The chemical structure is given of a film formed by plasma polymerization from pyridine monomers. The film has a hydrophilic chemical structure, its molecular weight is 900, and the molecular system is C55H50N10O3. The electrical characteristics of a plasma polymerized film are described. The film has good insulating properties and was successfully applied as video disc coating. Etching resistance properties make it possible to use the film as a resist in etching. The characteristics of plasma polymer formed from monomers containing tetramethyltin are discussed. The polymer is in film form, displays good adhesiveness, is similar to UV film UV 35 in light absorption and is highly insulating

Hashimoto, H.

Hozumi, K.

Kitamura, K.

English

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NASA TECINICAL MEMORANDUM	 NASA TM-75910
CHEMICAL STRUCTURE OF FLASMA POLYMERIZED
FILM FORMED FROM PYRIDINE MONOMER
K. Kitamura, H. Hashimoto, and K. Hozumi
Kyoto College of Pharmacy
Translation of "Kai 10 Kai Purazuma Kagaku Kenkyukai, Koen
Yoshi," Kyoto University, November 28, 1980, pp. 1-6
(NASA-TR-75910) HIGHLIGHTS OF 10TH PLASMA
CHBRISTBY RENTING (National Aeronautics aad
Space Adainistratiou) 11 p HC A02/RF A01
CSCL 07C
1181-21197
onclas
63/27 41943
NATIONAL AERONAUTICS AND SPACE ADMINISTRATION
WASHINGTON, D.C.  20546	 :YEBRUARY 1981
00
rw
NAS"Q
it
'i
1. Rqur tie.
NASA TM-35910
2. Govo.rrrswt Acceesien tie. Reci►iart's Cehleg Ns.
a. Title MW su1•sitl.• s'HIGHLIGHTS OF 10TH PLASMA CHEMISTRY F`^tsARY 1981
6. PerlewialovsisesienC44MEETING AT KYOTO UFIVEKSITY, NOV.' 28,
1980
7. Arrtber(A •. Ps.ferming ots"sesiee Rpers Ne.
K. Kitamura, H. Hashimoto and K. Hazumi
W. Herb unit me.
11. C.~ e. Gees Ne.
NASW-31999. Psrlsraing OrgeA:setioa Neese end Address
13. Typ el Rgert sad P96ed Ce eredLeh Kanner Associates
Redwood City, California 94063
Translation
12. SMmsering Agency Nees sad Address
National Aeronautics and Space Adminis-
tration, Washington, D.C. 20546
14. Soestarieg Mlency C.d.
15. sutte leffaawy Noss
Translation of "Dai 10 Kai Purazuma Kagaku Kenkyukai, Koen
I
Yoshi," Kyoto University, November 28, 1980, pp. 1-6
16.	 A►strsct
This paper consists of three articles.	 The first gives the
chemical structure of a film whioh was formed by plasma poly-
merization from pyridine monomer. 	 The film has a hydro-
philic chemical structure, its molecular weight is 900, and
the molecular system is C 55HSON100 3 .	 The second article de-
scribes the electrical characteristics of a plasma polymer-
ized film.
	
The film has good insulating properties and was
saacessfully applied as'video disc coating.	 Etching resis-
tance properties make it possible to use the film as a re-
sist in etching.	 The third article concerns the character-
istics of plasma polymer formed from monomer containing
tetramethyltin.	 The polymer is in film form, displays good
adhesiveness, is similar to UV film-UV-35 in light absorb-
tion and is highly insulating.
17. Key Words tselected by Author($)) 10.	 Distribution Stotee»nt
Unlimited - Unclassified
19.	 Securi ty Clessif. (of this report) 2D. Seevrity Ciessil. (el this pge) 21. tie. of Peg** 22. Price
Unclassified Unclassified 9
.eo
CHEMICAL STRUCTURE OF PLASMA POLYMERIZED
FILM FORMED FROM PYRIDINE MONOMER
K. Kitamura, H. Hashimoto, and K. Hozumi
-Kyoto'Cellegt br Ptarpacy
1. Introduction
A film, plasma polymerized from monomer of a nitrogen containing /1*
compound, displayed the characteristics of hydrophilic semipermeable
film when formed on a porous substrate. As a result the film was invt.
vestigated for its value as film with reverse osmosis. The hydrophi-
lic_chemical structure of the film proved interesting.
In this experiment the nitrogen containing monomer was an aroma-
tic compound with isomeric rings. The film was formed by low pressure
glow discharge using pyridine. In addition to finding the chemical
components and molecular weight, structural analysis was conducted
focusing on the form of the nitrogen existing inside the molecules.
The means of analysis were elemental analysis, measurement of
molecular weight by the vapor-pressure osmotic method, infrared ab-
sorption spectrum, the proton and carbon-13-NMR spectrum and high re-
solving pooer masa spectrum. The film substance was chemically modi-
fied as necessary for quantitative analysis of sulfur and halogen.
2. The Experiment
The film substance was formed inside a pyrex chamber (diameter
7 cm, length 30 cm). After eduction with acetone, the acetone was re-
moved and the dried sample used for the structural analysis. The dis-
charge system was a coil wound around the outside of a vertical cham-
ber. The system was electrodeless, the frequency was 13.56 MHz and
the output was 35 W.
*Numbers in the margin indicate pagination in the foreign text.
1
3. Results and Discussion
The mean molecular weight of the film substance by the vapor
pressure osmosis method (standard mass: ben$yl) was 900. This and
the atomic components obtained by elemental analysis give the mole-	 12
cular system C 55HSON1003' This corresponds to 11 times the weight of
the monomer. This is explained by the fact that one of the nitrogen
atoms was eliminated. Also, existence of oxygen atoms which the
monomer did not contain was noted.
Concerning the form of the nitrogen, there were pyridine rings,
nitryl radicals, first and second order amine, and amide.
The following methods were used to measure the amounts of each
of the above.
The pyridine rings were investigated from the integral ratio in
the proton NMR spectrum. In the case of nitryl radicals and first
order amide, methyl esterification was done and the number of methyl
radicals introduced found by the proton NMR spectrum. For the amine,
modification was done by acetylation and with carbon disulfide and
the sulfur measured by potentiometric titration. Concerning the
amide, its existence was confirmed and it was measured using the strong
acylating agent N-mythylbis (trifluoroacetoamide).
Concerning the substitution position of the pyridine rings, by
using the IR spectrum and proton NMR spectrum, it was learned that two
position monosubstitution bodies and 2.6 position bisubstitution
bodies existed.
From the high resolving mass spectrum analysis, the structure of
the pyridine rings was found to be as follows. (In the above measure-
ments, the number of pyridine rings was found to be four for each
molecule).
Also, it was noted from the elemental analysis that the film
2
( 	 /H
'N H=
tN'^N^ X or (X	 x
X = C,N
	 0
took in oxygen atoms. From the lasults thus far, it is believed that
the oxygen atoms in the film exist as acid amide and pyridine-N-oxide.
It is believed that these and the partial structure described thus far
which contains nitrogen contribute greatly to the hydrophilic cherri--
cal structure of the film.
3
CHARACTERISTICS OF PLASMA POLYMERIZED
FIB+! AS ELECTRICAL MATERIAL
I. Taniguchi, M. Nakayama, Kitsuneto and S. Kume
Doshisha University, Department of Engineering
When plasma polymerized film is considered as electrical mater-	 !3
ial, dielectric characteristics, insulating characteristics and ion
resisivity are involved. Here, for the most part, the characteristics
of styrene polymer film are discussed. It is believed that this film
can be used as a thin film insulating layer or as a resist in plasma
etching.
1) Concerning Film Formation
When polymer film is grown by the direct method at a comparatively
low frequency (1 - 100 KHz) on a substrate, factors causing film forma-
tion can be toughly divided into the bombardment effect in which poly-
merization takes place due to cations bombarding the adsorbed mono-
mers and the transport effect in which polymerization takes place from
the accumulation of free radicals formed inside the plasma or trans-
ported by the ions. The ratio of these is about 3:1.
In the case of styrene film, the effective cross section achieved
by ion bombardment is polymerization by ion bombardment is about 200
A2 . 5-6 styrene monomers are polymerized by one cation [1].
2) Electrical Characteristics of the Film
The merits and weaknesses of the electric characteristics of the
film are expressed by resistivity p, dielectric tangency d and dielec-
tric breakdown voltage B.C.V.
i) tan 6: In general the tan 6 of the polymer membrane was in-
ferior to that of scientifically manufactured polystyrene by about
one unit. This is because there was bridging at the time of polymer-
ization, divergence from three-dimensional regularity, and increase
4
i•
•
a
in dipole moment due to bonding of residual radicals to oxygen.
•
•	 •'^w^j
i
i^
l	 '3
•
Fig. 1
M	 ew
Fig. 2
was dcne.
In this case the residual radi-
cals took in the oxygen, and car- /4
bonyl radicals were formed, and
this is believed to have caused an
increase in tan S. The infrared
spectrum also supports this.
4
C
4
yi
A
Figure 1 shows the change- in
tan d when the initial degree of
vacuum was changed and oxygen was
deliberately introduced during film
formation.
Figure 2 shows the changes in
tan d when the film was exposed
to the air immediately after forma-
tion and when heat treatment was
conducted at 200 0 C without break-
ing the vacuum.
•^)^	 Results showed that in making
I»	 'N the same film layer, when the cur-
tew^er•t• ►ti ( • t )
rent density was reduced and the
time increased, the tan d decreased
more than when the reverse of this
This thought to be the result:.o g ion bombardment'..°
ii) p and B.D.V.
One of the features of plasma polymerized film is the small quan-
tity of pin holes. Because of this it is easy to make film of p>10M
(Q cm) and B.D.V.>10 6 . Figure 3 is an example showing the changes in
V-I characteristics due to the introduction of oxygen. Takeing advan-
tage of the good insulating properties the film was tried as video
5
Fig. 3
disk coating with tentative success.
.irc Otte
	
//j
•WL •t'C 3)	 Ion Resistance Pro erties
• (Etching Charact eristics
An interesting fact was dis-
t._-_
covered when the plasma polymerized
•
film was exposed a second time to
1. the plasma.	 The styrene film ob-
tained by plasma polymerization
•^ was easily etched in oxygen plas-
1
'+
ma, but when it was exposed be-
forehand to CF 4 gas discharge, the
^ 1 two ft" rM+. t g mw etching resistant properties in-
creased so that it is possible to
use the film as a resist.
Jw
• wt
mot '
n	 ^
twou ft" IftVq t i wpm)
6
Taniguchi,
Z
roo	 ^—
^.o	 r
b
:o
a" Goo .00 Sao "a lno ONOOK l[MGTN	 lo")
A. POLMM AoU 0%. O. POLYMM MM t+KNS6
C POLTUM POW Wb sb. C. on 0Ito.
6. VV FILM NV_n. O. VV • 3I .4. VV-Yl. I, V-Vds
Fig. 2. Transmission Curves
for Polymer Films Prepared
by Glow Discharge Polymeri-
zation
CHARACTERISTICS OF PLASMA POLYMERIZED TETRAMETHYLTIN
K. Inagaki and Y. Katsuura
Shizuoka University
1. Introduction
taining a functional group. Making
use of this characteristic, polymer
containing metal or semimetal can
be easily produced. Such polymer
can be expected to have characteris-
tics not seen in polymer of the
past. In the present experiment
tetramythyltin was used as the mono-
0 or 04 as 6.4 t0
"o , 'E0`"	 mer and several characteristics of
' Si1`"
54
0010	 the polymer formed from this were
Fig. L. Polymer Deposition	 studied.
Rate as a Runction of Flow
Rate of Monomers
'0'
W ^
~
0
2. Experiment
(slow discharge polymerization has many peculiarities compared to
regular methods of polymerization. One of these is that polymer can
be obtained from monomer not con-
II
to
A tube type reaction vessel
was used and polymerization conducted
under the conditions of 13.56 MHz
and 25 W.
3. Results
The polymer obtained under the
experimental conditions was all in
film form. The polymer deposition
rate was fast. Compared with me- 	 /6
thane containing no tin, it was ex-
ceedingly fast. ( Figure 1). When
8
oxygen or methane was added the polymer deposition rate dropped.
It is very unlikely that conpolymerization occurred.
The polymer formed was not soluble in ordinary organic solvent.
The polymer contained Sn. C and 0 and the composition was approxi-
mately CISn - 6.9, 0/Sn - 3.1. Infrared absorption was noted for
Sn-C, Sn-O-Sn and Ch 2 radicals. The tin was not simply taken in by
the polymer, but the polymer is one which contains tin.
The adhesiveness of the polymer to the substrate was good and
with the exception of polypropylene, it displayed good adhesiveness
to other polymer.
TABLE 1. Absorption Characteristics of Polymer Films Pre-
pared by Glow Discharge Polymerization
Konover Thic ►nest I TSp TrS XTSp	^T75(u) tom) (^+) tom)
CH& 1.15 346 377 31
S1 (C"3)4 1.15 309 332 23
Sn(CH 3 )4 7.0 427 440 13
(oaldl:ee) 7.0 351 3" 1S
UV -31 310 320 10
Uv -35 350 36S 15
v-r43 430 460 20
Concerning light transmittance, absorption was at less than 450
nm (Figure 2). When the polymer was oxidized, the absorption band
differed from the short wave length and the rise in absorption was
sharp. This is similar to the commercial UV film.- -UV-35.
The polymer shows no electrical conductivity and is highly
insulating.
9
J*
M...


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