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1 A. R F. 1938E Binnig, Roher 1986Binnig, Quate, Gerber

2

3 µ µ

4 m m m

5 5.2 60kV 0.005nm λ = 1.5 V

6 B A B 110 b c A a 10nm b µ a 110

7 Composite Interfaces, 6,247(1999).

8 (20) (11) (10) (10) (a) 223 K (b) 243 K (c) 324 K (d) 348 K

9 TEM EFTEM performs EELS and ESI EELS: Electron Energy Loss Spectroscopy ESI: Electron Spectroscopic Imaging

10

11 LEO922

12

13 ナノレベルの局所化学分析を可能にするEFTEMにおける3つの機能 Functions of EFTEM: Nanoscale chemical analysis by ESI and EELS コアロス像からBG の影響を取り除き 元素マッピング像 を得る 損失エネルギーを 変化させながら連 続的に電子分光像 を取り込む フィルターにより分散された非弾性 散乱電子をそのままカメラで撮影 し シグナル強度を損失エネル ギーに対してプロットする

14 (PS) (PBD) (PMA) K. Varlota, J.M. Martina, C. Quetb, Polymer 41,4599 (2000).

15 C. A. Correa, E. Hage, Jr. Polymer, 40,2171(1999).

16 µ (A) EFTEM T. Hayakawa, S. Horiuchi, Angew. Chem. Int. Ed., 42, 2285(2003).

17 AIST PBT / TEM SiOC 50nm EELS

18 SIS 74nm 2 PI Ia3d H. Jinnai Y. Nishikawa, R. J. Spontak, S. D. Smith, D. A. Agard, T. Hashimoto, Phys. Rev. Lett., 84, 518 (2000).

19 5.3

20 SEM(1kV)AFM(D.Vezie)

21 FESEM 10 µm OTS SiO 2

22 SPM STM1981 SPM Atomic Force Microscope (Lateral Force Microscope) (Scanning Viscoelasticity Microscope) (Chemical Force Microscope) (Molecular Force Probe)

23 AFM

24

25 Z Y X A B C D A B C D (A+B)(C+D) Z Y X A B C D Z Y X

26 block (PSb PMMA, Mn(PS): Mn(PMMA): ) LangmuirBlodgett J. Kumaki, Y. Nishikawa, T. Hashimoto, J. Am. Chem. Soc., 118, 3321 (1996)

27 (HDPE Mw=520k) 343K (a) (b) (c) scanning direction 3 µm 3 µm cantilever 2nm Kajiyama Takahara 1999

28 5 µm Height/nm Lateral distance / µm dps PMMA Si SiOX P( Stb MMA) AFM 25nm L dps SiOX PMMA (n+1/2)l

29 10 nm 5 ED nm Highresolution AFM image 15 mn m 1 OTS molecule in a hexagonal manner (10) spacing : 0.42 nm OTS C 18 H 37 SiCl 3 Distance between Si atoms : 0.58 nm

30 (OTS/FOETS)(50/50) C 18 H 37 SiCl 3 C 8 7 C H SiCl 3 Surface pressure/mn m SiCl OTS Area / nm 2 molecule 1 Height/nm FOETS FOETS 1µm OTS Lateral distance / µ m

31 13nm

32 OTSC18 FOETS 1 µm 6 mv 61 mv FOETS DOTSC22 1 µm 263 mv 326 mv (OTSC18/FOETS)(50/50) (DOTSC22/FOETS)(50/50) TATSC30 FOETS 1 µm DDTSC12 OTSC18 5 µm 39 mv 98 mv 187 mv 209 mv (TATS C30/FOETS)(50/50) (DDTS C12/OTS)(50/50)

33 Measured at 293 K in air Isotropic Hexagonal Rectangular Lateral force / a.u. FDOPTES FOETS DOTS OTS DDTS HDTS Chem OTS NTS COOH NTS TATS Alkylsilane Fluorolkylsilane Number of carbon

34 C 18 H 37 SiCl 3 C 8 7 C H SiCl 3 [BSA 0.1 mg ml 1 OTS FOETS

35 [BSA 0.1 mg ml 1 (a) ph=7.5 (b) ph=4.7 1 µm 1 µm adsorbed BSA adsorbed BSA FOETS OTS Siwafer FOETS OTS Siwafer

36 µ (a) ph7.5, 10 min (b) ph7.5, 30 min OTS OTS Height/nm OTS Distance/µm Height/nm OTS Distance/µm

37 µ (a) ph4.7, 10min (b) ph4.7, 30min OTS OTS Height/nm OTS Height/nm OTS Distance/µm Distance/µm

38 ph7.5 BSA FOETS BSA BSA SA in PBS(pH 7.5) FOETS OTS Electrostatic repulsion Siwafer Rinse FOETS OTS Siwafer Weak adsorption Strong adsorption

39 AFM BSA BSA BSA unfolding BSA

40 pka=5.5cooh BSA BSA BSA

41 olystyrene(ps) /Poly(vinyl methyl ether) (PVME) (63/38w/w) rich Srich (a) Topography (b) Modulus PVMErich 0.5µm PVMErich 0.5µm Modulus/a.u. Height/nm Line Profile in AFM PSrich Distance/nm PSrich PVMErich PVMErich PSrich PSrich 5.6 Line Profile in SVM Distance/nm Bulk Tg PS 372K PVME 249K

42 Normalized phase lag(svm) PS with M n of 140k 1. SVM 2. LFM Temperature / K cbu(ch 2 CH) n H Bulk T g Normalized lateral force(lfm) Tg/K R.T. 1. surface (SVM) 2. surface (LFM) 3. bulk (DSC) M n Tg

43 δs tanδ M n = 4.9k T g s M n = 90k T g s T g b δ s / a.u. M n = 30k T g s M n = 54k T g s T g b T g b Bulk tanδ / a.u Temperature / K δ s / a.u. M n = 250k M n = 1,450k T g s T g b T g s T g b T g b Temperature / K Bulk tanδ / a.u. δ δ N. Satomi, A. Takahara, T. Kajiyama: Macromolecules, 32, 4474(1999).

44 PSH T gs T gb T g / K Room temperature 1 1. : Surface M n 2. : Bulk Scaling analysis T T s g s = g s g, obsd T K M S 0.5 n K = 365 M S 0.5 n Fox K S Tg = Tg M n

45 sec C 4 H 9 ( CH 2 CH ) H n LMWhPS sec C 4 H 9 ( CD 2 CD ) H n D D D D D dps847k 200nm PS Si 423K

46 Lateral force/a.u (PS19.7k/dPS847k) ν = 10 3 nm s 1 PS 19.7k bulk fraction / vol.% St secbuli benzene MeOH secbu(ch 2 CH) n H protonterminated PS T gs /K hps19.7k 279 dps847k Temperature / K

47 Tg/K bulk (DSC) 2. surface (LFM) Additivity rule hps bulk fraction / Vol.% 2 φ = 1 T T s s g,2 g, blend T T s s g,2 g,1

48 (LMWhPS/HMWdPS) Surface hps fraction / Vol% (PS19.7k/dPS847k) LFM 2. SSIMS 3. NR 4. Hariharan et al Bulk PS19.7k fraction / vol.%

49

50 5µm ajiyama Takahara µm µm µ µ

51 PE : n a =n. b =1.51 n c =1.58( ) n=n c n a =0.07. a b PE : a=0.493 nm b=0.740 nm c=0.253 nm γ β α β a c b

52 (PHB) NSOM CH 3 C O H CH 2 O C 2µm 2µm R. L. Williamson, M. J. Miles, J. Vac. Sci. Tech., B14, 809(1996).

53 n r n c 5µm ) (B) H. Ade, R. ToledoCrow, M. )Topograph (D) VaezIrvani, R. J. Spontak,

54 (Sccanning Thermal Microscopy: SThM) Wollaston probe Pt/Rh(9/1) wire

55 (PVC/PBD) blend

56 Photoresit

57 Patterned PMMA on Silica Substrate

58 Si 10nm50nmPS X q A4 A4

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