Dynamic SIMS Static SIMS µ µ

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1 . (Secondary Ion Mass Spectroscopy:SIMS) 1) SIMS SIMS

2 Dynamic SIMS Static SIMS µ µ

3 SIMS DSIMS) 3. DSIMS) 4. DSIMS) SSIMS) 8. SSIMS) 9. SSIMS) SIMS 1. 2.

4 = O - Cs +

5

6 µ µ µ

7 SIMS

8 4keV O 2 + B Si

9 end-labeled dps secc 4 H 9 ( CD 2 CD ) CH n 2 D D D D D CH Secondary ion intensity/cps <S 2 0 > 1/2 = 3.3 nm M n =15k Secondary ion intensity/a.u 4.4 nm Depth / nm DSIMS air-polymer interface 3.0keV, 6-7nA C x100µm 2 D H Depth / nm Macromolecules, Vol.29, 3040 (1996).

10 end-labeled dps 10 8 secc ( CD 2 CD ) 4 H 9 CH n 2 D D D D D Mn=15k <S 0 > 1/2 =3.2nm CH Secondary ion intensity/cps air-polymer interface 12 + C 2 + DSIMS D 3.0keV, 6-7nA x100µm H Depth / nm Macromolecules, Vol.29, 3040 (1996).

11 DSIMS D (hps29k/dps29k) Secondary ion intensity / a.u. dps 1 3 hps 2 H + D + C Etching time / min dps layer Au dps-690k buffer hps dps Si wafer (hps/dps) bilayer

12 DSIMS 84% I D+ (z) / a.u. hps layer dps layer 16% z = ( z m - z g ) z ; interfacial thickness di D+ (z) / dz center of interface 2σ z g ; instrumental function annealing time = 0h) z m ; measured interfacial thickness annealing time > 0h z i (i = g or m) Distance from interface / nm

13 (hps29k/dps29k) Interfacial thickness / nm at 400K, above Tg b at 393K, above Tg b at 380K, above Tg b at 370K, below T b g at 365K, below Tg b at 355K, below Tg b Mn = 29k T g s =264 K T g b =376 K slope=1/ Annealing time / s 4 Tg 10nm Macromolecules, 34, 6164 (2001).

14 Poly(dSt-block-MMA) (PS) PS PS Si (PMMA)

15 PS mass=91 (SSIMS)

16 PMMA S-SIMS ToF ToF SIMS S-SIMS 30keV Ga + 2keV Ar + Primary dose ions cm ions cm -2 A. J. Eccles, J. C. Vickerman, JVST, A7, 234(1989).

17 Au-S SO 3- Au Ag Ag G. Gillen et al., Anal. Chem., 66, 2170(1994).

18 m/z=443 Ga + In + Bryan et al., Proc. SIMS XI, p.459(1998). B ToF SIMS

19 PET F.-R. Lang, Y. Pitton, H. J. Mathieu, D. Landolt, E. M. Moser, Fresenius J Anal Chem., 358, 251 (1997)

20 PS19.7k/dPS847k) Counts Counts Counts sec C 4 H 9 dps847k C 7 H 7 + ( CH 2 CH ) H n LMW-hPS (hps19.7k/dps847k)(41.5/58.5v/v) hps19.7k Mass[m/z] Mass[m/z] sec C 4 H 9 ( CD 2 CD ) H n D D D D D dps-847k C 7 D 7 + ToF-SIMS PHI TRIFT II 15kV Ga Pulse source 2nA 100 x 100 µm 2 Tropylium ion

21 hps19.7k/dps847k) Surface hps fraction / vol% Surface hps fraction = I 91 /(I 91 +I 98 ) Bulk hps fraction / wt% hps Appl. Surf. Sci., (2003).

22 LMW-hPS/HMW-dPS)(50/50w/w (hps-53.4k/dps-847k) hps Mass[m/z] (hps-4.9k/dps-847k) dps ToF-SIMS PHI TRIFT II 15kV Ga Pulse source 2 na 100 x 100 µm 2 Tropylium ion Mass[m/z] hps

23 ToF SIMS K. Reihs M. Voetz M. Kruft D. Wolany, A. Benninghoven, Fresenius J Anal Chem., 358, (1997) A

24 CD pit Spacial resolved molecular weight determination at the surface of a polycarbonate core of a compact disc (CD optical image with grazing illumination) as a technical application

25 Secondary Ion Mapping by ToF-SIMS Ga-source 300nm beam diameter Line pattern of fluoroalkylsilane monolayer CF 3 (CF 2 ) 6 CH 2 CH 2 Si(OCH 3 ) 3

26 d p 3 λ 1 10 M = = = 4πk εcln10 ερln10 Absorption and reflection spectra of polystyrene film coated on quartz disk. d p is nm(>XPS, <IR)

27 Application of UV Reflection Spectroscopy to Analysis of Surface Composition of (PS/PVME) Blend Film Surface PVME content(uv)< Surface PVME content (XPS) -difference in detection depth S. Lee, C. S. P. Sung, Macromolecules, 34, 599(2001).

28 2) (SFG: Sum Frequency Generation) ω VIS ω IR ω VIS +ω IR P (2) (ω SF =ω VIS +ω IR )=χ (2) E(ω VIS )E(ω IR ) P (2) : χ (2) : P (2) χ (2)

29 Surface molecular motion of PP Random orientation of CH 2 reduced the intensity of symmetric CH 2 stretch at 2850cm -1. SFG spectra of (a) APP and (b) IPP below and above the glass transition temperature. D. H. GRACIAS, Z. CHEN, Y. R. SHEN, G. A. SOMORJAI, Acc. Chem. Res., 32, (1999).

30 SFG at liquid/solid interface OTS P Guyot-Sionnest R Superfine J H Hunt Y R Shen Chem Phys Lett

31 ) High Resolution Electron Energy Loss Spectroscopy(HREELS). 10eV)

32 PS-PEO diblock copolymer Mw =22.2k, Mw/Mn =1.07 M W,PS =3.8k, M W,PEO =18.4k PS 720cm -1 C-H out of plane 3060cm -1 aromatic C-H stretching PEO 2920cm -1 CH 2 stretching PS fraction Casting Spin-coating Bulk As prepared Annealed (a) High-resolution electron energy loss spectra taken at an incident energy of 5 ev, incident angle of 60, and analysis angle of 30, of PS(3.8k)-PEO(18.5k) diblock copolymer films spread from CCl 4 solutions: (a) cast followed by solvent evaporation; (b) spin-coated; (I) spectra immediately taken after solvent evaporation; (II) spectra taken after film annealing at 373K for 24 h. (A. M. Botelho do Rego, Olivier Pellegrino,J. M. G. Martinho, and J. Lopes da Silva, Langmuir 16, 2385(2000).)

33 (ISS) e +,Ne +,Ar eV) θ E E /2 = cos θ ( M2 / M1 sin θ) /(1 + M2 / M1) 2

34 PVC G. E. Thomas et al, Appl. Surf. Sci., 6, 204(1980).

35 PMMA O/C J. A. Gardella, Jr., Appl. Surf. Sci., 31, 72(1988).

36 CF 3 (CF 2 ) 5 (CH 2 ) 2 (CH 3 ) 2 Si[CH 2 CH(C 6 H 5 )] 29 F S. Affrossman et al., Macromolecules, 29, 5432(1996).

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