Quantitative Analysis of Surface Oxidation of Carbon Materials Using Soft X-Ray Absorption Spectroscopy with Total Electron Yield Methods

Transcription

1 X Eric M.Gullikson Quantitative Analysis of Surface xidation of Carbon Materials Using Soft X-Ray Absorption Spectroscopy with Total Electron Yield Methods Satoshi UEDA, Yasuji MURAMATSU and Eric M.GULLIKSN Copyright The Discussion Group of X-Ray Analysis, The Japan Society for Analytical Chemistry

2

3 X Eric M. Gullikson Quantitative Analysis of Surface xidation of Carbon Materials Using Soft X-Ray Absorption Spectroscopy with Total Electron Yield Methods Satoshi UEDA, Yasuji MURAMATSU and Eric M. GULLIKSN Graduate School of Engineering, University of Hyogo 2167 Shosha, Himeji, Hyogo , Japan Lawrence Berkeley National Laboratory 1 Cyclotron Road, Berkeley, CA 9472, USA (Received 21 December 26, Revised 18 January 27, Accepted 19 January 27) We have proposed a quantitative analysis method of the surface oxygen on carbon materials using total-electron-yield soft X-ray absorption spectroscopy. In this method, absorption peak intensity ratio of the K/CK edges in standard samples can be plotted as the /C ratio, which can be the calibration curve for the quantitative analysis of oxygen in carbon. We have successfully obtained the calibration curve using the standard samples of polyaromatic hydrocarbons having various oxygenated functional groups. [Key words] Synchrotron radiation, Soft X-ray, X-ray absorption, Carbon materials, xidation, Quantitative analysis X TEY-XAS K/CK /C TEY-XAS K/CK /C Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 9472, USA corresponding author: murama@eng.u-hyogo.ac.jp Adv. X-Ray. Chem. Anal., Japan 38, pp (27)

4 Kσ*/CKσ* /C X X 1. X X XANES: X-ray absorption nearedge structure X XANES 1 I (I) I/I I/I X X X X X X TEY: total electron yield X nm 2 TEY X X TEY-XAS: TEY X-ray absorption spectroscopy TEY-XAS 3-6 CK K TEY-XAS 7 TEY TEY

5 TEY-XAS TEY-XAS TEY-XAS TEY-XAS 2. TEY-XAS TEY-XAS A B Fig.1 X TEY-XAS A B A B h A, h B A B TEY-XAS h B /h A B/A TEY-XAS h B /h A B/A A B TEY X-ray absorption spectrum Total electron yield A-edge h A B-edge h B Energy Fig.1 Principle of quantitative analysis for B in A elements using soft X-ray absorption spectroscopy with total electron yield methods. Relative peak intensity ratio of h B /h A can be obtained from the measured absorption edges of A and B. The h B /h A will be plotted against the B/A ratio, which can be the calibration curve of quantitative analysis for B in A

6 3. TEY-XAS h /h C K/ CK /C C H (a) Phloroglucinol (g) 1,1'-Bi-2-naphthol CH (m) Anthraquinone- 2-carboxylic Acid (b) 1-Naphthol C (h) 9-Anthraldegyde C (c) 1,4-Naphthalenedicarboxylic Acid C (d) 1-Naphthoic Acid (e) 1,2-Naphthoquinone C (i) Xanthone C (j) 9-Anthracenecarboxylic Acid (k) Quinizarin (n) Anthrarobin H (o) Anthraflavic Acid HC (f) 2,6-Naphthalenedicarboxylic Acid (l) Anthrarufin (p) Bianthrone Fig.2 Polyaromatic hydrocarbons having various oxygenated functional groups, whose TEY-XAS are measured to plot the calibration curve for quantitative analysis of oxygen in carbon

7 Fig.2 16 TEY-XAS - -C -C= -- TEY-XAS Advanced Light Source ALS BL /mm 5 µm K 265 ev CK ( 285 ev) K ( 53 ev) 2 ev 6 ev E/ E 15, 2 ev 1,5 6 ev 9 I I/I TEY-XAS Pa a p TEY-XAS Fig.3 CK K 285 ev 53 ev K ev 2 ev 6 ev CK K 1 Fig.3 TEY-XAS K/CK /C quinizarin TEY-XAS Fig.4 TEY-XAS CK K π* σ* K/CK

8 K 2nd order CK K (a) (b) Total Electron Yield (arb. units) (c) (d) (e) (f) (g) (h) (i) (j) (k) (l) (m) (n) (o) Fig.3 TEY-XAS in the 2-6 ev region of the polyaromatic hydrocarbons. (p) Photon energy / ev TEY (arb. units) K (2nd) CK π* σ* (k) Quinizarin K π* σ* Photon energy / ev Fig.4 TEY-XAS of Quinizarin

9 Kσ*/CKσ* Kπ*/CKσ* Kσ*/CKπ* Kπ*/CKπ* 4 4 /C K /CK Fig.5 R 2 Kσ*/CKσ*.873 Kσ*/ CKσ* K/CK 3 π* π* σ* π* 3 K/CK σ* Kσ*/CKσ* Kσ*/CKσ*.45 Peak intensity ratio, K/CK 2 1 Kσ*/CKσ* R 2 = Atomic ratio, /C.5 Peak intensity ratio, K/CK 1.5 Kπ*/CKσ* R 2 = Atomic ratio, /C.5 Peak intensity ratio, K/CK 2 1 Kσ*/CKπ* R 2 = Atomic ratio, /C.5 Peak intensity ratio, K/CK 1.5 Kπ*/CKπ* R 2 = Atomic ratio, /C Fig.5 Atomic ratio (/C) dependence of the absorption peak intensity ratio (K/CK) in the TEY- XAS of the measured polyaromatic hydrocarbons. The K/CK ratios of Kσ*/CKσ* Kπ*/CKσ* Kσ*/CKπ* and Kπ*/CKπ* are plotted in the figures

10 % % % 5. TEY-XAS K/CK /C TEY-XAS K/CK /C K/CK σ* Kσ*/CKσ* /C % X 9 TEY-XAS X NEXAFS Spectroscopy J.Stöhr (Springer, Berlin, Heidelberg, New York, 1992). 2 M.P.Seah, W.A.Dench: Surf. Interface Anal., 1, 2-11 (1979). 3 : X 3, (1999). 4 R.C.C.Perera: X 31, (2). 5 E.M.Gullikson, R.C.C.Perera: X 35, (24). 6 Y.Muramatsu, E.M.Gullikson, R.C.C.Perera: Phys. Scr., T115, (25). 7 Y.Muramatsu, M.Yamashita, M.Motoyama, M.Hirose, J.D.Denlinger, E.M.Gullikson, R.C.C.Perera: X-Ray Spectrom., 34, (25). 8 J.H.Underwood, E.M.Gullikson, M.Koike, P.J.Batson, P.E.Denham, K.D.Franck, R.E.Tackaberry, W.F.Steele: Rev. Sci. Instrum., 67, 3372 (1996). 9 Y.Muramatsu K.Kuramoto, E.M.Gullikson, R.C.C.Perera: Surf. Rev. Lett., 9, (22)