TW554260B - A below 193 nm UVU transmitting glass photomask, the method of making their blank, the method of making said glass and the method of making homogenous glass optical element - Google Patents

Abstract

High purity direct deposit vitrified silicon oxyfluoride glass suitable for use as a photomask substrates for photolithography applications in the VUV wavelength region below 190 nm is disclosed. The inventive direct deposit vitrified silicon oxyfluoride glass is transmissive at wavelengths around 157 nm, making it particularly useful as a photomask substrate at the 157 nm wavelength region. The inventive photomask substrate is a dry direct deposit vitrified silicon oxyfluoride glass which exhibits very high transmittance in the vacuum ultraviolet (VUV) wavelength region while maintaining the excellent thermal and physical properties generally associated with high purity fused silica. In addition to containing fluorine and having little or no OH content, the inventive direct deposit vitrified silicon oxyfluoride glass suitable for use as a photomask substrate at 157 nm is also characterized by having less than 1x10<17> molecules/cm<3> of molecular hydrogen and low chlorine levels.

Description

554260 A7 B7 V. Description of Invention (l) Related applications: This application claims priority based on the following patents: US Provisional Patent Application No. 60/258132, filed on December 22, 2000. The patent name is `` Substantially Dry, Silica-Containing Soot,

Fused Silica And Optical Fiber Soot Preforms, Apparatus, Methods And Burners For Manufacturing

Same And Method Therefore "and the provisional US Patent Application No. 60/271136, filed on February 24, 2001, entitled" Vacuu [n

Ultraviolet Transmitting Silicon Oxyfluride Lithography Glass' and U.S. Patent No. 60/271 135, filed on February 24, 2001, entitled "0xygen D〇ping 〇; f Silicon Oxyfluride Glass", and September 2000 The provisional patent of World Patent Organization No. WO 01/17919, filed on the 8th, is entitled "Pure Fused Silica, Furnace And Method '. These patents are incorporated herein by reference. Field of the Invention: Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs This invention relates to the light lithography method, and in particular to the light lithography printing glass for use in the light lithography system, which uses vacuum ultraviolet (VUV) below 193nm The wavelength is preferably lower than 175nm, and more preferably lower than 164nm, for example, a VUV projection light lithography system using a wavelength of 157nm is used. The present invention relates to a VUV transmission glass, which is transmissive at a wavelength below 193 nm. In particular, a light-shielding silicon oxyfluoride glass is suitable for use in a vacuum ultraviolet (VUV) wavelength region of 157 nm. Background of the invention: This paper size is applicable to China National Standards (CNS) A4 (210X 297 mm> 554260 Α7 Β7) 5. Description of the invention (: 2) Printed by the Consumer Cooperative of the Central Bureau of the Ministry of Economic Affairs, collimated optical element Highly transmissive materials are required. For smaller and smaller semiconducting ft. Gu needs 248 and 193 reading length, high-purity smelting stone Xixian has been shown to require a minimum transmission of 99% or better. Daily use below 193M1 The vacuum ultraviolet wavelength projection light lithographic printing system provides the advantage of achieving a smaller size. The system using a vacuum ultraviolet wavelength in the 157nm wavelength region has the potential to improve the collective circuit with a smaller size. Currently in the manufacturing of collective circuit semiconductor industry The light lithography system used has been developed towards shorter wavelengths of light, such as 248 and 193nm wavelengths, but the use of vacuum ultraviolet wavelengths below 193, such as 157nm, is blocked by the characteristics of vacuum ultraviolet wavelengths transmitted through the 157nm region through optical materials The slow progress of the semiconductor industry using VUV light below 175 such as 15711 {11 is due to The lack is caused by the economical manufacture of light-shielding blanks by optically transmissive materials. For the advantages of vacuum UV lithography in the 157 coffee region, such as the VUV frequency window of the emission spectrum of the excimer laser used in the production of collective lines, there is a mask. There is a need for mask hair embryos, which have beneficial optical characteristics such as good transmission properties below 164nm and 157nm, and can be economically manufactured. The present invention overcomes some of the problems of the prior art and provides economically high-quality improved mask hair Embryo and VUV transmitted light lithographic printing glass, which can be used to improve the production of collective circuits using vacuum ultraviolet wavelengths. Use of high-purity fused silica for light lithography originates from high-purity fused silica in a wide wavelength range from infrared to deep In the ultraviolet region, it is transmissive. In addition, high-purity silica exhibits very good chemical durability and dimensional stability. In European Patent No. 0636586A1, in order to apply the Chinese National Standard (CNS) A4 specification at 248nm, this paper standard ( 21〇χ297 公 楚) (Please read the note on the back and then this page) Teach 554260 A7 B7 3. Description of the invention (3) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs to a wavelength of 193nm is suitable as a mosquito-light ^ printing and printing-like masking substrate. High-purity fused silica produced by the direct flame method must contain 10π to 101 g molecules / cubic centimeter of a large amount of molecular hydrogen. Similarly, the Jp patent does not disclose that synthetic quartz glass is used as a light masking material, and its optical characteristics change due to spraying, plasma etching, or excimer irradiation. The material can The original conditions are restored by heat treating the glass in hydrogen. In particular, this document describes the effects of exposure of synthetic quartz to wavelengths of 248 and 193 nm. The effect of exposure to 248nm and 193nm wavelengths on fused silica is also explained in Densifi cat ion of Fused Silica under 193 nm excitation &quot;, J. Opt. Soc. Am. B / Vol. 14, No. 7, pp. 1606 1615 (July 1997); and n193nm excimer -laser-induced densification of fused silica 'Optics Letters, Vol. 21, No. 24, pp. 1960-1962 (Dec. 5, 1996) by Allan et al. . ’We have previously revealed several effective methods to improve the optical properties of high-purity fused silica used as optical lenses in light lithography in the 248nm and 193nm wavelength regions. See, for example, U.S. Patent Nos. 5,616,159, 5668067, and 57359 21, the description of which is incorporated herein by reference. Therefore, the object of the present invention is to reveal the VUV transmissive direct deposition of vitrified siloxyfluoride glass for use at a VUV wavelength below 193nm, which wavelength is preferentially in the region of F2 excimer laser 157nm. Method for drying and directly depositing vitrified lithograph glass objects. Summary of the invention: In the present invention, we reveal that VUV transmissive dry direct-deposited glass (please read the precautions on the back side before ^^ this page) The size of the paper is applicable to China National Standard (CNS) A4 specification (210 &amp; 297) (%) 554260 A7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (φ) Silicon oxyfluoride light lithographic printing glass is suitable as an optical element. It is used as a lens or preferentially as a VUV below 193nm. Wavelength optical masking matrix. In particular, the present invention directly deposits vitrified oxyfluoride glass products exhibiting advantages that are particularly suitable for use as light lithographic printing objects and near 157nm excimer laser wavelengths and wavelength regions below i93nm. The object of the present invention is achieved by direct deposition of vitrified synthetic silicon oxyfluoride glass using dry low-hydroxy-doped fluorine Si (Mf), which exhibits high transmittance in the vacuum ultraviolet (VUV) wavelength region and simultaneously exhibits Very good thermal and physical properties. The so-called "dry" means having a plutonium content of less than 50 ppm by weight, preferably dehydrogenation of less than 10111 by weight and most preferably less than 1 ppm by weight. Another aspect of the present invention The object of the project is to ensure that the directly deposited glassy siloxyfluoride glass does not substantially contain gas by drying. Another object of the present invention is to ensure that the molecular hydrogen content in the dry directly deposited glass is low. This refers to molecular hydrogen ( H2) content is less than lxio17 molecules / cubic centimeter. In the preferred embodiment of the present invention, the fluorine content of the VUV transmissive dry direct deposition vitrified silicon oxyfluoride glass is in the range of 0.1 to 0.4% by weight, which shows The absorption caused by the laser irradiation and the durability of the laser irradiation are provided, and the minimum transmission loss is at 157.6 nm after prolonged irradiation. The present invention includes a VUV transmission glass lower than 193 nm The glass optical mask substrate is used as a light lithograph with a wavelength of 157 nm. It uses high-purity drying to directly deposit vitrified sand oxyfluoride glass, where the content of 0H is less than 50ppm by weight, the content of hydrogen is less than 1xlO17 molecules / cubic centimeter, and fluorine. The content is from 0.1 to 0.4 (please read the precautions on the back before this page)

-5T »礞 This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm 554260 A7 B7) 5. Description of the invention (7) The ratio range. The invention includes a silicon oxyfluoride glass for the production of VUV transmissive glass, It includes providing a carbon oxide burner containing no hydrogen fuel; providing a direct deposition high temperature furnace containing heating; providing a carbon monoxide supply source and an oxygen supply source to the carbon monoxide burner to form a carbon monoxide combustion reaction flame; providing a dry glass deposition surface adjacent to the flame, supplying Si—glass precursor product raw material and F-glass precursor product raw material to the carbon monoxide burner, wherein the Si-glass precursor product raw material and glass precursor product raw material react in a flame to form oxyfluoride glass dust onto the glass deposition surface, the Dust is simultaneously deposited directly and vitrified into a dry directly deposited vitrified silicon oxyfluoride glass object. The staff of the Central Bureau of Economic Affairs will print it for consumption. The present invention includes dry directly deposited vitrified siloxyfluoride. Glass, which does not substantially contain 0H groups, is small 5xl016 molecules / cm3 molecular hydrogen, and the fluoride content is in the range of 0.1 to 0.4% by weight. The present invention includes dry direct vitrified stone oxoxide glass, whose OH content is less than 5ρρπι weight ratio and C1 content is less than 5ppm weight ratio, Η2 content is less than 1x10π molecules / cm3, and fluoride content is in the range of 0.1 to 0.4% by weight, and the transmittance at 157nm is at least 85% / cm. The present invention includes a VUV pattern printing method, which It includes the following steps: providing a radiation source below 164nm to produce VUV photons, providing dry direct-deposited vitrified stone oxide glass, with an OH weight ratio of less than 5 ppm, a C1 weight ratio of less than 5 ppm, and a fluoride content &lt; 0.5 weight Ratio, and the measured transmittance of I57nm and 165nm is at least 75% / 5mm. The graph printing method includes transmitting νυν photons by drying and directly depositing vitrified silicon oxyfluoride glass, using νυν photons to form a pattern, and projecting the pattern to VUV radiation The paper size on the sensitive printing pattern applies the Chinese national standard (CNS &gt; Α4 size (210X 297 mm)) Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 260 A7 B7 V. Description of the invention (&gt;). The present invention includes dry direct deposition vitrified νυν transmission silicon oxyfluoride glass, the content of 0Η is less than 5ppm by weight, the content of fluoride is at least 0.1% by weight, glass Contains Si, 0, and F, after exposure to 21.5mJ / cm2-pulse of 157nm laser 41.5 million pulses, the internal transmission is at least 85% / cm in the wavelength range of 157nm to 175nm and the absorption at 165nm is less than 0.4 ( Absorptive unit / 5 deleted). The present invention comprises a lithographic printing of 157nm wavelength with an optical mask substrate of VUV transmission glass below 193nm. The glass mask substrate contains dry directly deposited vitrified siloxane glass with an OH content lower than 20 ppm by weight, C1 content is less than 0.1% by weight, and fluorine content is in the range of 0.01 to 7% by weight. The invention includes a method for manufacturing a UV-transmissive light lithographic printing glass below 193 nm to transmit a wavelength of 157 nm. The method includes providing a carbon monoxide burner containing no hydrogen fuel; providing a carbon monoxide source and an oxygen source to the carbon monoxide burner to form a carbon monoxide reaction flame. Provide a direct glass deposition surface close to the flame, and supply Si-glass precursor product raw materials and F-glass precursor product raw materials to a carbon monoxide burner, where the Si-glass precursor product raw materials and F-glass precursor product raw materials react to become silicon oxide in the flame. Fluoride glass dust is projected on the glass deposition surface, and the dust is simultaneously directly deposited and vitrified into a silicon fluoride glass object. The invention includes a method for manufacturing a uniform glass light lithographic printing element. The method comprises providing a carbon monoxide burner containing no hydrogen fuel; providing a carbon monoxide supply source and an oxygen supply source to the carbon monoxide burner to form a carbon monoxide combustion reaction flame, and providing direct glass deposition surface proximity. For the flame, supply Si-glass precursor product raw materials and dopant R-glass precursor product raw materials to this paper size applicable to China National Standard (CNS) A4 specifications (210X297 mm)

554260 A7 B7 V. Description of the invention (7) Carbon monoxide burner, in which the raw material of the Si-glass precursor product and the raw material of the dopant R-glass precursor product react in the flame to become dry doped R silica glass dust projected onto the glass deposition surface, The dust is simultaneously deposited and vitrified into a dry and uniformly doped silica glass object, and the directly formed deposited vitrified glass object is a uniform glazed lithographic printing element. In a preferred embodiment of the method for manufacturing a dry-doped R silica glass, a glass dopant is selected from the types of F, Ti, Ge, B, P, and A1 glass dopants. The invention includes a method for manufacturing a uniform glass lithographic printing element. The method comprises providing a carbon monoxide burner containing no hydrogen fuel; providing a carbon monoxide supply source and an oxygen supply source to the carbon monoxide burner to form a flame of a monoxide combustion reaction. The direct glass deposition surface is adjacent to the flame, and the Si-glass precursor product raw material is supplied to the carbon monoxide burner. The &amp; -glass precursor product raw material reacts in the flame to become dry high-purity silica glass dust, which is projected onto the glass deposition surface. The dust is simultaneously Deposited and vitrified silica glass objects that are dry and uniformly doped with R, and directly formed deposited vitrified glass objects are homogeneous vitreous lithographic printing elements. Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back of this page before this page). The method of manufacturing UV-transmissive silicon oxyfluoride glass below 193nmV includes providing a burner that does not contain hydrogen fuel, preferably hydrogen fuel. The burner is a carbon monoxide burner. The method includes providing a carbon dioxide fuel supply source containing no hydrogen fuel and an oxygen supply source to a burner to form a carbon monoxide combustion reaction flame, which is contained in a direct deposition high temperature furnace containing heating. A direct glass deposition surface is provided in the high temperature furnace adjacent to and below the monoxide anti-burner and flame. Another type of combustion fuel that does not contain hydrogen fuel contains carbon monoxide and carbon oxysulfide. One of the carbon oxides supplied to the burner and this paper size are in accordance with Chinese national standards (CNS &gt; A4 specifications (210X297 mm> 554260 A7 ___ B7) V. Description of the invention (f) The oxygen supply source maintains the oxidizing flame, a precursor of Si-glass The raw material and the raw material of the F-glass precursor product are supplied to the flame. The raw material of the glass precursor product is preferably hydrogen-free, such as stone tetrachloride and tetraisocyanate [Si (NC0) 4]. 'Basis The processing process and the device of the present invention produce non-water-containing silica glass. The processing process and the device of manufacturing the non-water-containing molten silica glass eliminate the possibility of forming water in the combustion gas. This is implemented in the first implementation. This is achieved by using hydrogen-free fuels such as carbon monoxide (co), carbon monoxide (GO), carbon oxysulfide (COS), etc. The use of hydrogen-free fuels will minimize water formation during combustion reactions. .According to the preferred embodiment, it is necessary to use a hydrogen-free material as the glass precursor of silica. Most preferably, a combination of hydrogen-free raw materials and thorium-free fuel is used. The hydrogen-free glass precursor Examples include silicon carbide (SiC), silicon monoxide (Si0), silicon nitride (S ^ 4), silicon tetrabromide (SiBn), silicon tetrachloride (siCh), silicon tetraiodide (Sih) , And silica (SiOO. Si (NC〇) 4 can also be used. According to the present invention, when using, for example, carbon monoxide as a fuel and combined with oxygen, pick up the product, carbon monoxide. This by-product is very easy to handle, and is anhydrous The reaction is generated by this treatment reaction. The reaction is expressed by the following formula: CO + l / 2〇2-> C02 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs People understand that the heat generated by carbon monoxide is approximately from natural gas ( Methane) generates a quarter of the heat. Therefore four times the fuel is required to produce the same amount of heat. However, only 0.5 mol of oxygen is needed to burn 1 mol. Therefore, the same volume of oxygen is required for any kind of heat to produce Same heat. The following formula shows that carbon monoxide fuel is not required to burn with the prior art process

Μ 554260 A7 B7 ο 5. Description of the invention (?) The amount of heat required for the production of monomolane by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs matches. 4CO + 2〇2- &gt; 4 Co2 The following formula shows the by-products of the prior art and sustains the combustion of oxygen to burn one mole of methane. CH4 + 2 〇2-&gt; 2M + C02 Thus, from the foregoing description, it is known that it is possible to produce a moisture-free silica glass. The invention provides a method for manufacturing a vitrified object. The novel method involves several steps. First, the heat generated by the burner is provided by igniting a flame generated by argon-free fuel. According to the invention, the flame is a source of heat. Second, the glass precursor product flows into the flame to produce silica-containing dust. Finally, silica-containing dust is deposited on the substrate and simultaneously transformed by flame heat (by flame heat) to form vitrified glass objects. In a preferred embodiment, the dust is deposited on a glass element containing stone stone, such as a smelting stone stone plate. According to this method, vitrified glass objects contain a very low amount of moisture. The product step is preferably performed in a high-temperature furnace, which contains a purge gas such as nitrogen gas provided therein. This method is suitable for producing uniform glass. According to the present invention, a carbon oxide burner containing no hydrogen fuel can be used. The burner includes supplying a glass precursor product at a first flow rate using a smoke passage, and a fuel passage surrounding the smoke passage, and using a fuel passage to supply fuel containing no hydrogen at a flow rate twenty times the first flow rate. The burner also includes an internal shield channel between the fuel channel and a smoke channel used to supply at least oxygen. The burner goes one step further and includes an outer screen channel surrounding the fuel channel to add other gases.

(Please read the precautions on the back first, then this page)-Installation 554260 A7 B7 Five invention description (丨 〇) Other features and advantages of the present invention will be disclosed in detail in the following detailed description, those who are familiar with this technology can immediately understand the department from the description The detailed description of the invention, the scope of patent application, and the drawings are made clear by implementing the present invention. It is understood that the general description and the following detailed description are examples of the invention, and are intended to provide concepts or frameworks to clarify the principles and characteristics of the invention as defined by the scope of the patent application. The drawings are intended to provide a further understanding of the invention, and are incorporated herein as part of the specification. The drawings illustrate various embodiments of the invention, and the accompanying description serves to explain the principles and operation of the invention. Detailed description: A detailed description will now be given of a preferred embodiment of the present invention, an example of which is shown in the accompanying drawings. We have revealed a high transmission below 190nm, especially below i75nm, and most preferentially at the A excimer laser wavelength in glass containing SiO2 fluoride by changing the 0H or water content of the glass Reduced to the minimum while providing an output with a central wavelength of approximately 157nm. In particular, we have revealed silicon oxyfluoride glass that exhibits low transmittance and low transmittance. Glass transmission characteristics are generally determined by the glass composition. In pure silica, printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs has shown that very small amounts (ppm or less) of metal contaminants can significantly reduce transmission in the UV region. We have confirmed that in addition to metallic impurities, the most important variables controlling the VUV transmission edge of silicon oxyfluoride glass include moisture or 0H content, and gas content. In particular, we found that the lower the 0H content, the better the transmission, and the higher the gas content, the lower the transmission in the 157nm region of VUV. In addition, we found that the amount of molecular hydrogen in the glass must be reduced to the minimum. This paper size applies to the Chinese National Standard (CNS) A4 (210X297 mm) \ 1 554260 Α7 --- Β7 Central Consumer Bureau of the Ministry of Economic Affairs Employee Consumer Cooperatives Printed 5. Description of invention U |). Preferably, the glass containing SiO2 has at least 0.5% by weight chlorine. In another preferred embodiment, the fluorine content of the silicon oxyfluoride glass is in the range of 0.1 to 0.4% by weight. In the preferred embodiment, a 2.7 micrometer glass infrared transmission measurement was used to quantify the OH content of the glass. The light lithographic printing optical mask substrate of the present invention for drying a high-purity direct-deposited vitrified siloxyfluoride glass is shown in Figs. 1-2 and indicated by reference numeral 20. As shown in FIG. 2, the light lithography method for manufacturing a light lithography pattern according to the present invention includes providing an illumination sub-system to manufacture and guide &lt; 300 nm ultraviolet light λ. A &lt; 200nm is preferred, and A &lt; i93nm is most preferred. The method includes providing a mask sub-system having a mask stage and a transmitted-light lithographic mask 22 including a dry high-purity direct-deposited vitrified silicon oxyfluoride glass wafer 20 having a light-lithographic printing pattern 24. The method includes providing a projection optical sub-system and a lambda Xingchang ray-sensitive printing sub-system, which includes a radiation-sensitive printing medium 26. As shown in FIG. 2, the method further includes aligning the illumination sub-system, the mask sub-system, the projection optical sub-system, and the radiation sensitive printing sub-system, and the illumination mask 22 is irradiated with the radiation Λ, and the radiation λ Running through the glass 20 causes the IC wafer lithographic pattern depicted on the glass wafer mask 22 to be projected onto the medium 26. FIG. 3 shows that the mask 22 has a 1C light lithographic pattern on a directly deposited vitrified silicon oxyfluoride glass substrate 20. For example, the 1C light lithographic printing pattern shown in FIG. 4 is formed by the mask 22 transmitting through the glass 20 with radiation λ, transmitted through the projection optical element and the 1C pattern is projected on the collective circuit wafer medium 26 as shown in FIG. 5 (please read first (Notes on the back page)

, Π This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297 mm) 554260 A7 B7 3 发明 1 5. Description of invention (丨 &gt;) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The light lithographic printing method of the present invention comprises transmitting a light lithographic printing pattern through glass in the form of a VUV photon having a wavelength of &lt; 193 nm, wherein the attenuation of the ray ray lithographic printing light is suppressed. In a preferred embodiment, the method includes providing an Fz excimer laser 28 that generates ultraviolet λ, and I includes a laser emission wavelength of 157 nm, as shown in FIG. In the preferred embodiment, the optical mask base of the VUV transmission glass below 193nm is used as a light lithography with a wavelength of 157nm. The substrate is a dry, high-purity direct-deposition glassy siloxyfluoride glass with an OH content of less than 20 ppm. The weight ratio, the C1 content is less than 0.1% by weight, and the fluorine content is in the range of 0.001 to 7% by weight. Preferentially drying high-purity direct-deposited vitrified silicon oxyfluoride glass 20 with a fluorine content in the range of 0.01 to 2% by weight, preferably a fluorine content in the range of 0.01 to 0.5% by weight, and The fluorine content is preferably in the range of 0.1 to 0.4% by weight. The C1 content of the high-purity direct-deposited vitrified silicon oxyfluoride glass 20 is preferentially dried at a weight ratio of 0.08%, more preferably the C1 content is $ 0.06% by weight, and the C1 content is more preferentially at a value of 0.004 〇2% 重量 比。% weight ratio, more preferably C1 content $ 0. 03% weight ratio, most preferably π content $ 0.02% weight ratio. In a preferred embodiment, the C1 content of the dry, high-purity direct-deposited vitrified siloxane glass 20 is less than 5 ppm, more preferably the C1 content is less than 1 ppm, and the most preferred direct-deposited vitrified siloxane glass is Contains no detectable gas. Preferentially drying the high-purity direct-deposited vitrified siloxyfluoride glass 20 has an OH content of less than 10 ppm by weight, and more preferably 0 [1 content and low ppm by weight. This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297) (Please read the precautions on the back before filling out this page) Order 554260 A7 B7 V. Description of the invention (G) Priority drying and high purity direct deposition vitrification The silicon oxyfluoride glass has a hydrogen content of less than 1x10π molecules / cm3. Preferentially drying the high-purity direct-deposited vitrified siloxane glass Fe content is less than 0.004% by weight. Preferentially drying the high-purity direct-deposited vitrified siloxyfluoride glass with a Zr content of not more than 0.00004% by weight. In a preferred embodiment, the dry, high-purity direct-deposited vitrified silicon oxyfluoride glass 20 contains a plurality of interstitial molecules, preferably with a concentration of at least 1015 mol / cc, and preferably -1016 mol. Ear / cc, preferentially $ 120,002 Moore / cc, and most preferably in the range of 1016 to 10,002 Moore / ⑺. In the preferred embodiment of the present invention, the glass substrate 20 is a non-single-piece annealed glass wafer, wherein the glass wafer 20 is not annealed in its actual form of the glass wafer substrate. In the preferred embodiment, the glass is annealed in the actual state of the preform. This state is different from and larger than the glass wafer glass substrate sheet. The glass is preferentially annealed to the glass preform disc 32 (Figure 7). The annealed glass preform The actual size is considerably larger than the glass wafer 20 (very large volume and very long maximum size; at least twice, preferably at least three times, and more preferably four times). Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs As shown in Figure 1, the optical lithographic printing optical mask rough glass substrate 20 has a maximum dimension length L. As shown in FIG. 7, the directly deposited vitrified silicon oxyfluoride glass preform disc 32 has a diameter of the preform disc D and a degree of the preform disc H, where D &gt; H. As shown in FIG. 7, it is preferred to directly deposit vitrified silicon oxyfluoride glass preforms. The dish 32 has a height H and a diameter D, and the diameter D is located on the sand plane defined by the x-axis and the y_ axis of the preform. The X-axis and the y-axis are perpendicular to the height H of the preform dish. The paper size of the dish is applicable to the Chinese national standard (CNS> A4 specification (2 丨 〇 &gt; &lt; 297 Gongchu) 554260 A7 B7 5. Description of the invention (I in) Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs As shown in the side view of the processing flow of the preform, as shown in Fig. 8a-c, the method includes the inclusions of the non-contaminant 32, the region containing no impurities, and the region 34 containing no impurities. The diameter of the shell is larger than that of rice. As shown in Figs. 8a and 8b, the present invention preferably includes keeping the preform dish-shaped X-axis, y-axis, and z-axis pointing, and simultaneously removed by the preform dish. ^ Contains impurity regions to provide silk county hair embryos 36, which have optical mask hair embryos X-sister tree X-axis, optical mask hair embryos preform y-doped prefabricated objects y-axis, and optical mask blank preform dish 2-axis. As shown in Figure 8b, gG and 1, the method includes forming an optical fresh side to become light; 5th edition printing optical mask blank ... 〃, there is a daring long size length L. In the preferred method of the present invention, the thickness of the optical mask hair embryo 2G of the light lithographic printing is τ, Lithographic printing optical mask hair embryo χ-axis, light lithography optical mask hair embryo y-axis, light lithographic printing optical mask hair embryo z-axis to round light lithography printing scale mask hair embryo χ-fine and light lithography Printing optical mask germ y-axis pairing Optical mask germ miscellaneous parts χ—drawing and optical mask germ miscellaneous parts y-axis. The longest dimension length L of optical mask germ 20 in optical lithography is located in the optical The mask germ is defined in the plane xy defined by the χ-axis and y-axis and the thickness of the lithography optical mask germ is τ aligned with the lithography optical mask germ z-thin and dangling optical mask The X-axis, y-axis, and thickness T of the embryo are smaller than [. Preferably, γ is much smaller than 1, and more preferably 10 TCL. The glassy Wei fluoride glass breaking preform 32 which is directly deposited by the method of the present invention has a flat geometric shape. , Preferably in the shape of a flat dish and a high cylindrical shape, in which the height in the ζ axis direction is larger than the size of the bottom of the plane. This paper size applies to the Chinese National Standard (CNS) 8.4 (7 mm).

V. Description of the Invention (Printed by the Consumer Cooperatives of the Central Standards Bureau, Ministry of Economic Affairs, K. 554260 The flat and high geometric preforms provide glass objects with uniform optical characteristics, which provide improved light lithographic printing characteristics. In the preferred embodiment Providing a pre-deposited vitrified glass preform dish 32 includes providing a preform dish 32 having the longest dimension diameter D, the diameter being greater than or equal to two times the height (D-2H), more preferably D-3H, And most preferably D-4H. The method of manufacturing the VUV transmissive glass optical mask substrate 20 below 193nm includes manufacturing a directly deposited vitrified silicon oxyfluoride glass object 32. Figures 9 and 10 show manufacturing and providing direct deposition Method for vitrified glass preform dish 32. In a preferred embodiment, the high-purity ^-glass precursor product raw material is conveyed as a gas through a transfer duct 38 to one of the carbon monoxide conversion site burners. The carbon oxide combustion flame 40 contains heat directly Deposition conversion site high temperature furnace 42, which converts Si &amp; F-containing raw materials into dry silicon oxyfluoride glass dust 44, which is projected to Deposited on the direct glass deposition surface 45, which is preferentially contained in the horizontally rotating collection cup 46 and the dust 44 simultaneously and directly deposited vitrified and consolidated into a high-purity dry siloxyfluoride glass object 48. Preferentially The high-temperature furnace 42 containing a heated direct deposition conversion site is manufactured from refractory objects of aluminum oxide, which has been used to remove pollutants. The high-temperature furnace 42 including cup 46 is preferentially alumina refractory block cleaned by elemental treatment. As a result, the refractory block does not contain pollutants and is preferably achieved by removing the pollutants before forming glass, such as using halogens> monthly cleaning / removal of pollutant gases, carbon-gasification. Preferentially low-pollution gasification and climbing The anti-fire material was disclosed in Kotacka et al. PCT W001 / 17919 patent published on September 8, 2000. Its patent name is pure Fused Silica, Furnace

And Method, which is incorporated herein by reference. Rotating cups This paper is sized for China National Standard (CNS) A4 (210X297 mm)

\ S

554260 A7 _____ B7 V. Description of the invention ([t) 46 is horizontally oriented (parallel Xy plane, perpendicular to 2 axes), except for rotating cup 46, which preferably uses χ-y oscillation table in xy plane Move with the vibrating movement pattern. As shown in FIG. 10, the gas and gas flow in the high-temperature furnace 42 is preferentially suppressed and minimized, so that a uniform glass object 48 is manufactured. The preferential direct deposition high temperature furnace was revealed on September 14, 1999

Paul Schermerhorn in US Patent No. 5,591,730. The temperature in the high-temperature furnace 42 containing heat is maintained at a high temperature to ensure that the deposited dust 44 is consolidated into a glass object, preferably the operating temperature of the high-temperature furnace 42 and the glass object is at least 1500 ° C, and more preferably at least 1600 ° C, and The highest priority is at least 1650 ° C. Utilizing the high temperature that allows objects to flow in the preferred embodiment, the cup 46 is manufactured with sloped walls as shown in Figure 10, which is not as steep as Figure 9 and promotes beneficial movement and flow of glass. Priority collection of cup containers was disclosed in John Maxon's December 16, 1997 Announcement No. 5898484 US Department of Economics Central Standards Bureau Staff Consumer Cooperative Cooperative Printed Patent, which is incorporated herein by reference. Preferably, the horizontally directed collection cup 46 has a collection cup height of CCH and a collection cup diameter of CCD, CCH &gt; H and CCD &D; D. The provided glass preform dish 32 includes the periphery of the discarded glass object 48, especially the periphery of the glass object 48 that is in contact with the cup 46, so that the optical mask blank originates from the non-outer peripheral portion of the glass object 48. As shown in Figs. 9-10, the glass object 48 is preferably contained in the direct deposition collection cup 46. In addition to containing a flowable glass form, the collection cup 46 protects glass objects from changes and impacts in the external environment and most preferentially suppresses the heat loss of glass objects in the cup 46, where the cup 46 is made of refractory insulation , And especially reduce the size of the glass object on the 48 side. The paper size applies the Chinese National Standard (CNS) A4 specification (2 丨 0X297). 5. Description of the invention (丨 17) The heat loss on the sides and bottom is higher than that of glass. The object 48 is generated by a carbon monoxide flame of one of the carbon monoxide burners 40 and by an auxiliary heat source such as a carbon monoxide combustion heat source burner, which is located in a high-temperature furnace conversion position 42 above the glass object 48 and the cup 46. In a preferred embodiment, the present invention comprises continuously depositing dust 44 in a cup 46 while consolidating the dust to directly deposit vitrified molten glass objects while maintaining the temperature of the stacked objects to be at least 1500 ° C. The stacked glass object 48 is preferably maintained at a temperature required for the consolidation vitrification (consolidation vitrification temperature) so that the temperature of the entire glass object is uniform. This temperature is preferably minimized by the heat loss from the glass object 48 throughout the manufacturing process. A flat dish geometry, such as a glass preform dish, has!)-211, which preferentially helps to minimize heat loss from the surface of the glass object 48. The flat dish-like object is preferentially contained in a heat-insulating cup, which minimizes the heat loss from the side of the object passing through the relatively heat source (the bottom of the object 48 relative to the heat source on the top of the high-temperature furnace 42) and the side of the object. Compared to the geometry of long tall pillars, this flat dish is good for inhibiting heat from passing through the bottom and sides. As shown in Figures 9 and 10, the dust 44 is preferentially projected onto the deposition surface 45 and runs downward along the deposition path of one of the monoxide anaerobic burners 40. It enters the cup of the Ministry of Economic Affairs' Central Standards Bureau's Consumer Cooperatives. The object 46 and the rotating cup 46 rotate in a rotation plane perpendicular to the downward deposition path of the dust 44. The rotation plane of the cup 46 is parallel to the plane defined by the X-axis of the preform and the y-axis of the preform dish. In addition to the rotation in the rotation plane parallel to the xy plane, the cup 46 is translationally moved in the xy parallel plane with an oscillating movement, and it is preferred to use the US Patent No. 5960038 of December 1997 and December 9, 1997. Oscillation rotation pattern disclosed in 554260 Α7 9 Β7 V. Description of the invention (| g) The patent name is Boule Oscillation Patterns In Methods of (Please read the precautions on the back before filling this page}

Producing Fused Silica Glass, the description of which is incorporated herein by reference. In the preferred embodiment, the glass preform dish 32 is annealed in a carbon monoxide direct deposition high temperature furnace 42 after the glass object 48 is completed and at the end of manufacturing and dust deposition. In the method for manufacturing a light lithographic optical mask blank 20, the glass is not annealed after being removed from the preform plate 32, and the optical mask blank 36 and the individual blanks 20 are not treated. annealing. In the preferred embodiment, any birefringence present in the glass in the large-scale preform dish 32 and the object 48 will be reduced and the preform dish processing process will not be reduced. 11, 11 to form an optical mask blank preform 36 that becomes a light lithographic printing optical mask. The blank 20 preferably includes a set of multiple optical mask blanks cut from the preform 36 and a polished optical mask blank. The invention further comprises forming a light lithographic pattern on the optical mask hair embryo 20 and transmitting radiation with a wavelength below 193 nm through the optical mask hair embryo. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. In the practice of the present invention, the diameter of the preformed dish 32 is greater than 20 inches (50 cm). For example, D is about 3 to 5 feet (0.91 to 1.5 cm). Feet) and a height of about 6 to 10 inches (15 to 25 cm), from which the mask hair embryos 20 are produced. The longest dimension L &lt; 12 inches (30 cm) makes the hair embryo size about 10 inches. Leaf χι0 inches (25 cm x 25 cm), 9 inches x 9 inches (22.8 cm x 22.8 cm), 6 inches x 6 inches (15 cm x 5 cm), thickness τ is about 1/4 inch Inches (0.63 cm). Many mask blanks 20 can be cut from larger preform plates 32. The large preform plate sizes provide improved light lithographic printing performance, especially with

554260 A7 V. Description of the invention (referred to as the optical mask base formed by the pillars __ = the size of the optical dimensions of the member. The figure shows the processing flow chart of the embryo 20 method. Prefabrication provided ; Niu Shang ::, 10 in the 'It uses carbon monoxide conversion flame to directly deposit the glass product processing process and smoke vibration rotating cup 46. The position of the light prefabricated puppet is located on the dish 32, and the use of the dish is preferably avoided. The center of the object 32. As shown in Figure η, the layout of the optical mask blank preform is preferentially staggered to prevent any miscellaneous inspection by the Central Consumers Bureau of the Ministry of Economic Affairs.

Li can be formed using non-staggered inspection boards aligned in rows and columns without inspecting the detectable impurities in the preform dish 32, so that the glass containing the impurities is discarded in subsequent processing. The optical mask blank preform 36 is arranged at the position of the optical mask blank preform 36, and the optical mask blank preform block 36 is cut out from the preform dish-shaped pith. A representative optical mask blank preform block 36 has a square base of approximately 6.5x6.5 inches (16.5 cm x 16.5 cm) and a height of approximately 5-6 inches (12 cm to 15 cm). The preform block 36 is cut and polished on three sides, and the inside of the glass is inspected and drawn. The internal inspection uses three polished sides by transmitting light through two opposite polished sides for identification, marking, and mapping of any impurities larger than 丨 micron size in the interior volume of the glass. The optical measurement system is preferentially used to scan and detect the laser beam (this scanning beam) 101 to identify impurities through the volume of the block 36, which uses the three polished sides to observe the impurities, so that the position of the impurities can be plotted and marked as Subsequent removal. Able to use, for example, Richard PriesUey's method and system of US Patent No. 09/458561 on December 9, 1999, the patent name is Automated System For Measurement Of An This paper size is applicable to China National Standard (CNS) A4 specification (210X297) (Centi) 554260 A7 _________B7 V. Description of Invention (W)

Optical Property, the description of which is incorporated herein by reference. The lumps 36 are cut into rough boards so that impurities can be identified and removed. When the thickness is about G · 4-0 · 5 inches (H · 3 cm), the impurities around the cutting blank are cut off. The cutting blank board is pre-polished with a chemical mechanical dressing agent to flatten the superimposed part, the flat plate is polished flat, and the edges are polished to provide a pre-trimmed mask blank. Measure the pre-masked mask blank as an optical element. In another embodiment, the glass optical element can be measured in the form of a block like an impurity inspection. It is possible to use, for example, Richard PHestley's patent method and system of US Patent No. 09/458561 dated December 9, 1999, which is named Automated System For

Measurement of An Optical Property, the description of which is incorporated herein by reference. The pre-trimmed mask blanks are then trimmed to provide trimmed glass matrix optical mask blanks. The final dressing preferably includes chemical mechanical polishing to ultra-polishing less than 5 angstrom dressing and flatness, cleaning and packaging for addition to the mask 22. As shown in FIG. 12, in order to obtain sufficient heat from the dried co flames, printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, the hydrogen-free CO fuel 126 and the glass raw material precursor product 124 are preferentially supplied at a predetermined flow rate. In particular, in order to generate sufficient heat, the ratio of the fuel flow to the flow of the glass precursor 124 should be greater than 20: 1. This can be achieved by various channels of appropriate size in the burner 125. One priority burner is shown in Figure 13. The CO burner as a combustion-free hydrogen should be expressed as a "dry burner". The dry CO burner 125 contains a central smoke tube 68 formed as an elongated tube and a precursor product used to supply the gas glass raw material. Preferentially, surrounding The smoke pipe 68 is the inner screen channel 74, which makes the paper size applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 13 554260 A7 ___ — —__ B7 5. Description of the invention (W) is used to transport oxygen. The ratio of oxygen miscellaneous material to gas content is 2: 1. Around the smoke pipe and the internal screen,% is the fuel channel 70, which is used to transport a large amount of plutonium fuel. Although not sure Consistently not showing the proportion, it is known that the cross-sectional area of the fuel passage 70 is much larger than the smoke official piece 68. Since the oxygen secret contains less heat during combustion, it will require a larger flow rate compared to methane. This can be increased. The design enables the glass body product 124 to be supplied to the burner at the first flow rate, the central smoke channel 68 and the non-hydrogen-containing fuel 126 to be supplied at 20 times the flow rate of the first flow rate, thereby generating sufficient The precursor product is oxidized. The burner 125 can include multiple input ports for maintaining hydrogen-free fuel 126 and oxygen 21 for maintaining combustion, thereby providing a more uniform flow distribution in the annular channel. In another embodiment of the present invention Fluorine can be added to the solution. There are several ways to achieve this in the present invention. First, fluorine can be included in the precursor product, such as using chlorofluorosilane as the precursor product 124. In this manner, the precursor product 124 is supplied to the smoke as a gas. Pipe fittings are oxidized by ⑺ flames to produce fluorine-doped dust. Variations can be made, and some fuels or oxygen can be supplied as hydrogen-free fuel. The Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs prints the second type of fluorine-added The method is by flowing fluorine or a fluorine-containing compound such as CF \ (¾SF6, NF3, SiF4 or a mixture thereof in the form of a gaseous raw material into the screen contained in the burner. Figure 14 shows that it can be used to produce sand gas. In the dust burner 125a, fluorine or a fluorine-containing raw material compound is supplied as a gas to the outer shield channel 72 surrounding the fuel channel 70. Water cooling jacket can be used to surround the fuel channel. Carbon monoxide burner is preferred. Paper size> A4_ (21 () χ2ϋ ^ 23 554260 A7 B7 V. Description of the invention (27 /) The embodiment has a central pipe 68, which Used to provide non-hydrogen glass precursor products into the flame area, the central tube is located along the central axis of the burner 125, 125a (Figure 13-14); the inner screen unit 74 is used to provide oxygen into the flame, and the inner screen unit is radially Off the central axis of the burner, the fuel unit 70 is radially off the central axis of the burner and is used to provide hydrogen-free fuel; the outer screen unit 72 is used to provide fluorine-containing gas to cover the flame, and the outer screen area is radially Off the burner's central axis and placed outside the inner panel unit and fuel unit, the burner is used to make moisture-free, fluorine-doped silica. According to the embodiment shown in FIG. 12, a glass object, such as a glass 86 dish, can be manufactured using a fuel containing no hydrogen. The molecules of the glass precursor product containing &amp; eve react in a CO flame 128 to form dust particles. These particles wo are deposited on the hot direct deposition surface of the object 132, where they consolidate into a very viscous fluid (deposition and simultaneous vitrification), which is subsequently cooled to a solid state. Printed by the Consumers' Cooperative of the China Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) Another embodiment of the present invention is to provide a method for manufacturing dry vitrified glass objects. The method preferably includes the following steps: the heat generated by the burner 125 has the ignition generated by igniting the hydrogen-free fuel 126, the hydrogen-free fuel flame 128 is a heat source, and the glass precursor product 124 is flowed into the flame 128 to manufacture The dust 130 containing the stone evening stone is deposited, and the dust containing the stone evening stone is deposited on the deposition surface substrate 132 and the consolidated dust is vitrified to form a vitrified glass object 86 at the same time. In the preferred embodiment, dust is deposited on a substrate 132, which itself is a silica-containing glass member, and most preferably a glass dish. By using hydrogen-free fuel, the glass paper material is in accordance with China National Standards (CNS) A4 (210X297) Chu 554260 A7 B7 5. Description of the invention (y) The body 86 contains water (OH) Less than a few ppm. In the embodiment shown, the deposition step is performed in a furnace 89 containing a heated high temperature. Preferably, the purge gas is provided in the tank, for example, with a moisture-free environment. Generally, it is necessary to provide pressurized gas in the tank 89, the pressure being greater than the atmospheric pressure outside the tank. In a preferred embodiment, providing a carbon monoxide supply source to a carbon monoxide burner to form a carbon monoxide combustion reaction flame includes providing a high-purity carbon monoxide supply gas and passing the high-purity carbon monoxide supply gas through a series of CO purification filters 300 located upstream of the carbon monoxide burner. A series of CO purification filters located upstream of the carbon monoxide burner removes water, iron, and pollutant metals from the high-purity carbon monoxide and transfers it to the burner to ensure a high-purity flame and produce South-purity glass from it. C0 purification filter for example from 丨 11 ip〇re

Waferpure Micro / Mini-XL / Megaline by Corporation

Gas Purifiers CO purification filters are suitable CO purification filters. 3 ° /。 Preferably the high purity carbon monoxide supply gas is at least 99.3 ° /. Purity CO. The method of printing and manufacturing sub-193nm VUV transmission glass optical mask substrate blanks as light lithographs with a wavelength of 157nm by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics includes providing a carbon oxide burner that does not contain hydrogen; providing a high temperature furnace containing direct deposition; Provide carbon monoxide and oxygen supply to monoxide; 5 carbon burner to form carbon monoxide reaction flame, provide direct glass deposition surface adjacent to CO flame, supply Si-glass precursor product raw material and F-glass precursor product raw material to carbon monoxide burner In the CO flame, the raw materials of the Si-glass precursor and the F-glass precursor are reacted as silicon fluoride glass dust, which is projected on the glass deposition surface, and the dust is simultaneously deposited directly and vitrified into the silicon oxide fluoride glass object. . The method includes the formation of directly deposited vitrified silicon oxyfluoride glass paper. The size of the paper is applicable to China National Standard (CNS) A4 (210X, 297 mm) 554260 A7 —-------—____ B7 ^ V. DESCRIPTION OF THE INVENTION (νρ) The glass object is an optical mask blank. Priority supply of Si-glass precursor product raw materials includes supply of chlorine-free Si-glass precursor product raw materials, which are directly deposited, and the vitrified silicon oxyfluoride glass is gas-free (preferential &amp; cl &lt; lppm) silicon oxyfluoride The glass and the glass object are formed into a chlorine-free silicon oxyfluoride glass optical mask blank. Preferably, the supply of the si-_precursor raw material includes the supply of the raw material of the Si-glass precursor product containing no hydrogen, in which the directly deposited vitrified = oxyfluoride glass is a dry silicon oxyfluoride glass whose 0H concentration &lt; 10ppm weight Ratio, and the 0H concentration &lt; 10 ppm weight ratio of the glass object formed as a dry silica glass optical mask blank. In the most preferred embodiment, the raw material of the Si-glass precursor product containing no gas and no hydrogen is silicon tetracyanate. Supply F—Glass raw materials preferentially include the supply of raw materials that are determined in advance.—The glass precursor product raw material flow, in which the fluorine concentration weight ratio of directly deposited vitrified silicon oxyfluoride glass is in the range of 0.01 to 7% by weight, more preferentially. In the range of 0.001 to 2% by weight, most preferably in the range of 0.01 to 0.5% by weight. Prioritizing the supply of oxygen includes providing a predetermined supply flow of 02, where the directly deposited vitrified glass is contained; preferably, the oxygen oxyfluoride glass contains 0% of molecules with a concentration of at least 1015 mol / cc. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, which includes heating and direct deposition of high-temperature furnaces, which preferentially include the cleaned alumina refractory blocks and the combination of this function to process and clean the alumina refractory blocks to form high-temperature furnaces, with the highest priority for refractory The block is made of alumina. The high-temperature direct-deposition furnace containing heating is composed of alumina refractory material, which is previously exposed to a reactive fungus-containing gas for reaction, and thus cleans refractory materials that contaminate metals. The high-temperature furnace, which preferably contains the top and adjacent to the co burner, is composed of alumina, and its top is covered with a consolidated glass object. This paper size applies Chinese National Standard (CNS) A4 specification (2 丨 0χ 297 mm) 554260 A7 B7 V. Description of the invention Preferentially, the high-temperature furnace cup made of alumina contains solidified glass objects. Preferably, the alumina refractory block is exposed to a cleaning process gas containing a reactive halogen. Preferentially, the alumina refractory block is a porous block with a porosity in the range of 25-70%, preferentially the overall density &lt; 3.9 g / cc, and more preferably the overall density of the refractory mono-oxide refractory—1 · 2 g / cm3. Printed by the Consumer Co-operation of the Central Bureau of Standards of the Ministry of Economics The present invention includes the production of a lithographic printing glass with VUV transmission light below 193 nm to transmit a wavelength of 157 nm. The method includes providing a carbon monoxide burner containing no hydrogen fuel; providing a carbon monoxide supply source and an oxygen supply source to the carbon monoxide burner to form a carbon monoxide combustion reaction flame, providing a direct glass deposition surface adjacent to the flame, supplying Si_glass precursor product raw materials, and F -Glass precursor product raw material to carbon monoxide burner, in which Si-glass precursor product raw material and F-glass precursor product raw material react in a flame into siloxane fluoride glass dust projected onto the glass deposition surface, and the dust is simultaneously deposited directly And vitrified glass objects. Preferably, the supply of Si-glass precursor product raw materials includes the supply of gas-free &amp; glass precursor product raw materials, in which the vitrified siloxyfluoride glass is directly deposited as chlorine-free (Cklppm) siloxyfluoride glass. Preferential supply &amp;-glass precursor product raw material includes supply of hydrogen-free Si_ glass precursor product raw material, in which vitrified siloxyfluoride glass is directly deposited as dry siloxyfluoride glass, and its OH concentration weight ratio &lt; 10 ppm. Priority supply of Si-glass precursor product raw materials includes supply of chlorine-free and hydrogen-free Si_glass precursor product raw materials, of which direct &gt; child glass vitrified silicon oxyfluoride glass is dry and gas-free silicon oxyfluoride, For glass, its OH concentration-to-weight ratio &lt; 10 ppm, most preferably, the raw material of the Si-glass precursor product containing no gas and no hydrogen is tetracyanite. Supply ρ_ glass precursor

554260 A7 B7 V. Description of the invention (it) The raw material preferentially includes the raw material supply flow of the base glass product, in which the fluorine concentration of the glassy siloxyfluoride glass directly deposited is 0.001% to 7% by weight Within the range, it is preferably in the range of 0.001% to 2% by weight, and more preferably in the range of 0.01% to 0.5% by weight. Providing an oxygen supply source preferably includes providing a predetermined 02 gas supply flow, wherein the concentration of O2 in the directly deposited vitrified silicon oxyfluoride glass is at least 1015 mol / cc. Printed by the Consumers' Cooperative of the Central Government Bureau of the Ministry of Economic Affairs The present invention includes a method for manufacturing a uniform glass lithographic printing element, the method comprising providing a carbon monoxide burner containing no hydrogen fuel; providing a carbon monoxide supply source and an oxygen supply source to the carbon monoxide burner To form a carbon monoxide reaction flame, provide a direct glass deposition surface adjacent to the flame, and supply the Si-glass precursor product raw material and dopant R-glass precursor product raw material to the carbon monoxide burner, wherein the Si-glass precursor product raw material and dopant R The raw material of a glass precursor product reacts in the flame as dry doped R silica glass dust is projected onto the glass deposition surface, the dust is simultaneously deposited directly and vitrified into a dry and uniform R doped silica glass object, and forms Directly deposited vitrified glass objects are uniform glass lithographic printing elements. The raw materials for the doped R-glass precursor products are preferably selected from the types of F, Ti, Ge, B, P, and A1 dopants R. The supply of Si-glass precursor product raw materials preferentially includes the supply of gas-free Si-glass precursor product raw materials, in which the vitrified glass directly deposited is chlorine-free (ClClppm) glass and the glass object is formed as a gas-free uniform glass optics element. The supply of the Si-glass precursor product raw materials preferentially includes the supply of hydrogen-free Si-glass precursor product raw materials, in which the directly deposited vitrified silicon oxyfluoride glass is a dry glass, with an OH concentration-to-weight ratio &lt; i ppm and glass objects Formed as a dry, non-chlorine uniform glass element, the OH concentration of this paper is in accordance with Chinese national standard (CNS> A4 specification (210X297 mm) 28554260 A7 _____ B7 _ 5. Description of the invention (y |) Degree weight ratio &lt; 10ppm More preferably, the raw material of the Si_glass precursor product which does not contain chlorine and hydrogen is tetracyanite. The present invention includes a method for manufacturing a uniform glass light lithographic printing element, which comprises providing a carbon oxide burner that does not contain hydrogen fuel. ; Provide a carbon monoxide supply source and an oxygen supply source to a carbon monoxide burner to form a carbon monoxide reaction flame, provide a direct glass deposition surface adjacent to the flame, and supply a Si-glass precursor product raw material to the carbon monoxide burner, wherein the Si-glass precursor product raw material is in the flame The intermediate reaction is that the dry silica glass dust is projected onto the glass deposition surface, and the dust is simultaneously and directly Deposited and vitrified into dry and uniformly doped silica glass objects, and glass-lithographic lithographic printing elements that form directly deposited vitrified glass objects are homogeneous. Preferential supply of Si-glass precursor products includes Raw materials for precursor products of gas Si-glass, in which vitrified glass directly deposited is gas-free (□ &lt; 1 卯 111) glass and the glass object is formed as a glass-free uniform optical element. Preferably, Si- The raw materials of glass precursor products include the supply of hydrogen-free Si-glass precursor products. Among them, directly deposited vitrified glass is dry glass, its 0H concentration weight ratio &lt; 10ppm, and glass objects are formed as dry uniform glass optical elements. Printed by the Bureau of Consumer Cooperation (Please read the notes on the back before filling out this page) Its 0H concentration weight ratio &lt; 10ppm, more preferentially, the 0H concentration weight ratio &lt; ippm. Supply in the preferred embodiment The raw material of the Si-glass precursor product includes the supply of the raw material of the Si-glass precursor product which is free of gas and hydrogen, and the vitrified silica glass is directly deposited for drying. The chlorine-containing silica glass has a 0H concentration-weight ratio <ippm and the glass object is formed as a dry, gas-free uniform glass element, and its 0H concentration-weight ratio ClOppm, preferably 0H concentration-weight ratio <ippm. Fluorine is the required component of the fused silica of the present invention, and the F containing fluorine-this paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 554260 A7 B7 V. Description of the invention (The raw material of the glass precursor product is fluorine Silicone, silicon tetrafluoride, and mixtures thereof can be used in the method of the present invention. In addition to the silicon fluoride raw material, the fluorine source raw material F-glass precursor product raw materials such as rhenium 4, SFe, F2, c3f8, and GF6 and containing The silicon raw material compound glass precursor product raw material reacts to produce fluorine-doped stone stone stone from fluoride stone stone stone dust. In addition to being preferentially free of 0H groups, doped with fluorine, and free of chlorine, we have found that the fused silica optical mask hair embryo molecular hydrogen of the present invention is low in concentration, preferably less than 1x1017 molecules / cm3, and more preferably less than 5x1. h molecule / cm3 molecular hydrogen. The 0H content is reduced to less than 50 ppm, less than 10 ppm, and most preferably less than 1 ppm, and silica glass doped with fluorine is provided to increase the transmission and reduce the thermal expansion of 157. Preferably, the transmittance of the fused silica glass optical mask substrate with low-Hi157nm transmission light lithography printed at 157nm is at least 80%, preferably at least 83%, and the thermal expansion is less than 0.55ppm / ° C, preferably Less than 0.53ppm / ° C. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs The present invention further includes lithographic printing glass with VUV light below 175nm. Light lithographic glass contains fused silica glass. Silicon fluoride glass has an OH content of less than 5ppm by weight, a C1 content of less than 5ppm by weight, an H2 content of less than 1 × 1017 molecules / cm3, a fluorine content of at least 0.1% by weight, and a glass internal transmission of 157nm of at least 80. % / Cm and preferably at least 85% / cm. Silicon oxyfluoride glass has a lower thermal expansion coefficient of fused silica, which is less than 0.55 ppm / ° C in the range of room temperature to 300 ° C. It is preferred that the internal transmission of the lithographic printing glass in the wavelength range of 157nm to 175nm be at least 80% / cm, and preferably at least 85% / cm. Preferentially, when exposed to 4 paper sizes, the Chinese national standard (CNS> A4 specification (210X 297 mm) 31 554260 A7 B7 _ V. Description of the invention (4) mJ / cm2-pulse contains F2 excimer with a wavelength of 157nm The absorption of lithographic lithographic glass of siloxyfluoride light lithographic glass at a laser irradiation of at least 0.96 × 106 pulses is less than 0.1 at 215 nm, and the optical density (10 such as transmittance) per millimeter is more preferably less than 0 at 215 nm. · 05 optical density, and most preferably no 215nm absorption band formation. Preferably the C1 content of the glass is less than 1 ppm and the OH content is less than 1 ppm, and more preferably the glass contains Si, 0, and F. Preferentially the glass does not contain metals and The metal Si_Si bond, and glass does not contain an absorption center of 165 nm, and its internal transmission is at least 85% / cm at 165 nm. In a preferred embodiment, a lithographic printing glass is used to make a VUV transmissive optical mask, in which VUV light is transmitted through Optical mask, preferably with a patterned deposited film (eg, Cr) on the surface of the light lithographic printing glass, which forms a transmissive light lithographic mask pattern. In another embodiment VUV phase-shifted optical masks are manufactured using light lithographic glass, in which the phase of VUV light lithography running through the glass is shifted and manipulated to form a constructive and / or destructive interference pattern. In another embodiment, reduction is used Light lithographic printing glass with a thermal expansion coefficient and a coefficient of thermal expansion of less than 0.55 ppm / ° C to produce a reflective optical mask, wherein the light lithographic printing mask pattern of the reflective pattern is supported by siloxane glass. The bureau ’s consumer cooperative prints the present invention and further includes a method for printing patterns by VUV light lithography. The method includes providing a radiation source below 164 nm to produce VUV light lithography printing photons, and providing silicon oxyfluoride light lithography printing glass. , Which has a weight ratio of less than 5 ppm OH, a weight ratio of less than 5 ppm C1, and a measured transmittance of 157nm and 165nm of at least 75% / 5 cm, and transmits VUV light lithographic printing photons through the provided oxyfluoride light lithographic printing glass Use of photons to form light stone plates (^ 0) Printing patterns, and reducing the formation of light lithographic printing patterns and projecting the formed patterns on νυν radiation-sensitive light lithographic printing media to form patterns of light lithographic printing. Silicone fluoride glass is preferred The ground includes providing a precursor product of Si-glass to reduce the νυν cutoff wavelength of the glass, and reducing the Η2,0Η, and C1 content of the directly deposited vitrified glass produced therefrom, and increasing the F content of the directly deposited vitrified glass to provide Direct deposition of vitrified silicon oxyfluoride glass, so that 50% transmission VUV cut-off wavelength is below 160nm. The glass provided preferably contains Si, O, and F and does not contain Si-Si bonds. The present invention provides an optical mask stage for a 157nm light lithography optical mask substrate and a 157nm light lithography printing device (I57nm illumination system, optical mask-mask stage, 157nm projection optical system, 157nm wafer stage), doped Low-OH fluorinated stone oxo 1-oxide optical mask stone oxite glass substrate, the content of which is less than 1 ppm, the fluorine content is in the range of 0.1 to 1.5% by weight, and the internal transmittance of 157 coffee is at least 50%, preferably The ground is at least 65%, and most preferably at least 83% / cm at 157 nm, preferably with a thermal expansion of less than 0.55 ppm, preferably less than 0.53 ppm, and most preferably less than or equal to 0.52 ppm / ° C. ·, Polishing substrate, 25mmx25nimxl · 5_ Thickness is prepared from silicon oxyfluoride glass. For comparison, a 25mmx25mnix 6.35mm thick substrate was also cut from a standard commercial Shi Xishi optical fresh substrate. The base f is cleaned in Wei / peroxide solution and shade cleaning agent, and then spin-dried and baked at i2 (rc, -1GG_ degree chromium film by spraying method. Film adhesion measurement by Use Nanoidenter II for engraving and scraping test., (Please read the precautions on the back before filling out this page) Revision of the paper size national standard (CNS) A4 specification (21〇 &gt; &lt; 297 public momentum ) 3 Luo 554260 A7 ____ B7 V. Description of the Invention (ll) 2 3 Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs = Under the same test conditions, the stratification of the diaphragm cannot be generated on any kind of substrate. These results show good The film adhesion of the soil M Shixi stone glass can be explained as & 04 tetrahedral mesh structure is bonded together at four corners and irregularly oriented relative to each other. Water addition structure becomes different. (Its The Ξ indicates that the bond is to the 4 reticular structure), so that the bond with the adjacent tetrahedron is broken at the 0 Η base. 0 吸收 absorbs in deep UV at 0 75 ηη. Fluorine is also added to the structure to form a reticular structure. Break at F atom Si-F bonding-related electron transitions are expected to be higher in energy (shorter wavelengths) than Si-0 network structure bonds. Fluorine-doped sparite structures are particularly resistant to F2 excimer laser radiation The damage caused. We have confirmed that in the fluorinated structure, the formation of E color centers is highly suppressed even in silica containing very low concentrations of fluorine. It is possible for fluorine to reduce the number of body product positions before the formation of color centers. This position is, for example, a weak or saturated bond and an oxygen-deficient Si-Si defect. In a preferred embodiment, the present invention includes a VUV-transmissive glass optical masking substrate below 193 nm as a light lithography with a wavelength of 157 nm. VUV-transmittance The glass matrix contains high-purity oxyfluoride glass with an OH content of less than 50% by weight, a hydrogen content of less than 1 × 1017 molecules / cubic centimeter, and a fluorine content in the range of 0.1 to 〇 · your weight ratio. .Glass C1 content is preferably less than 5ppm, more preferably less than 1ppm, and most preferably the glass does not contain gas. Preferentially, the glass has a molecular hydrogen content of less than 3 x 1016 molecules per cubic centimeter, and more preferably The ground has an undetectable molecular hydrogen content. Preferentially the glass has a 0H content below 10 ppm by weight, more preferably below ippm by weight, and most preferably has an undetectable 0H content and substantially does not. Contains OH. The glass is preferentially made of Si (please read the precautions on the back—M-- then this page) The size of the paper is applicable to China National Standard (CNS) A4 (210X 297 mm) 33554260 A7 B7 V. Description of the invention (U) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs. It is composed of 0, and F and does not contain OH, Cl and Η2. Preferentially, the internal transmittance of the silicon oxyfluoride optical mask substrate at 157 nm is at least 89% / cm, and the most preferred basis mass is measured by about 6 thickness of the substrate, for example, 6 mm thickness of the optical substrate. Is 79%. In a preferred embodiment, the present invention includes a process for manufacturing a VUV transmission glass that is highly resistant to optical damage by excimer laser irradiation in the 157 nm wavelength region. The treatment process includes forming non-porous monomers of dry and transparent molten siloxyfluoride glass with a fluorine content of less than 0.5% by weight. The invention contains F2 laser which causes absorption-resistant siloxyfluoride glass and is suitable for use in the 157nm wavelength region. The glass has stability and high transmission under the condition of 157-6nm, and the fluorine content is less than 0.5% by weight, which makes the glass exposed. After 60 million pulses of F2 excimer laser at 0 · lmJ / cm2-pulse, the transmission loss at 157.6 nm is &lt; 1%. The silicon oxyfluoride glass preferably does not contain 0h groups, has less than 5 × 1016 molecules / cm3 of molecular hydrogen, and has a fluorine content in the range of 0.1 to 0.4% by weight. The present invention includes F2 laser-induced absorption-resistant light lithographic printing glass, which includes silicon oxyfluoride glass, the glass 0H content is less than 5 ppm by weight, the C1 content is less than 5 ppm by weight, and the fluorine content is between 0.1 and 0.4%. Within the weight ratio range, the internal transmission at 157 nm is at least 80% / cm, and more preferably 85% / cm. It is preferred that the glass has a scandium content of less than 1 × 1017 molecules / cm3. Shixi oxyfluoride glass resists absorption caused by laser and transmission loss at <157% at 157nm after exposure to 60 million pulses of F2 excimer laser at lmj / cm2_pulse. Siloxyfluoride glass is resistant to absorption caused by 157.6 nm, and the lack of fluorine center suppresses absorption at 165 nm. Prior to exposure to 2mj / cm2, please read the I item on the back first, and then the paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm 5Γ 34554260 A7 B7) V. Description of the invention Cooperative Du-printing-Pulse of 157nm laser 41.5 million pulses, the absorption of glass 16511111 is less than 0.4 (absorption unit / 5 deleted), and most preferentially the absorption of 165 is less than 0.2 (absorption unit / 5mm). Priority The content of ground C1 is less than 1 ppm and the content of 0H is less than ippm, preferably composed of Si, 0, and F. In the embodiment, the glass is a νυν transmissive optical mask. In the embodiment, the glass is a VUV phase shift optical mask .Glass optical masks are preferentially resistant to oxygen deficiency centers caused by lasers. Preferentially glass does not contain metal-to-metal Si-Si bond and 165nm absorption center and the internal transmittance is at least 85% at 165nm / cm. The invention includes a method for printing a VUV pattern. The method for printing a pattern includes providing a light source of radiation below 164 nm as a VUV photon, and providing a silicon oxyfluoride glass having a weight ratio of 0H to less than 5 ppm, C1 At a weight ratio of 5ppm, a fluorine content of less than 0.5% by weight, and a transmission measured at I57nm and 165nm of at least 75% / 5mm. The method includes transmitting VUV photons through a silicon oxyfluoride glass, using Li photons to form a pattern, and A pattern is projected onto a radiation-sensitive sensitive printing medium to form a printed pattern. In a preferred embodiment, a νυν light lithographic printing pattern printing method includes providing a VUV light lithographic printing photon radiation source, providing 0H less than 1 ppm of silicon oxide. Fluoride glass, transmission of VUV light lithography photons pass through silicon oxyfluoride light lithography glass, use νυν photons to form light lithography printing patterns, and project light lithography printing patterns onto VUV radiation-sensitive light lithography printing media to form printing Photolithographic lithographic printing. The method of VUV printing includes preferentially reducing the VUV cut-off wavelength of silicon oxyfluoride glass by providing a precursor for Si-glass formation and doping with F to provide 50% transmission VUV of oxyfluoride glass The cut-off wavelength is below 160nm and the glass is exposed to 21.5MJ / cm2-pulse at 157nm laser 41.5 million pulses (please read the back Please fill in this page if you want to pay attention to matters),-The size of the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 554260 A7 B7 5. Description of the invention (yV) The absorption at 165nm is less than 0.4 (absorption unit / 5 delete 8% / 6 The invention provides high purity and dryness (&lt; lppm of 0Η) by using silicon oxyfluoride glass, which provides very good transmittance in VUV. The glass of the present invention provides a transmission of 157nm, such as 79.8% / 6 35mm (and 90% / cm internal transmittance). Siloxyfluoride glass is preferentially used as a 157nm light lithographic printing module, especially for optical mask substrates, films, thin lenses, and glass. For these light lithographic applications, it is not only important that the glass exhibit high initial transmission, but the transmission must not be reduced when exposed to F2 excimer lasers. After exposure to 0 · lmj / cm2—pulse &amp; excimer laser 60 million pulses, the glass produced &lt; 1% transmission loss at 157.6 nm. Our preference is to use silicon fluoride glass components with improved resistance to absorption caused by F2 lasers. * We have found that although the addition of fluorine to dry silica glass will improve the transmission of vacuum UV rays, especially near the edges of UV rays (for example at radon), high concentrations of fluorine in glass are not beneficial for laser damage resistance. In particular, we find that the absorption in glass caused by F2 excimer laser radiation is proportional to the fluorine content of the glass. When the fluorine content increases, the resulting 157.6 nm absorption will increase. 5% 重量 比。 Printed by the Ministry of Economic Affairs of the Central Bureau of Consumers of the Ministry of Economic Affairs on consumer cooperation. Priority: Silicon fluoride glass has a fluorine content of less than 0.5% by weight. Our &lt; 0.5% by weight dry silicon oxyfluoride glass exhibits good laser durability and is suitable for a variety of applications including exposure to F2 excimer laser radiation. A 1% component that achieves high initial transmission and results in low absorption is in the range of 0.4%. In the present invention, the OH content of the VUV-transmissive silicon oxyfluoride glass is less than 5 ppm by weight, and the fluorine content is at least 0.1% by weight. Preferentially, the glass is printed by Si, 0 and this paper size (CNS) 8 4 specifications (21QX297 mm) 36554260 A7 B7 V. Description of the invention nf) The Ministry of Economic Affairs Central Government Standards Bureau employee consumer cooperatives F In the composition, the internal transmission of the glass in the wavelength range of 157nm to 175nm is at least 85% / cm. Preferentially, the 165nm absorption of glass after exposure to 2niJ / cm2-pulsed 157nm laser 41.5 million pulses is less than 0.4 (absorption unit / 5 deleted). Example: In order to achieve the required transmission at 157nm (85 ° /./ 6 · 35 delete (measurement), 0H, C1, metal (such as Fe, Zr) concentration, essential defects (such as peroxy link), and visible to the naked eye Defects (eg, bubbles) must be minimized. Directly—The glass drying combustion process uses CO fuel as the preferred method to produce dry F-doped Si02 glass for this and other applications. Dry dopant-containing Si. 2 The glass is manufactured directly in a single-step process. Due to the presence of H, the oxane burner is effectively limited to the production of quite moist dust, which requires additional drying and consolidation to produce dry glass. Step-based processing. Note that although thorium burners may directly produce dry glass, this burner is preferentially used in the following cases: (i) a source of Si-free Si (such as SiCh) and (ii) Exclude η external sources (such as air leakage). In addition to being able to manufacture dry, doped SiO 2 glass, the present invention has the following advantages (i) increased glass purity (co and most metals A drum base should be formed), and (ii) CF4 consumption / reduction is reduced (compared with jr-doped consolidation &amp; 02 dust, the dry combustion process requires very little 邙 4 to achieve the same F number). Although development As a 157nm optical mask plate, the present invention provides the use of dry combustion to produce dry dopant-containing glass for use as an optical element. The glass is preferably manufactured directly in a single step. The dopant can be F, Or one or more required oxides (including τ 丨 〇2, with 仏, β2〇3, I appropriate scale, one paper, one standard, one standard)

4 A 5 N (Please read the notes on the back before filling this page) -i- 口 554260 Α7 37 --- Β7 V. Description of the invention (j) P205) to produce the required characteristics. (Please read the precautions on the back and save this page)

The present invention focuses on the manufacture of dry-doped! 7 silica glass, which has a transmittance of -85% / 6.35mm at 157nm to use as an optical cover for light lithography. In order to achieve the required transmission, the following concentrations must be minimal: (i) impurities (mainly water (OH), Cl, and metals (eg Fe, Zr)), (ii) essential defects (mainly oxygen defect centers and Peroxidation), and (iii) visual defects (mainly air bubbles). Perform experimental and theoretical work to determine processing conditions that affect impurity and defect concentrations. The main focus is on thermodynamic prediction and 0H, C1, metal debris, and essential defects. Table 丨 lists the experimental results of most suitable drying and combustion operations. Moisture: Water damage (0H in glass) reduces VUV transmission. For example, HPFS (Corning No. 7890), produced by the flame hydrolysis process (where CH4 is the fuel and 0: 1 ^ is the source of Shi Xi), does not transmit light below the wavelength of 170nm. Ministry of Economic Affairs Printed by the Consumer Standards Cooperative of the Central Bureau of Standards due to the high moisture content (usually 800 ppm of OH), as shown in Figure 15. The minimization of moisture in the glass is the driving force that mainly forms the dry combustion treatment process, where H is eliminated by replacing the input fuel CH4 with CO and OMCTS with SiCh in a single burner high temperature furnace (Figure 12). Once the nitrogen curtain is configured to help exclude humid air from leaving the high-temperature furnace, dry glass (1 ppm 0H) is produced, with and without dopant F, but co is always used as fuel and SiCl4 is used as Si source β. It significantly reduces the C content of glass. When 0MCTS does not contain C1, the Si source is replaced by SiCh in the operation DC6, which is too humid (about 420ppm OH) and does not transmit in VUV (Figure 15 shows that due to moisture The resulting paper size applies to China National Standards (CNS) A4 specifications (210 × 297 mm) 38554260 Μ B7 Duo printed by the staff of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Production description (Flying η) absorption edge). Chlorine: Similar to water, C1 will reduce VUV transmission, and there is a strong correlation between the absorption at the ultraviolet edge and the residual gas in Shi Xishi glass, and because of the relatively high absorption cross section at 157 nm (6 · about For 0 ({40% of the case), the application contains only a very small amount of α. Very unfortunately, surprisingly, the use of S1CI4, hydrogen-free, but si-containing si sources results in high quantities ^ in the glass produced by the dry combustion process. Dry combustion process * SiCh produces glass containing about 0.08% by weight Cl (DG0. Minimizing □ in glass becomes the main focus in developing dry combustion process. Evaluate the following ways to minimize C1 in glass : (I) Use a source that does not contain ^ (eliminate Q in glass by eliminating C1 in the system), (ii) increase 〇2 (minimize C1 in glass by increasing 〇2 in the combustion gas) (Iii) Increase CF (minimize C1 in the glass by increasing F addition). Theory and / or experiments show that all four methods will result in glasses with lower C1 content; however, only (ii) and (丨 丨 丨) can be implemented without adding η to the system. Common use increases 〇2 and CF4 to achieve about 0.02% weight ratio C1 (75% reduction from the initial condition DG). Si (NCO) 4 can be used as a benefit The main idea is that (0 completely excludes C1 from the system, and clearly the best way to eliminate / minimize C1 in the glass. The main idea is (i) adding 0 to the combustion gas will prevent Cl_ from being added Response, the following reaction shifts to the left: · 5 Cl2 (gas) + Si〇2 (glass) - &gt; SiOuCK C1-doped glass) + 〇2 (gas) (Read Notes on the back and then fill the page) it, τ

This paper size applies Chinese National Standard (CNS) A4 specification (210X &lt; 297 mm 554260 A7 — ___B7) V. Description of the invention (cut) Figure 16 shows the expected effect of increasing 〇2. The main idea is that ρ is in SiO2 Occupying the site and increasing the f concentration will reduce the C1 concentration in the glass. The theory and experiments have shown that this method is useful. Increasing the O2 and reducing the SiCl4 flow will lead to the use of Sich as the &amp; source (DC5, About 0.02% by weight ci) Drying and burning to produce glass is the lowest. 0 ,, metal chips: Since metal chips are known to reduce the transmission of ultraviolet rays, the object of the present invention is to produce high-purity glass containing Minimal metal debris. However, the C1 concentration in these glasses is quite high, and the transmission loss due to the presence of metal debris is a second-order effect. As shown in Table 1, the Fe and Zr concentrations (main metal debris) are determined by The use of purified CO and a significant reduction in DC10 by replacing Al2O3 with zirconium refractory materials (Fe is reduced by about 2 times and Zr is reduced by about 10 times). Axl (T2 ° cm2 σχ1 (Γ2 ° αη2) 1% of 157nm / cm Transmission 1% / cm of 193nm / cm Transmission (157nm) (193nm) Loss (ppm weight ratio) Loss (ppm weight Ratio) * C1 6.3 2 (C1) Jan 16.8 0 · 4 (0H) A1 33.6 0. 56 (Al2〇3) Na 57.9 1.6 0 · 2 (Na2〇) 7 (Na2〇) Zr 748 6.4 0 · 06 (Zr 〇2) 7 (Zr〇2) Fe 879 658 0.03 (FeO) 0 · 04 (FeO) This absorption cross-section study at 157nm and 193nm shows that the standard of China National Standards (CNS) A4 is used for the paper size of alumina. (21 × x 297 mm) 554260 A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 5. Description of the Invention (Vi) Advantages of 157nm glass made of refractory materials. Essential defects: Oxidation and reduction effects are known to reduce 157nm. Transmission, so the goal of the present invention is to produce neutral (ie, no oxidation or reduction) glass with the smallest two defects. It is known that Si metal-metal bond defects are the main reason for the i65nm absorption band, and the absorption is significantly reduced 157ηπι transmission. Essential defects naturally occur in the preparation of silicic acid under high temperature equilibrium conditions In salt glass, temperature and chemical calculations are known to affect concentration. We show that the absorption band at 165nm can reduce the F concentration in the glass to a minimum / elimination. As shown in the figure, the i65nm absorption band appears in all cases except DC7 (no F), DC8 (low M.28% weight ratio), and DC10 (low F, 0.22% weight ratio). It is well known The skilled person can make various changes and modifications to the present invention, but does not depart from the spirit and scope of the present invention. Therefore, the scope of the following patent applications and their equivalents will cover the various changes and changes of the present invention. (Please read the (Please fill in this page again)

Claims (1)

41554260 A8 B8 C8 D8 Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs, patent application scope1. A type of optical masking substrate for vacuum ultraviolet (VUV) transmission glass below 193nm, which is used as a lithographic printing plate with a wavelength of 157nm. The glass optical mask substrate is composed of dry, high-purity, directly deposited vitrified silicon oxyfluoride glass. Its 0H content is less than 20ppm by weight, C1 content is less than 0.1% by weight, and fluorine content is in the range of 0.01 to 7% by weight. Inside. 01 · 2% 重量 比 范围 内。 2. According to the scope of the patent application of the glass optics _ mask substrate, wherein the fluorine content of the dried high-purity direct deposition vitrified silicon oxyfluoride glass is in the range of 0.01 to 2% by weight. 3. The glass optical mask substrate according to item 1 of the scope of the patent application, wherein the fluorine content of the dried high-purity direct-deposited vitrified silicon oxyfluoride glass is in the range of 0.01 to 0.5% by weight. 4. The glass optical mask substrate according to item 1 of the scope of the patent application, wherein the fluorine content of the dried high-purity directly deposited vitrified siloxane glass is in the range of 0.1 to 0.4% by weight. 5. The glass optical masking matrix according to item 1 of the scope of patent application, wherein the C1 content of the dried high-purity direct-deposited vitrified oxyfluoride glass is $ 0.08 by weight. 6. The glass optical mask substrate according to item 1 of the scope of the patent application, wherein the C1 content of the dried high-purity direct-deposited vitrified oxyfluoride glass is $ 0.06% by weight. 7. The glass optical mask according to item 1 of the scope of patent application, wherein the C1 content of the dried high-purity direct-deposited vitrified silicon oxyfluoride glass is $ 0.04 ° / 0 weight ratio. 8. The glass optical mask substrate according to item 1 of the scope of patent application, which is dry (please read the precautions on the back before filling this page) ， 1T wood paper size applies Chinese National Standard (CNS) A4 specification (2 〖OX297mm） 42554260 A8 B8 C8 D8 VI. Application scope of patents High-purity direct deposition vitrified silicon oxide printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 03% 重量 比。 C1 content of fluoride glass SO. 03% by weight. 9. The glass optical mask substrate according to item 1 of the scope of the patent application, wherein the Cl content of the dry, high-purity, directly deposited vitrified siloxyfluoride glass is 0.02 / 0 by weight. 10. The glass optical mask substrate according to item 1 of the scope of the patent application, wherein the content of dried high-purity directly deposited vitrified siloxane glass is less than 5 ppm. 11. The glass optical mask substrate according to item 1 of the scope of the patent application, wherein the content of 2C1 of the dried high-purity direct-deposited vitrified silica deoxidized glass is lower than that. 12. The glass optical masking matrix according to item 1 of the scope of patent application, wherein the dried high-purity directly deposited vitrified siloxane glass is free of gas. 13. The glass optical mask substrate according to item 丨 of the scope of application for patents, wherein the content of tritium in the dried high-purity directly deposited vitrified siloxane glass is less than 10 ppm. 14. The glass optical masking substrate according to item 丨 of the scope of application for patents, wherein the content of the dried high-purity directly deposited vitrified silicon oxyfluoride glass is lower than ^^. 15. The glass optical masking matrix according to item 丨 of the patent application scope, wherein the dry and high-purity directly deposited vitrified silicon oxyfluoride glass has a low content of M1x1101 molecules / cm3. 16. According to the scope of patent application! The glass optical mask substrate of the item, in which the dry and high-purity directly deposited glass sintered glass material Fe content is not more than 0.00004% by weight. ^ Based on the glass optical mask substrate according to item 1 of the scope of the patent application, in which the purity of the dried product is visualized and the chemical ratio of the chemical fluoride is 0.00004% by weight. Reference paper size is applicable to Chinese countries --- (Please read the notes on the back before filling this page) Order --- 554260 8 8 8 8 ABCD 43 (Please read the notes on the back before filling this page} is. Ministry of Economic Affairs Printed by the Central Bureau of Standardization and Shellfish Consumer Cooperatives 6. Scope of patent application 18 · According to the first scope of the patent application, the glass optical mask substrate, in which the purity of the dried osmium oxyfluoride glass directly deposited vitrified glass contains multiple. 2 molecules 19. The glass optical masking matrix according to item 1 of the scope of patent application, wherein the dried and directly deposited vitrified stone oxofluoride glass contains a plurality of 02 molecules, of which the degree of agriculture is at least 1 〇15molecules / cc. 20. A method for manufacturing a matrix of vacuum mask (VUV) transmission glass optical mask below I93nm, the method comprises: providing a carbon monoxide burner; providing a high-temperature direct deposition furnace containing heating; providing carbon monoxide supply Source and oxygen supply source to the carbon monoxide burner to form a carbon monoxide reaction flame; provide a direct glass deposition surface close to the flame; supply Si-glass The glass precursor product raw material and the F glass precursor product raw material to the carbon monoxide burner, in which the Si-glass precursor product raw material and the p-glass precursor product raw material react in a flame to form siloxane fluoride glass dust, which is projected on the glass deposition surface, and the dust is simultaneously The glassy stone oxyfluoride glass object is directly deposited on the ground, and the glassy silicon oxyfluoride glass object is directly deposited as an optical mask hair embryo. 21 · The method according to item 20 of the scope of patent application, which is supplied The raw material of the Si-glass precursor product includes the supply of the raw material of the non-gas Si-glass precursor product, wherein the directly deposited vitrified silicon oxyfluoride glass is a chlorine-free silicon oxyfluoride glass and the glass object is formed as a chlorine-free Silicon oxyfluoride glass optical mask.} Paper size: China National Standard (CNS) A4 (210X297), &quot; ---------- 554260 8 8 8 8 ABCD 44 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 22. The method according to item 20 of the scope of patent application, wherein the supply of the raw materials of the Si-glass precursor products includes the supply of the raw materials of the Si-glass precursor products that do not contain hydrogen, in which the glassy Shixi Oxide Glass is dry_crushed oxyfluoride glass, its 0H concentration weight ratio &lt; 10ppm OH and glass objects are formed as dry Shisi oxyfluoride glass optical mask, its 0H concentration weight ratio &lt; 10ppm 0H . 23. According to the method of claim 20 of the scope of patent application, the supply of the raw material of the Si-glass precursor product in the dream includes the supply of the raw material of the Si-glass precursor product that does not contain hydrogen, wherein the directly deposited vitrified stone oxyfluoride glass is dried stone oxidized glass. For chemical glass, the 0H concentration-weight ratio <i0ppm OH and the glass object are formed as a dry C1-free silicon oxyfluoride glass optical mask, and the 0H concentration-weight ratio <i0ppm OH. 24. The method according to item 23 of the scope of patent application, wherein the raw material of the Si-glass precursor product without C1 and hydrogen is silicon tetracyanate. 25. The method according to item 23 of the scope of patent application, wherein the supply of the raw material of the F-glass precursor product includes the supply of a predetermined raw material gas stream of the F-glass precursor product, wherein the directly deposited vitrified silicon oxyfluoride glass has an F concentration weight ratio of 0.01 To 7% by weight. 26. The method according to item 25 of the scope of patent application, wherein the directly deposited vitrified silicon oxyfluoride glass has an F concentration weight ratio in the range of 0.01 to 2% by weight F. 27. The method according to item 25 of the scope of patent application, wherein the directly deposited vitrified siloxyfluoride glass has a concentration-to-weight ratio in the range of 0.01 to 0.5% by weight F. 28. The method according to item 23 of the scope of patent application, wherein providing an oxygen supply source includes providing a predetermined supply airflow of 02, in which the directly-deposited vitrified silicon private paper scale is suitable for financial and economic standards (CNS) 8-4 inspection ( 210 &gt; &lt; 297 public directors) f Please read the notes on the back before filling in this page) Order 45554260 A8 Β8 C8 D8 Patent Application Scope The Ministry of Economic Affairs Central Standardization Bureau employee consumer cooperative printed oxyfluoride glass contains 〇2. 29. The method according to item 20 of the scope of patent application, wherein providing a high-temperature furnace containing direct deposition containing heating is provided by providing a high-temperature furnace containing direct deposition containing heating! | Vegetable Alumina refractory. 30. The method according to item 20 of the scope of patent application, wherein a carbon monoxide supply source is provided to a carbon monoxide burner to form a monoxide combustion reaction flame comprising providing a high-purity carbon monoxide supply gas and passing a high-purity carbon monoxide supply gas through a CO purification filter, which Located upstream of the carbon monoxide burner. 31. The method according to item 20 of the scope of application for a patent, wherein the method produces a vuv-transmissive glass optical mask substrate as the light lithography of the 157nm wavelength optical mask blank. 32 · —A method for manufacturing a vacuum ultraviolet (VUV) transmission glass below 193 nm, the glass transmitting at a wavelength of 157 nm, the method comprising: providing a carbon monoxide burner; providing a carbon monoxide supply source and an oxygen supply source to the carbon monoxide burner to form Carbon monoxide combustion reaction flame; Provide direct glass deposition surface close to the flame; Supply Si-glass precursor product raw material and F glass precursor product raw material to carbon monoxide burner, where Si-glass precursor product raw material and F-glass precursor product raw material are in flame The intermediate reaction becomes the stone oxyfluoride glass dust projected on the glass deposition surface, and the dust is directly deposited and vitrified into the silicon oxyfluoride glass object at the same time. 33. The method according to item 32 of the scope of patent application, wherein the supply of raw materials for si-glass precursor products includes the supply of raw materials for Si-glass precursor products that do not contain chlorine. The size of the paper is applicable to China National Standard (CNS) A4 specifications (210X297 mm). ) (Please read the precautions on the back before filling this page) _ 46554260 A8 B8 C8 D8 VI. Application for Patent Scope Printed by the Consumers' Cooperative of the Central Economic and Technical Bureau of the Ministry of Economic Affairs. Chlorite stone minus glass. 34. The method according to item 32 of the scope of patent application, wherein the raw material for supplying the glass precursor product comprises supplying the raw material for the Si_glass precursor product containing no hydrogen, wherein the Wei fluoride glass directly deposited by Bong Cong is the surface fluoride glass, and its 0H concentration Heavy Q [j. 35. The method according to item 32 of the scope of patent application, wherein the raw material for supplying the glass precursor product comprises supplying the raw material for the Si-glass precursor product containing no hydrogen, wherein the second oxyfluoride glass directly deposited on the glass peach is the surface fluoride glass, which The 0H concentration was ittXiOppm. 36. The method according to item 35 of the scope of the patent application, wherein the raw material of the Si-glass precursor product containing no rhenium gas is silicon tetracyanate. 37. The method according to item 35 of the scope of patent application, wherein the supply of the raw material of the F-glass precursor product includes the supply of a predetermined raw material gas stream of the F-glass precursor product, wherein the directly deposited vitrified silicon oxyfluoride glass has an F concentration weight ratio of 0.01 To 7% by weight. 38. The method according to item 37 of the scope of patent application, wherein the directly deposited vitrified silicon oxyfluoride glass has an F concentration-weight ratio in the range of 0.00% to 2% by weight F. 39. The method according to item 37 of the scope of patent application, wherein the directly deposited vitrified siloxyfluoride glass has an F concentration weight ratio in the range of 0.001 to 0.5% weight ratio F. ^ The method according to item 35 of the patent application, wherein providing an oxygen supply source includes providing a predetermined 002 supply airflow, wherein the size of the directly deposited vitrified private paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ( (Please read the notes on the back before filling out this page) Order 554260 夂 、 Application scope ABCD Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. Shixi oxyfluoride glass contains a concentration of at least 10i50 molecules / cc. 41. A method for manufacturing a uniform glass optical element, the method comprising: providing a carbon monoxide burner; providing a carbon monoxide supply source and an oxygen supply source to the carbon monoxide burner to form a carbon monoxide combustion reaction flame; providing a direct glass deposition surface close to the flame ; Supply Si-glass precursor product raw material and dopant glass precursor product raw material to carbon monoxide burner, where Si-glass precursor product raw material and dopant R-glass precursor product raw material react in flame to become dry doped silica dust projection On the glass deposition surface, and the dust is simultaneously directly deposited and vitrified into a silicon oxyfluoride glass object, forming a directly deposited glassy glass object as a uniform glass optical element. 42. The method according to item 41 of the scope of patent application, wherein the supply of the si-glass precursor product raw material includes the supply of chlorine-free Si-glass precursor product raw material, wherein the directly deposited vitrified glass is a chlorine-free glass object and the glass object is formed It is a homogeneous glass optical element without chlorine. 43. The method according to item 41 of the scope of patent application, wherein the supply of the raw material of the Si-glass precursor product includes the supply of the raw material of the Si-glass precursor product without hydrogen, wherein the directly deposited vitrified silicon oxyfluoride glass is a dry silicon oxyfluoride The glass has a 0H concentration-to-weight ratio <10 ppm 0H and the glass object is formed as a dry uniform glass optical element, and the 0H concentration-to-weight ratio <10 ppm 0H. 44. The method according to item 41 of the scope of patent application, wherein the raw material for supplying the Si-broken precursor product comprises supplying the raw material for the Si-glass precursor product containing no chlorine and no hydrogen, wherein the directly deposited vitrified silicon oxyfluoride glass is dried Oxygen per second (please read the notes on the back of the results before writing this page), the paper size of the table is applicable to China National Standards (CNS) A4 specifications (210 × 297 mm) 48554260 A8 B8 C8 D8 The standard bureau's consumer cooperative prints compound glass with an 0H concentration-to-weight ratio <10 ppm and the glass object is formed as a dry uniform glass optical element with an 0H concentration-to-weight ratio <ippm ppmH. 45. The method according to item 44 of the scope of patent application, wherein the raw material of the Si-glass precursor product without Cl and hydrogen is tetracyanite. 46. The method according to item 41 of the scope of patent application, wherein the method produces a uniform glass lithographic printing element. 47. A method of manufacturing a homogeneous glass optical element, the method comprising: providing a carbon monoxide burner; providing a carbon monoxide supply source and an oxygen supply source to the carbon monoxide burner to form a carbon monoxide combustion reaction flame; providing a direct glass deposition surface Close to the flame; supply Si-glass precursor product raw materials to the carbon monoxide burner, where the Si-glass precursor product raw materials react in the flame to become dry silica glass dust projected on the glass deposition surface, and the dust is simultaneously directly deposited and vitrified into Silicon oxyfluoride glass objects, forming directly deposited glassy glass objects are uniform glass optical elements. 48. The method according to item 47 of the scope of patent application, wherein the supply of the raw material of the si-glass precursor product includes the supply of the raw material of the non-gas Si_ glass precursor product, wherein the directly deposited vitrified glass is a glass object containing no chlorine and a glass object Formed as a gas-free uniform glass optical element. 49. The method according to item 47 of the scope of patent application, wherein the supply of the si-glass precursor product raw material includes the supply of hydrogen-free Si-glass precursor product raw material, wherein the directly deposited vitrified glass is dry glass, and its 0H concentration weight ratio &lt; 10ppm OH and glass objects are formed into dry and uniform glass optical elements, whose OH concentration (please read the precautions on the back before filling out this page) Yan wood paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) 554260 Sixth, the scope of patent application 8 8 8 8 ABCD 49 weight ratio &lt; 10ppm 0H. 50. According to the method of application scope 苐 47, in which the supply of Si-wall-breaking precursor product raw materials includes the supply of chlorine-free and hydrogen- Raw materials of glass precursor products, where directly deposited vitrified glass is dry glass, its 0% concentration weight ratio &lt; 10ppm and glass objects are formed as dry uniform glass optical elements, its 0H concentration weight ratio &lt; 10ppm 0H. (Please read the back first (Please note that this page is to be completed before filling out this page.) The Central Consumers Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives, prints moderate-sized sheets of paper. Cm 7 7 2