Recent Topics in TOF-SIMS Instrumentation

at ULVAC-PHI

ULVAC-PHI Inc., Analytical Laboratory

Shin-ichi IIDA

1

The 18th Scientific International Symposium on SIMS Related Techniques Based on Ion-Solid Interactions (SISS)

23th July, 2016

Outline

Company Introduction

Introduction of PHI nanoTOF II

Applications

2

1) FIB-TOF-SIMS

2) MS/MS

Summary

XPS

About ULVAC-PHI -The World Leading Manufacturer of Surface Analysis Instruments-

PHI Quantera II PHI VersaProbe III PHI X-tool

3

SIMSAES

PHI 710 PHI nanoTOF IITime-of-Flight SIMS

PHI 4800 PHI ADEPT-1010Quadrupole SIMS

PHI VersaProbe III PHI 4800

PHI New Products

4

Scanning micro focus X-ray source

High sensitivity

Ultimate depth resolution

Various types of options

SCA analyzer enables us to obtain the AES spectrum with high sensitivity, and high energy resolution

Detailed AES chemical map

Introduction of PHI nanoTOF II

After releasing PHI After releasing PHI nanoTOFnanoTOF in 2006, we have provided many components. in 2006, we have provided many components.

Ar gas cluster ion gun

Ar/O2 ion gun

FIB gun

5

C60 ion gun

Cs ion gun

Transfer VesselSpecimen Stage (standard)

Specimen Stage Options

6

Cold Stage(-150～+150 ℃)

Hot Stage(RT ～ +600 ℃)

Zalar Rotation

XPSIntro Camera Photo

Scanning X-ray image

SE Image Live view Sample Camera image

AES TOF-SIMS

Common Operation Software “SmartSoft”

7

XPS spectra XPS mapSIM Image

AES spectra AES maps

We provide “We provide “SmartSoftSmartSoftTMTM” for ” for all types of our instruments.all types of our instruments.The same software interface makes us easy to master The same software interface makes us easy to master

the operation of all PHI instruments. the operation of all PHI instruments.

R：Pt-

G：C2-

10 m

Overlay ImageSIM Image

FIB Cross-section

FIB Cross-section

FIB

Pt

PC

FIB Fabrication of Inorganic/Organic Material

Sample: Pt/Polycarbonate

8

FIB causes damage on the cut surface and leads to no chemical information.

10 m

Ga+O

Ga+C2

20 40 60 80 100 120 1400

2.0E4

4.0E4

6.0E4

35 48

12

16

24

109 117101

60 9372

85

C6C5

C4

C2

O

CGa+C4

Ga+O2

Ga+C2O

m/z (Negative ions)

Negative ion spectrum from FIB cross-section

x20

Counts

Removal of FIB Induced Damaged Layer

10 m 10 m

C14H11O2C14H11O2

After removing the damaged layer by Ar-GCIB...

Negative ion spectrum from FIB cross-section

9

Combination of FIB and Ar-GCIB enables us to discover the chemical information underneath the metal layer.

50 100 150 2000

2.0E3

4.0E3

6.0E3

97 1174113373

2119349C4H

C6H

250m/z (Negative ions)

C14H11O2

C9H9O

C6H5O

=

C8H5O

C8H

Counts

Negative ion spectrum from FIB cross-section

Introduction -Why is MS/MS needed?-

（1）Unpredictable fragment pattern

（2）Commercial use of cluster ion beam

Need to take a spectrum of standard sample in advance.

Sensitivity of high mass molecular ions are dramatically enhanced.

Interpretation of a TOF-SIMS spectrum Quite difficult !

10

（3）Conventional TOF-SIMS instrument

Sensitivity of high mass molecular ions are dramatically enhanced.Many peaks are observed at high mass region.

For molecular ions > 200 Da, difficult to determine the chemical formula from measured mass.

Possible Chemical Formula (C,H,N,O)Peak Identification in TOF-SIMS

282.285

Cou

nts

0

200

400

600

800

1000

Introduction -Why is MS/MS needed?-

11

m/z, Negative ions270 275 280 285 290 295

0

MS/MS system in TOF-SIMS enables us to overcome the difficulty of the peak identification.

ES2 ES1

Linear TOFCID Cell

Detector(MS2)ES1ES2

Conventional TOF-SIMS MS/MS in TOF-SIMS

MS/MS in TOF-SIMS

12

ES3Detector

LMIG

Sample

Detector(MS1)

ES3

Sample

LMIGMS1/MS2

Switch

Features of the MS/MS in TOF-SIMS

1) Parallel detectionCollect both MS1 and MS2 data from the same area simultaneously.

2) Width of mass selection within 1 Da

3) Easy operationOnly input the mass number into the software.

Linear TOFCID Cell

Detector

Detector(MS2)ES1ES2

ES3

13

3) Easy operationOnly input the mass number into the software.

4) High speed acquisitionMaintain the TOF-SIMS repetition rate

5) Simple MS2 spectrum

Detector(MS1)

Sample

LMIGMS1/MS2

Switch

For further information on the applications of parallel imaging MS/MS,

please see the presentation by G.L.Fisher, Physical Electronics

14

please see the presentation by G.L.Fisher, Physical Electronics

on Friday at 2:50 pm

Sample

Sample

Several unknown additives in PP

Analysis Conditions

• Primary ions: 30 keV Bi3+

n

CH2 CH

CH3

Polypropylene (PP)

15

• Primary ions: 30 keV Bi3• Measurement time: 8 min

• PIDD: 7.6 × 1011 ions/cm2

0 100 200 300 4000

2.0E+54.0E+56.0E+58.0E+51.0E+61.2E+6

212134

2969

9123

39 58

481

284

304

256312

332

Cou

nts

500

Conventional TOF-SIMS Spectrum

368

MS1 (conventional TOF-SIMS) spectrum from PP surface

×20

C7H7

C3H8NNa

K

C9H12N

16

0 100 200 300 400 500m/z, Positive Ions

Spectrum was complicated, and difficult to determine the chemical formula for compound identification.

MS2 spectra of m/z 304, 284 and 481 were acquired.

To reveal the details of them,

0

5.0E+4

1.0E+5

1.5E+5

2.0E+5

×20C

ount

s C3H8NC7H7 C14H30N

C21H38N304

212

91

58

135C9H13N

50 100 150 200 250 300m/z, Positive Ions

Chemical Structure Analysis of m/z 304

MS2 Spectrum of m/z 304

17

N+

91

Benzalkonium

21258

135

m/z, Positive Ions

0 50 100 150 200 2500

10000

20000

30000284

300

60

43

7185

m/z, Positive Ions

C3H7

(CH3)3NHC5H11

C6H13Cou

nts

×20

Chemical Structure Analysis of m/z 284

MS2 Spectrum of m/z 284C19H42N

18

m/z, Positive Ions

Hexadecyltrimethylammonium

60

N+

CH3 CH3

CH3 43 71 85

Chemical Structure Analysis m/z 481

MS2 Spectrum of m/z 481

C3H8NC9H18N

C28H53N2O4

C19H36NO4C9H15

0 100 200 300 400m/z, Positive Ions

5000

20000

40000

60000

80000C

ount

s481

140

58

342

×15

123

19

Tinuvin770140

342

123

58

m/z, Positive Ions

0 100 200 300 4000

2.0E+54.0E+56.0E+58.0E+51.0E+61.2E+6

212134

2969

9123

39 58

481

284

304

256312

332

Cou

nts

500

368

MS1 spectrum from PP surface

×20

C7H7

C3H8NNa

K

C14H30NC9H12N

Identification of the Compounds

20

0 100 200 300 400 500m/z, Positive Ions

Massweight (u)

Chemicalformula

Compound name

284 C19H42N Hexadecyltrimethylammonium304 C21H38N Benzalkonium481 C28H53N2O4 Tinuvin770

In this presentation, we introduced our latest options and applications of In this presentation, we introduced our latest options and applications of nanoTOFnanoTOF II. II.

FIBFIB--TOFTOF--SIMSSIMS<Cross<Cross--section imaging of organic/inorganic material>section imaging of organic/inorganic material>

It was possible to remove the damaged layer by It was possible to remove the damaged layer by ArAr--GCIB.GCIB.Combination of FIB and Combination of FIB and ArAr--GCIB enables us to discover GCIB enables us to discover the chemical information underneath the metal layer.the chemical information underneath the metal layer.

Summary

21

the chemical information underneath the metal layer.the chemical information underneath the metal layer.

MS/MSMS/MS<Identification of unknown additives on polymer surface><Identification of unknown additives on polymer surface>

From the MSFrom the MS22 spectrum analyses, we can obtain spectrum analyses, we can obtain the detailed information on chemical structure, and the detailed information on chemical structure, and identify the compound.identify the compound.