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8-1-2016
Directed Self-Assembly of Block Copolymer, No1
Hiromichi Yamamoto Singh Center, [email protected]
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Yamamoto, Hiromichi, "Directed Self-Assembly of Block Copolymer, No1", Protocols and Reports. Paper 27. https://repository.upenn.edu/scn_protocols/27
This paper is posted at ScholarlyCommons. https://repository.upenn.edu/scn_protocols/27 For more information, please contact [email protected]. Directed Self-Assembly of Block Copolymer, No1
Abstract The PS-rich and neutral PS-b-PMMA block copolymer (BCP) films were spin coated on the neutral random copolymer hydroxyl-terminated PS-r-PMMA layers grafted on the native oxide and 50 nm thick PECVD amorphous silicon oxide layers. Relationship between the grafting density of BCP and surface density of hydroxyl moiety on silicon oxide is discussed. Furthermore, optimization of annealing BCP films is reported, and wetted and de-wetted BCP films are shown in optical microscope images. In addition, finger print and nanopore structures of BCP films are also indicated in SEM images.
Keywords directed self-assembly, block-copolymer, grafting, hydroxylated silicon oxide
Disciplines Biochemical and Biomolecular Engineering | Biological and Chemical Physics | Membrane Science | Nanoscience and Nanotechnology | Other Chemistry | Physical Chemistry | Polymer and Organic Materials | Polymer Chemistry | Polymer Science
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This technical report is available at ScholarlyCommons: https://repository.upenn.edu/scn_protocols/27 Document No: Technical Report Revision: Directed Self-Assembly of Author: Hiromichi Yamamoto Block Copolymer, No1
1. Introduction Directed self-assembly of block copolymer (BCP) is considered as one of the most promising advanced lithography, 1 and can make nanometer scale patterns on the 6-inch diameter substrate at the same time without expensive cost, using the self-assembly of BCP and guide pattern created by a conventional lithography tool. Up to now, sub-10 nm patterns of high-χ BCP ( χ: Flory-Huggins interaction parameter) have been reported. 2,3 The goal of this project is to make this technique available at Quattrone Nanofabrication Facility (QNF).
Figure 1 shows a schematic diagram of multi-layer structure of block copolymer on random copolymer grafted on the Si substrate. In actual devices, a guide pattern is added to the multi-layer structure. 4 The morphology of BCP is controlled by chemical affinity of the underlying random copolymer grafted (or immobilized) on the substrate and by the thickness of BCP film. 5 This report describes a graft (or immobilization) of the random copolymer on the Si substrate and optimization of commensurability between the film thickness of BCP and the polymer domain spacing (or Lamellar spacing).
Figure 1. Schematic diagram of multi-layer structure of block copolymer on random copolymer grafted on the Si substrate. The morphology of the block copolymer is controlled by the chemical affinity with the underlying film and by the film thickness.
1 M. C. Smayling, Proc. SPIE, 9777 , 977702 (2016). 2 N. Kihara et al., J. Micro/Nanolith. MEMS MOEMS 14 , 023502 (2015). 3 W. J. Durand et al., J. Polym. Sci., Part A: Polym. Chem. 53 , 344–352 (2015). 4 C. Liu et al., Macromolecules 44 , 1876 (2011). 5 J. N. L. Albert and T. H. Epps, Mater. Today, 13 , 24 (2010). Page 1 Technical Report Directed Self-Assembly of Block Copolymer, No1
2. Experimental Section A. Materials
BCP poly(styrene-block -methyl methacrylate) (PS-b-PMMA) with the average molecular weight Mn of poly-styrene = 6 15000, Mn of poly-methyl methacrylate = 15000, expressed by 15k-b-15k, and PDI ≤ 1.2 was purchased from Sigma-Aldrich. Furthermore, two kinds of BCP PS-b-PMMA (poly-methyl methacrylate rich in syndiotactic contents 6 > 78 or 80 %) with M n of 33k-b-33k and 46k-b-21k and PDI = 1.09 were purchased from Polymer Source. The three
BCPs were used as received. Hereafter, the BCPs with Mn of 15k-b-15k and 33k-b-33k are referred to as “neutral PS(15k)-b-PMMA(15k)” and “neutral PS(33k)-b-PMMA(33k)”, respectively, or simply “neutral PS-b-PMMA”, where
the “neutral” means 50 to 50 mol%, while the BCP with Mn of 46k-b-21k is referred to as “PS-rich PS-b-PMMA”.
Hydroxyl-terminated random copolymer poly(styrene-r-methyl methacrylate), α-hydroxyl-ω-tempo moiety 6 terminated, with Mn = 5400 (PS content 60 mol%) and PDI = 1.40 was also purchased from Polymer Source, and used as received. Hereafter, the random copolymer is referred to as “brush-OH” or ”PS-r-PMMA-OH”. The brush- OH with PS content of 60 mol% is considered to be “neutral”. A CMOS grade toluene (trace impurity level, 10-200 ppb) was purchased from J. T. Baker, and used as received.
B. Deposition of 50 nm thick silicon oxide film A (100) Si wafer was sonicated in acetone and isopropyl alcohol (IPA) for 5 min each, and then dried using a nitrogen gun. A 50 nm thick amorphous silicon oxide was deposited on the Si wafer, using Oxford Plasma Lab 100 (Plasma Enhanced Chemical Vapor Deposition (PECVD)).
C. Grafting the brush-OH film on the hydroxylated silicon oxide surface on Si wafer The 1.2-1.5 nm thick native oxide and the 50 nm thick silicon oxide films were hydroxylated, respectively, by 7 8 treatment of nitric acid (70 wt%) or piranha solution at 80 °C for 30-40 min. O2 plasma treatment was not carried out for the hydroxylation, due to possible cross-contamination in the tool frequently used in QNF. The samples hydroxylated were sonicated in de-ionized (DI) water for 2 min, and then dried using nitrogen gun. Furthermore, the samples were dehydrated at ~150 °C for 5 min in a vacuum oven. A ~20 nm thick brush-OH film was spin coated at 4000 rpm on the Si substrate with and without the 50 nm thick silicon oxide film on its surface from the
0.9 wt% toluene solution, and grafted on the hydroxylated silicon oxide by annealing itself in the oven filled with N 2 or in vacuum. The annealing time and temperature are shown later. After annealing, the unreacted brush-OH polymer was removed by repeated 30 min sonication in toluene (3 times).
D. Film preparation of BCPs Various thick neutral and PS-rich PS-b-PMMA films were spin coated at various spin speeds on the brush layers grafted on the Si substrates from 1.2 wt% PS(15k)-b-PMMA(15k), 1.7 wt% PS(33k)-b-PMMA(33k), and 1.7 wt%