Method for treating antireflection coatings on an optical substrate, the thus obtained optical substrate and device for carrying gout said method

Abstract

Method for treating antireflection coatings on an optical substrate (17) involves a stage for carrying out the physical vacuum-deposit of a fluorinated polymer-containing layer having a low refractive index and is characterized in that the stage includes in deposing a silicium or magnesium fluoride/fluorinated polymer hybrid layer (21d) by simultaneous vacuum evaporation of silicium or magnesium fluoride and the fluorinated polymer, In a preferred embodiment, the fluorinated polymer is embodied in the form of a polymer or tetrafluorethylen polymer and the components are evaporated by a Joule effect or by electron bombardment. The method is advantageously used for improving the adherence of a low refractive index layer to a subjacent layer of a pile of antireflection coatings which is deposited on any optical substrate or the inventive substrate. The substrate produced by the method and a device for carrying out the method are also disclosed.

Claims

1. A method for applying an antireflection treatment to an optical substrate, comprising: depositing by physical vapor-phase deposition (PVD) in a vacuum a low index layer having a low refractive index and including a fluorinated polymer, wherein said depositing step consists in depositing a hybrid silica (SiO.sub.2) or magnesium fluoride (MgF.sub.2)/fluorinated polymer layer as said low index layer by a simultaneous co-evaporation, in a vacuum, of the silica or magnesium fluoride and the fluorinated polymer, the fluorinated polymer being a homopolymer of tetrafluoroethylene.

2. The method according to claim 1, wherein the silica or magnesium fluoride and the fluorinated polymer are co-evaporated so that the silica or magnesium fluoride and the fluorinated polymer are present in constant proportions throughout a thickness of the low index layer.

3. The method according to claim 2, wherein a quantity of the fluorinated polymer in the low index layer is kept less than or equal to approximately 30% by volume, and a remaining quantity in the low index layer consists of the silica or magnesium fluoride.

4. The method according to claim 2, further comprising successive steps of: continuously measuring, as measurements, one of i) a refractive index of the low index layer as the low index layer is formed and ii) respective rates of deposition of the silica or magnesium fluoride and the fluorinated polymer; determining from said measurements respective quantities of deposited silica or magnesium fluoride and deposited fluorinated polymer; and regulating deposition parameters of the silica or magnesium fluoride and/or the fluorinated polymer in order to deposit the silica or magnesium fluoride and the fluorinated polymer in selected proportions throughout the thickness of the low index layer.

5. The method according to claim 1, wherein, when co-evaporating the silica or magnesium fluoride and the fluorinated polymer, proportions of the silica or magnesium fluoride and the fluorinated polymer are allowed to vary in a controlled manner over a whole of or a portion of the thickness of the low index layer.

6. The method according to claim 5, wherein a quantity of fluorinated polymer in the low index layer is from zero to approximately 80% by volume in a direction from the substrate toward a surface of the low index layer, and a remaining quantity in the low index layer consists of the silica or magnesium fluoride.

7. The method according to claim 1, wherein the silica or magnesium fluoride and fluorinated polymer are evaporated by means of the Joule effect or by means of an electron gun.

8. The method according to claim 1, wherein the silica or magnesium fluoride is evaporated by means of an electron gun and the fluorinated polymer is evaporated by means of the Joule effect.

9. The method according to claim 1, wherein the substrate is an organic material substrate.

10. The method according to claim 1, wherein the low index layer is an outside layer of an antireflection multilayer film deposited on the optical substrate.

11. The method according to claim 10, wherein the antireflection multilayer film is fabricated by successive steps of physical vapor-phase deposition (PVD) in a vacuum of three layers of the type ZrO.sub.2/SiO.sub.2/ZrO.sub.2, and then said deposition of the low index layer as the outside layer.

12. The method according to claim 11, wherein each successive step of physical vapor-phase deposition is effected at a pressure less than or equal to approximately 10.sup.2 Pa.

13. A method for applying an antireflection treatment to an optical substrate, comprising: depositing by physical vapor-phase deposition (PVD) in a vacuum a low index layer having a low refractive index and including a fluorinated polymer, wherein said depositing step consists in depositing a hybrid silica (SiO.sub.2)/fluorinated polymer layer as said low index layer by a simultaneous co-evaporation, in a vacuum, of the silica and the fluorinated polymer, the fluorinated polymer being a homopolymer of tetrafluoroethylene.

14. A method for applying an antireflection treatment to an optical substrate, comprising: depositing by physical vapor-phase deposition (PVD) in a vacuum a low index layer having a low refractive index and including a fluorinated polymer, wherein said depositing step consists in depositing a hybrid magnesium fluoride (MgF.sub.2)/fluorinated polymer layer as said low index layer by a simultaneous co-evaporation, in a vacuum, of the magnesium fluoride and the fluorinated polymer, the fluorinated polymer being a homopolymer of tetrafluoroethylene.

Description

(1) The features and advantages of the invention emerge from the following description given by way of example and with reference to the appended diagrammatic drawings, in which:

(2) FIG. 1 is a diagram of the configuration of a device for implementing the method of the invention; and

(3) FIG. 2 represents an antireflection multilayer film obtained using a preferred embodiment of the invention.

(4) In the embodiment shown, the device 10 for implementing the antireflection treatment method of the invention takes the form of a Leybold Heraeus 700 QE evaporation machine consisting of a frame 11 defining a deposition chamber 12.

(5) A pumping system (not shown in FIG. 1 for simplicity) is also provided to establish a vacuum inside the deposition chamber 12. A cold trap (Meissner trap), also not shown in FIG. 1 for simplicity, is also disposed inside the machine 10 to increase the water pumping rate. It is therefore possible to reduce the pressure from atmospheric pressure to the treatment pressure (which in practice is of the order of 10.sup.2 Pa) in a few minutes.

(6) The machine 10 is also equipped with a Leybold ESV 6 electron gun 13 with a rotary crucible with four cavities and a Joule effect evaporation source 14.

(7) Two quartz microbalances 15 separated by a mask 16 measure and control the rates of deposition. To this end they are connected to the evaporation sources by a control loop.

(8) Control of the composition of a layer deposited is based, to a first approximation, on the ratio of the two set rates of deposition.

(9) A conventional turntable, also not shown for simplicity, serves as a substrate-carrier within the chamber 12.

(10) In the embodiment shown, only one substrate 17 can be seen.

(11) An ion gun 18, for example a Commonwealth Mark II ion gun, is also disposed inside the deposition chamber 12 to carry out initial cleaning of the substrate 17 before deposition of the first antireflection thin layer.

(12) FIG. 2 shows one example of a multilayer film that can be obtained by the method of the invention.

(13) In the embodiment shown in this figure, an organic substrate 17, here of CR39 coated with commercially available anti-abrasion varnish (ORMA SUPRA) is coated with an antireflection multilayer film 21 comprising alternating thin layers 21a-21d with high and low refractive indices.

(14) In the preferred embodiment shown in FIG. 2, the material of the first layer 21a has a high refractive index (i.e. a refractive index greater than 1.6). Here this material is zirconium oxide (ZrO.sub.2) and is typically deposited to a physical thickness from 10 to 40 nm.

(15) The second layer 21b deposited on the first layer 21a here consists of silica (SiO.sub.2), which has a low refractive index, and typically has a thickness from 10 to 55 nm.

(16) The third layer 21c deposited is identical here to the first layer 21a (ZrO.sub.2 layer), except for the thickness, which is from 30 to 200 nm, and preferably from 120 to 150 nm.

(17) The above three layers are deposited successively by evaporation in a vacuum using the machine 10 shown in FIG. 1.

(18) In other embodiments, the materials constituting the three anti-reflection layers 21a-21c and those constituting the substrate 17 or the anti-abrasion varnish 20 may be replaced by other equivalent materials well known to the person skilled in the art.

(19) According to the invention, the antireflection multilayer film 21 further includes a hybrid outside layer 21d from 70 to 110 nm thick having a low refractive index.

(20) In the preferred embodiment, this hybrid layer is formed of a mixture of silica (SiO.sub.2) and an amorphous copolymer of 2,2-bistrifluoromethyl-4,5,difluoro-1,3-dioxole and tetrafluoroethylene, commercially available as Teflon AF 1600 or Teflon AF 2400. These amorphous fluorinated copolymers are soluble in perfluorinated solvents and their structural formula is as follows (the ratio b:a, i.e. the dioxole/tetrafluoroethylene ratio, is 2 for AF 1600 and 4.56 for AF 2400):

(21) ##STR00001##

(22) The above compounds are deposited by co-evaporation in a vacuum (physical vapor-phase deposition in a vacuum) using the machine 10 shown in FIG. 1 so that they are present in constant proportions throughout the thickness of the low index layer 21d.

(23) In practice, the silica is evaporated by the electron gun 13 and the amorphous copolymer is evaporated by means of the Joule effect by the Joule effect evaporation source 14.

(24) Conventionally, an anti-soiling layer is further deposited onto a multilayer film of the above kind.

(25) In the case of the present invention, the deposition of a layer of this kind is no longer essential in that the hybrid outside layer already provides this anti-soiling function.

(26) Moreover, the volume concentration of amorphous fluorinated copolymer in the hybrid layer 21d is kept around 30% in this preferred embodiment.

(27) In this regard, it should be pointed out that Teflon AF 2400 is liquefied by the Joule effect evaporation source 14 before it is evaporated by the same source.

(28) Moreover, as already stated hereinabove, in other embodiments the silica may be replaced by magnesium fluoride (MgF.sub.2) and the amorphous fluorinated copolymer referred to above may be replaced by polytetrafluoroethylene in particular. In a preferred embodiment, these amorphous fluorinated copolymers may be replaced by Teflon MP 1600 taking the form of microparticles with an average size of 0.2 mm.

(29) In a first example, the hybrid layer was obtained by co-evaporation of silica and polytetrafluoroethylene (Teflon MP 1600) with a constant proportion of Teflon equal to 30%.

(30) The substrate 17 obtained in the above manner was subjected to the N10 blows test described in the international patent application WO 99/49097. That test loads the adhesion of the thin layers deposited onto an organic substrate. It has been found that the multilayer film 21 has good adhesion properties and in particular that the hybrid layer 21d adheres in an entirely satisfactory manner to the underlying ZrO.sub.2 layer.

(31) The substrate 17 was also subjected to the steel wool test, whereby five two-way strokes with extra fine steel wool are carried out on a coated substrate in order to assess the resistance to scratching thereof. This test also showed that the antireflection multilayer film 21 had entirely satisfactory resistance to scratching. Furthermore, measuring the refractive index of the hybrid layer reveals a highly beneficial value of 1.42 at a wavelength of 630 nm. It will also be appreciated that the hybrid layer 21d obtained by the method of the invention has a homogeneous structure, is of constant refractive index throughout its thickness, and is perfectly transparent in the visible spectrum.

(32) In a second example, by controlling the rates of deposition, a hybrid layer is obtained whose index varies in linear fashion from 1.46 to 1.33 from the substrate toward the surface, corresponding to volume proportions of Teflon from zero to around 80%.

(33) More generally, it has been proved that the method of the invention produces antireflection multilayer films having thin layers with highly satisfactory characteristics from the points of view of adhesion, resistance to scratching, corrosion resistance and ease of cleaning.

(34) Of course, the present invention is not limited to the embodiment described and shown, and encompasses any variant execution thereof.