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bias voltage

VB

RF power supply matching unit

gas inlet

to pumps

RF powered substrate- holder sample

Vis lamp

Spectrometer

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/

Reflectance

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0.16

in) Time (m

(b)

Reflectance

0.12

0.08

0.04

0.00

0

5

10

15

20

25

30

Time (min)

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0.5

(a)

Reflectance

0.4 0.3 0.2 0.1 0.0

0

2.50

2

4

6

8

10

(b)

14

16

18

Calculated profile Model profile

2.25

Refractive Index nout

12

2.00 1.75 1.50 1.25 1.00

0

2

4

6

8

10

12

14

16

18

Time (min)

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1.0

1.8

0.8

Reflectance

2.0

1.6 1.4 1.2

0.6 0.4 0.2

1.0

0.0

1.8

0.8

Reflectance

0.8

1.6 1.4 1.2

0.6 0.4 0.2

1.0 0.8

0.0

1.8

0.8

Reflectance

(c)

Indice de réfraction n

(b)

Indice de réfraction n

(a)

Indice de réfraction n

- 

1.6 1.4 1.2

0.4 0.2

1.0 0.8 -1000

0.6

0

1000

2000

3000

Distance du substrat [nm]

4000

0.0 200

400

600

800

1000 1200 1400

Longueur d'onde [nm]

ScG 0 h - 6 A T @3A -54&%'4,++ @ $,`&% A B 25$,+ Q3$,+ *2/% A $,+ A 1  B %'$,+67`,TVZ @CBDA B - +'TV. $&.0% A $ B ]13.*2/% A $Z\132/%#-5`,TV1*`'(*$,+ o tU ]13.*2/% A $ A 1  B %'$+ B .*+ [email protected] T QX-5+ B %#-5TV.$&% ~` 13.*2/% A $ A 1  B %'$ B P$,` [email protected] T QX-5+ B %#-5TV.h

--

1.0

(b) Reflectance

0.8

(a)

0.4

1.8

0.2

1.7

0.0 1.0

(c)

1.6 0.8 1.5

1.4 0

1000

2000

3000

4000

5000

Distance du susbstrat [nm]

6000

Reflectance

Indice de réfraction n

1.9

sinusoïde 0.6

exp(sinusoïde)

0.6

0.4

0.2

0.0 200

400

600

800

1000

1200

Longueur d'onde [nm]

ScG 0 h 60  $&%QLR 13.ƒ2542$ A `'( B . $&Z[$&.0%QX1 @3A T *2=QLR -/.*QX-5`,$QLR 13. *2/% A $ A 1  B %'$ˆ+#1 A +'TV.+ @ $,`&% A $\Q3$ A 4C$,`&% B .*`,$ 6 B @3A T *25+13%#-/2/- + B .0%13.?+#-/.01*+ t% A B -/% @ 25$&-/. y$&%y2SR $gf @ TV.*$&.0%#-5$&2]QLR 13.?+#-/.01*+ @ TV-/. %#-/2/254,+ go tU A 4 C$,`&% B .*`,$ QX1 *2/% A $ #6./ o ~` A 4C$,`&% B .*`,$ QX1*2/% A $ (  #6./  h

1400

1.0

1.8

0.8

Reflectance

1.9

1.7

1.6

H=0 0.6

0.4

0.2

1.4 1.9

0.0 1.0

1.8

0.8

Reflectance

1.5

1.7

1.6

H=2 0.6

0.4

1.5

0.2

1.4 1.9

0.0 1.0

1.8

0.8

Reflectance

(c)

Indice de réfraction n

(b)

Indice de réfraction n

(a)

Indice de réfraction n

- 

1.7

1.6

1.5

H=4

0.6

0.4

0.2

1.4 0

1000

2000

3000

4000

5000

Distance du susbstrat [nm]

6000

0.0 200

400

600

800

1000

1200

Longueur d'onde [nm]

cS G 0 h X/ 6  $&% QLR 13.`'( B . $&Z[$&.0%:QX1 @CBDA B Z[)&% A $  Q B .*+ƒ2 B  TV.*`&%#-5TV.vQLR [email protected] T QX-5+ B %#-5TV.  $&./&% A $ Q3$ B -5+'$ A +#1 A 25$p+ @ $,`&% A $ Q3$ A 4C $,`&% B .*`,$7h

1400

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0 

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 TV1*+ B PTV.*+P 1 @ 2/1*+y( B 13%25$,+ @3A T @3A -54&%'4,+4&%'TV.3. B .0%'$,+ Q3$,+ *2/% A $,+ A 1  B %'$,+ hC.P B $&% SP -5$&.*+  Q B .*+ 2SR $,+ @CB `,$:Q3$64*TV1 A -5$ A .*TV1*+ @ $ A Z[$&%[QLR B `,`,$ @ %'$ A + B .*+  B  TV.2 B +#1 @[email protected] $,+'+#-5TV.Q3$,+ ( BDA Z[T  .3-5n01*$,+ $&%Q3$,+ 25TVU $,+ 2 B %'4 A B 1XfLh3$ @ $&.*Q B .0% o Q B .*+ 13. $,+ @CB `,$ @ 2/1*+ A 4,$&2So-/2=+'$ A B -/% U TV.ƒQ3$y% A TV13P$ A 13.:Z[T e $&.?Q3$ + R $gf @ 2/-5n01*$ A o B P$,`\Q3$,+`,TV.*`,$ @ %'++#-/Z @ 25$,+$&%-/.0%#13-/%#-  + o325$ @ TV1 A n01*TV-Q3$O`,$,+QX-5+ @CB  $  B - A $ƒQ B .*+\25$,+ @CBDA B  A [email protected] (*$,+pn013-+#13-/P$&.0% oH$&. A $,`,TV1 A B .0% A -/%#-5TV.*+ h R $,+#%ˆ`,$ƒn01*$ b#$ %'$&.0%'$ A B -Q3 B 1Xf QX- B  A B Z Z[$,+yQLR B QXZ -/%#% B .*`,$7o*n013-L+'TV.0% @ 2/1*+ 4&.*4 A B 25$&Z[$&.0%y13%#-/2/-5+'4,+Q B .*+c25$` B +Q3$`,TV1*`'(*$,+ (*TVZ[T)&.*$,+ h]TV1*+ˆP$ A#A TV.*+ `,TVZ Z[$&.0% 25$,+  A B QX-5$&.0%'+[QLR -/.*QX-5`,$ Q B .*+ `,$,+*2/% A $,+  TV.0 %  B - A $ Q3$,+ + ˆ2SR B QXZ -/%#% B .*`,$\$&% B 19`,T 8$ 7ƒ`&-5$&.0%Q3$ A 4 C$gfX-5TV.`,TVZ @ 25$gf3$OQ B .*+25$*2/Z9h @3A T QX- $, TVZ Z[$.*TV1*+ 2SR B PTV.*+ P 1ˆQ B .*+ 25$,+ @CBDA B  A [email protected] (*$,+ @3A 4,`,4,Q3$&.0%'+ oD2SR 13%#-/2/-5+ B %#-5TV. QLR 13.*2/% A $ A 1  B %'$ +#-/Z @ 25$7o + B .*+ [email protected] T QX-5+ B %#-5TV.o @ $ A Z[$&%2SR 4&2/-/Z -/. B %#-5TV.v`,TVZ @ 25)&%'$pQ3$,+( BDA Z[TV.3-5n01*$,+ QLR T A Q A $,+ +#1 @ 4 A -5$&1 A +]+#1 A 25$+ @ $,`&% A $7hVHTV1 A `,TVZ @3A $&.*Q A $y`,TVZ Z[$&.0% +'$ @3A T QX13-/%]`,$&%#%'$c4&2/-/Z -/. B %#-5TV.o&b,R B -X% A B `,4c+#1 A 2 B /71 A $ h 8 25$yQX- B  A B Z Z[$QLR B QXZ -/%#% B .*`,$QLR 13.*2/% A $yZ\132/%#-5`,TV1*`'(*$ $&% `,$&2/13- QLR 13.*2/% A $ A 1  B %'$7o ˆ2 B 25TV. 71*$&1 A QLR TV.*Q3$O`,T A#A $,+ @ TV.*Q B .0 % \2 B U B .*Q3$ Q3$ A 4 C$gfX-5TV.h* TV1*+y25$,+Q3$&1Xf:TV.0%4&%'4 Q34*.3-5+ Q3$ Z B .3-5) A  $  B PTV- A 13.*$ U B .*Q3$\Q3$ A 4 C$gfX-5TV.  -  .3Z9hC$,+yQX- B  A B Z Z[$,+Q3$,+ *2/% A $,+ A 1  B %'$,+ +'TV.0% @ 2/1*+ A $&% B +'+'4,+P$ A +25$ @ TV-/.0% - o  t25$\QX- B  A B Z Z[$pQX1 *2/% A $ B P$,` [email protected] T QX-5+ B %#-5TV. B,e0B .0%13.*$

-8

100

1.0

80 60 40

Im(Y)

Reflectance

0.8 0.6 0.4

20 0 -20 -40 -60

0.2

-80 0.0 200

-100 400

600

800

1000

1200

0

1400

20

40

60

80 100 120 140 160 180 200

40

1.0

30 20

0.6

Im(Y)

Reflectance

0.8

0.4

10 0 -10 -20

0.2

-30 0.0 200

-40 400

600

800

1000

1200

1400

0

1.0

10

20

30

40

50

60

70

10 8 6 4

Im(Y)

Reflectance

0.8 0.6 0.4

2 0 -2 -4 -6

0.2

-8 0.0 200

-10 400

600

800

1000

1200

Longueur d'onde [nm]

1400

0

2

4

6

8

10 12

14 16 18

Re(Y)

ScG 0 h 8 36 TVZ @CBDA B -5+'TV.:$&.0% A $25$,+QX- B  A B Z Z[$,+cQLR B QXZ -/%#% B .*`,$  -  .3Z B OQLR 13. *2/% A $ƒZ\132/%#-5`,TV1*`'(*$,+ o tU OQLR 13. *2/% A $ A 1  B %'$

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20

- 

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` B + QLR 13.*2/% A $Z\132/%#-5`,TV1*`'(*$7o 2 B P BDA - B %#-5TV.ƒQ3$2SR 4 @CB -5+'+'$&1 A T @ %#-5n01*$ $&% Q3TV.*`Q3$c2 B@ ( B +'$yQ3$ Q34 @ $&.*Qƒ13.3-5n01*$&Z[$&.0%QX1 `'( B . $&Z[$&.0%yQ3$ @ T7+#-/%#-5TV. Q B .*+ 25$ *2/% A $$&% .*TV. Q3$2SR -/.*QX-5`,$7o n013-=$,+#% `,TV.*+#% B .0%\Q B .*+ `'( B n01*$ `,TV1*`'(*$7o B 25T A + n01*$ Q B .*+25$*2/% A $ A 1  B %'$7o`,$&%#%'$pP BDA - B %#-5TV.v+'$ B -/% @ 2/1*+ A [email protected] -5Q3$&Z[$&.0% oCQX1*$ ˆ2 B  TV-5+ ˆ13.*$ Q34 @ $&.*Q B .*`,$ B 19`'( B . $&Z[$&.0%Q3$ @ T7+#-/%#-5TV. =[Q B .*+25$ *2/% A $ 21 ! # B 1v`'( B . $&Z[$&.0%pQ3$p2SR -/.*QX-5`, $ 9:2 

 B .*+2 B /71 A $ h oX25$,+ B QXZ -/%#% B .*`,$,++'TV.0%% A B `,4,$,+ˆ2 B 25TV. 71*$&1 A QLR TV.*Q3$O`,T A#A $,+ @ TV.*Q B .0%  2 Bƒ@3A $&Z -5) A $p( BDA Z[TV.3-5n01*$ / / /H.3Z ghL B .*+25$p` B + QX1 *2/% A $ˆZ\132/%#-5`,TV1*`'(*$7o `,TVZ Z[$ˆ25$,+ `,TV1*`'(*$,+ +'TV.0%(*TVZ[T)&.*$,+ o0% A - @ 25$ A 25$&1 A 4 @CB -5+'+'$&1 A T @ %#-5n01*$ ~$&. QX-/Z -/.01 B .0%yQX1ƒ%#-5$ A +2 B 25TV. 71*$&1 A QLR TV.*Q3$ B[@ TV1 A $  $&%Q3$\PTV- A 2SR B QXZ -/%#% B .*`,$ 4&PTV2/1*4,$p$&. A $,+#13-/P B .0% $gf B `&%'$&Z[$&.0%25$\Z&Z[$ˆ% A B `,4ˆn01 [2 B 25TV. 71*$&1 A QLR TV.*Q3$ Q3$p2 B U B .*Q3$ @3A -/.*`&- @CB 25$ -  .3Z t25$,+ `,TV1*`'(*$,+\n013-]4&% B -5$&.0%\n01 BDA % QLR TV.*Q3$  -  .3Z +'TV.0% Z B -/.0%'$&. B .0%[% A TV-5+ n01 BDA % QLR TV.*Q3$ / / /H.3Z #& TV. A $&% A TV13P$:Q3TV.*` 13.*$ U B .*Q3$ Q3$ A 4 C$gfX-5TV.r+'$&Z\U32 B U325 $  2 B U B .*Q3 $  -  .3Z9oZ B -5+ @ 2/1*+O4&% A TV-/%'$7o @ 13-5+'n01R  `,$&%#%'$[25TV. 71*$&1 A QLR TV.*Q3$7oC13 .  B -/U325$\`'( B . $&Z[$&.0%OQ3$\2 B @ T7+#-/%#-5TV.?Q B .*+2 B `,TV1*`'(*$ @3A T QX13-/%13.W`'( B . $&Z[$&.0% @ 2/1*+  A B .*QQ3$O2SR 4 @CB -5+'+'$&1 A T @ %#-5n01*$ t%'TV13%$,+#% A $&2 B %#-   2 B 25TV. 71*$&1 A QLR TV.*Q3$\TVU*+'$ A P4,$ ghC B .*+25$O` B + QX1 *2/% A $ A 1  B %'$7oL-/2 +'$ @3A T QX13-/%O13. @ (*4&.*TVZ[)&.*$ƒ$gfX% A B T A QX-/. B - A $ &25$  A B QX-5$&.0%ˆQLR -/.*QX-5`, $  B -/%\$&. +'T A %'$n01R -/2 e B 13.*$ + e Z[4&% A -5$ $&.0% A $2SR 4&PTV2/13%#-5TV.9Q3$ {Q B .*+c2 B Q3$&Z - @ 4 A -5T Q3$QLR -/.*QX-5`,$ 4&25$&P4 $&%\`,$&2/25$[Q B .*+ 2 B Q3$&Z - @ 4 A -5T Q3$[QLR -/.*QX-5`, $  B -/U325$7hH$&%#%'$[+ e Z[4&% A -5 $  B -/%O$&.r+'T A %'$ n01*$ A $&P -5$&.0%  +'TV. @ TV-/.0%Q3$\Q34 @CBDA %$&%n01*$ 2 B A 4 C$,`&% B .*`,$ A 4,+#132/% B .0%'$ˆ$,+#%`,$&2/25$\QX1?+#13U*+#% A B % h= (*$ ‡ 25$*2/% A $ B P$,` [email protected] T QX-5+ B %#-5TV.oL`,$&%#%'$ + e Z[4&% A -5$p+'$ A 4 @ )&%'$  @ 2/1*+#-5$&1 A + A $ @3A -5+'$,+ o B P$,`[Q3$,+P BDA - B %#-5TV.*+OQ3$ QLR B Z @ 2/-/%#1*Q3$OP BDA - B U325$7h

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- /

(a) Débit N2O [sccm]

40 30 20 10 0

Débit NH3 [sccm]

30 25 20 15 10 5 0

0.0

0.5

1.0

1.5

2.0

2.5

Temps [heures]

(b)

1.0

Transmittance

0.8 0.6 0.4 0.2 0.0 300

400

500

600

700

800

Longueur d'onde [nm]

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- 8

(a)

Débit N2O [sccm]

35 30 25 20 15 10 5 0

Débit NH3 [sccm]

30 25 20 15 10 5 0 0.0

0.5

1.0

1.5

2.0

2.5

Temps [heures] (b)

Transmittance

1.0 0.8 0.6 0.4 0.2 0.0 300

400

500

600

700

800

Longueur d'onde [nm]

ScG 0 h 8 674 @ YV% +#1 A 6 B H4&PTV2/13%#-5TV.ƒQ3$,+]Q34&U3-/%'+]%'$&25+ n01*$ Z[$,+#1 A 4,+ QX1 A B .0%H25$ Q34 @ YV% o tU + @ $,`&% A $ Q3$]% A B .*+#Z -/%  % B .*`,$ Z[$,+#1 A 47h ~4 @CB -5+'+'$&1 A Q3$ - - Z

- 

(a) Débit N2O [sccm]

40 30 20 10 0

design mesure

Débit NH3 [sccm]

30 25 20 15 10 5 0 0.0

0.5

1.0

1.5

2.0

2.5

Temps [heures]

(b) Transmittance

1.0 0.8 0.6 0.4 0.2

sur verre sur PC

0.0 200

400

600

800 1000 1200 1400

Longueur d'onde [nm]

ScG 0 h 6  4 @ YV%+#-/Z\132/% B .*4 #+ 1 A P $ #A A $p$&%+#1 A   6 B Q34&U3-/%'+?Q3$r  $&%Q3$r!  @3A T A B Z Z[4,+ t% A B -/%'+ :$&% Z[$,+#1 A 4,+ @ TV-/.0%'+ go tU \`,TVZ @CBDA B -5+'TV.Q3$,+ A 4C $,`&% B .*`,$,+ h ~4 @CB -5+'+'$&1 A Q3$ - - Z

- 

cS G 0 h 6*  $&%Q3$ 2SR 4&%#- A $&Z[$&.0% 9QLR 13. @3A T *2 QLR -/.*QX-5`,$ +#1 A +'TV.9+ @ $,`&% A $7h

- 5

%'TV13%Q3$\+#13-/%'$ˆn01*$ 2 B @CBDA %#-5$\% A TV.*n01*4,$ˆ$,+'`,TVZ @ %'4,$ˆQX1 @3A T *2H13%#-/2/-5+ B .0%2 B  $&./&% A $O2 B @ 2/1*+2 BDA $ QLR -/.*QX-5`,$ B  $,`&%'$ @ $&1O25$ + @ $,`&% A $ ~TV.\.*$ PTV-/% [email protected]@CBDA B % A $ B 1*`&13.*$ ( BDA Z[TV.3-5n01*$ #&†25$ @3A T *20% A TV.*n01*4 Q3$p2 B /71 A $ h $,+#% @3A TVU B U325$&Z[$&.0%ˆ$gf B 4 A 47o$&%O.*$ `,T A#A $,+ @ TV.*Q @CB +:`,$ n01*$p2SR TV.vPTV-/%\Q B .*+ .*T7+ $gf @ 4 A -5$&.*`,$,+ o +#1 A %'TV13% 25T A +'n01*$\25$ @3A T *2 $,+#% T A %'$&Z[$&.0% [email protected] T QX-5+'47o=.*$p`,TVZ @3A $&. B .0%\n01*$ @ $&1 Q3$ A 427-5TV.*+\T 25$ Q34&U3-/% @3A $&.*QvQ3$,+ P B 25$&1 A + -/.  4 A -5$&1 A $,+ B 1vQ34&U3-/%OZ -/.3-/Z B 2 `,TV.0% A YV2 B U325$ @CBDA 25$ Q34&U3-/%#Z[)&% A $7hC.*$OQX-  4 A $&.*`,$O.*TV% B U325$\Q3$,+y+ @ $,`&% A $,+Q3$2 B /71 A $ h 5 $,+#%2 B 2 BDA $&1 A Q3$,+U B .*Q3$,+ Q3$ A 4 C$gfX-5TV. &CQ B .*+y25$\` B +Q3$OZ\132/%#-5`,TV1*`'(* $  T A Z[4,$\Q3$ 2 B Z[$,+n01 BDA % QLR TV.*Q3$ˆQLR -/.*QX-5`,$,+ 9  ƒ$&% 9=oX-/2 $,+#%U3-5$&.`,TV.3.01n01*$2 B 2 BDA $&1 A Q3$ U B .*Q3$O$,+#%yQ3TV.3.*4,$ @CBDA 2SR 4,n01 B %#-5TV.?+#13-/P B .0%'$[6 

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h-

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- .

|nmax-nmin| petit |nmax-nmin| grand

(a) Débit N 2O [sccm]

35 30 25 20 15 10 5 0 30

Débit NH 3 [sccm]

25 20 15 10 5 0 0.0

0.6

1.1

1.7

2.2

2.8

Temps [heures]

(b)

Transmittance

1.0 0.8 0.6 0.4 0.2 0.0 300

400

500

600

700

800

Longueur d'onde [nm]

ScG 0 h 5 6  f3$&Z A 4C $,`&% B .*`,$ @ TV1 Q3$ 9  > 9  

@ 52 $ $gf @ $ A -/Z[$&.0% B 2yQX1 A Q3$,+ Q3$,+#- 7.*+ B P$,` QX- 

oZ B -5+v2 B Z&Z[$ 4 @CB ~4 [email protected] B -5+'+'$&1 A +Q3$ - - Z $&% - /Xh Z

`'( B . $&Z[$&.0%ƒQ3$ 4 A $&.0%'$,+ P B 25$&1 A + -5+'+'$&1 A T @ %#-5n01*$7h

- 9

(a) Débit N2O [sccm]

30 25 20 15 10 5 22

Débit NH3 [sccm]

20 18 16 14 12 10 8 6 4 0.0

0.5

1.0

1.5

2.0

2.5

Temps [heures]

(b)

1.0

Transmittance

0.8 0.6 0.4 0.2

avec apodisation sans apodisation

0.0 300

400

500

600

700

800

Longueur d'onde (nm)

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Effect of interface on the characteristics of functional films deposited on polycarbonate in dual-frequency plasma J. E. Klemberg-Sapieha, D. Poitras, and L. Martinua)

Engineering Physics Department and Groupe des Couches Minces (GCM), E´cole Polytechnique, Montre´al, Que´bec H3C 3A7, Canada

N. L. S. Yamasaki Optical Coating Laboratory, Inc. (OCLI), Santa Rosa, California

C. W. Lantman Flex Products, Inc., Santa Rosa, California

~Received 28 October 1996; accepted 27 January 1997! Functional coatings are used in increasingly demanding applications that require specific optical characteristics, resistance to damage and good adhesion to different types of substrate materials, including polymers. In the present work we investigate thin films fabricated by low pressure plasma-enhanced chemical vapor deposition, using a dual-mode microwave/radio-frequency ~MW/ RF! plasma approach. The substrates are exposed to the principal dense microwave ~MW, 2.45 GHz! plasma, while applying a RF-induced negative bias voltage. This technique provides independent control of the energy and flux of bombarding ions, and it allows one to deposit dense films at ambient substrate temperature at a high rate over large areas. We optimized the deposition process for amorphous hydrogenated silicon nitride ~SiN1.3! obtained from SiH4/NH3 mixture. Using an average ion energy of about 150 eV, we obtained low-stress (,100 MPa) films with a refractive index of 1.89, at deposition rates around 30 Å/s. MW plasma pretreatments with different gases have been investigated in order to further enhance adhesion of the SiN1.3 coatings on polycarbonate ~PC! substrates—the highest adhesion, determined by the microscratch- and the adhesive-tape peel tests, was found when PC was pretreated in N2 plasma. The adhesion is related to the thickness and chemical structure of the interface. In fact, spectrophotometry and x-ray photoelectron spectroscopy analysis suggest the presence of a graded interface region, up to 40 nm thick, part of which contains Si–C, Si–O–C, and Si–N–C chemical links. © 1997 American Vacuum Society. @S0734-2101~97!05203-2#

I. INTRODUCTION Polycarbonate ~PC! thermoplastics are presently widely used in industry and they represent a good candidate to meet optical needs. Their impact strength, dimensional stability ~low molding shrinkage! and rigidity, along with their transparency to visible light and resistance to sunlight irradiation, make them a logical choice for various purposes,1 including compact disk protective coatings, security goggles and space applications.2,3 A problem frequently encountered with polymeric substrates is the poor adhesion of deposited metallic and dielectric films; therefore, numerous studies have concentrated on interface analysis and surface pretreatment. Plasma surface modification of polymers is very efficient for adhesion enhancement due to a combination of plasma-induced effects involving surface cleaning, ablation, crosslinking, and surface chemical functionalization ~for reviews, see, for example, Refs. 4–6!. Major contributors to the modification of the polymer surface are believed to be the chemically active species and energetic photons generated by the discharge.4,7 During the deposition itself one must also face the fact that most plastics are sensitive to elevated temperatures which a!

Author to whom all correspondence should be addressed; Electronic mail: [email protected]

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may drive off plasticizing agents and soften the pieces, so that their optical figure quality may become compromised.2 In the case of polycarbonate, the process temperature should not exceed 150 °C. Low pressure plasma techniques provide a possibility to tailor the characteristics of functional coatings: in the context of the present work, the films are required to fulfill specific optical requirements, and to serve as protective layers against mechanical and chemical attack at the same time. Plasma processing is a particularly suitable technique because it combines, under the same vacuum, the polymer pretreatment for enhanced adhesion and a high film deposition rate at a low substrate temperature. In our laboratory, we have recently developed a dualmode microwave/radio-frequency ~MW/RF! plasma approach for materials processing.8–10 This technique is based on a ‘‘synergistic’’ effect arising from the simultaneous application of a dense MW plasma, rich in excited species, and a RF signal applied to the substrate holder which creates a negative bias voltage on the sample. Varying the parameters of the two discharges allows one to selectively control the ion flux reaching the surface ~controlled by the MW component! and the ion energy ~controlled via the RF-induced bias!. One can thus choose appropriate ion bombardment conditions and fabricate dense films at high deposition rates

0734-2101/97/15(3)/985/7/$10.00

©1997 American Vacuum Society

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Klemberg-Sapieha et al.: Effect of interface on the characteristics of functional films

TABLE I. Deposition rate rD and refractive index n of SiN1.3 films fabricated under RF and MW/RF plasma conditions. r D ~Å/s!

SiN1.3

n ~550 nm!

RF

MW/RF

RF

MW/RF

7.5

33

1.86

1.89

986

pressure 200 mTorr and treatment time 60 s, the same as in our previous work on adhesion enhancement of metals on fluoropolymers.14 The PC substrates used in this work were precision injection molded without release agents. The substrates were 2.5 mm thick with an area of 75320 mm2 and were supplied by Netra, a division of OCLI. B. Film characterization

while keeping the substrate temperature low. Use of the MW/RF plasma system has been demonstrated for the deposition of multilayer and graded index ~inhomogeneous! optical coatings,11 and for batch and continuous plasma processing using pilot and production systems.12 In the present work, our main objective is to study the effect of plasma pretreatment on the adhesion enhancement of amorphous hydrogenated silicon nitride ~SiN1.3! films on PC in the context of their use as protective coatings. Throughout the work, we pay particular attention to the structure of the film/substrate interface, studied both by x-ray photoelectron spectroscopy ~XPS! and by optical methods. II. EXPERIMENT A. Surface pretreatment and plasma deposition

Plasma pretreatments and depositions were performed in the MW/RF plasma system described in more detail in our previous publications.8–11 The substrates were placed on a substrate holder electrode ~18 cm in diameter!. After pumping the reactor down to a base pressure of 1024 Torr, a working gas was admitted using Sierra ~model 840! mass flow controllers, and the desired pressure was adjusted using a throttling valve and a MKS baratron capacitance pressure gauge. Microwave power ~MW, 2.45 GHz! was supplied to the reactor from a 30 cm long MW periodic slow wave structure via a fused silica window placed about 4 cm in front of the substrates. The substrate holder was capacitively coupled to a radio-frequency ~RF, 13.56 MHz! power supply. The negative dc substrate-bias voltage ~and hence the ion bombarding energy! was controlled by the applied RF power.13 The substrate holder was not thermostatically controlled, so that the substrate temperature may have slightly exceeded the ambient temperature ~TS ;40260 °C! due to plasma exposure. When optimizing the deposition conditions of SiN1.3 films, the flow rates were varied from 8 to 30 sccm for SiH4 , and from 24 to 90 sccm for NH3 . The working pressure was 120 mTorr for most of the depositions. The MW power was 150 W, and the negative substrate bias V B ranged from 2150 to 2350 V, corresponding to RF power levels from 30 to 130 W. The latter parameter was adjusted to assure an appropriate mean energy of the bombarding ions close to the critical ion energy required for the films densification10 and adjustment of the refractive index.11 In subsequent experiments prior to the SiN1.3 deposition, the PC substrate was pretreated in pure MW plasma ~power of 150 W! using different gases: Ar, NH3 , N2 , H2 and N2O. Typical treatment conditions were flow rate 20 sccm, J. Vac. Sci. Technol. A, Vol. 15, No. 3, May/Jun 1997

Optical characteristics of the samples were determined from reflectance measurements in the visible region using a Perkin Elmer l-19 spectrophotometer. The thickness of the films, the refractive index, n(l), and extinction coefficient, k(l), of the substrate, of the films and of the interfacial layer ~or ‘‘interphase’’! were evaluated by curve-fit optimization using WVASE3215 and FILM*STAR16 software packages. For simplicity, we considered the Cauchy dispersion relation to describe the optical parameters of the materials used. The adhesion quality of the coatings was inspected qualitatively by an adhesive-tape peel test ~M 610 type!, and semiquantitatively by a scratch test, using a CSEM ~Switzerland! microscratch-tester ~MST! instrument. In the MST, a hemispherical diamond stylus ~200 m m radius! was moved along the film surface, and a critical load, L c , was determined when the film started to delaminate from the interface.17,18 After the first round of adhesion tests, the samples were exposed to high humidity at an elevated temperature @relative humidity (RH) 5 97%, 50 °C, 24 h#, and the adhesion tests were repeated. After the deposition or surface treatment the samples were exposed to the ambient atmosphere for about 10–20 min, and then introduced into the VG-ESCALAB 3MkII instrument for XPS analysis, using Mg K a radiation. The XPS spectra measured were not smoothed prior to deconvolution. The inelastic background was subtracted using Shirley’s method.19 A curve-fitting SURFSOFT program was used which permits a variation of parameters such as the Gaussian/ Lorentzian ratio, the full width at half-maximum ~FWHM!,

FIG. 1. Critical load, L c , for SiN1.3 films ~0.4 m m thick! deposited on PC following MW plasma pretreatment with different gases.

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FIG. 2. Measured reflectance of a SiN1.3 layer ~300 nm! on PC compared with simulated reflectance considering different index profiles at the SiN1.3/PC interface: ~a! abrupt interface and ~b! quasi-linear interface.

and the peak’s position. The curve-fitting was evaluated by the chi-square convergence.

III. RESULTS AND DISCUSSION A. Refractive index and deposition rate

Prior to adhesion study, preliminary depositions were made to optimize the refractive index and the deposition rate ~r D ! of SiN1.3 films on PC substrates. Table I shows the n and r D values of films deposited in RF and MW/RF discharges. Higher n for SiN1.3 is reached when using MW/RF plasma deposition due to the greater ion energy and ion flux at the surface. Enhanced ion bombardment gives rise to resputtering and ‘‘knock-in’’ effects and to higher surface mobility of the arriving species. This then leads to an increased film packing density, documented by rising n values,11 and by a substantial drop in the dielectric loss factor.10 For the present SiN1.3 films deposited simultaneously on Si, we found a density of about 2.6 g/cm3 . The deposition rate is higher when the MW/RF technique is used as compared to RF plasma alone due to a higher density of energetic species in the MW discharge.20 It should be pointed out that the maximum r D values are still limited by the applied gas flow and pressure parameters of our plasma system, and by its JVST A - Vacuum, Surfaces, and Films

pumping speed. Rates well over 100 Å/s have been demonstrated in the literature for silica-based optical waveguides.21 The refractive index of SiN1.3 obtained in this work is lower than the values given in the literature for films deposited by similar techniques.22 The difference may be caused by oxygen contamination from the background gas23 and by the presence of hydrogen which amounts to about 14 at. %.10 For SiN1.3 films deposited on Si substrates, our earlier study indicated about 2–6 at. % of oxygen uniformly distributed through the film depth.10 Lower concentrations were achieved when using a higher ion energy ~more than ;100 eV! and/or a longer pump-down time prior to deposition. Based on our previous optical characterizations,11 we conclude that the film microstructure remains constant throughout the bulk of the SiN1.3 film. The refractive index of SiN1.3 was found to be lower on PC than on Si, particularly in the case of thinner (,20 nm) films. This lower effective index value is believed to be the consequence of a thick interfacial region between the PC substrate and the growing film due to the chemical reaction of the deposited species and of the substrate material ~see Sec. III C!. B. Adhesion and plasma pretreatment

In the present study we evaluated adhesion of 0.4 m m thick SiN1.3 films that were being considered for protective

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FIG. 3. C(1s) high resolution XPS spectra of untreated PC and of N2 plasma treated PC.

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FIG. 5. Si(2 p) and C(1s) high resolution XPS spectra of a ;50 Å thick SiN1.3 film deposited onto N2 plasma treated PC. Different take-off angles correspond to a different depth, approximately: u590°;100 Å, u545°; 50 Å, and u520°;20 Å.

applications. As-deposited films on PC did not show any delamination when applying the adhesive-tape peel test, and the MST measurements indicated a corresponding critical load, L c , of 3.260.2 N. All films successfully passed the peel test after exposing the samples to high humidity (RH 597%) at an elevated temperature ~50 °C! for 24 h, while the L c values dropped by 5% at most, which is comparable to the measuring error. Nevertheless, we attempted to further enhance this adhesion by plasma pretreatment of the PC substrate prior to film deposition. Using different working gases, we found that the critical load for SiN1.3 markedly increased when N2 O, Ar, and N2 were applied ~see Fig. 1!. Interestingly, such adhesion enhancement is in good agreement with adhesion studies performed on a completely different combination of materials, namely Cu and Teflon PFA14 or Ag and polyethylene.24 In these studies, too, N2 plasma treatment resulted in the highest adhesion, an effect related to the formation of film–N–C chemical bonds at the interface. Such a result was also confirmed for our SiN1.3/PC system ~see Sec. III C 2!. On the other hand, the use of hydrogen, or of hydrogen-containing gas ~e.g., NH3 ! did not significantly increase the adhesion. It has been proposed25 that the presence of hydrogen may lead to the formation of C–H bonds, which contribute to a weaker interface. C. Analysis of the SiN1.3/PC interface

1. Refractive index profile FIG. 4. Si(2 p) and C(1s) high resolution XPS spectra of a ;50 Å thick SiN1.3 layer deposited on untreated PC. Different take-off angles, u , correspond to a different depth, approximately: u590°;100 Å, u545°;50 Å, and u520°;20 Å. J. Vac. Sci. Technol. A, Vol. 15, No. 3, May/Jun 1997

Spectrophotometric measurements on SiN1.3 films with thicknesses around 50, 120, and 300 nm on PC substrates were analyzed in order to investigate a possible change of the refractive index profile near the SiN1.3/PC interface. A clear

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TABLE II. XPS analysis at different take-off angles of untreated and N2 plasma treated PC, and the SiN1.3 /PC interface when ultrathin SiN1.3 layers (;50 Å) were deposited on untreated and N2 plasma treated PC.

PC theoretical PC PC/SiN1.3 PC/SiN1.3 PC/SiN1.3 PC/SiN1.3 PC/N2 PC/N2 /SiN1.3 PC/N2 /SiN1.3

u ~deg!

Si ~at. %!

N ~at. %!

O ~at. %!

C ~at. %!

90 90 90 60 45 20 90 90 20

••• ••• 34.6 38.1 37.1 33.9 ••• 36.3 28.1

••• ••• 35.6 34.2 36.2 28.6 16 42.2 32.2

15.8 15 14.7 15.3 16.9 18.8 12.6 10.6 26.1

84.2 85 14.8 12.4 8.8 18.7 72.4 10.9 12.6

improvement of the reflectance fit was observed when a graded interfacial region was introduced to the model ~see Fig. 2!. Ultraviolet ~UV!-induced crosslinking may occur at the polymer surface during exposure to the plasma environment,4,7 thus forming a polymer sublayer with a higher density near the surface.26 UV light absorption will decrease with penetration depth exponentially and, as a first approximation, the refractive index profile may follow the same behavior. In addition, traces of residual oxygen in the deposition chamber and oxygen contained on the PC surface may also react with the growing SiN1.3 film and transform it near the interface into a SiOx Ny layer with a lower refractive index. The reaction with oxygen from the surface is expected to decrease as the SiN1.3 layer becomes thicker, leaving a SiOx Ny graded-index layer in the interfacial region. It is not simple to derive the shape of the refractive index profile from ex situ spectrophotometric measurements, however, the quasi-linear profile shown in Fig. 2 ~for a SiN1.3 film 300 nm thick! and an estimated thickness of the transition region of about 40 nm for all films tested lead to the lowest error function when comparing the simulated and experimental data. It is expected that our future in situ optical measurements during the very first steps of the deposition will help us to determine the shape of the index profile at the interface more precisely. For now, it is sufficient to conclude from our analysis that the SiN1.3/PC interface is not abrupt but about 40 nm thick: This, in turn, has an important effect on the optical properties of the films and it may also be responsible for the good SiN1.3/PC adhesion. 2. XPS analysis

Additional insight into the mechanism of adhesion and the optical properties may be gained by XPS analysis of the SiN1.3/PC interface region. XPS results are shown for untreated and N2 plasma treated PC ~Fig. 3!, PC coated with ;50 Å of SiN1.3 ~Fig. 4!, and N2 plasma pretreated PC coated with ;50 Å of SiN1.3 ~Fig. 5!. Table II gives a detailed comparison of composition for these four conditions, while Table III provides a reference compilation of XPS assignments. The precision of the elemental concentration values is about 2%. During curve fitting, we based the assignment of the peaks on the consistency between the overall JVST A - Vacuum, Surfaces, and Films

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TABLE III. Identification of the deconvoluted XPS C(1s) and Si(2 p) peaks from Figs. 3–5, and their corresponding chemical structure. The peak positions are in eV. PC

PC/SiN1.3

PC/N2

PC/N2 /SiN1.3

C0

•••

283.9 Si–C

•••

•••

C1

285.0 C–C C–H

285.0 C–C C–H

285.0 C–C C–H

285.0 C–C C–H

C2

286.5 C–O

286.3 C–O C–O–Si

286.5 C–O C–N C–N

286.7 C–O–Si C–N–Si O–C–N–Si

C3

•••

288.6–289.2 O5C–O O5C5O5Si O–C–O–Si

288.7 C5O O–C5N C[N

289.3 O–C–O–Si i O C–O–C I –O–Si O–C–O u O

C4

290.9 O–C–O i O

•••

290.8 O–C–O i O

•••

C5

292.6 Shake-up

•••

292.6 Shake-up

•••

Si0

•••

100.3 Si–C

•••

•••

Si1

•••

101.8 Si–N

•••

101.6 Si–N

Si2

•••

102.9 Si–Ox

•••

103.0 Si–Ox

composition and the intensities of the deconvoluted peaks, on the XPS data for PC and SiN1.3 available in literature,27,28 and on the realistically expected chemical structure of the modified interface. The positions of the deconvoluted peaks in Figs. 3–5 and in Table III are determined with an accuracy of about 0.1 eV. Analysis of the as received PC revealed a composition in agreement with the polymer’s chemical structure ~see Fig. 3 and Tables II and III!. The high resolution C(1s) spectrum clearly shows the presence of C–C and C–H groups ~peak C1!, C–O groups ~C2!, the characteristic carbonate structure ~C4! and the shake-up ~C5! associated with aromatic bonding. When a 50 Å thick SiN1.3 layer is deposited on PC, the chemical structure of the interface is substantially modified, and it varies with depth, as probed by increasing the take-off angle from 20° to 90° ~see Fig. 4 and Table III, column PC/SiN1.3!. The PC characteristic features ~peaks C4 and C5! are not detected beyond the interface ~u 590°!, but chemical bonding between the layer and the substrate can be seen: peaks C2 and C3 are shifted by contributions of C–O–Si and O5C–O–Si ~or O–C–O–Si! bonds, respectively. Peak C0

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appears in the C(1s) spectrum and it indicates additional formation of Si–C bonds. Si–C bonding is also visible in the Si(2 p) spectrum ~peak Si0 in Fig. 4!, together with Si–N and Si–Ox bonds ~peaks Si1 and Si2!. In addition, the Si2 peak in the Si(2p) spectrum ~Fig. 4! may also contain a component corresponding to Si–O–C bonds. Further from the interface and closer to the coating’s surface ~lower takeoff angle! the concentration of Si–C bonds decreases, and Si–N bonds predominate; Si–Ox bonds also become more abundant, most probably due to the reaction with atmospheric oxygen during the sample transfer. The chemical bonding between SiN1.3 and PC at the interface explains the good adhesion described above ~Sec. III B!. On the other hand, varying the take-off angle reveals a gradual change in composition in this interfacial region, which may be linked to the continuous change in the refractive index, discussed in more detail in Sec. III C 1. We have seen above that the surface pretreatment substantially enhances the adhesion of SiN1.3 layers; when N2 was used, 16 at. % of N was found bonded on the PC surface ~see Table II!. This surface was analyzed, and the deconvoluted C(1s) peak is shown in Fig. 3 and Table III, column PC/N2 . One can distinguish new chemical groups, such as C–N (C5N) and O–C5N, contributing, respectively, to peaks C2 and C3, while the typical PC features ~peaks C4 and C5! are still preserved. Following N2 plasma pretreatment, a very thin SiN1.3 film, again about 50 Å thick, was deposited without breaking vacuum. No direct bonding between Si and C was detected in this case; however, C–N–Si and C–O–Si bonds ~see Table III, column PC/N2 /SiN1.3! were identified, and they contribute to peaks C2 and C3. In the Si(2 p) peak structure, mainly Si–N and Si–Ox bonds are observed at the interface, while higher oxygen concentration close to the surface was probably caused by atmospheric oxidation due to a longer exposure to air. It follows from the above described results that the film material reacts by forming Si–O–C or Si–C bonds when SiN1.3 is directly deposited onto PC, whereas C–N–Si bonds form in the case of N2 plasma treatment. In the latter case the N2 plasma pretreatment substantially modifies the PC surface ~for example, by breaking weaker chemical bonds, crosslinking and functionalization!. When SiN1.3 is subsequently deposited, not enough reactive sites with carbon are present, and Si–N–C and Si–O–C bonds are formed. The observed higher adhesion may, therefore, be linked with stronger bonds containing N. It is interesting to note that the highest adhesion has also been correlated with the formation of metal–N–C bonds in the case of silver on polyethylene24 and copper on fluoropolymers.14 Following Ar plasma pretreatment, a significant increase of L c was observed ~see Fig. 1!. In this case, however, no nitrogen-containing bonds are formed at the interface, but, rather, C–Si and C–O–Si linkages were detected.26 The substantial enhancement of adhesion in this case can, therefore, be attributed to the mechanical stabilization of the interface J. Vac. Sci. Technol. A, Vol. 15, No. 3, May/Jun 1997

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due to crosslinking4 caused by energetic vaccum ultraviolet radiation.7 IV. CONCLUSIONS In the present work, protective SiN1.3 films were successfully deposited onto PC substrates in a dual-mode microwave/radio-frequency plasma. The adhesion, determined by scratch- and peel-tape methods, was found satisfactory after a weathering test involving elevated temperature and humidity. The adhesion of SiN1.3 films was further enhanced when the PC surface was plasma pretreated prior to film deposition. The highest adhesion was observed following a surface modification in N2 plasma. XPS analysis of the SiN1.3/PC interface region indicated formation of Si–C and Si–O–C bonds for films deposited without pretreatment, whereas Si–N–C bonds form following N2 plasma treatment. The chemical composition was found to gradually vary throughout the interface region: This change was also identified by optical modeling. In fact, the graded interface ~about 40 nm thick! is believed to be responsible for the substantially enhanced adhesion, and also for the optical performance. ACKNOWLEDGMENTS This work was supported in part by the Natural Sciences and Engineering Research Council ~NSERC! of Canada, by the Fonds Formation de Chercheurs et Aide a` la Recherche ~FCAR! of Que´bec and by the Optical Coating Laboratory Inc., Contract Nos. CDT-P2022 and CDT-P2077. 1

C. A. Harper, Handbook of Plastics, Elastomers and Composites, 2nd ed. ~McGraw-Hill, New York, 1992!. J. D. Lytle, Devices, Measurements, and Properties, edited by M. Bass, E. W. Van Stryland, D. R. Williams, and W. L. Wolfe ~McGraw-Hill, New York, 1995! Vol. II, Chap. 34. 3 C. L. Bungay, T. E. Tiwald, M. J. DeVries, D. W. Thompson, and J. A. Woollam, Thin Solid Films ~submitted!. 4 E. M. Liston, L. Martinu, and M. R. Wertheimer, J. Adhes. Sci. Technol. 7, 1091 ~1993!. 5 F. D. Egitto and L. J. Matienzo, IBM J. Res. Dev. 38, 423 ~1994!. 6 M. R. Wertheimer, L. Martinu, and E. M. Liston, Handbook of Thin Film Process Technology ~IOP, Bristol, UK, 1996!, Chap. E3.0. 7 A. Hollander and M. R. Wertheimer, J. Vac. Sci. Technol. A 12, 879 ~1994!. 8 L. Martinu, J. E. Klemberg-Sapieha, and M. R. Wertheimer, Appl. Phys. Lett. 54, 2645 ~1989!. 9 J. E. Klemberg-Sapieha, O. M. Kuttel, L. Martinu, and M. R. Wertheimer, Thin Solid Films 193/194, 965 ~1990!. 10 L. Martinu, J. E. Klemberg-Sapieha, O. M. Kuttel, A. Raveh, and M. R. Wertheimer, J. Vac. Sci. Technol. A 12, 1360 ~1994!. 11 D. Poitras, P. Leroux, J. E. Klemberg-Sapieha, S. C. Gujrathi, and L. Martinu, Opt. Eng. 35, 2693 ~1996!. 12 M. R. Wertheimer, H. R. Thomas, M. J. Perri, J. E. Klemberg-Sapieha, and L. Martinu, Pure Appl. Chem. 68, 1047 ~1996!. 13 P. Reinke, S. Bureau, J. E. Klemberg-Sapieha, and L. Martinu, J. Appl. Phys. 78, 4855 ~1995!. 14 M. K. Shi, A. Selmani, L. Martinu, E. Sacher, M. R. Wertheimer, and A. Yelon, J. Adhes. Sci. Technol. 8, 1129 ~1994!. 15 J. A. Woollam Co., Inc., Lincoln, NE. 16 F. T. G. Software Associates, Princeton, NJ. 17 P. Leroux, A. Raveh, J. E. Klemberg-Sapieha, and L. Martinu, Proceedings of the 36th Annual Technological Conference of the Society of Vacuum Coaters, Dallas, TX, 1993, p. 472. 18 C. Julia-Schmutz and H. E. Hintermann, Surf. Coat. Technol. 48, 1 ~1991!. 19 D. A. Shirley, Phys. Rev. B 5, 4709 ~1972!. 2

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20

O. M. Ku¨ttel, J. E. Klemberg-Sapieha, L. Martinu, and M. R. Wertheimer, Thin Solid Films 193/194, 155 ~1990!. 21 K. Kasper, C. Wagner, and P. P. Deimel, IEEE Trans. Photonics Technol. Lett. 3, 1096 ~1991!. 22 P. V. Bulkin, P. L. Swart, and B. M. Larquet, Opt. Eng. 33, 2894 ~1994!. 23 W. G. Sainty, W. D. McFall, D. R. McKenzie, and Y. Yin, Appl. Opt. 34, 5659 ~1995!. 24 L. J. Gerenser, J. Vac. Sci. Technol. A 6, 2897 ~1988!. 25 M. K. Shi, J. E. Klemberg-Sapieha, G. Czeremuszkin, L. Martinu, and E.

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Sacher, Proceedings of the 12th International Symposium on Plasma Chemistry, University of Minnesota, August 1995, p. 51. S. Vallon, B. Dre´villon, F. Poncin-Epaillard, J. E. Klemberg-Sapieha, and L. Martinu, J. Vac. Sci. Technol. A 14, 3194 ~1996!. 27 G. Beamson and D. Briggs, High Resolution XPS of Organic Polymers ~Wiley, New York, 1992!. 28 J. F. Moulder, W. F. Stickle, P. E. Sobol, K. D. Bonibeu, Handbook of X-ray Photoelectron Spectroscopy, edited by J. Chastain ~Perkin-Elmer, Eden Prairie, MN, 1992!. 26



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