Poly(dimethylsiloxane-b-methyl methacrylate): a promising candidate for sub-10 nm patterning

Transcription

1 Supporting information Poly(dimethylsiloxane-b-methyl methacrylate): a promising candidate for sub-10 nm patterning Yingdong Luo,, Damien Montarnal, Sangwon Kim,,# Weichao Shi, Katherine P. Barteau,, Christian W. Pester, Phillip D. Hustad, φ Matthew D. Christianson, % Glenn H. Fredrickson,* Edward J. Kramer, Craig J. Hawker* Materials Research Laboratory, University of California, Santa Barbara, California 93106, United States Department of Chemistry and Biochemistry, University of California, Santa Barbara 93106, United States Materials Department, University of California, Santa Barbara, California 93106, United States Department of Chemical Engineering, University of California, Santa Barbara, California 93106, United States # Department of Polymer Science and Engineering, Inha University, Incheon, , Republic of Korea φdow Electronic Materials, Marlborough, Massachusetts 01752, United States % The Dow Chemical Company, Midland, Michigan 48674, United States Edward J. Kramer passed away on Dec. 27 th 2014 Table of content General procedure of preparation of α-alkynyl-pmma and α-alkynyl-ps Details of RPA theory and χ fitting analysis GPC of PDMS-b-PMMA block copolymers (Figure S1-S8) AFM images (Figure S9-S15) GISAXS of PDMS-b-PMMA thin film studies (Figure S16) Etching rate test (Table S1) COSY of PDMS-b-PMMA (Figure S17) S2 S3 S3 S8 S12 S12 S13 S1

2 General procedure of preparation of α-alkynyl-pmma. A 50 ml Schlenk flask was charged with PMDETA (87 mg, mmol), methyl methacrylate (5.05 g, 50.4 mmol) and 5 ml of toluene. Freeze-pump-thaw operation was performed twice and CuCl (49 mg, mmol) was added under an Ar atmosphere. After an additional freeze-pump-thaw cycle, the Schlenk flask was kept at 70 C for several minutes and stirred to allow the CuCl to dissolve. Propargyl α-bromoisobutyrate (103 mg, mmol) was then added to initiate the polymerization and the solution was kept at 70 C. The reaction was stopped at desired time by immersing in liquid nitrogen bath and opening to air. 10 ml of DCM was added and the suspension was filtered through an activated basic alumina plug. The filtrate was precipitated into 1 L of hexane twice. The white solid was dried under high-vacuum for 24 hours. General procedure of preparation of α-alkynyl-ps. A 50 ml Schlenk flask was charged with PMDETA (61.8 mg, mmol), CuBr 2 /PMDETA (28.3 mg, mmol) and 5 ml of styrene (5.2 g, 50 mmol). Freeze-pump-thaw was performed twice and CuBr (51 mg, mmol) was added under Ar atmosphere. After an additional freeze-pump-thaw cycle, the Schlenk flask was kept at 90 C for several minutes and stirred to allow all CuBr to dissolve. Propargyl α-bromoisobutyrate (73.5 mg, mmol) was then added to initiate the polymerization and the solution was kept at 90 C. The reaction was stopped at desired time by immersing in liquid nitrogen bath and opening to air. 10 ml of DCM was added and the suspension was filtered through an activated basic alumina plug. The filtrate was precipitated into 1 L of methanol twice. The white solid was dried under high-vacuum for 24 hours. S2

3 Flory-Huggins parameter fitting analysis 1, 2 = 2 S q = <S MMA,MMA q > v + 2<S MMA,DMS q > v + <S DMS,DMS q > v W q = <S MMA,MMA q > v<s DMS,DMS q > v - <S MMA,DMS q > v 2 <S X,X q > v = r c,n X,n 2 g 2 X,n q <S MMA,DMS q > v = r c,n MMA DMS g 1 MMA,n q g 1 DMS,n q r c,n = MMA N MMA,n + DMS N DMS,n / 0 g 1 X,n q = 1/χ X,n {1 - [χ X,n λ X ]- λ X } g 2 X,n q = 2/χ X,n2 {-1 + χ X,n + [χ X,n λ X ] - λ X } χ X,n N X,n b x 2 /6 q 2 λ X,n = N X,w / N X,n X refers to either PMMA or PS. Monomer volume were S = nm 3 ; MMA = nm 3 ; DMS = nm 3 ; 0 = 0.1 nm 3. Four parameters including the statistical segment length of both polymers (b X, b DMS ), the amplitude K and the Flory-Huggins parameter χ were optimized to fit the SAXS pattern at each temperature. S3

4 Figure S1. GPC of D 1.7 S 3.3 (solid line) compared to starting homopolymers Figure S2. GPC of D 2.8 S 4.1 (solid line) compared to starting homopolymers S4

5 Figure S3. GPC of D 1.0 M 2.3 (solid line) compared to starting homopolymers Figure S4. GPC of D 1.1 M 2.3 (solid line) compared to starting homopolymers S5

6 Figure S5. GPC of D 1.7 M 2.2 (solid line) compared to starting homopolymers Figure S6. GPC of D 3.7 M 2.2 (solid line) compared to starting homopolymers S6

7 Figure S7. GPC of D 1.7 M 5.1 (solid line) compared to starting homopolymers Figure S8. GPC of D 2.8 M 6.0 (solid line) compared to starting homopolymers S7

8 Figure S9. AFM phase image of D 1.7 M 5.1 monolayer thermally annealed after 5s CF 4 E. Figure S10. AFM height image of thermal annealed multilayer of D 1.7 M 5.1 after 5s CF 4 E. S8

9 Figure S11. AFM height image of NMP annealed monolayer of D 2.8 M 6.0 after 10s CF 4 E. Figure S12. AFM height image of acetonitrile annealed monolayer of D 2.8 M 6.0 after 10s CF 4 E. S9

10 Figure S13. AFM height (left) and phase (right) image of thermal annealed multilayer of D 1.7 M5.1 after 5s CF 4 E. Figure S14. AFM height (left) and phase (right) image of NMP annealed monolayer of D 2.8 M 6.0 after 10s CF 4 E. S10

11 Figure S15. AFM height (left) and phase (right) image of acetonitrile annealed monolayer of D 2.8 M 6.0 after 10s CF 4 E. S11

12 Figure S16 Grazing incidence small-angle X-ray scattering (GISAXS) at an incident angle of 0.19 of a) D 1.7 M 5.1 multilayer thermally annealed with 5s CF 4 E; b) D 2.8 M 6.0 monolayer annealed in NMP after 10s CF 4 E; c) D 2.8 M 6.0 monolayer annealed in acetonitrile after 10s CF 4 E. Table S1. Etching rate test. Polymer as cast (nm) after annealing after etch (nm) etched concentration (nm) thickness (nm) 0.5% % % % E condition: CF 4 20 sccm, 0.3 pa, 50W BIAS, 20W POWER. S12

13 Figure S17 2D COSY of D 1.7 M 2.2 correlated to 1D 1 H NMR spectra. Peak b and d correlate; peak d and e correlate. This confirmed that peak b is the CH 2 on PDMS side and next to nitrogen atom. And peak c is the CH 2 on PMMA side and next to oxygen. Reference 1. Feldman, K. E.; Kade, M. J.; Meijer, E. W.; Hawker, C. J.; Kramer, E. J. Macromolecules 2010, 43, Sakamoto, N.; Hashimoto, T. Macromolecules 1995, 28, S13