GB2165266A - Infra red transparent optical components - Google Patents

Infra red transparent optical components Download PDF

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Publication number
GB2165266A
GB2165266A GB08524696A GB8524696A GB2165266A GB 2165266 A GB2165266 A GB 2165266A GB 08524696 A GB08524696 A GB 08524696A GB 8524696 A GB8524696 A GB 8524696A GB 2165266 A GB2165266 A GB 2165266A
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United Kingdom
Prior art keywords
coating
component
lens
substrate
layer
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.)
Granted
Application number
GB08524696A
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GB2165266B (en
GB8524696D0 (en
Inventor
Geoffrey William Green
Alan Harold Lettington
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National Research Development Corp UK
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National Research Development Corp UK
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Priority to GB08524696A priority Critical patent/GB2165266B/en
Publication of GB8524696D0 publication Critical patent/GB8524696D0/en
Publication of GB2165266A publication Critical patent/GB2165266A/en
Application granted granted Critical
Publication of GB2165266B publication Critical patent/GB2165266B/en
Expired legal-status Critical Current

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Classifications

    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C23C16/029—Graded interfaces
    • 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
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C23C16/325—Silicon carbide
    • 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
    • G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation

Abstract

An optical component comprises a lens or window of infra red transparent material, e.g. germanium, silicon, zinc sulphide, or zinc selenide. A hard infra red coating of GexC1@x or SixC1@x, 0<x<1, is formed on a surface of the lens or window. The value of x may vary across the the coating thickness. A bonding layer may be used between the window and coating. Several coating layers may be employed, and may be arranged to give an anti-reflection coating.

Description

SPECIFICATION Method and apparatus for depositing coatings in a glow discharge The invention concerns a method and apparatus for depositing coatings in a glow discharge plasma. Coating may be of hard carbon, silicon, germanium or other suitable materials capable of being deposited from suitable plasma.
Carbon coatings are useful on for example germanium lenses used in infra red imagers since the cargon coatings are very hard, wearresistant and substantially transparent to infrared radiation. Both silicon and germanium are transparent to infra red and are useful in various infra red equipments.
There are a number of techniques for coating substrates. For example a substrate may be suspended above a cathode target of the coating material in a vacuum. Argon ions are caused to strike the target thereby knocking off small particles of the target material which adhere to the substrate. Such a technique is known as sputtering. Carbon can be sputtered but the deposition rate is low and the coating may be graphitic.
Coatings may be grown in a plasma. For example a substrate may be used as a cathode in a D.C. or A.C. excited hydrocarbon plasma. Carbon ions are attracted to strike the substrate and form a carbon layer which for appropriate temperature and pressure conditions, is diamond-like.
Techniques for growing carbon films are described in the following articles and their associated references: Thin Film Solids 58 (1979) 101-105, 106, 107-116, 117-120; Patent Specifications Nos. G.B. 2,047,877 A, 2,067, 304 A, 2,069,008 A, 2,082,562 A, 2,083,841 A.
Techniques for growing amorphous layers of silicon and germanium by glow discharge are described in the following articles and its associated references: Spear W. E., Doped Amorphous Semiconductor, Advances in Physics 1977 Vol. 26, No. 6, 811-845.
A disadvantage with the prior art flow discharge deposition is that in order to achieve reasonable deposition rates high potentials have to be applied or developed at the cathode, so that the substrate is subjected to high energy incident particles. This tends to affect the stress in the coating and increases the back sputtering rate. In some cases this prevents deposition of a layer at all.
According to this invention a method of depositing coatings containing carbon and another element comprises the steps of providing a plasma containing the materials to be deposited as a coating in a chamber having a cathode structure, arranging a substrate to be coated on the cathode, and maintaining the substrate at an elevated temperature during growth.
The elevated temperature is high enough, e.g. above about 400"C, to drive out the required amount of hydrogen. A typical temperature is about 530"C although most hydrogen is driven out below this e.g. at about 500"C.
According to this invention apparatus for depositing a coating on a substrate comprises a vacuum tight chamber, a pump for maintaining a vacuum within the chamber, means for supplying a mixture of at least two gases into the chamber, an anode and a cathode structure within the chamber, a cathode heater, a power supply for providing a glow discharge in the chamber adjacent the cathode, the arrangement being such that a plasma of at least two gaseous materials is established in the chamber so that ions of the material deposit on the substrate arranged on the cathode to form a coating.
Alternatively one of the gas supplies may be replaced by a molecular beam oven or an ion beam source etc to provide one of the materials in the plasma. This oven or source may be mounted in the chamber and direct its contents into the region around the cathode.
According to this invention a lens or window is provided with a coating by the above method.
The coating may be a thin coating on the surface of a component such as a lens or window or may be grown as a thick layer self supporting after removal of the substrate.
The coating may be of Gexcl x, Si,C1 where O < x < 1. Small amounts of Ge, Si give a hard carbon coating that is relatively strain free due to the inclusion of Ge, Si. Thus quite thick strain free layers may be grown. Also the high temperature of growth results in little if any H2 within the layer. This results in a coating which absorbs little infra red light. In contrast hard carbon layers grown by the prior art methods contain hydrogen and interstitial carbon which gives rise to black absorbing layers and highly strained layers.
The glow discharge may be provided by D.C. or A.C. at any suitable frequency.
The invention will now be described by way of example only with reference to the accompanying drawings of which: Figure 1 is a sectional view of apparatus for growing a coating; Figure 2 is a sectional view of a lens coated by the apparatus of Fig. 1.
The apparatus of Fig. 1 comprises a vacuum tight container 1 formed by an annular wall 2 and earthed top and bottom plates 3, 4 respectively. A pump 5 is connected through an exhaust pipe 6 and valve 7 to the chamber 1.
Gas supplies of argon, germane and a hydrocarbon gas such as butane are fed into the chamber via inlet pipes 8, 9, 10, 11 and valves 12, 13 14, 15. A cathode structure 16 is supported inside the chamber 1 and electrically insulated from the bottom plate 4 by a sleeve 17. Inside the cathode structure is a heater 18 for heating a substrate 19 arranged on the cathode 16. Cathode temperature is controlled by a heater control 20 which also supplies power to the heater 18. A power supply 21 feeds electrical power to the cathode 16. This power may be D.C., or A.C. via a blocking capacitor 22. Alternatively an A.C.
coil may surround the chamber 1 and induce a plasma within the chamber.
A germanium lens Fig. 2 may be coated with a layer of hard carbon as follows. The lens 19 is mounted on the cathode 16 with the surface 22 to be coated uppermost. The chamber 1 is evacuated by the pump 5 to less than 10 5 Torr. to remove contaminants.
Argon gas is admitted through the valve 13 and the chamber pressure kept at about 10 2 Torr. on an air calibrated gauge.
A plasma is generated in argon by energising the cathode 16 from the power supply 21. This provides an argon ion bombardment of the surface 22 to clean it prior to coating.
About 2 minutes cleaning is usually adequate.
The cathode heater 18 is operated to raise the lens 19 temperature to above about 500" typically 530"C and maintain it at this value during growth of the coating.
The argon is removed by the pump 5 and a mixture of germane (GeH4) and butane (CH4) admitted via the inlet pipe 8, 10, 11 and valves 12, 14, 15. Pressure is maintained at around 0.7 to 1.10 2 Torr. A.C. power of typically 1 kvolt at 13 MHz and 200 watts power level is applied to create a plasma. Positively charged ions of C, and of Ge strike and remain on the lens surface gradually building up a layer 23 of hard carbon with small amounts of Ge included.
The layer thickness is time and composition dependent and is selected for optical properties (anti-reflection) and required durability.
Typical layer thickness is 1 to 10 ,um, The discharge is stopped when the required thickness is grown and the substrate allowed to cool.
To assist in growing a uniform layer the substrate 19 may be rotated during growth.
The proportion of Ge in the C varies with the proportions of germane and butane gas admitted. For a hard carbon layer only small amounts of Ge are needed to provide a transparent carbon layer of extreme durability and hardness approaching that of diamond. The high substrate temperature prevents the inclusion of H2 within the coating. An advantage of Ge within the coating is the good bond achieved by the coating direct with the bulk Ge lens. Thus for some applications no bonding layers are needed.
The coating composition may vary within the thickness of the coating by adjusting the germane: butane ratio. The value of x in the coating composition Gexc1-x is variable between 0 and 1, although the coating may not be homogeneous on a microscopic scale. For example the initial deposits may have an x value around 1 to give a good bonding; subsequent depositions may have an x value approaching zero to give a very hard surface.
The presence of small amounts of C in Ge helps to prevent an absorbing coating being grown. As previously noted small amounts of Ge (and Si) in hard C coatings reduces the presence of interstitial carbon to give a very hard infra red transparent layer.
Substrates other than germanium may be coated. For example ZnS, ZnSe to give an infra red transparent lens or window with a hard wear resistant outer surface.
Coatings of silicon carbide SixC. x (O < x < 1) may also be grown as above but using silane instead of germane. Regular and irregular objects may be coated. For example cutting tool tips may be given a hard wear resistant coating. Also circular cross section articles such as glass fibres may be coated using a shaped cathode as described in G.B. Patent Application No. 2,099,212 A. This cathode may take the form of a flat strip wound into an open spiral surrounding the fibre which is slowly drawn through. Alternatively the cathode may be segments arranged along a helix, or a perforated tube.
The plasma may be generated by D.C.
power typically at -2 kvolt. Both conducting and insulating substrates may be coated. Insulating substrates may need a cathode structure of large area compared to substrate area.

Claims (7)

1. An infra red transparent optical component comprising a piece of germanium material coated on at least one surface with a layer, less than 10 tom thick, of GexC,
2. An infra red transparent optical component comprising a piece of ZnS or ZnSe material coated on at least one surface with a layer, less than 10 ,um thick, of SixC,
3. A method of depositing coatings comprising the steps of providing a vacuum chamber containing a cathode structure, arranging a substrate to be coated on the cathode, providing in the chamber a glow discharge plasma containing carbon and another element to be deposited as a coating and maintaining the substrate temperature above 400"C during growth of the coating.
4. The method of claim 3 wherein the substrate temperature is above 400"C during growth of the coating.
5. The method of claim 3 wherein a hydrocarbon gas and germane are admitted to the chamber to form the plasma.
6. The method claim 3 wherein a hydrocarbon gas and silane are admitted to the chamber to form the plasma.
7. The method of claim 3 wherein at least one of the elements forming the coating is provided by a molecular beam oven.
8. The method of claim 3 wherein at least one of the elements forming the coating is provided by an ion beam source.
7. The component of claim 1 constructed, arranged and adapted to operate substantially as hereinbefore described with reference to the accompanying drawings.
7. The method of claim 3 wherein the substrate is a piece of germanium material.
8. The method of claim 9 wherein the coating is of the material Gexc1-x where O < x < 1.
9. The method of claim 3 wherein the substrate is a piece of silicon material.
10. The method of claim 11 wherein the coating is of the material SixC, x where O < x < 1.
11. The method of claim 3 wherein the proportions of the hydrocarbon and the other element are varied to give a value of x that varies across the thickness of the coating.
CLAIMS Amendments to the claims have been filed, and have the following effect: (b) New or textually amended claims have been filed as follows:
1. An optical component comprising an infra red transparent lens or window coated with at least one layer of GexCi , or Si,C1 where 0x1, said layer being substantially hydrogen and strain free.
2. The component of claim 1 wherein the lens or window is of Ge, Si, ZnS, ZnSe material.
3. The component of claim 1 or claim 2 wherein the value of x varies across the thickness of the coating.
4. The component of any one of claims 1 to 3 wherein a bonding layer is formed on the lens or window under the the coating.
5. The component of any one of claims 1 to 4 wherein several coatings of GexCi , or SiXC, x are formed on the lens or window, each coating having a different value of x with the final coating having the higher value of x.
6. The component of any one of claims 1 to 5 wherein the value of x and thickness of coating is arranged to give an anti-reflection coating.
GB08524696A 1982-10-12 1985-10-07 Infra red transparent optical components Expired GB2165266B (en)

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GB08524696A GB2165266B (en) 1982-10-12 1985-10-07 Infra red transparent optical components

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GB8229124 1982-10-12
GB08524696A GB2165266B (en) 1982-10-12 1985-10-07 Infra red transparent optical components

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GB2165266A true GB2165266A (en) 1986-04-09
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2192733A (en) * 1986-06-18 1988-01-20 Raytheon Co Impact resistant and tempered optical elements
WO1989006707A1 (en) * 1988-01-21 1989-07-27 The National Research Development Corporation Infra-red transparent materials
GB2213835A (en) * 1987-12-18 1989-08-23 Gen Electric Co Plc Deposition apparatus
US4907846A (en) * 1987-11-20 1990-03-13 Raytheon Company Thick, impact resistant antireflection coatings for IR transparent optical elements
WO1990004189A1 (en) * 1988-10-14 1990-04-19 Northrop Corporation Optically transparent electrically conductive semiconductor windows and methods of manufacture
GB2233984A (en) * 1988-01-21 1991-01-23 Secr Defence Infra-red transparent materials
US4995684A (en) * 1986-06-18 1991-02-26 Raytheon Company Impact resistant and tempered optical elements
US5067781A (en) * 1989-11-21 1991-11-26 Raytheon Company Optical elements and method of manufacture
US5120602A (en) * 1990-02-02 1992-06-09 Raytheon Company Optical elements and method of manufacture
GB2280201A (en) * 1987-06-15 1995-01-25 Secr Defence Infra red transparent window
EP0712943A1 (en) * 1994-08-15 1996-05-22 BIOTRONIK Mess- und Therapiegeräte GmbH & Co Ingenieurbüro Berlin Method for making non-collapsible intravascular prosthesis (stent)
EP0776989A1 (en) * 1995-11-29 1997-06-04 ANTEC Angewandte Neue Technologien GmbH Method of making a coloured coating
US5900289A (en) * 1995-11-29 1999-05-04 Antec Angewandte Neue Technologien Gmbh Method of producing a colorating coating
EP0911601A3 (en) * 1997-10-22 1999-06-23 Global Target Systems Limited Aerial target system
WO2000043564A1 (en) * 1999-01-20 2000-07-27 Marconi Caswell Limited Method of, and apparatus for, depositing materials

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1560110A (en) * 1976-01-02 1980-01-30 Avco Corp Silicon carbide coated filaments and ribbons
EP0030638A1 (en) * 1979-12-12 1981-06-24 International Business Machines Corporation Method for depositing silicon or germanium containing films
GB2069008A (en) * 1980-01-16 1981-08-19 Secr Defence Coating in a glow discharge
GB2081695A (en) * 1980-07-30 1982-02-24 Avco Corp Surface treatment for carbon
GB2082562A (en) * 1980-08-21 1982-03-10 Secr Defence Coating germanium or silica with carbon
GB2083841A (en) * 1980-08-21 1982-03-31 Secr Defence Glow discharge coating
GB2132636A (en) * 1982-10-12 1984-07-11 Secr Defence Glow discharge coating method

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1560110A (en) * 1976-01-02 1980-01-30 Avco Corp Silicon carbide coated filaments and ribbons
EP0030638A1 (en) * 1979-12-12 1981-06-24 International Business Machines Corporation Method for depositing silicon or germanium containing films
GB2069008A (en) * 1980-01-16 1981-08-19 Secr Defence Coating in a glow discharge
GB2081695A (en) * 1980-07-30 1982-02-24 Avco Corp Surface treatment for carbon
GB2082562A (en) * 1980-08-21 1982-03-10 Secr Defence Coating germanium or silica with carbon
GB2083841A (en) * 1980-08-21 1982-03-31 Secr Defence Glow discharge coating
GB2132636A (en) * 1982-10-12 1984-07-11 Secr Defence Glow discharge coating method

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4995684A (en) * 1986-06-18 1991-02-26 Raytheon Company Impact resistant and tempered optical elements
GB2192733A (en) * 1986-06-18 1988-01-20 Raytheon Co Impact resistant and tempered optical elements
FR2606165A1 (en) * 1986-06-18 1988-05-06 Raytheon Co METHOD FOR ADHERING A CARBON LAYER ON A BASE, IN PARTICULAR FOR OPTICAL ELEMENTS
FR2606164A1 (en) * 1986-06-18 1988-05-06 Raytheon Co IMPACT-RESISTANT OPTICAL ELEMENTS AND METHOD OF MANUFACTURING SUCH ELEMENTS
GB2192733B (en) * 1986-06-18 1991-02-06 Raytheon Co Impact resistant and tempered optical elements
GB2280201B (en) * 1987-06-15 1995-06-28 Secr Defence Infra red transparent windows
GB2280201A (en) * 1987-06-15 1995-01-25 Secr Defence Infra red transparent window
US4907846A (en) * 1987-11-20 1990-03-13 Raytheon Company Thick, impact resistant antireflection coatings for IR transparent optical elements
GB2213835A (en) * 1987-12-18 1989-08-23 Gen Electric Co Plc Deposition apparatus
GB2213835B (en) * 1987-12-18 1992-07-08 Gen Electric Co Plc Deposition apparatus
US5143018A (en) * 1987-12-18 1992-09-01 The General Electric Company, P.L.C. Apparatus for depositing uniform films by how-pressure chemical vapor deposition
GB2233984A (en) * 1988-01-21 1991-01-23 Secr Defence Infra-red transparent materials
US5723207A (en) * 1988-01-21 1998-03-03 The National Research Development Corporation Infra-red transparant materials
WO1989006707A1 (en) * 1988-01-21 1989-07-27 The National Research Development Corporation Infra-red transparent materials
GB2233984B (en) * 1988-01-21 1992-08-26 Secr Defence Infra-red transparent materials
WO1990004189A1 (en) * 1988-10-14 1990-04-19 Northrop Corporation Optically transparent electrically conductive semiconductor windows and methods of manufacture
US5067781A (en) * 1989-11-21 1991-11-26 Raytheon Company Optical elements and method of manufacture
US5120602A (en) * 1990-02-02 1992-06-09 Raytheon Company Optical elements and method of manufacture
EP0712943A1 (en) * 1994-08-15 1996-05-22 BIOTRONIK Mess- und Therapiegeräte GmbH & Co Ingenieurbüro Berlin Method for making non-collapsible intravascular prosthesis (stent)
US5735896A (en) * 1994-08-15 1998-04-07 Biotronik Biocompatible prosthesis
US5849206A (en) * 1994-08-15 1998-12-15 Biotronik Mess- Und Therapiegerate Gmbh & Co. Ingenieurburo Berlin Method of producing a biocompatible prosthesis
EP0776989A1 (en) * 1995-11-29 1997-06-04 ANTEC Angewandte Neue Technologien GmbH Method of making a coloured coating
US5900289A (en) * 1995-11-29 1999-05-04 Antec Angewandte Neue Technologien Gmbh Method of producing a colorating coating
EP0911601A3 (en) * 1997-10-22 1999-06-23 Global Target Systems Limited Aerial target system
WO2000043564A1 (en) * 1999-01-20 2000-07-27 Marconi Caswell Limited Method of, and apparatus for, depositing materials

Also Published As

Publication number Publication date
GB2165266B (en) 1987-09-23
GB8524696D0 (en) 1985-11-13

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Date Code Title Description
732 Registration of transactions, instruments or events in the register (sect. 32/1977)
PE20 Patent expired after termination of 20 years

Effective date: 20031009