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Frontiers of Chemical Science and Engineering

Front. Chem. Sci. Eng.    2019, Vol. 13 Issue (3) : 475-484
A non-lithographic plasma nanoassembly technology for polymeric nanodot and silicon nanopillar fabrication
Athanasios Smyrnakis1(), Angelos Zeniou1,2, Kamil Awsiuk3, Vassilios Constantoudis1, Evangelos Gogolides1
1. Institute of Nanoscience & Nanotechnology, NCSR “Demokritos”, Ag. Paraskevi, 15341 Attica, Greece
2. Department of Physics, University of Patras, 26504 Patras, Greece
3. M. Smoluchowski Institute of Physics, Jagiellonian University, 30-348 Krakow, Poland
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In this work, we present plasma etching alone as a directed assembly method to both create the nanodot pattern on an etched polymeric (PMMA) film and transfer it to a silicon substrate for the fabrication of silicon nanopillars or cone-like nanostructuring. By using a shield to control sputtering from inside the plasma reactor, the size and shape of the resulting nanodots can be better controlled by varying plasma parameters as the bias power. The effect of the shield on inhibitor deposition on the etched surfaces was investigated by time-of-flight secondary ion mass spectroscopy (ToF-SIMS) measurements. The fabrication of quasi-ordered PMMA nanodots of a diameter of 25 nm and period of 54 nm is demonstrated. Pattern transfer to the silicon substrate using the same plasma reactor was performed in two ways: (a) a mixed fluorine-fluorocarbon-oxygen nanoscale etch plasma process was employed to fabricate silicon nanopillars with a diameter of 25 nm and an aspect ratio of 5.6, which show the same periodicity as the nanodot pattern, and (b) high etch rate cryogenic plasma process was used for pattern transfer. The result is the nanostructuring of Si by high aspect ratio nanotip or nanocone-like features that show excellent antireflective properties.

Keywords plasma      nanoassembly      etching      nanodots      nanopillars      nanofabrication     
Corresponding Authors: Athanasios Smyrnakis   
Just Accepted Date: 27 March 2019   Online First Date: 06 May 2019    Issue Date: 22 August 2019
 Cite this article:   
Athanasios Smyrnakis,Angelos Zeniou,Kamil Awsiuk, et al. A non-lithographic plasma nanoassembly technology for polymeric nanodot and silicon nanopillar fabrication[J]. Front. Chem. Sci. Eng., 2019, 13(3): 475-484.
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Athanasios Smyrnakis
Angelos Zeniou
Kamil Awsiuk
Vassilios Constantoudis
Evangelos Gogolides
Bias power /W Bias voltage /V PMMA etch rate /(μm·min1)
Unshielded Shielded Unshielded Shielded
0 10 8 0.37 0.44
50 22 133 0.90 1.30
150 88 262 1.07 2.00
250 136 348 1.57 2.50
Tab.1  Bias voltage and PMMA etch rate in O2 plasma as a function of the bias power for unshielded and shielded electrodes
Fig.1  ToF-SIMS measurements showing the amount (normalized peak intensity of the mass spectrum) of (a) aluminum (Al+), (b), AlO , and (c) AlO2, on PMMA surfaces etched in O2 plasma for 5 min, under different bias power conditions, with or without the clamping ring shield
Fig.2  (a) AFM image of PMMA surface (2 mm × 2 mm, 512 × 512 points) after 2 min O2 plasma treatment using 0 W bias power and without the shield (inset: AFM line scan of the nanodots profile, and the nanodot height is ~15?20 nm; SEM images (tilted 45°) of PMMA surfaces etched in O2 plasma for 2 min); (b) under 136 V bias voltage (250 W bias power) without the shield; (c) under 130 V bias voltage (50 W bias power) with the shield placed on the clamping ring of the electrode, and the nanodot height is ~47 nm. Notice the large process window for bias and the large height of the nanodots. Plasma conditions: antenna power 1900 W, O2 flow 100 sccm at pressure of 0.75 Pa and temperature 15°C
Fig.3  Top-down SEM images of plasma-etched PMMA films under different bias power (Pbias) conditions and under different etching time conditions. The shield is applied on the electrode in all cases. Plasma conditions are (a) Pbias = 50 W, t = 60 s, (b) Pbias = 100 W, t = 60 s, (c) Pbias = 150 W, t = 60 s, (d) Pbias = 50 W, t = 30 s, (e) Pbias = 50 W, t = 90 s, and (f) Pbias = 50 W, t = 120 s
Fig.4  (a) Mean width of the PMMA nanodots versus etching time and bias power, (b) period and height of the nanodots versus bias power, (c) NNI of the nanodots versus etching time and bias power, and (d) circularly averaged Fourier Transform versus the bias power. All values extracted by the SEM image analysis shown in Fig. 3 using the nanoTOPO-SEM™ software from Nanometrisis
Fig.5  (a) Tilted at 45° and (b) top-down SEM images of silicon nanopillars as a result of plasma etching (room-temperature mixed process) using as a mask for the PMMA nanodots; (c) Circularly average Fourier Transform of the PMMA nanodots before pattern transfer (red line) and the Si nanopillars resulting after pattern transfer (black line), obtained by SEM image analysis using the nano-TOPO-SEM™ software. The observed peak indicates the order of the nanostructures
Fig.6  (a–b) SEM images (tilted 70°) of silicon surfaces after cryogenic plasma etching for 25 s and 85 s, respectively, having the PMMA nanodots as etching mask; (c) SEM images (tilted 70°) of silicon surface after 85 s of cryogenic plasma etching an o bare surface without nanopattering (reference sample); (d) Weighted reflectance (total, specular and diffuse) of nanostructured Si surfaces by the cryogenic plasma process (etching time from 25 to 120 s) having as mask pattern the plasma directed assembly PMMA nanodots. The weighted reflectance of a polished silicon wafer (t = 0 s) is also plotted as a reference
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