Please wait a minute...

Frontiers of Chemical Science and Engineering

Front. Chem. Sci. Eng.    2019, Vol. 13 Issue (3) : 475-484     https://doi.org/10.1007/s11705-019-1809-0
RESEARCH ARTICLE
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
Download: PDF(3361 KB)   HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks
Abstract

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.
 URL:  
http://journal.hep.com.cn/fcse/EN/10.1007/s11705-019-1809-0
http://journal.hep.com.cn/fcse/EN/Y2019/V13/I3/475
Service
E-mail this article
E-mail Alert
RSS
Articles by authors
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
1 E Gogolides, C Vassilios, K George, K Dimitrios, T Katerina, B George, V Marilena, T Angeliki. Controlling roughness: From etching to nanotexturing and plasma-directed organization on organic and inorganic materials. Journal of Physics. D, Applied Physics, 2011, 44(17): 174021
2 S Franssila. Optical Lithography. Introduction to Microfabrication. Hoboken: John Wiley & Sons, Ltd., 2010, 103–113
3 R H Stulen, D W Sweeney. Extreme ultraviolet lithography. IEEE Journal of Quantum Electronics, 1999, 35(5): 694–699
4 H C Pfeiffer. Direct write electron beam lithography: A historical overview. In: Proceedings of SPIE Photomask Technology. Monterey: SPIE, 2010, 782316
5 S Y Chou, P R Krauss, P J Renstrom. Nanoimprint lithography. Journal of Vacuum Science & Technology. B, 1996, 14(6): 4129–4133
6 H Schift. Nanoimprint lithography: An old story in modern times? A review. Journal of Vacuum Science & Technology. B, 2008, 26(2): 458
7 P Colson, C Henrist, R Cloots. Nanosphere lithography: A powerful method for the controlled manufacturing of nanomaterials. Journal of Nanomaterials, 2013, 2013: 1–19
8 G Zhang, D Wang. Colloidal lithography—the art of nanochemical patterning. Chemistry, an Asian Journal, 2009, 4(2): 236–245
9 C Haynes, P Van Duyne. Nanosphere lithography: A versatile nanofabrication tool for studies of size-dependent nanoparticle optics. Journal of Physical Chemistry B, 2001, 105: 5599–5611
10 I W Hamley. Nanostructure fabrication using block copolymers—Review. Nanotechnology, 2003, 14: 16
11 S Tallegas, T Baron, G Gay, C Aggrafeil, B Salhi, T Chevolleau, G Cunge, A Bsiesy, R Tiron, X Chevalier, et al. Block copolymer technology applied to nanoelectronics. Physica Status Solidi. C, Current Topics in Solid State Physics, 2013, 10(9): 1195–1206
12 K Seeger, R E Palmer. Fabrication of silicon cones and pillars using rough metal films as plasma etching masks. Applied Physics Letters, 1999, 74(11): 1627–1629
13 K Ostrikov. Plasma nanoscience: From nature’s mastery to deterministic plasma-aided nanofabrication. IEEE Transactions on Plasma Science, 2007, 35(2): 127–136
14 I Levchenko, K Ostrikov, K Diwan, K Winkler, D Mariotti. Plasma-driven self-organization of Ni nanodot arrays on Si(100). Applied Physics Letters, 2008, 93(18): 183102
15 C H Hsu, H C Lo, C F Chen, C T Wu, J S Hwang, D Das, J Tsai, L C Chen, K H Chen. Generally applicable self-masked dry etching technique for nanotip array fabrication. Nano Letters, 2004, 4(3): 471–475
16 M Gharghi, S Sivoththaman. Formation of nanoscale columnar structures in silicon by a maskless reactive ion etching process. Journal of Vacuum Science & Technology. A, Vacuum, Surfaces, and Films, 2006, 24(3): 723
17 J Muñoz-García, L Vázquez, M Castro, R Gago, A Redondo-Cubero, A Moreno-Barrado, R Cuerno. Self-organized nanopatterning of silicon surfaces by ion beam sputtering. Materials Science and Engineering R Reports, 2014, 86: 1–44
18 R Gago, L Vázquez, O Plantevin, T H Metzger, J Muñoz-García, R Cuerno, M Castro. Order enhancement and coarsening of self-organized silicon nanodot patterns induced by ion-beam sputtering. Applied Physics Letters, 2006, 89(23): 233101
19 F Frost, B Ziberi, A Schindler, B Rauschenbach. Surface engineering with ion beams: From self-organized nanostructures to ultra-smooth surfaces. Applied Physics. A, Materials Science & Processing, 2008, 91(4): 551–559
20 N Vourdas, D Kontziampasis, G Kokkoris, V Constantoudis, A Goodyear, A Tserepi, M Cooke, E Gogolides. Plasma directed assembly and organization: Bottom-up nanopatterning using top-down technology. Nanotechnology, 2010, 21(8): 85302
21 E Gogolides, A Tserepi, V Constandoudis, N Vourdas, G Boulousis, M E Vlachopoulou, K Tsougeni, D Kontziampasis. Method for the fabrication of periodic structures on polymers using plasma processes. European Patent, EP2300214, 2009-12-17
22 D Kontziampasis, V Constantoudis, E Gogolides. Plasma directed organization of nanodots on polymers: Effects of polymer type and etching time on morphology and order. Plasma Processes and Polymers, 2012, 9(9): 866–872
23 G Kokkoris, E Gogolides. The potential of ion-driven etching with simultaneous deposition of impurities for inducing periodic dots on surfaces. Journal of Physics. D, Applied Physics, 2012, 45(16): 165204
24 G Kokkoris. Towards control of plasma-induced surface roughness: Simultaneous to plasma etching deposition. European Physical Journal Applied Physics, 2011, 56(2): 24012
25 E Gogolides, A Zeniou. Variable Faraday shield for a substrate holder, a clamping ring, or an electrode, or their combination in a plasma reactor. European Patent, EP3261111, 2017-04-26
26 M K Vijaya-Kumar, V Constantoudis, E Gogolides, A V Pret, R Gronheid. Contact edge roughness metrology in nanostructures: Frequency analysis and variations. Microelectronic Engineering, 2012, 90: 126–130
27 G Kokkoris, N Vourdas, E Gogolides. Plasma etching and roughening of thin polymeric films: A fast, accurate, in situ method of surface roughness measurement. Plasma Processes and Polymers, 2008, 5(9): 825–833
28 R Dussart, T Tillocher, P Lefaucheux, M Boufnichel. Plasma cryogenic etching of silicon: From the early days to today’s advanced technologies. Journal of Physics. D, Applied Physics, 2014, 47(12): 123001
29 A Smyrnakis, E Almpanis, V Constantoudis, N Papanikolaou, E Gogolides. Optical properties of high aspect ratio plasma etched silicon nanowires: Fabrication-induced variability dramatically reduces reflectance. Nanotechnology, 2015, 26(8): 085301
30 K Ellinas, A Smyrnakis, A Malainou, A Tserepi, E Gogolides. “Mesh-assisted” colloidal lithography and plasma etching: A route to large-area, uniform, ordered nano-pillar and nanopost fabrication on versatile substrates. Microelectronic Engineering, 2011, 88(8): 2547–2551
31 H V Jansen. The black silicon method II. Microelectronic Engineering, 1995, 27: 475–480
32 H V Jansen. Black silicon method. VIII. A study of the performance of etching silicon using SF6-O2-based chemistry with cryogenical wafer cooling and a high density ICP source. Microelectronics Journal, 2001, 32: 769–777
Related articles from Frontiers Journals
[1] Tingting Zhao, Niamat Ullah, Yajun Hui, Zhenhua Li. Review of plasma-assisted reactions and potential applications for modification of metal–organic frameworks[J]. Front. Chem. Sci. Eng., 2019, 13(3): 444-457.
[2] Aswathy Vasudevan, Vasyl Shvalya, Aleksander Zidanšek, Uroš Cvelbar. Tailoring electrical conductivity of two dimensional nanomaterials using plasma for edge electronics: A mini review[J]. Front. Chem. Sci. Eng., 2019, 13(3): 427-443.
[3] Michael Bonitz, Alexey Filinov, Jan-Willem Abraham, Karsten Balzer, Hanno Kählert, Eckhard Pehlke, Franz X. Bronold, Matthias Pamperin, Markus Becker, Dettlef Loffhagen, Holger Fehske. Towards an integrated modeling of the plasma-solid interface[J]. Front. Chem. Sci. Eng., 2019, 13(2): 201-237.
[4] Xiuqi Fang, Carles Corbella, Denis B. Zolotukhin, Michael Keidar. Plasma-enabled healing of graphene nano-platelets layer[J]. Front. Chem. Sci. Eng., 2019, 13(2): 350-359.
[5] Rusen Zhou, Renwu Zhou, Xianhui Zhang, Kateryna Bazaka, Kostya (Ken) Ostrikov. Continuous flow removal of acid fuchsine by dielectric barrier discharge plasma water bed enhanced by activated carbon adsorption[J]. Front. Chem. Sci. Eng., 2019, 13(2): 340-349.
[6] Ana Mora-Boza, Francisco J. Aparicio, María Alcaire, Carmen López-Santos, Juan P. Espinós, Daniel Torres-Lagares, Ana Borrás, Angel Barranco. Multifunctional antimicrobial chlorhexidine polymers by remote plasma assisted vacuum deposition[J]. Front. Chem. Sci. Eng., 2019, 13(2): 330-339.
[7] Pascal Brault, William Chamorro-Coral, Sotheara Chuon, Amaël Caillard, Jean-Marc Bauchire, Stève Baranton, Christophe Coutanceau, Erik Neyts. Molecular dynamics simulations of initial Pd and PdO nanocluster growth in a magnetron gas aggregation source[J]. Front. Chem. Sci. Eng., 2019, 13(2): 324-329.
[8] J. Christopher Whitehead. Plasma-catalysis: Is it just a question of scale?[J]. Front. Chem. Sci. Eng., 2019, 13(2): 264-273.
[9] Annemie Bogaerts, Maksudbek Yusupov, Jamoliddin Razzokov, Jonas Van der Paal. Plasma for cancer treatment: How can RONS penetrate through the cell membrane? Answers from computer modeling[J]. Front. Chem. Sci. Eng., 2019, 13(2): 253-263.
[10] Anna Khlyustova, Cédric Labay, Zdenko Machala, Maria-Pau Ginebra, Cristina Canal. Important parameters in plasma jets for the production of RONS in liquids for plasma medicine: A brief review[J]. Front. Chem. Sci. Eng., 2019, 13(2): 238-252.
[11] Erik C. Neyts. Atomistic simulations of plasma catalytic processes[J]. Front. Chem. Sci. Eng., 2018, 12(1): 145-154.
[12] Andrew Michelmore, Jason D. Whittle, James W. Bradley, Robert D. Short. Where physics meets chemistry: Thin film deposition from reactive plasmas[J]. Front. Chem. Sci. Eng., 2016, 10(4): 441-458.
[13] Harinarayanan Puliyalil,Petr Slobodian,Michal Sedlacik,Ruhan Benlikaya,Pavel Riha,Kostya (Ken) Ostrikov,Uroš Cvelbar. Plasma-enabled sensing of urea and related amides on polyaniline[J]. Front. Chem. Sci. Eng., 2016, 10(2): 265-272.
[14] Erik C. Neyts. The role of ions in plasma catalytic carbon nanotube growth: A review[J]. Front. Chem. Sci. Eng., 2015, 9(2): 154-162.
[15] Yan LI,Zhehao WEI,Yong WANG. Ni/MgO catalyst prepared via dielectric-barrier discharge plasma with improved catalytic performance for carbon dioxide reforming of methane[J]. Front. Chem. Sci. Eng., 2014, 8(2): 133-140.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed