KR20030082606A - Oxygen doping of silicon oxyfluoride glass - Google Patents

Abstract

The present invention relates to high purity silicon oxyfluoride glass suitable for photomask substrates for photolithography applications in the VUV wavelength region below 190 nm. The doped glass 20 is made by providing an O ₂ doping atmosphere 26 to the silicon oxyfluoride glass 22 in the doping vessel 28. The silicon oxyfluoride glass of the present invention is particularly useful as a photomask substrate in the 157 nm wavelength region by transmitting at a wavelength near 157 nm. The photomask substrate of the present invention is a "dry" silicon oxyfluoride glass containing doped O ₂ molecules and exhibiting very high transmittance and laser transmission durability in the vacuum ultraviolet (VUV) wavelength region. The silicone oxyfluoride glass of the present invention, in addition to containing fluorine and low or no OH content, contains intersticial O ₂ molecules that provide improved durability to laser exposure. Silicon oxyfluoride glasses, preferably doped with O ₂ , are characterized by having hydrogen molecules of less than 1 × 10 ¹⁷ molecules / cm ³ and low chlorine levels.

Description

Oxygen doping of silicon oxyfluoride glass {OXYGEN DOPING OF SILICON OXYFLUORIDE GLASS}

Refractive lenses require materials with high transmission. For applications in semiconductors that require increasingly smaller features at wavelengths of 248 and 193 nm, high purity fused silica exhibited a transmittance of over 99% / cm required.

Projection optical photolithography systems using vacuum ultraviolet wavelength light of less than 193 nm have the advantage of obtaining a smaller range. Such systems using vacuum ultraviolet wavelengths in the 157 nm wavelength region can improve integrated circuits with smaller sizes. In the manufacture of integrated circuits, conventional optical lithography systems used by the semiconductor industry have generally developed to shorter wavelengths of light, such as wavelengths of 248 nm and 193 nm, but commercial applications of vacuum ultraviolet wavelengths below 193 nm, such as 157 nm, and Adoption has been delayed by the transmission characteristics of the vacuum ultraviolet wavelength in the 157 nm region passing through the optical material. Such a slow development by the semiconductor industry using sub-UV VUV light, such as 157 nm light, is also due to defects in photomask blanks that can be economically produced from optically transmissive materials. For the advantages of vacuum ultraviolet photolithography in the 157 nm region, such as the emission spectrum VUV window of the F ₂ excimer laser used in the manufacture of integrated circuits, it has beneficial optical properties including good transmission below 164 nm and at 157 nm. There is a need for glass that is highly durable and economically manufactured.

The present invention overcomes the aforementioned problems of the prior art and provides an economical high purity improved photomask blank and VUV transmissive lithography glass that can be used to improve the fabrication of integrated circuits with vacuum ultraviolet wavelengths.

Summary of the Invention

The inventors have found that dry high purity fused silica (<1 ppm OH) exhibits excellent permeability in deep ultraviolet light as compared to “wet” high purity fused silica (eg, Corning code 7980). With the addition of fluorine, the permeation of dry silica in the VUV can be much improved. For this glass, transmissions such as 79.8% / 6.35 mm (90% / cm internal T) at 157 nm were measured. Such materials are particularly important for devices for 157 nm lithography such as photomask substrates, thin films, thin lenses and windows. This application is important not only in that the glass exhibits a high initial transmission, but also that the transmission should not be reduced under exposure to an F ₂ excimer laser. For a 157 nm photomask material, the glass preferably has a <1% transmission decrease at 157.6 nm after exposure to an F ₂ excimer laser for 60 million pulses at 0.1 mJ / cm ² . The present invention describes a silicon oxyfluoride glass containing a high level of oxygen molecules and a method for producing the same, which exhibits a low F ₂ laser induced absorption compared to an oxygen free glass.

The present invention includes a method of making a VUV-transmissive glass for transmission of VUV wavelengths below 200 nm, such as the 157 nm wavelength produced by an F ₂ excimer laser. The method of silicon oxyfluoride comprising: providing a glass, the method comprising: providing a plurality of O ₂ molecules, and epilepsy (intersticial) VUV transmissive silicon oxyfluoride silicon the O ₂ molecules in order to provide a glass containing an O ₂ molecule Doping into the oxyfluoride glass.

The present invention includes a method of making a laser durable VUV-permeable silicon oxyfluoride glass that is resistant to F ₂ laser induced absorption and preferably resistant to F ₂ excimer laser exposure. The method includes providing a solidified silicon oxyfluoride glass and providing an O ₂ doped treatment atmosphere. The method includes enclosing the silicon oxyfluoride glass in an O ₂ doped treatment atmosphere and dissolving a plurality of O ₂ molecules from the atmosphere into the silicon oxyfluoride glass to provide insoluble O ₂ molecules.

The present invention includes a method of making a VUV-transmitting silicon oxyfluoride glass that is durable to lasers. The method includes providing a non-solidified silicon oxyfluoride glass precursor and providing a freezing furnace having a heated solidification region for solidifying the non-solidified glass precursor. The method includes supplying an oxygen doping atmosphere to a solidification furnace and solidifying the glass precursor with the solidified silicon oxyfluoride glass, wherein the O ₂ molecules are in the solidified silicon oxyfluoride glass Dissolves.

The present invention includes a VUV transmissive glass photomask substrate. The photomask substrate comprises silicon oxyfluoride glass doped with a plurality of O ₂ molecules.

The present invention includes VUV-permeable silicone oxyfluoride glass. The VUV transmissive silicon oxyfluoride glass contains a plurality of doped O ₂ molecules and is resistant to the absorption band of VUV laser induction.

It is to be noted that both the foregoing general description and the following detailed description are merely illustrative of the invention and are intended to provide an overview or framework for understanding the features and nature of the claimed invention. The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings will illustrate various embodiments of the invention together with a description to explain the principles and operation of the invention.

This application claims the priority of US Provisional Application No. 60 / 271,135, filed Feb. 24, 2001, and US Patent Application No. 09 / 997,782, filed Nov. 28, 2001.

This application is currently incorporated under US Patent No. 6,242,136. US Patent Application No. 09 / 397,573, filed Sep. 16, 1999, by the name of vacuum ultraviolet transmission silicon oxyfluoride lithography glass by Lisa A. Moore and Charlene Smith. do. This application is directed to George Berkey, Lisa A. Moore and Michelle D. George Bulky, Lisa A., filed September 16, 1999, under the name Projection Lithography Photomask and its manufacturing method by Michelle D. Pierson, US Patent No. 6,265,115. Mr. Moore and Charlie. Vacuum ultraviolet light by U.S. Patent Application Serial No. 09 / 397,577, filed Sep. 16, 1999, under the name Projection Lithography Photomask Blanks, Preforms and Manufacturing Methods by Charles C. Yu, and by Charlene Smith and Lisa Moore. US Provisional Patent Application No. 60 / 271,136 filed on February 24, 2001 under the name of permeable silicon oxyfluoride lithography glass, which is incorporated herein by reference.

The present invention generally utilizes vacuum ultraviolet light (VUV) wavelengths of 193 nm or less, preferably 175 nm or less, and more preferably 164 nm or less, such as lithography, specifically VUV projection lithography systems using wavelengths in the 157 nm region. An optical photolithography glass for use in an optical photolithography system.

FIELD OF THE INVENTION The present invention relates to VUV transmissive glass transmitted at wavelengths below 193 nm, and in particular to photomask silicon oxy fluorides suitable for use in the vacuum ultraviolet (VUV) 157 nm wavelength region.

1 shows a glass and a method according to the invention.

2 shows a glass and a method according to the invention.

3 shows a glass, VUV lithography system and method according to the present invention.

4 shows a glass, VUV lithography system and method according to the present invention.

Figure 5 shows a VUV transmissive silicon oxyfluoride glass photomask substrate in accordance with the present invention (Figure 5A top view, Figure 5B side).

FIG. 6 shows the exposure to F ₂ excimer laser (open circle, 0), after F ₂ excimer laser exposure (open square, □) for 10.6E6 pulses at 2mJ / cm ² -pulse (open square, □), and F ₂ excimer laser exposure The VUV absorption spectrum of the silicon oxyfluoride glass after oxygen treatment (1 O ₂ atmosphere at 1000 ° C. for 7 days) (closed diamond, ◆) is shown.

FIG. 7 shows the VUV absorption spectrum of silicon oxyfluoride glass heated in oxygen (open circle, 0) and then F ₂ excimer laser exposed (closed diamond, ◆) for 9.92E6 pulses at 2mJ / cm ² -pulse. . VUV absorption spectral curves for the same glass without oxygen pretreatment with the same laser conditions (10.6E6 pulses at 2mJ / cm ² -pulse, open square, □) are included for comparison.

The present invention includes a method for producing a VUV-permeable glass. The VUV transmissive glass provides transmission of VUV wavelengths of 200 nm or less, such as 157 nm wavelength radiation of an F ₂ excimer laser. The VUV transmissive glass is resistant to F ₂ excimer laser exposure and resistant to the induced absorption of the F ₂ laser. The method includes providing a silicon oxyfluoride glass and providing a plurality of O ₂ molecules. The method includes doping the O ₂ molecules into the silicon oxyfluoride glass to provide a VUV-permeable silicon oxyfluoride glass containing interstitial O ₂ molecules. Providing the silicon oxyfluoride glass preferably comprises silicon oxyfluoride glass containing fluorine in the range of at least 0.1% by weight, more preferably in the range of 0.1 to 2% by weight. Preferred fluorine content is in the range of 0.1 to 0.4% by weight. Preferred fluorine content ranges from 0.1 to 0.4% by weight. Preferred fluorine content is about 0.2 (± 0.3) wt% F. Providing the silicon oxyfluoride glass preferably comprises providing a dry silicon oxyfluoride glass having an OH content of 50 ppm or less by weight. Preferably the dry silicon oxyfluoride glass has <10 ppm OH by weight, more preferably <5 ppm OH by weight, most preferably <1 ppm OH by weight. Providing the silicon oxyfluoride glass preferably comprises providing the silicon oxyfluoride glass having a Cl content of less than 5 ppm by weight, more preferably a Cl content of <1 ppm by weight. The step of doping the O ₂ molecule when the manufacturing steps are completed, the O ₂ molecules, and preferably the steps include the dissolving into the silicon oxyfluoride glass, wherein the phase O ₂ molecules are dissolved in the glass It preferably has a step of remaining as O ₂ molecules in the glass, and the glass is injected for the wavelength of transmitted light. O ₂ molecules remain as O ₂ molecules in the glass at the end of the preparation step, and the glass contains interstitial O ₂ molecules as insoluble O ₂ molecules.

1 shows one embodiment of a method of manufacturing a VUV-permeable glass 20. The method includes providing an O ₂ doped atmosphere 26, wherein the O ₂ doped atmosphere has an O ₂ concentration of at least 10 ¹⁵ O ₂ molecules / cc. Preferably the O ₂ doping treatment atmosphere has an O ₂ concentration of ≧ 10 ¹⁶ O ₂ molecules / cc. Preferably the O ₂ doping treatment atmosphere has an O ₂ concentration of <10 ²⁰ O ₂ molecules / cc. Specifically preferred O ₂ concentrations are in the range of about 10 ¹⁶ to 10 ²⁰ O ₂ molecules / cc. The method preferably includes the step of providing an O ₂ doped vessel 28 for containing an O ₂ atmosphere and doped silicon oxyfluoride glass 22. The method preferably comprises heating the treatment atmosphere 26 and glass 22 to a predetermined O ₂ doping temperature, wherein the method is effective for doping O ₂ molecules into the glass. Preferably, the O ₂ doping temperature is at least 600 ° C. Preferably the O ₂ doping treatment atmosphere is at least one O ₂ atmosphere. In one embodiment, the present invention includes the step of hipping the glass 22 to balance heat compression in the presence of the O ₂ molecular atmosphere. In one embodiment, the present invention includes pressurizing the interior of the O ₂ doping vessel such that the glass 22 is doped with O ₂ from the pressurized O ₂ treatment atmosphere. Preferably the O ₂ doped processing vessel 28 comprises a non-fouling refractory material. More preferably the non-polluting refractory material treatment vessel is a non-metal bell vessel such as a silica quartz muffle furnace or a bell vessel in any base metal. As shown in FIG. 2, in one embodiment, the method includes solidifying the silicon oxyfluoride glass with O ₂ molecules in the presence of O ₂ molecules. In FIG. 2, the non-solidified glass 24 is solidified with the solidified glass 22 such that the solidified silicon oxyfluoride glass 20 contains doped O ₂ molecules.

The present invention includes a method for producing laser durable VUV-permeable silicon oxyfluoride glass. The method includes providing silicon oxyfluoride glass 22. The method includes providing an O ₂ doped treatment atmosphere. The method includes enclosing silicon oxyfluoride glass in the O ₂ doped treatment atmosphere to provide a silicon oxyfluoride glass having insoluble O ₂ molecules. Dissolving a plurality of O ₂ molecules from the atmosphere into the silicon oxyfluoride glass. As can be seen from FIG. 1, the vessel 28 contains a solidified glass 22 and an O ₂ molecular atmosphere 26 provided by an oxygen source so that the glass is surrounded in an O ₂ doped treatment atmosphere. . Preferably the method comprises heating the O ₂ doped atmosphere and the silicon oxyfluoride glass to a predetermined O ₂ doping temperature, preferably> 600 ° C. Preferred O ₂ doping temperature is about 1000 (± 100) ° C., most preferably about one oxygen atmosphere. Providing the O ₂ doped treatment atmosphere 26 preferably provides an atmosphere having an O ₂ concentration of at least 10 ¹⁵ O ₂ molecules / cc, more preferably at least 10 ¹⁶ O ₂ molecules / cc. Include. Preferably the O ₂ concentration in the atmosphere is less than 10 ²⁰ O ₂ molecules / cc. Preferred O ₂ concentrations in the doping treatment atmosphere range from about 10 ¹⁶ to 10 ¹⁸ O ₂ molecules / cc.

The present invention includes a method for producing laser durable VUV-permeable silicon oxyfluoride glass. One embodiment of the present invention is shown in FIG. The method includes providing a glass solidification furnace having a thermal solidification region 32 for solidification of a non-solidified silicon oxyfluoride glass precursor. The method includes providing an oxygen doped atmosphere 26 to the solidification furnace 30 to solidify the glass precursor into a solidified silicon oxyfluoride glass, wherein the O ₂ molecules are dissolved in the solidified silicon oxyfluoride glass. do. Preferably the method comprises heating the oxygen doped atmosphere and the glass 24 to be solidified to a predetermined O ₂ doped solidification temperature. In one embodiment, the glass solidifying furnace 30 comprises providing a non-metal silica muffle furnace of non-polluting refractory material. In one embodiment, providing the glass solidification furnace 30 includes providing a solidification furnace of plasma discharge glass. In one embodiment, the plasma discharge of the solidification furnace of the plasma discharge glass is used to heat and solidify the non-solidified precursor to the solidified glass in the presence of O ₂ . For example, non-solidified glass particles or other Si containing raw materials are fed to the plasma discharge with oxygen in a direct laydown plasma process. Providing an oxygen doped atmosphere preferably includes providing an atmosphere having an O ₂ concentration of at least 10 ¹⁵ O ₂ molecules / cc, more preferably ≧ 10 ¹⁶ O ₂ molecules / cc. Preferably the oxygen doping atmosphere has an O ₂ concentration of less than 10 ²⁰ O ₂ molecules / cc. Preferably the doping atmosphere has an O ₂ concentration in the range of 10 ¹⁶ to 10 ¹⁸ O ₂ molecules / cc. Preferably the non-solidified glass is a soot body preform and the glass is solidified under a high oxidizing atmosphere having an O ₂ volume of at least 50%. The glass doped with O ₂ is solidified and synthesized as above to contain O ₂ molecules.

The present invention includes a VUV transmissive glass photomask substrate. 3 to 5 show a VUV transmissive glass photomask substrate 34. The VUV transmissive glass photomask substrate 34 comprises silicon oxyfluoride glass doped with a plurality of O ₂ molecules. Preferably the silicon oxyfluoride glass contains at least 0.1% by weight fluorine, more preferably the fluorine content is in the range of 0.1 to 2% by weight F. Preferred fluorine content ranges from 0.2 to 1.2% by weight. Preferred fluorine content is in the range of 0.1 to 0.4% by weight. The preferred range of fluorine content is about 1.2 (± 0.3) wt% F. Preferably the silicon oxyfluoride glass doped with O ₂ is a dry glass and preferably has an OH content of up to 50 ppm by weight. The low OH content silicon oxyfluoride glass photomask substrate blank 34 doped with O ₂ is <10 ppm by weight, more preferably <5 ppm by weight, and most preferably <1 ppm by weight. It has an OH content. Preferably the dry silicon oxyfluoride glass doped with O ₂ has a Cl content of less than 5 ppm by weight, more preferably a Cl content of less than 1 ppm by weight. Preferably the photomask substrate glass has a 165 nm absorption of less than 0.2 absorption units / 5.1 mm. Preferably the photomask substrate glass has a absorption of 215 nm of less than 0.2 absorption units / 5.1 mm. Preferably the silicon oxyfluoride glass is resistant to the 165 nm absorption band of 157 nm laser induction of the F ₂ excimer. Preferably the silicon oxyfluoride glass has an absorption of 165 nm of less than 0.3 absorption units / 5.1 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Preferably the silicon oxyfluoride glass has a 215 nm absorption of less than 0.2 absorption units / 5.1 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Preferably the silicon oxyfluoride glass has a 157 nm absorption of less than 0.4 absorption units / 5.1 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Preferably the silicon oxyfluoride glass has a 157 nm laser induced delta absorption of <0.20 absorption units / 5 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse.

The present invention includes VUV transmission silicon oxyfluoride lithography glass for transmission wavelengths up to 200 nm. The VUV-permeable silicone oxyfluoride glass of the present invention is shown in cross section in FIGS. The VUV transmissive silicon oxyfluoride glass of the present invention contains a plurality of doped O ₂ molecules and is resistant to VUV laser induced absorption bands. The VUV transmissive glass comprises silicon oxyfluoride glass doped with a plurality of interstitial O ₂ molecules. Preferably the silicon oxyfluoride glass contains at least 0.1% by weight fluorine and more preferably contains fluorine in the range of 0.1 to 2% by weight. The preferred fluorine content range is 0.2 to 1.2% by weight F. The preferred fluorine content range is 0.1 to 0.4 wt.% F. The preferred fluorine content range is about 1.2 (± 0.3) wt% F. Preferably the silicon oxyfluoride glass doped with O ₂ is a dry glass and preferably has an OH content of up to 50 ppm by weight. The lower OH silicon oxyfluoride glass doped with O ₂ has an OH content of <10 ppm by weight, more preferably <5 ppm by weight, most preferably <1 ppm by weight. Preferably the dry silicon oxyfluoride glass doped with O ₂ has a Cl content of less than 5 ppm by weight, more preferably a Cl content of less than 1 ppm by weight. Preferably the glass has an absorption of 165 nm of less than 0.2 absorption units / 5.1 mm. Preferably the glass has an absorption of 215 nm of less than 0.2 absorption units / 5.1 mm. Preferably the silicon oxyfluoride glass is resistant to a 165 nm absorption band of 157 nm laser induction of the F ₂ excimer. Preferably the silicon oxyfluoride glass has an absorption of 165 nm of less than 0.3 absorption units / 5.1 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Preferably the silicon oxyfluoride glass has a 215 nm absorption of less than 0.2 absorption units / 5.1 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Preferably the silicon oxyfluoride glass has a 157 nm absorption of less than 0.4 absorption units / 5.1 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Preferably the silicon oxyfluoride glass has a 157 nm laser induced delta absorption of <0.20 absorption units / 5 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse.

The inventors of the present invention have found that the induced absorption in dry silicon oxyfluoride glass that has been exposed to an F ₂ excimer laser can be significantly shifted by heat treatment of the glass under oxygen atmosphere. FIG. 6 shows the prepared silicon oxyfluoride glass (open circle, 0, lowest curve) in the doped (1.2 wt% F) dry state (<1 ppm OH) and then 10.6 E6 at 157 nm, ² mJ / cm ² -pulse The VUV spectrum of the glass (open square,?, Peak curve) exposed by pulses is shown. As with the more important 165nm band, the E'center at 215nm was apparent. The glass was then kept in the presence of oxygen (1 atm) at 1000 ° C. for 7 days. In addition to the 215 nm band, the 165 nm band has disappeared under these conditions (closed diamond, ◆, intermediate curve)

The inventors of the present invention show that dry silicon oxyfluoride silica glass containing high levels of oxygen molecules exhibits significantly lower induced absorption when exposed to F ₂ excimer laser than silicon oxyfluoride silica glass that does not contain excess oxygen. Found. FIG. 7 shows the same silicon oxyfluoride glass (open circle 0, lowest curve) as in FIG. 6 pre-treated in oxygen, followed by exposure to an F ₂ excimer laser for 9.92E6 pulses at 2mJ / cm ² -pulse. Shows the VUV spectrum of glass (closed diamond, ◆, middle curve). The lowest curved spectrum of the open circle is the glass after O ₂ loading before exposure. The middle curve spectrum of the closed diamond is O ₂ loaded glass exposed at 157 nm for about 10E6 pulses, and the highest curve spectrum of the open square (□) is the glass prepared as in FIG. 6 and exposed to 10.6E6 pulses ( For comparison). A feature distinguished by this comparison is the absence of a 165 nm band (ODC) in the O ₂ -containing glass. The presence of oxygen indicates the formation of the 165 nm band. Since the 165 nm band is close to 157 nm, the reduction of the absorption band reduces the induced absorption at 157 nm. The results are summarized in Table 1 below:

Sample Absorption rate / 5mm (transmittance (T) / 5mm) Delta absorption (delta transmittance (T) / 5mm) Manufactured 0.18 (66) - O ₂ treated 0.18 (66) - Exposed after manufacture 0.49 (32) 0.31 (-34) Exposed after O ₂ treatment 0.35 (45) 0.17 (-21)

Silicone oxyfluoride glass containing excessive oxygen can be produced by several methods. First, as described above, the glass, such as the prepared silicon oxyfluoride glass, may be exposed to an oxygen atmosphere at elevated temperatures to diffuse O ₂ into the structure. Secondly, the glass can be synthesized to contain excessive oxygen. Silica glass made by a direct laydown process (eg, plasma) was made with a high level of excess oxygen as compared to glass made by the process from soot preform bodies to solidified glass bodies. Finally, the oxygen content of the silicon oxyfluoride glass produced by the process from the soot preform body to the solidified glass body can be increased by solidification under high oxidizing atmospheres (eg, 50-100% O ₂ ). .

The present invention provides a silicon oxyfluoride glass having improved resistance to F2 laser induced absorption and a method of making the same. The silicon oxyfluoride glass materials of the present invention are useful for 157 nm lithography applications such as, for example, photomasks, lenses, thin films, and windows.

It will be apparent to those skilled in the art that various modifications and variations of the present invention can be made without departing from the scope of protection of the present invention. Accordingly, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

Claims (50)

Providing a silicon oxyfluoride glass; Providing a plurality of O ₂ molecules; And Doping the silicon oxyfluoride glass with O ₂ molecules to provide a VUV-permeable silicon oxyfluoride glass containing O ₂ molecules; Method for producing a VUV-permeable glass comprising a. The method of claim 1, wherein the method comprises dissolving O ₂ molecules in the silicon oxyfluoride glass. The method of claim 1, wherein the method comprises solidifying the silicon oxyfluoride glass with O ₂ molecules. The method of claim 1, wherein the method comprises providing a silicon oxyfluoride glass containing at least 0.1% by weight fluorine. The method of claim 1, wherein the method comprises providing a silicon oxyfluoride glass having an OH content of less than or equal to 50 ppm by weight. The method of claim 1, wherein the method comprises providing a silicon oxyfluoride glass having a Cl content of 5 ppm or less by weight. The method of claim 1, said method comprising the comprising the step of providing an O ₂ atmosphere and doping process, O ₂ O ₂ concentration of the doping process atmosphere is at least 10 ¹⁵ O ₂ molecules / cc. The method of claim 7, said method comprising the steps of: providing a O ₂ doped container for containing the O ₂ atmosphere and doped silicon oxyfluoride glass. The method of claim 8, wherein the method comprises heating the treatment atmosphere and glass to an O ₂ doping temperature. 10. The method of claim 9, wherein the O ₂ doped processing vessel comprises a non-fouling refractory material. Providing a solidified silicon oxyfluoride glass; Providing an O ₂ doping treatment atmosphere; Surrounding the silicon oxyfluoride glass with the O ₂ doping treatment atmosphere and dissolving a plurality of O ₂ molecules from the atmosphere into the silicon oxyfluoride glass to provide a silicon oxyfluoride glass having insoluble O ₂ molecules; Method for producing a durable VUV-transmitted silicon oxyfluoride glass to a laser comprising a. The method of claim 11, wherein the method comprises heating the atmosphere and silicon oxyfluoride glass to a predetermined O ₂ doping temperature. The method of claim 11, wherein providing the O ₂ doping treatment atmosphere comprises providing an atmosphere having an O ₂ concentration of at least 10 ¹⁵ O ₂ molecules / cc. The method of claim 11, wherein providing the O ₂ doping treatment atmosphere comprises providing an atmosphere having an O ₂ concentration of at least 10 ¹⁶ O ₂ molecules / cc. The method of claim 13, wherein the atmospheric O ₂ concentration is 10 ²⁰ O ₂ molecules / cc or less. Providing a non-solidified silicon oxyfluoride glass precursor; Providing a glass solidification furnace having a heated solidification region for solidifying the non-solidified glass precursor; And Supplying an oxygen doping atmosphere to the solidification furnace and solidifying the glass precursor with a solidified silicon oxyfluoride glass, wherein O ₂ molecules are dissolved in the solidified silicon oxyfluoride glass; Method for producing a durable VUV-transmitted silicon oxyfluoride glass to a laser comprising a. The method of claim 16, wherein the method comprises heating the oxygen doping atmosphere to a predetermined O ₂ doping solidification temperature. The method of claim 16, wherein supplying the oxygen doped atmosphere comprises providing an atmosphere having an O ₂ concentration of at least 10 ¹⁵ O ₂ molecules / cc. The method of claim 16, wherein supplying the oxygen doped atmosphere comprises providing an atmosphere having an O ₂ concentration of at least 10 ¹⁶ O ₂ molecules / cc. The method of claim 18, wherein the O ₂ concentration is 10 ²⁰ O ₂ molecules / cc or less. 17. The method of claim 16, wherein providing the glass solidification furnace comprises providing a silica muffle furnace. 17. The method of claim 16, wherein providing the glass solidifying furnace comprises providing a plasma discharge. A VUV-permeable glass photomask substrate comprising silicon oxyfluoride glass doped with a plurality of O ₂ molecules. 24. The photomask substrate of claim 23, wherein said silicon oxyfluoride glass contains at least 0.1 weight percent fluorine. The photomask substrate of claim 23, wherein the silicon oxyfluoride glass has an OH content of 50 ppm or less by weight. 24. The photomask substrate of claim 23, wherein the silicon oxyfluoride glass has an OH content of 10 ppm or less by weight. 24. The photomask substrate of claim 23, wherein the silicon oxyfluoride glass has an OH content of 5 ppm or less by weight. The photomask substrate of claim 23, wherein the silicon oxyfluoride glass has an OH content of 1 ppm or less by weight. 24. The photomask substrate of claim 23, wherein the silicon oxyfluoride glass has a Cl content of 5 ppm or less by weight. The photomask substrate of claim 23, wherein the silicon oxyfluoride glass has an absorption of 165 nm of less than 0.2 absorption units / 5.1 mm. The photomask substrate of claim 23, wherein the silicon oxyfluoride glass has a 215 nm absorption of less than 0.2 absorption units / 5.1 mm. 24. The photomask substrate of claim 23, wherein the silicon oxyfluoride glass is resistant to a 165 nm absorption band of laser induction. The photomask of claim 23, wherein the silicon oxyfluoride glass has an absorption of 165 nm of less than 0.3 absorption units / 5.1 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Board. The photomask of claim 23, wherein the silicon oxyfluoride glass has a 215 nm absorption of less than 0.2 absorption units / 5.1 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Board. 24. The method of claim 23, wherein the silicon oxyfluoride glass has an absorption of laser induction at 157 nm of less than 0.4 absorption units / 5 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Photomask substrate. 24. The method of claim 23, wherein the silicon oxyfluoride glass has a 157 nm laser induced delta absorption of <0.20 absorption units / 5 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Photomask substrate. A VUV transmissive silicon oxyfluoride glass characterized by being resistant to a VUV laser induced absorption band and containing a plurality of doped O ₂ molecules. 38. The VUV-permeable silicon oxyfluoride glass of claim 37, wherein the silicon oxyfluoride glass contains at least 0.1 wt% fluorine. 38. The VUV-permeable silicon oxyfluoride glass according to claim 37, wherein the silicon oxyfluoride glass has an OH content of 50 ppm or less by weight. 38. The VUV-permeable silicone oxyfluoride glass of claim 37, wherein the silicon oxyfluoride glass has an OH content of 10 ppm or less by weight. 38. The VUV-permeable silicone oxyfluoride glass according to claim 37, wherein the silicon oxyfluoride glass has an OH content of 5 ppm or less by weight. 38. The VUV-permeable silicon oxyfluoride glass of claim 37, wherein the silicon oxyfluoride glass has an OH content of 1 ppm or less by weight. 38. The VUV-permeable silicon oxyfluoride glass according to claim 37, wherein the silicon oxyfluoride glass has a Cl content of 5 ppm or less by weight. 38. The VUV-permeable silicon oxyfluoride glass of claim 37, wherein the silicon oxyfluoride glass has a 165 nm absorption of less than 0.2 absorption units / 5.1 mm. 38. The VUV-transmitting silicon oxyfluoride glass of claim 37, wherein the silicon oxyfluoride glass has a 215 nm absorption of less than 0.2 absorption units / 5.1 mm. 38. The VUV-transmitting silicon oxyfluoride glass of claim 37, wherein the silicon oxyfluoride glass is resistant to 165 nm absorption bands of laser induction. 38. The VUV transmission of claim 37, wherein the silicon oxyfluoride glass has an absorption of 165 nm of less than 0.3 absorption units / 5.1 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Silicone oxyfluoride glass. 38. The VUV transmission of claim 37, wherein the silicon oxyfluoride glass has a 215 nm absorption of less than 0.2 absorption units / 5.1 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. Silicone oxyfluoride glass. 38. The method of claim 37, wherein the silicon oxyfluoride glass has a laser induced absorption at 157 nm of less than 0.4 absorption units / 5 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. VUV-permeable silicone oxyfluoride glass. 38. The method of claim 37, wherein the silicon oxyfluoride glass has a 157 nm laser induced delta absorption of <0.20 absorption units / 5 mm after F ₂ excimer laser exposure of at least 9.92 E6 pulses at ² mJ / cm ² -pulse. VUV-permeable silicone oxyfluoride glass.