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1 TOF-SIMS

2 SIMS TOF-SIMS SIMS Mass Spectrometer ABCDE + ABC+ DE + Primary Ions: 1 12 ions/cm 2 Molecular Fragmentation Region ABCDE ABCDE 1 15 atoms/cm 2 Molecular Desorption Region Why TOF-SIMS?

3 TOF-SIMS M/ M 1 - M 1 mamu M/M 1 ppm M 1 amu - Ga + Au n+ D-SIMS

4 TOF-SIMS

5 TOF-SIMS SIMS SIMS Damage cross section Precursor model - - Damage cross section Damage cross section Au TOF-SIMS

6 SIMS Damage Cross Section; Disappearance Cross Section Damage cross section σ 1 SIMS

7 SIMS Damage Cross Section; Disappearance Cross Section lnn(counts) Θ(t)=Θ exp[-σνt] ν=i P /Ae Θ: N I P A: e σ σ νt (ions/cm 2 ) t(sec) or νt(ions/cm 2 ) νt 1/σ σ= cm 2 νt < ions/cm 2

8 SIMS /Ag D. van Leyen et al., J. Vac. Sci. Technol. A7(3), 179 (1989) m/z 22 6: Ag-cationized oligomers, (nr+ag) + R: repeat unit with m=14 amu

9 SIMS /Ag Disappearance cross section, σ σ m=1 σ = cm 2 3n m=69 σ = cm 2 7nm

10 Precursor model Desorption active area A D E(r): E D : r R E(r) E r R D E(r) E D A D R r R D Precursor : Preformed ion

11 (counts/channel) NO 2 SO C 3 3 H 29 9 Si + C 4 H 12 N C 2 H 6 SiO m/z NO x SO x UV ( 5 ) (18 5 ) UV + (18 5 )

12 28 Si PP DHF PP DHF ( 4) ( 2) ( 8) 13 CH - 25 C 2 H C 14 H 27 O C 16 H 31 O C 18 H 35 O 2 -

13 Precursor model E(r): E D : σ E D D.Rading et al., J. Vac. Sci. Technol. A 18(2), 312 (2) A D : Desorption active area E D σ σ

14 Desorption energy E D, damage cross section σ, and the distance r from the point of primary ion impact Thiol E D /ev σ/1-16 cm 2 r /nm BT(n=4) HT(n=6) OT(n=8) DT(n=1) DDT(n=12) BDT(n=14) HDT(n=16) ODT(n=18) TSA (M-H) TSA (M-COOH) MCP (M-H) /Au σ cm 2 Alkanethiol n=8 1 σ E D σ σ E D 1.3 2eV σ

15 Desorption active area A D

16 vs. B TOF-SIMS νt= ions/cm 2, A=1 m (a) 69 Ga + SF 5+, Au n+, Bi n+, (CsI) n Cs +, C 6+, ReO 4, etc. (b) 115 In +

17 TOF-SIMS SIMS SIMS Damage cross section Precursor model - - Damage cross section Damage cross section Au TOF-SIMS

18 Au Si Primary Ion: Au 3 + 1µm Total ion SiH x O y - 85 C 4 H 5 O C 9 H 13 O 4 - Primary Ion: Ga + 1µm Total ion SiH x O - y 85 C 4 H 5 O C 9 H 13 O - 4 TOF-SIMS images of Si wafer surface with the foreign substance.

19 Intensity (counts) O - CH - O - 8 O 85 - O O - CH 3 O - 1 CH - SiHO Au Si O - O 1 M / Z 2 3 OCH O OCH 3 Primary Ion: Au 3 + O - OCH 3 Primary Ion: Ga + Ga + 85 C 4 H 5 O 2- Au C 4 H 5 O C 8 H 13 O C 9 H 13 O 4-

20 Au Intensity (counts) 1 4 C 4 H 7 + C 3 H HO CH HO N N N OH C 5 H 11 C 5 H 11 CH 2 OH 569 HO 774 OH OH Intensity (counts) 1E7 1E6 1E5 1E4 1E3 1E2 1E1 1E M / Z Ga + Au + Au + 3 Ca + Ba + 15 CH C 3 H C 15 H 23 O C 4 H 57 O C 22 H 3 N 3 O C 54 H 78 O + 3

21 Influence of primary ion bombardment conditions on the emission of molecular secondary ions R.Kersting et al., Appl. Surf. Sci. 231/232, 261(24)

22 Molecular secondary ion formation under cluster bombardment: A fundamental review A.Wucher, Appl. Surf. Sci. 252, 6482(26) C 6+ Erosion depth > Range?!

23 C 6+ J.Cheng et al., Anal Chem. 77, 3651(25)

24 SIMS Damage cross section Molecular imaging SIMS Damage cross section

25 TOF-SIMS SIMS SIMS Damage cross section Precursor model - - Damage cross section Damage cross section Au TOF-SIMS

26 TOF-SIMS SIMS - Damage cross section

Dynamic SIMS Static SIMS µ µ

Dynamic SIMS Static SIMS µ µ . (Secondary Ion Mass Spectroscopy:SIMS) 1) SIMS SIMS Dynamic SIMS Static SIMS µ µ SIMS 1. 2. DSIMS) 3. DSIMS) 4. DSIMS) 5. 6. 7. SSIMS) 8. SSIMS) 9. SSIMS) SIMS 1. 2. = O - Cs + µ µ µ SIMS 4keV O 2 +

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