Abstract
The formation of self-assembled monolayer (SAM) films onto aluminum and copper oxide surfaces by reaction with 1H,1H,2H,2H-perfluorodecylphosphonic acid (PFDP), octadecylphosphonic acid (ODP), decylphosphonic acid (DP), octylphosphonic acid (OP), and 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane (PFMS) is discussed in this chapter. The properties and chemical stability of the films have been investigated using complementary surface analysis techniques: X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), friction force microscopy (FFM), a derivative of AFM, contact anglemeasurements, and Fourier transform infrared reflection/absorption spectroscopy (FT-IRRAS). XPS data confirm the presence of alkylphosphonate (perfluorinated and nonperfluorinated) and perfluorosiloxy molecules in the PFDP/Al, ODP/Al, DP/Al, OP/Al, and PFMS/Al SAMs formed on aluminum oxide surfaces. The sessile drop static contact angles of deionized water on PFDP/Al and PFMS/Al are typically more than 130◦ and on ODP/Al, DP/Al, and OP/Al typically more than 125◦, indicating that Al surfaces reacted with alkylphosphonic acids and alkylsilanes are very hydrophobic. The surface roughness for PFDP/Al, ODP/Al, DP/Al, OP/Al, PFMS/Al, and unmodified Al is approximately 35 nm, as determined by AFM. The critical surface tension for PFDP/Al has been determined to be approximately 11 mJm−2 (mNm−1) by the Zisman plot method compared with 16, 20, 21, and 25 mJm−2 for PFMS/Al, ODP/Al, DP/Al, and OP/Al, respectively. PFDP/Al gives the lowest adhesion and friction force, while unmodified Al gives the highest. The adhesion and friction forces for ODP/Al and DP/Al SAMs are in-between those of PFDP/Al and Al. The influence of relative humidity, temperature, and sliding velocity on the friction and adhesion behavior has also been studied. Failure mechanisms of SAMs have been investigated by wear tests. The chemical stability of ODP/Al, PFDP/Al, DP/Al, OP/Al, and PFMS/Al SAMs has been tested by exposure to warm nitric acid (pH 1.8, 30 min, 60– 95 ◦C). The XPS data and stability against harsh chemical conditions indicate that a type of bond forms between a phosphonic acid or silane molecule and the oxidized Al surface. Stability tests using warm nitric acid (pH 1.8, 30 min, 60–95 ◦C) show ODP/Al SAMs to be most stable, followed by PFDP/Al, DP/Al, PFMS/Al, and OP/Al. Hydrophobic, low adhesion, and robust Al surfaces have useful applications for microelectromechanical/nanoelectromechanical systems (MEMS/NEMS), such as the digital micromirror device. These studies are expected to aid in the design and selection of proper lubricants and antistiction coatings forMEMS/NEMS. The PFMS SAM on Cu is found to be extremely hydrophobic, typically having sessile drop static contact angles of more than 130◦ for deionized water and a critical surface tension of 14 mJm−2. FFM shows a significant reduction in the adhesive force and friction coefficient of PFMS-modified Cu (PFMS/Cu) compared with unmodified Cu. Treatment by exposure to harsh conditions shows that a PFMS/CuSAMcan withstand boiling nitric acid (pH 1.8), boiling water, and warm sodium hydroxide (pH 12, 60 ◦C) solutions for at least 30 min. Furthermore, no SAM degradation is observed when PFMS/Cu is exposed to warm nitric acid solution for up to 70 min at 60 ◦C or 50 min at 80 ◦C. XPS and FT-IRRAS data reveal a coordination of the PFMS Si atom with a cuprate (CuO) molecule present on the oxidized Cu substrate. The data give good evidence that the stability of the SAM film on the PFMS-modified oxidized Cu surface is largely due to 236 E. Hoque et al. the formation of a siloxy–copper (–Si–O-Cu–) bond via a condensation reaction between silanol (–Si–OH) and copper hydroxide (CuOH). Extremely hydrophobic (low surface energy) and stable PFMS/Cu SAMs films could be useful for surface passivation, corrosion inhibition and/or as antiwetting/low-adhesion promoters in microelectronical/nanoelectromechanical devices or on heat-exchange surfaces (dropwise condensation).
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Ulman A (1996) Chem Rev 96:1533–1554
Ulman A, Evans SD, Shnidman Y, Sharma R, Eilers JE, Chang JC (1991) J Am Chem Soc 113:1499–1506
Schreiber F (2000) Prog Surf Sci 65:151–256
Scherer J, Vogt MR, Magnussen OM, Behm RJ (1997) Langmuir 13:7045–7051
Jennings GK, Laibinis PE (1996) Colloids Surf A 116:105–114
Tan YS, Srinivasan MP, Pehkonen SO, Chooi SYM (2004) J Vac Sci Technol A 22:1917–1925
Tremont R, De Jesús-Cardona H, Garcia-Orozco J, Castro RJ, Cabrera CR (2000) J Appl Electrochem 30:737–743
Xiao X, Hu J, Charych DH, Salmeron M (1996) Langmuir 12:235–237
Blackman GS, Mate CM, Philpott MR (1990) Phys Rev Lett 65:2270–2273
Bhushan B, Cichomski M, Hoque E, DeRose JA, Hoffmann P, Mathieu HJ (2006) Microsyst Technol 12:588–596
Hoque E, DeRose JA, Kulik G, Hoffmann P, Mathieu HJ, Bhushan B (2006) J Phys Chem B 110:10855–10861
Bhushan B (ed) (2005) Nanotribology and nanomechanics—an introduction. Springer, Berlin
Kim S, Choi GY, Ulman A, Fleischer C (1997) Langmuir 13:6850–6856
Salomon A, Cahen D, Lindsay S, Tomfohr J, Engelkes VB, Frisbie CD (2003) Adv Matter 15:1881–1890
Halik M, Klauk H, Zschieschang U, Schmid G, Dehm C, Schütz M, Maisch S, Effenberger F, Brunnbauer M, Stellacci F (2004) Nature 431:963–966
Rawlett AM, Hopson TJ, Amlani I, Zhang R, Tresek J, Nagahara LA, Tsui RK, Goronkin H (2003) Nanotechnology 14:377–384
Troisi A, Ratner MA (2004) Nano Lett 4:591–595
Love JC, Estroff LA, Kriebel JK, Nuzzo RG, Whitesides GM (2005) Chem Rev 105:1103–1169
Hoque E, DeRose JA, Hoffmann P, Mathieu HJ, Bhushan B, Cichomski M (2006) J Chem Phys 124:174710–174715
Hoque E, DeRose JA, Hoffmann P, Mathieu HJ (2006) J Surf Anal 13:178–184
Hoque E, DeRose JA, Houriet R, Hoffmann P, Mathieu HJ (2007) Chem Mater 19:798–804
Hoque E, DeRose JA, Hoffmann P, Mathieu HJ (2006) Surf Interface Anal 38:62–68
Ulman A (1991) An introduction to ultrathin organic films: from Langmuir-Blodgett to self-assembly. Academic, San Diego
Allara DL, Nuzzo RG (1985) Langmuir 1:45–52
Allara DL, Nuzzo RG (1985) Langmuir 1:52–66
Brovelli D, Häner G, Ruiz L, Hofer R, Kraus G, Waldner A, Schlösser J, Oroszlan P, Ehrat M, Spencer ND (1999) Langmuir 15:4324–4327
Textor M, Ruiz L, Hofer R, Rossi A, Feldman K, Hähner G, Spencer ND (2000) Langmuir 16:3257–3271
Pellerite MJ, Dunbar TD, Boardman LD, Wood EJ J Phys Chem B 16:3257–3271
Liakos IL, Newman RC, McAlpine E, Alexander MR (2004) Surf Interface Anal 36:347–354
Kelley TW, Boardman LD, Dunbar TD, Muyres DV, Pellerite MJ, Smith TP (2003) J Phys Chem B 107:5877–5881
Adolphi B, Jähne E, Busch G, Cai X (2004) Anal Bioanal Chem 379:646–652
Frisbie CD, Rozsnyai LF, Noy A, Wrighton MS, Lieber CM (1994) Science 265:2071–2074
Kasai T, Bhushan B, Kulik G, Barbieri L, Hoffmann P (2005) J Vac Sci Technol B 23:995–1003
Wei G, Bhushan B, Jacobs SJ (2004) Ultramicroscopy 100:375–389
Hornbeck LJ (2001) MRS Bull 26:325–327
Tambe NS, Bhushan B (2005) Nanotechnology 16:1549–1558
Bhushan B (1998) Tribology issues and opportunities in MEMS. Kluwer, Dordrecht
Bhushan B (2003) J Vac Sci Technol B 21:2262–2296
Bhushan B, Liu H (2004) Nanotechnology 15:1785–1791
Bhushan B (2007) Springer handbook of nanotechnology, 2nd edn. Springer, Heidelberg
Bhushan B (1999) Handbook of micro/nano tribology, 2nd edn. CRC, Boca Raton
Hoque E, DeRose JA, Hoffmann P, Bhushan B, Mathieu HJ (2007) J Phys Chem C 111:3956–3962
Pellerite MJ, Wood EJ, Jones VW (2002) J Phys Chem B 106:4746–4754
Laiho T, Leiro JA, Heinonen MH, Mattila SS, Lukkari J (2005) J Electron Spectrosc Relat Phenom 142:105–112
Sung MM, Kim Y (2001) Bull Korean Chem Soc 22:748–752
Whelan CM, Kinsella M, Ho HM, Maex K (2004) J Electrochem Soc 151:B33–B38
Skolnik AM, Hughes WC, Augustine BH (2000) Chem Educator 5:8–13
Laibinis PE, Whitesides GM (1992) J Am Chem Soc 114:9022–9028
Rose JW (2002) Proc Inst Mech Eng Part A J Power Energy 215:115–128
Leach RN, Stevens F, Langford SC, Dickinson JT (2006) Langmuir 22:8864–8872
Izumi M, Kumagai S, Shimada R, Yamakawa N (2004) Exp Therm Fluid Sci 28:243–248
Ganzevles FLA, van der Geld CWM (2002) Int J Heat Mass Transfer 45:3233–3243
Das AK, Kitty HP, Marto PJ, Andeen GB, Kumar K (2000) J Heat Transfer Trans ASME 122:278–286
Hoque E, DeRose JA, Hoffmann P, Bhushan B, Mathieu HJ (2007) J Chem Phys 126:114706–114713
Somlo B, Gupta V (2001) Mech Mater 33:471–480
Hansal WEG, Hansal S, Pölzler M, Kornherr A, Zifferer G, Nauer GE (2006) Surf Coat Technol 200:3056–3063
Du T, Luo Y, Desai V (2004) Microelectron Eng 71:90–97
Briggs D, Seah MP (1990) Practical surface analysis by Auger and X-ray photoelectron spectroscopy, vol 1, 2nd edn. Wiley, New York
Du T, Tamboli D, Desai V, Seal S (2004) J Electrochem Soc 151:G230–G235
Hernandez J, Wrschka P, Oehrleinc GS (2001) J Electrochem Soc 148:G389–G397
Ramsier RD, Henriksen PN, Gent AN (1988) Surf Sci 203:72–88
Moulder JF, Stickle WF, Sobol PE, Bomben KD (1992) Handbook of X-ray photoelectron spectroscopy. PerkinElmer, MN
Allara DL, Parikh AN, Judge E (1994) J Chem Phys 100:1761–1764
Leung YL, Zhou MY, Wong PC, Mitchell KAR (1992) Appl Surf Sci 59:23–29
Franquet A, Biesemans M, Terryn H, Willem R, Vereecken J (2006) Surf Interface Anal 38:172–175
Wagner CD, Passoja DE, Hillery HF, Kinisky TG, Six HA, Taylor WT (1982) J Vac Sci Technol 21:933–944
Schnyder B, Lippert T, Kötz R, Wokaun A, Graubner V-M, Nuyken O (2003) Surf Sci 532–535:1067–1071
Korösi G, Kováts ES (1981) J Chem Eng Data 26:323–332
Xu X, He J-W, Goodman DW (1993) Surf Sci 284:103–108
da Cruz RS, de Silva JM, Arnold U, Sercheli MS, Schuchardt U (2002) J Braz Chem Soc 13:170–176
Bhushan B, Liu H (2001) Phys Rev B 63:245412-1–245412-11
Chidsey CED, Loiacono DN (1990) Langmuir 6:682–691
Clark ES (1999) Polymer 40:4659–4665
Liu H, Bhushan B (2002) Ultramicroscopy 91:185–202
McDermott M, Green J, Porter M (1997) Langmuir 13:2504–2510
Lide DR (ed) (2004) Handbook of chemistry and physics, 85th edn. CRC, Boaca Raton
Tambe NS, Bhushan B (2005) Nanotechnology 16:2309–2324
Wallace RM, Chen PJ, Henck SA, Webb DA (1995) J Vac Sci Technol A 13:1345–1350
Chen PJ, Wallace RM, Henck SA (1998) J Vac Sci Technol A 16:700–706
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2008 Springer-Verlag Berlin Heidelberg
About this chapter
Cite this chapter
Hoque, E., DeRose, J., Bhushan, B., Mathieu, H. (2008). Self-Assembled Monolayers on Aluminum and Copper Oxide Surfaces: Surface and Interface Characteristics, Nanotribological Properties, and Chemical Stability. In: Tomitori, M., Bhushan, B., Fuchs, H. (eds) Applied Scanning Probe Methods IX. Nano Science and Technolgy. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-540-74083-4_10
Download citation
DOI: https://doi.org/10.1007/978-3-540-74083-4_10
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-540-74082-7
Online ISBN: 978-3-540-74083-4
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)