US4894303A — High energy beam-sensitive glasses

Claim 1

Independent Claim 312 words

A photo tool used in photolithographic processes comprising a glass plate bearing a recorded image readable in actinic radiation, said glass plate having an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion-exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said glass layer to render said IIES layer sensitive to high energy beams, said glass composition comprising of at least one alkali metaloxide selected from the groups of Li 2 O, Na 2 O, K 2 O, Cs 2 O and Rb 2 O, at least one photosensitivity inhibitor and/or RS-Suppression agent, SiO 2 , and up to saturation of chloride in its glass melts, said IIES layer having Ag + ions therein and/or a large number of AgCl-containing and/or Ag 2 O-containing and/or Ag + ion-containing microcrystals and/or microphases therein, containing silanol groups and/or water in the concentration range between about 0.01-12% by weight H 2 O, the concentrations of alkali metal ions in said IIES layer being less with an increase in the concentrations of Ag + ions, said IIES layer containing at least a portion of the amount of the photosensitivity inhibitors, the RS-Suppression agents, the glass network formers and chloride contained in said glass composition, the glass composition containing a sufficient amount of the photosensitivity inhibitors to render the IIES layer insensitive to at least the spectral portion of the actinic radiation having wavelengths longer than 300 nm, the surface quality and surface figure of said IIES layer remaining substantially the same before and after ion exchange reactions, said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image.

Claim 2

Dependent Claim 312 words

A photo tool used in photolithographic processes comprising a glass plate bearing a recorded image readable in actinic radiation, said glass plate having an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion-exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said glass layer to render said IIES layer sensitive to high energy beams, said glass composition comprising of at least one alkali metaloxide selected from the groups of Li 2 O, Na 2 O, K 2 O, Cs 2 O and Rb 2 O, at least one photosensitivity inhibitor and/or RS-Suppression agent, SiO 2 , and up to saturation of chloride in its glass melts, said IIES layer having Ag + ions therein and/or a large number of AgCl-containing and/or Ag 2 O-containing and/or Ag + ion-containing microcrystals and/or microphases therein, containing silanol groups and/or water in the concentration range between about 0.01-12% by weight H 2 O, the concentrations of alkali metal ions in said IIES layer being less with an increase in the concentrations of Ag + ions, said IIES layer containing at least a portion of the amount of the photosensitivity inhibitors, the RS-Suppression agents, the glass network formers and chloride contained in said glass composition, the glass composition containing a sufficient amount of the photosensitivity inhibitors to render the IIES layer insensitive to at least the spectral portion of the actinic radiation having wavelengths longer than 300 nm, the surface quality and surface figure of said IIES layer remaining substantially the same before and after ion exchange reactions, said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image.

Claim 3

Dependent Claim 135 words

The photo tool according to claim 1 wherein said glass composition consisting essentially of, in mole percent on the oxide basis, 3-25% of one or more alkali metal oxides. 0.5-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents, provided and effective amount of PI agents is included to render the IIEES layer insensitive to at least said spectral portion of actinic radiation, including at least 0.5% TiO 2 , up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 20% BaO, up to 25% P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 20-93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition.

Claim 4

Dependent Claim 150 words

The photo tool according to claim 2 wherein said glass composition consisting essentially of, in mole percent on the oxide basis. about 3-25% Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O and combinations thereof, 0.5-8.4% total of photosensitivity inhibitors (PI agents) and RS-Suppression agents (RSS agents). the composition containing at least an effective amount of PI agents to render said IIES layer insensitive to at least said spectral portion of the actinic radiation, including 0.5 to 7.4% TiO 2 , 3.6-7.6% ZnO, 0.6-2.4% A1203, up to 10.8% MgO, up to 4% CaO, up to 4% BaO, up to 3.5% PbO, up to 4% SrO, up to 7.2% B 2 O 3 , up to 7.2% P 2 O 5 , up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof, 0.2-6% Cl, and 58.5-73.2% SiO 2 ,

Claim 5

Dependent Claim 36 words

The photo tool according to claim 3 wherein said glass composition contains about 10-20% Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O and combinations thereof, and about 0.8-6% Cl.

Claim 6

Dependent Claim 29 words

The photo tool according to claim 3 wherein said glass composition contains about 12-16% Li 2 O, Na 2 O, K 2 O and combinations thereof and 0.4-3% Cl.

Claim 7

Dependent Claim 109 words

The photo tool according to claim 2 wherein said glass composition consisting essentially of, in mole percent on the oxide basis, about 12-18% Li 2 O, Na 2 O, K 2 O and combinations thereof, about 3-10% oxides of transition metals having 1 to 4 d-electrons in the atomic state, including about 3-10% TiO 2 , the glass composition containing a sufficient amount of the oxides of transition metals having 1 to 4 d-electrons in the atomic state to render the IIES layer insensitive to at least said spectral portion of the actinic radiation. about 4-15% ZnO, about 0.5-5% A1203, about 0.4-3% Cl, and about 65-75% SiO 2 .

Claim 8

Dependent Claim 57 words

The photo tool according to claim 6 wherein said glass composition c 12-16% Li 2 O, Na 2 O, K 2 O and combination thereof, 3% to 10% TiO 2 , the glass composition containing a sufficient amount of TiO 2 to render the IIES layer insensitive to at least said spectral portion of the actinic radiation.

Claim 9

Dependent Claim 23 words

The photo tool according to claim 1 wherein said spectral portion of actinic radiation has wavelengths equal to and longer than 365 nm.

Claim 10

Dependent Claim 42 words

The photo tool according to claim 1 wherein the IIES layer is sensitive to high energy beams selected from high voltage electron beams, ion beams, atomic beams, molecular beams, x-ray, and deep uv radiation having wavelengths of less than about 300 nm.

Claim 11

Dependent Claim 170 words

The photo tool according to claim I wherein said glass composition consisting essentially of, in mole percent on the oxide basis, about 5-25% of one or more alkali metal oxides, at least 1.5%, but less than 35% of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 5 , and combinations thereof, the composition containing at least an effective amount of the photosensitivity inhibitors to render the IIES layer insensitive to at least said spectral portion of the actinic radiation, 0-about 15% MgO, 0-about 15% CaO, 0-about I5% SrO, - about 20% AnO, 0-about 15% Al 2 O 3 , 0-about 15% PbO, 0-about 15% BaO, 0-about I5% B 2 O 3 , about 2-35% of at least one acid-durability-and glass-network-strengtheners (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, 0-about 3% F, Br and I, 0-about 6% Cl, and about 50-89% SiO 2 .

Claim 12

Dependent Claim 135 words

The photo tool according to claim 1 wherein said glass composition consisting essentially of, in mole percent on the oxide basis, about 5-25% of one or more alkali metal oxides, about 0.5-35% total of at least one photosensitivity inhibitor (PI agent) and RS-Suppression agent (RSS agent) selected from oxides of transition metals having 1 to 4 d-electrons in the atomic state. 0-about 15% MgO, 0-about 15% CaO 0-about 15% SrO about 2-20% ZnO 0-about 15% Al 2 O 3 , 0-about 15% PbO, provided that the amount of acid-durability durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO is from about 2% to 35%, 0-about 15% B 2 O 3 , 0-about 3% F, Br and I, 0-about 6% Cl, and about 50-89% SiO 2 .

Claim 13

Dependent Claim 75 words

The phototool according to claim 1, wherein the photolithographic processes are employed in the production of prerecorded disks bearing readable information selected from a group consisting of digital information and servo tracks, in the production of flat panel displays having a predetermined two dimensional pattern, in the production of hybrid circuits, surface-mount or fine-line printed circuit boards and in the production of other products by methods which employs photomasks and/or reticles in the photolithographic processes.

Claim 14

Dependent Claim 312 words

A photo tool used in photolithographic processes comprising a glass plate bearing a recorded image readable in actinic radiation, said glass plate having an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion-exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said glass layer to render said IIES layer sensitive to high energy beams, said glass composition comprising of at least one alkali metal oxide selected from the groups of Li 2 O, Na 2 O, K 2 O, Cs 2 O and Rb 2 O, at least one photosensitivity inhibitor and/or RS-Suppression agent, SiO 2 , and up to saturation of chloride in its glass melts, said IIES layer having Ag + ions therein and/or a large number of AgCl-containing and/or Ag 2 O-containing and/or Ag+ ioncontaining microcrystals and/or microphases therein, containing silanol groups and/or water in the concentration range between about 0.01-12% by weight H 2 O, the concentrations of alkali metal ions in said IIES layer being less with an increase in the concentration of Ag + ions, said IIES layer containing at least a portion of the amount of the photosensitivity inhibitors, the RS-Suppression agents, the glass network formers and chloride contained in said glass composition, the glass composition containing a sufficient amount of the photosensitivity inhibitors to render the IIES layer insensitive to at least the spectral portion of the actinic radiation having wavelengths longer than 400 nm, the surface quality and surface figure of said IIES layer remaining substantially the same before and after ion exchange reactions, said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image.

Claim 15

Dependent Claim 312 words

A photo tool used in photolithographic processes comprising a glass plate bearing a recorded image readable in actinic radiation, said glass plate having an integral ion-exchanged surface layer (IIES layer) bearing the recorded image, said IIES layer composed of a glass layer of a glass composition that has been ion-exchanged with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said glass layer to render said IIES layer sensitive to high energy beams, said glass composition comprising of at least one alkali metal oxide selected from the groups of Li 2 O, Na 2 O, K 2 O, Cs 2 O and Rb 2 O, at least one photosensitivity inhibitor and/or RS-Suppression agent, SiO 2 , and up to saturation of chloride in its glass melts, said IIES layer having Ag + ions therein and/or a large number of AgCl-containing and/or Ag 2 O-containing and/or Ag+ ioncontaining microcrystals and/or microphases therein, containing silanol groups and/or water in the concentration range between about 0.01-12% by weight H 2 O, the concentrations of alkali metal ions in said IIES layer being less with an increase in the concentration of Ag + ions, said IIES layer containing at least a portion of the amount of the photosensitivity inhibitors, the RS-Suppression agents, the glass network formers and chloride contained in said glass composition, the glass composition containing a sufficient amount of the photosensitivity inhibitors to render the IIES layer insensitive to at least the spectral portion of the actinic radiation having wavelengths longer than 400 nm, the surface quality and surface figure of said IIES layer remaining substantially the same before and after ion exchange reactions, said IIES layer having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said IIES layer to elemental silver to produce the recorded image.

Claim 16

Dependent Claim 131 words

The photo tool according to claim 13 wherein said glass composition consisting essentially of, in mole percent on the oxide basis, 3-25% of one or more alkali metal oxides. 0.5-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents, provided an effective amount of PI agents is included to render the IIEES layer insensitive to at least said spectral portion of actinic radiation, including at least 0.5% TiO 2 , up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 20% BaO, up to 25% P205, up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 20-93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the glass composition.

Claim 17

Dependent Claim 39 words

The photo tool according to claim 13 wherein said glass composition consisting essentially of, in mole percent on the oxide basis, about 3-25% Li 2 O, NaO, K 2 O, Rb 2 O, Cs 2 O and combinations thereof,

Claim 18

Dependent Claim 113 words

5-8.4% total of photosensitivity inhibitors (PI agents) and RS-Suppression agents (RSS agents), the composition containing at least an effective amount of PI agents to render said IIES layer insensitive to at least said spectral portion of the actinic radiation, including 0.5 to 7.4% TiO 2 , 3.6-7.6% ZnO, 0.6-2.4% Al 2 O 3 , up to 10.8% MgO, up to 4% CaO, up to 4% BaO, up to 3.5% PbO, up to 4% SrO, up to 7.2% B 2 O 3 , up to 7.2% P 2 O 5 , up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof, 0.2-6% C, and 58.5-73.2% SiO 2 ,

Claim 19

Dependent Claim 113 words

5-8.4% total of photosensitivity inhibitors (PI agents) and RS-Suppression agents (RSS agents), the composition containing at least an effective amount of PI agents to render said IIES layer insensitive to at least said spectral portion of the actinic radiation, including 0.5 to 7.4% TiO 2 , 3.6-7.6% ZnO, 0.6-2.4% Al 2 O 3 , up to 10.8% MgO, up to 4% CaO, up to 4% BaO, up to 3.5% PbO, up to 4% SrO, up to 7.2% B 2 O 3 , up to 7.2% P 2 O 5 , up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof, 0.2-6% C, and 58.5-73.2% SiO 2 ,

Claim 20

Dependent Claim 36 words

The photo tool according to claim 15 wherein said glass composition contains about 10-20% Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O and combinations thereof, and about 0.8-6% Cl.

Claim 21

Dependent Claim 29 words

The photo tool according to claim 15 wherein said glass composition contains about 12-16% Li 2 O, Na 2 O, K 2 O and combinations thereof and 0.4-3% Cl.

Claim 22

Dependent Claim 113 words

The photo tool according to claim 13 wherein said glass composition consisting essentially of, in mole percent on the oxide basis, about 12-18% Li 2 O, Na 2 O, K 2 O and combinations thereof, about 3-10% oxides of transition metals having 1 to 4 d-electrons in the atomic state, including about 3-10% TiO 2 , the glass composition containing a sufficient amount of the oxides of transition metals having 1 to 4 d-electrons in the atomic state to render the IIES layer insensitive to at least said spectral portion of the actinic radiation. about 4-15% ZnO, about 0.5-5% Al 2 O 3 , about 0.4-3% Cl, and about 65-75% SiO 2 .

Claim 23

Dependent Claim 57 words

The photo tool according to claim 18 wherein said glass composition contains 12-16% Li 2 O, Na 2 O, K 2 O and combination thereof, 3% to 10% TiO 2 , the glass composition containing a sufficient amount of TiO 2 to render the IIES layer insensitive to at least said spectral portion of the actinic radiation.

Claim 24

Dependent Claim 23 words

The photo tool according to claim 13 wherein said spectral portion of actinic radiation has wavelengths equal to and longer than 436 nm.

Claim 25

Dependent Claim 42 words

The photo tool according to claim 13 wherein the IES layer is sensitive to high energy beams selected from high voltage electron beams, ion beams, atomic beams, molecular beams, x-ray, and deep uv radiation having wavelengths of 1is than about 400 nm.

Claim 26

Dependent Claim 168 words

The photo tool according to claim 13 wherein said lass composition consisting essentially of, in mole percent on the oxide basis, about 5-25% of one or more alkali metal oxides, at least 1.5%, but less than 35% of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 5 , and combinations thereof, the composition containing at least an effective amount of the photosensitivity inhibitors to render the IIES layer insensitive to at least said spectral portion of the actinic radiation, 0-about 15% MgO, 0-about 15% CaO, 0-about 15% SrO, 0-about 20% ZnO, 0-about 15% Al 2 O 3 , 0-15% PbO, 0-about 15% BaO, 0-about I5% B 2 O 3 , about 2-35% of at least one acid-durability-and glass-network-strengtheners (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, 0-about 3% F, Br and I, 0-about 6% Cl, and about 50-89% SiO 2 .

Claim 27

Dependent Claim 136 words

The photo tool according to claim 13 wherein said glass composition consisting essentially of , in mole percent on the oxide basis, about 5-25% of one or more alkali metal oxides, about 0.5-35% total of at least one photosensitivity inhibitor (PI agent) and RS-Suppression agent (RSS agent) selected from oxides of transition metals having 1 to 4 d-electrons in the atomic state. 0-about 15% MgO, 0-about I5% CaO 0-about I5% SrO about 2-20% ZnO 0-about 15% Al 2 O 3 , 0-about 15% PbO, provided that the amount of acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO is from about 2% to 35%, 0-about 15% B 2 O 3 , 0-about 3% F, Br and I, - about 6% Cl, and about 50-89% SiO 2 .

Claim 28

Dependent Claim 82 words

The phototool according to claim 13, wherein the photolithographic processes are employed in the production of semiconductor chip products, in the production of prerecorded disks bearing readable information selected from a group consisting of digital information and servo tracks, in the production of flat panel displays having a predetermined two dimensional pattern, in the production of hybrid circuits, surface-mount or fine-line printed circuit boards and in the production of other products by methods which employs photomasks and/or reticles in the photolithographic processes.

Claim 29

Dependent Claim 200 words

A high-energy-beam-sensitive glass article bearing a recorded image readable in actinic radiation comprising a body portion and an integral ion exchanged surface layer bearing the recorded image, wherein said surface layer comprises a high-energy-beam-sensitive glass exhibiting photoinsensitivity and/or inertness to at least a portion of the actinic spectrum, said glass of said surface layer comprising SiO 2 , at least one alkali metal oxide, an amount of chloride up to its saturation level in the glass melt, at least one photosensitivity inhibitor and/or RS-suppression agent, silver components comprising Ag + ions and/or AgCl-containing and/or Ag 2 O-containing and/or Ag + ion-containing microcrystals and/or microphases and, silanol groups and/or water in the concentration range equivalent to about 0.01-12% by weight H 2 O, the amount of said silver components and photosensitivity inhibitors in said glass of said surface layer being effective to render the glass substantially photoinsensitive to substantially all actinic radiation photosensitive to radiation of energy higher than that of a wavelength of about 365 nm, said glass having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said glass to elemental silver to produce the recorded image.

Claim 30

Dependent Claim 200 words

A high-energy-beam-sensitive glass article bearing a recorded image readable in actinic radiation comprising a body portion and an integral ion exchanged surface layer bearing the recorded image, wherein said surface layer comprises a high-energy-beam-sensitive glass exhibiting photoinsensitivity and/or inertness to at least a portion of the actinic spectrum, said glass of said surface layer comprising SiO 2 , at least one alkali metal oxide, an amount of chloride up to its saturation level in the glass melt, at least one photosensitivity inhibitor and/or RS-suppression agent, silver components comprising Ag + ions and/or AgCl-containing and/or Ag 2 O-containing and/or Ag + ion-containing microcrystals and/or microphases and, silanol groups and/or water in the concentration range equivalent to about 0.01-12% by weight H 2 O, the amount of said silver components and photosensitivity inhibitors in said glass of said surface layer being effective to render the glass substantially photoinsensitive to substantially all actinic radiation photosensitive to radiation of energy higher than that of a wavelength of about 365 nm, said glass having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said glass to elemental silver to produce the recorded image.

Claim 31

Dependent Claim 30 words

A glass article of claim 25 wherein the glass article is a glass product selected from glass filter, encoder disks, glass scales, optical reticles, photo tools and the like products.

Claim 32

Dependent Claim 72 words

A glass article of claim 25 wherein said photosensitivity inhibitor and/or RS-suppression agent is an amount of at least one oxide of a transition metal which has 1 to 4 d-electrons in the atomic state, effective to render said glass photo insensitive to substantially all actinic radiation having a wavelength longer than about 365 nm and photo sensitive to radiation of energy higher than that of a wavelength of about 365 nm.

Claim 33

Dependent Claim 40 words

A glass article of claim 27 wherein said amount is effective to render said glass photoinsensitive to substantially all actinic radiation having a wavelength longer than about 300 nm and sensitive to radiation of energy higher than about 300 nm.

Claim 34

Dependent Claim 38 words

A glass article of claim 25 wherein said surface layer has been prepared by ion exchanging silver ions into a precursor glass containing the same components as said glass of said surface layer except for said silver components.

Claim 35

Dependent Claim 44 words

A glass article of claim 94 wherein said ion exchange is effected with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said precursor glass to render the resultant ion-exchanged glass of said surface layer sensitive to high energy beams.

Claim 36

Dependent Claim 61 words

A glass article of claim 29 wherein said silver ions exchange with alkali metal ions in said precursor glass whereby the concentration of alkali metal ions in the resultant ion exchanged glass surface layer is lower than that of the precursor glass body in proportion to the concentration of the Ag + ions exchanged into the glass of said surface layer.

Claim 37

Dependent Claim 42 words

A glass article of claim 28 which is sensitive to high energy beam which is a high voltage electron beam, an ion beam, an atomic beam, a molecular beam, x-ray radiation or deep uv radiation having wavelengths shorter than about 300 nm.

Claim 38

Dependent Claim 35 words

A glass article of claim 29 wherein the surface of said precursor glass which is ion exchanged has substantially the same surface quality and surface figure after the ion exchange treatment as before said treatment.

Claim 39

Dependent Claim 38 words

A glass article of claim 28 wherein said surface layer has been prepared by ion exchanging silver ions into a precursor glass containing the same components as said glass of said surface layer except for said silver components.

Claim 40

Dependent Claim 63 words

A glass article of claim 25 wherein the glass article is an optical software disk employed to load programs into various computers as well as supplying a recording medium to serve the market for personal computers, video games, office systems, data distribution systems and other information systems, and said pre-recorded image is selected from a group consisting of digital information and servo tracks.

Claim 41

Dependent Claim 25 words

A glass article of claim 25 wherein modes of exposure to said high energy beams being selected from bit by bit exposure and flood exposure.

Claim 42

Dependent Claim 18 words

A glass article of claim 36 wherein said flood exposure includes electron image projection printing and contact printing.

Claim 43

Dependent Claim 23 words

The glass article according to claim 36 wherein at least a portion of said glass is uniformly darkened to form the recorded image.

Claim 44

Dependent Claim 135 words

The glass article according to claim 30 wherein said precursor glass consisting essentially of, in mole percent on the oxide basis, 3-25% of one or more alkali metal oxides, 0.5-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents, provided an effective amount of PI agents is included to render the glass photoinsensitive to at least said spectral portion of actinic radiation, including at least 0.5% TiO 2 , up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 20% BaO, up to 25 % P 2 O 5 , up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 20-93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the precursor glass.

Claim 45

Dependent Claim 148 words

The glass article according to claim 25 wherein said precursor glass consisting essentially of, in mole percent on the oxide basis, about 3-25% Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O and combinations thereof, 0.5-8.4% total of photosensitivity inhibitors )PI agents) and RS-suppression agents (RSS agents), the precursor glass containing at least an effective amount of PI agents to render said glass photoinsensitive to said spectral portion of the actinic radiation, including 0.5 to 7.4% TiO 2 , 3.6-7.6% ZnO, 0.6-2.4% Al 2 O 3 , up to 4% CaO, up to 4% BaO, up to 3.5% PbO, up to 4% SrO, up to 7.2% B 2 O 3 , up to 7.2% P 2 O 5 , up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof, 0.2-6% Cl, and 58.5-73.2% SiO 2 ,

Claim 46

Dependent Claim 36 words

The glass article according to claim 40 wherein said precursor glass contains about 10-20% Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O and combinations thereof, and about 0.8-6% Cl.

Claim 47

Dependent Claim 29 words

The glass article according to claim 40 wherein said precursor glass contains about 12-16% Li 2 O, Na 2 O, K 2 O and combinations thereof and 0.4-3% Cl.

Claim 48

Dependent Claim 110 words

The glass article according to claim 35 wherein said precursor glass consisting essentially of, in mole percent on the oxide basis, about 12-8% Li 2 O, Na 2 O, K 2 O and combinations thereof, about 3-10% oxides of transition metals having 1 to 4 d-electrons in the atomic state, including about 3-10% TiOs, the precursor glass containing a sufficient amount of the oxides of transition metals having 1 to 4 d-electrons in the atomic state to render the glass photoinsensitive to at least said spectral portion of the actinic radiation. about 4-15% ZnO, about 0.5-5% Al 2 O 3 , about 0.4-3% Cl, and about 65-75% SiO 2 .

Claim 49

Dependent Claim 53 words

The glass article of claim 43 wherein said precursor glass contains 12-16% Li 2 O, Na 2 O, K 2 O and combination thereof, 3% to 10% TiO 2 , the precursor glass containing an effective amount of TiO 2 to render the glass photoinsensitive to said spectral portion of the actinic radiation.

Claim 50

Dependent Claim 165 words

The glass article of claim 30 wherein said precursor glass consisting essentially of, in mole percent on the oxide basis, about 5-25% of one or more alkali metal oxides, at least 1.5%, but less than 35% of photosensitivity inhibitors (PI agents ) selected from the group consisting of TiO 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 5 , and combinations thereof, the precursor glass containing an effective amount of the photosensitivity inhibitors to render the glass photoinsensitive to said spectral portion of the actinic radiation, 0-about 15% MgO, 0-about 1% CaO, 0-about 15% SrO, 0-about 20% ZnO, 0-about 15% Al 2 O 3 , 0-about 15% PbO, 0-about 15% BaO, 0-about 15% B 2 O 3 , about 2-35% of at least one acid-durability-and glass-network-strengtheners (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, 0-about 3% F, Br and I, 0-about 6% Cl, and 0-about 50-89% SiO 2 .

Claim 51

Dependent Claim 129 words

The glass article according to claim 30 wherein said precursor glass consisting essentially of, in mole percent on the oxide basis, about 5-25% of one or more alkali metal oxides, about 0.5-35% total of at lest one photosensitivity inhibitor (PI agent) and RS-suppression agent (RSS agent) selected from oxides of transition metals having 1 to 4 d-electrons in the atomic 0-about 15% MgO, 0-about 15% CaO, 0-about 15% SrO, about 2-20% ZnO, 0-about 15% A1203 0-about 15% PbO, provided that the amount of acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO is from about 2% to 35% 0-about 15% B 2 O 3 , 0-about 3% F, Br and I, 0-about 6% Cl, and about 50-89% SiO 2 .

Claim 52

Dependent Claim 209 words

A high-energy-beam-sensitive glass article bearing a recorded image readable in actinic radiation comprising a body portion and an integral ion exchange surface layer bearing the recorded image, wherein said surface layer comprises a high-energy-beam-sensitive glass exhibiting photoinsensitivity and/or inertness to at least a portion of the actinic spectrum, said glass of said surface layer comprising SiO 2 , at least one alkali metal oxide, an amount of chloride up to its saturation level in the glass melt, at least one photosensitivity inhibitor and/or RS-suppression agent, Silver components comprising Ag + ions and/or AgCl-containing and/or Ag 2 O-containing and/or Ag + ion-containing microcrystals and/or microphases and, silanol groups and/or water in the concentration range equivalent to about 0.01-12% by weight H 2 O, the amount of said silver components and photosensitivity inhibitors in said glass of said surface layer being effective to render the glass substantially photoinsensitive to substantially all actinic radiation having a wavelength longer than about 436 nm and photosensitive to radiation of energy higher than that of a wavelength of about 436 nm, said glass having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said glass to elemental silver to produce the recorded image.

Claim 53

Dependent Claim 209 words

A high-energy-beam-sensitive glass article bearing a recorded image readable in actinic radiation comprising a body portion and an integral ion exchange surface layer bearing the recorded image, wherein said surface layer comprises a high-energy-beam-sensitive glass exhibiting photoinsensitivity and/or inertness to at least a portion of the actinic spectrum, said glass of said surface layer comprising SiO 2 , at least one alkali metal oxide, an amount of chloride up to its saturation level in the glass melt, at least one photosensitivity inhibitor and/or RS-suppression agent, Silver components comprising Ag + ions and/or AgCl-containing and/or Ag 2 O-containing and/or Ag + ion-containing microcrystals and/or microphases and, silanol groups and/or water in the concentration range equivalent to about 0.01-12% by weight H 2 O, the amount of said silver components and photosensitivity inhibitors in said glass of said surface layer being effective to render the glass substantially photoinsensitive to substantially all actinic radiation having a wavelength longer than about 436 nm and photosensitive to radiation of energy higher than that of a wavelength of about 436 nm, said glass having been exposed to high energy beams in a predetermined pattern to reduce at least a portion of the silver ions of said glass to elemental silver to produce the recorded image.

Claim 54

Dependent Claim 30 words

A glass article of claim 47 wherein the glass article is a glass product selected from glass filter, encoder disks, glass scales, optical reticles, photo tools and the like products.

Claim 55

Dependent Claim 71 words

A glass article of claim 47 wherein said photosensitivity inhibitor and/or RS-suppression agent is an amount of at least one oxide of a transition metal which has 1 to 4 d-electrons in the atomic state, effective to render said glass photo insensitive to substantially all actinic radiation having a wavelength longer than about 436 nm and photosensitive to radiation of energy higher than that of a wavelength of about 436 nm.

Claim 56

Dependent Claim 40 words

A glass article of claim 49 wherein said amount is effective to render said glass photoinsensitive to substantially all actinic radiation having a wavelength longer than about 400 nm and sensitive to radiation of energy higher than about 400 nm.

Claim 57

Dependent Claim 44 words

A glass article of claim 47 wherein said surface layer has been prepared by ion exchanging silver ions into a precursor glass containing the same components as said glass of said surface layer except for said silver components and said silanol groups and/or water.

Claim 58

Dependent Claim 44 words

A glass article of claim 51 wherein said ion exchange is effected with an acidic aqueous solution containing soluble ionic silver to diffuse silver ions into said precursor glass to render the resultant ion-exchanged glass of said surface layer sensitive to high energy beams.

Claim 59

Dependent Claim 61 words

A glass article of claim 51 wherein said silver ions exchange with alkali metal ions in said precursor glass whereby the concentration of alkali metal ions in the resultant ion exchanged glass surface layer is lower than that of the precursor glass body in proportion to the concentration of the Ag + ions exchanged into the glass of said surface layer.

Claim 60

Dependent Claim 41 words

A glass article of claim 50 which is sensitive to high energy beam which is a high voltage electron beam, an ion beam, an atomic beam, a molecular beam, x-ray radiation or uv radiation having wavelengths shorter than about 400 nm.

Claim 61

Dependent Claim 35 words

A glass article of claim 51 wherein the surface of said precursor glass which is ion exchanged has substantially the same surface quality and surface figure after the ion exchange treatment as before said treatment.

Claim 62

Dependent Claim 38 words

A glass article of claim 50 wherein said surface layer has been prepared by ion exchanging silver ions into a precursor glass containing the same components as said glass of said surface layer except for said silver components.

Claim 63

Dependent Claim 63 words

A glass article of claim 47 wherein the glass article is an optical software disk employed to load programs into various computers as well as supplying a recording medium to serve the market for personal computers, video games, office systems, data distribution systems and other information systems, and said pre-recorded image is selected from a group consisting of digital information and servo tracks.

Claim 64

Dependent Claim 25 words

A glass article of claim 47 wherein modes of exposure to said high energy beams being selected from bit by bit exposure and flood exposure.

Claim 65

Dependent Claim 18 words

A glass article o claim 58 wherein said flood exposure includes electron image projection printing and contact printing.

Claim 66

Dependent Claim 23 words

The glass article according to claim 58 wherein at least a portion of said glass is uniformly darkened to form the recorded image.

Claim 67

Dependent Claim 130 words

The glass article according to claim 52 wherein said precursor glass consisting essentially of, in mole percent on the oxide basis, 3-25% of one or more alkali metal oxides. 0.5-35% total of photosensitivity inhibitors (PI agents) and RS-suppression agents, provided an effective amount of PI agents is included to render the glass photoinsensitive to at least said spectral portion of actinic radiation, including at least 0.5% TiO 2 , up to 35% of acid-durability-and-glass-network strengtheners (ADAGNS), up to 20% BaO, up to 25% P203, up to 25% B 2 O 3 , up to 4% F, up to 6% Cl, up to 2% Br, up to 2% I, and 20-93% SiO 2 , the sum amount of the above components constituting at least 75 mole percent of the precursor glass.

Claim 68

Dependent Claim 82 words

The glass article according to claim 52 wherein said precursor glass consisting essentially of, in mole percent on the oxide basis, about 3-25% Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O and combinations thereof, 0.5-8.4% total of photosensitivity inhibitors (PI agents) and RS-Suppression agents (RSS agents). the precursor glass containing at least an effective amount of PI agents to render said glass photoinsensitive to said spectral portion of the actinic radiation, including 0.5 to 7.4%

Claim 69

Dependent Claim 67 words

6-7.6% ZnO, 0.6-2.4% Al 2 O 3 , up to 10.8% MgO, up to 4% CaO, up to 4% BaO, up to 3.5% PbO, up to 4% SrO, up to 7.2% B 2 O 3 , up to 7.2% P 2 O 5 , up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof, 0.2-6% Cl, and 58.5-73.2% SiO 2 ,

Claim 70

Dependent Claim 67 words

6-7.6% ZnO, 0.6-2.4% Al 2 O 3 , up to 10.8% MgO, up to 4% CaO, up to 4% BaO, up to 3.5% PbO, up to 4% SrO, up to 7.2% B 2 O 3 , up to 7.2% P 2 O 5 , up to 1.5% halide selected from the group consisting of F, Br, I and combinations thereof, 0.2-6% Cl, and 58.5-73.2% SiO 2 ,

Claim 71

Dependent Claim 36 words

The glass article according to claim 62 wherein said precursor glass contains about 10-20% Li 2 O, Na 2 O, K 2 O, Rb 2 O, Cs 2 O and combinations thereof, and about 0.8-6% Cl.

Claim 72

Dependent Claim 29 words

The glass article according to claim 62 wherein said precursor glass contains about 12-16% Li 2 O, Na 2 O, K 2 O and combinations thereof and 0.4-3% Cl.

Claim 73

Dependent Claim 112 words

The glass article according to claim 52 wherein said precursor glass consisting essentially of, in mole percent on the oxide basis, about 12-18% Li 2 O, Na 2 O, K 2 O and combinations thereof, about 3-10% oxides of transition metals having 1 to 4 d-electrons in the atomic state, including about 3-10% TiO 2 , the precursor glass containing a sufficient amount of the oxides of transition metals having 1 to 4 d-electrons in the atomic state to render the glass photoinsensitive to at least said spectral portion of the actinic radiation. about 4-15% ZnO, about 0.5-5% Al 2 O 3 , about 0.4-3% Cl, and about 65-75% SiO 2 .

Claim 74

Dependent Claim 53 words

The glass article of claim 65 wherein said precursor glass contains 12-16% Li 2 O, Na 2 O, K 2 O and combination thereof, 3% to 10% TiO 2 , the precursor glass containing an effective amount of TiO 2 to render the glass photoinsensitive to said spectral portion of the actinic radiation.

Claim 75

Dependent Claim 164 words

The glass article of claim 52 wherein said precursor glass consisting essentially of, in mole percent on the oxide basis, about 5-25% of one or more alkali metal oxides, at least 1.5% but less than 35% of photosensitivity inhibitors (PI agents) selected from the group consisting of TiO 2 , Nb 2 O 5 , Y 2 O 3 , Ta 2 O 3 , and combinations thereof, the precursor glass containing an effective amount of the photosensitivity inhibitors to render the glass photoinsensitive to said spectral portion of the actinic radiation, 0-about 15% MgO, 0-about 15% CaO, 0-about 15% SrO, 0-about 20% ZnO, 0-about 15% Al 2 O 3 , 0-about 15% PbO, 0-about 15% BaO, 0-about 15% B 2 O 3 , about 2-35% of at least one acid-durability-and glass-network-strengtheners (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO, 0-about 3% F, Br and I, 0-about 6% Cl, and about 50-89% SiO 2 .

Claim 76

Dependent Claim 134 words

The glass article according to claim 52 wherein said precursor glass consisting essentially of, in mole percent on the oxide basis, about 5-25% of one or more alkali metal oxides, about 0.5-35% total of at least one photosensitivity inhibitor (PI agent) and RS-Suppression agent (RSS agent) selected from oxides of transition metals having 1 to 4 d-electrons in the atomic state. 0-about 15% MgO, 0-about 15% CaO 0-about 15% SrO about 2-20% ZnO 0-about 5% Al 2 O 3 , 0-about 15% PbO, provided that the amount of acid-durability-and-glass-network-strengthener (ADAGNS) selected from the group consisting of MgO, ZnO, Al 2 O 3 , PbO and CaO is from about 2% to 35%, 0-about 15% B 2 O 3 , 0-about 3% F, Br and I, 0-about 6% Cl, and about 50-89% SiO 2 .

Annuity Stage	Window Opens	Payment Deadline	Surcharge Period Until	Estimated Fee	Status
3.5 Years (Year 4)	1993-01-15	1993-07-17	1994-01-16	$2000.00	Window Closed / Lapsed
7.5 Years (Year 8)	1997-01-15	1997-07-17	1998-01-16	$3760.00	Window Closed / Lapsed
11.5 Years (Year 12)	2001-01-15	2001-07-17	2002-01-16	$7700.00	Window Closed / Lapsed

High energy beam-sensitive glasses

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