CN1688739A - Method for obtaining a thin, stabilized fluorine-doped silica layer, resulting thin layer and use thereof in ophthalmic optics - Google Patents

Method for obtaining a thin, stabilized fluorine-doped silica layer, resulting thin layer and use thereof in ophthalmic optics Download PDF

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CN1688739A
CN1688739A CNA038239000A CN03823900A CN1688739A CN 1688739 A CN1688739 A CN 1688739A CN A038239000 A CNA038239000 A CN A038239000A CN 03823900 A CN03823900 A CN 03823900A CN 1688739 A CN1688739 A CN 1688739A
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layer
sio
nanometer
silicon
thickness
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CN100473754C (en
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K·谢勒
P·拉康
P·鲁瓦松
R·博斯曼
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EssilorLuxottica SA
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Essilor International Compagnie Generale dOptique SA
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    • 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
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/10—Glass or silica
    • G02B1/105—
    • 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
    • G02B1/113—Anti-reflection coatings using inorganic layer materials 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
    • G02B1/14—Protective coatings, e.g. hard coatings

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  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
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  • Engineering & Computer Science (AREA)
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  • Surface Treatment Of Optical Elements (AREA)
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Abstract

The invention concerns a method for forming on a SiOxFy layer a protective coating of silica SiO2 and/or of a metal oxide by ion-assisted vapour phase deposition, consisting in bombarding the layer being formed with a beam of positive ions formed from a rare gas, oxygen or a mixture of both or more of said gases by sputtering a silicon or metal layer followed by a step which consists in oxidizing the silicon or metal layer. The invention is useful for producing antireflection coatings.

Description

Make the method for stable fluorine-doped silica thin layer, the thin layer of making and the application in opticianry thereof
The present invention relates generally to and makes stable fluorine-doped silica thin layer (SiO xF y) method, this thin layer and the application in opticianry thereof, more particularly, relate to the method for making the multi-layer anti-reflection coating be used for ophthalmic lens.
At optical field, more specifically, in the opticianry field, be extensive use of silicon dioxide base (SiO 2) thin layer.This silicon dioxide base thin layer is used in the antireflecting coating especially.This antireflecting coating is to be made by the inorganic materials of multiple-level stack traditionally.These multilayer anti-reflectives generally include one or more layers layer with low-refraction that is made of the silicon dioxide base thin layer.
The deposition technique of this silicon dioxide base thin layer is very various, is a kind of the most frequently used technology but deposit by vacuum-evaporation.These SiO 2The base thin layer has very gratifying mechanical property and the wavelength of about 630 nanometers is about 1.48 specific refractory power usually.
Yet, for the optical property that can improve the antireflection lamination and produce novel antireflection lamination system, need when keeping its gratifying mechanical property, can reduce the specific refractory power of this low-index layer.
In order to solve this technical problem, proposed to generate porous silica (SiO 2) layer, promptly can catch air in this layer.
Regrettably, except using complicated manufacturing technology, the layer that makes thus also has unsafty mechanical property, and it is lower than the mechanical property of traditional silicon dioxide thin layer.
In addition, in other technical field, particularly in microelectronic, known use fluorine-doped silica thin layer.In this case, the effect of expectation is the reduction of static permittivity.
These layers can obtain by carry out the auxiliary chemical Vapor deposition process of plasma body on silicon chip.
The problem relevant with the use of this fluorine-doped silica layer is that their character can pass in time and changes.
Patent application EP0975017 discloses the SiO that contains useful silicon oxynitride (SiON) coating 2/ SiO xF yThe semi-conductor of mixolimnion its objective is to prevent that fluorine is diffused into these mixolimnion outsides.
This patent application is more specifically pointed out, at SiO 2/ SiO xF yOnly deposit one deck SiO on the mixolimnion 2Layer can not prevent that fluorine is diffused into described mixolimnion outside, and this diffusion may take place in being up to the dark silicon dioxide layer of hundreds of nanometer.
Significantly, can change the character of fluorine-doped silica layer and on two-layer interface, produce attachment issue like this.
Therefore, an object of the present invention is to provide a kind of manufacturing SiO xF yFluorine-doped silica is stablized the method for thin layer, and more specifically, this layer has low-refraction, and stability and durability also has at least and the suitable mechanical property of layer of the prior art.
Another object of the present invention provides a kind of stable fluorine-doped silica layer, more specifically, and aforesaid fluorine-doped silica layer.
Another object of the present invention provides a kind of multi-layer anti-reflection coating, and wherein one deck low-index layer is stable fluorine-doped silica layer at least.
Another purpose of the present invention provides a kind of ophthalmic lens with antireflecting coating for example mentioned above.
According to the present invention, make stable SiO xF yLayer comprises the vapour deposition process by Assisted by Ion Beam or then the method that described metal or silicon layer carry out oxidation step is made SiO by cathode sputtering metal or silicon layer xF yLayer covers silicon dioxide layer of protection and/or metal oxide.
Assisted by Ion Beam is meant at SiO 2In silicon-dioxide and/or the metal oxide layer formation process, use by rare gas, by oxygen or the positively charged ion bundle bombardment SiO that generates by the mixture of two or more these class gases 2Silicon-dioxide and/or metal oxide layer.
The example that can be used as the metal oxide of supercoat material within the scope of the invention comprises:
Al 2O 3(alumina), BaTiO 3, BI 2O 3, B 2O 3, CeO 2, Cr 2O 3, Ga 2O 3, GeO 2, Fe 2O 3, HfO 2, In 2O 3, indium-tin-oxide, La 2O 3, MgO, Nd 2O 3, Nb 2O 5, Pr 2O 3, Sb 2O 3, Sc 2O 3, SnO 2, Ta 2O 5, TiO, TiO 2, TiO 3, WO 3, Y 2O 3, Yb 2O 3, ZnO, ZrO 2
Preferred within the scope of the invention protective layer is silicon-dioxide and/or alumina layer, preferred SiO 2Silicon dioxide layer.
Generally speaking, recommend the low thickness protective layer of deposition and than low-refraction (very near SiO xF yThe specific refractory power of layer) material.
Protective layer is preferably 2 to 40 nanometer thickness, preferred 5 to 30 nanometer thickness, more preferably 5 to 20 nanometer thickness.
If the thickness of protective layer is very low, just can use the higher protective layer of specific refractory power.
More properly, if the thickness of protective layer is higher than 15 nanometers, the specific refractory power of protective layer preferably is lower than 1.65.
If protective layer is 10 to 15 nanometer thickness, can use specific refractory power up to 2 material material as protective layer.
Yet, generally speaking,, preferably use specific refractory power to be less than or equal to 1.65, to be more preferably less than or to equal 1.6, most preferably be less than or equal to 1.55 material as the material of protective layer.
In optimum implementation of the present invention, the specific refractory power of protective layer material is less than or equal to 1.50.
Above-mentioned specific refractory power is in 550 nano wave lengths and the specific refractory power under 25 ℃.
It should be noted that silicon-dioxide and/or metal oxide deposition especially, can obtain SiO by low-down thickness (be usually less than 40 nanometers, and generally be about 10 nanometers or lower) xF yThe protection of the excellence of layer.
Because protective layer thickness is very low, the latter can not change SiO nocuously xF yTherefore the optical property of layer can make full use of SiO xF yThe antireflection lamination that the low-refraction obtained performance of layer improves to some extent than prior art.
Be used for the auxiliary gas of ion and be preferably argon, xenon and oxygen, more preferably argon and xenon.
Can make SiO by any known method xF yThe fluorine silicon oxide layer.
At article " by the SiO of ion beam assisted depositing method preparation xF yThe character of thin layer " (Characteristics of SiP xF yThin Films Prepared by Ion Beam AssistedDeposition) (OSA Technical Digest, Optical Interference Coatings, 1998.6) in a kind of method is disclosed, F.J.Lee and C.K.Hwangbo have specifically described the SiO that on glass and silicon substrate deposit thickness is about 600 nanometers xF yFilm.Basic vacuum pressure is 1.2 * 10 -4Pa, base material temperature are about 150 ℃.In the chamber, exist under the situation of oxygen and utilize electron beam evaporation silicon, and in the sedimentary forming process of silicon oxide, use with CF 4Gas is that this silicon oxide of polyfluorohydroearbon ion beam bombardment raw material, that generate by ion gun deposits.
Also can use ion auxiliary sedimentation altogether.This method is: evaporation silicon and/or silicon oxide, and the silicon and/or the silicon oxide of evaporation be deposited on the substrate surface to form silicon oxide layer, the positively charged ion bundle of using the mixture by polyfluorohydroearbon compound or these compounds to form in its forming process bombards this silicon oxide layer, but also uses the positively charged ion bundle that is formed by rare gas or rare gas mixture to bombard this silicon oxide layer in its forming process.
In order to form silicon oxide layer, can use the following silicon oxide of molecular formula: the SiO of x＜2 x, SiO 2Or SiO x/ SiO 2Mixture.The preferred SiO that uses 2As the SiO that uses x＜2 xOr SiO x/ SiO 2During mixture, surrounding medium must contain oxygen O 2
The polyfluorohydroearbon compound can be straight chain, side chain or the ring-type perfluorocarbon compound, is preferably straight chain or ring-type perfluorocarbon compound.
The straight chain perfluorocarbon compound can comprise CF 4, C 2F 6, C 3F 8, C 4F 10The ring-type perfluorocarbon compound can comprise C 3F 6And C 4F 8Preferred straight chain perfluorocarbon compound is CF 4, preferred ring compound is C 4F 8
Also can use the mixture of perfluorocarbon compound.
The polyfluorohydroearbon compound also can be hydrofluorocarbons (hydrogeno fluorocarbon), is preferably selected from CHF 3, CH 2F 2, C 2F 4H 2Hydrofluorocarbons also can be straight chain, side chain or cyclic.
Certainly, can use the mixture of perfluoro-carbon and hydrofluorocarbons compound.
Rare gas is preferably selected from xenon, krypton and their mixture.Preferred rare gas is xenon.If desired, can use oxygen that common booster action is provided.
In the deposition process of fluorine-doped silica layer, the temperature of base material is usually less than 150 ℃, preferably is less than or equal to 120 ℃, and more preferably 30 ℃ are not waited to 100 ℃.
Preferably, the temperature of base material is 50 to 90 ℃ and does not wait.
At pressure is 10 -2To 10 -3Carry out SiO in the vacuum chamber of Pa xF yThe deposition of layer.If desired, can in layer deposition process, in vacuum chamber, import oxygen.
Can be as deposit fluorine silicon oxide layer: the cathode sputtering silicon layer, silicon layer is carried out oxidation step existing under the situation of fluorinated gas then, for example, there is CF 4And so on the situation of fluorinated gas under utilize oxygen plasma to carry out oxidation.
The method of vapour deposition is preferred than cathode sputtering.
The thickness of fluorine-doped silica layer is generally 5 to 300 nanometers, is preferably 30 to 160 nanometers, more preferably 30 to 100 nanometers.
The fluorine-doped silica layer of making has 1.38 to 1.44 refractive index n (for the radiation in 25 ℃ of following wavelength X=632.8 nanometers) usually.
Preferably, be total to auxiliary situation deposit SiO without any ion xF yLayer.
Heavily stressed by having usually in the auxiliary and sedimentary layer of the ion that uses rare gas or oxygen, this mechanical property to them is harmful, and when these layers are lamination a part of, can be harmful to its overall performance.
Yet in the present invention, it is minimum that low-down protective layer thickness can make this effect reduce to, and observed, and contains through the stable SiO of protective layer xF yThe antireflection lamination of layer has the very desirable mechanical property that is equivalent to traditional antireflection lamination.
Therefore the present invention also relates to and contains at least one deck according to SiO of the present invention xF yStablize the multi-layer anti-reflection coating of thin layer.
Such as is known to persons skilled in the art, traditional antireflecting coating is by single layer stack with low-refraction (LI) or multilayer laminated making; For example high refractive index (HI)/low-refraction (LI) is double-deck, (LI/HI/LI) three layers, (HI/LI/HI/LI) four layers, and their specific refractory power and thickness are through suitably selecting, to obtain the antireflection effect.
Usually, low-index layer is based on SiO 2Silicon-dioxide.
The used material with high refractive index (HI) is specific refractory power more than or equal to 1.55, be preferably greater than or equal 1.60, more preferably greater than or equal 1.65 material.
The used material with low-refraction (LI) preferably has the specific refractory power that is less than or equal to 1.52, preferably is less than or equal to 1.50.
Generally speaking, unless otherwise specified, said specific refractory power is the specific refractory power under 550 nano wave lengths and 25 ℃.
Each layer in the antireflection lamination also can be made by the oxidation step of the cathode sputtering of metal or silicon and metal subsequently or silicon.Use the cathode sputtering method, can make all layer and SiO in the lamination by changing splash-proofing sputtering metal simply and in oxidation step, in oxygen, importing the fluorine precursor gases when needed with individual equipment xF yLayer and SiO 2Or metal oxide protective layer.
The method and apparatus of making metal oxide and silicon dioxide layer by cathode sputtering is known.Can mention can be available from the Metamode of OCLI Corporation Technology and Applied VisionRFX10 sputtering equipment.
According to the present invention, use stable SiO xF y/ SiO 2And/or metal oxide layer is made low-index layer.
In the laminated coating that contains two-layer or multilayer low-index layer, one deck low-index layer is by SiO of the present invention at least xF y/ SiO 2And/or the metal oxide bilayer is made.Preferably, with SiO of the present invention xF y/ SiO 2And/or the metal oxide bilayer is used for the low-index layer of lamination higher position, just from the nearest layer of air, because this is the situation that antireflection is improved fullest.
The antireflecting coating that contains four layers of HI/LI/HI/LI from substrate surface, the thickness of these layers preferably changes according to following each in proper order from substrate surface:
HI:10 to 40 nanometer
LI:10 to 55 nanometer, preferred 10 to 45 nanometers
HI:30 to 155 nanometer, preferred 40 to 150 nanometers, more preferably 120 to 150 nanometers
LI (SiO xF yLayer): 70 to 110 nanometers
Protective layer: 2 to 50 nanometers.
Antireflecting coating of the present invention also can contain from substrate surface according to following each the order six layers: HI/LI/HI/LI/HI/LI.
In this case, the thickness of described each layer preferably changes according to following each in proper order from substrate surface:
HI:10 to 30 nanometer
LI:10 to 55 nanometer, preferred 10 to 45 nanometers
HI:10 to 160 nanometer
LI:10 to 45 nanometer
HI:35 to 170 nanometer
LI:70 to 95 nanometer
Protective layer: 2 to 40 nanometers.
Antireflecting coating of the present invention can obtain the reflection R m ( average reflection 400 and 700 nanometers between) lower than prior art coating with suitable lamination.
Antireflecting coating of the present invention have usually be lower than 0.6%, preferably be lower than 0.5%, more preferably less than or equal 0.4% Rm (described antireflecting coating is near a side of the base material that applies).
Can obtain Rm and be lower than 0.3% antireflecting coating.
The definition of reflection coefficient under setted wavelength (p) and Rm (average reflection between 400 and 700 nanometers) is well known by persons skilled in the art, and record to some extent in standard ISO/WD 8980-4 (test specification of antagonistic reflex coating and method).
SiO of the present invention xF y/ SiO 2And/or the metal oxide bilayer, and the antireflecting coating that contains this bilayer, can be deposited on any suitable substrates, for example silicon, unorganic glass or synthetic glass base material, plexiglass lens for example, these base materials optionally scribble wear-resisting or the anti-impact film, or other film of using of tradition.
Certainly, antireflecting coating of the present invention can contain the coating that is useful on its surface properties of change, for example antifouling hydrophobic coating.These are the silicon fluoride section bar material of several nanometer thickness normally.
The rest part of specification sheets with reference to the accompanying drawings, they are represented respectively:
Fig. 1 implements the equipment synoptic diagram that the inventive method is used;
Fig. 2, the schematic top view of the equipment of Fig. 1;
Fig. 3, deposit antireflecting coating of the present invention and the antireflecting coating that can buy after, the function relation figure of reflection coefficient and wavelength;
Fig. 4, the reflection coefficient of antireflecting coating of the present invention and the funtcional relationship of wavelength and time dependent figure thereof;
Fig. 5 is used for the Metamode of depositing metal oxide layer The schema of technology.
Fig. 6 is used to implement Metamode The top view of the Applied Vision sputtering equipment of technology.
Equipment by the deposit film of Assisted by Ion Beam shown in Fig. 1 and 2 is standard equipment.This equipment comprises vacuum chamber 1, first end 2 that is connected with one or more vacuum pumps, and another opposite end comprises door 3.Can in this chamber, the position near the end 2 that links to each other with vacuum pump be installed by cold-trap 4.In chamber 1, electron beam gun 5 is installed, it contains and is useful on the crucible 6 that holds silicon-dioxide to be evaporated.Base material A to be coated is placed near on the bearing of quartz crystal microbalance 9.If desired, can be to chamber 10 supply oxygens.Utilize hot-cathode pressure warning unit 8 measuring chamber internal pressures.The supply line 11 of ion gun 7 links to each other with three feeding gas driving mechanisms, and these three feeding gas driving mechanisms can be simultaneously or had the gas of required character and/or flow velocity independently to the ion gun supply.
In this example, vacuum chamber is to be suitable for reaching 5 * 10 -5The LeyboldHeraeus chamber of the basic vacuum of Pa, ion gun are MARK II Commonwealth rifles, and electron beam gun is a Leybold ESV rifle.
In the feeding gas driving mechanism of ion gun, use the BROOKS mass flow controller for argon gas, itself is subjected to the control of MARK II controller.What be used to supply with xenon and polyfluorohydroearbon compound is the mass flow controller of many Gas controllers MKS 647 B and so on, wherein can be to the character and the flow velocity programming of multiple gases.
For not using the auxiliary altogether SiO that carries out of any ion xF yDeposition also can be used identical equipment.
Can on base material, deposit stable fluorine-doped silica layer of the present invention according to following manner:
Chamber 1 is placed 2 * 10 -3(measure) under the vacuum of Pa by hot-cathode pressure warning unit 8.Cause ion gun 7 with argon gas, import CF with selected flow velocity then 4Gas (and non-essential Xe and so on rare gas) also interrupts argon gas stream (or be made as selected flow velocity with it).With the silicon-dioxide (SiO in the electron beam gun preheating crucible 6 2) particle.When in the chamber, using oxygen, can it be imported with controlled flow velocity.Electron beam gun 5 and ion gun 7 all are furnished with connector (plug), and the connector of electron beam gun and ion gun is opened simultaneously.Adjust deposit thickness by near the quartz crystal microbalance the substrate sample 9.When obtaining required SiO xF yDuring layer thickness, two connectors are all closed, and the emission of electron beam gun 5 reduces, and import Ar gas or Xe gas (or O with selected flow velocity in ion gun 7 2Gas), stop CF then 4Stream.When the anode voltage of ion gun 7 and anodic current were stablized, two connectors were all opened, thus at Assisted by Ion Beam deposit SiO 2Layer (SiO 2IAD).When obtaining selected SiO 2During the IAD layer thickness, two connectors are all closed, and cut off electron beam 5 and ion gun 7, stop supplies all gases, and the vacuum in the open chamber 1.
If use Ar/CF 4Or Xe/CF 4Or O 2/ CF 4Mixture deposition SiO xF yLayer is when reaching selected SiO xF yDuring layer thickness, stop CF 4Stream is also adjusted Ar or Xe or O 2Selected flow velocity.Deposit SiO thus 2The IAD layer.When reaching selected SiO 2During the IAD layer thickness, two connectors are all closed, and cut off electron beam and ion gun, stop supplies all gases, and the vacuum in the open chamber 1.
Certainly, for deposition SiO xF yLayer can not use ion auxiliary altogether.In this case, should in ion gun 7, not import any rare gas.
The following example is set forth the present invention for example.
By operating as mentioned above, the silicon sample of flat surface is coated the fluorine-doped silica layer.
Sedimentation rate is constant in 0.8 nm/sec.
The comparative example A
In this Comparative Examples, do not deposit any protective layer.SiO xF yThe mode of deposition and the thickness of layer are as shown in the table.
SiO xF y The mode of deposition of layer
Reference number Thickness SiO xF y[nanometer] ?CF 4Flow velocity [cm 3/ minute] Anodic current [A] Anode voltage [V]
The comparative example A ??230 ?3 ??0.7 ??100
Embodiment 1 to 6
CF 4
(CF 4, Ar, Xe in Mark II, O 2Around)
??SiO xF yThe mode of deposition of layer The mode of deposition of protective layer
??N° Thickness SiO xF y[nanometer] Flow velocity CF 4??[cm 2/min] Gas flow rate [cm 3/min] ??O 2Flow velocity [cm 3/min] Anodic current [A] Anode voltage [V] Barrier layer thickness [nanometer] Gas flow rate [cm 3/min] Anodic current [A] Anode voltage [V]
??1 ??185 ??2.5 ??4 ??0.4 ??100 ??95 ??1.8 * ??0.6 ??100
??2 ??185 ??2.5 ??0.4 ??100 ??45 ??1.5 * ??0.6 ??100
??3 ??195 ??2.5 ??1.7 * ??4 ??1.9 ??100 ??10 ??1.7 * ??0.6 ??100
??4 ??190 ??3 ??0.7 ??120 ??45 ??1.8 * ??0.6 ??100
??5 ??190 ??2 ??7 + ??2.8 ??100 ??45 ??6 + ??1 ??100
*Xe， +Ar
C 2F 6
(C 2F 6With Xe in Mark II)
??N° Thickness SiO xF y[nanometer] ??C 2F 6Flow velocity [cm 2/min] Anodic current [A] Anode voltage [V] Barrier layer thickness [nanometer] Xe gas flow rate [cm 3/min] Anodic current [A] Anode voltage [V]
??6 ??210 ??3 ??0.7 ??100 ??45 ??0.6 ??0.6 ??100
Measure gained SiO at 25 ℃ by elliptical polarized light spectrum (ellipsometry spectra) xF yLayer is for the specific refractory power of λ=632 nanometers.
By in the infrared spectra of this layer, whether having 3400 to 3600cm -1Between the peak determine SiO xF yWhether there is water in the layer.
The results are shown in the following table:
The comparative example A ??1 ??2 ??3 ??4 ??5 ??6
The post-depositional time ??n ??(SiO xF y) to 632 nanometers There is water ??n ??(SiO xF y) to 632 nanometers There is water ??n ??(SiO xF y) to 632 nanometers There is water ??n ??(SiO xF y) to 632 nanometers There is water ??n ??(SiO xF y) to 632 nanometers There is water ??n ??(SiO xF y) to 632 nanometers There is water ??n ??(SiO xF y) to 632 nanometers There is water
10 minutes ??1.396 Not
1 hour ??1.400 Not Not Not Not Not ??1.434 Not
2 hours ??1.403 ??1.411 Not ??1.417 Not ??1.421 Not ??1.385 Not ??1.404 Not
3 days ??1.440 Be ??1.412 Not ??1.415 Not ??1.422 Not ??1.384 Not ??1.400 Not
January ??1.458 Be ??1.418 Not ??1.421 Not ??1.383 Not ??1.394 Not
3.5 month ??1.432 Not
June ??1.404 ??1.416 Not ??1.424 Not ??1.400 Not
August ??1.388 Not
For unprotected SiO xF yLayer increases to 1.46 (SiO through a month specific refractory power from 1.40 2And for shielded layer of the present invention, specific refractory power all not have change in the some months at least specific refractory power).
Embodiment 7
Embodiment 7 is embodiment of antireflecting coating, and it can use SiO of the present invention xF y/ SiO 2Layer carries out.
The base material that forms this antireflecting coating thereon is the Orma that scribbles epoxy silane hydrolyzate type wear resistant paint Base material (diallyl carbonic acid glycol ether ester group material).Used wear resistant paint is following making: the HCL that dropwise adds 80.5 parts of 0.1N in the solution that contains 224 parts of γ-Huan Yangbingyangbingjisanjiayangjiguiwans and 120 parts of dimethyldiethoxysilanes.Hydrating solution was at room temperature stirred 24 hours, add the methanol solution of 718 part of 30% colloidal silica, 15 parts of aluminium acetylacetonates and 44 parts of ethyl cellosolves then.
Add low quantity of surfactant.
The base material that scribbles this lacquer carries out prebake step 15 minute at 60 ℃, places 3 hours in 100 ℃ steaming vessel then.
Coating among the embodiment 7 is formed by multiple-level stack, begins the bottom that contacts to base material from higher level, comprising:
-SiO 2The IAD layer, 10 nanometer thickness;
-SiO xF yLayer, 92 nanometer thickness (n=1.42);
-ZrO 2Layer, 42 nanometer thickness;
-SiO 2Layer, 41 nanometer thickness;
-ZrO 2Layer, 25 nanometer thickness;
This coating have 0.5 Rm and 0.4 Rv (such as among the above-mentioned ISO WD 8930-4 definition).
Make SiO as mentioned above with following operational condition xF yAnd SiO 2IAD layer (blocking layer).
??SiO xF yThe mode of deposition of layer The mode of deposition of protective layer
Embodiment Thickness SiO xF y[nanometer] Flow velocity CF 4??[cm 2/min] Ar flow velocity [cm 3/min] ??O 2Flow velocity [cm 3/min] Anodic current [A] Anode voltage [V] Barrier layer thickness [nanometer] Ar flow velocity [cm 3/min] Anodic current [A] Anode voltage [V]
??7 ??92 ??2.0 ??6 ??2.2 ??100 ??10 ??6 ??1 ??100
Other layer in the lamination is that gas phase is sedimentary under conventional conditions well known by persons skilled in the art.
On the antireflection lamination of embodiment 7, carried out " n * 10 are impacted " test.The cycle number that lamination can bear is at least 12.
Fig. 4 has deposited the coating of embodiment 7 and has deposited commercial CRIZAL on identical base material The function relation figure of the reflection coefficient of substrate surface and wavelength after the antireflecting coating;
Fig. 5 be after deposition, back 20 days of deposition and deposit the reflection coefficient of coating of back 3 months embodiment 7 and the function relation figure of wavelength.
In those figure, but block curve representative is the sort of to be similar to the coating of embodiment 7 reflection coefficient of the coating by conventional art moulding well known by persons skilled in the art and the function relation figure of coating wavelength.
As can be seen, antireflecting coating of the present invention has the durable stability of the excellence that can compare with conventional coatings.
Measuring method and test are described
N * 10 shock tests
N * 10 shock tests have been described in patent application WO/9949097.
In brief, using fabric through the lens surface of anti-reflex treated and colloid is being pressed on the fabric.Make natural gum and base material relative movement then according to seesawing.A circulation is represented and is seesawed for 10 times.
The result represents the lens of process anti-reflex treated in the cycle index that occurs can bearing before any defective.
The refractometry method
Usually, measure specific refractory power by the ellipsometry on the silicon planar disk.
For the layer among the comparative example A, use SENTECHSE 400 ellipsometers of SENTECH Corporation calibration.
Measure under the wavelength of 632.8 nanometers with 70 ° of angles.Use following model, by bidimensional Newton method by tan Ψ and cos Δ calculated thickness:
?SiOF(n，t)
Natural SiO 2(2 nanometers, n=1.457)
?Si(n＝3,881，k＝0.020)
For SiO xF yLayer+protection (stopping) layer uses SOPRA GESP 5VASE variable-angle ellipsometer.This equipment is calibrated according to the program that SOPRA recommends.For 65 ° of three input angles, 70 ° and tan Ψ and the cos Δ spectrum of 75 ° of measurements between 300 and 850.Utilization uses following model to carry out the sphere coupling on 3 spectrum according to the Return Law of Levenberg-Marquardt.
??SiO 2(t 1，a 1)
??SiOF(t 2，A 2)
Natural SiO 2
??Si
Si and SiO 2The dispersion plot of (natural) comes from the file that SOPRA provides.For SiOF and SiO 2The blocking layer supposes that dispersion plot follows Cauchy law (n=A+B λ 2=C/ λ 4, λ is a micron), wherein B=0.003 and C=0.
The planar disk characteristic
If { 100}, 500 micron thickness, p doping (B), resistivity＞100 Ω cm, polishing both surfaces; (measuring for IR) cuts 6 samples on 50 millimeters Φ disks; Each sample--〉qqs (～3) cm 2
The following example has been described feasible antireflecting coating, and it contains through the stable SiO of protective layer of the present invention (in the blocking layer) xF yLayer has also been described their optical property.
By measuring optical property (reflection coefficient) from the FILMSTAR DESIGN business software of FTG Software Associates-Princetown New Jersey and being shown in hereinafter.
Do not use above-mentioned software, according to well known by persons skilled in the art, more specifically, according to the thin layer optical ultimate principle that proposes among works " Thin Film Filter " (Thin film optical filters) the Adam Higer Ltd-Bristol 1969H.A.Mc Loed-Professor of Optical Sciences-University of Arizona-Tuckson, also can measure the optical property of these laminations by simple calculating.
In the following example and table, unless otherwise specified, the unit of layer thickness is nanometer (nm).
Similarly, unless otherwise specified, specific refractory power is the specific refractory power under 550 nanometers, 25 ℃.
Material used among these embodiment is as follows:
The material label Material character Specific refractory power
??O ??SiO xF y ??1.423
??N ??SiO xF y ??1.388
??Q ??SiO 2 ??1.473
??Z ??ZrO 2 ??1.997
??A ??Al 2O 3 ??1.646
Embodiment 8 to 10
Embodiment 8 to 10 exemplifies three kinds and is deposited on based on CR39 ORMA Antireflection lamination of the present invention on glass.
Use successively respectively is that the silicon dioxide layer, alumina layer, zirconia layer of 10 nanometer thickness is as protective layer.
Begin to describe lamination from the bottom that contacts with base material until higher level (LI-protective layer).
Embodiment 8 Embodiment 9 Embodiment 10
Layer character Material Thickness Material Thickness Material Thickness
HI ????Z ????13 ??Z ????13 ??Z ????33
LI ????Q ????38 ??Q ????38 ??Q ????21
HI ????Z ????135 ??Z ????135 ??Z ????67
LI ????N ????82 ??N ????76 ??N ????68
Protective layer ????Q ????10 ??A ????10 ??Z ????10
Rm (%) lamination ????0.21 ??0.26 ??0.53
Above-mentioned table has been illustrated the following fact: in order to obtain minimum Rm value, need to use the relatively low protective layer of specific refractory power, more specifically, based on SiO 2Protective layer.
Yet as can be seen, even use the blocking layer of high refractive index, as long as this layer thickness lower (10 nanometer) also can obtain low Rm value.
Embodiment 11 to 17
These examples have been described antireflecting coating or the lamination that contains four layers and a protective layer, and protective layer is sedimentary last one deck.
Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17
Layer character Material Thickness (layer) [nanometer]
HI ??Z ??40 ??10 ??13 ??14 ??19 ??25 ??26
LI ??Q ??16 ??31 ??45 ??25 ??38 ??39 ??10
HI ??Z ??64 ??126 ??137 ??117 ??150 ??40 ??94
LI ??O ??84 ??76 ??82 ??70 ??84 ??94 ??78
Protective layer ??Q ??10 ??10 ??10 ??10 ??10 ??10 ??10
Rm (％) ??0.5 ??0.4 ??0.42 ??0.49 ??0.47 ??0.47 ??0.45
Embodiment 18 to 24
Embodiment 18 to 24 has exemplified identical with embodiment 11 to 17 types but has used low-refraction SiO xF yLayer (N layer) is as the antireflection lamination of low-index layer (being sedimentary last one deck).
Embodiment 18 Embodiment 19 Embodiment 20 Embodiment 21 Embodiment 22 Embodiment 23 Embodiment 24
Layer character Material 1 Thickness (layer) [nanometer]
HI ????Z ????40 ????10 ????10 ????20 ????12 ????19 ????26
LI ????Q ????18 ????20 ????55 ????37 ????29 ????50 ????10
HI ????Z ????59 ????127 ????136 ????155 ????123 ????30 ????95
LI ????N ????86 ????82 ????83 ????85 ????70 ????100 ????78
Protective layer ????Q ????10 ????10 ????10 ????10 ????10 ????10 ????10
Rm (％) ????0.43 ????0.38 ????0.46 ????0.47 ????0.44 ????0.44 ????0.40
Embodiment 25 to 28
At embodiment 25 to 28, the thickness on blocking layer is changed.
Embodiment 25 Embodiment 26 Embodiment 27 Embodiment 28
Layer character Material Thickness (layer) (nanometer)
HI ????Z ????13 ????13 ????13 ????13
LI ????Q ????38 ????38 ????38 ????37
HI ????Z ????134 ????135 ????135 ????135
LI ????N ????92 ????82 ????63 ????41
Protective layer ????Q ????2 ????10 ????25 ????45
Rm (％) ????0.2 ????0.21 ????0.27 ????0.44
Embodiment 29 to 31
Embodiment 29 to 31 has described the antireflection lamination that contains six layers and protective layer (sedimentary last one deck).
Embodiment 29 Embodiment 30 Embodiment 31
Layer character Material Thickness (layer) (nanometer)
??HI ??Z ??16 ??10 ??10
??LI ??Q ??33 ??66 ??10
??HI ??Z ??157 ??23 ??10
??LI ??Q ??17 ??41 ??11
??HI ??Z ??150 ??139 ??109
??LI ??O ??81 ??79 ??78
Protective layer ??Q ??10 ??10 ??10
??Rm(％) ??0.29 ??0.40 ??0.39
As mentioned above, depositing metal oxide or silicon oxide protective layer and SiO xF yThe another kind of method of layer is negative electrode sprayed deposit or sputter, carries out oxidation step then or carry out oxidation in the presence of fluorinated gas.
Preferably, depositing metal oxide or silicon layer carry out according to the following step successively:
1) by cathode sputtering metal refining or silicon thin layer.
2) with oxygen, the thin layer preferably made with the form oxidation of plasma active,
And repeat these operations on demand for several times to obtain required protective layer thickness.
Deposition step 1) with oxidation step 2) preferably carry out at two different treatment zones in part.
The sputtering technology of metal or silicon thin layer (step 1)) is direct-current discharge (dc sputter) and carrying out under vacuum normally.
According to this technology, with the direct-current machine of number kV to by target or the negative electrode power supply for the treatment of that deposition material (metal or silicon) is made.Base material to be coated is placed on the anode, with relative by water cycle refrigerative target.After setting up vacuum, to wherein importing gas (the most frequently used is argon gas), and target applied negative voltage to cause plasma body.The positively charged ion that exists in the plasma body quickens to target, launches target atom.Ion impact also can be launched some electronics, promptly so-called secondary electron, and they quicken and collide with gas atom, and plasma body can be kept.In a single day target atoms penetrates, and just is deposited on and also forms thin layer on the base material thus.
Other more complicated cathode sputtering technological selection is used to carry out the present invention.
Therefore, preferably, use the anode of the independent power supply that does not contact with base material.
Still preferably, use magnetron cathode.These negative electrodes are diode-type negative electrodes, and wherein magnetic field is an electron trap.Electric current with all vertical direction of electric field and magnetic field on move according to the cycloid path.Thus, they obtain higher energy, and, more importantly, its move distance much longer than in the continuous diode technology.Ionizing collision is therefore more, and the ion current density on the target also so higher.
At works " deposition technique handbook (the Handbook of depositiontechnologies for films and coatings) Science that is used for film and coating, Technology and Applications, Rointan F.Bunshah 2 NdMagnetron has more specifically been described among the Edition 1994pp280-292.
As for above-mentioned steps 2), use oxygen plasma or oxygen-fluorinated gas mixtures (CF for example 4).Oxygen plasma becomes very active Sauerstoffatom with molecule breaking.The generation of active oxygen atom has strengthened the oxidation of base material.
The example of preferred cathode sputtering method is the Metamode from OCLI TMMethod, it comprises all above-mentioned features, its schema is shown among Fig. 5.
With reference to Fig. 5, use Metamode It is to carry out in two different chambers that method obtains metal oxide layer, and promptly the cathode sputtering chamber 1.At this, to the lens 4 that place on the pallet 5, pallet 5 is installed on the rotary-tray 6 from the metal sputtering of negative electrode 3.Depositing metal layers as mentioned above.
In case deposited metal level, the lens 4 that will scribble metal level with regard to rotary-tray 6 are delivered in the oxidizing chamber 2.In described chamber 2, producing oxygen plasma (maybe needs to obtain SiO xF yAnd so on oxyfluoride the time, produce oxygen and CF 4And so on the plasma body of fluorinated gas) to make metal oxide or silicon layer.
Metal/oxidation cathode sputtering circulation is repeated the number of times of needs, so that final metal oxide or SiO 2Final layer has desired thickness.
Perhaps, for example, can change the character of splash-proofing sputtering metal, repeat metallic cathode sputter/oxidation cycle, have metal oxide stack of different nature thereby make in order to make the antireflection lamination.
Can use the sputtering equipment of the Applied Vision RFX10 device shown in Fig. 6 (fish-eye view) to implement Metamode Method.
As shown in Figure 6, this equipment comprises two cathode sputtering chambers 1,2, and they are furnished with the inert gas source of argon gas and so on separately, also comprises be furnished with gas source (oxygen or oxygen and CF 4And so on the mixture of fluorinated gas) reaction chamber 3 (oxidation or fluorine oxidation).These chambers link to each other with vacuum system (Fig. 6 does not indicate).Base material to be coated is placed on the pallet, and offer the universal stage 4 of this equipment by loading airlock 5.This equipment also comprises the device 6 that monitors that vacuum is used, and for example the Penning table also comprises the monitoring device 7 that is used for cathode sputtering and oxidizing condition.
By universal stage 4, will infeed by the base material to be coated that loading airlock is sent in cathode sputtering chamber 1 or 2, at this coated with metal or silicon layer as mentioned above.Behind metal or the silicon-containing layer deposition, base material is sent into oxidation or the fluorine oxidation of carrying out metal or silicon layer in the reaction chamber 3.
Last in treating processes, with coated base material by air-lock 5 unloadings.
Embodiment 32
Use Metamode Method is coated with the silicon flat substrates with lower floor:
1) by negative electrode spraying (sputter) sedimentary SiOF layer and
2) equally by cathode sputtering deposition SiO 2Protective layer.
SiOF +SiO 2 The mode of deposition on blocking layer
Import CF by the tracheae identical with oxygen 4
Power on the magnetron of silicon: 1.5kW is arranged
The power of plasma gun (oxygen plasma): 100W
The deposition of SiOF layer: (900 seconds time;=＞thickness 165 nanometers)
Ar flow velocity (for the Si sputter): 12sccm
O 2Flow velocity: 4sccm
CF 4Flow velocity: 2sccm
P：3mTorr(0.4Pa)
The deposition on blocking layer: (90 seconds time;=＞thickness 15 nanometers)
Ar flow velocity (for the Si sputter): 12sccm
O 2Flow velocity: 4sccm
CF 4Flow velocity:---
P：2.6mTorr(0.35Pa)
Between two-layer, deposition is preferred pauses about 30 seconds to guarantee not having more CF 4Remain in the system.
The result: the SiOF layer is in specific refractory power=1.415 of 632.8 nanometers, and is durable stable.

Claims (21)

1. make stable SiO for one kind xF yThe method of fluorine-doped silica thin layer is characterized in that this method comprises by following method at SiO xF yForm SiO on the fluorine silicon oxide layer 2Silicon-dioxide and/or metal oxide protective layer: by the vapour deposition process of Assisted by Ion Beam, it comprise use by rare gas, by oxygen or by the positively charged ion bundle bombardment that the mixture of two or more these class gases forms forms layer; Or then sedimentary metal level or silicon layer are carried out the method for oxidation step by cathode sputtering metal level or silicon layer.
2. according to the method for claim 1, it is characterized in that protective layer is 2 to 40 nanometer thickness, preferred 5 to 30 nanometer thickness, more preferably 5 to 20 nanometer thickness.
3. according to the method for claim 1 or 2, it is characterized in that the gas that is used for Assisted by Ion Beam is selected from argon, xenon and oxygen, is preferably argon and xenon.
4. require each method according to aforesaid right, it is characterized in that SiO xF yLayer is 5 to 300 nanometer thickness, is preferably 30 to 100 nanometer thickness.
5. require each method according to aforesaid right, it is characterized in that at 25 ℃ of following SiO xF yLayer is 1.38 to 1.44 for the specific refractory power of the wavelength of 630 nanometers.
6. require each method according to aforesaid right, it is characterized in that by silicon cathode sputtering then at for example CF 4Fluorinated gas situation about existing under carry out oxidation step and make SiO xF yLayer.
7. stable SiO xF yThe fluorine-doped silica thin layer, it is characterized in that it scribbles silicon-dioxide and/or the metal oxide protective layer that makes by following method: by the vapour deposition process of Assisted by Ion Beam, it comprise use by rare gas, by oxygen or by the positively charged ion bundle bombardment that the mixture of two or more these class gases forms forms layer; Or then silicon layer or metal level are carried out the method for oxidation step by cathode sputtering metal level or silicon layer.
8. according to the thin layer of claim 7, it is characterized in that protective layer is 2 to 40 nanometer thickness, preferred 5 to 30 nanometer thickness, more preferably 5 to 20 nanometer thickness.
9. according to the thin layer of claim 7 or 8, it is characterized in that the gas that is used for Assisted by Ion Beam is selected from argon, xenon and oxygen, is preferably argon and xenon.
10. according to each thin layer of claim 7 to 9, it is characterized in that SiO xF yLayer is 5 to 300 nanometer thickness, is preferably 30 to 100 nanometer thickness.
11. require 7 to 10 each thin layers according to aforesaid right, it is characterized in that at 25 ℃ of following SiO xF yLayer is 1.38 to 1.44 for the specific refractory power of the wavelength of 630 nanometers.
12. require 7 to 11 each thin layers according to aforesaid right, it is characterized in that cathode sputtering by silicon layer is then at for example CF 4Fluorinated gas situation about existing under carry out oxidation step and make the fluorine-doped silica layer.
13. the antireflection multilayer coating that forms on base material is characterized in that it contains one deck at least according to each stable thin layer of claim 7 to 12.
14. according to the antireflecting coating of claim 11, it is characterized in that it contains the lamination of high refractive index (HI) and low-refraction (LI) layer, the described low-index layer of one deck is by constituting according to each thin layer of claim 7 to 12 at least.
15., it is characterized in that by the low-index layer that constitutes according to each thin layer of claim 7 to 12 it being the layer of higher position in this lamination according to the antireflecting coating of claim 14.
16., it is characterized in that it contains four layers from substrate surface in proper order according to following each: HI/LI/HI/LI according to the antireflecting coating of claim 15.
17., it is characterized in that the thickness of described each layer changes according to following each in proper order from substrate surface according to the antireflecting coating of claim 16:
HI:10 to 40 nanometer
LI:10 to 55 nanometer, preferred 10 to 45
HI:30 to 155 nanometer, preferred 40 to 150 nanometers, more preferably 120 to 150 nanometers
LI (SiO xF yLayer): 70 to 110 nanometers
Protective layer: 2 to 50 nanometers.
18., it is characterized in that it contains six layers from substrate surface in proper order according to following each: HI/LI/HI/LI/HI/LI according to the antireflecting coating of claim 15.
19., it is characterized in that the thickness of described each layer changes according to following each in proper order from substrate surface according to the antireflecting coating of claim 18:
HI:10 to 30 nanometer
LI:10 to 55 nanometer, preferred 10 to 45 nanometers
HI:10 to 160 nanometer
LI:10 to 45 nanometer
HI:35 to 170 nanometer
LI:70 to 95 nanometer
Protective layer: 2 to 40 nanometers.
20. according to each antireflecting coating of claim 13 to 19, it is characterized in that base material is a synthetic glass, it optionally has wear-resistant coating and/or anti-impact coating.
21., it is characterized in that it comprises according to each antireflecting coating of claim 13 to 20 by the ophthalmic lens that synthetic glass is made.
CNB038239000A 2002-08-08 2003-08-07 Method for obtaining a thin, stabilized fluorine-doped silica layer, resulting thin layer and use thereof in ophthalmic optics Expired - Fee Related CN100473754C (en)

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FR0210110 2002-08-08
FR0210110A FR2843406A1 (en) 2002-08-08 2002-08-08 Production of a stabilized thin layer of silica doped with silica oxyfluoride for ophthalmic applications by vapor phase deposition of a protective layer of silica or metal oxide with ionic bombardment

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CN102477527A (en) * 2010-11-23 2012-05-30 鸿富锦精密工业（深圳）有限公司 Manufacture method of shell and shell manufactured by method
CN102534486A (en) * 2010-12-29 2012-07-04 鸿富锦精密工业（深圳）有限公司 Film coated piece and preparation method thereof
TWI496910B (en) * 2011-01-04 2015-08-21 Hon Hai Prec Ind Co Ltd Vacuum depositing article and method for making the same
CN109487234A (en) * 2018-12-18 2019-03-19 湖北大学 Super oleophobic coating and its preparation method and application

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US6300672B1 (en) * 1998-07-22 2001-10-09 Siemens Aktiengesellschaft Silicon oxynitride cap for fluorinated silicate glass film in intermetal dielectric semiconductor fabrication
FR2812664B1 (en) * 2000-08-01 2002-11-08 Essilor Int METHOD FOR DEPOSITING A FLUORINE DOPED SILICA LAYER AND ITS APPLICATION IN OPHTHALMIC OPTICS

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CN102477527A (en) * 2010-11-23 2012-05-30 鸿富锦精密工业（深圳）有限公司 Manufacture method of shell and shell manufactured by method
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TWI496910B (en) * 2011-01-04 2015-08-21 Hon Hai Prec Ind Co Ltd Vacuum depositing article and method for making the same
CN109487234A (en) * 2018-12-18 2019-03-19 湖北大学 Super oleophobic coating and its preparation method and application

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