Neutron reflection (NR), spectroscopic ellipsometry (SE), and atomic force microscopy (AFM) have been used to characterize the structure of self-assembled octadecyltrichlorosilane (OTS) layers on silicon. The first two of these techniques rely on modeling of the experimental data and may thus result in the unrealistic representation of the composition and structure at the interface. Ambiguities arise from model-dependent analysis complicated by the lack of sufficient external constraints to converge nonunique solutions to a unique one. We show in this work that AFM measurements provide extra constraints to allow us to obtain a physical description closer to the actual structure of the film. It was found that “the simpler the better” modeling strategy very often employed during the fitting of ellipsometric and neutron reflection data is, therefore, not necessarily the best way to obtain a reliable description of the interfacial structure. Our AFM findings necessitated the refit of both neutron and ellipsometric data that were previously described by a single-layer model. Interpretation of the structure of thin layers that is based only on indirect measurements such as SE, NR, and x-ray reflection techniques may be, therefore, misleading. A combined analysis of SE, NR, and AFM data suggests that the OTS film may comprise a rough layer, with pinholes down to bare silicon oxide surface, consisting at least of mono-, bi- and trilayers of OTS molecules.

1.
J.
Sagiv
,
J. Am. Chem. Soc.
102
,
92
(
1980
).
2.
J.
Ruhe
,
V. J.
Novotny
,
K. K.
Kanazawa
,
T.
Clarke
, and
G. B.
Street
,
Langmuir
9
,
2383
(
1992
).
3.
S. R.
Wasserman
,
G. M.
Whitesides
,
I. M.
Tidswell
,
B. M.
Ocko
,
P. S.
Pershan
, and
J. D.
Axe
,
J. Am. Chem. Soc.
111
,
5852
(
1989
).
4.
V.
DePalma
and
N.
Tillman
,
Langmuir
5
,
868
(
1989
).
5.
P.
Silberman
,
L.
Leger
,
D.
Ausserre
, and
J. J.
Benattar
,
Langmuir
7
,
1647
(
1991
).
6.
T.
Nakagawa
and
K.
Ogawa
,
Langmuir
10
,
525
(
1994
).
7.
H. O.
Finkles
,
L. R.
Robinson
,
A.
Blackburn
,
B.
Richer
,
D.
Allara
, and
T.
Bright
,
Langmuir
2
,
239
(
1986
).
8.
J. D.
Le Grange
,
J. L.
Markham
, and
C. R.
Kurkjian
,
Langmuir
9
,
1749
(
1993
).
9.
G.
Fragneto
,
R. K.
Thomas
,
A. R.
Rennie
, and
J.
Penfold
,
Science
267
,
657
(
1995
).
10.
X. M.
Zhao
,
Y. M.
Xia
, and
G. M.
Whitesides
,
J. Mater. Chem.
7
,
1069
(
1997
).
11.
Y. N.
Xia
and
G. M.
Whitesides
,
Annu. Rev. Mater. Sci.
28
,
153
(
1998
).
12.
Y.
Xia
,
M.
Mrksich
,
E.
Kim
, and
G. M.
Whitesides
,
J. Am. Chem. Soc.
117
,
9576
(
1995
).
13.
G.
Fragneto
,
J. R.
Lu
,
D. C.
Mc Dermott
,
R. K.
Thomas
,
A. R.
Rennie
,
P. D.
Gallagher
, and
S. K.
Satija
,
Langmuir
12
,
477
(
1996
).
14.
R. M. A. Azzam and N. M. Bashara, in Ellipsometry and Polarized Light (North Holland, Amsterdam, 1977).
15.
J.
Penfold
and
R. K.
Thomas
,
J. Phys.: Condens. Matter
2
,
1369
(
1990
).
16.
R. Wiesendanger, Scanning Probe Microscopy and Spectroscopy (Cambridge University Press, Cambridge, 1994).
17.
S. N. Magonov and M. H. Whangbo, Surface Analysis with STM and AFM (VCH, Weinheim, 1996).
18.
T.
Gesang
,
D.
Fanter
,
R.
Hoper
,
W.
Possart
, and
O. D.
Hennemann
,
Surf. Interface Anal.
23
,
797
(
1995
).
19.
B. B.
Sauer
and
D. J.
Walsh
,
Mater. Charact.
24
,
5948
(
1991
).
20.
C.
Glorieux
,
P.
de Schrijver
, and
J.
Thoen
,
J. Phys. D
30
,
2656
(
1997
).
21.
P. N.
Thirtle
,
Z. X.
Li
,
R. K.
Thomas
,
A. R.
Rennie
,
S. K.
Satija
, and
L. P.
Sung
,
Langmuir
13
,
5451
(
1997
).
22.
A. N.
Parikh
,
D. L.
Allara
,
I. B.
Azouz
, and
F.
Rondelez
,
J. Phys. Chem.
98
,
7577
(
1994
).
23.
J. R. Lu, T. J. Su, R. K. Thomas, A. R. Rennie, and R. Cubitt, J. Coll. Interface Sci. (in press).
24.
E. M.
Lee
,
E. A.
Simister
,
R. K.
Thomas
, and
J.
Penfold
,
J. Phys. Chem.
93
,
381
(
1989
).
25.
E. D. Palik, Handbook of Optical Constants of Solids (Academic, London, 1985).
26.
N.
Tillman
,
A.
Ulman
,
J. S.
Schildkraut
, and
T. L.
Penner
,
J. Am. Chem. Soc.
110
,
6136
(
1988
).
27.
R. B. Beevers, Laboratory Practice, No. 4, 272 (1973).
28.
A. I.
Vogel
,
J. Chem. Soc., Part II
1842
(
1948
).
29.
Z. X.
Wu
,
E. B.
Sirota
,
S. K.
Sinha
,
B. M.
Ocko
, and
M.
Deutsch
,
Phys. Rev. Lett.
70
,
958
(
1993
).
30.
D. E.
Aspnes
,
J. B.
Theeten
, and
F.
Hottier
,
Phys. Rev. B
20
,
3292
(
1979
).
31.
D. L.
Angst
and
G. W.
Simmons
,
Langmuir
7
,
2236
(
1991
).
32.
Digital Instruments, Nanoscope III, Manual.
33.
E. H.
Korte
and
A.
Roseler
,
Analyst
123
,
647
(
1998
).
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