so on [43]. These particular advantages
ing features and mechanism of HF/HNO3 etchant are investig- combined with the directional etching ability of HF/HNO3
ated. Besides, we further confirm its directional etching abil- etchant provide a promising commercialization strategy for
ity of HF/HNO3 etchant through electron beam lithography the preparation of diversified functional structures with
(EBL) and SPL technologies. MCCs.

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J. Micromech. Microeng. 31 (2021) 095002 B Peng et al

Figure 1. Directional etching of HF/HNO3 etchant. (a)–(e) Schematic diagrams showing the fabrication process of nanopore array with
specific HF/HNO3 etchant. (f) SEM image of periodic nanopore array achieved by 1/100 (volume ratio) HF/HNO3 etching for 30 s (the
corresponding SEM images are listed in figures S1–S3).

Figure 1 shows the detailed fabrication strategy of peri- 3. Results and discussion
odic nanopore arrays with the HF/HNO3 etchant. The
detailed material and characterization infromation are lis- 3.1. Directional etching features of HF/HNO3 etchant
ted in the supporting information (S1 and S2) (available
For wet etching, the solution proportioning, etching time
online at stacks.iop.org/JMM/31/095002/mmedia). Firstly, a
and the temperature usually have a significant effect on the
high-quality and large-area MCCs layer composed of PS
final nanostructures. For instance, the morphology of nano-
nanoparticles is self-assembled on the silicon surface with
structures is highly dependent on the solution proportion-
the interfacial capillary-force-driven self-assembly approach
ing and etching time, while the etching rate and surface
(figures 1(a) and S1) [21]. It is noted that the formed natural
roughness are related to etching temperature. Certainly, there
MCCs are tightly packed hexagon structures, which should be
may be more complex synergies between them. Hence, we
etched to expose the space of colloidal interparticle for sub-
firstly investigate the directional etching features of HF/HNO3
sequent HF/HNO3 etching. Here, we employ the RIE method
etchant through regulating the etching parameters to build
to decreasing the diameter of colloidal particles to expose the
a controllable nanofabrication approach. Besides, we fur-
space of the colloidal interparticle. After etching the MCC-
ther characterize the obtained nanostructures by using trans-
covered silicon samples in the RIE system for 8 min with
mission electron microscopy (TEM) to confirm the crystal
30 sccm O2 flow rate and 30 W power, the diameter of PS
structures.
nanoparticles can be decreased from 500 nm to about 410 nm
(figures 1(b) and S2). Subsequently, an 20 nm thick Cr layer is
deposited on the etched sample to cover and protect the silicon 3.1.1. Effects of HF/HNO3 proportioning on nanostructures.
surface (figure 1(c)). Certainly, the other metal films (such as To achieve useable nanostructure arrays, the etchants must
Ni and Ti) that cannot be etched by the HF/HNO3 etchant also have the ability of directional etching for bulk materials. How-
can be chosen other than Cr metal film. After further remov- ever, the conventional experiment results are indicated that the
ing the MCC templates with acetone in an ultrasonic pool for HF/HNO3 solution is an intrinsic isotropic etchant. Hence, we
∼5 min, a periodic nanopore template is formed on the sil- first investigate the optimal proportioning range of HF/HNO3
icon surface (figures 1(d) and S3), which serves as a protective solution to achieve directional etching of silicon. As shown in
layer in HF/HNO3 solution. Finally, the Cr mask covered sil- figure 2(a), the HF/HNO3 solution indeed exhibits typical iso-
icon sample is immersed in the HF/HNO3 etchant without any tropic etching property when the volume ratio of HF/HNO3
agitation (23 ◦ C, water bath heating) for 20–180 s. After taking solution exceeds 1/30, which is consistent with the represent-
out the etched sample and cleaning it with the deionized water ative experimental results [44]. Such results suggested that
for ∼3 min, a periodic silicon nanopore array can be formed the oxidized Si by HNO3 are etched away immediately by
on the bulk silicon surface (figure 1(e)). The experiment res- the HF molecules. In other words, oxidation and dissolution
ults demonstrate that the HF/HNO3 etchant indeed can achieve almost a synchronous process. This is also the main reason of
directional etching on the silicon surface (figure 1(f)) and HF/HNO3 solution shows intrinsic isotropic etching property.
achieve nonplanar nanostructure (the inset in figure 1(f)), thus If the dissolution process of oxidized silicon can be suppressed
providing a promising strategy for fabricating various periodic in HF/HNO3 solution, the etchant should exhibit directional
cambered structure arrays. etching ability for silicon.

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J. Micromech. Microeng. 31 (2021) 095002 B Peng et al

Figure 2. Typical SEM images of as-fabricated nanostructures on Si(100) surface. (a) Rough silicon surface formed in 1:1–1:20 HF/HNO3
etchants. (b) Shallow pit arrays obtained in 1:30 HF/HNO3 etchants. (c) Poor-quality cambered nanopore arrays obtained in 1:40 HF/HNO3
etchants. (d) High-quality cambered nanopores obtained in 1:50–1:200 HF/HNO3 etchants. (e) Periodic cambered nanopores obtained in
1:100 HF/HNO3 etchants. (f) Aspect ratios of cambered nanopores obtained in different volume ratio of HF/HNO3 etchants. The etching
time of sample a–d are 30 s, while sample e is 120 s.

Therefore, we further decrease the HF concentration of HF/HNO3 solution, as shown in figure 2(e). As can be seen,
HF/HNO3 solution to verify this assumption. As expected, the aspect ratios of as-fabricated nanopores increase with the
periodic silicon nanostructures can be obtained in 1/30, 1/40, further dilution of HF. However, when the volume ratio of
1/50, 1/100 and 1/200 HF/HNO3 solution (figures 2(c)–(e), the HF solution is further diluted to 1/200, the aspect ratio of
detailed parameters, such as diameter, depth, lateral and ver- nanopores decreases rapidly from 0.52 to 0.28. This distinct
tical etch rate are listed in table S1). However, the surface qual- attenuation demonstrates the over-diluted HF goes against the
ity of obtained silicon nanostructures in 1/40 HF/HNO3 solu- improvement of the directional etching ability of HF/HNO3
tion is poor due to its relatively fast etching rate (figure 2(c)). etchant. Hence, the proportioning range of HF/HNO3 solution
Namely, the asynchronized degree of the oxidation and dis- to achieve directional etching of silicon is from 1/40 to 1/200,
solution process needs to be further enlarged through decreas- while the maximum aspect ratio only can be obtained in 1/100
ing HF concentration in HF/HNO3 solution. As shown in HF/HNO3 solution. Based on this fabrication strategy, the
figures 2(d) and (e), the surface quality of fabricated nano- high-quality and large-scale nanopore arrays can be formed
structures is smooth and without the over-etching features on Si(100) surface (figure 2(f)).
when the volume ratio of HF/HNO3 solution was further
decreased to 1/50-1/200. With the increase of etching time,
the formed nanopores gradually became shallow (figure 2(e)). 3.1.2. Effects of etching time on nanostructures. The
Therefore, the tipping point where the formation and removal HF/HNO3 solution exhibit obvious directional etching ability
of the oxidized silicon are equal may achieve when the pro- within 1/40–1/200 volume ratio rather than isotropic etching
portioning of HF/HNO3 solution reach to about 1/30. Because property. Namely, the HF/HNO3 solution can serve as a new
there is without periodic nanostructures on Si(100) surface directional etchant to fabricate various nanostructures through
if the proportioning of HF/HNO3 solution greater than 1/30 the wet etching technique. Hence, we further investigate the
(figure 2(a)). Until the HF/HNO3 etchant is further diluted to effects of etching time on the morphology of nanopores to bet-
1/30, the sample surface began to form shallow and periodic ter understand the directional etching features of HF/HNO3
nanostructures (∼22 nm deep and 465 nm wide), as shown in solution.
figures 2(b) and (f). Finally, these results confirm that decreas- Figures 3(a)–(e) shows the cross-section SEM images of
ing the HF concentration in HF/HNO3 solution indeed changes as-fabricated nanopores after etching for 20, 30, 60, 120 and
the synchronous oxidation and dissolution process, which is a 180 s in 1/100 HF/HNO3 solution. These results indicate
feasible strategy to achieve its directional etching ability for that although nanopores can be obtained over a wide time
silicon. range, their morphology exhibit obvious dependence on etch-
The aspect ratio of as-fabricated nanostructures is the key ing time. On the one hand, the etching depth increases rapidly
index to evaluate the directional etching ability of etchants to ∼252 nm within 30 s, thereafter which gradually become
[35]. To better evaluate the directional etching property of shallow with a decay rate of about 1.1 nm s−1 (figure 3(g)).
HF/HNO3 solution, we plot the correlation between the To better understand the etching process, we plot the curve of
aspect ratios of as-fabricated nanopores and volume ratios of etching time and the relative etching rate based on the obtained

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J. Micromech. Microeng. 31 (2021) 095002 B Peng et al

Figure 3. Effect of etching time on the nanopores. (a)–(e) Cross-section SEM images of nanopores after etching for 20, 30, 60, 120, 180 s
in 1/100 HF/HNO3 solution. (f) Large-scale and high-quality cambered nanopore arrays (etching by 1/100 HF/HNO3 solution for 30 s).
(g) Interrelation between etching time and etching depth as well as diameter of nanopores. All the etching experiments operate under 23 ◦ C.
(h) Interrelation between the etching time and the relative etching rate of cambered nanopores. (i) Effect of etching time on the aspect ratio
of nanopores.

experimental data, as shown in figure 3(h). With the increas- 3.1.3. Effects of etching temperature on nanostructures.
ing of etching time, the changes of the relative etching rate of The etching temperature is a key process parameter in chem-
cambered nanopores show two different stages: the first stage ical etching, as the etching rate, and surface roughness of nano-
is from 10 to 30 s, the relative etching rate is positive and structures are highly dependent on it. Generally, high etching
changes from 7.5 to 9.2 nm s−1 ; the second stage lies between temperature can increase the etching rate of etchants, while
40 and 180 s, the etching rate is negative and remain at about the surface roughness of as-fabricated nanostructures trends
−1 nm s−1 . Combined with the SEM results, we can find the to be rough. Here, we also investigate the effects of etching
nanopore arrays are formed and deepen in the first stage under temperature on nanostructures in HF/HNO3 etchant. Firstly,
the synergistic effect of Cr mask and HNO3 -rich HF/HNO3 we find that the Cr mask layer generate obvious cracks and
etchant, thus we call the first stage as directional etching stage. bulges when the Cr template-covered silicon substrates were
Once the etching time is over 40 s, the depth of formed nan- immersed into 40 ◦ C HF/HNO3 etchant (V HF :V HNO3 = 1:100)
opores gradually trends to shallower. During this stage, the for 60 s. Then, after further removing the covered Cr mask
original directional etching was replaced by intrinsic isotropic layer, without obvious nanopores are formed on the silicon
etching of HF/HNO3 etchants. The details are demonstrated in surface (figure 4(c)). Namely, high etching temperatures go
the etching mechanism (section 3.2). against not only the mask protection but also the directional
Here, for ∼200 nm spacing MCC templates, the maximal etching of HF/HNO3 etchant. Subsequently, we further invest-
etching depth is about 252 nm, which can be achieved within igate the effect of low temperature on the HF/HNO3 etching
30 s in 1/100 HF/HNO3 solution. On the other hand, the dia- by controlling the etchant temperature in ice–water mixture
meter of nanopores is enlarged from 477 to 574 nm before (0 ◦ C). According to our observations, the color of samples
90 s and then tended to be constant (∼580 nm). Such lateral usually changes from light blue to dark blue, and finally to
etching character suggests although the isotropic etching abil- light blue with the increase of etching time at normal temper-
ity of HF/HNO3 solution is inhibited by the decrease of HF, atures and pressures. However, in 0 ◦ C HF/HNO3 etchants,
which still exhibits weak isotropic etching. Hence, prolonging the sample surface only showed slight color change within
the etching time is not conducive to the improvement of aspect the first 1 min. Until the next 1 min, the sample began to
ratios (figure 3(i)). show visible color changes. Such results indicate the low

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J. Micromech. Microeng. 31 (2021) 095002 B Peng et al

Figure 4. Typical SEM images of nanopore arrays obtained in 1/100 HF/HNO3 etchant. The etching temperature of (a)–(c) are 0, 23 ◦ C and
40 ◦ C, respectively. Among them, 23 ◦ C and 40 ◦ C were controlled by water bath heater, 0 ◦ C was hold by ice-water mixture. The etching
time of (b) and (c) are 60 s while the (a) is 120 s. The scale bar of all the insets are 500 nm.

Figure 5. XTEM detection on the as-fabricated silicon nanopores. (a) XTEM images of nanopore after being etched by 1/100 HF/HNO3
solution etching for 30 s. (b), (c) Enlarged images of side wall and bottom of the nanopore.

temperature greatly inhibits the etching kinetics process of Figure 5 displays the typical XTEM detection results of
HF/HNO3 etchants, which is consistent with the chemical the as-fabricated silicon nanopores. As can be seen, the
etching theory. Figure 4(a) shows the typical microtopography internal surface of the nanopore exhibits smooth transition
of nanopore arrays (∼170 nm deep), which was obtained in (figure 5(a)), which indicates that the etching process is
0 ◦ C HF/HNO3 etchants after etching for 120 s. The quality of relatively gentle in HF/HNO3 solution. Such a smooth sur-
the nanopores obtained at low temperature is similar to that at face is beneficial to prepare the various continuous functional
room temperature (23 ◦ C, figure 4(b)), but the etching time film, thereby achieving repeatable and stable performance.
is at least two times longer. Hence, room temperature may The enlarged XTEM image and SAD pattern of side wall
be propitious to achieve the nanofabrication with HF/HNO3 (figure 5(b)) and bottom (figure 5(c)) of the nanopore indicate
etchant. Besides, chemical etching under room temperature that its original monocrystal structures are perfectly preserved
does not need to provide additional energy and equipment, during the etching process. Hence, the HF/HNO3 solution is
which is more conducive to process integration and large-scale a nondestructive etchant, various smooth and monocrystalline
commercial production. nanostructures can be fabricated conveniently.

3.2. Directional etching mechanism of HF/HNO3 etchant

3.1.4. TEM characterization of nanostructures. The
amorphous and monocrystal nanostructures usually exhibit HF/HNO3 solution is a typical isotropic etchant for silicon
significant performance differences in super-sensitive optical substrates, but it exhibits obvious directional etching features
and electron devices [45]. Hence, accurate characterization when the volume ratio of HF/HNO3 solution is decreased to
of the crystal structure of nanostructures is very import- 1/40. Namely, such an HNO3 -rich HF/HNO3 solution exhibits
ant for their practical applications. Here, to better evalu- a distinct difference in etching mechanism compare with the
ate the structural features of nanostructures fabricated by common HF/HNO3 solution. In this regard, it is urgent to need
HF/HNO3 etchant, we further analyze their crystal structure to understand the directional etching mechanism of HF/HNO3
by using the XTEM and selected-area diffraction (SAD). etchant to promote its wide application.
The XTEM samples are prepared by focused ion beam tech- Figure 6(a) shows the schematic diagrams of the dir-
nique after depositing a protective glue layer on the top of the ectional etching mechanism of HF/HNO3 etchant. Firstly,
samples. the HF/HNO3 solution remains its isotropic etching ability

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J. Micromech. Microeng. 31 (2021) 095002 B Peng et al

Figure 6. Directional etching mechanism of HF/HNO3 etchant. (a) Schematic diagrams showing the directional etching mechanism of
HF/HNO3 etchant. (b) SEM image of Cr mask pattern. (c), (d) SEM images shows the lateral etching process of silicon substrates in 1/100
HF/HNO3 etchant.

(figure 3), but which is inhibited greatly by the dilution of 3.3. Application of HF/HNO3 etchant
HF. Because the synchronous oxidation and dissolution pro-
For many high-performance optical, electron and sensing
cess is the main reason for isotropic etching of HF/HNO3
devices, their matched functional structures usually need ultra-
solution. The dilution of HF does not completely change
precision lithography technology [46]. Here, we employ the
the intrinsic isotropic etching feature of HF/HNO3 solution
EBL to confirm the directional etching ability of HF/HNO3
but turns the synchronous oxidation and dissolution process
etchant (figure 7(a)). Firstly, an electron beam photoresist
into asynchronous process, thereby decreasing the etching
(PMMA) is coated on silicon surface via spin coating method
rate of silicon underneath the mask layer. For such HNO3 -
(coating with 500 rmp for 10 s, and thinning with 2500 rmp
rich HF/HNO3 solution, the etching rate is limited by the HF
for 45 s), and then drying it at 130 ◦ C–150 ◦ C for 5 min.
concentration. Hence, the etching process preferentially takes
Secondly, the PMMA coated silicon samples are exposed and
place on the exposed silicon surface rather than the covered
developed by the standard electron-beam lithography method
silicon surface underneath the Cr mask layer (stage II and
[47]. Subsequently, 20 nm thick Cr mask patterns are depos-
figure 6(b)), thereby form obvious nanostructures. However,
ited by metal evaporation and lift-off processes. After further
the silicon surface underneath the Cr mask layer is gradually
etching these samples in HF/HNO3 etchant for 30 s, various
exposed to the HF/HNO3 solution with the increase of etch-
nanostructures can be fabricated on the silicon surface. Here,
ing time (stage III and figure 6(c)). When the covered silicon based on this approach, some letters (figure 7(b)), and com-
surface is just fully exposed, the nanopores reach maximum plex pattern (figure 7(c)) have been achieved on the silicon
etching depth. Subsequently, the etching depth of nanopores surface.
is gradually shallow due to the etching rate of the side wall is Later, we further confirm the directional etching ability
about two times (double-sided etching) than that of the bot- of HF/HNO3 etchant through combing with the SPL. The
tom silicon surface (stage IV and figure 6(d)). At this stage, whole fabrication process includes three main steps: Cr film
the mask layer is no longer protects the underneath silicon deposition, tip scratching, and HF/HNO3 etching. Among
materials. them, the tip scratching processes were finished on the self-
In brief, the decrease of volume ratio of HF solution is developed in-situ nanomechanical system by using a 1 µm
conducive to promote the asynchronous oxidation and dis- (nominal radius) spherical diamond tip. The film deposition
solution process, thus ensuring that the Cr mask layer can and HF/HNO3 etching processes are the same as in previ-
protect the covered silicon surface. This unique wet etching ous experiments. After clearing the as-fabricated samples with
mechanism provides a new idea for the development of direc- deionized water, a high-quality nanochannel is successfully
tional etchants. formed on the silicon substrate (figures 7(d) and (e)).

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J. Micromech. Microeng. 31 (2021) 095002 B Peng et al

Figure 7. Expanded application of HF/HNO3 etchant. (a) Schematic diagrams show the EBL assisted HF/HNO3 etching process. (b),
(c) Optical (grayness) and SEM (black) images of nanopatterns fabricated with the EBL assisted HF/HNO3 etching method. The scale bars
are 20 µm. (d) Optical image of nanochannel array fabricated with the SPL assisted HF/HNO3 etching method. (e) AFM image of the
as-fabricated nanochannel.

4. Conclusion ORCID iD

In summary, we develop a new directional etchant by chan- Hongbo Wang  https://orcid.org/0000-0002-8031-5533

ging the synchronous process of oxidation and dissolution of
HF/HNO3 into an asynchronous process. The etching mech-
anism of this HNO3 -rich HF/HNO3 etchant is based on the References
synergistic effect of controllable isotropic etching and mask
effect, which is different from the conventional selective etch- [1] Huang G, Han J, Lu Z, Wei D, Kashani H, Watanabe K and
ing mechanism. Based on this directional etchant and mech- Chen M 2020 Ultrastable silicon anode by
anism, an cambered morphology can be achieved on the sil- three-dimensional nanoarchitecture design ACS Nano
14 4374–82
icon surface. Particularly, the directional etching ability of
[2] Yoshikawa K et al 2017 Silicon heterojunction solar cell with
HNO3 -rich HF/HNO3 etchant is confirmed by combining with interdigitated back contacts for a photoconversion
EBL and SPL technologies. Furthermore, various nanostruc- efficiency over 26% Nat. Energy 2 1–8
tures, such as nanopore array, letters, nanochannels and other [3] Liu Z, Sofia S E, Laine H S, Woodhouse M, Wieghold S,
complex patterns are successfully achieved on the monocrys- Peters I M and Buonassisi T 2020 Revisiting thin silicon for
photovoltaics: a technoeconomic perspective Energy
talline silicon surface by using this new directional etchant.
Environ. Sci. 13 12–23
Hence, this directional etching mechanism and etchant provide [4] Zhao Y, Yu J, Xu G, Sojic N and Loget G 2019 Photoinduced
a promising strategy to achieve cambered morphology nano- electrochemiluminescence at silicon electrodes in water J.
pores on the monocrystalline silicon surface. Am. Chem. Soc. 141 13013–6
[5] Luo Z, Wang T and Gong J 2019 Single-crystal silicon-based
electrodes for unbiased solar water splitting: current status
Data availability statement and prospects Chem. Soc. Rev. 48 2158–81
[6] Zhang Z, Wang Y, Stensby Hansen P A, Du K, Gustavsen K R,
All data that support the findings of this study are included Liu G, Karlsen F, Nilsen O, Xue C and Wang K 2019 Black
within the article (and any supplementary files). silicon with order-disordered structures for enhanced light
trapping and photothermic conversion Nano Energy
65 103992
Acknowledgments [7] Li R, Mao H, Shi M, Zhao Q, Chen D and Xiong J 2020
Parahydrophobic 3D nanohybrid substrates with two
pathways of molecular enrichment and multilevel plasmon
We gratefully acknowledge the support from the Sci-
hybridization Sens. Actuators B 320 128357
ence and Technology Plan Project of Sichuan Province [8] Wang H, Jiang X, Lee S T and He Y 2014 Silicon
(2019YFG0511), the Education Department of Sichuan nanohybrid-based surface-enhanced Raman scattering
Province Project (11ZA001), the National Natural Science sensors Small 10 4455–68
Foundation of China (52003037) and the China Postdoctoral [9] Moeinian A, Gur F N, Gonzalez-Torres J, Zhou L,
Murugesan V D, Dashtestani A D, Guo H, Schmidt T L and
Science Foundation (2020M673176). Strehle S 2019 Highly localized sers measurements using
single silicon nanowires decorated with DNA
origami-based SERS probe Nano Lett. 19 1061–6
Notes [10] Um H D, Solanki A, Jayaraman A, Gordon R G and Habbal F
2019 Electrostatically doped silicon nanowire arrays for
The authors declare no conflict of interest. multispectral photodetectors ACS Nano 13 11717–25

8
J. Micromech. Microeng. 31 (2021) 095002 B Peng et al

[11] Jiang C, Li X, Tian H, Wang C, Shao J, Ding Y and Wang L [31] Chen C Y and Wong C P 2015 Unveiling the shape-diversified
2014 Lateral flow through a parallel gap driven by surface silicon nanowires made by HF/HNO3 isotropic etching with
hydrophilicity and liquid edge pinning for creating the assistance of silver Nanoscale 7 1216–23
microlens array ACS Appl. Mater. Interfaces 6 18450–6 [32] Wu L, Zhang P, Feng C, Gao J, Yu B and Qian L 2020
[12] Li X, Ding Y, Shao J, Tian H and Liu H 2012 Fabrication of Scanning probe-based nanolithography: nondestructive
microlens arrays with well-controlled curvature by liquid structures fabricated on silicon surface via distinctive
trapping and electrohydrodynamic deformation in anisotropic etching in HF/HNO3 mixtures J. Mater. Sci.
microholes Adv. Mater. 24 165–9 56 3887–99
[13] Li X, Tian H, Ding Y, Shao J and Wei Y 2013 Electrically [33] Zandi K, Arzi E, Izadi N, Mohajerzadeh S, Haji S, Abdi Y and
templated dewetting of a UV-curable prepolymer film for Asl Soleimani E 2006 Study of bulk micromachining for
the fabrication of a concave microlens array with <100> silicon Eur. Phys. J. Appl. Phys. 35 7–12
well-defined curvature ACS Appl. Mater. Interfaces [34] Hilleringmann U 2004 Silizium-halbleitertechnologie:
5 9957–82 grundlagen mikroelektronischer integrationstechnik
[14] Zhang Y L, Tian Y, Wang H, Ma Z C, Han D D, Niu L G, Ätzösungen Fur Die Nasschemische Strukturierung (Berlin:
Chen Q D and Sun H B 2019 Dual-3D femtosecond laser Springer) pp 68–71
nanofabrication enables dynamic actuation ACS Nano [35] Tool C J J, Coletti G, Granek F J and Hoornstra J 2005 17%
13 4041–8 mc-Si solar cell efficiency using full in-line processing with
[15] Li W, Zhan X, Song X, Si S, Chen R, Liu J, Wang Z, He J and improved texturing and screen-printed contacts on
Xiao X 2019 A review of recent applications of ion beam high-ohmic emitters Presented at the 20th European
techniques on nanomaterial surface modification: design of Photovoltaic Solar Energy Conf. and Exhibition vol 6 p 10
nanostructures and energy harvesting Small 15 e1901820 [36] Bauhuber M, Mikrievskij A and Lechner A 2013 Isotropic wet
[16] Garcia R, Knoll A W and Riedo E 2014 Advanced scanning chemical etching of deep channels with optical surface
probe lithography Nat. Nanotechnol. 9 577–87 quality in silicon with HNA based etching solutions Mater.
[17] Wang H, Yu B, Jiang S, Chen C and Qian L 2018 Simple and Sci. Semicond. Proc. 16 1428–33
low-cost nanofabrication process of nanoimprint templates [37] Negi S and Bhandari R 2012 Silicon isotropic and anisotropic
for high-quality master gratings: friction-induced selective etching for MEMS applications Microsyst. Technol.
etching Appl. Surf. Sci. 454 23–9 19 203–10
[18] Hui F and Lanza M 2019 Scanning probe microscopy for [38] Lee J K, Choi J C, Jang W I, Kim H-R and Kong S H 2012
advanced nanoelectronics Nat. Electron. 2 221–9 Electrowetting lens employing hemispherical cavity formed
[19] Wang H et al 2021 Low field gradient and highly enhanced by hydrofluoric acid, nitric acid, and acetic acid etching of
plasmonic nanocavity array for supersensitive silicon Japan. J. Appl. Phys. 51 06FL05
determination of multiple hazardous chemical residues J. [39] Hamzah A A, Abd Aziz N, Yeop Majlis B, Yunas J, Dee C F
Phys. Chem. C 125 4710–9 and Bais B 2012 Optimization of HNA etching parameters
[20] Wang Y, Zhang M, Lai Y and Chi L 2018 Advanced colloidal to produce high aspect ratio solid silicon microneedles J.
lithography: from patterning to applications Nano Today Micromech. Microeng. 22 095017
22 36–61 [40] Wang H, Deng C, Xiao C, Liu L, Liu J, Peng Y, Yu B and
[21] Wang H et al 2020 Interfacial capillary-force-driven Qian L 2019 Fast and maskless nanofabrication for
self-assembly of monolayer colloidal crystals for high-quality nanochannels Sens. Actuators B 288 383–91
supersensitive plasmonic sensors Small 16 e1905480 [41] Son T, Lee D, Lee C, Moon G, Ha G E, Lee H, Kwak H,
[22] Liu J, Pang B, Xue R, Li R, Song J, Zhao X, Wang D, Hu X, Cheong E and Kim D 2019 Superlocalized
Lu Y and Wang L 2020 Sacrificial layer-assisted nanoscale three-dimensional live imaging of mitochondrial dynamics
transfer printing Microsyst. Nanoeng. 6 1–10 in neurons using plasmonic nanohole arrays ACS Nano
[23] Lei Z, Liu L, Zhao H, Liang F, Chang S, Li L, Zhang Y, Lin Z, 13 3063–74
Kroger J and Lei Y 2020 Nanoelectrode design from [42] Baek S W, Molet P, Choi M J, Biondi M, Ouellette O, Fan J,
microminiaturized honeycomb monolith with ultrathin and Hoogland S, Garcia De Arquer F P, Mihi A and Sargent E H
stiff nanoscaffold for high-energy micro-supercapacitors 2019 Nanostructured back reflectors for efficient colloidal
Nat. Commun. 11 1–10 quantum-dot infrared optoelectronics Adv. Mater.
[24] Bhushan B 2010 Introduction to micro-/nanofabrication 31 1901745
Handbook of Nanotechnology (Berlin: Springer) pp 231–65 [43] Xu W, Li Z and Yin Y 2018 Colloidal assembly approaches to
[25] Nojiri K 2015 Mechanism of dry etching Dry Etching micro/nanostructures of complex morphologies Small
Technology for Semiconductors (Berlin: Springer) pp 11–30 14 e1801083
[26] Wang H, Yu B, Jiang S, Jiang L and Qian L 2017 [44] Kulesza G, Panek P and Zie˛ba P 2014 Time efficient
UV/ozone-assisted tribochemistry-induced nanofabrication texturization of multicrystalline silicon in the HF/HNO3
on Si(100) surfaces RSC Adv. 7 39651–6 solutions and its effect on optoelectronic parameters of
[27] Zhou C, Li J, Wu L, Guo G, Wang H, Chen P, Yu B and solar cells Arch. Civ. Mech. Eng. 14 595–601
Qian L 2018 Friction-induced selective etching on silicon [45] Singh J 2007 Structural properties of semiconductors
by TMAH solution RSC Adv. 8 36043–8 Electronic and Optoelectronic Properties of Semiconductor
[28] Kovacs G T A, Maluf N I and Petersen K E 1998 Bulk Structures (Cambridge: Cambridge University Press)
micromachining of silicon Proc. IEEE 86 1536–51 pp 1–41
[29] Guo J, Xiao C, Peng B and Qian L 2015 [46] Hu G, Edwards H and Lee M 2019 Silicon integrated circuit
Tribochemistry-induced direct fabrication of nondestructive thermoelectric generators with a high specific power
nanochannels on silicon surface RSC Adv. 5 100769–74 generation capacity Nat. Electron. 2 300–6
[30] Guo J, Yu B, Chen L and Qian L 2015 Nondestructive [47] Wang Y et al 2020 Record-low subthreshold-swing
nanofabrication on Si(100) surface by negative-capacitance 2D field-effect transistors Adv. Mater.
tribochemistry-induced selective etching Sci. Rep. 5 1–7 32 e2005353