CA1202598A - Diamond-like film and process for producing same - Google Patents

Diamond-like film and process for producing same

Info

Publication number
CA1202598A
CA1202598A CA 413200 CA413200A CA1202598A CA 1202598 A CA1202598 A CA 1202598A CA 413200 CA413200 CA 413200 CA 413200 A CA413200 A CA 413200A CA 1202598 A CA1202598 A CA 1202598A
Authority
CA
Grant status
Grant
Patent type
Prior art keywords
film
process
defined
pair
electrodes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA 413200
Other languages
French (fr)
Inventor
Joseph Zelez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
RCA Corp
Original Assignee
RCA Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26Deposition of carbon only
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00Coatings on glass
    • C03C2217/20Materials for coating a single layer on glass
    • C03C2217/28Other inorganic materials
    • C03C2217/282Carbides, silicides
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00Methods for coating glass
    • C03C2218/10Deposition methods
    • C03C2218/15Deposition methods from the vapour phase
    • C03C2218/152Deposition methods from the vapour phase by cvd
    • C03C2218/153Deposition methods from the vapour phase by cvd by plasma-enhanced cvd

Abstract

NOVEL AND IMPROVED DIAMOND-LIKE FILM AND PROCESS
FOR PRODUCING SAME

Abstract of the Disclosure An amorphous, carbonaceous, diamond-like film and a process for producing the same is disclosed. The film has an extremely low hydrogen content and an extremely low stress, is resistant to both acids and alkalis, and adheres tenaciously to many type of substrates including glasses, plastic, metals, and semiconductors. The process for producing this film is a hybrid process using radio frequency plasma decomposition of an alkane and a pair of spaced carbon electrodes.

Description

z~
RC~ 76, 636 -NOVEL AND IMPROVED DIAMOND~I.IKE FILM AND PROCESS
FOR PRODUCING SAME
This invention relates to an improved amorphous, carbonaceous, diamond-like film. Additionally, the ; 5 invention pertains to an improved process for producing such an amorphous, carbonaceous film having diamond-like properties.
sack~round of the Invention Carbonaceous diamond-like film o~ films having diamond-like properties, s~ch as the film of this invention, are well-known in the prior ar~. These fi~ms are particularly useful in applications such as thè coating of optical lenses to increase the optical transmission throuyh the lens and the coating of mirrors to improve the light reflectivity from the mirror. Such films also find useful applications as protective films in abrasive applications, such as the coating of writing instruments, as a general anti-reflective coating, and as a dielectric or protective coating for silicon and silicon-containing devices. In fact, the diamond-like films disclosed in this invention find many other useful applications in commerce and industry where film~ which are clear, extremely hard, extremely adherent, abrasion-resistant, corrosion-resistant, and which possess good optical properties; are needed.
While the amorphous, carbonaceous/ diamond-like ~ilms of the prior art have much to commend them, the search has continued for improved amorphous, carbonaceous films having diamond-like properties. Particularly such a film having increased hardness and increased adherence to various substrates has continued to be sought, as well as a process for producing such a filmr The novel and improved carbonaceous diamond-like film of this invention is an improvement over presently-3S known films in that it has an extremely low stress, hasthe ability to tenaciously adhere to many, varied substrates, has a low hydrogen content, and is extremely hard.
... ' ~ .

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- 2 - RCA 76,636 1 Su~ar~ of the Invention With this invention, I have produced a novel and improved, amorphous, carbonaceous, diamond-like ~ilm which has an extremely low hydrogen content and an extremely low stress. This film is resistant to both acids and alkalis and has a hardness similar to that of diamond. The film has a refractive index, a dielectric constant, and a thermal coefficient of expansion similar to that of diamond~
In addition, the film adheres well to many types of substrates, such as glasses, plastics, metals, semi~
conductors and the likeO
Detailed Description of the Invention The improved amorphous, carbonaceous, diamond-like film o~ this invention, in addition to possessing the above-enumerated properties and qualities, differ~
from other presently-known carbonaceous films in that it possesses an extremely low hydrogen content; on the order of about one atomic percent or less of hydrogen. Tha prior art carbonaceous films contain hydrogen in an amount of up 2~ to about 25 atomic percen~ or more.
The diamond-like film of this invention addit.ionally differs ~rom prior art carbonaceous films in that is has an extremely low stress; the stress may be either a compressive or a tensile stress~ The film of this invention exhibits a stress on the order of 107 to 108 dynes/cm2, while the ilms of the prior art exhibit a stress on the order of 10ll dynes/cm2. It is believed that the stress of these carbonaceous films is related to their hydrogen content, and that the lower the hydrogen content of the film, the lower the stress in the filmO
Due to the extremely low stress~ the film of this invention is extremely adherent and adheres tenaciously to a great number and variety of substrates on which it is deposited.
The carbonaceous, diamond-like films o this invention are extremely resistant to acids, such as H2SO4, HF, HC1, and HCl:HNO3, and alkalis such as NaOH, XOH, RbOH, and CsOH.
The amorphous, carbonaceous, diamond-like film e,,~

- 3 - RCA 76,636 1 Of this invention is produced by a hybrid process in a deposition chamber using a radio frequency plasma decomposition from an alkane, such as n-butane, using a pair of spaced, generally parallel, carbon electrodes, preferably ultra pure carbon electrodes. While most films of this invention were deposited using normal butane, other alkan~s, such as methane, ethane, propane, pentane, and hexane can be substituted in the process of this invention to produce the improved carbonaceous, diamond-like film thereof.
The deposition chamber, such as a stainlesssteel chamber, includes a pair of generally parallel and horizontal, vertically spaced, pure carbon electrodes with the substrate to be coated positioned on the lower carbon electrode. The electrodes are typically positioned about 2 up to about 8 centimeters apart from each other, with the preferred electrode spacing being approximately 2.5 centimeters. The chamber is evacuated to its ultimate pressurej generally in the region of about 10 7 torr, and 2~ then backfilled with an alkane, such as n-butane, to ~
pressure of approximately 8 x 10-4 torr. Thereafter, the vacuum system is throttled to a pressure in the range of approximately 25 to 100 millitorr~ After stabilization of the pressure, the radio frequency power is applied to the pair of pure carbon elactrodes with the lower electrode (substrate target~ being biased in the range of about 0 to about -lO0 volts, and the upper electrode being biased in the range of about -200 to about -3500 volts.
Radio Erequency plasma decomposition is begun, and an amorphous, carbonaceous, diamond like film is deposited onto the substrate at rates varying between about 8 up to about 35 angstroms per minute, to produce a film of up to about 5 mic~ometers in thickness.
The films produced by the above process have an extremely low stress. The stress for the films prodllced by the process has been measured and determined to be in the range of about 107 to 108 dynes/cm2. As has been previously stated, the stress may be either a compressive , Z~

- 4 - RCA 76,636 1 'or tensile stress. It has been determined that the resultant stress of ~he film produced by this proceSs, be it either a compressive or tensile stress, is dependent on the potential applied to the upper carbon electrode.
The following specific examples are included ' in order to illus~rate the invention and the improvements thereof with greater particularity. However, it is to be understood that these examples are not intended to limit the invention in any way.
EX~M
In this example, a stainless steel deposition chamber, as described above, was prepared for deposition of the improved carbonaceous diamond-like film of this invention.~ The~deposition chamber was stabilized with n-butane at a deposition pressure of approximately 50 millitorr with the pair of ultra pure carbon eIectrodes being horizontally positioned and at a vertical spacing of approximately 6 centimeters from each other. A glass substrate for deposition of the film was positioned on the lower carbon electrode. The lower electrode (substrate target) was maintained at a potentiaI of -50 volts and the upper electrode was maintained at a potential of -500 volts.
A film was then deposited by radio frequency plasma decomposition from n-butane onto the glass substrate under the above conditions at a rate of about 10 angstroms per minute to a thickness of approximately 1.45 micrometers. The stress of the resultant film was measured and determined to be a stress of about 7 x loB
dynes/cm2, tensile stress. The resultant film had a hydrogen content of less than 1~0 atomic percent.
In a similar experiment, it was determined that when the potential of the upper electrode was decreased and maintained at a -300 volts, while maintaining the potential of the lower electrode (substrate target) at, -50 volts, the film deposited under such conditions at a rate of approximately lO angstroms per minute to a thickness of 1.5 micrometers had a compressive stress.

~o~o~
~ 5 _ RCA 76,636 1 The stre~s of the film in this experiment was measured and determined to be about 8 x 1o8 dynes/cm2, compressive stress. The hydrogen content of the film obtained in this experiment was measured and determined to be less than l.O atomic.percent hydrogen.
In a series of additional experiments, similar to the above, improved carbonaceous diamond-like films, like the above, were deposited on other substrates. These substrates included~metals, such as stainless steel, molybdenum, tungstén, and tantalum; various gla~ses, sîlicon, silicon dioxide, and aluminum oxide, as well a5 .
plastics, such as polycarbonate, s~yrene, acrylic~
styrene~acrylic copolymer, and other resins.
: EXAMPLE II
1.5 In this example, a series of experiments were performed as in Example I to deposit the improved carbonaceous, diamond-like film of this invention under a varie-ty of potentials applied to the upper electrode and lower electrode or substrate karget. The voltage~ employed and the results obtained in each of these experiments are set forth hereinbelow;

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-- 6 -- RCA 76, 636 æ

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-o o o l-- o i~ ~ ~ i~ o ~ ~ ~3 2~ o y ~ o ~ ~o ~I ,p ul ~I ~ ~D ~-oo ao ~ ou~ Ul ~ O ~ i~
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o o o o . ~ o o o o o o u~
It ID

. _. . A , )2~
- 7 - RCA 76,636 The hydrogen content of the above films was measured and determined to be less than 1.0 atomic percent hydrogen.
EX~MPLE III
In this example, a number of high quality plastic lenses were coated with the improved carbonaceous, diamond-like film of this invention using the stainless steel deposition chamber and process of this invention as described in Example I. After evacuation~ the chamber was backfilled with normal butane. and stabilized at a deposition pressure of approximately 80 millitorr. The pair of ultra pure carbon electrodes were positioned at a spacing of about 2.5 centimeter with the plastic lens to be coated positioned on the lower electrodeO This lower electrode (substrate target) was maintained at a potential of -50 volts while the upper elec~rode was maintained at a potential of -2500 volts. A film was th n r.f. plasma deposited onto the plastic lens under these conditions at a rate of approximately 25 angstroms per minute to a thickness of llO0 angstroms. Another lens was coated on both of its sides with the film of this inventionJ wi~h the film on each side having a thickness of llO0 angstroms A third plastic lens was coated on one side with the fi~m of this invention to a thickness of ll,000 angstroms. In all cases, the films of this example 2B exhibited the same low stress and low hydrogen content as the films produced in the previous examples set orth above. Additionàlly, the optical properties (absorption, transmission, and reflection) of the coated plastic lenses were maintained at approximately the same level, and .Ln many cases these optical properties were improved by the film of this invention having been coated on their surface.

Claims (15)

CLAIMS:
1. An amorphous, carbonaceous film having diamond-like properties and having a stress of about 107 to about 108 dynes/cm2 and a hydrogen content of 1 or less atomic percent.
2. An amorphous, carbonaceous film as defined in claim 1, wherein said stress of said film is a tensile stress.
3. An amorphous, carbonaceous film as defined in claim l, wherein said stress of said film is a compressive stress.
4. An article of manufacture comprising an amorphous, carbonaceous film as defined in claim 1 deposited on a substrate.
5. An article of manufacture as defined in claim 4 wherein said substrate is selected from the group consisting of glasses, plastics, metals, and semiconductor materials.
6. A process of forming an amorphous, carbonaceous film as claimed in claim 1 on a substrate comprising the steps of:
(a) providing a pair of spaced, generally parallel carbon electrodes, (b) positioning said substrate closely adjacent one of said pair of electrodes, and (c) depositing said film on said substrate by a radio frequency plasma decomposition of an alkane containing from 1 up to about 6 carbon atoms.
7. A process as defined in claim 6 wherein said alkane is n-butane.
8. A process as defined in claim 6 wherein said spacing of said parallel electrodes is from about 2 up to about 8 centimeters.
9. A process as defined in claim 6 wherein said one electrode of said pair of electrodes most closely adjacent said substrate is biased in the range of from about 0 to about -100 volts and the other of said pair of electrodes is biased in the range of from about -200 to about -3500 volts.
10. A process of depositing an amorphous, carbonaceous film as claimed in claim 1, on a substrate, comprising the steps of.
(a) providing an evacuated deposition chamber having an internal pair of generally horizontal and parallel carbon electrodes, said pair of electrodes being vertically spaced a distance of from about 2 up to about 8 centimeters, and means for applying radio frequency power to said pair of electrodes;
(b) positioning said substrate on the lower electrode of said pair of electrodes;
(c) stabilizing said deposition chamber with an alkane at a pressure of from about 25 up to about 100 millitorr, said alkane containing from 1 up to about 6 carbon atoms;
(d) applying radio frequency power to said pair of electrodes; and (e) biasing the upper electrode of said pair in the range of from about -200 to about -3500 volts and said lower electrode in the range of from about 0 to about -100 volts, whereby said film deposits on said substrate by radio frequency plasma decomposition of said alkane.
11. A process as defined in claim 10 wherein said vertical spacing of said pair of electrodes is from about 2.5 to about 6.0 centimeters.
12. A process as defined in claim 10 wherein said deposition chamber is stabilized at a pressure of from about 35 up to about 85 millitorr.
13. A process as defined in claim 10 wherein said lower alkane is n-butane.
14. A process as defined in claim 10 wherein said upper electrode is biased in the range of from about -250 to about -2500 volts.
15. A process as defined in claim 10 wherein said lower electrode is biased in the range of from about -25 to about -75 volts.
CA 413200 1981-10-21 1982-10-12 Diamond-like film and process for producing same Expired CA1202598A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
GB8131794 1981-10-21
GB8131794 1981-10-21
US34802182 true 1982-02-11 1982-02-11
US348,021 1982-02-11

Publications (1)

Publication Number Publication Date
CA1202598A true CA1202598A (en) 1986-04-01

Family

ID=26281036

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 413200 Expired CA1202598A (en) 1981-10-21 1982-10-12 Diamond-like film and process for producing same

Country Status (5)

Country Link
JP (1) JPH0699807B2 (en)
CA (1) CA1202598A (en)
DE (1) DE3237851A1 (en)
FR (1) FR2514743B1 (en)
GB (1) GB2109012B (en)

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DE3442208C3 (en) * 1984-11-19 1998-06-10 Leybold Ag Method and apparatus for manufacturing of hard carbon layers
DE3608887C2 (en) * 1985-03-22 1990-05-23 Canon K.K., Tokio/Tokyo, Jp
DE3609503C2 (en) * 1985-03-22 1990-10-31 Canon K.K., Tokio/Tokyo, Jp
US4845513A (en) * 1985-03-23 1989-07-04 Canon Kabushiki Kaisha Thermal recording head
DE3609456C2 (en) * 1985-03-23 1990-10-31 Canon K.K., Tokio/Tokyo, Jp
DE3609691C2 (en) * 1985-03-23 1991-12-05 Canon K.K., Tokio/Tokyo, Jp
GB2175252B (en) * 1985-03-25 1990-09-19 Canon Kk Thermal recording head
GB2176443B (en) * 1985-06-10 1990-11-14 Canon Kk Liquid jet recording head and recording system incorporating the same
JPS62202899A (en) * 1986-03-03 1987-09-07 Nippon Gakki Seizo Kk Production of decorative article
JPH0676666B2 (en) * 1987-02-10 1994-09-28 株式会社半導体エネルギ−研究所 Carbon film manufacturing method
DE3706340A1 (en) * 1987-02-27 1988-09-08 Winter & Sohn Ernst A method for applying a wear and thereafter made produce
JPH01103310A (en) * 1987-10-16 1989-04-20 Sumitomo Electric Ind Ltd Surface acoustic wave element
DE3815457C2 (en) * 1988-05-06 1992-06-25 Sipra Patententwicklungs- Und Beteiligungsgesellschaft Mbh, 7470 Albstadt, De
GB2240114B (en) * 1990-01-18 1993-03-24 Stc Plc Film nucleation process
GB9214697D0 (en) * 1991-07-23 1992-08-19 Flouroware Inc Diamond coated carrier
JP2574934Y2 (en) * 1993-03-02 1998-06-18 シチズン時計株式会社 Parts for knitting machine
JPH0676383U (en) * 1993-04-06 1994-10-28 シチズン時計株式会社 Textile related machinery parts
GB2286347B (en) * 1994-02-10 1998-04-29 Aea Technology Plc Improved load-bearing polymeric materials
WO2007057478A1 (en) * 2005-11-15 2007-05-24 Fundacion Tekniker Part having an outer polymer surface with a metallic finish, production method thereof and use of same

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US3961103A (en) * 1972-07-12 1976-06-01 Space Sciences, Inc. Film deposition
US4060660A (en) * 1976-01-15 1977-11-29 Rca Corporation Deposition of transparent amorphous carbon films
JPS5838952B2 (en) * 1976-01-22 1983-08-26 Nippon Electric Co
GB1582231A (en) * 1976-08-13 1981-01-07 Nat Res Dev Application of a layer of carbonaceous material to a surface
JPS6023406B2 (en) * 1977-05-18 1985-06-07 Nippon Electric Co
JPS5825041B2 (en) * 1979-08-03 1983-05-25 Nippon Telegraph & Telephone
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GB2069008B (en) * 1980-01-16 1984-09-12 Secr Defence Coating in a glow discharge
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Also Published As

Publication number Publication date Type
GB2109012A (en) 1983-05-25 application
GB2109012B (en) 1986-09-03 grant
JPH0699807B2 (en) 1994-12-07 grant
FR2514743B1 (en) 1986-05-09 grant
JPS5879807A (en) 1983-05-13 application
FR2514743A1 (en) 1983-04-22 application
DE3237851A1 (en) 1983-04-28 application
CA1202598A1 (en) grant

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