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Formation of three-dimensional GaAs


microstructures by combination of wet and
metal-assisted chemical...

Article in physica status solidi (RRL) - Rapid Research Letters · April 2014
DOI: 10.1002/pssr.201409046

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Phys. Status Solidi RRL, 1–4 (2014) / DOI 10.1002/pssr.201409046

Formation of three-dimensional GaAs www.pss-rapid.com


microstructures by combination
of wet and metal-assisted chemical etching
A Ri Lee**, 1, Jungkil Kim**, 2, Suk-Ho Choi2, and Jae Cheol Shin*, 1
1
Photonic Bioresearch Center, Korea Photonics Technology Institute, Gwangju 500-779, South Korea
2
Department of Applied Physics, College of Applied Science, Kyung Hee University, Yongin 446-701, South Korea

Received 25 January 2014, revised 17 February 2014, accepted 17 February 2014


Published online 24 February 2014

Keywords GaAs, wet etching, metal-assisted chemical etching, 3D microstructures, micropillars, microcones, microhole arrays,
Au patterns

**
Corresponding author: e-mail jcshin@kopti.re.kr, Phone: +82 62 605 9282, Fax: +82 62 605 9549
**
These authors contributed equally to this work.

Previously, plasma-enhanced dry etching has been used to [HF] : [H2O2] : [EtOH] as an etching solution, and their taper
generate three-dimensional GaAs semiconductor structures, angle can be tuned by changing the molar ratio of the etching
however, dry etching induces surface damages that degrade solution. In addition, GaAs microholes are formed when UV
optical properties. Here, we demonstrate the fabrication me- light is illuminated during the etching process. Since the wet
thod forming various types of GaAs microstructures through etching process is free of the surface damage compared to the
the combination etching process using the wet-chemical solu- dry etching process, the GaAs microstructures demonstrated
tion. In this method, a gold (Au)-pattern is employed as an et- to be well formed here are promising for the applications of
ching mask to facilitate not only the typical wet etching but III–V optoelectronic devices such as solar cells, laser diodes,
also the metal-assisted chemical etching (MacEtch). High- and photonic crystal devices.
aspect-ratio, tapered GaAs micropillars are produced by using

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1 Introduction The formation of semiconductor mi- to generate the aforementioned structures. Plasma-assisted
cro/nanostructures of various aspect ratios and surface dry etching process (i.e., RIE), however, entails ion colli-
morphologies is increasingly important in many applica- sions on the semiconductor, resulting in atomically rough
tions [1–4]. In III–V compound semiconductors, control of etched surface which degrades the optical properties of the
the surface structures is essential to improve the function- semiconductor significantly [12]. Alternatively, metal-
ality of the optical devices. For example, high-aspect-ratio assisted chemical etching (MacEtch) which is an anisot-
tapered pillar array changes the refractive indices gradually ropic etching method by using a metal catalyst has been
from air to semiconductor, providing excellent antireflec- employed to form high-aspect-ratio semiconductor struc-
tion of high-efficiency solar cells [5]; cone-shaped struc- tures [13]. The MacEtch can achieve a lateral resolution as
tures enhance light extraction efficiency of the light- high as 10 nm through various metal-pattern techniques in-
emitting diodes (LEDs) [6]; holes with smooth and vertical cluding electron (e)-beam lithography [14], colloidal li-
sidewalls reduce the propagation loss of the photonic crys- thography [15, 16], or nano-imprint lithography [17]. Mo-
tal waveguide [7, 8]. Moreover, the use of microstructures reover, the MacEtch is free of surface damage compared to
with refractive index matched to substrate is important for the RIE because high-energy ions cannot be involved dur-
enabling optimum light extraction efficiency in LEDs [9]. ing the etching process and the etching takes place at room
Recent experimental works with refractive-index matched temperature. Even though the MacEtch has been success-
photonic crystals [10] and colloidal microsphere arrays fully utilized in forming various types of silicon (Si) struc-
[11] had also been implemented on LEDs. Since wet chem- tures [18–20], only a few studies have been explored for
ical etching has a poor controllability of the etching direc- the III–V semiconductors [21, 22]. The main challenge of
tion, reactive ion etching (RIE) methods have been utilized the III–V MacEtch is to find the etching condition resulting

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim


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2 A Ri Lee et al.: Formation of three-dimensional GaAs microstructures

in a differential etch rate for the semiconductor with and with sonication). This process resulted in a dot-grid-
without metal present. Recently, Li et al. have provided the patterned Au layer on the GaAs substrate, where the di-
III–V MacEtch solution composed of [H2SO4]:[KMnO4] ameter of the exposed windows is 2 μm separated by a
[2]. In this solution, the KMnO4 which is the oxidizing spacing of 2 μm. The generated Au pattern can be seen in
agent with weak potential suppresses the nonmetal- Fig. 1(a). Note that the diffraction effects of the photo-
catalyzed etching while maintaining a reasonable etch rate lithography limit the accuracy of the 2-μm-sized pattern
in the presence of metal. Therefore, the semiconductor transfer, often providing slightly larger diameter of the
etching proceeds only with the gold (Au) catalyst, generat- opening windows. The patterned GaAs samples were im-
ing high-aspect-ratio GaAs nanowires. An increase of mersed in mixed solutions of HF (48–51 wt%), H2O2
KMnO4 ratio in the solution results in faster MacEtch of (50 wt%) and EtOH with various molar ratios, resulting in
the GaAs. In this Letter, we have developed a fabrication the formation of three different types of GaAs structures,
method for forming diverse three-dimensional (3-D) GaAs as shown in Fig. 1(b–d). For the UV illumination, UV
microstructures through the combination etching process in lamp (λ = 253.7 nm) with an intensity of 2 mW/cm2 was
the [HF] :[H2O2] :[EtOH] wet–solution. An Au pattern is used as the light source. The MacEtch process was
employed as an etching mask to facilitate not only the typ- performed at room temperature. The structural and mor-
ical wet etching but also the MacEtch. More importantly, phological properties of the MacEtch-generated GaAs
the combination etching method allows that the etching structures were examined by a Hitachi S-4700 scanning
proceeds with different etch rate at the exposed semicon- electron microscopy (SEM).
ductor surface and the metal–semiconductor interface,
generating three different types of GaAs microstructures: 3 Results and discussion Shown in Fig. 1(b)–(d) are
GaAs micro-pillars, micro-cones, and micro-hole arrays. the SEM images of the GaAs microstructures which are
The controlled surface morphologies of the GaAs are fur- formed after immersing the Au-patterned GaAs sample
ther examined with the different molar ratios of the etching (see Fig. 1a) in the [HF] :[H2O2]:[EtOH] solution. Three
solution. different types of representative structures are generated
from the identical Au-mesh pattern: micropillars with ta-
2 Experimental Epi-ready n-type (n = 2 × 1018/cm–3) pered ends (Fig. 1b), microcones (Fig. 1c), and microholes
GaAs(100) wafers were prepared (AXT Inc.) for the wet (Fig. 1d). In Fig. 1(b), one can notice that the etching takes
chemical etching process. Standard photolithography proc- place mostly at the metal–semiconductor interface which is
ess using a photomask was performed to generate a dot- a common phenomenon of the MacEtch. As a result of the
array photoresist pattern on the GaAs substrate. Photoresist MacEtch, the Au layer sinks into the semiconductor, gen-
and developer used for the photolithography were AZ1512 erating a high-aspect-ratio micropillar structure. The mi-
and MIF 312 (AZ Electronic Materials Inc.), respecti- cropillars, however, have a tapered end, indicating that the
vely. 20-nm-thick gold (Au) was then deposited on the semiconductor etching proceeds at the sidewall of the mi-
patterned samples using an e-beam evaporator, followed cropillars during the MacEtch. The etched structure be-
by lift-off process (i.e., soaking in acetone for 10 min comes more tapered with the increase of the H2O2 ratio in
the solution, forming a microcone array as seen in the
Fig. 1(c). Interestingly, the GaAs etching performed under
UV illumination produces the microhole structure (Fig. 1d),
implying the etching is nearly suppressed at the metal–
semiconductor interface but takes place on the UV-
exposed GaAs surface. We attributed the various GaAs
structures generated here to the combination etching proc-
ess utilizing both the typical wet etching and the MacEtch
with controlling relative etch rate.
The MacEtch process which is an anisotropic etching
method is illustrated on the left side of Fig. 2(a). In the
mixed solution, the catalytic metal (Au in this work) ex-
tracts electrons from the underlying GaAs through the qua-
si-Schottky interface between the Au and the GaAs, result-
ing in a reduction of oxidizing agent (i.e., H2O2) and an in-
crease of positive holes (h+) in the GaAs. Subsequently,
GaAs beneath the Au layer undergoes oxidative dissolu-
Figure 1 (a) Top-view SEM image of the Au-mesh patterned
tion in the solution containing HF. The maintenance of
GaAs substrate. 45° tilted view SEM images of the GaAs struc- Au–GaAs contact enables the continued vertical movement
tures produced after 10 min wet etching in HF/H2O2/EtOH solu- of the etching front, generating high-aspect-ratio GaAs
tions of (b) 30/1/30, (c) 30/3/30, and (d) 30/3/30, respectively. structures [2]. In addition to the MacEtch, typical wet
The sample shown in (d) was etched under UV illumination. chemical etching proceeds on the exposed GaAs surface in

© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.pss-rapid.com


Rapid
Research Letter

Phys. Status Solidi RRL (2014) 3

Figure 3 (a) Illustrations of the etching process under UV illu-


mination. (b) Side-view SEM images of the generated GaAs
structures after 3 min wet etching in a HF/H2O2/EtOH (30/3/30)
solution under UV illumination. e––h+ pairs (underlined) are ge-
nerated by UV illumination while e––h+ is formed by oxidation of
Figure 2 (a) Illustrations of the etching process and side-view metal catalysts.
SEM images of the MacEtch generated GaAs structures after
3 min wet etching in HF/H2O2/EtOH solutions of (b) 30/0.5/10, reduced MacEtch. Figure 3(a) is an illustration of the etch-
(b) 30/2/10 and (c) 30/4/10. ing process of the Au-patterned GaAs sample in the
[HF] :[H2O2]:[EtOH] solution under UV illumination.
[HF] :[H2O2]:[EtOH] solution (see Fig. 2a, right). H2O2 Illuminating light whose energy is larger than the band-
molecules can directly extract electrons from the exposed gap energy creates electron–hole (e––h+) pairs in the
GaAs which then turns into ion states such as Ga3+, As3+ semiconductor beneath the exposed area. In the
(or As5+). The oxidized GaAs dissolves in the solution as [HF] :[H2O2]:[EtOH] solution, the oxidizing agent (i.e.,
ion states or by-products through HF acid. The EtOH is H2O2) can interrupt the recombination process of the elec-
used as a dilution. If the concentration of EtOH increases, trons and holes because the electrons in the GaAs conduc-
the etching will go mild. In the typical wet etching, the tion band can be taken by the oxidizing agent. Thus, the
etch rate commonly differs depending on the plane direc- wet etching on the UV-exposed GaAs becomes highly
tion of the crystal structure. A GaAs(111) plane where the activated by the excessive holes as illustrated in Fig. 3(a)
atoms are most closely packed has a faster etch rate than [24]. In the meantime, the free holes generated beneath the
other planes. Thus, the protrusion part on GaAs(100) sur- Au layer can recombine with the electrons which are dif-
face becomes cone-shaped as the typical wet etching pro- fused from the UV-exposed GaAs surface. Figure 3(b) is
ceeds, as seen on the right side of Fig. 2(a). Note that the the cross-section SEM image of the GaAs microhole
relative etch rate of the typical wet etching and the Mac- formed after 3 min etching of the Au-patterned GaAs sam-
Etch can be controlled by changing the molar ratios of the ple in the [HF] :[H2O2] :[EtOH] solution under UV illumi-
etching solution. In the etching solution, the activation en- nation. Note that the etched microhole has round sidewalls
ergy for the GaAs etching can be significantly reduced with increased opening diameter, indicating that the GaAs
with Au because of the high catalytic activity of the Au for etching under UV illumination is an isotropic etching
H2O2 decomposition [23]. Thus, the GaAs etching pro- process which is hardly affected by the crystal orientation.
ceeds much faster with the Au layer than without one in Based on the GaAs microstructures generated by
the solution of low H2O2 concentration. With increasing [HF] :[H2O2]:[EtOH] etching system, the three-phase dia-
H2O2 ratio in the solution, however, the GaAs etching be- gram is illustrated in Fig. 4. The structural formations and
comes active without Au (i.e., typical wet etching). Fig- surface morphologies of the etched GaAs are indicated by
ure 2(b)–(d) are the cross-section SEM images of the GaAs different symbols in the phase diagram. The area where the
microstructures produced after immersing the Au-patterned HF to H2O2 ratio is high is marked by purple color. Then,
GaAs in the [HF] :[H2O2]:[EtOH] recipes of 30 :0.5 :10, the background color in the phase diagram is changed from
30 :2 :10 and 30 :4 :10, respectively. The vertical etch rate the purple to the red gradually with decreasing HF to H2O2
of the GaAs structure shown in Fig. 2(b), (c) and (d) is ratio in the solution. In the purple-colored region, the
600 nm/min, 390 nm/min, and 310 nm/min, respectively. MacEtch dominantly occurs at the Au–GaAs interface,
An increase of H2O2 ratio in the solution suppresses the while the typical wet etching is nearly suppressed because
vertical etch rate while promoting the nonmetal-catalyzed the low amount of the H2O2 mostly decomposes with the
etching at the exposed GaAs surface. As a result, the Au. A porous surface, however, is observed instead of
etched GaAs structure becomes more tapered and shal- generating GaAs microstructures in the solution of ex-
lower with an increase of the H2O2 ratio in the solution. tremely high HF to H2O2 ratio. The GaAs underneath the
Asoh et al. have previously demonstrated the metal- Au layer may not be uniformly oxidized by the extremely
assisted photodissolution effect [24]. In this demonstration, low H2O2 concentration and thus the excess HF dissolves
an exposed InP surface around a metal-coated area is the partially oxidized GaAs surface [25–27]. The solid sur-
etched very fast with UV irradiation due to the enhanced face morphologies are found in the region surrounded
photodissolution effect. Similarly, the typical wet etch- by the yellow dashed line, indicating that components of
ing of the UV-exposed GaAs dramatically increases with etching solution are well balanced for both the typical wet

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References
[1] W. Chern, K. Hsu, I. S. Chun, B. P. D. Azeredo, N. Ahmed,
K.-H. Kim, J.-M. Zuo, N. Fang, P. Ferreira, and X. Li, Nano
Lett. 10, 1582 (2010).
[2] M. DeJarld, J. C. Shin, W. Chern, D. Chanda, K. Balasunda-
ram, J. A. Rogers, and X. Li, Nano Lett. 11, 5259 (2011).
[3] J. C. Shin, C. Zhang, and X. Li, Nanotechnology 23, 305305
(2012).
[4] J. C. Shin, D. Chanda, W. Chern, K. J. Yu, J. A. Rogers, and
X. Li, IEEE J. Photovoltaics 2, 129 (2012).
[5] D. Liang, Y. Kang, Y. Huo, Y. Chen, Y. Cui, and J. S. Har-
ris, Nano Lett. 13, 4850 (2013).
[6] B. Sun, L. Zhao, T. Wei, X. Yi, Z. Liu, G. Wang, and J. Li,
J. Appl. Phys. 113, 243104 (2013).
[7] R. Ferrini, B. Lombardet, B. Wild, R. Houdre, and G. H.
Duan, Appl. Phys. Lett. 82, 1009 (2003).
[8] L. O’Faolain, X. Yuan, D. McIntyre, S. Thoms, H. Chong,
Figure 4 Phase diagram of the HF–H2O2–EtOH etching system R. M. De La Rue, and T. F. Krauss, Electron. Lett. 42, 1454
with various molar ratios. General etching phenomena are drawn (2006).
by colored area, where the resulted surface morphology is marked [9] P. Zhu, G. Liu, J. Zhang, and N. Tansu, J. Disp. Technol. 9,
by different symbols. 317 (2013).
[10] J. Jewell, D. Simeonov, S.-C. Huang, Y.-L. Hu, S. Naka-
mura, J. Speck, and C. Weisbuch, Appl. Phys. Lett. 100,
etching and the MacEtch. In this region, the GaAs mi- 171105 (2012).
cropillars and microcone structures can be generated by [11] X.-H. Li, P. Zhu, G. Liu, J. Zhang, R. Song, Y.-K. Ee,
tuning the HF to the H2O2 ratio. The GaAs microhole P. Kumnorkaew, J. F. Gilchrist, and N. Tansu, J. Disp.
structure is also formed in this region when the etching Technol. 9, 324 (2013).
process is performed under UV illumination. In the area of [12] H. F. Wong, D. L. Green, T. Y. Liu, D. G. Lishan,
very low HF to H2O2 ratio (i.e., red-colored region), porous M. Bellis, E. L. Hu, P. M. Petroff, P. O. Holtz, and J. L.
and rough morphology is also generated on the GaAs sur- Merz, J. Vac. Sci. Technol. B 6, 1906 (1988).
face. High concentration of H2O2 in the solution oxidizes [13] X. Li and P. W. Bohn, Appl. Phys. Lett. 77, 2572 (2000).
the GaAs surface very fast while the preferential dissolu- [14] I. S. Chun, E. K. Chow, and X. Li, Appl. Phys. Lett. 92,
tion of the oxidized GaAs can partially occur under the 191113 (2008).
small amount of HF. [15] X.-H. Li, R. Song, Y.-K. Ee, P. Kumnorkaew, J. F.
Gilchrist, and N. Tansu, IEEE Photon. J. 3, 489 (2011).
4 Conclusion Various 3-D GaAs structures have been [16] Y.-K. Ee, P. Kumnorkaew, R. A. Arif, H. Tong, H. Zhao,
fabricated via the wet etching process combined with the J. F. Gilchrist, and N. Tansu, J. Sel. Top. Quantum Electron.
15, 1218 (2009).
MacEtch. High-aspect-ratio GaAs micropillar and micro-
[17] J. A. Rogers and R. G. Nuzzo, Materials Today 8, 50
cone structures are formed by controlling the molar ratio of
(2005).
the [HF] :[H2O2] :[EtOH] etching solution. Interestingly,
[18] J. Kim, Y. H. Kim, S. H. Choi, and W. Lee, ACS Nano 5,
GaAs microholes are produced under UV illumination be- 5242 (2011).
cause the MacEtch is nearly deactivated with increased [19] J. Kim, H. Han, Y. H. Kim, S. H. Choi, J. C. Kim, and
typical wet etching on the UV-exposed GaAs. The struc- W. Lee, ACS Nano 5, 3222 (2011).
ture formations and surface morphologies of the GaAs [20] J. Kim, H. Rhu, and W. Lee, J. Mater. Chem. 21, 15889
generated by the [HF] :[H2O2] :[EtOH] etching solution are (2011).
systematically examined with a three-phase diagram. Tak- [21] Y. Yasukawa, H. Asoh, and S. Ono, Electrochem. Commun.
ing advantage of that wet chemical etching process hardly 10, 757 (2008).
damages the etched surface, the GaAs microstructures [22] Y. Yasukawa, H. Asoh, and S. Ono, J. Electrochem. Soc.
demonstrated here offer promising opportunities to de- 156, H777 (2009).
velop optical and electrical properties of the III–V semi- [23] K. Goszner and H. Bischof, J. Catalysis 32, 175 (1974).
conductor optoelectronic devices such as solar cells, LEDs, [24] H. Asoh, T. Yokoyama, and S. Ono, Jpn. J. Appl. Phys. 49,
and photonic crystals. 046505 (2010).
[25] R. L. Smith and S. D. Collins, J. Appl. Phys. 71, R1 (1992).
Acknowledgements This research was supported by Basic [26] A. G. Cullis, L. T. Canham, and P. D. Calcott, J. Appl.
Science Research Program through the National Research Foun- Phys. 82, 909 (1997).
dation of Korea (NRF) funded by the Ministry of Education, Sci- [27] A. I. Hochbaum, D. Gargas, Y. J. Hwang, and P. Yang, Na-
ence and Technology (NRF-2013R1A1A2065935). no Lett. 9, 3550 (2009).

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