INFRA RED TRANSPARENT OPTICAL COMPONENTS

Abstract: A method of coating a substrate in a glow discharge chamber uses a source of hydrocarbon and another element. For example butane and germane are used to deposit a coating of Ge x C 1-x where 0 < x < 1 onto a germanium substrate. The substrate temperature is maintained above 400°C typically 530°C during growth to prevent inclusion of H₂ in the coating. The presence of Ge in the coating allows thick, strain free, layers to be grown. Alternatively butane and silane may be used to deposit Si x C 1-x . Varying the proportions of the hydrocarbon and germane or silane allows a variation in the value of x.

Description: 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 thermal imagers since the cargon coatings are very hard, wear-resistant and substantially transparent to infra-red 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 knows 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, 'n7-116, 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 article and its associated references: Spear V. 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 4000C, to drive out the required amount of hydrogen. A typical temperature is about 5300C although most hydrogen is driven out below this e.g. at about 5000C. 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 ln 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 GexC1 SixC1 = where 0 < i < 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 Figure 1. The apparatus of Figure 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 Figure 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 I 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 50C typically 53t 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 (GeR ) 4 and butane (CH ) admitted via the inlet pipe 8, 10, 11 and 4 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 z 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 P . 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 GexCl 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 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 SixCl 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: Claims: 1. A method of depositing coatings comprising the steps of providing a vacuuum 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 4000C during growth of the coating. 2. The method of claim 1 wherein the substrate temperature is above 400 C during growth of the coating. 3. The method of claim l wherein a hydrocarbon gas and germane are admitted to the chamber to form the plasma. 4. The method claim 1 wherein a hydrocarbon gas and silane are admitted to the chamber to form the plasma. 5. The method of claim l wherein at least one of the elements forming the coating is provided by a molecular beam oven. 6. The method of claim 1 wherein at least one of the elements forming the coating is provided by an ion beam source. 7. The method of claim 1 wherein the substrate is a piece of germanium material. 8. The method of claim 7 wherein the coating is of the material GexCl¯x where 0 < x < 1. 9. The method of claim 1 wherein the substrate is a piece of silicon material. 10. The method of claim 9 wherein the coating is of the material SixCl x where 0 < x < 1. 11. The method of claim 1 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. 12. An infra red transparent optical component comprising a piece of germanium material coated on at least one surface with a layer, less than 10 tm thick, of GexCl x 13. 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 Zm thick, of Si C x l-x

Inventors: GREEN, GEOFFREY WILLIAM, LETTINGTON, ALAN HAROLD
Applicants: NATIONAL RESEARCH DEVELOPMENT CORPORATION
Application year: 1983
Main classification: C23C16
IPC codes: C01B31, G02B1, C23C16