Shou-Jun Xiao 萧守軍 hysz.nju/sjxiao

1. Multiple Transmission-Reflection Infrared Spectroscopy and Silicon Surface Organic Chemistry for Biological Applications Shou-Jun Xiao 萧守軍 http://hysz.nju.edu.cn/sjxiao Nanjing University Presented at Institute of Ruder Boskovic, Zagreb, Sept. 29, 2015

2. 2 Outline MTR-IR Spectroscopy (Multiple Transmission-Reflection Infrared Spectroscopy) 1 A Sensitive Tool for Infrared-(Semi)Transparent Semiconductors Silicon Surface Organic Chemistry for Biological Applications

3. Spacer d < 5nm Head Base Self-Assembled Molecular Film on Silicon Surface 1 XPS AES for elements and concentrations AFM STM for molecular topologies IR for reactions, molecular structures and orientations

4. How to Characterize Molecular Film on Planar Silicon with IR ? • Brewster-Angle Single Transmission BST • Multiple Internal Reflection MIR • Grazing-Angle Attenuated Total Reflection GATR We developed GMBR and MTR from 2004 on • Grazing-Angle Mirror Backed ReflectionGMBR • Multiple Transmission-Reflection MTR

5. Known Measurement Methods Coupling from high-refractive index media Coupling from air media MIR (100 USD/prism) Si/monolayer/air IRRAS (for metal) air/monolayer/Si p-polarized BST (weak signal) air/monolayer/Si GATR (tricky) Ge/monolayer/Si

6. T = 1-R silicon θ R IR Beam Reflection and Transmission of Silicon Brewster angle 73.60 Absorance A = -log(R/R0) Absorption depth ∆R = R0 – R R0－No monolayer R－Monolayer A ∆R

7. Grazing Angle Mirror Backed Reflection (GMBR) Multiple Transmission Reflection (MTR) Our Development

8. gold mirror silicon θ Detector Infrared light GMBR (Grazing Angle Mirror Backed Reflection) • Energy conversation • Reflection and two transmission J. Phys. Chem. B2006, 36, 17702

9. Examples of GMBR Measurement NHS ester UA

10. MTR-IR CHEMPHYSCHEM, 2008, 9, 1979 JPC. A, 2008, 112, 12372-7

11. O O O O O O O OH O O OH O P P P P P OH O O O O O O O TiO2 Si/SiO2 TiO2 O O O O O O O OH O O OH O P P P P P OH O O O O O O O TiO2 Si/SiO2 TiO2 PO4-(CH2)15-CH3 Dynamic Assembly of Alkanephosphate on TiO2 CHEMPHYSCHEM, 2008, 9, 1979

12. Langmuir-Blodgett Arachidic Acid Film MTR-IR for AA LB Films J. Phy. Chem. C, 2010, 114，333

13. MTR-IR Accessory (commercially available) Scienco LTD

14. Publications of Other Groups by MTR－IR Spencer’s group > 8 Using MTR-IR Prof. N.D. Spencer at ETHZ, Switzerland Prof. Zhan Chen at Univ. of Michigan Prof. Mingdi Yan at Portland State Univ.

15. MTR-IR Application in Industry：Impurity of O and C in Silicon Polycrystalline Si Single Crystal Si Solar Cell Si Purity >(99.99999%), or 7N, <10 ppm Electronic Si Purity >(99.999999999%) , or11N, <1 ppb Si Solar Cell Polycrystalline Si in China：120,000 tons in 2012，half production of the world.

16. Principle of Infrared Measurement Si-C Si-O A = a • b • c

17. An Example Comparison of MTR-IR and standard IR for the same sample N＝6，Amtr= 6 Air Single Crystalline Silicon Polycrystalline Silicon

18. Advantages by Using MTR-IR for [Oi] and [Cs] • One order of magnitude higher sensitivity than the current standard IR method for the same silicon sample (thickness: 2 mm to 0.1 mm) • Especially beneficial for thin crystalline silicon slices (0.1 ~ 0.3 mm): quantitative, reproducible, and no-interference-interrupting measurement • Excellent for polycrystalline silicon by statistical averaging measurement • Semi standards in authentication: see Semi web http://downloads.semi.org/web/wstdsbal.nsf/b8865fa87d9e7b57882579fb005c3cd7/1aeb492ac6acc27688257ca5003076a2!OpenDocument • http://downloads.semi.org/web/wstdsbal.nsf/b8865fa87d9e7b57882579fb005c3cd7/57bbdfb

19. 2 Silicon Surface Organic Chemistry for Biological Applications

20. Planar and Porous Silicon

21. Self-Assembled Monolayers on Silicon Surfaces Beginning from Silane Chemistry since 1946 Bigelow, W. C., Pickett, D. L. & Zisman, W. A.J. Colloid Sci. 1, 513 (1946)

22. Focus on Wet Hydrosilylation Chemistry Thermal Chemistry (heating, -wave ) Photochemistry H R RX R H Si Si -wave … R H X=vinyl(C=C) or acetylenyl(CC), Br, azide, diazirine Linford, M. R.; Chidsey, C. E. D. J. Am. Chem. Soc. 1993, 115, 12631

23. Molecular monolayerPhoto-active groups for covalent attachment Diazirene End-Azide R－N3

24. Polymer Brushes

25. MTR-IR spectroscopy characterization NHS Ester

26. MTR-IR spectroscopy characterization N-H

27. Binding of FITC-labeled His-tag Protein

28. Click Chemistry JCIS

29. Surface Chemistry Details Cross-linkers

30. Details of surface organic chemistry AuC AuCM AuCMP

31. O O C O N O Infrared spectra of AuCM surfaces 0.009 NHS ester str O 0.008 mal C=O asy str N 0.007 O 0.006 amide II 0.005 AuCM6 0.004 AuCM11 Absorbance units AuCM8 0.003 AuCM4 0.002 AuCM3 AuCMP 0.001 AuCMB 0 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 Wavenumber (cm-1)

32. One specific example AuCM6 AuCM6P

33. IR spectra of the above reactions 1665: amide I 1540: amide II AuCM6P Absorbance units AuCM6 Wavenumber (cm-1)

34. Different EDC/NHS Activation Mechanisms between PAA and PMAA O-acylisourea

35. PAA PMAA

36. Amide Yield from NHS-ester Amide Yield from Anhydride ≈ 30% ≈ 70%

37. EDC/NHS Activation Mechanism of PMAA: Anhydride vs NHS-ester Gem-Dialkyl Effect is the Reason for Anhydride RSC Advances, 2015, 5, 69939-47

38. Macro-patterning：Microarray Based on NTA Monolayer p, freshly etched; a, undecylenic acid modified; b, NHS-funtionalized; c, NTA-grafted; d, NiII-loaded; e, His-tag protein immobilized PSi

39. Microarray by Printing (Plotting) His-tag Thx-Urodilatin His-tag Aprotinin

40. Dynamic Response of Microarray Science China Chemistry 2010

41. Micro-patterning：Microarray by Hydrogel Membrane

42. Lab on a Chip, 2009, 756

43. Thanks to my students:

44. $$$ • NSFC • MOST of China • Jiangsu Province • Nanjing Univ. Collaborators： Prof. Nicholas D. Spencer， ETHZ Prof. Marcus Textor， ETHZ Prof. Nadrian C. Seeman, New York Univ Prof. Anton-Harm Klok, EPFL Prof. Thomas Laurell, Lund Univ. Dr. Goran Baranovic Dr. Susana Segota Institute of Ruder Boskovic