In this work, the effect of transition metal salts on the initiated chemical vapor deposition of polymer thin films was studied using x-ray photoelectron spectroscopy. The polymerizations of 4-vinyl pyridine and 1H,1H,2H,2H-perfluorodecyl acrylate were studied using copper(II) chloride (CuCl2) and iron(III) chloride (FeCl3) as the transition metal salts. It was found that the surface coverages of both poly(4-vinyl pyridine) (P4VP) and poly(1H,1H,2H,2H-perfluorodecyl acrylate) were decreased on CuCl2, while the surface coverage of only P4VP was decreased on FeCl3. The decreased polymer surface coverage was found to be due to quenching of the propagating radicals by the salt, which led to a reduction of the oxidation state of the metal. The identification of this reaction mechanism allowed for tuning of the effectiveness of the salts to decrease the polymer surface coverage through the adjustment of processing parameters such as the filament temperature. Additionally, it was demonstrated that the ability of transition metal salts to decrease the polymer surface coverage could be extended to the fabrication of patterned cross-linked coatings, which is important for many practical applications such as sensors and microelectronics.

1.
S.
Seidel
,
C.
Riche
, and
M.
Gupta
, “
Chemical vapor deposition of polymer films
,” in
Encyclopedia of Polymer Science and Technology
(
Wiley
,
New York
,
2011
).
2.
Y.
Lei
,
W.
Wang
,
H.
Yu
,
Y.
Luo
,
T.
Li
,
Y.
Jin
,
H.
Zhang
, and
Z.
Li
,
J. Micromech. Microeng.
19
,
035013
(
2009
).
3.
S.
Mehrabani
,
P.
Kwong
,
M.
Gupta
, and
A. M.
Armani
,
Appl. Phys. Lett.
102
,
241101
(
2013
).
4.
J. T. W.
Kuo
,
B. J.
Kim
,
S. A.
Hara
,
C. D.
Lee
,
C. A.
Gutierrez
,
T. Q.
Hoang
, and
E.
Meng
,
Lab Chip
13
,
554
(
2013
).
5.
P.
Kwong
and
M.
Gupta
,
Anal. Chem.
84
,
10129
(
2012
).
6.
P.
Kwong
,
C. A.
Flowers
, and
M.
Gupta
,
Langmuir
27
,
10634
(
2011
).
7.
H.-Y.
Chen
and
J.
Lahann
,
Adv. Mater.
19
,
3801
(
2007
).
8.
Y.
Mao
,
N. M.
Felix
,
P. T.
Nguyen
,
C. K.
Ober
, and
K. K.
Gleason
,
J. Vac. Sci. Technol. B
22
,
2473
(
2004
).
9.
W. I.
Bengough
and
W. H.
Fairservice
,
Trans. Faraday Soc.
61
,
1206
(
1965
).
10.
W. I.
Bengough
and
W. H.
Fairservice
,
Trans. Faraday Soc.
63
,
382
(
1967
).
11.
C. H.
Bamford
,
A. D.
Jenkins
, and
R.
Johnston
,
Proc. R. Soc. London, Ser. A
239
,
214
(
1957
).
12.
C. H.
Bamford
,
A. D.
Jenkins
, and
R.
Johnston
,
Trans. Faraday Soc.
58
,
1212
(
1962
).
13.
A. A.
Katbab
,
R. P.
Burford
, and
J. L.
Garnett
,
Int. J. Radiat. Appl. Instrum. Part C
39
,
293
(
1992
).
14.
J.-S.
Wang
and
K.
Matyjaszewski
,
J. Am. Chem. Soc.
117
,
5614
(
1995
).
15.
K.
Matyjaszewski
and
J.
Xia
,
Chem. Rev.
101
,
2921
(
2001
).
16.
K. M.
Vaeth
and
K. F.
Jensen
,
Adv. Mater.
11
,
814
(
1999
).
17.
K. M.
Vaeth
and
K. F.
Jensen
,
Chem. Mater.
12
,
1305
(
2000
).
18.
B.
Chen
,
P.
Kwong
, and
M.
Gupta
,
ACS Appl. Mater. Interfaces
5
,
12701
(
2013
).
19.
M.
Bobrowski
,
Comput. Theor. Chem.
991
,
56
(
2012
).
20.
V.
Nock
,
R. J.
Blaikie
, and
T.
David
,
Lab Chip
8
,
1300
(
2008
).
21.
A. P.
Grosvenor
,
B. A.
Kobe
,
M. C.
Biesinger
, and
N. S.
McIntyre
,
Surf. Interface Anal.
36
,
1564
(
2004
).
22.
M. C.
Biesinger
,
L. W. M.
Lau
,
A. R.
Gerson
, and
R. St.C.
Smart
,
Appl. Surf. Sci.
257
,
887
(
2010
).
23.
K. K. S.
Lau
and
K. K.
Gleason
,
Macromolecules
39
,
3688
(
2006
).
24.
C. H.
Bamford
,
A. D.
Jenkins
, and
R.
Johnston
,
Nature
177
,
992
(
1956
).
25.
G.
Moad
and
D. H.
Solomon
,
The Chemistry of Radical Polymerization
, 2nd ed. (
Elsevier
,
Oxford, UK
,
2006
), pp.
265
273
.
26.
G. C.
Eastmond
,
Comprehensive Chemical Kinetics
, edited by
C. H.
Bamford
and
C. F. H.
Tipper
(
Elsevier
,
Amsterdam
,
1976
), Vol. 14A, pp.
153
271
.
27.
C. H.
Bamford
,
A. D.
Jenkins
, and
R.
Johnston
,
Trans. Faraday Soc.
55
,
418
(
1959
).
28.
D. H.
Shaw
and
H. O.
Pritchard
,
Can. J. Chem.
46
,
2721
(
1968
).
29.
G.
Ozaydin-Ince
and
K. K.
Gleason
,
J. Vac. Sci. Technol. A
27
,
1135
(
2009
).
30.
T. H. T.
Wu
,
R. S.
Rosler
,
B. C.
Lamartine
,
R. B.
Gregory
, and
H. G.
Tompkins
,
J. Vac. Sci. Technol. B
6
,
1707
(
1988
).
31.
L.
Wang
,
Z.
Wang
,
X.
Zhang
, and
J.
Shen
,
Macromol. Rapid Commun.
18
,
509
(
1997
).
32.
D. L.
Pavia
,
G. M.
Lampman
, and
G. S.
Kriz
,
Introduction to Spectroscopy
, 3rd ed. (
Brooks Cole
,
Pacific Grove
,
2001
), pp.
41
43
.
You do not currently have access to this content.