Diamond Coating Technologies v. Nissan North America et. al

7/27/2019 Diamond Coating Technologies v. Nissan North America et. al.

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).P.1901 Avenue of the Stars, Suite 950

Iqsph S. G_ri4qter \TX24092188 pro hac vice to be filed)SUSMAN GODFREY L.L.P.1000 Louisiana, Suite 5100m

DIAMOND COATING TECHNOLOGIES,LLC,Plaintiff,

Case No.SACV13-01481 JVS (JPRX)COMPLAINT FOR PATENTINFRINGEMENTJURY TRIAL DEMANDED

s:ff L:.'- c/,,,.'-" lrli- ''' - T--iL.- -.r f\);i : (,^);-';-t -o;--- Li1 _-._l i::l a+il G)' --tAttorneys for Plaintiff Diamond Coating Technologies LLCUNITED STATES DISTRICT COURT

CENTRAL DISTRICT OF CALIFORNIASOUTHERN DIVISION

VS

NISSAN NORTH AMEzuCA, INC. ANDNISSAN MOTOR CO., LTD.Defendants.

2859604v1 /013643 COMPLAINT FOR PATENT INFRINGEMENT

Case 8:13-cv-01481-DOC-DFM Document 1 Filed 09/23/13 Page 1 of 135 Page ID #:1


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1COMPLAINT FOR PATENT INFRINGEMENT

2859604v1/013643

COMPLAINT FOR PATENT INFRINGEMENT

Plaintiff Diamond Coating Technologies LLC files this Complaint for patent

infringement against Nissan Motor Co., Ltd. and Nissan North America, Inc.

(collectively, Defendants). Plaintiff Diamond Coating Technologies LLC

alleges:

THE PARTIES

1. Plaintiff Diamond Coating Technologies LLC (DCT) is a limitedliability company duly organized and existing under the laws of Delaware with its

principal place of business in 3945 Freedom Circle, Suite 900, Santa Clara, CA

95054-1226.

2. DCT is the assignee and owner of four patents at issue in this action,U.S. Patent Nos. 5,629,086; 6,066,399; 6,071,103; and 6,354,008.

3. DCT is informed and believes, and on that basis alleges, thatDefendant Nissan Motor Co., Ltd. (NMC) is a Japanese corporation having a

registered head office at 2, Takara-cho, Kanagawa-ku, Yokohama-shi, Kanagawa

220-8623, Japan, and global headquarters at 1-1, Takashima 1-chome, Nishi-ku

Yokohama-shi, Kanagawa 220-8686, Japan. NMC is the parent corporation ofNissan North America, Inc. NMC, through its various entities, designs

manufactures, markets, distributes and sells Nissan and Infinity automobiles in

California and multiple other locations in the United States and worldwide.

4. DCT is informed and believes, and on that basis alleges, that NissanNorth America, Inc. (NNA) is a corporation duly organized under the laws of the

State of California and having its principal place of business at One Nissan Way

Franklin, TN 37067. NNA is NMCs headquarters for management of North

American operations and manufacturing. NNA manufactures and distributes

Nissan and Infinity vehicles and sells these vehicles through its network of dealers.



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2859604v1/013643

JURISDICTION AND VENUE

5. This Court has subject matter jurisdiction pursuant to 28 U.S.C. 1331 and 1338(a) because this action arises under the patent laws of the United

States, 35 U.S.C. 1 et seq.

6. Venue is proper in this federal district pursuant to 28 U.S.C. 1391(b)-(c) and 1400(b).

7. Defendants have done business in this District, have sold infringingproducts in this District, and continue to sell infringing products in this District

entitling DCT to relief.

INFRINGEMENT OF U.S. PATENT NO. 5,629,086

8. On May 13, 1997, United States Patent No. 5,629,086 (the 086patent) was duly and legally issued for an invention entitled Hard-Carbon-Film-

Coated Substrate and Apparatus for Forming the Same. DCT was later assigned

the 086 patent and continues to hold all rights and interest in the 086 patent. A

true and correct copy of the 086 patent is attached hereto as Exhibit A.

9. Defendants have infringed and continue to infringe the 086 patent.Defendants manufacture, sell, import and/or offer for sale Nissan and Infinityvehicles utilizing parts coated with infringing hard carbon films. For example

defendants sell vehicles with engines containing parts, including, but not limited to

valve lifters and pistons, with infringing hard carbon film coatings. The use of hard

carbon film coatings allows for a reduction of engine friction, wear reduction, and

improved engine fuel efficiency. DCT is informed and believes, and on that basis

alleges, that Nissan engine models containing parts with infringing hard carbon film

coatings include, but are not limited to, HR16DE, MR16DDT, MRA8DE,

QR25DE, VQ35DE, VQ37VHR, VR48DETT. DCT expressly also accuses all

Nissan engine models not identified above that use the infringing hard carbon film

coating. Defendants vehicles with engines and other components containing parts

with hard carbon film coating infringe the 086 patent under 35 U.S.C. 271.



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2859604v1/013643

10. Defendants acts of infringement have caused damage to DCT, andDCT is entitled to recover from Defendants the damages sustained by DCT as a

result of Defendants wrongful acts in an amount subject to proof at trial

Defendants infringement of DCTs exclusive rights under the 086 patent will

continue to damage DCT, causing irreparable harm for which there is no adequate

remedy at law, unless enjoined by this Court.


11. On May 23, 2000, United States Patent No. 6,066,399 (the 399patent) was duly and legally issued for an invention entitled Hard Carbon Thin

Film and Method of Forming the Same. DCT was later assigned the 399 patent

and continues to hold all rights and interest in the 399 patent. A true and correct

copy of the 399 patent is attached hereto as Exhibit B.

12. Defendants have infringed and continue to infringe the 399 patent.Defendants manufacture, sell, import and/or offer for sale Nissan and Infinity

vehicles utilizing parts coated with infringing hard carbon films. For example


valve lifters and pistons, with infringing hard carbon film coatings. The use of hardcarbon film coatings allows for a reduction of engine friction, wear reduction, and












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2859604v1/013643





14. On June 6, 2000, United States Patent No. 6,071,103 (the 103patent) was duly and legally issued for an invention entitled Member Having

Sliding Contact Surface, Compressor and Rotary Compressor. DCT was later

assigned the 103 patent and continues to hold all rights and interest in the 103

patent. A true and correct copy of the 103 patent is attached hereto as Exhibit C.







alleges, that Nissan engine models containing parts with infringing hard carbon filmcoatings include, but are not limited to, HR16DE, MR16DDT, MRA8DE,












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2859604v1/013643


17. On March 12, 2002, United States Patent No. 6,354,008 (the 008patent) was duly and legally issued for an invention entitled Sliding Member

Inner and Outer Blades of an Electronic Shaver and Film-Forming Method. DCT

was assigned the 008 patent and continues to hold all rights and interest in the 008

patent. A true and correct copy of the 008 patent is attached hereto as Exhibit D.










Nissan engine models not identified above that use the infringing hard carbon filmcoating. Defendants vehicles with engines and other components containing parts







WILLFUL INFRINGEMENT

20. Upon information and belief, the Defendants infringement of any orall of the above-named patents is willful and deliberate, entitling DCT to increased



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2859604v1/013643

damages under 35 U.S.C. 284 and to attorneys fees and costs incurred in

prosecuting this action under 35 U.S.C. 285.

21. Defendants had prior knowledge of the patented technology becauseDCT provided notice of the patents to Defendants in 2008 and 2011. Moreover

DCT met with Defendants and attempted unsuccessfully to negotiate a license with

them.

JURY DEMAND

22. DCT demands a trial by jury on all issues.PRAYER FOR RELIEF

WHEREFORE, Plaintiff DCT requests entry of judgment in its favor and

against Defendants as follows:

a) Declaration that Defendants have infringed directly, and/or indirectlyU.S. Patent Nos. 5,629,086, 6,066,399, 6,071,103, and 6,354,008;

b) Permanently enjoining Defendants and their respective officersagents, employees, and those acting in privity with them, from further infringement

contributory infringement and/or inducing infringement of U.S. Patent Nos.

5,629,086, 6,066,399, 6,071,103, and 6,354,008;c) Awarding the damages arising out of Defendants infringement of U.S

Patent Nos. 5,629,086, 6,066,399, 6,071,103, and 6,354,008, including enhanced

damages pursuant to 35 U.S.C. 284 together with prejudgment and post-judgment

interest, in an amount according to proof;

d) An award of attorneys fees pursuant to 35 U.S.C. 285 or asotherwise permitted by law; and



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2859604v1/013643

For such other costs and further relief as the Court may deem just and proper.

Date : Septem er 23, 2013 KATHRYN P. HOEK OLEG ELKHUNOVICHJOSEPH S. GRINSTEIN

SUSMAN GODFREY L.L.P.

By:Kat ryn P. HoeAttorneys for Plaintiff DCT



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Exhibit A



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United S t a t e s Patent [ 1 9 ]Hirano e t a l .

US005629

[ 5 4 ] HARD-CARBON-FILM-COATED SU BSTRATEAND APPARATUS FOR FORMING THESAME[ 7 5 ] I n v e n t o r s : H i t o s h i H i r a n o ; K e i i c h i K u r a m o t o ;

Y o i c h i D o m o t o ; S e i i c h i K i y a m a , a l l o fM o r i g u c h i , J a p a n[ 7 3 ] A s s i g n e e : S a n y o E l e c t r i c C 0 . , L t d . , M o r i g u c h i ,J a p a n[ 2 1 ] A p p l . N o . : 4 6 4 , 5 4 4[ 2 2 ] F i l e d : J u n . 5 , 1 9 9 5

R e l a t e d US. p p l i c a t i o n D a t a[ 6 2 ] D i v i s i o n o f S e r . N o . 2 5 9 , 4 8 0 , J u n . 1 4 , 1 9 9 4 .[ 3 0 ] F o r e i g n A p p l i c a t i o n P r i o r i t y D a t a

J u l . 7 , 1993 [ J P ] Japan . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-167866J u l . 2 9 , 1 9 9 3 [ J P ] J a p a n 5 - 1 8 8 0 8 4Aug. 2 3 , 1 9 9 3 [ J P ] J a p a n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-207912

[ s 1 ] I n t . C l . 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . C04B 1/85[ 5 2 ] US. l . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2 8 / 3 3 6 ; 4 2 8 / 4 0 8 ; 4 2 8 / 4 4 6 ;

4 2 8 / 4 5 7 ; 4 2 8 / 4 6 9 ; 4 2 8 / 6 9 8 ; 4 2 8 / 7 0 1 ; 4 2 8 / 7 0 2[ 5 8 ] F i e l d Of Search . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2 8 / 4 0 8 , 4 4 6 ,4 2 8 / 4 5 7 , 4 6 9 , 6 9 8 , 3 3 6 , 7 0 1 , 7 0 2

086A[ 1 1 ] P a t e n t Number: 5 , 6 2 9 , 0 8 6[ 4 5 ] D a t e o f P a t en t : Ma y 1 3 , 1 9 9 7

[ 5 6 ] R e f e r e n c e s C i t e dU . S . PATENT DOCUMENTS

4,647,494 3/1987 Meyerson e t a 1 . . . . . . . . . . . . . . . . . . . . . . 4 2 8 / 4 4 64,707,384 11/1987 Schachneretal. . . 428/4085,380,349 1/1995 Taniguchi m1. . . . . . . . . . . . . . . . . . . . . . . . 65/286

FOREIGN PATENT DOCUMENTS3 0 4 7 8 8 8 7 / 1 9 8 2 G e r m a n y .

P r i m a r y E x a m i n e r - A r c h e n e T u r n e rA t t o m e y , A g e n t , o r FirmW. G . F a s s e ; W. F . F a s s e[ 5 7 ] ABSTRACTA a r d - c a r b o n - ? l m - c o a t e d s u b s t r a t e i n c l u d e s i n s t a c k e ds e q u e n c e a s u b s t r a t e , a n i n t e r m e d i a t e l a y e r , and a h a r dc a r b o n ? l m . Th e s u b s t r a t e c o n s i s t s o f a m e t a l o r a n a l l o ym a i n l y composed o f Ni o r A l , o r s t a i n l e s s s t e e l . The i n t e rm e d i a t e l a y e r i s m a i n l y c o m p o s e d o f R u , S i , Ge o r c a r b o n ,o r i s a mixed l a y e r i n c l u d i n g R u , S i , o r Ge mixed w i t h a tl e a s t o n e o f c a r b o n , n i t r o g e n o r o x y g e n , w i t h a c o m p o s i t i o ng r a d i e n t a c r o s s i t s t h i c k n e s s . An a p p a r a t u s f o r f o r m i n g t h ec o a t e d s u b s t r a t e e s p ec i a l l y i n c l u d e s m e a n s f o r f o r m i n g t h ei n t e r m e d i a t e l a y e r a n d means f o r f o r m i n g t h e h a r d c a r b o n?l m i n t h e same vacu u m c h a m b e r .

2 9 C l a i m s , 1 1 D r a w i n g S h e e t s

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US. Patent May 1 3 , 1 9 9 7 S h e e t 1 o f 1 1 5 , 6 2 9 , 0 8 6

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a s p e c t o f t h e p r e s e n t i n v e n t i o n i s a d a p t e d t o f o r m a h a r dcarbon ?l m on a s u b s t r a t e , and c o m p r i s e s a vacuumc h a m b e r , a s u b s t r a t e h o l d e r w h i c h i s r o t a t a b l y p r o v i d e d i nt h e vacuum c h a m b e r , a s h i e l d i n g c o v e r h a v i n g a n o p e n i n g



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t h e p l a s m a w h i c h i s g e n e r a t e d f r o m t h e p l a s m a g e n e r a t i o nm e a n s , and a h i g h - f r e q u e n c y powe r s o u r c e f o r a p p l y i n g ah i g h - f r e q u e n c y v o l t a g e t o t h e s u b s t r a t e h o l d e r s o t h a t as e l f - b i a s w h i c h i s d e v e l o p e d i n t h e s u b s t r a t e g o e s n e g a t i v e .

Ahard c a r b o n ?lm o r m i n g a p p a r a t u s a c c o r d i n g t o a s i x t ha s p e c t o f t h e p r e s e n t i n v e n t i o n i s a d a p t e d t o f o r m a ni n t e r m e d i a t e l a y e r o n a s u b s t r a t e f o r f u r t h e r f o r m i n g a h a r dc a r b o n ?l m on t h e i n t e r m e d i a t e l a y e r , an d c o m p r i s e s avacuum c h a m b e r , a s u b s t r a t e h o l d e r which i s r o t a t a b l yp r o v i d e d i n t h e vacuum c h a m b e r , a s h i e l d i n g c o v e r h a v i n g? r s t a n d s e c o n d o p e n i n g s t h e r e i n , w h i c h i s p r o v i d e d t oe n c l o s e a p e r i p h e r a l s u r f a c e o f t h e s u b s t r a t e h o l d e r , p l a s m ag e n e r a t i o n means f o r g e n e r a t i n g a p l a s m a i n t h e vacuumc h a m b e r a n d e m i t t i n g t h e p l a s m a t o w a r d t h e s u b s t r a t et h r o u g h t h e ? r s t o p e n i n g , r e a c t i o n g a s i n l e t m e a n s f o rs u p p l y i n g a r e a c t i o n g a s c o n t a i n i n g c a r b o n i n t o t h e p l a s m aw h i c h i s g e n e r a t e d f r o m t h e p l a s m a g e n e r a t i o n m e a n s , ah i g h - f r e q u e n c y p o w e r s o u r c e f o r a p p l y i n g a h i g h - f r e q u e n c yv o l t a g e t o t h e s u b s t r a t e h o l d e r s o t h a t a s e l f - b i a s which i sd e v e l o p e d i n t h e s u b s t r a t e g o e s n e g a t i v e , a n d i n t e r m e d i a t el a y e r f o r m i n g means p r o v i d e d i n t h e vacuum c h a m b e r f o re m i t t i n g m a t e r i a l a t o m s f o r f o r m i n g a n i n t e r m e d i a t e l a y e rt o w a r d t h e s u b s t r a t e t h r o u g h t h e s e c o n d o p e n i n g .

A n a p p a r a t u s a c c o r d i n g t o a s e v e n t h a s p e c t o f t h e p r e s e n ti n v e n t i o n i s a n e x e m p l a r y a p p a r a t u s a c c o r d i n g t o t h e s i x t ha s p e c t , a n d i s c h a r a c t e r i z e d i n t h a t t h e i n t e r m e d i a t e l a y e rf o r m i n g means c o m p r i s e s a n e v a p o r a t i o n s o u r c e p r o v i d e d i nt h e vacuum chamber f o r e m i t t i n g t h e m a t e r i a l a t o m s f o rf o r m i n g a n i n t e r m e d i a t e l a y e r t o w a r d t h e s u b s t r a t e t h r o u g ht h e s e c o n d o p e n i n g , a n d a n i o n gun f o r e m i t t i n g i o n s o f a ni n e r t g a s t o w a r d t h e s u b s t r a t e t h r o u g h t h e s e c o n d o p e n i n gs i m u l t a n e o u s l y w i t h e m i s s i o n o f t h e m a t e r i a l a t o m s f r o m t h ee v a p o r a t i o n s o u r c e .

A n a p p a r a t u s a c c o r d i n g t o a n e i g h t h a s p e c t o f t h e p r e s e n ti n v e n t i o n i s a n o t h e r e x e m p l a r y a p p a r a t u s a c c o r d i n g t o t h es i x t h a s p e c t , a n d i s c h a r a c t e r i z e d i n t h a t t h e i n t e r m e d i a t el a y e r f o r m i n g m e a n s c o m p r i s e s a t a r g e t c o n s i s t i n g o f t h em a t e r i a l a t o m s f o r f o r m i n g a n i n t e r m e d i a t e l a y e r , w h i c ht a r g e t i s p r o v i d e d i n t h e vacuum c h a m b e r f o r s p u t t e r i n g t h em a t e r i a l a t o m s t o w a r d t h e s u b s t r a t e t h r o u g h t h e s e c o n do p e n i n g , a n d a n i o n g u n f o r e m i t t i n g i o n s o f a n i n e r t g a st o w a r d t h e t a r g e t f o r s p u t t e r i n g t h e s a m e .

I n t h e a p p a r a t u s a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n , t h ep l a s m a g e n e r a t i o n m e a n s i s p r e f e r a b l y a n e l e c t r o n c y c l o t r o nr e s o n a n c e p l a s m a CVD p p a r a t u s .

I n t h e a p p a r a t u s a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n , t h es h i e l d i n g c o v e r i s p r e f e r a b l y s e p a r a t e d f r o m t h e p e r i p h e r a ls u r f a c e o f t h e s u b s t r a t e h o l d e r a t a d i s t a n c e o f n o t more t h a na mean f r e e p a t h o f t h e g a s m o l e c u l e s , an d more p r e f e r a b l y1 / 1 0 o f t h e mean f r e e p a t h o f t h e g a s m o l e c u l e s .

I n t h e a p p a r a t u s a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n , t h es h i e l d i n g c o v e r i s p r e f e r a b l y m a i n t a i n e d a t a p r e s c r i b e dp o t e n t i a l , a n d i s m o r e p r e f e r a b l y g r o u n d e d .

I n t h e a p p a r a t u s a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n , t h em a t e r i a l atoms f o r f o r m i n g a n i n t e r m e d i a t e l a y e r a r e a t o m so f i , R u , c a r b o n o r G e , o r a m i x t u r e o f i , R u , c a r b o n o r Gea n d a t l e a s t o n e o f c a r b o n , n i t r o g e n and o x y g e n , f o re x a m p l e , a n d t h e h a r d c a r b o n ?lm i s f o r m e d a t l e a s t i n d ir e c t l y o n a s u b s t r a t e c o n s i s t i n g o f a m e t a l o r a n a l l o y m a i n l ycomposed o f N i o r A l , o r s t a i n l e s s s t e e l , f o r e x a m p l e ,t h r o u g h s u c h a n i n t e r m e d i a t e l a y e r .The a p p a r a t u s a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n co mp r i s e s t h e s u b s t r a t e h o l d e r w h i c h i s r o t a t a b l y p r o v i d e d n t h e

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5 5

6I n t h e a p p a r a t u s a c c o r d i n g t o t h e p r e s e n t i n v e n t i o n , t h es h i e l d i n g c o v e r i s p r o v i d e d t o e n c l o s e t h e p e r i p h e r a l s u r f a c e

o f t h e s u b s t r a t e , s o t h a t t h e p l a s m a w h i c h i s g e n e r a t e d f r o mt h e p l a s m a g e n e r a t i o n m e a n s i s e m i t t e d t h r o u g h t h e o p e n i n go f t h e s h i e l d i n g c o v e r f o r f o r m i n g t h e h a r d c a r b o n ?l m o nt h e s u b s t r a t e . Due t o s u c h a s h i e l d i n g c o v e r , i t i s p o s s i b l e t op r e v e n t t h e o c c u r r e n c e o f d i s c h a r g e a t l o c a t i o n s o t h e r t h a nt h o s e w h e r e i t i s i n t e n d e d t o form t h e ? l m , t h e r e b y s u pp r e s s i n g a t e m p e r a t u r e i n c r e a s e o f t h e s u b s t r a t e .A ethod o f f o r m i n g t h e h a r d - c a r b o n - ? l m - c o a t e d s u bs t r a t e a c c o r d i n g t o a n i n t h a s p e c t o f t h e p r e s e n t i n v e n t i o n

c o m p r i s e s a s t e p o f s u p p l y i n g a g a s c o n t a i n i n g m a t e r i a la t o m s f o r f o r m i n g a n i n t e r m e d i a t e l a y e r i n t o a vacuumc h a m b e r f o r f o r m i n g a p l a s m a a n d e m i t t i n g t h e p l a s m at o w a r d a s u b s t r a t e t h e r e b y f o r m i n g a n i n t e r m e d i a t e l a y e r o nt h e s u b s t r a t e . T h i s method f u r t h e r c o m p r i s e s a s t e p o fs u p p l y i n g a r e a c t i o n g a s c o n t a i n i n g c a r b o n i n t o t h e vacuumc h a m b e r f o r f o n n i n g a p l a s m a a n d e m i t t i n g t h e p l a s m at o w a r d t h e i n t e r m e d i a t e l a y e r t h e r e b y f o r m i n g a h a r d c a r b o n?l m on t h e i n t e r m e d i a te l a y e r .A c c o r d i n g t o t h e s i x t h a s p e c t o f t h e p r e s e n t i n v e n t i o n , t h ei n t e r m e d i a t e l a y e r f o r m i n g m e a n s i s p r o v i d e d f o r e m i t t i n gt h e m a t e r i a l a t o m s f o r f o r m i n g a n i n t e r m e d i a t e l a y e r t o w a r dt h e s u b s t r a t e t h r o u g h t h e s e c o n d o p e n i n g o f t h e s h i e l d i n gc o v e r . T h e r e f o r e , t i s p o s s i b l e t o f o r m t h e i n t e r m e d i a t e la y e ra s w e l l a s t h e h a r d c a r b o n ?l m w i t h a s i n g l e e v a c u a t i o n .F u r t h e r , i t i s p o s s i b l e t o c o n t r o l t h e f o r m a t i o n o f t h e h a r dc a r b o n ?lm a n d t h a t o f t h e i n t e r m e d i a t e l a y e r i n d e p e n d e n t l yo f e a c h o t h e r . T h u s , i t i s p o s s i b l e t o f o r m t h e h a r d c a r b o n?l m a f t e r a d e s i r e d i n t e r m e d i a t e l a y e r i s formed on t h es u b s t r a t e .F u r t h e r , i t i s p o s s i b l e t o c o n t r o l t h e m a t e r i a l c o m p o s i t i o nr a t i o o f t h e i n t e r m e d i a t e l ay e r a s d e s i r e d b y a l t e r n a t e l yr e p e a t i n g d e p o s i t i o n o f t h e c a r b o n ? l m b y p l a s m a CVDt h r o u g h t h e ? r s t o p e n i n g a n d d e p o s i t i o n o f t h e m a t e r i a la t o m s f o r f o r m i n g a n i n t e r m e d i a t e l a y e r t h r o u g h t h e s e c o n do p e n i n g . T h u s , i t i s p o s s i b l e t o b r i n g t h e m a t e r i a l c o m p o s it i o n r a t i o o f t h e i n t e r m e d i a t e l a y e r i n t o a g r a d e d s t r u c t u r eg r a d u a l l y a p p r o a c h i n g t h e c o m p o s i t i o n o f t h e h a r d c a r b o n?l m t o w a r d t h e h a r d c a r b o n ?l m Due t o f o r m a t i o n o f t h ei n t e r m e d i a t e l a y e r h a v i n g s u c h a g r a d e d s t r u c t u r e , i t i sp o s s i b l e t o f u r t h e r i m p r o v e a d h e s i o n b e t w e e n t h e s u b s t r a t ea n d t h e h a r d c a r b o n ? l m .

I n t h e a p p a r a t u s a c c o r d i n g t o t h e ? f t h a s p e c t o f t h e p r e s e n ti n v e n t i o n , t h e s u b s t r a t e h o l d e r i s p r o v i d e d i n t h e vacuumchamber, s o t h a t a number o f s u b s t r a t e s ca n be mounted o nt h e s u b s t r a t e h o l d e r . T h u s , i t i s p o s s i b l e t o i n c r e a s e t h enumber o f s u b s t r a t e s t h a t c a n be t r e a t e d i n a s i n g l e e v a c ua t i o n .

The s h i e l d i n g c o v e r i s p r o v i d e d a r o u n d t h e s u b s t r a t eh o l d e r , w h e r e b y i t i s p o s s i b l e t o p r e v e n t t h e o c c u r r e n c e o fd i s c h a r g e i n t h e v i c i n i t y o f a s u b s t r a t e p o r t i o n o t h e r t h a n h a tw h i c h i s t o b e p r o v i d e d w i t h t h e ? l m . T h u s , i t i s p o s s i b l e t oform t h e ?l m w h i l e m a i n t a i n i n g t h e s u b s t r a t e a t a l owt e m p e r a t u r e , w h e r e b y t i s u n n e c e s s a r y t o c o n s i d e r t h e h e a tr e s i s t a n c e o f t h e s u b s t r a t e .

The a p p a r a t u s a c c o r d i n g t o t h e s i x t h a s p e c t o f t h e p r e s e n ti n v e n t i o n i s f u r t h e r p r o v i d e d w i t h t h e i n t e r m e d i a t e l a y e rf o r m i n g m e a n s . T h u s , t i s p o s s i b l e t o f o r m t h e i n t e r m e d i a t el a y e r o n t h e s u b s t r a t e i n a s i n g l e e v a c u a t i o n s t e p .F u r t h e r , i t i s p o s s i b l e t o c h a n g e t h e m a t e r i a l c o m p o s i t i o nr a t i o o f t h e i n t e r m e d i a t e l a y e r b y a l t e r n a t e l y f o r m i n g t h i n? l m s b y t h e p l a s m a g e n e r a t i o n m e a n s a n d b y t h e i n t e r m ed i a t e l a y e r f o r m i n g m e a n s a n d c h a n g i n g t h e r e s p e c t i v e t h i n



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T h e f o r e g o i n g a n d o t h e r o b j e c t s , f e a t u r e s , a s p e c t s a n da d v a n t a g e s o f t h e p r e s e n t i n v e n t i o n w i l l become morea p p a r e n t f r o m t h e f o l l o w i n g d e t a i l e d d e s c r i p t i o n o f t h ep r e s e n t i n v e n t i o n w hen t a k e n i n c o n j u n c t i o n w i t h t h ea c c o m p a n y i n g d r a w i n g s .BRIEF DESCRIPTION OF THE DRAWINGS

F I G . 1 i s a s c h e m a t i c s e c t i o n a l view s h o w i n g a h a r dc a r b o n ?lm f o r m i n g a p p a r a t u s i n a n e m b o d i m e n t a c c o r d i n gt o t h e ? f t h a s p e c t o f t h e p r e s e n t i n v e n t i o n ;

F I G . 2 s a p l a n view s h o w i n g a p o r t i o n a r o u n d a f o r w a r de n d o f a r e a c t i o n g a s i n l e t p i p e p r o v i d e d i n t h e e m b o d i m e n tshown i n F I G . 1 ;

F I G . 3 i l l u s t r a t e s t h e e l a t i o n s b e t w e e n ?lm o r m i n g t i m e sa n d s u b s t r a t e t e m p e r a t u r e s i n a n e x a m p l e o f t h e p r e s e n ti n v e n t i o n a n d c o m p a r a t i v e e x a m p l e s ;

F I G . 4 i s a s c h e m a t i c s e c t i o n a l view s h o w i n g a h a r dc a r b o n ?l m f o r m i n g a p p a r a t u s i n a n e m b o d i m e n t a c c o r d i n gt o t h e s e v e n t h a s p e c t o f t h e p r e s e n t i n v e n t i o n ;

F I G . 5 i l l u s t r a t e s t h e r e l a t i o n b e t w e e n a ?h n o r m i n g t i m ean d a CH4 ?ow a t e i n t h e f o r m a t i o n o f a n i n t e r m e d i a t e l a y e rh a v i n g a g r a d e d s t r u c t u r e w i t h t h e a p p a r a t u s o f t h e e m b o d iment a c c o r d i n g t o t h e s e v e n t h a s pe c t o f t h e p r e s e n t i n v e nt i o n ;

F I G . 6 i l l u s t r a t e s t h e r e l a t i o n b e t w e e n t h e ?hn f o r m i n gt i m e a n d a n e v a p o r a t i o n r a t e i n t h e f o r m a t i o n o f t h e i n t e rm e d i a t e l a y e r h a v i n g a g r a d e d s t r u c t u r e w i t h t h e a p p a r a t u so f t h e e m b o d i m e n t a c c o r d i n g t o t h e s e v e n t h a s p e c t o f t h ep r e s e n t i n v e n t i o n ;

F I G . 7 i s a s c h e m a t i c s e c t i o n a l view showing a h a r dc a r b o n ?lm f o r m i n g a p p a r a t u s i n a n e m b o d i m e n t a c c o r d i n gt o t h e e i g h t h a s p e c t o f t h e p r e s e n t i n v e n t i o n ;

F I G . 8 i l l u s t r a t e s t h e r e l a t i o n b e t w e e n a ?l m o r m i n g t i m ean d a CH4 ?ow a t e i n t h e f o r m a t i o n o f a n i n t e r m e d i a t e l a y e rh a v i n g a g r a d e d s t r u c t u r e w i t h t h e a p p a r a t u s o f t h e e m b o d im e n t a c c o r d i n g t o t h e e i g h t h a s p e c t o f h e p r e s e n t i n v e n t i o n ;

F I G . 9 i l l u s t r a t e s t h e r e l a t i o n b e t w e e n t h e ?l m f o r m i n gt i m e a n d a n i o n c u r r e n t d e n s i t y i n t h e f o r m a t i o n o f t h ei n t e r m e d i a t e l a y e r h a v i n g a g r a d e d s t r u c t u r e w i t h t h e a p p ar a t u s o f t h e e m b o d i m e n t a c c o r d i n g t o t h e e i g h t h a s p e c t o f t h ep r e s e n t i n v e n t i o n ;

F I G . 1 0 i s a s e c t i o n a l v i e w showing a d i a m o n d - l i k ec a r b o n ?l m d i r e c t l y formed on a s u b s t r a t e a c c o r d i n g t o ane x a m p l e o f t h e p r e s e n t i n v e n t i o n ;

F I G . 1 1 i s a s e c t i o n a l v i e w s h o w i n g a n i n t e r m e d i a t e l a y e rformed on a s u b s t r a t e and a d i a m o n d - l i k e carbon ? l mf o r m e d t h e r e o n a c c o r d i n g t o a n o t h e r e x a m p l e o f t h e p r e s e n ti n v e n t i o n ;

F I G . 12 s a s c h e m a t i c s e c t i o n a l view showing a convent i o n a l h a r d c a r b o n ?lm f o r m i n g a p p a r a t u s ;F I G . 1 3 i l l u s t r a t e s t h e r e l a t i o n s b e t w e e n p a r t i a l p r e s s u r e s

f o r s u p p l y i n g A r g a s a n d v a l u e s o f ?l m a r d n e s s i n a methodo f f o r m i n g a h a r d c a r b o n ?l m a c c o r d i n g t o t h e p r e s e n ti n v e n t i o n ; a n d

F I G . 1 4 i l l u s t r a t e s t h e r e l a t i o n b e t w e e n a s e l f - b i a s d e v e loped i n a s u b s t r a t e and ?l m h a r d n e s s i n t h e method o ff o r m i n g a h a r d c a r b o n ?l m a c c o r d i n g t o t h e p r e s e n t i n v e nt i o n .

DESCRIPTION O F THE REFERRED

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8e r a t i o n chamber 4 i s p r o v i d e d i n a vacuum chamber 8 . Ane n d o f a w a v e g u i d e 2 s mounted o n t h e p l a s m a g e n e r a t i o nc h a m b e r , w h i l e m i c r o w a v e s u p p l y m e a n s 1 i s p r o v i d e d o na n o t h e r end o f t h e w a v e g u i d e 2 . A microwave t h a t i sg e n e r a t e d i n t h e m i c r o w a v e s u p p l y m e a n s 1 p a s s e s t h r o u g ht h e waveguide 2 and a microwave i n l e t w i n d o w 3 , t o beg u i d e d i n t o t h e p l a s m a g e n e r a t i o n c h a m b e r 4 . The p l a s m ag e n e r a t i o n c h a m b e r 4 i s p r o v i d e d w i t h a d i s c h a r g e g a s i n l e tp i p e 5 f o r i n t r o d u c i n g a d i s c h a r g e g a s s u c h a s a r g o n ( A r ) g a si n t o t h e p l a s m a g e n e r a t i o n c h a m b e r 4 . F u r t h e r , a p l a s m am a g n e t i c ? e l d g e n e r a t o r 6 i s p r o v i d e d a r o u n d t h e p l a s m ag e n e r a t i o n c h a m b e r . A l a s m a o f h i g h d e n s i t y i s f o r m e d i nt h e p l a s m a g e n e r a t i o n c h a m b e r 4 b y t h e a c t i o n s o f a h i g hf r e q u e n c y m a g n e t i c ? e l d f o r m e d b y t h e m i c r o w a v e a n d am a g n e t i c ? e l d g e n e r a t e d b y t h e p l a s m a m a g n e t i c ? e l dg e n e r a t o r 6 .A y l i n d r i c a l s u b s t r a t e h o l d e r 1 2 i s p r o v i d e d i n t h evacuum chamber 8 . T h i s c y l i n d r i c a l s u b s t r a t e h o l d e r 1 2 i s

r o t a t a b l e a b o u t a s h a f t ( n o t s h o w n ) w h i c h i s a r r a n g e dp e r p e n d i c u l a r l y t o w a l l s u r f a c e s o f t h e vacuum chamber 8 .A l u r a l i t y o f s u b s t r a t e s 1 3 a r e mounted on a p e r i p h e r a ls u r f a c e o f t h e s u b s t r a t e h o l d e r 1 2 a t r e g u l a r i n t e r v a l s .A c c o r d i n g t o t h i s e m b o d i m e n t , 2 4 n i c k e l ( N i ) s u b s t r a t e s 1 3a r e mounted on t h e p e r i p h e r a l s u r f a c e o f t h e s u b s t r a t e h o l d e r1 2 . A i g h - f r e q u e n c y power s o u r c e 1 0 i s c o n n e c t e d t o t h es u b s t r a t e h o l d e r 1 2 .A y l i n d r i c a l s h i e l d i n g c o v e r 1 4 o f a m e t a l i s p r o v i d e d

a r o u n d t h e s u b s t r a t e h o l d e r 1 2 a t a p r e s c r i b e d d i s t a n c e . T h i ss h i e l d i n g c o v e r 1 4 i s c o n n e c t e d t o a g r o u n d e l e c t r o d e . T h i ss h i e l d i n g c o v e r 1 4 i s a d a p t e d t o p r e v e n t d i s c h ar g e a c r o s sp o r t i o n s o f t h e s u b s t r a t e h o l d e r 1 2 o t h e r t h a n t h o s e i n t e n d e df o r ?lm f o r m a t i o n a n d t h e vacuum c h a m b e r 8 c a u s e d b y t h eRF v o l t a g e t h a t i s a p p l i e d t o t h e s u b s t r a t e h o l d e r 1 2 i nf o r m a t i o n o f t h e ? l m s . The s u b s t r a t e h o l d e r 12 and t h es h i e l d i n g c o v e r 14 a r e s o a r r a n g e d t h a t t h e d i s t a n c e t h e rebetween i s n o t more t h a n t h e mean f r e e p a t h o f g a sm o l e c u l e s . The mean f r e e p a t h o f t h e g a s m o l e c u l e s i s l e s st h a n o r e q u a l t o t h e mean d i s t a n c e t h a t i o n s and e l e c t r o n st h a t a r e g e n e r a t e d by some c a u s e and a c c e l e r a t e d by a ne l e c t r i c ? e l d c a n t r a v e l w i t h no c o l l i s i o n . Th e d i s t a n c eb e t w e e n t h e s u b s t r a t e h o l d e r 1 2 a n d t h e s h i e l d i n g c o v e r 1 4i s s e t t o be n o t more t h a n t h e mean f r e e p a t h o f t h e g a sm o l e c u l e s , s o a s t o r e d u c e t h e p r o b a b i l i t y t h a t i o n s a n de l e c t r o n s w i l l c o l l i d e w i t h t h e g a s m o l e c u l e s , th e r e b y p r ev e n t i n g a c h a i n p r o g r e s s i o n o f i o n i z a t i o n .

The d i s t a n c e b e t w e e n t h e s u b s t r a t e h o l d e r 1 2 a n d t h es h i e l d i n g c o v e r 1 4 i s p r e f e r a b l y s e t t o b e n o t more t h a n 1 / 1 0o f t h e mean f r e e p a t h o f t h e g a s m o l e c u l e s , i n p a r t i c u l a r .A c c o r d i n g t o t h i s e m b o d i m e n t , t h e d i s t a n c e b e t w e e n t h es u b s t r a t e h o l d e r an d t h e s h i e l d i n g c o v e r 1 4 i s s e t a t a b o u t 5m m , which s n o t more t h a n 1 / 1 0 o f t h e mean f r e e p a t h o f t h eg a s m o l e c u l e s .

The s h i e l d i n g c o v e r 1 4 h a s a n o p e n i n g 1 5 . The p l a s m a i sd r a w n f r o m t h e p l a s m a g e n e r a t i o n c h a m b e r 4 a n d p a s s e st h r o u g h t h e o p e n i n g 1 5 , t o b e e m i t t e d t o w a r d t h e r e s p e c t i v es u b s t r a t e 13 mounted on t h e s u b s t r a t e h o l d e r 12 t a p o s i t i o na t t h e o p e n i n g 1 5 . The vacuum c h a m b e r 8 i s p r o v i d e dt h e r e i n w i t h a r e a c t i o n g a s i n l e t p i p e 1 6 . A o r w a r d e n d o ft h e r e a c t i o n g a s i n l e t p i p e 1 6 i s l o c a t e d a b o v e t h e o p e n i n g1 5 . F I G . 2 i s a p l a n v i e w s h o w i n g a p o r t i o n a r o u n d t h ef o r w a r d e n d o f t h e r e a c t i o n g a s i n l e t p i p e 1 6 . R e f e r r i n g t oF I G . 2 , t h e r e a c t i o n g a s i n l e t p i p e 1 6 i n c l u d e s a g a s i n l e t p a r t



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o f t h e d i r e c t i o n o f r o t a t i o n a b o v e t h e o p e n i n g 1 5 . The g a sd i s c h a r g e p a r t 1 6 b i s p r o v i d e d w i t h a p l u r a l i t y o f h o l e s 2 1which a r e downwardly d i r e c t e d a t a n a n g l e o f a b o u t 4 5 .A c c o r d i n g t o t h i s e m b o d i m e n t , e i g h t h o l e s 2 1 a r e p r o v i d e da t s p a c i n g i n t e r v a l s t h a t a r e g r a d u a l l y m ade n a r r o w e r fromt h e c e n t e r t o w a r d b o t h s i d e s . T h u s , t h e CH4 g a s w h i c h i si n t r o d u c e d f r o m t h e g a s i n l e t p a r t 1 6 a i s s u b s t a n t i a l l yu n i f o r m l y d i s c h a r g e d f r o m t h e r e s p e c t i v e h o l e s 2 1 .An e x a m p l e f o r f o r m i n g d i a m o n d - l i k e c a r b o n ? l m s s e r vi n g a s h a r d c a r b o n ?lms on n i c k e l s u b s t r a t e s t h r o u g h t h ea p p a r a t u s shown i n FIG. 1 i s n o w d e s c r i b e d .

F i r s t , 24 Ni s u b s t r a t e s 1 3 were mounted on t h e p e r i p h e r a ls u r f a c e o f t h e s u b s t r a t e h o l d e r 1 2 a t r e g u l a r i n t e r v a l s . T h e n ,t h e vacuum chamber 8 was e v a c u a t e d t o 1 0 5 t o 1 0 - 7 T o r r ,and t h e s u b s t r a t e h o l d e r 12 was r o t a t e d a t a s p e e d o f a b o u t1 0 r p m . T h e n , Ar g a s was s u p p l i e d from t h e d i s c h a r e g a si n l e t p i p e 5 o f a n ECR l a s m a g e n e r a t o r a t 5 . 7 > < 1 0 > < T o r r ,w h i l e a microwave o f 2 . 4 5 GH z r e q u e n c y a n d 1 0 0 W owerwas s u p p l i e d from h e microwave s u p p l y means , s o t h a t anAr l a s m a f o r m e d i n t h e p l a s m a g e n e r a t i o n c h a m b e r 4 w a se m i t t e d o n t o t h e s u r f a c e o f e a c h s u b s t r a t e 1 3 . At t h e samet i m e , a n RF o l t a g e o f 1 3 . 5 6 MHz r e q u e n c y was a p p l i e d t ot h e s u b s t r a t e h o l d e r 1 2 f r o m t h e h i g h - f r e q u e n c y powers o u r c e 1 0 , s o t h a t a s e l f - b i a s d e v e l o p e d i n e a c h s u b s t r a t e 1 3was 20 . CH 4 a s was s u p p l i e d from h e r e a c t i o n g a s i n l e tp i p e 1 6 a t 1 3 x 1 0 3 T o r r . T h e CH 4 g a s s u p p l i e d f r o m t h er e a c t i o n g a s i n l e t p i p e 1 6 w a s d e c o m p o s e d b y a n a c t i o n o ft h e plasma s o t h a t c a r b o n e n t e r e d an i o n i c o r n e u t r al a c t i v es t a t e h a v i n g h i g h r e a c t i v i t y t o b e e m i t t e d o n t o t h e s u r f a c e o fe a c h s u b s t r a t e 1 3 .

The a f o r e m e n t i o n e d s t e p was c a r r i e d o u t f o r a b o u t 1 5m i n u t e s , t o form a d i a m o n d - l i k e c a r b o n ?l m o f 1 2 0 0 A nt h i c k n e s s on t h e s u r f a c e o f e a c h s u b s t r a t e 1 3 . F I G . 10 i s as e c t i o n a l v i e w s h o w i n g a d i a m o n d - l i k e c a r b o n ?l m f o r m e don each s u b s t r a t e 13 i n t h e a f o r e m e n t i o n e d m a n n e r . Referr i n g t o F I G . 1 0 , a d i a m o n d - l i k e c a r b o n ?l m 1 i s formed ont h e s u b s t r a t e 1 3 .

F I G . 3 i l l u s t r a t e s t h e r e l a t i o n b e t w e e n a ?l m o r m i n g t i m ea n d a s u b s t r a t e t e m p e r a t u r e i n t h e a f o r e m e n t i o n e d Example( h e r e i n a f t e r r e f e r r e d t o a s E x a m p l e 1 ) , i n c o m p a r i s o n t od a t a o f a c o m p a r a t i v e e x a m p l e 1 i n w h i c h d i a m o n d - l i k ec a r b o n ? l m s w e r e f o r m e d s i m i l a r l y t o E x a m p l e 1 e x c e p t t h a tt h e s u b s t r a t e h o l d e r was n o t r o t a t e d , and a c o m p a r a t i v ee x a m p l e 2 n which d i a m o n d - l i k e c a r b o n ?lms w e r e formedi n an a p p a r a t u s w i t h o u t a s h i e l d i n g c o v e r and w i t h o u tr o t a t i o n o f a s u b s t r a te h o l d e r . As u n d e r s t o o d f r o m F I G . 3 , t h es u b s t r a t e t e m p e r a t u r e was a b o u t 4 5 C . i n Example 1 a t at i m e 1 5 m i n u t e s a f t e r s t a r t i n g ?l m f o r m a t i o n , w h i l e t h es u b s t r a t e t e m p e r a t u r e s a t t h a t same p o i n t i n t i m e i n co mp a r a t i v e e x a m p l e s 1 a n d 2 w e r e a b o u t 6 0 C . a n d a b o u t 1 5 0 C . r e s p e c t i v e l y . The s u b s t r a t e t e m p e r a t u r e w a s e x t r e m e l yi n c r e a s e d i n c o m p a r a t i v e e x a m p l e 2 , c o n c e i v a b l y b e c a u s ed i s c h a r g e was c a u s e d between t h e vacuum chamber andp o r t i o n s o f t h e s u b s t r a t e h o l d e r o t h e r t h a n t h o s e f o r f o r m i n gt h e ? l m s . T h e s u b s t r a t e t e m p e r a t u r e i n c o m p a r a t i v e e x a m p l e1 w a s l o w e r t h a n t h a t i n c o m p a r a t i v e e x a m p l e 2 , w h i c hs h o w s t h a t i t i s p o s s i b l e t o r e d u c e t h e s u b s t r a t e t e m p e r a t u r eb y p r o v i d i n g t h e s h i e l d i n g c o v e r . The s u b s t r a t e t e m p e r a t u r ei n E x a m p l e 1 w a s l o w e r t h a n t h a t i n c o m p a r a t i v e e x a m p l e 1 ,c o n c e i v a b l y b e c a u s e i n E x a m p l e 1 , t h e p o r t i o n s h e a t e d b yp l a s m a d i s c h a r g e w e r e s u c c e s s i v e l y moved s t h e s u b s t r a t eh o l d e r was r o t a t e d , t o s u p p r e s s t h e i n c r e a s e i n s u b s t r a t et e m p e r a t u r e . A c c o r d i n g t o t h e p r e s e n t i n v e n t i o n , i t i s p o ss i b l e t o s e l e c t t h e t y p e o f t h e s u b s t r a t e s w i t h o u t c o n s i d e r

10

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1 0s u b s t r a t e s w e r e ~5 0 V h i l e CH 4 a s was s u p p l i e d from h er e a c t i o n g a s i n l e t p i p e a t p a r t i a l p r e s s u r e s o f 3 . 0 X l 0 4 T o r r ,1 . 0 > < 1 0 _ 3 T o r r a n d 1 3 x 1 0 3 T o r r r e s p e c t i v e l y , f o r i n v e s t ig a t i n g t h e r e l a t i o n s b e t w e e n t h e p a r t i a l p r e s s u r e s a n d v a l u e so f h a r d n e s s o f t h e r e s u l t i n g d i a m o n d - l i k e c a r b o n ?lms a sf o r m e d .

F I G . 1 3 i l l u s t r a t e s t h e r e l a t i o n s b e t w e e n t h e p a r t i a l p r e ss u r e s f o r s u p p l y i n g Ar g a s a n d t h e v a l u es o f V i c k e r s h a r dn e s s o f t h e ? l m s , which were measured on t h e b a s i s o f HSG 0 2 0 2 .

As shown i n F I G . 1 3 . t h e v a l u e s o f h a r d n e s s o f t h e ?lmsw e r e a b o u t 3 0 0 0 H v r e g a r d l e s s o f t h e p a r t i a l p r e s s u r e s f o rs u p p l y i n g Ar a s . F u r t h e r , s u b s t a n t i a l l y s i m i l a r r e s u l t s w e r eo b t a i n e d a l s o w h e n t h e p a r t i a l p r e s s u r e s f o r s u p p l y i n g CH 4g a s w e r e c h a n g e d . T h u s , i t i s u n d e r s t o o d t o b e p o s s i b l e t of o r m d i a m o n d - l i k e c a r b o n ? l m s h a v i n g p r e s c r i b e d v a l u e s o f?l m h a r d n e s s o n s u b s t r a t e s r e g a r d l e s s o f t h e p a r t i a l p r e ss u r e s f o r s u p p l y i n g Ar g a s a n d CH 4 g a s .

T h e n , t h e Ar a s a n d t h e CH4 g a s w e r e s u p p l i e d a t p a r t i a lp r e s s u r e s o f 5 . 7 > < 1 0 ~ 4 T o r r a n d 1 0 x 1 0 3 T o r r r e s p e c t i v e l y ,w h i l e t h e o u t p u t from h e h i g h - f r e q u e n c y power s o u r c e wasc h a n g e d t o v a r y t h e s e l f - b i a s e s d e v e l o p e d i n t h e s u b s t r a t e s .F I G . 1 4 i l l u s t r a t e s t h e r e l a t i o n b e t w e e n t h e s e l f - b i a s d e v e lo p e d i n e a c h s u b s t r a t e a n d ?l m a r d n e s s o f t h e d i a m o n d - l i k ecarbon ?l m a s f o r m e d .

As shown n F I G . 1 4 , t h e ?l m a r d n e s s was t a low a l u eo f a b o u t 5 0 0 Hv when t h e s e l f - b i a s d e v e l o p e d i n e a c hs u b s t r a t e was 0 V . Th e ?l m h a r d n e s s i n c r e a s e d c o r r e s p o n di n g l y w i t h t h e a b s o l u t e v a l u e o f t h e s e l f - b i a s v o l t a g e a s i tv a r i e d t h r o u g h t h e r a n g e o f 0 V o ~2 0 . Th e ?l m a r d n e s swas a t a h i g h v a l u e o f a b o u t 300 0 Hv hen t h e s e l f - b i a s was~ 2 0 V . T h i s ?lm h a r d n e s s o f a b o u t 3 0 0 0 Hv s u b s t a n t i a l l yr e m a i n e d u n c h a n g e d when t h e s e l f - b i a s was r e d u c e d b e l o w~2 0 V . T h u s , i t i s u n d e r s t o o d t h a t i t i s p o s s i b l e t o f o r md i a m o n d - l i k e c a r b o n ?lms o f a b o u t 3000 H v n h a r d n e s s ons u b s t r a t e s b y s e t t i n g t h e RF v o l t a g e o f t h e h i g h - f r e q u e n c ypower s o u r c e s o t h a t t h e s e l f - b i a s d e v e l o p e d i n e a c h s u bs t r a t e i s n o t more t h a n ~2 0 V , r e g a r d l e s s o f t h e p a r t i a lp r e s s u r e s f o r s u p p l y i n g Ar g a s a n d CH4 g a s .

A r e s u l t s i m i l a r t o t h a t shown n F I G . 14 was o b t a i n e d a l s owhen h e p a r t i a l p r e s s u r e s f o r s u p p l y i n g Ar a s a n d CH4 a swere v a r i e d i n a r a n g e o f l . 0 > < 1 0 _ 4 t o 2 0 . O > < 1 0 ' 4 T o r r .

A n o t h e r e m b o d i m e n t , f o r f o r m i n g i n t e r m e d i a t e l a y e r s o ns u b s t r a t e s a n d t h e n f o r m i n g d i a m o n d - l i k e c a r b o n ?lms s e r vi n g a s h a r d c a r b o n ?lms on t h e i n t e r m e d i a t e l a y e r s , w i l l n o wbe d e s c r i b e d .

F I G . 1 1 i s a s e c t i o n a l v i e w s h o w i n g a n i n t e r m e d i a t e l a y e r2 2 formed on a s u b s t r a t e 1 3 , and a h a r d c a r b o n ?l m 21formed on h i s i n t e r m e d i a t e l a y e r 2 2 .

F I G . 4 i s a s c h e m a t i c s e c t i o n a l view showing a h a r dc a r b o n ?lm o r m i n g a p p a r a t u s a c c o r d i n g t o t h i s e m b o d i m e n to f t h e p r e s e n t i n v e n t i o n . R e f e r r i n g t o F I G . 4 , a s h i e l d i n gc o v e r 44 s p r o v i d e d a r o u n d a s u b s t r a t e h o l d e r 12 which i sa r r a n g e d i n a vacuum chamber . T h i s s h i e l d i n g c o v e r 44 sp r o v i d e d w i t h ? r s t a n d s e c o n d o p e n i n g s 4 5 a n d 4 3 . A c c o r di n g t o t h i s e m b o d i m e n t , t h e ? r s t a n d s e c o n d o p e n i n g s 4 5 a n d4 3 a r e f o r m e d i n s u b s t a n t i a l l y o p p o s i t e p o s i t i o n s . The ? r s to p e n i n g 4 5 i s f o r m e d s i m i l a r l y t o t h e o p e n i n g 1 5 s h o w n i nF I G . 1 , s o t h a t a f o r w a r d en d o f a r e a c t i o n g a s i n l e t p i p e 1 6i s l o c a t e d a b o v e t h e ? r s t o p e n i n g 4 5 , s i m i l a r l y t o t h ea p p a r a t u s shown i n F I G . 1 .

An e v a p o r a t i o n s o u r c e 4 1 i s p r o v i d e d u n d e r t h e s e c o n d



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i n e r t g a s f o r s u p p l y i n g t h e m a t e r i a l a t o m s e v a p o r a t e d f r o mt h e e v a p o r a t i o n s o u r c e 41 w i t h e n e r g y . A c c o r d i n g t o t h i se m b o d i m e n t , t h e i n e r t g a s i s Ar g a s , a n d t h e i n t e r m e d i a t el a y e r f o r m i n g m e a n s c o m p r i s e t h e e v a p o r a t i o n s o u r c e 4 1and t h e i o n gun 4 2 . Th e e v a p o r a ti o n s o u r c e 41 and t h e i o ng u n 42 e m i t t h e m a t e r i a l a t o m s f o r f o r m i n g i n t e r m e d i a t el a y e r s o n t o t h e s u b s t r a t e s 1 3 t h r o u g h t h e s e c o n d o p e n i n g 4 3 .

O t h e r s t r u c t u r e s o f h i s embodiment r e s i m i l a r t o t h o s e o ft h e embodiment shown i n F I G . 1 . T h u s , e l e m e n t s c o r r es p o n d i n g t o t h o s e i n F I G . 1 a r e d e n o t e d by t h e samer e f e r e n c e n u m e r a l s , a n d a r e d u n d a n t d e s c r i p t i o n t h e r e o f i so m i t t e d .

A n o t h e r i n v e n t i v e e x a m p l e w i l l no w b e d e s c r i b e d ,n a m e l y a n e x a m p l e f o r f o r m i n g i n t e r m e d i a t e l a y e r s f r o m as i n g l e e l e m e n t , a n d t h e n f o r m i n g d i a m o n d - l i k e c a r b o n ? l m so n t h e i n t e r m e d i a t e l a y e r s .

S i m i l a r l y t o t h e a b o v e d e s c r i b e d E x a m p l e 1 , 2 4 N is u b s t r a t e s 13 were mo unted on a p e r i p h e r a l s u r f a c e o f t h es u b s t r a t e h o l d e r 12 t r e g u l a r i n t e r v a l s . Th e vacu u m cha mb e r 8 was e v a c u a t e d t o 1 0 - 5 t o 1 0 7 T o r r , a n d t h e s u b s t r a t eh o l d e r 12 was r o t a t e d a t a s p e e d o f a b o u t 1 0 r p m . T h e n , t h ei o n gun 4 2 w as s u p p l i e d w i t h Ar g a s , s o t h a t Ar i o n s weree j e c t e d a n d e m i t t ed o n t o t h e s u r f a c e o f e a c h s u b s t r a t e 1 3 . Att h i s t i m e , t h e Ar i o n s were s e t a t a n a c c e l e r a t i o n v o l t a g e o f400 eV a n d i o n c u r r e n t d e n s i t y o f 0 . 3 mA/cm2. S i m u l t an e o u s l y w i t h t h e e m i s s i o n o f t h e Ar i o n s , t h e e v a p o r a t i o ns o u r c e 41 was d r i v e n t o e v a p o r a t e Ru a t o m s , f o r e m i t t i n g t h esame o n t o t h e s u r f a c e o f e a c h s u b s t r a t e 1 3 . Th e Ru e v a p or a t i o n r a t e w as s e t t o be 42 0 A m i n . i n t e r m s o f a ?l mf o r m i n g r a t e on e a c h s u b s t r a t e 1 3 .

Th e a f o r e m e n t i o n e d s t e p was c a r r i e d o u t f o r a b o u t 5m i n u t e s , t o f o r m a n i n t e r m e d i a t e l a y e r o f Ru h a v i n g at h i c k n e s s o f 200 A n t h e s u r f a c e o f e a c h s u b s t r a t e 1 3 .

T h e n , t h e e m i s s i o n o f Ru a t o m s f r o m t h e e v a p o r a t i o ns o u r c e 41 and t h e e m i s s i o n o f Ar i o n s from t h e i o n gun 4 2were s t o p p e d , and t h e r e a f t e r Ar g a s was s u p p l i e d from ad i s c h a r g e g a s i n l e t p i p e 5 o f a n ECR p l a s m a g e n e r a t o r a t5 . 7 > < 1 0 ' 4 T o r r w h i l e a m i c r o w a v e o f 2 . 4 5 GH Z f r e q u e n c ya n d 1 0 0 W ower w a s s u p p l i e d f r o m m i c r o w a v e s u p p l ymeans , t o e m i t a n Ar plasma formed n a plasma e n e r a t i o nchamber 4 o n t o t h e s u r f a c e o f e a c h s u b s t r a t e 1 3 . At t h e samet i m e , a n RF v o l t a g e o f 1 3 . 5 6 MHZ r e q u e n c y was a p p l i e dfrom a h i g h - f r e q u e n c y power s o u r c e 1 0 t o t h e s u b s t r a t eh o l d e r 1 2 and CH4 was s u p p l i e d from a r e a c t i o n g a s i n l e tp i p e 1 6 a t 13x103 T o r r , s o t h a t a s e l f - b i a s o f 20 Vd e v e l o p e d i n e a c h s u b s t r a t e 1 3 .Th e a f o r e m e n t i o n e d s t e p was c a r r i e d o u t f o r a b o u t 1 5m i n u t e s , t o form a d i a m o n d - l i k e c a r b o n ?l m o f 1 2 0 0 A nt h i c k n e s s on t h e i n t e r m e d i a t e l a y e r t h a t had b e e n formed one a c h s u b s t r a t e 1 3 .

As a r e s u l t o f t h e a f o r e m e n t i o n e d two t e p s , a l a y e r e d t h i n?l m n c l u d i n g t h e i n t e r m e d i a t e l a y e r 2 2 o f Ru o r m e d o n t h es u r f a c e o f e a c h s u b s t r a t e 1 3 a n d t h e d i a m o n d - l i k e c a r b o n?l m 21 formed on t h e i n t e r m e d i a t e l a y e r 2 2 , was o b t a i n e d a sshown n F I G . 1 1 . Due o s u c h f o r m a t i o n o f t h e i n t e r m e d i a t el a y e r 2 2 , i t i s p o s s i b l e t o r e l a x s t r e s s i n t h e d i a m o n d - l i k ec a r b o n ?l m 1 , t h e r e b y i m p r o v i n g t h e a d h e s i o n b e t w e e n t h es u b s t r a t e 13 a n d t h e d i a m o n d - l i k e c a r b o n ?l m 1 . Th e t r e s si n t h e d i a m o n d - l i k e c a r b o n ?l m 1 c a n b e r e l a x e d c o n c e i va b l y b e c a u s e i t i s p o s s i b l e t o r e l a x t h e r m a l s t r e s s c a u s e d b ya d i f f e r e n c e i n t h e r m a l e x p a n s i o n c o e f ? c i e n t s b e t w e e n t h e

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1 2d i a m o n d - l i k e c a r b o n ?lms t h e r e o n . I n t h i s e x a m p l e , a na p p a r a t u s s i m i l a r t o t h a t shown i n F I G . 4 was e m p l o y e d .

S i m i l a r l y t o t h e a b o v e d e s c r i b e d E x a m p l e 1 , 2 4 N is u b s t r a t e s 1 3 were mounted on t h e p e r i p h e r a l s u r f a c e o f t h es u b s t r a t e h o l d e r 12 a t r e g u l a r i n t e r v a l s . Th e vacu u m cha mb e r 8 was e v a c u a t e d t o 1 0 - 5 t o 1 0 7 T o r r , a n d t h e s u b s t r a t eh o l d e r 12 was r o t a t e d a t a s p e e d o f a b o u t 1 0 r p m .

T h e n , Ar g a s was s u p p l i e d f r o m t h e d i s c h a r g e g a s i n l e tp i p e 5 o f t h e ECR l a s m a g e n e r a t o r a t 5 . 7 > < l O _ 4 T o r r , w h i l ea microwave o f 2 . 4 5 GHZ r e q u e n c y and 1 0 0 W ower wass u p p l i e d from t h e microwave s u p p l y means 1 t o e m i t a n Arp l a s m a f o r m e d i n t h e p l a s m a g e n e r a t i o n c h a m b e r 4 o n t o t h es u r f a c e o f e a c h s u b s t r a t e 1 3 . At h e same t i m e , a n RF o l t a g eo f 1 3 . 5 6 MHz r e q u e n c y was a p p l i e d t o t h e s u b s t r a t e h o l d e r1 2 from t h e h i g h - f r e q u e n c y power s o u r c e 1 0 w h i l e CH 4 a swas s u p p l i e d from t h e r e a c t i o n g a s i n l e t p i p e 1 6 , s o t h a t as e l f - b i a s o f -2 0 V as d e v e l o p e d i n e a c h s u b s t r a te 1 3 . Th es u p p l y q u a n t i t y o f t h e CH 4 a s w a s g r a d u a l l y i n c r e a s ed w i t ht i m e a s shown n F I G . 5 , t o b e 1 0 0 s c c m , i . e . , 1 . 3 > < l 0 ' 3 T o r r ,a f t e r a l a p s e o f 5 m i n u t e s .

S i m u l t a n e o u s l y w i t h t h e a f o r e m e n t i o n e d ?l m f o r m a t i o nb y t h e ECR l a s m a g e n e r a t o r , Ar o n s w e r e e m i t t e d f r o m t h ei o n gun 4 2 a n d Ru a t o m s were e m i t t e d from t h e e v a p o r a t i o ns o u r c e 41 t o t h e s u r f a c e o f e a c h s u b s t r a t e 1 3 . At h i s t i m e ,t h e Ar o n s were e t a t a n a c c e l e r a t i o n v o l t a g e o f 4 0 0 e V andi o n c u r r e n t d e n s i t y o f 0 . 3 m A / c m 2 . F u r t h e r , t h e Ru e v a p or a t i o n r a t e was g r a d u a l l y r e d u c e d w i t h t i m e from 420 / m i n .i n t e r m s o f a ?l m o r m i n g r a t e on e a c h s u b s t r a t e 13 t o r e a c h0 a f t e r a l a p s e o f 5 m i n u t e s , a s shown n F I G . 6 . Th ee m i s si o n o f t h e Ar i o n s from t h e i o n g un 42 was s t o p p e dwhen t h e Ru e v a p o r a t i o n r a t e r e a c h e d 0 A / m i n , i . e . , a f t e r al a p s e o f 5 m i n u t e s

As h e r e i n a b o v e d e s c r i b e d , c a r b o n ?l m f o r m a t i o n b yp l a s m a CVD n d Ru e v a p o r a t i o n w e r e s i m u l t a n e o u s l y c a rr i e d o u t i n t h e ? r s t and s e c o n d o p e n i n g s 45 and 43r e s p e c t i v e l y , t o f o r m a n i n t e r m e d i a t e l a y e r c o n t a i n i n g Rua n d C i n a mixed s t a t e . A c c o r d i n g t o t h i s E x a m p l e , t h ea f o r e m e n t i o n e d s t e p was c a r r i e d o u t f o r a b o u t 5 m i n u t e s , t oform a mixed l a y e r o f Ru a n d C a v i n g a t o t a l t h i c k n e s s o f200 A n t h e s u r f a c e o f e a c h s u b s t r a t e 1 3 . As shown i nF I G S . 5 a n d 6 , t h e e v a p o r a t i o n v o l u m e o f Ru was r e d u c e dand h e amount o f c a r b o n ?l m o r m a t i o n was n c r e a s e d w i t ht i m e . T h u s , t h e i n t e r m e d i a t e l a y e r ha d a g r a d e d s t r u c t u r e o rc o m p o s i t i o n g r a d i e n t s u c h t h a t t h e Ru o n t e n t w a s g r a d u a l l yr e d u c e d and t h e C o n t e n t was g r a d u a l l y i n c r e a s e d a s t h ed i s t a n c e f r o m t h e s u r f a c e o f e a c h s u b s t r a t e 1 3 , i n c r e a s e d .Then, a d i a m o n d - l i k e c a r b o n ?l m w as formed on eachi n t e r m e d i a t e l a y e r . CH4 g a s w a s s u p p l i e d f r o m t h e r ea c t i o ng a s i n l e t p i p e 1 6 a t a c o n s t a n t p a r t i a l p r e s s u r e o f 1 . 3 > < l 0 ' 3T o r r , t o c o n t i n u o u s l y c a r r y o u t ?l m f o r m a t i o n b y t h e ECRp l a s m a g e n e r a t o r i n t h e a f o r e m e n t i o n e d s t e p . T h i s s t e p wasc a r r i e d o u t f o r a b o u t 1 5 m i n u t e s , t o form a d i a m o n d - l i k ec a r b o n ?l m f 1 2 0 0 A n t h i c k n e s s o n t h e i n t e r m e d i a t e l a y e rt h a t ha d b e e n formed on e a c h s u b s t r a te 1 3 .

As a e s u l t , a l a y e r e d ?l m n c l u d i n g a n i n t e r m e d i a t e l a y e rc o n s i s t i n g o f Ru a n d C h a v i n g a g r a d e d s t r u c t u r e a n d ad i a m o n d - l i k e c a r b o n ?l m was formed on e a c h s u b s t r a t e 1 3 .Such a n i n t e r m e d i a t e l a y e r h a v i n g a g r a d e d s t r u c t u r e c a nf u r t h e r i m p r o v e t h e a d h e s i o n b e t w e e n t h e s u b s t r a t e a n d t h ed i a m o n d - l i k e c a r b o n ?l m a s c o m p a r e d w i t h t h e a f o r e m e nt i o n e d i n t e r m ed i a t e l a y e r c o n s i s t i n g o f a s i n g l e e l e m e n t .



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5 , 6 2 9 , 0 8 61 3

Ru on Ni s u b s t r a t e s a n d t h e n f o r m i n g d i a m o n d - l i k e c a r b o n? l m s o n t h e i n t e r m e d i a t e l a y e r s ( E x a m p l e 2 ) , b y f o r m i n gi n t e r m e d i a t e l a y e r s o f m i x e d l a y e r s c o n s i s t i n g o f Ru a n d Co n Ni s u b s t r a t e s a n d t h e n f o r m i n g d i a m o n d - l i k e c a r b o n ?lmso n t h e i n t e r m e d i a t e l a y e r s ( E x a m p l e 3 ) , a n d b y e m p l o y i n ga n S i e v a p o r a t i o n s o u r c e f o r f o n n i n g i n t e r m e d i a t e l a y e r sc o n s i s t i n g o f S i o n N i s u b s t r a t e s a n d t h e n f o r m i n g d i a m o n dl i k e c a r b o n ? l m s o n t h e i n t e r m e d i a t e l a y e r s ( E x a m p l e 4 ) .Adhesion wa s e v a l u a t e d b y an i n d e n t a t i o n t e s t w i t h c o n s t a n tl o a d s ( 1 k g ) e m p l o y i n g V r c k e r s i n d e n t e r s . 5 0 s a m p l e s w e r ep r e p a r e d f o r e a c h E x a m p l e , a n d t h e n u m b e r s o f t h o s ec a u s i n g s e p a r a t i o n o f t h e d i a m o n d - l i k e c a r b o n ? l m s f o r m e don t h e Ni s u b s t r a t e s were c o u n t e d . T a b l e 1 shows t h e r e s u l t s .

TABLEE x a m p l e E x a m p l e E x a m p l e E x a m p l e

1 2 3 4Number o f S a m p l e s 4 3 7 0 1 6C a u s i n g S e p a r a t i o n

As o b v i o u s f r o m T a b l e 1 , t h e n u m b e r s o f s a m p l e s c a u s i n gs e p a r a t i o n w e r e r e d u c e d i n E x a m p l e s 2 , 3 a n d , w h i c h w e r ep r o v i d e d w i th t h e i n t e r m e d i a t e l a y e r s , a s c o m p a r e d w i t hExample 1 , w h i c h was n o t p r o v i d e d w i t h a n i n t e r m e d i a t el a y e r . T h u s , t i s u n d e r s t o o d h a t i t i s p o s s i b l e t o i m p r o v e t h ea d h e si o n o f t h e d i a m o n d - l i k e c a r b o n ? l m s b y p r o v i d i n g t h ei n t e r m e d i a t e l a y e r s . P a r t i c u l a r l y f r o m E x a m p l e 3 , i t i sc l e a r l y u n d e r s t o o d t h a t i t i s p o s s i b l e t o r e m a r k a b l y i m p r o v et h e a d h e s i o n o f t h e d i a m o n d - l i k e c a r b o n ? l m s b y f o r m i n gt h e i n t e r m e d i a t e l a y e r s o f Ru a n d C h a v i n g g r a d ed s t r u ct u r e s .

C o m p a r i n g E x a m p l e s 2 a n d 4 w i t h e a c h o t h e r , i t i su n d e r s t o o d t h a t Ru i s s u p e r i o r t o S i a s m a t e r i a l a t o m s f o rf o r m i n g i n t e r m e d i a t e l a y e r s w i t h r e s p e c t t o N i s u b s t r a t e s .

F I G . 7 i s a s c h e m a t i c s e c t i o n a l view showing a h a r dc a r b o n ?lm f o r m i n g a p p a r a t u s a c c o r d i n g t o s t i l l a n o t h e re m b o d i m e n t o f t h e p r e s e n t i n v e n t i o n . R e f e r r i n g t o F I G . 7 , as h i e l d i n g c o v e r 44 s p r o v i d e d a r o u n d a s u b s t r a t e h o l d e r 1 2which i s a r r a n g e d i n a vacuum chamber 8 . Th e s h i e l d i n gc o v e r 44 h a s a ? r s t o p e n i n g 45 s i m i l a r t o t h e o p e n i n g 1 5shown n FIG. 1 , s o t h a t a forward end f a e a c t i o n g a s i n l e tp i p e 1 6 i s l o c a t e d a b o v e t h e ? r s t o p e n i n g 4 5 , s i m i l a r l y t o t h ea p p a r a t u s shown i n F I G . 1 .A a r g e t 46 o f m a t e r i a l a t o m s f o r f o r m i n g i n t e r m e d i a t el a y e r s i s p r o v i d e d u n d e r a s e c o n d o p e n i n g 43 o f t h e s h i e l d

i n g c o v e r 4 4 . F u r t h e r , a n i o n g u n 47 i s p r o v i d e d i n t h ev i c i n i t y o f t h e t a r g e t 4 6 , f o r e mi t t i n g i o n s o f a n i n e r t g a s t ot h e t a r g e t 4 6 t h e r e b y s p u t t e r i n g t h e t a r g e t 4 6 . A c c o r d i n g t ot h i s e m b o d i m e n t , t h e i n e r t g a s i s Ar a s a n d t h e i n t e r m e d i a t el a y e r f o r m i n g m e a n s c o m p r i s e s t h e t a r g e t 4 6 a n d h e i o n g u n4 7 , w h i l e t h i n - ? l m h e a d s 48 a r e mo unted on t h e s u b s t r a t eh o l d e r 1 2 a s s u b s t r a t e s . Th e a r g e t 46 a n d t h e i o n gun 47 e m i tt h e m a t e r i a l a t o m s f o r f o r m i n g i n t e r m e d i a t e l a y e r s o n t o t h et h i n - ? l m h e a d s 4 8 t h r o u g h t h e s e c o n d o p e n i n g 4 3 .

Th e i o n s from t h e i o n gun 47 a r e a p p l i e d n o t o n l y t o t h et a r g e t 4 6 b u t a l s o t o t h e t h i n - ? l m h e a d 4 8 .

Other s t r u c t u r e s o f t h i s embodiment a r e s i m i l a r t o t h o s e o ft h e embodiment shown i n F I G . 1 . T h u s , e l e m e n t s c o r r es p o n d i n g t o t h o s e i n F I G . 1 a r e d e n o t e d by t h e samer e f e r e n c e n u m e r a l s , a n d a r e d u n d a n t d e s c r i p t i o n i s o m i t t e dA u r t h e r i n v e n t i v e e x a m p l e w i l l now b e d e s c r i b e d ,n a m e l y a n e x a m p l e f o r f o r m i n g i n t e r m e d i a t e l a y e r s f r o m a

1 0

20

2 5

3 0

35

50

55

1 4s u b s t r a t e h o l d e r 12 a t r e g u l a r i n t e r v a l s . Th e vacuum chamb e r 8 was e v a c u a t e d t o 1 0 7 5 t o 1 0 7 T o r r , a n d t h e s u b s t r a t eh o l d e r 12 was r o t a t e d a t a s p e e d o f a b o u t 1 0 r p m . T h e n , Arg a s was s u p p l i e d t o t h e i o n gun 4 7 , s o t h a t Ar i o n s weree j e c t e d a n d e m i t t e d o n t o a s u r f a c e o f t h e t a r g e t 4 6 c o n s i s t i n go f S i . At h i s t i m e , t h e Ar i o n s w e r e s e t a t a n a c c e l e r a t i o nv o l t a g e o f 9 0 0 eV a n d i o n c u r r e n t d e n s i t y o f 0 . 3 mA/cm2.

Th e a f o r e m e n t i o n e d s t e p was c a r r i e d o u t f o r a b o u t 2m i n u t e s , t o f o r m a n i n t e r m e d i a t e l a y e r o f S i h a v i n g at h i c k n e s s o f 60 A n t h e s u r f a c e o f e a c h t h i n - ? l m head 4 8 .

T h e n , t h e e m i s s i o n o f t h e Ar o n s from h e i o n gun 47 wass t o p p e d a n d Ar g a s was s u p p l i e d from a d i s c h a r g e g a s i n l e tp i p e 5 o f a n ECR l a s m a g e n e r a t o r a t 5 . 7 X 1 0 _ 4 T o r r , w h i l ea microwave o f 2 . 4 5 GHz r e q u e n c y a n d 1 0 0 W ower wass u p p l i e d from microwave s u p p l y means 1 , t o e m i t a n Arp l a s m a f o r m e d i n a p l a s m a g e n e r a t i o n c h a m b e r 4 o n t o t h es u r f a c e o f e a c h t h i n - ? l m head 4 8 . At t h e same t i m e , an RFv o l t a g e o f 1 3 . 5 6 MHz r e q u e n c y w a s a p p l i e d t o t h e s u b s t r a t eh o l d e r 12 from a h i g h - f r e q u e n c y power s o u r c e 1 0 a n d CH 4g a s was s u p p l i e d from a r e a c t i o n g a s i n l e t p i p e 1 6 a t1 . 3 > < 1 0 * 3 T o r r , s o t h a t a s e l f - b i a s o f -2 0 V as d e v e l o p e d i ne a c h t h i n - ? l m h e a d 4 8 .

Th e a f o r e m e n t i o n e d s t e p was c a r r i e d o u t f o r a b o u t 2 . 5m i n u t e s , t o f o r m a d i a m o n d - l i k e c a r b o n ?l m o f 2 0 0 A nt h i c k n e s s on t h e i n t e r m e d i a t e l a y e r t h a t had b e e n formed one a c h t h i n - ? l m h e a d 4 8 .

As a r e s u l t o f t h e a f o r e m e n t i o n e d two s t e p s , a l a y e r e d t h i n?l m w as formed on t h e s u r f a c e o f e a c h t h i n - ? l m head 4 8 ,i n c l u d i n g t h e i n t e r m e d i a t e l a y e r o f S i a n d t h e d i a m o n d - l i k ec a r b o n ?l m formed t h e r e o n . Du e t o s u c h f o r m a t i o n o f a ni n t e r m e d i a t e l a y e r , i t i s p o s s i b l e t o r e l a x s t r e s s i n a diamondl i k e c a r b o n ? l m . t h e r e b y i m p r o v i n g t h e a d h e s i o n b e t w e e n as u b s t r a t e a n d t h e d i a m o n d - l i k e c a r b o n ? l m . Th e t r e s s i n t h ed i a m o n d - l i k e c a r b o n ?l m c a n b e r e l a x ed c o n c e i v a b l yb e c a u s e i t i s p o s s i b l e t o r e l a x t h e t h e r m a l s t r e s s c a u s e d b yt h e d i t f e r e n c e i n t h e r m a l e x p a n s i o n c o e f ? c i e n t s b e t w e e n t h es u b s t r a t e a n d t h e d i a m o n d - l i k e c a r b o n ? l m , d u e t o t h ep r e s e n c e o f t h e i n t e r m e d i a t e l a y e r . F u r t h e r , t h e i n t e r m e d i a t el a y e r i s f o r m e d w i t h h i g h e r a d h e s i o n s i n c e t h e Ar i o n s a r ea p p l i e d n o t o n l y t o t h e t a r g e t b u t a l s o t o e a c h t h i n - ? l m h e a dd u r i n g f o r m a t i o n o f t h e i n t e r m e d i a t e l a y e r .

A n o t h e r i n v e n t i v e e x a m p l e w i l l now b e d e s c r i b e d ,n a m e l y a n e x a m p l e f o r f o r m i n g m i x e d l a y e r s o f m a t e r i a la t o m s a n d c a r b o n a s i n t e r m e d i a t e l a y e r s a n d f o r m i n gd i a m o n d - l i k e c a r b o n ?lms t h e r e o n . A l s o i n t h i s e x a m p l e , a na p p a r a t u s s i m i l a r t o t h a t shown i n F I G . 7 was e m p l o y e d .

F i r s t , 24 t h i n - ? l m h e a d s 48 were mounted on t h e p e r i p he r a l s u r f a c e o f t h e s u b s t r a t e h o l d e r 1 2 a t r e g u l a r i n t e r v a l s .The vacuu m chamber 8 was e v a c u a t e d t o 1 0 - 5 t o 1 0 - 7 T o r r ,and t h e s u b s t r a t e h o l d e r 12 w as r o t a t e d a t a s p e e d o f a b o u t1 0 r p m .

T h e n , Ar g a s was s u p p l i e d f r o m t h e d i s c h a r g e g a s i n l e tp i p e 5 o f t h e ECR l a s m a g e n e r a t o r a t 5 . 7 > < 1 0 ' 4 T o r r w h i l ea microwave o f 2 . 4 5 GH z r e q u e n c y and 1 0 0 W ower wass u p p l i e d ?'om t h e microwave s u p p l y means 1 , t o e m i t a n Arp l a s m a f o r m e d i n t h e p l a s m a g e n e r a t i o n c h a m b e r 4 t o t h es u r f a c e o f e a c h t h i n - ? l m head 4 8 . At t h e same t i m e , an RFv o l t a g e o f 1 3 . 5 6 MHZ r e q u e n c y w a s a p p l i e d f r o m t h eh i g h - f r e q u e n c y power s o u r c e 1 0 t o t h e s u b s t r a t e h o l d e r 12a n d CH4 g a s w a s s u p p l i e d f r o m t h e r e a c t i o n g a s i n l e t p i p e1 6 , s o t h a t a s e l f - b i a s o f 2 0 V was d e v e l o p e d i n e a c ht h i n - ? l m h e a d 4 8 . A t t h i s t i m e , t h e s u p p l y q u a n t i t y o f t h eCH 4 g a s was g r a d u a l l y i n c r e a s e d w i t h t i m e t o r e a c h 1 0 0



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Exhibit B



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U S 0060663 99AUlllted States Patent [ 1 9 ] [ 1 1 ] P a t e n t N u m b e r : 6 , 0 6 6 , 3 9 9Hiran0 e t a l . [ 4 5 ] D a t e o f P a t e n t : May 3 , 2 0 0 0[ 5 4 ] HARD CARBON H IN FILM AND METHOD [ 5 6 ] R e f e r e n c e s C i t e d

0F FORMING THE SAME U . S . PATENT DOCUMENTS[ 7 5 ] I n v e n t o r s l HitOShi Hiram), Nishinomiya; Y?ichi 4 , 6 4 7 , 4 9 4 3 / 1 9 8 7 Meyerson e t a l . . . . . . . . . . . . . . . . . . . . . . . 4 2 8 / 4 0 8

D0m0t0, Ikoma; K e i i c h i Kuramoto, 4 , 7 7 7, 0 9 0 1 0 / 1 9 8 8 O v s h i n s k y e t a l . . 4 2 8 / 4 0 8Kadoma, a l l o f J a p a n 4 , 8 7 7 , 6 7 7 1 0 / 1 9 8 9 H i r o c h i e t a l . 4 2 8 / 4 0 85 , 1 7 3 , 0 8 9 1 2/1 9 9 2 Tanab e e161. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51/293

[ 7 3 ] A s s i g n e e : Sanyo E l e c t r i c C o . , L t d . , M o r i g u c h i , 5 , 2 3 7, 9 6 7 8 / 1 9 9 3 W i l l e r m e t e t a 1 . .5 ,3 6 8 , 93 7 1 1 / 1 9 94 ItOh . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428/408J a p a n

[ 2 1 ] A p p l . N o . : 0 9 / 0 4 5 , 1 6 3[ 2 2 ] F i l e d : M a r . 1 9 , 1 9 9 8[ 3 0 ] F o r e i g n A p p l i c a t i o n P r i o r i t y D a t aMar. 1 9 , 1 997 [ J P ] Japan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 -0 6 6 12 5M a r . 1 9 , 1997 [ J P ] J a p a n . .S e p . 2 5 , 19 9 7 [ J P ] Japan . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9-259833

[ 5 1 ] I n t . C l . 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B32B / 0 6 ; C23C 16/00[ 5 2 ] US. l . . . . . . . . . . . . . . . . . . . . . . . . . . . 428/408; 428/212; 428/697;

4 2 8 / 6 9 8 ; 4 2 8 / 6 9 9 ; 4 2 8 / 7 0 1 ; 4 2 8 / 7 0 2 ; 4 2 7 / 2 4 9[ 5 8 ] Field of Se a rc h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 428/212, 408,

4 2 8 / 6 9 7 , 6 9 9 , 7 0 1 , 7 0 2 ; 4 2 7 / 2 4 9

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FOREIGN PATENT DOCUMENTS131 71 97 12/1989 Japan .

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BACKGROUND OF THE INVENTIONF i e l d o f t h e I n v e n t i o n

Th e p r e s e n t i n v e n t i o n r e l a t e s t o a h a r d c a r b o n t h i n ?l ma n d a method o f f o r m i n g t h e h a r d c a r b o n t h i n ? l m .

D e sc r i p t i o n o f R e l a t e d A r tHard c a r b o n t h i n ?lms e x h i b i t e x c e l l e n t h a r d n e s s ,r e s i s t i v i t y , c h e m i c a l s t a b i l i t y a n d t h e o t h e r s , a n d h a v e g a t h

e r e d e x p e c t a t i o n s f o r t h e i r a p p l i c a t i o n s t o f u n c t i o n a l t h i n?lms f o r e l e c t r o n i c d e v i c e s a n d s e m i c o n d u c t o r s , e . g . p r ot e c t i v e c o a t i n g s on s l i d i n g p a r t s f o r c o m p r e s s o r s s u c h a sr o t a r y c o m p r e s s o r s , p r o t e c t i v e c o a t i n g s on b l a d e s s u c h a se l e c t r i c s h a v e r b l a d e s , p r o t e c t i v e c o a t i n g s o n m a s k s f o rscreen deposition a s Well a s o n squeegees, c o n s t i t u e n t ?l ml a y e r s o f s o l a r c e l l s , p r o t e c t i v e c o a t i n g s o n t h i n ?lm m a gn e t i c h e a d s , a n d p r o t e c t i v e c o a t i n g s o n SAW e v i c e s .

I n t h e a b o v e a p p l i c a t i o n s , p o o r a d h e s i o n o f t h e h a r dc a r b o n t h i n ?l m o a n u n d e r l y i n g l a y e r becomes r o b l e m a t i co c c a s i o n a l l y . A e c h n i q u e t o i m p r o v e i t s a d h e s i o n t o t h eu n d e r l y i n g l a y e r s u c h a s a s u b s t r a t e h a s b e e n p r o p o s e dW h i c h p r o v i d e s a s i l i c o n i n t e r l a y e r b e t W e e n t h e u n d e r l y i n gl a y e r a n d t h e h a r d c a r b o n t h i n ?lm ( S e e , f o r e x a m p l e ,J a p a n e s e P a t e n t L a y i n g - O p e n N o . H e i 1 - 3 1 7 1 9 7 ( 1 9 8 9 ) ) .

A l t h o u g h t h e c o n v e n t i o n a l t e c h n i q ue s s u c h a s m e n t i o n e da b o v e h a v e a p o t e n t i a l a d v a n t a g e o f i m p a r t i n g i n c r e a s e da d h e s i o n , d e l a m i n a t i o n o f t h e h a r d c a r b o n t h i n ?l m from t h eu n d e r l y i n g l a y e r i s d i s a d v an t a g eo u s l y o c c a s i o n e d Wheni n ? u e n c e d b y t h e i n t e r n a l s t r e s s o f t h e h a r d c a r b o n t h i n ?l mWhich b e c o m es g r e a t e r a s a t h i c k n e s s t h e r e o f i n c r e a s e s .A l s o , t h e i n t e r l a y e r m u s t b e f o r m e d i n a s e p a r a t e s t e p Whichr e s u l t s i n a c o m p l i c a t e d f a b r i c a t i o n .

I n vieW o f t h e a b o v e , t h e r e h a s b e e n a c o n t i n u i n g n e e d f o ra h a r d c a r b o n t h i n ?l m Which i s c a p a b l e o f e x h i b i t i n g a nimproved a d h e r e n c e t o a n u n d e r l y i n g l a y e r s u c h a s a s u bs t r a t e .A r y s t a l l i n e h a r d c a r b o n t h i n ? l m , a s g e n e r a l l y c a l l e d ad i a m o n d t h i n ? l m , i s t y p i c a l l y f o r m e d t h r o u g h t h e r m a l

decomposition o f a m a t e r i a l g a s such a s methane u s i n g a h o t? l a m e n t . S u c h a t e c h n i q u e i s h o W e v e r a c c o m p a n i e d by t h ee l e v a t i o n o f a s u b s t r a t e t e m p e r a t u r e up t o a b o u t 1000 C .Which l i m i t s t h e m a t e r i a l t y p e o f a s u

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