CA1269061A - Process for the production of diamond-like carbon coatings - Google Patents
Process for the production of diamond-like carbon coatingsInfo
- Publication number
- CA1269061A CA1269061A CA000483754A CA483754A CA1269061A CA 1269061 A CA1269061 A CA 1269061A CA 000483754 A CA000483754 A CA 000483754A CA 483754 A CA483754 A CA 483754A CA 1269061 A CA1269061 A CA 1269061A
- Authority
- CA
- Canada
- Prior art keywords
- substrate
- hydrocarbon
- gas
- plasma discharge
- coated
- 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 - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical 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
- C23C16/26—Deposition of carbon only
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/28—Other inorganic materials
- C03C2217/282—Carbides, silicides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/152—Deposition methods from the vapour phase by cvd
- C03C2218/153—Deposition methods from the vapour phase by cvd by plasma-enhanced cvd
Abstract
Diamond-like, transparent, clear and uncolored carbon coatings with low internal stresses are generated on substrates by plasma discharge from the gas phase. For this purpose, a hydrocarbon gas or a mixture of hydrocarbon gases and pure hydrogen, if necessary in the presence of a noble gas, are admitted onto the substrate to be coated at a temperature between room temperature and -100.degree.C. Around the substrate an oxygen-free plasma discharge is produced by high-frequency excitation which is sustained by the gases admitted. The gases are excited, dissociated and ionized during plasma discharge and accelerated toward the substrate.
Description
Description The invention relates to a process for the production of diamond-like carbon coatings in which hydrocarbons and hydrogen, if necessary in the presence of a noble gas are 5 ionized by plasma discharge.
Diamond-like carbon coatings are used in particular for coating IR optical systems, e.g. lenses, mirrors or the like. Coating of optical systems like this takes place under vacuum conditions, a gas mixture consist~ing of hydrocarbons, e.g. acetylene, and a noble gas, e.g. argon, being exposed to a plasma discharge. The coatings thus produced are not transparent in the visible spectrum; they are of yellow, brownish, blue or black color. This is why these coatings cannot be used as scratch-resistant coatings for optical systems in the visible spectra region but only for the IR spectrum. A process for the deposition of a diamond-like carbon film has been described in GB-A-2 128 637, in which the carbon ions and other ions are generated in separate stationary sources, directed toward the surface of the substrate to be coated, and accelerated. The second ion species has the function to remove the undesired carbon species from the film formed by chemical sputtering. For this purpose hydrogen is used among other materials. The substrate is heated to a temperature of 100 to 200C. In this way, yellow to brown-colored coatings are obtained that are likewise suitable for IR optical systems. In conventional methods that use stationary sources the substrate has to be rotated relative to the sources in order to achieve homogeneous all-round coating. The simultaneous coating of medium production volumes is technologically feasible at a high expenditure. A further disadvantage consists in the fact that the growth rate of typically 0.1 to 1 m per hour is relatively low. Besides, only comparably thin .
ilms can be produced because the internal stresses in the diamond-like carbon films at film thicknesses of more than about 1~ m cause the coatings to tear. Hence, hard material coating has only a very limited wear reserve so that its application is restricted if possibilities are considered which coatings like this could cover if they could be produced in greater thickness.
The present invention is aimed at a process for the production of diamond-like carbon coatings which are transparent uncolored and clear even in the visible region and in addition show low internal stresses. Moreover, the process design should permit the simultaneous homogeneous all-round coating of large production volumes.
This problem has been solved by the invention in that a hydro-carbon gas or a mixture of hydrocarbon gases and pure hydrogen is passed onto the substrate to be coated at room temperature or cooled down to -100C and that around the substrate an oxygen-free plasma discharge is produced by high-frequency excitation which is sustained by the gases admitted, the gases in the plasma discharge being excited, dissociated, ionized, and acce]erated toward the substrate. The partial pressure of the hydrocarbon gas is preferably between 10 3 and 1 mbar and the ratio of the partial pressures of hydrocarbon:hydrogen ranges between 0.05 and 20, preferably between O.S and 10.
When carrying out the process in the presence of a noble gas, preferably argon, the ratio of the partial pressures of hydrocarbon:noble gas ranges between 0.1 and 10, preferably between 1 and 5.
Coating is initiated under vacuum conditions, preferably at a residual gas pressure of below 2 x 10 5 mbar.
~ . .
' .: - , .
': '', ~i9~
Coating according to the invention is carried out without heating of the substrate being necessary prior or during coating. The preferred substrate temperature is between 10 and 20C. Cooling down to -100C is possible.
Plasma discharge takes place at low voltages, e.g. between 50 and 600 v, preferably at 150 to 250 v. High-frequency excitation in the kilohertz to megahertz range, from 30 KHz to 10 MHz is required to produce and sustain plasma discharge.
According to an embodiment of the process according to the invention, the coating process is carried out in-termittently. During the temporary interruptions the hydrocarbon supply is discontinued so that the substrate is bombarded only with noble gas and/or hydrogen. This may lead to an increase of the partial pressure of the noble gas and/or hydrogen. At a total duration which is chosen such that the desired film thickness is achieved, the coating period may range between, say, 1 sec and 20 min, preferably between 2 sec up to 2 min, while the hydrocarbon supply may be interrupted between 1 sec and 10 min, preferably between 1 sec and 1 min.
The hydrocarbon~ used may be any saturated or unsaturated hydrocarbons, if possible with no more than 10 hydrocarbon atoms, e.q. acetylene, ethylene, methanol and the like.
Pure hydrogen and pure noble gases are used according to the invention. All working gases can be mixed and admitted in the specified composition or are individually supplied to the discharge chamber where they are mixed.
According to the invention, the coating apparatus, e.g. a diode installation, triode or thermally assisted triode .~ ,, ;, ..~.~
, .
: - .
system but also magnetic-field-assisted installations is, if possible, evacuated to a pressure of less than ~ x 10 5mbar. Thereupon, the working gases are admitted in the desired mixing ratio.
The process is carried out dynamically, i.e. gas supply is controlled such that the working indicated above is reached while the vacuum pump is in operation. After the working pressure has been adjusted, plasma discharge is ignited and, upon proper process control, burns homogeneously around the substrate to be coated.
Normally, a high-frequency excitation is used to sustain plasma discharge.
The working gases are excited in the plasma chamber, dissociated and ionized. By the negative bias at the substrate precleaned in conventional manner the ions are attracted by the substrate from the plasma chamber. They impinge with a sufficiently high energy to that the crystal lattice of the coating assumes an at least partial diamond structure.
The measures covered by the invention permit the production of transparent, clear and uncolored films even in the visible spectrum. On the other hand, greater film thicknesses can be generated because the coatings deposited according to the process covered by the invention have lower internal stresses. The diamond-like carbon coatings also show a high hardness of more than 3.500 HV, a high specific resistance of up to 10 5 cm, a low coefficient of friction mainly in vacuum which qualifies them in an outstanding manner also for space applications. In addition, ! "
l~t~3~
the process according to the invention features a high growth rate of up to 10~ m per sec. Since the substrates can be coated all-round in the vacuum without rotation, it is possible to coat great production volumes during one cycle at the same time.
The invention is described in further detail by way of the following examples:
Example 1 A glass sheet, 5 x 5 cm in size, which was intended as substrate for the carbon coating, was cleaned in an ultra-sonic bath by means of solvents, rinsed with distilled water and cleaned again for 15 min each in two ultrasonic baths using acetone and methanol, respectively.
The glass sheet then was placed in a commercial coating apparatus which was evacuated to a residual gas pressure of less than about 2 x 10 5mbar and ion-etched for 10 min at a discharge voltage of 400 V while argon was admitted with a partial pressure of 5 x 10 3mbar. Thereupon the apparatus was evacuated to the pressure indicated above.
The following gases were admitted into the apparatus up to the partial pressures indicated: acetylene (2 x 10 3mbar), hydrogen (1 x 10 3mbar) and argon (3 x 10 3mbar). The discharge voltage was adjusted at 300 V. After a coating period of 25 min, a firmly adhering clean and hard coating was obtained which was transparent even in the visible spectrum, had a thickness of 0.5 ~m and showed a low internal stress.
Example 2 A glass cylinder with a diameter of 3.5 mm and a length l~tj~O~,~
of 25 mm was cleaned as described in Example 1. After evacuation of the coating apparatus to the values indi-cated in Example 1 the following gases were admitted:
ethylene (3 x 10 3mbar) and hydrogen (1 x 10 3mbar), The discharge voltage amounted to 150 V. The coating period was 40 min. The coat thickness totalled 3 ~m.
The coating adhered very firmly and was very hard.
Example 3 A stainless steel sheet 18 x 18 mm in size was cleaned according to the procedure described in Example 1.
After evacuation of the apparatus the following gases were introduced: acetylene (8 x 10 3mbar), hydrogen (8 x 10 4mbar), and argon (1 x 10 3mbar). The discharge voltage was 200 v. After a coating time of 10 min the acetylene supply was switched off for ~ min and the partial pressure of hydrogen was increased to 5 x 10 mbar and that of argon to 8 x 10 3mbar. This process was repeated 15 times. The coat thickness totalled 4.5 ~m. The coating was very hard and free of internal stress.
~ 'l ~ ' `-. ', ":
:
-
Diamond-like carbon coatings are used in particular for coating IR optical systems, e.g. lenses, mirrors or the like. Coating of optical systems like this takes place under vacuum conditions, a gas mixture consist~ing of hydrocarbons, e.g. acetylene, and a noble gas, e.g. argon, being exposed to a plasma discharge. The coatings thus produced are not transparent in the visible spectrum; they are of yellow, brownish, blue or black color. This is why these coatings cannot be used as scratch-resistant coatings for optical systems in the visible spectra region but only for the IR spectrum. A process for the deposition of a diamond-like carbon film has been described in GB-A-2 128 637, in which the carbon ions and other ions are generated in separate stationary sources, directed toward the surface of the substrate to be coated, and accelerated. The second ion species has the function to remove the undesired carbon species from the film formed by chemical sputtering. For this purpose hydrogen is used among other materials. The substrate is heated to a temperature of 100 to 200C. In this way, yellow to brown-colored coatings are obtained that are likewise suitable for IR optical systems. In conventional methods that use stationary sources the substrate has to be rotated relative to the sources in order to achieve homogeneous all-round coating. The simultaneous coating of medium production volumes is technologically feasible at a high expenditure. A further disadvantage consists in the fact that the growth rate of typically 0.1 to 1 m per hour is relatively low. Besides, only comparably thin .
ilms can be produced because the internal stresses in the diamond-like carbon films at film thicknesses of more than about 1~ m cause the coatings to tear. Hence, hard material coating has only a very limited wear reserve so that its application is restricted if possibilities are considered which coatings like this could cover if they could be produced in greater thickness.
The present invention is aimed at a process for the production of diamond-like carbon coatings which are transparent uncolored and clear even in the visible region and in addition show low internal stresses. Moreover, the process design should permit the simultaneous homogeneous all-round coating of large production volumes.
This problem has been solved by the invention in that a hydro-carbon gas or a mixture of hydrocarbon gases and pure hydrogen is passed onto the substrate to be coated at room temperature or cooled down to -100C and that around the substrate an oxygen-free plasma discharge is produced by high-frequency excitation which is sustained by the gases admitted, the gases in the plasma discharge being excited, dissociated, ionized, and acce]erated toward the substrate. The partial pressure of the hydrocarbon gas is preferably between 10 3 and 1 mbar and the ratio of the partial pressures of hydrocarbon:hydrogen ranges between 0.05 and 20, preferably between O.S and 10.
When carrying out the process in the presence of a noble gas, preferably argon, the ratio of the partial pressures of hydrocarbon:noble gas ranges between 0.1 and 10, preferably between 1 and 5.
Coating is initiated under vacuum conditions, preferably at a residual gas pressure of below 2 x 10 5 mbar.
~ . .
' .: - , .
': '', ~i9~
Coating according to the invention is carried out without heating of the substrate being necessary prior or during coating. The preferred substrate temperature is between 10 and 20C. Cooling down to -100C is possible.
Plasma discharge takes place at low voltages, e.g. between 50 and 600 v, preferably at 150 to 250 v. High-frequency excitation in the kilohertz to megahertz range, from 30 KHz to 10 MHz is required to produce and sustain plasma discharge.
According to an embodiment of the process according to the invention, the coating process is carried out in-termittently. During the temporary interruptions the hydrocarbon supply is discontinued so that the substrate is bombarded only with noble gas and/or hydrogen. This may lead to an increase of the partial pressure of the noble gas and/or hydrogen. At a total duration which is chosen such that the desired film thickness is achieved, the coating period may range between, say, 1 sec and 20 min, preferably between 2 sec up to 2 min, while the hydrocarbon supply may be interrupted between 1 sec and 10 min, preferably between 1 sec and 1 min.
The hydrocarbon~ used may be any saturated or unsaturated hydrocarbons, if possible with no more than 10 hydrocarbon atoms, e.q. acetylene, ethylene, methanol and the like.
Pure hydrogen and pure noble gases are used according to the invention. All working gases can be mixed and admitted in the specified composition or are individually supplied to the discharge chamber where they are mixed.
According to the invention, the coating apparatus, e.g. a diode installation, triode or thermally assisted triode .~ ,, ;, ..~.~
, .
: - .
system but also magnetic-field-assisted installations is, if possible, evacuated to a pressure of less than ~ x 10 5mbar. Thereupon, the working gases are admitted in the desired mixing ratio.
The process is carried out dynamically, i.e. gas supply is controlled such that the working indicated above is reached while the vacuum pump is in operation. After the working pressure has been adjusted, plasma discharge is ignited and, upon proper process control, burns homogeneously around the substrate to be coated.
Normally, a high-frequency excitation is used to sustain plasma discharge.
The working gases are excited in the plasma chamber, dissociated and ionized. By the negative bias at the substrate precleaned in conventional manner the ions are attracted by the substrate from the plasma chamber. They impinge with a sufficiently high energy to that the crystal lattice of the coating assumes an at least partial diamond structure.
The measures covered by the invention permit the production of transparent, clear and uncolored films even in the visible spectrum. On the other hand, greater film thicknesses can be generated because the coatings deposited according to the process covered by the invention have lower internal stresses. The diamond-like carbon coatings also show a high hardness of more than 3.500 HV, a high specific resistance of up to 10 5 cm, a low coefficient of friction mainly in vacuum which qualifies them in an outstanding manner also for space applications. In addition, ! "
l~t~3~
the process according to the invention features a high growth rate of up to 10~ m per sec. Since the substrates can be coated all-round in the vacuum without rotation, it is possible to coat great production volumes during one cycle at the same time.
The invention is described in further detail by way of the following examples:
Example 1 A glass sheet, 5 x 5 cm in size, which was intended as substrate for the carbon coating, was cleaned in an ultra-sonic bath by means of solvents, rinsed with distilled water and cleaned again for 15 min each in two ultrasonic baths using acetone and methanol, respectively.
The glass sheet then was placed in a commercial coating apparatus which was evacuated to a residual gas pressure of less than about 2 x 10 5mbar and ion-etched for 10 min at a discharge voltage of 400 V while argon was admitted with a partial pressure of 5 x 10 3mbar. Thereupon the apparatus was evacuated to the pressure indicated above.
The following gases were admitted into the apparatus up to the partial pressures indicated: acetylene (2 x 10 3mbar), hydrogen (1 x 10 3mbar) and argon (3 x 10 3mbar). The discharge voltage was adjusted at 300 V. After a coating period of 25 min, a firmly adhering clean and hard coating was obtained which was transparent even in the visible spectrum, had a thickness of 0.5 ~m and showed a low internal stress.
Example 2 A glass cylinder with a diameter of 3.5 mm and a length l~tj~O~,~
of 25 mm was cleaned as described in Example 1. After evacuation of the coating apparatus to the values indi-cated in Example 1 the following gases were admitted:
ethylene (3 x 10 3mbar) and hydrogen (1 x 10 3mbar), The discharge voltage amounted to 150 V. The coating period was 40 min. The coat thickness totalled 3 ~m.
The coating adhered very firmly and was very hard.
Example 3 A stainless steel sheet 18 x 18 mm in size was cleaned according to the procedure described in Example 1.
After evacuation of the apparatus the following gases were introduced: acetylene (8 x 10 3mbar), hydrogen (8 x 10 4mbar), and argon (1 x 10 3mbar). The discharge voltage was 200 v. After a coating time of 10 min the acetylene supply was switched off for ~ min and the partial pressure of hydrogen was increased to 5 x 10 mbar and that of argon to 8 x 10 3mbar. This process was repeated 15 times. The coat thickness totalled 4.5 ~m. The coating was very hard and free of internal stress.
~ 'l ~ ' `-. ', ":
:
-
Claims (12)
1. Method of producing diamond-like carbon coatings in which a gas selected from a hydrocarbon gas and mixtures thereof with at least one of pure hydrogen and a noble gas are ionized by plasma discharge, comprising placing a substrate to be coated in a coating apparatus and evacuating the apparatus to a residual gas pressure of below 2 x 10-5 mbar, then passing a gas selected from a hydrocarbon gas and mixtures thereof with at least one of pure hydrogen and a noble gas onto the substrate to be coated which is at a temperature between room temperature and -100°C, and producing around the substrate an oxygen-free plasma discharge by high-frequency excitation which is sustained by the gases admitted, the gases being excited, dissociated, ionized and accelerated toward the substrate during the plasma discharge, wherein the partial pressure of the hydrocarbon gas is adjusted between 10-3 and 1 mbar.
2. Method as claimed in claim 1 wherein the ratio of the partial pressures of hydrocarbon:hydrogen is between 0.05 and 20.
3. Method as claimed in claim 1 wherein the ratio of the partial pressures of hydrocarbon:noble gas is between 0.5 and 10.
4. Method as claimed in claim 1 wherein the ratio of the partial pressures of hydrocarbon:noble gas is between 0.1 and 10.
5. Method as claimed in claim 4 wherein the noble gas is argon and the ratio for the partial pressures of hydrocarbon:
argon is between 1 and 5.
argon is between 1 and 5.
6. Method as claimed in claim 1 wherein the substrate to be coated is at a temperature of 10° to 20°C.
7. Method as claimed in claim 1 wherein plasma discharge is carried out at a voltage of 50 to 600 V.
8. Method as claimed in claim 7 wherein plasma discharge is carried out at a voltage of 150 to 250 V.
9. Method as claimed in claim 1 wherein frequencies between 300 KHz and 14 MHz are used for plasma discharge.
10. Method as claimed in claim 1 wherein coating with said gas mixture is carried out intermittently and during the temporary interruptions of the coating process the hydrocarbon supply is discontinued so that the substrate is bombarded with noble gas or hydrogen.
11. Method as claimed in claim 1 wherein the substrate is coated for a period of 1 second to 20 minutes, the hydrocarbon supply is interrupted for periods of 1 second to 10 minutes and this procedure is repeated until the desired film thickness is achieved.
12. Method as claimed in claim 11 wherein the substrate is coated for a period of 2 seconds to 2 minutes, the hydrocarbon supply is interrupted for periods of 1 second to 10 minutes and this procedure is repeated until the desired film thickness is achieved.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19843421739 DE3421739A1 (en) | 1984-06-12 | 1984-06-12 | METHOD FOR PRODUCING DIAMOND-LIKE CARBON LAYERS |
| DEP3421739.8 | 1984-06-12 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA1269061A true CA1269061A (en) | 1990-05-15 |
| CA1269061C CA1269061C (en) | 1990-05-15 |
Family
ID=6238146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA483754A Expired - Lifetime CA1269061C (en) | 1984-06-12 | 1985-06-12 | Process for the production of diamond-like carbon coatings |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4728529A (en) |
| EP (1) | EP0182889B1 (en) |
| JP (1) | JPS61502403A (en) |
| CA (1) | CA1269061C (en) |
| DE (2) | DE3421739A1 (en) |
| DK (1) | DK260785A (en) |
| WO (1) | WO1986000093A1 (en) |
Families Citing this family (55)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3442208C3 (en) * | 1984-11-19 | 1998-06-10 | Leybold Ag | Method and device for producing hard carbon layers |
| DE3538261A1 (en) * | 1985-10-28 | 1987-04-30 | Battelle Institut E V | VALVE ELEMENTS FOR MIXING FITTINGS |
| DD243514B1 (en) * | 1985-12-17 | 1989-04-26 | Karl Marx Stadt Tech Hochschul | HARD COATINGS FOR MECHANICAL AND CORROSIVE CLADDED PARTS |
| JPS62202899A (en) * | 1986-03-03 | 1987-09-07 | Nippon Gakki Seizo Kk | Production of decorative article |
| GB2192733B (en) * | 1986-06-18 | 1991-02-06 | Raytheon Co | Impact resistant and tempered optical elements |
| DE3630418C1 (en) * | 1986-09-06 | 1987-12-17 | Kernforschungsanlage Juelich | Process for coating workpieces with amorphous, hydrogen-containing carbon |
| DE3630419A1 (en) * | 1986-09-06 | 1988-03-10 | Kernforschungsanlage Juelich | METHOD FOR COATING COMPONENTS EXPOSED TO HIGH THERMAL LOADS WITH AN AMORPHOUS HYDROCARBON LAYER |
| JPH0676666B2 (en) * | 1987-02-10 | 1994-09-28 | 株式会社半導体エネルギ−研究所 | Carbon film production method |
| DE3706340A1 (en) * | 1987-02-27 | 1988-09-08 | Winter & Sohn Ernst | METHOD FOR APPLYING A WEAR PROTECTIVE LAYER AND PRODUCT PRODUCED THEREOF |
| JPH0672306B2 (en) * | 1987-04-27 | 1994-09-14 | 株式会社半導体エネルギー研究所 | Plasma processing apparatus and plasma processing method |
| JPS6461396A (en) * | 1987-09-01 | 1989-03-08 | Idemitsu Petrochemical Co | Synthesis of diamond and installation therefor |
| NL8800911A (en) * | 1987-09-30 | 1989-04-17 | Pelt & Hooykaas | OPTICAL ELEMENT FOR TREATING LIGHT, METHOD FOR MANUFACTURING SUCH OPTICAL ELEMENT AND SUCH OPTICAL ELEMENTS INCLUDING LASER SETUP. |
| US4992298A (en) * | 1988-10-11 | 1991-02-12 | Beamalloy Corporation | Dual ion beam ballistic alloying process |
| US5055318A (en) * | 1988-10-11 | 1991-10-08 | Beamalloy Corporation | Dual ion beam ballistic alloying process |
| US4958590A (en) * | 1989-09-06 | 1990-09-25 | General Atomics | Microwave traveling-wave diamond production device and method |
| US5023109A (en) * | 1989-09-06 | 1991-06-11 | General Atomics | Deposition of synthetic diamonds |
| US4976324A (en) * | 1989-09-22 | 1990-12-11 | Baker Hughes Incorporated | Drill bit having diamond film cutting surface |
| US5095052A (en) * | 1990-06-28 | 1992-03-10 | The United States Of America As Represented By The Secretary Of The Air Force | Low impulse coatings |
| US5337844A (en) * | 1992-07-16 | 1994-08-16 | Baker Hughes, Incorporated | Drill bit having diamond film cutting elements |
| US5470661A (en) * | 1993-01-07 | 1995-11-28 | International Business Machines Corporation | Diamond-like carbon films from a hydrocarbon helium plasma |
| JPH0676383U (en) * | 1993-04-06 | 1994-10-28 | シチズン時計株式会社 | Textile related machine parts |
| US5474816A (en) * | 1993-04-16 | 1995-12-12 | The Regents Of The University Of California | Fabrication of amorphous diamond films |
| DE19544498C2 (en) * | 1994-12-10 | 1997-10-30 | Antec Angewandte Neue Technolo | Process for the plasma-assisted deposition of thin layers |
| US5677003A (en) * | 1995-10-30 | 1997-10-14 | Sam Shin Precision, Co., Ltd. | Method for coating diamond-like carbon on head drums of a video cassette recorder |
| US5986857A (en) * | 1997-02-13 | 1999-11-16 | Sanyo Electric Co., Ltd. | Thin film magnetic head including adhesion enhancing interlayers, and upper and lower gap insulative layers having different hydrogen contents and internal stress states |
| US6660365B1 (en) * | 1998-12-21 | 2003-12-09 | Cardinal Cg Company | Soil-resistant coating for glass surfaces |
| US6964731B1 (en) * | 1998-12-21 | 2005-11-15 | Cardinal Cg Company | Soil-resistant coating for glass surfaces |
| US6974629B1 (en) * | 1999-08-06 | 2005-12-13 | Cardinal Cg Company | Low-emissivity, soil-resistant coating for glass surfaces |
| US6572935B1 (en) * | 1999-03-13 | 2003-06-03 | The Regents Of The University Of California | Optically transparent, scratch-resistant, diamond-like carbon coatings |
| US6303225B1 (en) * | 2000-05-24 | 2001-10-16 | Guardian Industries Corporation | Hydrophilic coating including DLC on substrate |
| US6261693B1 (en) * | 1999-05-03 | 2001-07-17 | Guardian Industries Corporation | Highly tetrahedral amorphous carbon coating on glass |
| US6447891B1 (en) * | 1999-05-03 | 2002-09-10 | Guardian Industries Corp. | Low-E coating system including protective DLC |
| US6461731B1 (en) * | 1999-05-03 | 2002-10-08 | Guardian Industries Corp. | Solar management coating system including protective DLC |
| US20010044027A1 (en) * | 1999-12-30 | 2001-11-22 | Anderson Jerrel Charles | Diamond-like carbon coating on glass for added hardness and abrasion resistance |
| US20040028906A1 (en) * | 2000-01-04 | 2004-02-12 | Anderson Jerrel Charles | Diamond-like carbon coating on glass and plastic for added hardness and abrasion resistance |
| US6713179B2 (en) | 2000-05-24 | 2004-03-30 | Guardian Industries Corp. | Hydrophilic DLC on substrate with UV exposure |
| US6524755B2 (en) | 2000-09-07 | 2003-02-25 | Gray Scale Technologies, Inc. | Phase-shift masks and methods of fabrication |
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| US6783253B2 (en) * | 2002-03-21 | 2004-08-31 | Guardian Industries Corp. | First surface mirror with DLC coating |
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| US20040154528A1 (en) * | 2003-02-11 | 2004-08-12 | Page Robert E. | Method for making synthetic gems comprising elements recovered from humans or animals and the product thereof |
| US7306778B2 (en) * | 2003-06-19 | 2007-12-11 | Nanotech Llc | Diamond films and methods of making diamond films |
| CA2550331A1 (en) * | 2003-12-22 | 2005-07-14 | Cardinal Cg Compagny | Graded photocatalytic coatings |
| US7713632B2 (en) | 2004-07-12 | 2010-05-11 | Cardinal Cg Company | Low-maintenance coatings |
| US8092660B2 (en) * | 2004-12-03 | 2012-01-10 | Cardinal Cg Company | Methods and equipment for depositing hydrophilic coatings, and deposition technologies for thin films |
| US7923114B2 (en) * | 2004-12-03 | 2011-04-12 | Cardinal Cg Company | Hydrophilic coatings, methods for depositing hydrophilic coatings, and improved deposition technology for thin films |
| JP2009534563A (en) * | 2006-04-19 | 2009-09-24 | 日本板硝子株式会社 | Opposing functional coating with equivalent single surface reflectivity |
| US20080011599A1 (en) | 2006-07-12 | 2008-01-17 | Brabender Dennis M | Sputtering apparatus including novel target mounting and/or control |
| KR101563197B1 (en) | 2007-09-14 | 2015-10-26 | 카디날 씨지 컴퍼니 | Low-maintenance coatings and methods for producing low-maintenance coatings |
| DE102010052971A1 (en) | 2010-11-30 | 2012-05-31 | Amg Coating Technologies Gmbh | Workpiece with Si-DLC coating and process for the production of coatings |
| EP2628817B1 (en) | 2012-02-15 | 2016-11-02 | IHI Hauzer Techno Coating B.V. | A coated article of martensitic steel and a method of forming a coated article of steel |
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| DE102012007763A1 (en) | 2012-04-20 | 2013-10-24 | Ulrich Schmidt | Modular frame for sockets and switches |
| DE102012007796A1 (en) | 2012-04-20 | 2013-10-24 | Amg Coating Technologies Gmbh | Workpiece, useful as e.g. component of internal combustion engine, comprises base body and covering layer that comprises three-fold layers including layer of silicon-diamond-like carbon, layer of diamond-like carbon and hydrogen |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3167449A (en) * | 1961-04-26 | 1965-01-26 | Gen Electric | Method of forming carbon coating |
| US3167444A (en) * | 1962-11-19 | 1965-01-26 | Nashua Corp | Heat responsive marking sheets |
| JPS5856249B2 (en) * | 1978-09-07 | 1983-12-14 | 松下電子工業株式会社 | Method for manufacturing thin films by plasma reaction |
| DE3047888A1 (en) * | 1980-12-19 | 1982-07-15 | Philips Patentverwaltung Gmbh, 2000 Hamburg | Cutting tools, esp. razor blades - where CVD activated by plasma is used to coat tool with carbon possessing structure similar to diamond |
| US4434188A (en) * | 1981-12-17 | 1984-02-28 | National Institute For Researches In Inorganic Materials | Method for synthesizing diamond |
| US4410504A (en) * | 1982-04-30 | 1983-10-18 | United Technologies Corporation | Method of producing high density carbon |
| US4486286A (en) * | 1982-09-28 | 1984-12-04 | Nerken Research Corp. | Method of depositing a carbon film on a substrate and products obtained thereby |
-
1984
- 1984-06-12 DE DE19843421739 patent/DE3421739A1/en active Granted
-
1985
- 1985-06-07 DE DE8585902985T patent/DE3581501D1/en not_active Expired - Lifetime
- 1985-06-07 JP JP60502667A patent/JPS61502403A/en active Pending
- 1985-06-07 EP EP85902985A patent/EP0182889B1/en not_active Expired - Lifetime
- 1985-06-07 WO PCT/EP1985/000275 patent/WO1986000093A1/en not_active Application Discontinuation
- 1985-06-07 US US06/813,280 patent/US4728529A/en not_active Expired - Fee Related
- 1985-06-11 DK DK260785A patent/DK260785A/en not_active Application Discontinuation
- 1985-06-12 CA CA483754A patent/CA1269061C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US4728529A (en) | 1988-03-01 |
| DE3421739C2 (en) | 1987-01-02 |
| EP0182889B1 (en) | 1991-01-23 |
| DE3421739A1 (en) | 1985-12-12 |
| DK260785A (en) | 1985-12-13 |
| WO1986000093A1 (en) | 1986-01-03 |
| DE3581501D1 (en) | 1991-02-28 |
| DK260785D0 (en) | 1985-06-11 |
| EP0182889A1 (en) | 1986-06-04 |
| JPS61502403A (en) | 1986-10-23 |
| CA1269061C (en) | 1990-05-15 |
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