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Article in physica status solidi (RRL) - Rapid Research Letters · April 2014
DOI: 10.1002/pssr.201409046
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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
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
solidi
physica
status
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
solidi
physica
status
4 A Ri Lee et al.: Formation of three-dimensional GaAs microstructures
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