CA2223273A1 - Electrically conductive anti-reflection coating - Google Patents
Electrically conductive anti-reflection coating Download PDFInfo
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- CA2223273A1 CA2223273A1 CA002223273A CA2223273A CA2223273A1 CA 2223273 A1 CA2223273 A1 CA 2223273A1 CA 002223273 A CA002223273 A CA 002223273A CA 2223273 A CA2223273 A CA 2223273A CA 2223273 A1 CA2223273 A1 CA 2223273A1
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- Prior art keywords
- layer
- ophthalmic lens
- refractive index
- electrically conductive
- refraction
- Prior art date
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Classifications
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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
- G02B1/113—Anti-reflection coatings using inorganic layer materials only
- G02B1/115—Multilayers
- G02B1/116—Multilayers including electrically conducting layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/00865—Applying coatings; tinting; colouring
-
- 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
- G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
Abstract
An anti-reflection coating that is soil resistant and easy to maintain is provided on a transparent substrate (10). Optionally, an adhesion-promoting layer (10A) may be provided between the substrate and anti-reflection coating. The anti-reflection coating comprises a multilayer film (11, 12) having: alternating layers of high and low refractive index materials that are transparent over a wavelength region near 550 nm. The multilayer film is formed by reacting metal with non-stoichiometric amounts of oxygen such that the coating has one or more layers of electrically conductive metal oxide material. The resultant conductivity prevents large static potentials from being developed on the coated substrate. The coating is particularly suited for ophthalmic applications.
Description
WO 96/41215 PcT~us9'~ /2 ELECTRICALLY CONDUCTIVE ANTI-REFLECTION COATING
Field of the Invention The present invention relates to anti-reflection coatings for ~ ,alellL
substrates such as ophfh~lmic lens and particularly to a method of fabricating anti-reflection coatings that are anti-static and easy to clean.
S Back~round of the Invention Ophth~lmic lenses have traditionally been formed as a single integral body of glass or plastic. Recently, lenses have been fabricated by l~min~ting two lens wafers together with Ll~nspa-cllL adhesive. Regardless of how it is constructed, an ophthalmic lens can include an anti-reflection coating to improve LlAn.~"~ nre of visible light.
Conventional anti-reflection co~tingc colllplise multilayer structures described for inct~n~e, in U.S. Patents 3,432,225 and 3,565,509. Conventional anti-reflection coating.c have a hydrophobic outer layer, which typically comprises a fluoroalkylchlorosilane, to promote soil reci.ct~nre and facilitate cleaning. Despite the ~l~sence of this outer layer, ophth~lmic lens surfaces nevertheless tend to attract airborne particles. Furthermore, oil col~lA~ on the lens surface tend to smudge Mther than wipe off cleanly, making the lenses difficult to m~int~in.
Summary of the Invention The present invention is directed to ~ )alenl articles such as ophth~lmic lens that are coated with an anti-reflection coating with inherent anti-static plopellies. In addition to not attracting dust and other air-borne conf~min~ntc, the durable inventive anti-reflection coating is also easy to clean.
Anti-reflection co~tin~.C of the present invention do not require a hydrophobic outer layer.
WO96/41215 PCT/U' r~ 1~71l2 Accordingly, one aspect of the invention is directed to a method of fabricating a high l~ ",ill;lnre article which comprises the steps of: providinga 11~ a1GI1I substrate; and forming, on a surface of said substrate, a ~ldl~alellL, electrically conductive anti-reflection coating.
Another aspect of the invention is directed to a method of fabricating a high tr~n~mitt~nre article which co~pfises the steps of:
providing a ~ ~Clll substrate; and forming, on a surface of said substrate, a Lldnsl,alell~ multilayer anti-reflection coating wherein at least one layer comprises an electrically conductive high refractive index material or an electrically conductive low refractive index material.
A feature of the invention is that the coating can be formed by reacting metal with oxygen such that the coating comprises one or more layers of electrically conductive metal oxide material. Techniques for accomplishing this include electron beam reactive evaporation, ion-~csi~ted deposition, and reactive ull~lillg of metal targets.
In yet another aspect, the invention is directed to a high tr~n~mitt~nre article colllplisillg:
a lldns~ substrate; and a ~ lll multilayer film col"~lisillg allellldtillg layers of electrically conductive high refractive index and electrically conductive low refractive index materials.
In a further aspect, the invention is directed to a subst~nti~lly static resistant ophth~lmir lens fabricated by a process that comprises the steps of:
providing a ~l~nspalcll~ substrate; and Wo 96/41215 PCT/US3G~'~, / / / >
depositing, onto a surface of said substrate, a Ll~lnsl alcnL multilayer anti-reflection coating wherein each layer comprises an electrically conductive high refractive index or an electrically conductive low refractive index material.
In another aspect, the invention is directed to a subst~nti~lly anti-static S ophth~lmic lens fabricated by a process that co~ ises the steps of:
providing a Llal-slJalellL substrate; and depositing, onto a surface of said substrate, a Llal1~palcnL multilayer film comprising allcll~~ g layers of high refractive index and low refractive index materials whelcill each layer is electrically conductive.
In a preferred embodiment, the multilayer film comprises:
(i) a first layer having an index of refraction from about 2.0 to about
Field of the Invention The present invention relates to anti-reflection coatings for ~ ,alellL
substrates such as ophfh~lmic lens and particularly to a method of fabricating anti-reflection coatings that are anti-static and easy to clean.
S Back~round of the Invention Ophth~lmic lenses have traditionally been formed as a single integral body of glass or plastic. Recently, lenses have been fabricated by l~min~ting two lens wafers together with Ll~nspa-cllL adhesive. Regardless of how it is constructed, an ophthalmic lens can include an anti-reflection coating to improve LlAn.~"~ nre of visible light.
Conventional anti-reflection co~tingc colllplise multilayer structures described for inct~n~e, in U.S. Patents 3,432,225 and 3,565,509. Conventional anti-reflection coating.c have a hydrophobic outer layer, which typically comprises a fluoroalkylchlorosilane, to promote soil reci.ct~nre and facilitate cleaning. Despite the ~l~sence of this outer layer, ophth~lmic lens surfaces nevertheless tend to attract airborne particles. Furthermore, oil col~lA~ on the lens surface tend to smudge Mther than wipe off cleanly, making the lenses difficult to m~int~in.
Summary of the Invention The present invention is directed to ~ )alenl articles such as ophth~lmic lens that are coated with an anti-reflection coating with inherent anti-static plopellies. In addition to not attracting dust and other air-borne conf~min~ntc, the durable inventive anti-reflection coating is also easy to clean.
Anti-reflection co~tin~.C of the present invention do not require a hydrophobic outer layer.
WO96/41215 PCT/U' r~ 1~71l2 Accordingly, one aspect of the invention is directed to a method of fabricating a high l~ ",ill;lnre article which comprises the steps of: providinga 11~ a1GI1I substrate; and forming, on a surface of said substrate, a ~ldl~alellL, electrically conductive anti-reflection coating.
Another aspect of the invention is directed to a method of fabricating a high tr~n~mitt~nre article which co~pfises the steps of:
providing a ~ ~Clll substrate; and forming, on a surface of said substrate, a Lldnsl,alell~ multilayer anti-reflection coating wherein at least one layer comprises an electrically conductive high refractive index material or an electrically conductive low refractive index material.
A feature of the invention is that the coating can be formed by reacting metal with oxygen such that the coating comprises one or more layers of electrically conductive metal oxide material. Techniques for accomplishing this include electron beam reactive evaporation, ion-~csi~ted deposition, and reactive ull~lillg of metal targets.
In yet another aspect, the invention is directed to a high tr~n~mitt~nre article colllplisillg:
a lldns~ substrate; and a ~ lll multilayer film col"~lisillg allellldtillg layers of electrically conductive high refractive index and electrically conductive low refractive index materials.
In a further aspect, the invention is directed to a subst~nti~lly static resistant ophth~lmir lens fabricated by a process that comprises the steps of:
providing a ~l~nspalcll~ substrate; and Wo 96/41215 PCT/US3G~'~, / / / >
depositing, onto a surface of said substrate, a Ll~lnsl alcnL multilayer anti-reflection coating wherein each layer comprises an electrically conductive high refractive index or an electrically conductive low refractive index material.
In another aspect, the invention is directed to a subst~nti~lly anti-static S ophth~lmic lens fabricated by a process that co~ ises the steps of:
providing a Llal-slJalellL substrate; and depositing, onto a surface of said substrate, a Llal1~palcnL multilayer film comprising allcll~~ g layers of high refractive index and low refractive index materials whelcill each layer is electrically conductive.
In a preferred embodiment, the multilayer film comprises:
(i) a first layer having an index of refraction from about 2.0 to about
2.55 and comprising a first metal oxide material;
(ii) a second layer having an index of refraction from about 1.38 to about 1.5 and comprising a second metal oxide;
(iii) a third layer having an index of refraction from about 2.0 to about 2.55 and c(JIn~lising the first metal oxide material; and (iv) a fourth layer having an index of refraction from about 1.38 to about 1.5 collll,lisillg the second metal oxide, wherein the indices of refraction are measured at a reference wavelength of 550 nanometers.
In a ~lcrellcd embodiment, the third layer is electrically conductive. In yet another prerellcd embodiment, the first and third layers comprise high refractive index materials selected from the group con~i~ting of li~ oxides niobium oxides, and t~nt~hlm oxides and the second and fourth layers comprise silicon dioxide. For substrates that comprise ophth~1mic lens, the lens surface ~ 25 preferably has an electric potential that is less than about 100 volts.
Wo 96/41215 PCT/US96/07772 Brief Description of the Drawin~s Figure 1 is a partial cross-sectional view of an ophth~lmic lens produced in accordance with this invention.
Figure 2 is a sch~m~tir diagram of an ion ~c.~i~te-l deposition a~paldLus 5 employed to produce the anti-reflection coating.
Figure 3 is a graph of electrostatic potential vs. Iayers in a coating.
Description of the Pl~felled EmboAim,?nt~
The present invention is based in part on the discovery that increasing the electrical conductivity in one or more layers of a multilayer anti-reflection 10 coating confers the coating with anti-static characteristics. Indeed, even when subjected to frictional forces, the inventive anti-reflection coating does not develop any appreciable amount of electrostatic charge.
The inventive anti-reflection coating demonstrates ill~prov~d resi~t~nre to dirt and stains as well, thereby obviating the need for employing a 15 hydrophobic outer layer over the anti-reflection coating. The presence of this hydrophobic outer layer can adversely effect the optical characteristics of the ophth~lmir lenses including, for in.~t~nre, color con~i~tenry and reflectivity, and increase their production costs.
However, prior to describing the invention is further detail, the 20 following terms will be definrd The term "substrate" refers to a material which preferably has superior structural and optical properties. Crystalline quartz, fused silica, soda-lime silicate glass, and plastics such as from polymers based on allyl diglycol carbonate monomers (available as CR-39~ from PPG Industries, Inc., Hartford, WO 96/41215 PCT~US96/07772 Conn.) and polycarbonates such as LexanTM, available from GeneMl Electric Co., are ple~lled substrate materials. Substrates include ophth~lmic lenses (including s~-ngl~sçs). Preferred ophth~lmir lenses also include l~min~ted lenses that are fabricated by bonding two lens wafers (i.e., a front wafer and aS back wafer) together with a transparent adhesive. T ~min~tecl lens wafers are described, for example, in U.S. Patents 5,149,181, 4,857,553, and 4,645,317 and U.K. Patent Application, GB 2,260,937A, all of which are incorporated herein. Commercially available plastic ophth~lmic lenses that are coated with a polymeric scratch reSict~n~e coating that may be about 1 ~m to about 12 ~4m 10 thick are also suitable substrates. The thirlrness of the polymeric scratch resict~nre coating will depend, in part, on the substrate material. Generally, plastic materials such as polycarbonates will require thicker coatings. Suitablesubstrates further include glass ophthalmic lenses, as described, for in~t~n~e, in U.S. Patents 3,899,315 and 3,899,314, both of which are incorporated herein.
15 As used herein the term "lens" refers to both single integral body and l~."ilul~d types.
The term "anti-reflection coating" or "AR coating" refers to a subst~nti~lly ll~llspal~nl multilayer film that is applied to optical systems (e.g., surfaces thereof) to subst~nti~lly elimin~te reflection over a relatively wide 20 portion of the visible spectrum, and thereby increase the tr~n.cmi~ion of light and reduce surface reflectance. Known anti-reflection coatings include multilayer films comprising ~ ting high and low refractive index materials (e.g., metal oxides) as described, for in~t~nre~ in U.S. Patents 3,432,225,
(ii) a second layer having an index of refraction from about 1.38 to about 1.5 and comprising a second metal oxide;
(iii) a third layer having an index of refraction from about 2.0 to about 2.55 and c(JIn~lising the first metal oxide material; and (iv) a fourth layer having an index of refraction from about 1.38 to about 1.5 collll,lisillg the second metal oxide, wherein the indices of refraction are measured at a reference wavelength of 550 nanometers.
In a ~lcrellcd embodiment, the third layer is electrically conductive. In yet another prerellcd embodiment, the first and third layers comprise high refractive index materials selected from the group con~i~ting of li~ oxides niobium oxides, and t~nt~hlm oxides and the second and fourth layers comprise silicon dioxide. For substrates that comprise ophth~1mic lens, the lens surface ~ 25 preferably has an electric potential that is less than about 100 volts.
Wo 96/41215 PCT/US96/07772 Brief Description of the Drawin~s Figure 1 is a partial cross-sectional view of an ophth~lmic lens produced in accordance with this invention.
Figure 2 is a sch~m~tir diagram of an ion ~c.~i~te-l deposition a~paldLus 5 employed to produce the anti-reflection coating.
Figure 3 is a graph of electrostatic potential vs. Iayers in a coating.
Description of the Pl~felled EmboAim,?nt~
The present invention is based in part on the discovery that increasing the electrical conductivity in one or more layers of a multilayer anti-reflection 10 coating confers the coating with anti-static characteristics. Indeed, even when subjected to frictional forces, the inventive anti-reflection coating does not develop any appreciable amount of electrostatic charge.
The inventive anti-reflection coating demonstrates ill~prov~d resi~t~nre to dirt and stains as well, thereby obviating the need for employing a 15 hydrophobic outer layer over the anti-reflection coating. The presence of this hydrophobic outer layer can adversely effect the optical characteristics of the ophth~lmir lenses including, for in.~t~nre, color con~i~tenry and reflectivity, and increase their production costs.
However, prior to describing the invention is further detail, the 20 following terms will be definrd The term "substrate" refers to a material which preferably has superior structural and optical properties. Crystalline quartz, fused silica, soda-lime silicate glass, and plastics such as from polymers based on allyl diglycol carbonate monomers (available as CR-39~ from PPG Industries, Inc., Hartford, WO 96/41215 PCT~US96/07772 Conn.) and polycarbonates such as LexanTM, available from GeneMl Electric Co., are ple~lled substrate materials. Substrates include ophth~lmic lenses (including s~-ngl~sçs). Preferred ophth~lmir lenses also include l~min~ted lenses that are fabricated by bonding two lens wafers (i.e., a front wafer and aS back wafer) together with a transparent adhesive. T ~min~tecl lens wafers are described, for example, in U.S. Patents 5,149,181, 4,857,553, and 4,645,317 and U.K. Patent Application, GB 2,260,937A, all of which are incorporated herein. Commercially available plastic ophth~lmic lenses that are coated with a polymeric scratch reSict~n~e coating that may be about 1 ~m to about 12 ~4m 10 thick are also suitable substrates. The thirlrness of the polymeric scratch resict~nre coating will depend, in part, on the substrate material. Generally, plastic materials such as polycarbonates will require thicker coatings. Suitablesubstrates further include glass ophthalmic lenses, as described, for in~t~n~e, in U.S. Patents 3,899,315 and 3,899,314, both of which are incorporated herein.
15 As used herein the term "lens" refers to both single integral body and l~."ilul~d types.
The term "anti-reflection coating" or "AR coating" refers to a subst~nti~lly ll~llspal~nl multilayer film that is applied to optical systems (e.g., surfaces thereof) to subst~nti~lly elimin~te reflection over a relatively wide 20 portion of the visible spectrum, and thereby increase the tr~n.cmi~ion of light and reduce surface reflectance. Known anti-reflection coatings include multilayer films comprising ~ ting high and low refractive index materials (e.g., metal oxides) as described, for in~t~nre~ in U.S. Patents 3,432,225,
3,565,509, 4,022,947, and 5,332,618, all of which are incorporated herein.
25 However, unlike prior art AR coatings, the inventive AR coatings employ one or more electrically conductive high and/or electrically conductive low refractive index layers. The thickness of the AR coating will depend on the thickness of each individual layer in the multilayer film and the total number of layers in the multilayer film. The inventive AR coating can include any 30 number of layers. Preferably, the AR coating for the ophth~lmic lens has about :
W O 96/4121~ PCT/U~ 7//~
3 to about 12 layers, more preferably about 4 to about 7 layers, and most prefeMbly about 4 layers. Preferably, the AR coating is about 100 to about 750 nm thick. For use with ophth~lmir lenses, the AR coating is preferably about 220 to about 500 nm thick.
The term "adhesion layer" refers to a film or coating that is formed on the l~al~syalellt substrate prior to depositing the multilayer film of the anti-reflection coating. The adhesion layer promotes bonding of the anti-reflection coating to the substrate. Any suitable l~ sya~ material can be used to form the adhesion layer including chl-onliu~ll oxide. Use of an adhesion layer is optional and the choice of material employed will depend, in part, on the substrate material and the material collly~ g the first layer of the multilayer anti-reflection coating. The thirkn~c~ of the adhesion layer is not critical although it is preferably kept to a thirkn~ss just sufficient to effectively bond the substrate to the anti-reflection coating but not to have a significant optical effect. If the chromium is not oxidized sufficiently or if the adhesion layer istoo thick, then this layer will cause absorption of light and reduce tr~n.cmi~ion through the AR coating. The adhesion layer may be electrically conductive which may further enh~nre the anti-static characteristics of the multilayer anti-reflection coating.
The term "high refractive index material" refers to materials having an index of refraction (at a ,cr.,lellced wavelength of about 550 nm) that is preferably greater than about 2.0, more preferably from about 2.1 to about 2.55, and most preferably from about 2.2 to about 2.4.
The term "low refractive index material" refers to materials having an index of refraction (at a referenced wavelength of about 550 nm) that is preferably less than about 1.5, more preferably from about 1.38 to about 1.5, and most preferably from about 1.45 to about 1.46.
WO 96/41215 PCT/U'' r~ ?17 / / ~
The term "anti-static" refers to the ability of a material not to retain or develop an appreciable amount of electrostatic charge. With respect to an ophth~lmic lens coated with the anti-reflection coating of the present invention, the lens surface preferably 5 remains subst~nti~lly elecll-,?~lalically neutral wherein the coated lens surface has an electric potential that is less than about 100 volts, more preferably less than about 75 volts, and most preferably less than about 50 volts, when measured in the neutral state or discharged state. By "neutral state" or "discharged state" is meant that the lens surface has not been subject to friction 10 or other electrostatic charge generating processes or devices within about 5 seconds prior to measurement. Conversely, the "charged state" refers to the condition of a lens imm~ tely, and up to about 5 seconds, after being subject to friction or other electrostatic charge geneldlhlg processes or devices.
Preferably, for an ophth~lmic lens coated with the anti-reflection 15 coating, the coated lens surface has an electric potential that is less than about 600 volts, and preferably about 0 to about 500 volts, and most preferably about O to about 300 volts or less when measured imm~ tely after being rubbed with a cloth made of a ~ylllhclic (e.g., polyester) or natural (e.g., cotton) material. Further, for an ophth~lmic lens coated with the anti-reflection 20 coating, preferably, the coated lens surface has an electric potential that is less than about 100 volts, more preferably about 0 to about 75 volts or less, and most preferably about 0 to about 50 volts or less within about 5 seconds after being rubbed. As is d~?~?alclll, one of the features of the inventive AR coatingis its ability to discharge or tliC~ip~te electric charge and prevent charge 25 buildup.
For purposes of this invention, volts shall include the m~ynit?~--les of both positive and negative voltages so that a lens surface having an electric potential of 100 volts or less, covers the range from -100 to +100 volts.
W O 96/41215 PCT/U~9 A preferred method of fabricating a conductive AR coating is to employ electrically conductive high and low refractive index materials that comprise metal oxides. Metal oxides with high refractive indices include, for example, oxides of li~ l, cerium, bisllluLIl, zinc, iron, niobium, t~nt~ m, zirconium, S chromium, tin, in~ lm, and mixtures thereof. Particularly plcfelled electrically conductive high refractive index materials are niobium oxides and tit~nillm oxides derived by reactive sputtering or evaporation. Metal oxides with low refractive indices include, for example, oxides of silicon; suitable low refractive index materials also include aluminllm oxyfluoride and m~g~ oxyfluoride.
10 Alternatively, one or more of the metal oxide materials can be replaced with non-oxide materials having the requisite refractive index. For in~t~n~e, zinc sulfide can be used in electrically conductive high refractive index material and m~n~illm fluoride and thorium fluoride can be employed in electrically conductive low refMctive index materials. These non-oxides are described in U.S. Patent 5,332,618.
The multilayer film, which forms the inventive AR coating, comprises at least one layer that is electrically conductive. It is believed that the presence of the one or more electrically conductive layer effectively prevents appreciable electrostatic charge buildup by continuously discharging the same. The result is20 an AR coating which is anti-static.
The terms "electrically conductive high refractive index material" and "electrically conductive low fcrla.;Live index material" refer to a high and lowrefractive index materials that are suitable for use in conductive anti-reflection coatings. Preferably, an electrically conductive high refractive index material 25 comprises a metal oxide having a high refractive index. Conversely, an electrically conductive low refractive index material comprises a metal oxide having a low refractive index.
Wo 96/41215 PCT/U~3 ~v ~
A preferred method of fabricating such materials is to synth~si~P- a metal oxide in an enviromnent so that the metal oxide film produced is non-stoichiometric or sub-oxidized. The res~-lting metal oxide film has the electrical properties described above.
As further described herein, in non-stoichiometric metal oxides the ratio of oxygen to metal is less than the theoretical stoichiometric ratio for any particular structure. (Metal oxides wherein the ratio of metal to oxygen is stoichiometric are generally referred to as dielectric materials that are non-electrically conductive.) However, the electrically conductive materials can also comprise a mixture of (1) stoichiometric metal oxides and (2) stoichiometric oxides and/or non-reacted metal atoms. Methods of synthesizing non-stoichiometric metal oxides include reactive s~lLLe~ g and evaporating of metal in oxygen deficient environments.
It is known that stoichiometric titanium dioxide (i.e., TiO2) has a specific conductivity of less than 10-~~ S/cm whereas TiO, 9995 yields a value of 10-' S/cm. Thus it is expected that suitable electrically conductive high refractive index materials can be fabricated by reacting ~ with a non-stoichiometric amount of oxygen such that the liL;lllilllll oxide produced has the nominal formula TiO,~ wh~lcill x is less than 2, preferably about 1.3 to about 1.9995, more preferably about 1.5 to about 1.9995, and most preferably about 1.7 to about 1.9995.
It is believed that TiO2 is the predominant form of ~ ll oxide formed. However, it is believed that other forms are produced as well. Thus, unless otherwise stated, TiO" will represent all forms of li~ illln oxide produced. It should be noted that when employing tit~nillm oxides as the layer of electrically conductive high lcrl~clive index material, the particular structure of the ~ lnl oxides produced is not critical so long as the layer has the desired optical characteristics (e.g., refractive index and Llal~a~ cy) wo 96/41215 PCT/US3C~ l l l2 nl~ces~ry for the anti-reflection coating, and the coated ophth~lmic lens has the anti-static plu~ellies defined above.
When the inventive AR coating is a multilayer film comprising a layer of electrically conductive low refractive index material, it is expected that 5 suitable electrically conductive low refractive index materials can be fabricated by reacting silicon with a non-stoichiometric amount of oxygen such that the silicon oxide has the nominal formula SiO" wherein x is less than 2, preferably about 1.5 to about 1.99, more preferably about 1.7 to about 1.99 and most preferably 1.8 to about 1.99.
Similarly, it is believed that SiO2 is the predominant form of silicon oxide formed. However, it is believed that other forms are produced as well.
Thus, unless otherwise stated, SiO,~ will represent all forms of silicon oxides produced. Likewise, when employing silicon oxides as the layer of electrically conductive low refractive index material, the particular structure of the silicon 15 oxides produced is not critical so long as the layer has the desired optical characteristics n~cess~ry for the anti-reflection coating and the coated ophth~lmir lens has the anti-static plol)ellies.
Thus, in general, when employing metal oxide materials to construct either a layer of low or high refractive index material, the particular formula or 20 structure of the metal oxide is not critical so long as the layer has the desired optical ~l~,pellies. In the case of forming a layer of electrically conductive low or high refractive index material, the other criterion is that the anti-reflection coating has the anti-static plopellies.
Since only one or more layers of the multilayer film of the inventive AR
25 coating needs to be electrically conductive, it is understood that, except in the case where all the layers are electrically conductive, the other non-electrically conductive layer(s) of the film can comprise conventional dielectric materials W O 96/41215 PcT~u~3~'~7/
~ - 11 -such as ~ ."il~", dioxide for the high refractive index layer and silicon dioxide for the low refractive index layer. It is further understood that the term "metal oxide" or "metal oxides" generally refers to both electrically conductive and nonconductive metal oxides. Thus, for in-ct~nre, tit~nillm oxides comprise S electrical conductive TiO% as defined above as well as tit~nillrn dioxide (i.e., TiO2) a dielectric. Similarly, silicon oxides c~ lplise electrical conductive SiO"
as defined above as well as silicon dioxide (i.e., SiO2) a dielectric.
In ~esigning and fabricating the multilayer film of an anti-reflection coating, selection of the material(s) for the electrically conductive layer should 10 take into account the electrical conductivities of the various metals available to form suitable metal oxides. Preferably, the electrically conductive high or low refractive materials should be formed from metals having the higher electrical conductivity.
A further method of fabricating electrically conductive materials is to 15 first produce the metal oxide dielectric films and thereafter introduce dopants into the film. The dopant is selected from conductive materials that can be the same material as the metal. This tçchniq~le is particularly suited if a non-oxide (e.g., MgF2) is employed. The dopant can be introduced by any suitable means including diffusion and ion implantation. See, for example, Wolf & Tauber, 20 "Silicon Proces~in~ for the VLSI Era," Vol. 1, pp. 242-332 (1986) which is incorporated herein by l~rele-lce.
Methodology The s lbst~nti~lly transparent multilayer film structure of the inventive AR coating can be fabricated by conventional film deposition terhniq~les 25 (ch~lnir31 and physical) inrlll-lin~ reactive sputter deposition, chrJniral vapor deposition and electron beam evaporation, with and without ion assist. These techniques are described in "Thin Film Processes" and "Thin Film Processes II," Vossen & Kern, editors (1978 and 1991) .Ac~ nir Press, which are WO 96/41215 PCT/U~ v7/l~
incorporated herein by lerclcllce. The method most suited will depend on, among other things, the substrate (material and size) and the particular conductive metal oxides employed.
Sputtering tçchniqu~.c involve the physical ejection of material from a 5 target as a result of ion bombardment. The ions are usually created by collisions between gas atoms and electrons in a glow discharge. The ions are accelerated into the target cathode by an electric field. A substrate is placed in a suitable location so that it hllel~;ept~ a portion of the ejected atoms. Thus, a coating is deposited on the surface of the substrate. In reactive ~ L~erillg, a 10 reactant gas forms a compound with the material which is s~ull~"cd from the target. When the target is silicon and the reactive gas is oxygen, for in~t~nre,silicon oxides, usually in the form of SiO2 is formed on the surface of the substrate. Another Slnlllclillg technique is to first form a s~ullclcd metal layer on a substrate and thelc~flel expose this layer to a reactive gas (e.g., oxygen)15 to form a metal oxide. S~IlLlclillg devices are described for in~t~nre in U.S.
Patents 5,047,131, 4,851,095 and 4,166,018, all of which are incorporated herein.
C:h~!nic~l vapor deposition is the formation of a non-volatile solid film on a substrate by the reaction of vapor phase ch~mir~l~ (re~ct~nt~) that contain20 the required con~tit lent~. The reactant gases are introduced into a reactionchamber and are decomposed and reacted by a heated surface to form the thin film.
The conditions required to effect such depositions are well known in the art. For example, ch~mir~l vapor deposition, including low-pressure rh~mir~l 25 vapor deposition (LPCVD), plasma enh~nred chemical vapor deposition (PECVD), photon-in~ recl ch~mi-~l vapor deposition (PHCVD), and the like, is described by Wolf & Tauber, "Silicon Processing for the VLSI Era," Vol. 1, pp. 161-197 (1986) which is incorporated herein by lefclcllce.
wo 96/41215 PCT/US96/07772 Other suitable film deposition techniques include electron beam evaporation and ion-~si~te~ deposition. In electron beam evaporation, an evaporation source (i.e., electron beam) is employed to vaporize the desired target material. The evaporated atoms condense on a substrate situated within 5 the vacuum chamber. See, "Thin Film Processes II" at pages 79-132. In ion-assisted deposition, low-energy ion bombardment of the substrate surface during deposition of evaporated atoms provides surface cleaning, improved nucleation and growth, and in situ ~nnP~ling which produces evaporated coatings of improved quality. For a ~ Cl~c~ion of ion-~si~ted deposition, see Stelmack, et.
10 al., "Review of Ion-Assisted Deposition: Research to Production" Nuclear Instruments and Methods in Physics Research B37/38 (1989) 787-793, which is incorporated herein.
A l lefelled embodiment of the invention is illustrated in Fig. 1 which comprises an ophth~lmic lens 10 that has a conductive anti-reflection coating 15 disposed on a surface. The coating comprises four Lldll~al~lll, substantiallycolorless layers 11-14 which are formed of at least two different materials, in which one is a high refractive index material and the other is a low refractive index material. Layers 11-14 comprise an anti-reflection coating which is also referred to as an "AR stack" or "stack." Preferably, prior to forming the AR
20 stack, an adhesion layer 10A comprising chrollliulll oxides is deposited on the substrate surface.
Preferably, the AR stack or coating colllplises allelllatil~ high and low refractive index m~teri~l~ such that each layer has a refractive index dirre~
from that of any adjoining layer. Preferably, the index of refraction of each 25 low refractive index material is less than about 1.5 at a wavelength of about- 550 nm, which is a prerelled designed wavelength for visible light tr~n~mi~sion; the index of refraction of each high refractive index m~t~ri~l is greater than about 2.0 at a wavelength of about 550 nm; and, each layer comprises a electrically conductive metal oxide The first layer of the AR
W O 96/41215 PCT/U~'17//~
stack, which is formed on the substrate (or on the adhesion promotion layer, which is optional) normally comprises a high index material.
In the embodiment as shown in Fig. 1, layers 11 and 13 comprise high refractive index materials, wherein layer 11 has a thir~n~s.s of about 7 nm to 5 about 15 nm, more preferably from about 9 nm to about 13 nm and most preferably from about 10 nm to about 12 nm and wherein layer 13 has a thirknPs.c of about 90 nm to about 130 nm, more preferably from about 100 nm to about 120 nm and most preferably from about 105 nm to about 115 nm.
Layer 11 is d~cign~t~(l the first layer of this 4 layer stack. Conversely, layers 12 and 14 comprise a low refractive index material wherein layer 12 has a thirlrnPss of about 15 nm to about 40 nm, more preferably from about 20 nm to about 35 nm, and most preferably from about 23 nm to about 31 nm, and wherein layer 14 has a thickness of about 55 nm to about 105 nm, more preferably from about 65 nm to about 95 nm, and most preferably from about 15 75 nm to about 85 nm.
The multilayer film forming the AR coating can co~ lise any suitable number of layers of high/low refractive index materials. For most optical applications, it is desirable that the AR coatings reduce the surface reflect~nre to an extremely low value over an extrntlecl spectral region so as to m~int~in 20 the proper color balance. The number of layers will depend .on, among other things, the substrate material, the particular anti-reflection ~r~llies desired and compositions of the high and low refractive index materials used.
Generally, greater anti-reflection can be achieved by hlclc~asillg the number oflayers of ~ ti~-g high and low refractive index layers but there is a 25 concomitant decrease in the spectral region of anti-reflection. Furthermore, as described, in U.S. Patents 3,432,225 (3-layer design), 3,565,509 (4-layer design), and 5,332,618 (8-layer design), mathematical formulas have been developed to sim~ te the optics of multilayer anti-reflection coatings so that their design can be optimi7.~
wo 96/41215 PCT/U~,~ l,7 Experimental The electron beam ion-assisted deposition appaldt~ls employed to produce AR stacks of the present invention is shown in Fig. 2 and comprises a vacuum chamber 100 which contains ion gun 102 and electron beam 5 evaporation source 106 that are positioned at the base of the vacuum chamber.
Baffle 108 sepalat~s the ion gun from the E-beam source. Located at the upper portion of the chamber are lens dome 112 and substrate support 110. The vacuum chamber is available from Balzer Ltd., Balzer, LiechL~l~leill, as model Balzer 1200 Box Coater. It is equipped with a Balzer EBS 420 Electron Beam 10 source. The ion gun is a Commonwealth mark II Ion Source from Commonwealth Scientific Corp., Alexandria, Virginia.
In operation, a substrate (e.g., ophth~lmir lens) is placed on the substrate support and thereafter a vacuum is created and m~int~in~ with vacuum pump 114. Initially, the ion gun shutter 104 is closed to prevent ion 15 energy from striking the substrate until the ion gun has stabilized to the preset energy level. Similarly, shutter 113 covers the E-beam source until the target is about to evaporate. Argon is employed as the ionizing gas for the ion gun.
Normally, the substrate surface is subject to ion etch prior to deposition of the chromium oxide adhesive layer. To produce a metal oxide layer, the E-beam 20 source is activated to produce a metal e~apolalll of the req~ ite concentration.
Oxygen from oxygen source 116 reacts with the evaporant to form metal oxide which is deposited on the substrate surface. Subsequent metal oxide layers are produced in a similar manner.
AR coatings having the structure as shown of Fig. 1 were fabricated 25 with the device of Fig. 2. Repl~sellLaLi~e opela~ing parameters in the - fabrication of a ~ d AR coating and the characteristics of the individual layers are set forth in Table 1. The substrates used were l~min~t~-l single vision lenses each having a scratch resistant coating.
W O 96/41215 PCTAU~"v7 Material Thickness Index ~ 550 QWOT* ~2 Pressure Deposition (nm) nm (mbar) rate (nm/sec) Adhes. Chromium <1 0 ~2.50 8 x 10-5 L~yer oxide Layer I Titanium oxide 11.33 2.271 0.1871 2 x 104 0.3 (TiO~) Layer 2 Silicon dioxide 27.30 1.461 0.2901 0.8 (si~2) Layer 3 Titanium oxide 111.07 2.271 1.8344 2 x 10~ 0.3 (TiO~) Layer 4 Silicon dioxide 80.91 1.461 0.8597 0.8 (si~2) *Quarter Wave Optical Thickness Prior to commencing deposition, the lens substrates were ultrasonically 10 cleaned using deionized water and then deg~secl at 95~C for 2 hours.
TheleafL~l, lenses were loaded on the substrate support and the ~,es~u~e in the chamber was lowered to about 6 X 10-6 mbar. The substrate surface was ion etched for approximately 4 ~ s with the ion gun operating at 0.9 A/110 V.
In forming the adhesive layer, chlollliulll target material was initially covered 15 with shutter 113 as the chromium is heated by the electron beam from the E-beam evaporation source. The shutter was removed before the chrollliulll evaporated. During the formation and deposition of the chl~llliulll oxide layer,oxygen was introduced sufficient to raise and m~int~in the ch~lllbel plCS~ulc to8 x 10-5 mbar. As is appa~lll, the ion gun shutter was also removed during 20 deposition. The succee~ling 4 layers that comprise the AR coating were deposited in a similar manner. Preferably, the overall p,cs~u,c of the vacuum chamber is m~int~in.od at about 2 x 104 mbar or less throughout the deposition of each of the layers. The second li~ oxide layer (layer 3) of the AR
coating for~ed was found to be electrically conductive.
Lenses coated with the inventive AR coating of Table 1 were tested for anti-static properties. To induce electrostatic charge buildup, the coatings were rubbed with a lint-free cotton ch~esecloth and a 100% polyester ~ llminl~x~
CA 02223273 l997-l2-02 WO 96/41215 PCTAU~5~'V
(Toray Industries, Inc., Tokyo, Japan) lens cleaning cloths. Measurements were con-1llcted in two sep~late environments: with and without air conditioning. Air conditioning tends to reduce the amount of moisture in the air and thereby affect static properties. Three measurements were made for 5 each lens. Prior to any rubbing, the lenses were taken out of their p2c~ging and allowed to acclimate to the environment for at least 30 minutes. The voltages on the front surfaces were then measured with a TI 300 static meter (Static Control Services, Inc., Palm Springs, CA). Next, each lens was rubbed for ten strokes (back and forth--four inches each way) on the ap~lo~iale 10 cloth, and the electrostatic measurement was made imm~ tPly The third measurement was made following a five seconds interval after the lenses were rubbed. Between each measurement, the lenses were placed in front of an Endstat 2000 Deionizer (Static Control Services, Inc.) to elimin~te any residualstatic charges.
The mea~u~.,lellLs, which are set forth in Table 2, demonstrate that lenses coated with the inventive AR coating developed in~ignifir~nt or no electrostatic charge.
NO RUB RUB RUB + 5 SEC
Without Air Conditioning Cotton Cheesecloth 0 -50 0 Polyester Cloth 0 100 0 With Air Conditioning Cotton Cheesecloth 0 -100 -25 Polyester Cloth 0 0 0 (Measurements were made in volts) W O 96/41215 PCT/U~ v7/l T ~min~ted single vision lenses each having a scratch resistant coating and coated with conventional anti-reflection coatings that included a hydrophobic outer layer were also tested for anti-static properties in the manner described above. These "stock" lenses were available from various ophth~lmic 5 lens m~nllf~cturers. The results are shown in Tables 3 through 6. The degree of hydrophobicity of the outer surface of each AR coating is proportional to itscontact angle which was measured with a Tantec Angle Meter, available from Tantec Inc., Schaumberg, IL.
Tables 3 (cotton cheesecloth) and 4 (polyester cloth) comprise 10 measurements taken in a room without air conditioning. Similarly, Tables 5 (cotton cheesecloth) and Table 6 (polyester cloth) comprise measurements taken in one with air conditioning. (Measurelllents were made in volts). As is appal~ l, lens number 1 in each of Tables 3-6 corresponds to the ~plopliat~
inventive lens in Table 2. Lens 2-7 of Table 3 had the same anti-reflection coatings as lens 2-7 of Table 4, respectively. Similarly, lens 2-9 of Table 5 had the same anti-reflection coatings as lens 2-9 of Table 6, respectively.
As is a~ ,lll from the comparative data, the inventive AR coating demonsll~t~d superior anti-static prol,~.lies compared to the prior art anti-reflection coatings available from ophth~lmic lens m~mlfartnrers. Furthermore, 20 the inventive AR coating does not require an outer hydrophobic coating which is present in all of the conventional AR coatings tested.
W O 96/41215 PCTAJS3C/~7//
Lenses No Rub Rub Rub +5 sec Contact Angle 0 -50 0 31 ~
2 -150 -700 -200 100~
3 0 -950 -300 95 ~
25 However, unlike prior art AR coatings, the inventive AR coatings employ one or more electrically conductive high and/or electrically conductive low refractive index layers. The thickness of the AR coating will depend on the thickness of each individual layer in the multilayer film and the total number of layers in the multilayer film. The inventive AR coating can include any 30 number of layers. Preferably, the AR coating for the ophth~lmic lens has about :
W O 96/4121~ PCT/U~ 7//~
3 to about 12 layers, more preferably about 4 to about 7 layers, and most prefeMbly about 4 layers. Preferably, the AR coating is about 100 to about 750 nm thick. For use with ophth~lmir lenses, the AR coating is preferably about 220 to about 500 nm thick.
The term "adhesion layer" refers to a film or coating that is formed on the l~al~syalellt substrate prior to depositing the multilayer film of the anti-reflection coating. The adhesion layer promotes bonding of the anti-reflection coating to the substrate. Any suitable l~ sya~ material can be used to form the adhesion layer including chl-onliu~ll oxide. Use of an adhesion layer is optional and the choice of material employed will depend, in part, on the substrate material and the material collly~ g the first layer of the multilayer anti-reflection coating. The thirkn~c~ of the adhesion layer is not critical although it is preferably kept to a thirkn~ss just sufficient to effectively bond the substrate to the anti-reflection coating but not to have a significant optical effect. If the chromium is not oxidized sufficiently or if the adhesion layer istoo thick, then this layer will cause absorption of light and reduce tr~n.cmi~ion through the AR coating. The adhesion layer may be electrically conductive which may further enh~nre the anti-static characteristics of the multilayer anti-reflection coating.
The term "high refractive index material" refers to materials having an index of refraction (at a ,cr.,lellced wavelength of about 550 nm) that is preferably greater than about 2.0, more preferably from about 2.1 to about 2.55, and most preferably from about 2.2 to about 2.4.
The term "low refractive index material" refers to materials having an index of refraction (at a referenced wavelength of about 550 nm) that is preferably less than about 1.5, more preferably from about 1.38 to about 1.5, and most preferably from about 1.45 to about 1.46.
WO 96/41215 PCT/U'' r~ ?17 / / ~
The term "anti-static" refers to the ability of a material not to retain or develop an appreciable amount of electrostatic charge. With respect to an ophth~lmic lens coated with the anti-reflection coating of the present invention, the lens surface preferably 5 remains subst~nti~lly elecll-,?~lalically neutral wherein the coated lens surface has an electric potential that is less than about 100 volts, more preferably less than about 75 volts, and most preferably less than about 50 volts, when measured in the neutral state or discharged state. By "neutral state" or "discharged state" is meant that the lens surface has not been subject to friction 10 or other electrostatic charge generating processes or devices within about 5 seconds prior to measurement. Conversely, the "charged state" refers to the condition of a lens imm~ tely, and up to about 5 seconds, after being subject to friction or other electrostatic charge geneldlhlg processes or devices.
Preferably, for an ophth~lmic lens coated with the anti-reflection 15 coating, the coated lens surface has an electric potential that is less than about 600 volts, and preferably about 0 to about 500 volts, and most preferably about O to about 300 volts or less when measured imm~ tely after being rubbed with a cloth made of a ~ylllhclic (e.g., polyester) or natural (e.g., cotton) material. Further, for an ophth~lmic lens coated with the anti-reflection 20 coating, preferably, the coated lens surface has an electric potential that is less than about 100 volts, more preferably about 0 to about 75 volts or less, and most preferably about 0 to about 50 volts or less within about 5 seconds after being rubbed. As is d~?~?alclll, one of the features of the inventive AR coatingis its ability to discharge or tliC~ip~te electric charge and prevent charge 25 buildup.
For purposes of this invention, volts shall include the m~ynit?~--les of both positive and negative voltages so that a lens surface having an electric potential of 100 volts or less, covers the range from -100 to +100 volts.
W O 96/41215 PCT/U~9 A preferred method of fabricating a conductive AR coating is to employ electrically conductive high and low refractive index materials that comprise metal oxides. Metal oxides with high refractive indices include, for example, oxides of li~ l, cerium, bisllluLIl, zinc, iron, niobium, t~nt~ m, zirconium, S chromium, tin, in~ lm, and mixtures thereof. Particularly plcfelled electrically conductive high refractive index materials are niobium oxides and tit~nillm oxides derived by reactive sputtering or evaporation. Metal oxides with low refractive indices include, for example, oxides of silicon; suitable low refractive index materials also include aluminllm oxyfluoride and m~g~ oxyfluoride.
10 Alternatively, one or more of the metal oxide materials can be replaced with non-oxide materials having the requisite refractive index. For in~t~n~e, zinc sulfide can be used in electrically conductive high refractive index material and m~n~illm fluoride and thorium fluoride can be employed in electrically conductive low refMctive index materials. These non-oxides are described in U.S. Patent 5,332,618.
The multilayer film, which forms the inventive AR coating, comprises at least one layer that is electrically conductive. It is believed that the presence of the one or more electrically conductive layer effectively prevents appreciable electrostatic charge buildup by continuously discharging the same. The result is20 an AR coating which is anti-static.
The terms "electrically conductive high refractive index material" and "electrically conductive low fcrla.;Live index material" refer to a high and lowrefractive index materials that are suitable for use in conductive anti-reflection coatings. Preferably, an electrically conductive high refractive index material 25 comprises a metal oxide having a high refractive index. Conversely, an electrically conductive low refractive index material comprises a metal oxide having a low refractive index.
Wo 96/41215 PCT/U~3 ~v ~
A preferred method of fabricating such materials is to synth~si~P- a metal oxide in an enviromnent so that the metal oxide film produced is non-stoichiometric or sub-oxidized. The res~-lting metal oxide film has the electrical properties described above.
As further described herein, in non-stoichiometric metal oxides the ratio of oxygen to metal is less than the theoretical stoichiometric ratio for any particular structure. (Metal oxides wherein the ratio of metal to oxygen is stoichiometric are generally referred to as dielectric materials that are non-electrically conductive.) However, the electrically conductive materials can also comprise a mixture of (1) stoichiometric metal oxides and (2) stoichiometric oxides and/or non-reacted metal atoms. Methods of synthesizing non-stoichiometric metal oxides include reactive s~lLLe~ g and evaporating of metal in oxygen deficient environments.
It is known that stoichiometric titanium dioxide (i.e., TiO2) has a specific conductivity of less than 10-~~ S/cm whereas TiO, 9995 yields a value of 10-' S/cm. Thus it is expected that suitable electrically conductive high refractive index materials can be fabricated by reacting ~ with a non-stoichiometric amount of oxygen such that the liL;lllilllll oxide produced has the nominal formula TiO,~ wh~lcill x is less than 2, preferably about 1.3 to about 1.9995, more preferably about 1.5 to about 1.9995, and most preferably about 1.7 to about 1.9995.
It is believed that TiO2 is the predominant form of ~ ll oxide formed. However, it is believed that other forms are produced as well. Thus, unless otherwise stated, TiO" will represent all forms of li~ illln oxide produced. It should be noted that when employing tit~nillm oxides as the layer of electrically conductive high lcrl~clive index material, the particular structure of the ~ lnl oxides produced is not critical so long as the layer has the desired optical characteristics (e.g., refractive index and Llal~a~ cy) wo 96/41215 PCT/US3C~ l l l2 nl~ces~ry for the anti-reflection coating, and the coated ophth~lmic lens has the anti-static plu~ellies defined above.
When the inventive AR coating is a multilayer film comprising a layer of electrically conductive low refractive index material, it is expected that 5 suitable electrically conductive low refractive index materials can be fabricated by reacting silicon with a non-stoichiometric amount of oxygen such that the silicon oxide has the nominal formula SiO" wherein x is less than 2, preferably about 1.5 to about 1.99, more preferably about 1.7 to about 1.99 and most preferably 1.8 to about 1.99.
Similarly, it is believed that SiO2 is the predominant form of silicon oxide formed. However, it is believed that other forms are produced as well.
Thus, unless otherwise stated, SiO,~ will represent all forms of silicon oxides produced. Likewise, when employing silicon oxides as the layer of electrically conductive low refractive index material, the particular structure of the silicon 15 oxides produced is not critical so long as the layer has the desired optical characteristics n~cess~ry for the anti-reflection coating and the coated ophth~lmir lens has the anti-static plol)ellies.
Thus, in general, when employing metal oxide materials to construct either a layer of low or high refractive index material, the particular formula or 20 structure of the metal oxide is not critical so long as the layer has the desired optical ~l~,pellies. In the case of forming a layer of electrically conductive low or high refractive index material, the other criterion is that the anti-reflection coating has the anti-static plopellies.
Since only one or more layers of the multilayer film of the inventive AR
25 coating needs to be electrically conductive, it is understood that, except in the case where all the layers are electrically conductive, the other non-electrically conductive layer(s) of the film can comprise conventional dielectric materials W O 96/41215 PcT~u~3~'~7/
~ - 11 -such as ~ ."il~", dioxide for the high refractive index layer and silicon dioxide for the low refractive index layer. It is further understood that the term "metal oxide" or "metal oxides" generally refers to both electrically conductive and nonconductive metal oxides. Thus, for in-ct~nre, tit~nillm oxides comprise S electrical conductive TiO% as defined above as well as tit~nillrn dioxide (i.e., TiO2) a dielectric. Similarly, silicon oxides c~ lplise electrical conductive SiO"
as defined above as well as silicon dioxide (i.e., SiO2) a dielectric.
In ~esigning and fabricating the multilayer film of an anti-reflection coating, selection of the material(s) for the electrically conductive layer should 10 take into account the electrical conductivities of the various metals available to form suitable metal oxides. Preferably, the electrically conductive high or low refractive materials should be formed from metals having the higher electrical conductivity.
A further method of fabricating electrically conductive materials is to 15 first produce the metal oxide dielectric films and thereafter introduce dopants into the film. The dopant is selected from conductive materials that can be the same material as the metal. This tçchniq~le is particularly suited if a non-oxide (e.g., MgF2) is employed. The dopant can be introduced by any suitable means including diffusion and ion implantation. See, for example, Wolf & Tauber, 20 "Silicon Proces~in~ for the VLSI Era," Vol. 1, pp. 242-332 (1986) which is incorporated herein by l~rele-lce.
Methodology The s lbst~nti~lly transparent multilayer film structure of the inventive AR coating can be fabricated by conventional film deposition terhniq~les 25 (ch~lnir31 and physical) inrlll-lin~ reactive sputter deposition, chrJniral vapor deposition and electron beam evaporation, with and without ion assist. These techniques are described in "Thin Film Processes" and "Thin Film Processes II," Vossen & Kern, editors (1978 and 1991) .Ac~ nir Press, which are WO 96/41215 PCT/U~ v7/l~
incorporated herein by lerclcllce. The method most suited will depend on, among other things, the substrate (material and size) and the particular conductive metal oxides employed.
Sputtering tçchniqu~.c involve the physical ejection of material from a 5 target as a result of ion bombardment. The ions are usually created by collisions between gas atoms and electrons in a glow discharge. The ions are accelerated into the target cathode by an electric field. A substrate is placed in a suitable location so that it hllel~;ept~ a portion of the ejected atoms. Thus, a coating is deposited on the surface of the substrate. In reactive ~ L~erillg, a 10 reactant gas forms a compound with the material which is s~ull~"cd from the target. When the target is silicon and the reactive gas is oxygen, for in~t~nre,silicon oxides, usually in the form of SiO2 is formed on the surface of the substrate. Another Slnlllclillg technique is to first form a s~ullclcd metal layer on a substrate and thelc~flel expose this layer to a reactive gas (e.g., oxygen)15 to form a metal oxide. S~IlLlclillg devices are described for in~t~nre in U.S.
Patents 5,047,131, 4,851,095 and 4,166,018, all of which are incorporated herein.
C:h~!nic~l vapor deposition is the formation of a non-volatile solid film on a substrate by the reaction of vapor phase ch~mir~l~ (re~ct~nt~) that contain20 the required con~tit lent~. The reactant gases are introduced into a reactionchamber and are decomposed and reacted by a heated surface to form the thin film.
The conditions required to effect such depositions are well known in the art. For example, ch~mir~l vapor deposition, including low-pressure rh~mir~l 25 vapor deposition (LPCVD), plasma enh~nred chemical vapor deposition (PECVD), photon-in~ recl ch~mi-~l vapor deposition (PHCVD), and the like, is described by Wolf & Tauber, "Silicon Processing for the VLSI Era," Vol. 1, pp. 161-197 (1986) which is incorporated herein by lefclcllce.
wo 96/41215 PCT/US96/07772 Other suitable film deposition techniques include electron beam evaporation and ion-~si~te~ deposition. In electron beam evaporation, an evaporation source (i.e., electron beam) is employed to vaporize the desired target material. The evaporated atoms condense on a substrate situated within 5 the vacuum chamber. See, "Thin Film Processes II" at pages 79-132. In ion-assisted deposition, low-energy ion bombardment of the substrate surface during deposition of evaporated atoms provides surface cleaning, improved nucleation and growth, and in situ ~nnP~ling which produces evaporated coatings of improved quality. For a ~ Cl~c~ion of ion-~si~ted deposition, see Stelmack, et.
10 al., "Review of Ion-Assisted Deposition: Research to Production" Nuclear Instruments and Methods in Physics Research B37/38 (1989) 787-793, which is incorporated herein.
A l lefelled embodiment of the invention is illustrated in Fig. 1 which comprises an ophth~lmic lens 10 that has a conductive anti-reflection coating 15 disposed on a surface. The coating comprises four Lldll~al~lll, substantiallycolorless layers 11-14 which are formed of at least two different materials, in which one is a high refractive index material and the other is a low refractive index material. Layers 11-14 comprise an anti-reflection coating which is also referred to as an "AR stack" or "stack." Preferably, prior to forming the AR
20 stack, an adhesion layer 10A comprising chrollliulll oxides is deposited on the substrate surface.
Preferably, the AR stack or coating colllplises allelllatil~ high and low refractive index m~teri~l~ such that each layer has a refractive index dirre~
from that of any adjoining layer. Preferably, the index of refraction of each 25 low refractive index material is less than about 1.5 at a wavelength of about- 550 nm, which is a prerelled designed wavelength for visible light tr~n~mi~sion; the index of refraction of each high refractive index m~t~ri~l is greater than about 2.0 at a wavelength of about 550 nm; and, each layer comprises a electrically conductive metal oxide The first layer of the AR
W O 96/41215 PCT/U~'17//~
stack, which is formed on the substrate (or on the adhesion promotion layer, which is optional) normally comprises a high index material.
In the embodiment as shown in Fig. 1, layers 11 and 13 comprise high refractive index materials, wherein layer 11 has a thir~n~s.s of about 7 nm to 5 about 15 nm, more preferably from about 9 nm to about 13 nm and most preferably from about 10 nm to about 12 nm and wherein layer 13 has a thirknPs.c of about 90 nm to about 130 nm, more preferably from about 100 nm to about 120 nm and most preferably from about 105 nm to about 115 nm.
Layer 11 is d~cign~t~(l the first layer of this 4 layer stack. Conversely, layers 12 and 14 comprise a low refractive index material wherein layer 12 has a thirlrnPss of about 15 nm to about 40 nm, more preferably from about 20 nm to about 35 nm, and most preferably from about 23 nm to about 31 nm, and wherein layer 14 has a thickness of about 55 nm to about 105 nm, more preferably from about 65 nm to about 95 nm, and most preferably from about 15 75 nm to about 85 nm.
The multilayer film forming the AR coating can co~ lise any suitable number of layers of high/low refractive index materials. For most optical applications, it is desirable that the AR coatings reduce the surface reflect~nre to an extremely low value over an extrntlecl spectral region so as to m~int~in 20 the proper color balance. The number of layers will depend .on, among other things, the substrate material, the particular anti-reflection ~r~llies desired and compositions of the high and low refractive index materials used.
Generally, greater anti-reflection can be achieved by hlclc~asillg the number oflayers of ~ ti~-g high and low refractive index layers but there is a 25 concomitant decrease in the spectral region of anti-reflection. Furthermore, as described, in U.S. Patents 3,432,225 (3-layer design), 3,565,509 (4-layer design), and 5,332,618 (8-layer design), mathematical formulas have been developed to sim~ te the optics of multilayer anti-reflection coatings so that their design can be optimi7.~
wo 96/41215 PCT/U~,~ l,7 Experimental The electron beam ion-assisted deposition appaldt~ls employed to produce AR stacks of the present invention is shown in Fig. 2 and comprises a vacuum chamber 100 which contains ion gun 102 and electron beam 5 evaporation source 106 that are positioned at the base of the vacuum chamber.
Baffle 108 sepalat~s the ion gun from the E-beam source. Located at the upper portion of the chamber are lens dome 112 and substrate support 110. The vacuum chamber is available from Balzer Ltd., Balzer, LiechL~l~leill, as model Balzer 1200 Box Coater. It is equipped with a Balzer EBS 420 Electron Beam 10 source. The ion gun is a Commonwealth mark II Ion Source from Commonwealth Scientific Corp., Alexandria, Virginia.
In operation, a substrate (e.g., ophth~lmir lens) is placed on the substrate support and thereafter a vacuum is created and m~int~in~ with vacuum pump 114. Initially, the ion gun shutter 104 is closed to prevent ion 15 energy from striking the substrate until the ion gun has stabilized to the preset energy level. Similarly, shutter 113 covers the E-beam source until the target is about to evaporate. Argon is employed as the ionizing gas for the ion gun.
Normally, the substrate surface is subject to ion etch prior to deposition of the chromium oxide adhesive layer. To produce a metal oxide layer, the E-beam 20 source is activated to produce a metal e~apolalll of the req~ ite concentration.
Oxygen from oxygen source 116 reacts with the evaporant to form metal oxide which is deposited on the substrate surface. Subsequent metal oxide layers are produced in a similar manner.
AR coatings having the structure as shown of Fig. 1 were fabricated 25 with the device of Fig. 2. Repl~sellLaLi~e opela~ing parameters in the - fabrication of a ~ d AR coating and the characteristics of the individual layers are set forth in Table 1. The substrates used were l~min~t~-l single vision lenses each having a scratch resistant coating.
W O 96/41215 PCTAU~"v7 Material Thickness Index ~ 550 QWOT* ~2 Pressure Deposition (nm) nm (mbar) rate (nm/sec) Adhes. Chromium <1 0 ~2.50 8 x 10-5 L~yer oxide Layer I Titanium oxide 11.33 2.271 0.1871 2 x 104 0.3 (TiO~) Layer 2 Silicon dioxide 27.30 1.461 0.2901 0.8 (si~2) Layer 3 Titanium oxide 111.07 2.271 1.8344 2 x 10~ 0.3 (TiO~) Layer 4 Silicon dioxide 80.91 1.461 0.8597 0.8 (si~2) *Quarter Wave Optical Thickness Prior to commencing deposition, the lens substrates were ultrasonically 10 cleaned using deionized water and then deg~secl at 95~C for 2 hours.
TheleafL~l, lenses were loaded on the substrate support and the ~,es~u~e in the chamber was lowered to about 6 X 10-6 mbar. The substrate surface was ion etched for approximately 4 ~ s with the ion gun operating at 0.9 A/110 V.
In forming the adhesive layer, chlollliulll target material was initially covered 15 with shutter 113 as the chromium is heated by the electron beam from the E-beam evaporation source. The shutter was removed before the chrollliulll evaporated. During the formation and deposition of the chl~llliulll oxide layer,oxygen was introduced sufficient to raise and m~int~in the ch~lllbel plCS~ulc to8 x 10-5 mbar. As is appa~lll, the ion gun shutter was also removed during 20 deposition. The succee~ling 4 layers that comprise the AR coating were deposited in a similar manner. Preferably, the overall p,cs~u,c of the vacuum chamber is m~int~in.od at about 2 x 104 mbar or less throughout the deposition of each of the layers. The second li~ oxide layer (layer 3) of the AR
coating for~ed was found to be electrically conductive.
Lenses coated with the inventive AR coating of Table 1 were tested for anti-static properties. To induce electrostatic charge buildup, the coatings were rubbed with a lint-free cotton ch~esecloth and a 100% polyester ~ llminl~x~
CA 02223273 l997-l2-02 WO 96/41215 PCTAU~5~'V
(Toray Industries, Inc., Tokyo, Japan) lens cleaning cloths. Measurements were con-1llcted in two sep~late environments: with and without air conditioning. Air conditioning tends to reduce the amount of moisture in the air and thereby affect static properties. Three measurements were made for 5 each lens. Prior to any rubbing, the lenses were taken out of their p2c~ging and allowed to acclimate to the environment for at least 30 minutes. The voltages on the front surfaces were then measured with a TI 300 static meter (Static Control Services, Inc., Palm Springs, CA). Next, each lens was rubbed for ten strokes (back and forth--four inches each way) on the ap~lo~iale 10 cloth, and the electrostatic measurement was made imm~ tPly The third measurement was made following a five seconds interval after the lenses were rubbed. Between each measurement, the lenses were placed in front of an Endstat 2000 Deionizer (Static Control Services, Inc.) to elimin~te any residualstatic charges.
The mea~u~.,lellLs, which are set forth in Table 2, demonstrate that lenses coated with the inventive AR coating developed in~ignifir~nt or no electrostatic charge.
NO RUB RUB RUB + 5 SEC
Without Air Conditioning Cotton Cheesecloth 0 -50 0 Polyester Cloth 0 100 0 With Air Conditioning Cotton Cheesecloth 0 -100 -25 Polyester Cloth 0 0 0 (Measurements were made in volts) W O 96/41215 PCT/U~ v7/l T ~min~ted single vision lenses each having a scratch resistant coating and coated with conventional anti-reflection coatings that included a hydrophobic outer layer were also tested for anti-static properties in the manner described above. These "stock" lenses were available from various ophth~lmic 5 lens m~nllf~cturers. The results are shown in Tables 3 through 6. The degree of hydrophobicity of the outer surface of each AR coating is proportional to itscontact angle which was measured with a Tantec Angle Meter, available from Tantec Inc., Schaumberg, IL.
Tables 3 (cotton cheesecloth) and 4 (polyester cloth) comprise 10 measurements taken in a room without air conditioning. Similarly, Tables 5 (cotton cheesecloth) and Table 6 (polyester cloth) comprise measurements taken in one with air conditioning. (Measurelllents were made in volts). As is appal~ l, lens number 1 in each of Tables 3-6 corresponds to the ~plopliat~
inventive lens in Table 2. Lens 2-7 of Table 3 had the same anti-reflection coatings as lens 2-7 of Table 4, respectively. Similarly, lens 2-9 of Table 5 had the same anti-reflection coatings as lens 2-9 of Table 6, respectively.
As is a~ ,lll from the comparative data, the inventive AR coating demonsll~t~d superior anti-static prol,~.lies compared to the prior art anti-reflection coatings available from ophth~lmic lens m~mlfartnrers. Furthermore, 20 the inventive AR coating does not require an outer hydrophobic coating which is present in all of the conventional AR coatings tested.
W O 96/41215 PCTAJS3C/~7//
Lenses No Rub Rub Rub +5 sec Contact Angle 0 -50 0 31 ~
2 -150 -700 -200 100~
3 0 -950 -300 95 ~
4 -250 -1000 -500 100~
-213 -2375 -1000 95 ~
6 -350 -3250 -2000 95 ~
7 -700 -4500 -2000 81 ~
LensesNo Rub RubRub +5 sec Contact Angle 0 100 0 31~
2 -150 -950 -325 100~
3 0 -1350 -150 95 ~
4 -250 -1000 -500 100~
-213 -4500 -2750 95~
6 --350 -5500 -4000 95 ~
7 -700 -3000 -2250 81~
-213 -2375 -1000 95 ~
6 -350 -3250 -2000 95 ~
7 -700 -4500 -2000 81 ~
LensesNo Rub RubRub +5 sec Contact Angle 0 100 0 31~
2 -150 -950 -325 100~
3 0 -1350 -150 95 ~
4 -250 -1000 -500 100~
-213 -4500 -2750 95~
6 --350 -5500 -4000 95 ~
7 -700 -3000 -2250 81~
5 PCT/US96/07772 Lenses No Rub Rub Rub +5 sec Contact Angle 0 -100 -25 31 ~
2 -100 -800 -500 100~
3 -lS0 -1750 -850 100~
4 0 -2000 -700 95 ~
-450 -3500 -2250 81 ~
2 -100 -800 -500 100~
3 -lS0 -1750 -850 100~
4 0 -2000 -700 95 ~
-450 -3500 -2250 81 ~
6 -163 -4500 -3250 95 ~
7 -500 -6500 -5000 95 ~
8 -250 -8500 -6000 100~
9 -1250 -10000 -9500 95 ~
Lenses No Rub RubRub +5 sec Contact Angle 0 0 0 31~
2 -100 -2250 -450 95 ~
3 -150 -1250 -600 100~
4 0 -2750 -650 100~
-163 -4500 -2250 81 ~
6 -500 -5875 -3500 95 ~
7 -450 -10000 -6000 95~
8 -250 -8000 -5000 100~
9 -1250 -10000 -9500 95~
Layer-by-layer Analysis of AR Coatin~
To d~te~ ille what significant effect, if any, the individual layers of the 25 AR coating had on the anti-static ~,rol)ellies of AR coatings, a layer-by-layer analysis of the AR coating having the five layer structure described in Table 1 was contlllcfed~ In this analysis, five plastic front wafers were coated, each -having a dirrelenl number of layers. (The wafers used were plastic and coated with a scratch resistant polymeric layer.) The first wafer was coated with (1) the Chlullliulll oxide adhesion layer only. The second wafer was coated with (1) the chromium oxide adhesion layer and (2) first TiOX, and so on, so that the5 fifth wafer comprised the five layer structure.
After formation of the five coated wafers, the voltage on the front surfaces of each wafer was measured with a TI 300 static meter. Each wafer was rubbed for ten strokes (back and forth--four inches each way) on a lint-free cotton cheesecloth and the measurements were made immPrli~tely. In the
Lenses No Rub RubRub +5 sec Contact Angle 0 0 0 31~
2 -100 -2250 -450 95 ~
3 -150 -1250 -600 100~
4 0 -2750 -650 100~
-163 -4500 -2250 81 ~
6 -500 -5875 -3500 95 ~
7 -450 -10000 -6000 95~
8 -250 -8000 -5000 100~
9 -1250 -10000 -9500 95~
Layer-by-layer Analysis of AR Coatin~
To d~te~ ille what significant effect, if any, the individual layers of the 25 AR coating had on the anti-static ~,rol)ellies of AR coatings, a layer-by-layer analysis of the AR coating having the five layer structure described in Table 1 was contlllcfed~ In this analysis, five plastic front wafers were coated, each -having a dirrelenl number of layers. (The wafers used were plastic and coated with a scratch resistant polymeric layer.) The first wafer was coated with (1) the Chlullliulll oxide adhesion layer only. The second wafer was coated with (1) the chromium oxide adhesion layer and (2) first TiOX, and so on, so that the5 fifth wafer comprised the five layer structure.
After formation of the five coated wafers, the voltage on the front surfaces of each wafer was measured with a TI 300 static meter. Each wafer was rubbed for ten strokes (back and forth--four inches each way) on a lint-free cotton cheesecloth and the measurements were made immPrli~tely. In the
10 third test, five seconds lapsed after the lenses were rubbed, before being measured. As a control, the electrostatic voltages of two plastic front wafers (i.e., controls 1 and 2) were also measured. Each control wafer was coated with a dirÇelclll scratch resistant polymeric coating. The five wafers tested had the same scratch resistant polymer coating as control 1.
It was found that the electrostatic charge remained high for the first, second, and third wafers; however, the fourth wafer which comprised: (1) the chromium oxide adhesive layer, (2) the first TiOX layer, (3) the first SiO2 layer, and (4) the second TiOX layer, showed a dramatic reduction is electrostatic charge. Analysis showed that for the second TiOX layer, x was about 1.78.
20 Thus, at least with respect to AR coatings having alLelllalillg high and low refractive index materials conl~,isillg ~ l,l, oxides and silicon oxides, the second high refractive index material preferably is TiOX wherein, x is about 1.3to about 1.9995, more preferably about 1.5 to about 1.9995, and most preferably about 1.7 to about 1.9995.
It should be emphasized that while the examples shown herein comprise only two dirr~re.ll high and low index materials (i.e., SiOx and TiOX) in the particular design, similar anti-reflection coating structures could be ~lesign~
with two or more high index materials and/or two or more low index materials, wo 96/41215 pcTluss6lo7772 or even a material such as alllmin~lm oxide of some intenn~ te refractive index.
Furthermore, in certain cases, it may be advantageous to use mixtures of materials or complex compounds. A mixture of cerium oxide and zinc oxide 5 could be used for the high index films and a mixture of silicon dioxide and ma~lesiulll fluoride for the low index films. Other mixtures might be chosen to suit a particular deposition technique or to take advantage of a particular optical or physical propelly of a material.
Ophth~lmic lens having the anti-reflection coating preferably has a tran~mitt~nre at 550 nm of between about 98.0 to about 99.5 %, more preferably bclwcen about 98.5 to about 99.5 %, and most preferably between about 99.0 to about 99.5 %. Moreover, the ophth~lmic lens has a reflectance at 550 nm of between about 0.5 to about 2.0%, more preferably between about 0.5 to about 1.5 % , and most preferably between about 0.5 to about 1.0%.
Although only l"cr~lled embodill.enL~ of the invention are specifically disclosed and described above, it will be app.ccidt~d that many modifications and variations of the present invention are possible in light of the above t~ hing~ and within the purview of the appended claims without departing from the spirit and intended scope of the invention.
It was found that the electrostatic charge remained high for the first, second, and third wafers; however, the fourth wafer which comprised: (1) the chromium oxide adhesive layer, (2) the first TiOX layer, (3) the first SiO2 layer, and (4) the second TiOX layer, showed a dramatic reduction is electrostatic charge. Analysis showed that for the second TiOX layer, x was about 1.78.
20 Thus, at least with respect to AR coatings having alLelllalillg high and low refractive index materials conl~,isillg ~ l,l, oxides and silicon oxides, the second high refractive index material preferably is TiOX wherein, x is about 1.3to about 1.9995, more preferably about 1.5 to about 1.9995, and most preferably about 1.7 to about 1.9995.
It should be emphasized that while the examples shown herein comprise only two dirr~re.ll high and low index materials (i.e., SiOx and TiOX) in the particular design, similar anti-reflection coating structures could be ~lesign~
with two or more high index materials and/or two or more low index materials, wo 96/41215 pcTluss6lo7772 or even a material such as alllmin~lm oxide of some intenn~ te refractive index.
Furthermore, in certain cases, it may be advantageous to use mixtures of materials or complex compounds. A mixture of cerium oxide and zinc oxide 5 could be used for the high index films and a mixture of silicon dioxide and ma~lesiulll fluoride for the low index films. Other mixtures might be chosen to suit a particular deposition technique or to take advantage of a particular optical or physical propelly of a material.
Ophth~lmic lens having the anti-reflection coating preferably has a tran~mitt~nre at 550 nm of between about 98.0 to about 99.5 %, more preferably bclwcen about 98.5 to about 99.5 %, and most preferably between about 99.0 to about 99.5 %. Moreover, the ophth~lmic lens has a reflectance at 550 nm of between about 0.5 to about 2.0%, more preferably between about 0.5 to about 1.5 % , and most preferably between about 0.5 to about 1.0%.
Although only l"cr~lled embodill.enL~ of the invention are specifically disclosed and described above, it will be app.ccidt~d that many modifications and variations of the present invention are possible in light of the above t~ hing~ and within the purview of the appended claims without departing from the spirit and intended scope of the invention.
Claims (48)
1. A method of fabricating a high transmittance ophthalmic lens which comprises the steps of:
providing a transparent ophthalmic lens (10); and forming, on a surface of said ophthalmic lens, a transparent, electrically conductive and substantially static resistant anti-reflection coating (11, 12) by reacting a metal with an effective non-stoichiometric amount of oxygen such that the coating comprises one or more layers of electrically conductive metal oxide material.
providing a transparent ophthalmic lens (10); and forming, on a surface of said ophthalmic lens, a transparent, electrically conductive and substantially static resistant anti-reflection coating (11, 12) by reacting a metal with an effective non-stoichiometric amount of oxygen such that the coating comprises one or more layers of electrically conductive metal oxide material.
2. The method of Claim 1 wherein the coating of the ophthalmic lens in the neutral state has an electric potential that is less than about 100 volts.
3. The method of Claim 1 or 2 wherein said coating is formed by electron beam ion-assisted deposition.
4. A method of fabricating a high transmittance ophthalmic lens which comprises the steps of:
providing a transparent ophthalmic lens (10); and forming, on a surface of said ophthalmic lens, a transparent, multilayer, substantially static resistant, anti-reflection coating (11, 12) wherein at least one layer is electrically conductive.
providing a transparent ophthalmic lens (10); and forming, on a surface of said ophthalmic lens, a transparent, multilayer, substantially static resistant, anti-reflection coating (11, 12) wherein at least one layer is electrically conductive.
5. The method of Claim 4 wherein the step of forming said coating comprises reacting a metal with an effective non-stoichiometric amount of oxygen such that the coating comprises one or more layers of electrically conductive metal oxide material.
6. The method of Claim 4 or 5 wherein each of the at least one electrically conductive layer is formed by electron beam evaporation whereby metal reacts with non-stoichiometric amounts of oxygen to form an electrically conductive metal oxide.
7. The method of any of Claims 4-6 wherein each of the at least one electrically conductive layer is a high refractive index material that comprisesniobium oxides.
8. The method of any of Claims 4-6 wherein each of the at least one electrically conductive layer is a high refractive index material that comprisestitanium oxides.
9. The method of any of Claims 4-8 wherein the multilayer anti-reflection coating comprises alternating high and low refractive index materials such that each layer has a refractive index different from that of any adjoining layer, wherein the index of refraction of each low refractive index material is less than about 1.5 at a wavelength of about 550 nm, wherein the index of refraction of each high refractive index material is greater than about 2.0 at a wavelength ofabout 550 nm, and wherein at least one layer comprises an electrically conductive metal oxide material.
10. The method of any of Claims 4-9 wherein the high refractive index material comprises titanium oxides and wherein the low refractive index material comprises silicon oxides.
11. The method of any of Claims 4-9 wherein the high refractive index material comprises niobium oxides and wherein the low refractive index material comprises silicon oxides.
12. The method of any of Claim 4-11 wherein the multilayer anti-reflection coating comprises:
(i) a first layer (11) having an index of refraction from about 2.0 to about 2.55 and that is about 7 to about 15 nm thick;
(ii) a second layer (12) having an index of refraction from about 1.38 to about 1.5 and that is about 15 to about 40 nm thick;
(iii) a third layer (13) having an index of refraction from about 2.0 to about 2.55 and that is about 90 to about 130 nm thick; and (iv) a fourth layer (14) having an index of refraction from about 1.38 to about 1.5 and that is about 55 to about 105 nm thick, wherein the indices of refraction are measured at a reference wavelength of 550 nm.
(i) a first layer (11) having an index of refraction from about 2.0 to about 2.55 and that is about 7 to about 15 nm thick;
(ii) a second layer (12) having an index of refraction from about 1.38 to about 1.5 and that is about 15 to about 40 nm thick;
(iii) a third layer (13) having an index of refraction from about 2.0 to about 2.55 and that is about 90 to about 130 nm thick; and (iv) a fourth layer (14) having an index of refraction from about 1.38 to about 1.5 and that is about 55 to about 105 nm thick, wherein the indices of refraction are measured at a reference wavelength of 550 nm.
13. The method of Claim 12 wherein the third layer is electrically conductive.
14. The method of any of Claims 4-13 further comprising the step of depositing an adhesion layer (10A) onto the ophthalmic lens surface prior to forming said multilayer anti-reflection coating thereon.
15. The method of any of Claims 4-14 wherein the at least one electrically conductive layer is formed by reactive sputtering whereby metal reacts with non-stoichiometric amounts of oxygen.
16. The method of any of Claims 1-15 wherein the coating has a thickness of about 200 to about 500 nm.
17. The method of any of Claims 4-16 wherein the at least one electrically conductive layer is formed by ion-assisted deposition.
18. The method of any of Claims 4-16 wherein the at least one electrically conductive layer is formed by electron beam ion-assisted deposition.
19. The lens of any of Claims 4-16 wherein the layer of electrically conductive metal oxide is formed by reactive sputtering.
20. The method of any of Claims 1-19 wherein the coating surface has an electric potential that is less than about 600 volts when measure immediately after being rubbed with a cloth.
21. The method of any of Claims 1-20 wherein the coating surface has an electric potential that is less than about 100 volts within about 5 seconds of being rubbed by the cloth.
22. The method of any of Claims 1-21 wherein the ophthalmic lens does not include a hydrophobic outer layer over the anti-reflection coating.
23. A high transmittance ophthalmic lens comprising:
an ophthalmic lens substrate (10); and a transparent, substantially static resistant multilayer film (11, 12) comprising alternating layers of high refractive index and low refractive index materials, wherein at least one layer of the multilayer film is electrically conductive.
an ophthalmic lens substrate (10); and a transparent, substantially static resistant multilayer film (11, 12) comprising alternating layers of high refractive index and low refractive index materials, wherein at least one layer of the multilayer film is electrically conductive.
24. The ophthalmic lens of Claim 23 wherein the multilayer film comprises alternating high and low refractive index materials such that each layer has a refractive index different from that of any adjoining layer, wherein the index of refraction of each low refractive index material is less than about 1.5 at a wavelength of about 550 nm, wherein the index of refraction of each high refractive index material is greater than about 2.0 at a wavelength of about 550 nm, and wherein said one or more electrically conductive layers comprise non-stoichiometric metal oxides.
25. The ophthalmic lens of Claim 23 or 24 wherein the high refractive index material comprises niobium oxides.
26. The ophthalmic lens of Claim 23 or 24 wherein the high refractive index material comprises titanium oxides.
27. The ophthalmic lens of any of Claims 23-26 wherein the low refractive index material comprises silicon oxides.
28. The ophthalmic lens of any of Claims 23-27 further comprising an adhesion layer (10A) interposed between the substrate and the multilayer film.
29. The ophthalmic lens of any of Claims 23-28 wherein the multilayer film comprises:
(i) a first layer (11) having an index of refraction from about 2.0 to about 2.55 and that is about 7 to about 15 nm thick;
(ii) a second layer (12) having an index of refraction from about 1.38 to about 1.5 and that is about 15 to about 40 nm thick;
(iii) a third layer (13) having an index of refraction from about 2.0 to about 2.55 and that is about 90 to about 130 nm thick; and (iv) a fourth layer (14) having an index of refraction from about 1.38 to about 1.5 and that is about 55 to about 105 nm thick, wherein the indices of refraction are measured at a reference wavelength of 550 nm.
(i) a first layer (11) having an index of refraction from about 2.0 to about 2.55 and that is about 7 to about 15 nm thick;
(ii) a second layer (12) having an index of refraction from about 1.38 to about 1.5 and that is about 15 to about 40 nm thick;
(iii) a third layer (13) having an index of refraction from about 2.0 to about 2.55 and that is about 90 to about 130 nm thick; and (iv) a fourth layer (14) having an index of refraction from about 1.38 to about 1.5 and that is about 55 to about 105 nm thick, wherein the indices of refraction are measured at a reference wavelength of 550 nm.
30. The ophthalmic lens of Claim 29 wherein the third layer is electrically conductive.
31. The ophthalmic lens of any of Claims 23-30 wherein the multilayer film surface has an electric potential that is less than about 600 volts when measured immediately after being rubbed with a cloth.
-27a-
-27a-
32. The ophthalmic lens of any of Claims 23-30 wherein the multilayer film surface has an electric potential that is less than about 100 volts within about 5 seconds of being rubbed by the cloth.
33. The ophthalmic lens of any of Claims 23-30 wherein the ophthalmic lens does not include a hydrophobic outer layer over the multilayer film.
34. An ophthalmic lens fabricated by a process that comprises the steps of:
providing a transparent ophthalmic lens substrate (10); and depositing, onto a surface of said substrate, a transparent, substantially static resistant multilayer anti-reflection coating (11, 12) wherein at least one layer is electrically conductive.
providing a transparent ophthalmic lens substrate (10); and depositing, onto a surface of said substrate, a transparent, substantially static resistant multilayer anti-reflection coating (11, 12) wherein at least one layer is electrically conductive.
35. The ophthalmic lens of Claim 34 wherein the step of depositing said coating comprises reacting metal with an effective non-stoichiometric amount of oxygen to form a layer of electrically conductive metal oxide.
36. The ophthalmic lens of Claim 34 or 35 wherein the layer of electrically conductive metal oxide is formed by electron beam evaporation.
37. The ophthalmic lens of Claim 35 wherein the layer of electrically conductive metal oxide is formed by reactive sputtering.
38. The ophthalmic lens of Claim 35 wherein the layer of electrically conductive metal oxide layer is formed by ion-assisted deposition.
39. The ophthalmic lens of Claim 35 wherein the layer of electrically conductive metal oxide layer is formed by electron beam ion-assisted deposition.
-27b-
-27b-
40. An ophthalmic lens fabricated by a process that comprises the steps of:
providing a transparent ophthalmic lens substrate (10); and depositing onto a surface of said substrate a transparent substantially anti-static multilayer film (11, 12) comprising alternating layers of high refractive index and low refractive index materials wherein at least one layer is electrically conductive.
providing a transparent ophthalmic lens substrate (10); and depositing onto a surface of said substrate a transparent substantially anti-static multilayer film (11, 12) comprising alternating layers of high refractive index and low refractive index materials wherein at least one layer is electrically conductive.
41. The ophthalmic lens of Claim 40 wherein the multilayer film of the ophthalmic lens in the neutral state has an electric potential that is less thanabout 100 volts.
42. The ophthalmic lens of Claim 40 or 41 wherein the multilayer film comprises:
alternating high and low refractive index materials such that each layer has a refractive index different from that of any adjoining layer wherein the index of refraction of each low refractive index material is less than about 1.5at a wavelength of about 550 nm, wherein the index of refraction of each high refractive index material is greater than about 2.0 at a wavelength of about 550 nm.
alternating high and low refractive index materials such that each layer has a refractive index different from that of any adjoining layer wherein the index of refraction of each low refractive index material is less than about 1.5at a wavelength of about 550 nm, wherein the index of refraction of each high refractive index material is greater than about 2.0 at a wavelength of about 550 nm.
43. The ophthalmic lens of any of Claims 40-42 wherein the high refractive index material comprises titanium oxides and wherein the low refractive index material comprises silicon oxides.
44. The ophthalmic lens of any of Claims 40-42 wherein the high refractive index material comprises niobium oxides and wherein the low refractive index material comprises silicon oxides.
45. The ophthalmic lens of any of Claims 40-42 wherein the multilayer film comprises:
-27c-(i) a first layer (11) having an index of refraction from about 2.0 to about 2.55 and that is about 7 to about 15 nm thick;
(ii) a second layer (12) having an index of refraction from about 1.38 to about 1.5 and that is about 15 to about 40 nm thick;
(iii) a third layer (13) having an index of refraction from about 2.0 to about 2.55 and that is about 90 to about 130 nm thick; and (iv) a fourth layer (14) having an index of refraction from about 1.38 to about 1.5 and that is about 55 to about 105 nm thick, wherein the indices of refraction are measured at a reference wavelength of 550 nm.
-27c-(i) a first layer (11) having an index of refraction from about 2.0 to about 2.55 and that is about 7 to about 15 nm thick;
(ii) a second layer (12) having an index of refraction from about 1.38 to about 1.5 and that is about 15 to about 40 nm thick;
(iii) a third layer (13) having an index of refraction from about 2.0 to about 2.55 and that is about 90 to about 130 nm thick; and (iv) a fourth layer (14) having an index of refraction from about 1.38 to about 1.5 and that is about 55 to about 105 nm thick, wherein the indices of refraction are measured at a reference wavelength of 550 nm.
46. The ophthalmic lens of Claim 45 wherein the third layer is electrically conductive.
47. The ophthalmic lens of any of Claims 40-46 further comprising an adhesion layer (10A) situated between the substrate surface and the multilayer film.
48. The ophthalmic lens of any of Claims 40-47 wherein the coating is formed by electron beam ion evaporation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/487,365 | 1995-06-07 | ||
| US08/487,365 US5719705A (en) | 1995-06-07 | 1995-06-07 | Anti-static anti-reflection coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2223273A1 true CA2223273A1 (en) | 1996-12-19 |
Family
ID=23935442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002223273A Abandoned CA2223273A1 (en) | 1995-06-07 | 1996-05-22 | Electrically conductive anti-reflection coating |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5719705A (en) |
| EP (1) | EP0834092B1 (en) |
| AU (1) | AU704597B2 (en) |
| CA (1) | CA2223273A1 (en) |
| DE (1) | DE69630526T2 (en) |
| WO (1) | WO1996041215A1 (en) |
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| US5989462A (en) | 1997-07-31 | 1999-11-23 | Q2100, Inc. | Method and composition for producing ultraviolent blocking lenses |
| US6212014B1 (en) * | 1997-09-29 | 2001-04-03 | Lsa, Inc. | MWIR polarizing beamsplitter cube and method of making the same |
| US6436541B1 (en) | 1998-04-07 | 2002-08-20 | Ppg Industries Ohio, Inc. | Conductive antireflective coatings and methods of producing same |
| US6319598B1 (en) * | 1998-07-23 | 2001-11-20 | Konica Corporation | Electromagnetic wave attenuating transparent member |
| JP2000147206A (en) * | 1998-11-11 | 2000-05-26 | Sony Corp | Antirefelection body |
| AUPP740798A0 (en) | 1998-11-30 | 1998-12-24 | Sola International Holdings Ltd | Customised coated lens |
| AU766852B2 (en) * | 1998-11-30 | 2003-10-23 | Carl Zeiss Vision Australia Holdings Ltd | Coated lens exhibiting substantially balanced reflectance |
| US6144479A (en) * | 1998-12-16 | 2000-11-07 | 3M Innovative Properties Company | Low reflectivity contrast enhancement filter |
| CN1145551C (en) * | 1998-12-28 | 2004-04-14 | 旭硝子株式会社 | Layered product and manufacture thereof |
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-
1995
- 1995-06-07 US US08/487,365 patent/US5719705A/en not_active Expired - Fee Related
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1996
- 1996-05-22 WO PCT/US1996/007772 patent/WO1996041215A1/en active IP Right Grant
- 1996-05-22 DE DE69630526T patent/DE69630526T2/en not_active Expired - Lifetime
- 1996-05-22 CA CA002223273A patent/CA2223273A1/en not_active Abandoned
- 1996-05-22 EP EP96916669A patent/EP0834092B1/en not_active Expired - Lifetime
- 1996-05-22 AU AU59347/96A patent/AU704597B2/en not_active Ceased
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| DE69630526T2 (en) | 2004-08-05 |
| US5719705A (en) | 1998-02-17 |
| MX9709675A (en) | 1998-06-30 |
| AU5934796A (en) | 1996-12-30 |
| EP0834092B1 (en) | 2003-10-29 |
| AU704597B2 (en) | 1999-04-29 |
| EP0834092A1 (en) | 1998-04-08 |
| EP0834092A4 (en) | 1999-08-11 |
| DE69630526D1 (en) | 2003-12-04 |
| WO1996041215A1 (en) | 1996-12-19 |
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