Structure and mechanism of photooxidation of self-assembled monolayers of alkylthiols on silver studied by XPS and static SIMS

被引:119
作者
Hutt, DA [1 ]
Cooper, E [1 ]
Leggett, GJ [1 ]
机构
[1] Univ Nottingham, Dept Mat Engn & Mat Design, Nottingham NG7 2RD, England
来源
JOURNAL OF PHYSICAL CHEMISTRY B | 1998年 / 102卷 / 01期
关键词
D O I
10.1021/jp972394v
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
)(PS and static SIMS have been employed to characterize the structures and the photooxidation of self-assembled monolayers (SAMs) of alkylthiols on silver. Samples were prepared by immersing silver substrates in thiol solutions for a range of times from 30 min to 40 h, but no changes were observed in either the compositions of the monolayers determined by XPS or the static SIMS spectra. Static SIMS spectra exhibited a range of characteristic molecular species that facilitated quantification of changes in the SAM structure following exposure to UV light. Photooxidation led to the formation of alkylsulfonate species at a rate that depended on the length of the adsorbate alkyl chain. However, evaluation of XPS compositional data suggested that significant amounts of unoxidized sulfur remain even when SIMS data indicate the absence of intact, unoxidized thiolate species in the monolayer. In agreement with the results of other workers, we propose that photoirradiation of SAMs on silver leads to two processes: photooxidation of thiol adsorbates to alkylsulfonates and sulfur-carbon bond scission. The latter process, not observed in an earlier study of SAMs on Au, leads to the formation of significant quantities of inorganic sulfur that are subsequently slowly oxidized to yield inorganic oxides of sulfur.
引用
收藏
页码:174 / 184
页数:11
相关论文
共 25 条
  • [1] COMBINING MICROMACHINING AND MOLECULAR SELF-ASSEMBLY TO FABRICATE MICROELECTRODES
    ABBOTT, NL
    ROLISON, DR
    WHITESIDES, GM
    [J]. LANGMUIR, 1994, 10 (08) : 2672 - 2682
  • [2] FORMATION OF MONOLAYER FILMS BY THE SPONTANEOUS ASSEMBLY OF ORGANIC THIOLS FROM SOLUTION ONTO GOLD
    BAIN, CD
    TROUGHTON, EB
    TAO, YT
    EVALL, J
    WHITESIDES, GM
    NUZZO, RG
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (01) : 321 - 335
  • [3] BRIGGS D, 1990, AUGER XRAY PHOTOELEC, V1, P604
  • [4] SUPERLATTICE STRUCTURE AT THE SURFACE OF A MONOLAYER OF OCTADECANETHIOL SELF-ASSEMBLED ON AU(111)
    CAMILLONE, N
    CHIDSEY, CED
    LIU, GY
    SCOLES, G
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (04) : 3503 - 3511
  • [5] Rates of attachment of fibroblasts to self-assembled monolayers formed by the adsorption of alkylthiols onto gold surfaces
    Cooper, E
    Wiggs, R
    Hutt, DA
    Parker, L
    Leggett, GJ
    Parker, TL
    [J]. JOURNAL OF MATERIALS CHEMISTRY, 1997, 7 (03) : 435 - 441
  • [6] REAL-SPACE OBSERVATION OF NANOSCALE MOLECULAR DOMAINS IN SELF-ASSEMBLED MONOLAYERS
    DELAMARCHE, E
    MICHEL, B
    GERBER, C
    ANSELMETTI, D
    GUNTHERODT, HJ
    WOLF, H
    RINGSDORF, H
    [J]. LANGMUIR, 1994, 10 (09) : 2869 - 2871
  • [7] STRUCTURE OF SELF-ASSEMBLED DECANETHIOL ON AG(111) - A MOLECULAR RESOLUTION SCANNING-TUNNELING-MICROSCOPY STUDY
    DHIRANI, A
    HINES, MA
    FISHER, AJ
    ISMAIL, O
    GUYOTSIONNEST, P
    [J]. LANGMUIR, 1995, 11 (07) : 2609 - 2614
  • [8] STRUCTURE OF CH3(CH2)17SH SELF-ASSEMBLED ON THE AG(111) SURFACE - AN INCOMMENSURATE MONOLAYER
    FENTER, P
    EISENBERGER, P
    LI, J
    CAMILLONE, N
    BERNASEK, S
    SCOLES, G
    RAMANARAYANAN, TA
    LIANG, KS
    [J]. LANGMUIR, 1991, 7 (10) : 2013 - 2016
  • [9] MOLECULAR IMAGING SECONDARY-ION MASS-SPECTROMETRY FOR THE CHARACTERIZATION OF PATTERNED SELF-ASSEMBLED MONOLAYERS ON SILVER AND GOLD
    GILLEN, G
    BENNETT, J
    TARLOV, MJ
    BURGESS, F
    [J]. ANALYTICAL CHEMISTRY, 1994, 66 (13) : 2170 - 2174
  • [10] SCANNING-TUNNELING-MICROSCOPY INVESTIGATION OF SULFIDE AND ALKANETHIOLATE ADLAYERS ON AG(111)
    HEINZ, R
    RABE, JP
    [J]. LANGMUIR, 1995, 11 (02) : 506 - 511