JP2013177299A - METHOD OF MANUFACTURING SILICA GLASS CONTAINING TiO2 - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a TiO-SiOglass suitable as a substrate having a small surface roughness.SOLUTION: A method is for manufacturing silica glass containing TiOand having a concentration of TiOof 1-12 mass%, a variation, Δn, of the refractive index of 2×10in a 30 mm×30 mm range in at least one plane and includes a process of flame-hydrolyzing raw materials for formation of glass to obtain fine particles of glass.

Description

The present invention relates to a method for producing a silica glass containing TiO ₂ (hereinafter referred to as TiO ₂ —SiO ₂ glass), and in particular, TiO ₂ — used as an optical material for an exposure apparatus used in EUV lithography. The present invention relates to a method for producing SiO ₂ glass. The EUV (Extreme Ultra Violet) light referred to in the present invention refers to light in the wavelength band of the soft X-ray region or the vacuum ultraviolet region, specifically, light having a wavelength of about 0.2 to 100 nm. .

Conventionally, in an optical lithography technique, an exposure apparatus for manufacturing an integrated circuit by transferring a fine circuit pattern onto a wafer has been widely used. As integrated circuits become highly integrated and highly functional, miniaturization of integrated circuits advances, and the exposure apparatus is required to form a high-resolution circuit pattern on the wafer surface with a deep focal depth. Short wavelength is being promoted. As an exposure light source, an ArF excimer laser (wavelength 193 nm) is going to be used, proceeding from conventional g-line (wavelength 436 nm), i-line (wavelength 365 nm) or KrF excimer laser (wavelength 248 nm). Further, in order to cope with a next-generation integrated circuit in which the line width of the circuit pattern is 100 nm or less, it is considered promising to use an F ₂ laser (wavelength 157 nm) as an exposure light source, which also has a line width of 70 nm. It is considered that only generations can be covered.

  In such a flow, a lithography technique that typically uses light having a wavelength of 13 nm among EUV light (extreme ultraviolet light) as an exposure light source is considered to be applicable over a plurality of generations after 50 nm, and is attracting attention. . The image forming principle of EUV lithography (hereinafter abbreviated as “EUVL”) is the same as that of conventional photolithography in that a mask pattern is transferred using a projection optical system. However, since there is no material that transmits light in the energy region of EUV light, the refractive optical system cannot be used, and all the optical systems are reflective optical systems.

  An exposure apparatus optical material used for EUVL is a photomask, a mirror, or the like. (1) Base material (2) Reflective multilayer film formed on the base material (3) Absorber layer formed on the reflective multilayer film It basically consists of As for the multilayer film, it is considered that Mo / Si alternately forms layers, and Ta and Cr are studied as film forming materials for the absorber layer. As the substrate, a material having a low thermal expansion coefficient is required so that distortion does not occur even under EUV light irradiation, and glass having a low thermal expansion coefficient has been studied.

TiO ₂ —SiO ₂ glass is known as an ultra-low thermal expansion material having a smaller coefficient of thermal expansion (CTE) than quartz glass, and the coefficient of thermal expansion can be controlled by the TiO ₂ content in the glass. In addition, a zero expansion glass having a thermal expansion coefficient close to 0 is obtained. Therefore, TiO ₂ —SiO ₂ glass has a possibility as a material used for an EUVL exposure apparatus optical material.

In a conventional method for producing TiO ₂ —SiO ₂ glass, first, a silica precursor and a titania precursor are converted into vapor forms and mixed. The mixture in vapor form is introduced into a burner and thermally decomposed to become TiO ₂ —SiO ₂ glass particles. The TiO ₂ —SiO ₂ glass particles are deposited in a refractory container and melted there at the same time as the deposition to become TiO ₂ —SiO ₂ glass.

However, in the TiO ₂ —SiO ₂ glass produced by this method, periodic fluctuations in the TiO ₂ / SiO ₂ composition ratio occurred, which appeared as stripe striae at a pitch of 100 to 200 μm.

Note that a method for obtaining a mask substrate after forming a TiO ₂ —SiO ₂ porous glass body into a glass body is disclosed in US Patent Application (for example, see Patent Document 1).

US Patent Application Publication No. 2002/157421

The striped striae of TiO ₂ —SiO ₂ glass are considered to occur because the refractive index difference increases due to the periodic fluctuation of the TiO ₂ / SiO ₂ composition ratio in the glass material. When used as an exposure apparatus optical material for EUVL, TiO ₂ —SiO ₂ glass must be polished so that the glass surface has ultra-high smoothness. However, in the TiO ₂ —SiO ₂ glass, the portions with different TiO ₂ / SiO ₂ composition ratios differ in mechanical and chemical properties of the glass depending on the composition ratio, so the polishing rate is not constant, and the polished glass It is difficult to finish so that the surface has ultra-high smoothness. In addition, when TiO ₂ —SiO ₂ glass with stripe striae is polished at a pitch of 100 to 200 μm, “undulation” having a pitch similar to the striae pitch is generated on the glass surface, and ultrahigh smoothness is achieved. It is very difficult to get.

In recent years, it has been said that it is necessary to reduce MSFR (Mid-Spatial Frequency Roughness) having a waviness pitch of 10 μm to 1 mm as a very important required characteristic of an EUVL exposure apparatus optical material. When conventional TiO ₂ —SiO ₂ glass is polished, it has undulations with a pitch of 100 to 200 μm for the above reasons, and therefore it is very difficult to reduce MSFR.

Accordingly, as an exposure tool for EUVL optical material, the glass surface after polishing the finish to have a super-high _smoothness, and reduce the TiO ₂ / SiO ₂ compositional ratio variation width of TiO 2 -SiO ₂ glass, the glass surface It is considered to be effective to make the polishing rate constant and to reduce the MSFR by making the striae pitch 10 μm or less.

Further, even in the case of a TiO ₂ —SiO ₂ glass substrate having the same level of smoothness (Roughness (rms)), it is possible to polish the convex portion more efficiently in a shorter time when the striae pitch is smaller than when it is larger. Therefore, it becomes easy to polish so as to have ultra-high smoothness.

Further, making the TiO ₂ / SiO ₂ composition ratio uniform in the TiO ₂ —SiO ₂ glass is important in terms of reducing variation in the thermal expansion coefficient within the glass. Therefore, it is preferable to reduce the TiO ₂ / SiO ₂ composition ratio fluctuation width in the entire region in addition to reducing the TiO ₂ / SiO ₂ composition ratio fluctuation width in the minute region as called striae.

Aspect 1 of the present invention is a TiO ₂ having a TiO ₂ concentration of 1 to 12% by mass and a refractive index fluctuation range (Δn) of 2 × 10 ⁻⁴ or less in a range of 30 mm × 30 mm in at least one plane. _A method for producing silica glass containing ₂ ,
Provided is a method for producing silica glass containing TiO ₂ , which comprises a step of subjecting a glass forming raw material to flame hydrolysis to obtain glass fine particles.

Aspect 2 is characterized in that, in aspect 1, after glass fine particles obtained by subjecting a glass forming raw material to flame hydrolysis are deposited on a substrate to obtain a porous glass body, the porous glass body is made into a transparent glass. And a method for producing silica glass containing TiO ₂ .

Aspect 3 is characterized in that, in aspect 2, glass fine particles obtained by subjecting a glass forming raw material to flame hydrolysis are deposited on a substrate rotating about an axis at a rotational speed of 25 revolutions / minute or more. _A method for producing silica glass containing ₂ is provided.

Aspect 4 provides a method for producing silica glass containing TiO ₂ , in which the porous glass body is heated to a transparent vitrification temperature of 1400 to 1700 ° C. to be transparent vitrified in aspect 2 or 3.

Aspect 5 is the production of silica glass containing TiO ₂ in any one of Aspects 2 to 4, wherein the transparent glass body obtained by transparent vitrification is heated to a temperature equal to or higher than the softening point and formed into a desired shape. Method.

Aspect 6 is a transparent glass body obtained by transparent vitrification in any one of Aspects 2-5, and after holding at a temperature of 600-1200 ° C. for 5 hours or more, at a temperature lowering rate of 10 ° C./hr or less Provided is a method for producing silica glass containing TiO ₂ , which performs an annealing process for lowering the temperature to 500 ° C. or lower.

According to the present invention, TiO ₂ —SiO ₂ glass having a small surface roughness can be obtained. Therefore, it is extremely suitable as a material for members constituting an optical system used in EUVL.

TiO ₂ —SiO ₂ glass is known to have a coefficient of thermal expansion that varies depending on the concentration of TiO ₂ contained, and the thermal expansion coefficient of TiO ₂ —SiO ₂ glass containing about 7% by mass of TiO ₂ is near room temperature. Nearly zero.

The TiO ₂ —SiO ₂ glass of the present invention is preferably a silica glass containing 1 to 12% by mass of TiO ₂ . This is because if the content of TiO ₂ is less than 1% by mass, zero expansion may not occur, and if it exceeds 12% by mass, the thermal expansion coefficient may be negative. The content of TiO ₂ is more preferably 5 to 9% by mass.

  The striae pitch is preferably 10 μm or less, and more preferably 7 μm or less. If the striae pitch exceeds 10 μm, it may be difficult to reduce the MSFR of the polished surface.

In this specification, “variation in TiO ₂ concentration” is defined as the difference between the maximum value and the minimum value of the TiO ₂ concentration in one plane. In the range of 30 mm × 30 mm, the variation in the TiO ₂ concentration in the minute region is 0.06% by mass or less, preferably 0.04% by mass or less. If the variation in the TiO ₂ concentration exceeds 0.06% by mass, it may be difficult to obtain sufficient smoothness when polished.

As a method for producing TiO ₂ —SiO ₂ glass with a variation in TiO ₂ concentration within 0.06% by mass, a Si precursor and a Ti precursor, which are glass forming raw materials, are subjected to flame hydrolysis or thermal decomposition by a soot method. TiO ₂ —SiO ₂ glass fine particles (soot) obtained in this manner are deposited and grown on a substrate to obtain a porous TiO ₂ —SiO ₂ glass body. There is a production method for obtaining a transparent TiO ₂ —SiO ₂ glass body by heating the obtained porous TiO ₂ —SiO ₂ glass body to a transparent vitrification temperature. As the substrate, a quartz glass seed rod or the like is used.

The inventor conducted a detailed study on the relationship between the rotational speed of the seed rod in the stage of obtaining the porous TiO ₂ —SiO ₂ glass body and the striae pitch of the transparent TiO ₂ —SiO ₂ glass body. It has been found that as the number of rotations increases, the variation in TiO ₂ concentration in the transparent TiO ₂ —SiO ₂ glass body decreases, and the striae pitch decreases.

Specifically, the rotation speed of the seed bar when forming the porous TiO ₂ —SiO ₂ glass body is preferably 25 rpm or more, more preferably 50 rpm or more, and 100 rpm. It is particularly preferable to carry out at a rate of at least / min. The TiO ₂ concentration variation of the transparent TiO ₂ —SiO ₂ glass body is 0.06% by mass or less, and the striae pitch is 10 μm or less.

  In this case, stabilizing the supply of the glass forming raw material is more preferable in reducing striae strength and pitch.

The striae seen in TiO ₂ —SiO ₂ glass is due to fluctuations in the TiO ₂ / SiO ₂ composition ratio. Further, when the TiO ₂ / SiO ₂ composition ratio varies, the absolute refractive index of the glass varies. For example, the refractive index of a part with a high TiO ₂ concentration is higher than that of a part with a low TiO ₂ concentration.

The inventors have, by measuring the absolute refractive index of several TiO ₂ -SiO ₂ glass having different TiO ₂ concentrations containing, in a range TiO ₂ concentration is less 12 mass%, of the TiO ₂ concentration and the refractive index I found that the following relationship holds:

By using Equation _1, it is possible to calculate the variation (ΔTiO ₂ ) of the TiO ₂ concentration from the fluctuation range (Δn) of the refractive index of the TiO ₂ —SiO ₂ glass. Specifically, when the fluctuation range (Δn) of the refractive index is 200 ppm, the TiO ₂ concentration variation (ΔTiO ₂ ) is 0.06% by mass.

  With respect to the striae pitch, the variation width Δn of the refractive index of the surface to be measured is measured, and the striae pitch is obtained by measuring the distance from the high refractive index part to the low part using a microscope.

The measurement method of the refractive index fluctuation range Δn is different depending on the refractive index fluctuation range Δn _{1 in} a minute region and the refractive index fluctuation range Δn _{2 in} a wide range as shown below.

The fluctuation range Δn ₁ of the refractive index in a minute region as called striae is measured as follows. A cube of about 40 mm × 40 mm × 40 mm, for example, is cut out from the transparent TiO ₂ —SiO ₂ glass body, sliced at a thickness of 1 mm from each surface of the cube, and a plate-like TiO ₂ —SiO ₂ glass block of 30 mm × 30 mm × 1 mm is obtained. obtain. With a Fizeau interferometer, helium neon laser light is vertically applied to the 30 mm x 30 mm surface of this glass block, and the refractive index distribution in the surface is expanded to a magnification at which, for example, 2 mm x 2 mm can be observed sufficiently. The refractive index fluctuation range Δn is measured.

When a 30 mm × 30 mm range is directly measured, the size of one pixel in the interferometer CCD may not be sufficiently small compared to the width of the striae, and the striae may not be detected. Therefore, the entire range of 30 mm × 30 mm is divided into a plurality of minute regions of about 2 mm × 2 mm, for example, and the refractive index variation width Δn ₁ in each minute region is measured, and the maximum value is in the range of 30 mm × 30 mm. It is assumed that the refractive index fluctuation range Δn.

For example, when a CCD having an effective number of pixels of 512 × 480 is used, one pixel corresponds to about 4 μm square in a 2 mm × 2 mm visual field. Therefore, striae with a pitch of 10 μm or more are sufficiently detected, but there is a possibility that they cannot be detected for striae below that. Therefore, when measuring striae of 10 μm or less, it is desirable that at least one pixel is about 1 to 2 μm square or less. In the embodiment of the present specification, an area of 2 mm × 2 mm is measured using a CCD having an effective pixel number of 900 × 900, and the refractive index fluctuation range Δn ₁ is set so that one pixel corresponds to about 2 μm square. It was measured.

On the other hand, the fluctuation range Δn ₂ of the refractive index in a wide range such as an area irradiated with EUV light used for exposure is measured as follows. A transparent TiO ₂ —SiO ₂ glass body molded into 160 mm × 160 mm × 150 mm is sliced into blocks having a thickness of 7 mm to obtain 160 mm × 160 mm × 7 mm TiO ₂ —SiO ₂ glass blocks. Using a Fizeau interferometer, helium neon laser light is vertically applied to the 160 mm × 160 mm surface of the glass block, the refractive index distribution in the 100 mm × 100 mm plane is examined, and the variation width Δn ₂ of the refractive index is measured.

In the embodiment of the present specification, an area of 100 mm × 100 mm is measured using a CCD having 320 × 240 effective pixels, and the refractive index fluctuation range Δn ₂ so that one pixel corresponds to about 300 to 400 μm square. Was measured. In this case, a difference in refractive index in a region of about 1 mm can be measured.

The above-described measuring method of the refractive index fluctuation range Δn ₁ in the minute region cannot measure the absolute value of the refractive index, but only obtains the refractive index difference. Therefore, the EUV light used for exposure is irradiated. If the entire region is measured and divided into minute regions without direct comparison, the refractive indexes at both ends of the member cannot be compared, and the fluctuation range of the refractive index may be estimated small. Therefore, the fluctuation range of the refractive index is measured over the entire area irradiated with the EUV light used for exposure, and the value is set as the fluctuation width Δn of the refractive index in the plane perpendicular to the incident direction.

In the same plane, when the refractive index fluctuation width of the micro area is measured by the above-described method, if the refractive index fluctuation width Δn ₁ in the micro area is larger than the refractive index fluctuation width Δn ₂ in the entire area, the micro area The refractive index fluctuation width Δn _{1 at} is defined as the refractive index fluctuation width Δn in the plane perpendicular to the incident direction.

When TiO ₂ —SiO ₂ glass is used as an exposure apparatus member for EUVL, it is possible to make the TiO ₂ / SiO ₂ composition ratio uniform over a wide range such as a region irradiated with EUV light used for exposure. It is extremely important in reducing variation in the thermal expansion coefficient. Since the fluctuation of the TiO ₂ / SiO ₂ composition ratio affects the refractive index of the glass, the fluctuation width of the refractive index can be used as an index of TiO ₂ —SiO ₂ composition uniformity.

Δn in a plane perpendicular to the light incident direction is preferably within 2 × 10 ⁻⁴ , more preferably within 1.5 × 10 ⁻⁴ , and particularly preferably within 1.0 × 10 ⁻⁴ .

Further, making the TiO ₂ / SiO ₂ composition ratio uniform in a minute region such as 30 mm × 30 mm is extremely important in terms of making the glass surface ultra-highly smooth by polishing. Δn in the range of 30 mm × 30 mm is preferably within 2 × 10 ⁻⁴ , more preferably within 1.5 × 10 ⁻⁴ , particularly preferably within 1.0 × 10 ^{−4, and} within 0.5 × 10 ^−4. Most preferred. When Δn exceeds the above range, the polishing rate is not constant depending on the location, and it is difficult to finish the polished glass surface to have ultrahigh smoothness.

Striae pitch obtained by the present invention was cut 10μm following TiO ₂ -SiO ₂ glass, or TiO ₂ concentration variation of 0.06 mass% or less of TiO ₂ -SiO ₂ glass to a size of 160 mm × 160 mm × 7 mm Thereafter, when a 160 mm × 160 mm surface is polished, the value of MSFR (Mid-Spatial Frequency Roughness) having a waviness pitch within the range of 10 μm to 1 mm, which is an index representing smoothness on the polished surface, is set to 1. It becomes 5 nm or less and is suitable as an exposure apparatus optical material for EUVL.

Also, the striae pitch is 10μm or more TiO ₂ -SiO ₂ glass or TiO ₂ concentration variation 0.06 mass% or more TiO ₂ -SiO ₂ glass, making the MSFR the polished surface 1.5nm or less This is difficult and may be insufficient as an optical material for an EUVL exposure apparatus.

In the TiO ₂ —SiO ₂ glass with striae, the composition variation and Δn are usually the largest in the striae. Therefore, in such a case, if the variation width of the refractive index and the variation in the TiO ₂ concentration are reduced by reducing the striae within a range of 30 mm × 30 mm on at least one surface, In this case, the fluctuation range of the refractive index and the variation of the TiO ₂ concentration can be reduced in the plane.

By using the TiO ₂ —SiO ₂ glass of the present invention, EUV lithography is made of TiO ₂ —SiO ₂ glass and has a refractive index variation width Δn of 2 × 10 ⁻⁴ or less in a plane perpendicular to the light incident direction. It becomes easy to obtain the optical member for use.

Further, in the present invention, since the strength of the striae is reduced, a refractive index fluctuation range Δn exceeding 2 × 10 ⁻⁴ is generated on a plane made of TiO ₂ —SiO ₂ glass and perpendicular to the light incident direction. It is possible to easily obtain an optical member for EUV lithography that does not have a striae to cause.

Furthermore, the maximum by using the TiO ₂ -SiO ₂ glass of the present invention consists of TiO ₂ -SiO ₂ glass TiO ₂ concentration is not less than 1 wt%, in a plane perpendicular to the incident direction of light, TiO ₂ concentration An optical member for EUV lithography in which the difference between the value and the minimum value is 0.06% by mass or less can be easily obtained.

Similarly, the maximum value and the minimum value of the TiO ₂ concentration exceeding 0.06% by mass in a plane perpendicular to the incident direction of light is made of TiO ₂ —SiO ₂ glass having a TiO ₂ concentration of 1% by mass or more. It is possible to easily obtain an optical member for EUV lithography that does not have any striae that cause a difference from the above.

Furthermore, in a wide temperature range of 0 to 100 ° C., the TiO ₂ —SiO ₂ glass can be made into a zero expansion glass having a thermal expansion coefficient in the range of 0 ± 200 ppb / ° C. Further, when the fictive temperature of TiO ₂ —SiO ₂ glass is 1100 ° C. or lower, the temperature range where the thermal expansion coefficient is almost zero becomes wider, and the thermal expansion coefficient is 0 ± 200 ppb / in the range of −50 to 150 ° C. Within the range of ° C.

When manufacturing an optical member for EUVL, by making the striae parallel to the pattern drawing surface, the variation width of the refractive index and the variation in TiO ₂ concentration on the surface perpendicular to the light incident direction are reduced. It is also possible to reduce the MSFR.

  The coefficient of thermal expansion is measured in the range of −150 to + 200 ° C. using a laser interference type thermal dilatometer (Laser dilatometer LIX-1 manufactured by ULVAC Riko Co., Ltd.).

The variation of the thermal expansion coefficient is measured as follows. A 160 mm × 160 mm × 150 mm TiO ₂ —SiO ₂ glass block is cut into 20 mm × 20 mm × 10 mm TiO ₂ —SiO ₂ glass pieces. By measuring the thermal expansion coefficient of each small piece according to the above-described method, the variation in the thermal expansion coefficient of the 160 mm × 160 mm × 30 mm TiO ₂ —SiO ₂ glass block is obtained.

The EUV lithography optical member is required to have a small variation in thermal expansion coefficient. In the TiO ₂ —SiO ₂ glass of the present invention, the difference between the maximum value and the minimum value of the TiO ₂ concentration is 0.06% by mass or less, and the thermal expansion coefficient of the TiO ₂ —SiO ₂ glass of the present invention is determined by a calibration curve. When the variation is obtained, it becomes about ± 5 ppb / ° C. or less at room temperature. Therefore, the TiO ₂ —SiO ₂ glass of the present invention can achieve a variation in thermal expansion coefficient of, for example, ± 5 ppb / ° C. or less at room temperature, and is suitable for an optical member for EUV lithography.

In order to produce the TiO ₂ —SiO ₂ glass of the present invention, the following production method can be employed.

(A) Process A seed made of quartz glass that rotates TiO ₂ —SiO ₂ glass fine particles obtained by flame hydrolysis of a Si precursor and a Ti precursor, which are glass forming raw materials, around a shaft at a certain speed A rod (for example, a seed rod described in Japanese Patent Publication No. 63-24973) is used as a base material, and is deposited and grown on this base material to form a porous TiO ₂ —SiO ₂ glass body. The glass forming raw material is not particularly limited as long as it is a gasifiable raw material. Examples of the Si precursor include chlorides such as SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , and SiH ₃ Cl, SiF ₄ , SiHF ₃ , fluorides such as SiH ₂ F _2, SiBr _4, bromides such as SiHBr _3, halogenated silicon compounds such as iodide such as SiI _{4, R n Si (OR) 4-} n ( wherein R is 1 to 4 carbon atoms In addition, the Ti precursors include titanium halide compounds such as TiCl ₄ and TiBr _4, and R _n Ti (OR) _{4 -n.} (Wherein R is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 0 to 3). In addition, Si and Ti compounds such as silicon titanium double alkoxide can be used as the Si precursor and the Ti precursor. The substrate is not limited to a rod shape, and a plate-like substrate may be used.

(B) step the porous TiO ₂ -SiO ₂ glass body was heated to a transparent vitrification temperature for transparent vitrification to obtain a transparent TiO ₂ -SiO ₂ glass body. In this specification, transparent vitrification means a state in which the porous glass body is densified until no voids can be confirmed with an optical microscope, and the transparent vitrification temperature means porous until no voids can be confirmed with an optical microscope. The temperature at which the glass body can be densified. The transparent vitrification temperature is usually 1400 to 1700 ° C, and particularly preferably 1450 to 1650 ° C. The atmosphere is preferably an atmosphere of 100% inert gas such as helium or an atmosphere mainly composed of an inert gas such as helium. The pressure may be reduced pressure or normal pressure. In particular, helium gas can be used at normal pressure. Moreover, in the case of pressure reduction, 13000 Pa or less is preferable. In the present specification, “Pa” means not a gauge pressure but an absolute pressure.

(C) Step The transparent TiO ₂ —SiO ₂ glass body obtained in the step (b) is heated to a temperature equal to or higher than the softening point and formed into a desired shape to obtain a formed TiO ₂ —SiO ₂ glass body. The molding process temperature is preferably 1500 to 1800 ° C. Below 1500 ° C., the viscosity of the TiO ₂ —SiO ₂ glass is high, so that substantially no self-weight deformation occurs, and the growth of cristobalite, which is the crystalline phase of SiO ₂ , or the growth of rutile or anatase, which is the crystalline phase of TiO _2. Occurs, so-called devitrification occurs. Above 1800 ° C., SiO ₂ sublimation cannot be ignored.

The formed TiO ₂ -SiO ₂ glass body obtained in step (d) (c) step, after 5 hours or more at a temperature of 600 to 1200 ° C., until 500 ° C. or less in the following cooling rate 10 ° C. / hr An annealing process for lowering the temperature is performed to control the calcination temperature of the TiO ₂ —SiO ₂ glass. After cooling down to 500 ° C. or lower, it can be allowed to cool. The atmosphere in this case is preferably an atmosphere of 100% inert gas such as helium, argon or nitrogen, an atmosphere containing such an inert gas as a main component, or an air atmosphere, and the pressure is preferably reduced or normal pressure.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. The glass compositions of the following examples are all TiO ₂ = 7.4% by mass and SiO ₂ = 92.6% by mass.

[Example 1]
TiCl ₄ and SiCl ₄ , which are glass forming raw materials for TiO ₂ —SiO ₂ glass, are each gasified, mixed, and then heated and hydrolyzed (flame hydrolysis) in an oxyhydrogen flame to obtain TiO ₂ —SiO _{2 2} Glass fine particles are deposited and grown on a seed rod made of quartz glass rotating at a speed of 25 rotations / minute to form a porous TiO ₂ —SiO ₂ glass body having a diameter of about 80 mm and a length of about 100 mm (process) (A)).

The obtained porous TiO ₂ —SiO ₂ glass body was heated to 1550 ° C. in a He 100% atmosphere, and kept at this temperature for 10 hours to form a transparent glass to obtain a transparent TiO ₂ —SiO ₂ glass body (step ( b)).

The obtained transparent TiO ₂ —SiO ₂ glass body is heated to 1650 ° C. above the softening point to be deformed by its own weight and formed into a block shape of 50 mm × 50 mm × 10 mm (step (c)), and then obtained. The block was placed in an electric furnace, held at 950 ° C. for 100 hours, then cooled to 500 ° C. at 5 ° C./hr, then allowed to cool to room temperature (step (d)), TiO ₂ —SiO ₂ glass Got.

[Example 2]
In the step (a) in Example 1, TiO ₂ —SiO ₂ glass fine particles were deposited and grown on a quartz glass seed rod rotating at a speed of 100 revolutions / minute. A TiO ₂ —SiO ₂ glass was obtained in the same manner as in Example 1 except for this.

[Example 3]
In step (a) in Example 1, TiO ₂ —SiO ₂ glass fine particles were deposited and grown on a seed rod made of quartz glass rotating at a speed of 250 rotations / minute. A TiO ₂ —SiO ₂ glass was obtained in the same manner as in Example 1 except for this.

[Example 4]
In the step (a) in Example 1, TiO ₂ —SiO ₂ glass fine particles were deposited and grown on a quartz glass seed rod rotating at a speed of 5 rotations / minute. A TiO ₂ —SiO ₂ glass was obtained in the same manner as in Example 1 except for this.

[Example 5]
TiCl ₄ and SiCl ₄ , which are glass forming raw materials for TiO ₂ —SiO ₂ glass, are each gasified, mixed, and then heated and hydrolyzed (flame hydrolysis) in an oxyhydrogen flame to obtain TiO ₂ —SiO _{2 2} Glass fine particles were deposited and grown on a seed rod made of quartz glass rotating at a speed of 25 rotations / minute to form a porous TiO ₂ —SiO ₂ glass body having a diameter of 30 cm and a length of 80 cm (step (a )). The obtained porous TiO ₂ —SiO ₂ glass body was heated to 1430 ° C. in a He 100% atmosphere and kept at this temperature for 2 hours to obtain a transparent glass body (step (b)). Further, in an air atmosphere, the sample was heated to 1680 ° C. above the softening point to be deformed by its own weight, and formed into a 160 mm × 160 mm × 150 mm block shape (step (c)). Thereafter, a 160 mm × 160 mm × 7 mm block obtained by slicing into a 7 mm thick block was placed in an electric furnace, held at 950 ° C. for 100 hours, and then cooled to 500 ° C. at 5 ° C./hr, Thereafter, the mixture was allowed to cool to room temperature (step (d)) to obtain TiO ₂ —SiO ₂ glass.

  About the evaluation method, it carried out according to the above-mentioned measuring method, respectively. The evaluation results of Examples 1 to 5 are summarized in Table 1. Here, Example 1, Example 2, Example 3, and Example 5 are examples, and Example 4 is a comparative example.

In Examples 1 and 2, the striae pitch is 10 μm or less, the fluctuation range of the refractive index in a minute region is 200 ppm or less, and the TiO ₂ concentration variation is 0.06% by mass or less in at least one plane. is there. The fluctuation range of the refractive index and the variation in TiO ₂ concentration are caused by striae, and the strength of the striae is reduced in Examples 1 and 2. Therefore, MSFR can be easily reduced by polishing. It becomes possible to have ultra-high smoothness.

Further, it can be seen that in these samples, the fluctuation range of the refractive index is 200 ppm or less and the variation in TiO ₂ concentration is 0.06% by mass or less in at least one plane orthogonal thereto.

In Example 3, the presence of striae was confirmed by visual observation, and it was confirmed by microscopic measurement that the striae pitch was 1 μm. However, since the change in the refractive index could not be detected by the above-described method, It can be considered that the fluctuation range of the rate is 50 ppm or less and the TiO ₂ concentration variation is 0.06 mass% or less. Therefore, Example 3 can more easily reduce the MSFR and can have ultra-high smoothness.

In Example 4, the striae pitch is 10 μm or more, the fluctuation range of the refractive index in the minute region is 200 ppm or more, and the TiO ₂ concentration variation is 0.06% by mass or more. The striae is very strong, and it has been difficult to reduce MSFR by polishing.

In Example 5, an optical member for EUV lithography in which the refractive index fluctuation range in a wide range is 200 ppm or less and the refractive index fluctuation range Δn is 2 × 10 ⁻⁴ or less in a plane perpendicular to the light incident direction. Can be obtained.

Claims (6)

A silica glass containing TiO ₂ having a TiO ₂ concentration of 1 to 12% by mass and a refractive index fluctuation range (Δn) of 2 × 10 ⁻⁴ or less within a range of 30 mm × 30 mm in at least one plane. A manufacturing method comprising:
A method for producing silica glass containing TiO ₂ comprising a step of flame-hydrolyzing a glass-forming raw material to obtain glass fine particles. 2. The porous glass body is formed into a transparent glass body after depositing glass fine particles obtained by hydrolyzing a glass-forming raw material on a substrate to obtain a porous glass body, according to claim 1. A method for producing silica glass containing TiO ₂ . _3. The TiO _{2 according} to claim 2, wherein glass fine particles obtained by flame hydrolysis of a glass forming raw material are deposited on a substrate that rotates about an axis at a rotation speed of 25 rotations / minute or more. The manufacturing method of the silica glass to contain. The method for producing silica glass containing TiO _{2 according} to claim 2 or 3, wherein the porous glass body is heated to a transparent vitrification temperature of 1400 to 1700 ° C to form a transparent glass. The transparent glass body obtained by the vitrification is formed into a desired shape by heating to a temperature above the softening point, method for producing a silica glass containing TiO ₂ according to any crab claims 2-4 . The transparent glass body obtained by transparent vitrification is subjected to an annealing treatment in which the temperature is lowered to 500 ° C. or lower at a temperature lowering rate of 10 ° C./hr or lower after holding at a temperature of 600 to 1200 ° C. for 5 hours or more. method for producing a silica glass containing TiO ₂ according to any one 2-5.