JP2001114530A - Silica glass optical material for excimer laser and excimer lamp - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silica glass optical material that has high initial transmission to the excimer laser or excimer lamp of 155-195 nm wavelengths and a small fluctuation range in the refractive index (Δn) and shows excellent durability under irradiation therewith. SOLUTION: This invention relates to a silica glass optical material for the rays or beams from an Eximer laser and Excimer lamp and characteristically has the following physical and chemical properties: this silica glass optical glass is ultra-high pure, has an OH group contento f 1-100 wt.ppm, a H2 content of 5×1016-5×1019 molecules/cm3, and a F content of 10-10,000 wt.ppm, substantially no content of halogens other than F and a fluctuation range in the refractive index (Δn) of 3×10-6-3×10-7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silica glass optical material, and more particularly to a silica glass optical material for a light beam using an excimer laser having a wavelength of 155 to 195 nm and an excimer lamp, and a method for producing the same.

[0002]

2. Description of the Related Art Silica glass optical materials as described above are:
For lenses, prisms, windows, reflectors, photomasks, tubes, etc. incorporated in excimer laser devices with wavelengths of 155 to 195 nm, irradiation devices for light cleaning using excimer lamps as light sources, exposure devices for integrated circuit production (optical lithography devices), etc. Used. Conventionally, ultraviolet light from a mercury lamp such as a g-line or an i-line has been used as a light source of an optical lithography apparatus that draws an integrated electronic circuit pattern on a silicon wafer. For lines, the resolution is limited, and an excimer laser with a shorter wavelength has attracted attention, and an optical lithography apparatus using a KrF excimer laser (248 nm) has been developed and is in the stage of implementation.

However, it is expected that the degree of integration of semiconductor devices will further increase in the near future, with a line width of 0.1 μm.
A light source capable of drawing the following fine patterns is required.
The light source is mainly an ArF excimer laser (193 nm),
ArCl excimer laser (175 nm), F ₂ excimer laser (157
nm) and other high-power vacuum ultraviolet rays with wavelengths of 155 to 195 nm have been considered, and their development has begun. However, since the high-output vacuum ultraviolet light has a higher output than the ultraviolet light used in the conventional photolithography apparatus, the irradiated optical material has a decrease in transmittance, an increase in refractive index, generation of distortion, and generation of fluorescence. In some cases, damage such as generation of microcracks occurs rapidly, and the optical material cannot be used.

At present, as a cleaning method for a semiconductor device, an ArF excimer laser (193 nm) and an F ₂ excimer laser (15
7nm), Xe ₂ excimer lamp (172nm), ArCl excimer lamp (175nm), etc., a dry cleaning method using high-power vacuum ultraviolet rays with a wavelength of 155 to 195nm is being developed. Large optical materials are required. However, when the size of the optical material is increased, the damage caused by the high-power vacuum ultraviolet rays is further increased, and the optical material cannot be used as an optical material. Under such circumstances, development of an optical material that causes less damage to an excimer laser or an excimer lamp, which is the high-output vacuum ultraviolet light, has been eagerly desired.

[0005]

As an optical material that satisfies the above demands, there is known an optical material disclosed in Japanese Patent Application Laid-Open No. 6-227827. That is, the optical material disclosed in the above publication is a transparent quartz glass obtained by heating a porous quartz glass body formed by depositing and growing quartz glass fine particles obtained by flame hydrolysis of a glass forming raw material on a substrate. In quartz glass, OH in the transparent quartz glass
It has a content of 10 ppm or less, contains halogen of 400 ppm or more, and contains hydrogen.

As an optical material meeting the above demand, the present inventor has disclosed in Japanese Patent Publication No. 6-48734 a laser having a hydrogen gas concentration of at least 5 × 10 ¹⁶ (molecules / cm ³ ) and an OH group concentration of 100 wt ppm or more. The optical member for light may be replaced with a gas having a hydrogen gas concentration of at least 5 in Japanese Patent Publication No. 6-27013.
× 10 ¹⁶ (molecules / cm ³ ) or more, OH group concentration of 50 wtppm or more, refractive index fluctuation distribution based on fictive temperature cancels refractive index fluctuation distribution based on OH group concentration distribution, and has substantially no refractive index fluctuation distribution A synthetic silica glass optical body was proposed.

However, when the optical material is a large optical element having a diameter of, for example, 200 mm × thickness of 30 mm, non-uniform distribution of hydrogen molecules, OH group concentration, and halogen is likely to occur. In, the transmittance and the refractive index change, and the optical characteristics deteriorate. Also, when the OH group concentration is as high as 100 wtppm or more in the silica glass optical material, the initial transmittance is reduced in the vacuum ultraviolet region, and the durability is reduced. That is, the optical materials proposed in the above publication have a problem that the initial transmittance in the 155 to 195 nm region is low and the durability is insufficient. Also,
In the optical material disclosed in JP-A-6-227827, halogen is used in general.
In such a case, it is easy to generate defects by ultraviolet irradiation,
There has been a major problem of deteriorating the performance of the optical material such as transmittance in a target spectral region.

The inventors of the present invention have conducted intensive studies and have found that the concentration of impurities contained in the optical material is higher than that of the optical material described in the above-mentioned publication (particularly, the concentrations of Mo and W are lower), and the OH The base concentration and the hydrogen molecule concentration are in a specific range, and after making their concentration distribution uniform, F is particularly selected from the halogens, and the F concentration is smaller than that of the above-described conventional technology. By doing so, it has been found that a synthetic silica glass optical material having a high transmittance, a small refractive index variation width Δn, and excellent durability against long-time irradiation with an excimer laser or an excimer lamp can be obtained. Also, by limiting the OH group concentration and the hydrogen molecule concentration in the synthetic silica glass optical material to a range narrower than the above range, the initial transmittance is particularly high even for an excimer laser having a wavelength of 155 to 195 nm, and the durability is also high. They have also found that they can be kept high, and have completed the present invention.

That is, the present invention provides a silica glass having a high initial transmittance, a small refractive index fluctuation width Δn, and excellent durability under long-time irradiation with respect to excimer lasers and excimer lamps having wavelengths of 155 to 195 nm. An object is to provide an optical material.

[0010]

Means for Solving the Problems The above object is achieved by the present invention according to any one of the following (1) to (10). (1) A silica glass optical material for light from an excimer laser and an excimer lamp with a wavelength 155～195Nm, an ultra high purity, 1～100Wtppm an OH group, a H ₂ 5 × 10 ¹⁶ ~5
× 10 ¹⁹ molecules / cm ³ , and F containing 10 to 10,000 wtppm,
It contains substantially no halogen other than F, the content of Mo and W is 0.1 wtppb or less, and the refractive index variation Δn is 3
A silica glass optical material characterized by having a size of × 10 ^{−6 to} 3 × 10 ⁻⁷ . (2) The silica glass optical material according to (1), wherein the OH group concentration variation ΔOH is within 30 wtppm and the F concentration variation ΔF is within 50 wtppm. (3) The silica glass optical material according to the above (1) or (2), wherein the H ₂ concentration fluctuation width ΔH ₂ is within 3 × 10 ¹⁷ molecules / cm 3. (4) 12 to 100 ppm by weight of OH group and 3 × 10 ¹⁷ to 1 × 10 ^{19 of} H ₂
The silica glass optical material according to any one of the above (1) to (3), which contains molecules / cm ³ . (5) The silica glass optical material according to any one of the above (1) to (4), containing 10 to 380 wtppm of F. (6) As impurities, Li, Na and K are each 5 wtppb or less, Ca and Mg are each 1 wtppb or less, Cr, Fe and Ni are each.
The silica glass optical material according to any one of the above (1) to (5), which has an ultra-high purity of 0.1 wtppb or less. (7) The above (1) to (6), wherein the concentration of oxygen-deficient defects producing a 7.6 eV absorption band is 1 × 10 ¹⁷ defects / cm ³ or less.
The silica glass optical material according to any of the above. (8) The silica glass optical material according to any one of (1) to (7), wherein the Cl content is 10 wtppm or less. (9) The silica glass optical material according to any one of (1) to (8), which is used for an optical element having an optical path length of a light beam from an excimer laser or an excimer lamp of 30 mm or more. (10) an OH group 1～100Wtppm, the ^{_{H 2 5 × 10 16 ~5 ×}} 10
^{When 19} molecules / cm ³ and 50 to 10,000 wt ppm of F are contained, and the amount of OH groups is a and the amount of F is b, the total amount of a and b is
The silica glass optical material according to any one of the above (1) to (9), wherein the silica glass optical material is at least 100 wtppm and b / a satisfies 1 to 1000.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention provides ultra-high purity,
Further improvement of initial transmittance, excimer laser resistance, excimer lamp resistance, and use of excimer laser and excimer lamp by combining six physical properties of fluorine F content, dissolved hydrogen gas, Mo and W concentrations, and refractive index fluctuation width Δn The improvement of the processing accuracy was achieved.

The reason why the combination of the six physical properties is necessary is as follows. The ultra-high purity refers to a material whose purity is higher than the optical material described in the above publication and whose impurity metal content is in the following range, and in the vacuum ultraviolet region by reducing the impurity metal concentration in silica glass. It is possible to improve transmittance and reduce energy absorption at the time of ultraviolet irradiation. Li, Na, and K are each 5 wtppb or less, and Ca and Mg are each 1 wtpp.
b or less, Cr, Fe and Ni are each 0.1 wtppb or less, and Mo and W are each 0.1 wtppb or less. Li, Na, K, Ca, Mg
Is contained as an impurity in various heat-resistant ceramics, and easily becomes a contaminant element when producing silica glass.
Fe, Ni, Mo, W are compositions of plant structural materials, especially Mo and W
Is used as a heat-resistant metal element and tends to be a contaminant element.

The OH group is a terminal portion of the glass network structure, and the structure is relaxed by containing an appropriate amount thereof, and the Si—O—Si
To a stable value. However, when the OH group is contained at a high concentration, it causes a decrease in transmittance in a vacuum ultraviolet region. Therefore, the OH group content is 1 to 100 wtppm, especially the irradiation energy density per unit area is high and the conditions are severe.
For excimer lasers of 155 to 195 nm, 12 to 100 wtppm is good.

F is the terminal of the glass network structure similarly to the OH group. Further, unlike other halogens, even if F is contained at a high concentration, it does not cause a decrease in transmittance in a vacuum ultraviolet region.
However, glass containing no OH group and containing only F at a high concentration is decomposed by heat treatment, and generates a 7.6 eV (about 165 nm) absorption band due to generation of F ₂ gas and generation of oxygen deficiency type. Therefore, it is important to simultaneously contain OH groups and F to suppress the thermal decomposition of glass and the generation of oxygen-deficient defects. From this viewpoint, when the amount of OH groups is a and the amount of F is b, the total amount of a and b is preferably 100 wtppm or more, and b / a preferably satisfies 1 to 1000. The value of b / a is particularly preferably from 10 to 100. In this case, the OH group is 1 to 100 wtppm, especially 12 to 100 wtpp.
It is preferable that m and F are contained at 50 to 10,000 wtppm, particularly 50 to 380 wtppm. The optical material of the present invention does not substantially contain any halogen other than F. In particular, Cl is irradiated with an excimer laser or an excimer lamp to irradiate a glass with a vacuum ultraviolet region (wavelength region of an excimer laser). Content of 10 wtpp
m or less.

Dissolved hydrogen gas, that is, hydrogen molecule H2 in the optical material, is irradiated with ultraviolet rays at the E 'center (called an e-prime center and showing an absorption band of about 215 nm) or the NBOH center (called a non-bridging, oxygen, or hole center). Action to suppress the generation of absorption bands at 260 nm and about 630 nm (S. Yamagata, Mineralogical Journal)
al, Vol 15, No. 8, 1991, pp. 333-342), and its content is 5 × 10 ^{16 to} 5 × 10 ¹⁹ molecules / cm ³ , especially 3 × 10
It is preferably ¹⁷ to 1 × 10 ¹⁹ molecules / cm ³ .

The optical material is the same as that of the above-mentioned JP-A-6-227827.
Thickness (optical path length through which laser passes) like a photomask like the optical material disclosed in Japanese Patent Publication No.
This is not a problem when used for products of the order of magnitude, but for products with a thickness of 30 mm or more, that is, optical elements such as lenses, if the refractive index fluctuation width Δn is large, the processing accuracy using it will decrease. , .DELTA.n should be as small as possible. However, as described above, it has been newly found that, when F is doped at a high concentration, Δn increases due to the concentration distribution. Therefore, in the optical material of the present invention, the refractive index fluctuation width Δn is set to a small value of 3 × 10 ^{−6 to} 3 × 10 ⁻⁷ by performing a process described in a manufacturing method described later. As described above, a small value of Δn means that a change in the density of the material is small, and as a result, the hydrogen gas can be dissolved at a uniform concentration. When Δn is 3 × 10 ⁻⁶ or less, it is necessary that at least one direction be stria-free. It is presumed that the concentration distribution of OH groups and F is not uniform in glass having a large Δn value, and the saturated hydrogen gas concentration is affected by the concentrations of these OH groups and F. From the above, in the optical material of the present invention, the OH group concentration fluctuation width ΔOH is within 30 wtppm,
Further, the F concentration fluctuation width ΔF is preferably within 50 wtppm, and the H ₂ concentration fluctuation width ΔH ₂ is preferably 3 × 10 ¹⁷ molecules / cm ³ or less. Further, the concentration of oxygen-deficient defects generating the 7.6 eV absorption band is preferably 1 × 10 ¹⁷ defects / cm ³ or less.

Next, the silica glass of the present invention described above
A method for manufacturing an optical material will be described. The silica of the present invention
The first step in manufacturing glass optical materials is to use silicon compounds as raw materials.
OH group-containing white soot by flame hydrolysis
To achieve. As the silicon compound, the silicon compound is used.
The SiCl_Four, SiHCl_Three, SiH_TwoCl_Two, SiCH_ThreeCl_Three, Si (CH_Three)_TwoCl
_Two, SiF_Four, SiHF_Three, SiH_TwoF_TwoEtc. can be used. fire
As the flame, use oxyhydrogen flame, propane oxygen flame, etc.
be able to. Next, the obtained OH group-containing white soot body was obtained.
Dope by heat treatment with fluorine-containing gas atmosphere
I do. As a fluorine-containing gas, SiF_Four, CHF_Three,SCIENCE FICTION₆Etc.
It is preferable to use a gas containing 0.1 to 100 vol.%.
No. Processing temperature is 400 ~ 1200 ℃, pressure is 0.1 ~ 10 kgf / cm^Two
It is preferable that Thereafter, the white soot body is transparent.
A vitrification treatment is performed. This treatment is 0.1 kgf / cm^TwoLess than
Under reduced pressure atmosphere (which may contain He)
It is preferably performed at 1600 ° C. Then, by flame heating
Molding into a rod-shaped transparent silica glass body and band melting rotation stirring
Work. These processes are based on USP2904713, USP3128166,
Perform using the method shown in USP3128169, USP3483613, etc.
be able to. In particular, as described above, the refractive index fluctuation width
Δn is 3 × 10^-6~ 3 × 10^-7Perform enough to be. this
After that, an annealing process for removing distortion is performed. The atmosphere of this process
As the atmosphere, the atmosphere is generally used.
Other inert gas atmospheres can also be used. Processing temperature
Is maintained at 900-1200 ° C for about 1-100 hours, then 500
Cool slowly at 1 ° C / hr to 10 ° C / hr below ℃. last
In addition, hydrogen gas doping treatment by heat treatment in an atmosphere containing hydrogen molecules
Work. As atmosphere containing hydrogen molecules, 100% hydrogen gas
Or use a mixed gas atmosphere of a rare gas such as Ar and hydrogen gas
Preferably. Processing temperature is 100 ~ 800 ℃, especially 200 ~ 4
Preferably it is 00 ° C. Higher than the above temperature range
When this occurs, the reducing action becomes stronger, generating oxygen-deficient defects,
At low temperatures, diffusion of hydrogen gas into transparent glass
It takes too long. Processing pressure is about 1 kgf / c of atmospheric pressure
m^TwoFrom 100 kgf / cm^TwoIs preferred. 1 kgf with 100% hydrogen gas
/cm^TwoHydrogen gas saturation dissolved concentration of the transparent glass body at about 1 ×
Ten¹⁷~ 4 × 10 ¹⁷Molecule / cm^Three, 10 kgf / cm^Two, 100 kgf / cm
^TwoThen 1 × 10 each¹⁸ ~ 4 × 10¹⁸, 1 × 10 ¹⁹ ~ 4 × 10¹⁹Minute
Child / cm^ThreeIt is. The obtained material has its outer surface ground.
And a desired shape.

[0018]

EXAMPLES First, an OH group-containing white soot was synthesized from silicon tetrachloride SiCl ₄ by a oxyhydrogen flame hydrolysis method. Then, the obtained OH group-containing white soot was subjected to SiF ₄ 5
In a gas atmosphere containing 0%, fluorine doping treatment was performed by heat treatment under the conditions of 1 kg / cm ² (almost the same as atmospheric pressure) and 700 to 1200 ° C. At this time, the OH group and the F content of the silica glass optical material of each example and each comparative example were changed as shown in Tables 1 and 2 by variously changing the heat treatment temperature and the treatment time. Then, add each white soot body to 0.00
Under a vacuum (reduced pressure) atmosphere of 1 kgf / cm ² or less,
The mixture was heated at 1600 ° C. to form a transparent glass. Thereafter, the material was softened by propane gas flame heating to obtain a rod-shaped material having a substantially circular cross section. The length of this rod material is about 2m
And the diameter was about 60 mm. The rod-shaped material was held at both ends, twisted while locally heating to propane gas flame heating, and a band melting rotary stirring process was performed. Heat the material to 20
It was performed so as to be about 00 ° C. By this band melting rotation stirring process, each material was made into a unidirectional stria-free transparent glass body. Comparative Example 3 has the same composition and the like as the material of Example 3 except that the zone melting rotation stirring process was not performed. After this, the size of the transparent glass body is 300 m in diameter.
m, heat molded to a thickness of about 70 mm, then placed in an electric furnace, kept at 1150 ° C for 20 hours under air atmosphere, gradually cooled to 800 ° C at 4 ° C / hr, and then turned on the electric furnace power. The cut was naturally cooled and an annealing treatment was performed. Next, the transparent glass body was placed in an electric furnace with a stainless steel jacket and a tungsten mesh heater, and hydrogen gas doping was performed under an atmosphere of 100% hydrogen under a pressure of 400 ° C. At this time, the pressure is 1
By changing to kgf / cm ² or 10 kgf / cm ² , the dissolved hydrogen amount of each material was changed as shown in the table. Finally, the outer surface of the transparent glass body was ground,
A cylindrical sample having a thickness of 250 mm and a thickness of 50 mm was obtained. In Comparative Example 1, an OH group-containing white soot body was synthesized under the same conditions as in Example 1, and then SiF ₄ 100% gas atmosphere, 1 kgf / cm ² , 1100
A sample was obtained by performing a rotary stirring process and a hydrogen doping process under the same conditions as in Examples 1 and 2 except that a heat treatment was performed at a temperature of ° C. to make the F-doped OH group free.

In Comparative Example 2, a sample was obtained in the same manner as in Examples 3 and 4, except that the hydrogen gas doping treatment was not performed. The obtained glass was a glass in which hydrogen gas was not dissolved.

In Comparative Example 3, a sample was obtained under the same conditions as in Comparative Example 2, except that the rotary stirring treatment was not performed as described above.

In Comparative Example 4, a sample was obtained in the same manner as in Example 2 except that F doping was not performed, and instead, Cl doping was performed in a Cl ₂ 100% gas atmosphere. The obtained glass contained 900 wtppm of Cl.

In Comparative Example 5, a sample was obtained in the same manner as in Example except that the F doping treatment was not performed.
The obtained glass contained 300 wtppm of OH groups. For the samples of the above Examples and Comparative Examples, in addition to the above OH group concentration, the OH group concentration fluctuation width ΔOH, the F concentration and the F concentration fluctuation width Δ
F, Cl concentration, dissolved hydrogen concentration and fluctuation range of dissolved hydrogen concentration Δ
H2 _, oxygen deficiency type defect concentration, refractive index fluctuation width Δn, strain amount,
The transmittance before and after the irradiation of the light from the laser and the lamp, and the homogeneity after the irradiation of the laser and the lamp, that is, the Δn value and the amount of strain, were measured. The results are shown in each table. Table 5 shows the impurity contents of the glasses of the samples of Examples 1, 2, 4, 5 and Comparative Example 3. The methods for measuring the physical properties and the like in the above Examples and Comparative Examples are as follows.

(I) Method for measuring OH group concentration: D.M. DODD and D.B. FRASE R, Optical determination
 of OH in fused silica, Journal of Applied Physic
s, Vol. 37 (1966) P.3911. (ii) Measurement method of OH group concentration fluctuation width and average value
At 10mm intervals in the diameter direction when viewed from the rotational symmetry axis direction.
OH group concentration measurement at 25 points. Maximum value of OH group concentration at 25 points
And the minimum value, the OH group concentration fluctuation width (Δ
OH) is calculated from the arithmetic mean of the OH group concentrations at 25 points.
Measurement method to calculate. (iii) A method for measuring the concentration of hydrogen molecules. V.K. KHOTIMCHENKO, et al., Determining the conten
t of hydrogen dissolved in quartz glass using the
methods of Raman scattering and mass spectrometry,
 Journal of Applied Spectroscopy, Vo.46, No.6 (198
7) Measurement method described in the literature of pp632-635. (iv) A method for measuring the fluctuation range and average value of the hydrogen molecule concentration. For cylindrical silica glass optical materials with a diameter of 250 mm and a thickness of 50 mm
At 10mm intervals in the diameter direction when viewed from the rotational symmetry axis direction.
H of 25 points_TwoPerform a concentration measurement. 25 points of H_TwoMaximum and maximum density
From small values to H in the entire optical material_TwoConcentration fluctuation range (ΔH_Two)
And 25 points of H_TwoH from the arithmetic mean of the concentration_TwoCalculate average concentration
Measurement method. (v) Method for measuring chlorine concentration. AgNO after decomposition with HF aqueous solution_ThreeBy turbidimetry by addition
Measurement method. (vi) Method for measuring fluorine concentration. After decomposition with an aqueous NaOH solution, measurement is performed by the ion electrode method. (vii) A method for measuring the fluctuation range and average value of fluorine concentration. For cylindrical silica glass optical materials with a diameter of 250 mm and a thickness of 50 mm
At 10mm intervals in the diameter direction when viewed from the rotational symmetry axis direction.
And measure the F concentration at 25 points. 25 points maximum and minimum F density
From the value, the fluorine concentration fluctuation width (ΔF) in the entire optical material
Is calculated from the arithmetic mean of the 25 F concentrations.
Way. (viii) Impurity measurement in silica glass Na, K, Mg, Ca, Fe are measured by atomic absorption spectrometry, L
i, Cr, Ni, Mo, W are measured by plasma mass spectrometry (IC
P-MS method). (ix) Measurement method of refractive index fluctuation width (Δn) Measurement by optical interferometry using He-Ne laser (633nm) as light source
Law. However, the values in the area of 230 mm in diameter are shown. (x) Birefringence (strain) measurement method. A retardation measurement method using a polarizing plate strain meter. However,
The values in the area of 230 mm in diameter are shown. (xi) Measurement of 193 nm transmittance after ArF excimer laser irradiation
Law. Size 30 x 20 x 10 mm thick, sun mirror-polished on both sides
193nm wavelength, half-width 3nm, half-width pulse life
17 nsec, energy density 30 mJ / cm^Two / Shot, frequency 200
 1 × 10 irradiation shots at Hz⁶ Immediately after shot laser irradiation
A measuring method for measuring the transmittance at 193 nm after 3 minutes. (xii) Xe_Two172nm wavelength transmittance after excimer lamp irradiation
Measurement method. Size 30 x 20 x 10 mm thick, sun mirror-polished on both sides
172nm wavelength, 14nm half width, lamp energy
Density 10 mW / cm^TwoAt 172nm 3 minutes after irradiation for 14 days
A measuring method for measuring transmittance. (xiii) A method for measuring the concentration of oxygen-deficient defects. H. Hosono, et al., Experimental evidence for the S
i-Si bond model of the 7.6 eV band in SiO_Two glass,
Physical Review B, Vol. 44, No. 21, (1991) pp. 12043
Measurement method described in -12045.

[Table 1] [Example]

[Table 2] [Example]

[Table 3] [Comparative example]

[Table 4] [Comparative example]

[Table 5] [Impurity analysis value] As is clear from the table, Examples 2, 3, and 4 are particularly excellent in ArF excimer laser resistance, and these Examples 2, 3, and
No. 4 was also particularly excellent in Xe ₂ excimer lamp resistance. Further, the glasses of Examples 1 to 6 had a Δn value of 3 × 10 even after excimer light irradiation.
^-6 or less, and the strain amount was 1 nm / cm or less, indicating high homogeneity.

On the other hand, in Comparative Example 1, no OH group was contained and F was
Since the glass contained 1600 wtppm, the glass was decomposed by various heat treatments to generate F ₂ gas, to generate oxygen-deficient defects having a 7.6 eV absorption band, and the excimer light resistance was poor.

In Comparative Example 2, excimer light resistance was poor because the glass did not dissolve hydrogen gas.

[0026] In Comparative Example 3, because you did not zone melting rotary stirring treatment, DerutaOH, [Delta] F, the value of [Delta] H ₂ has become larger than the other, the value of Δn is also large numbers. Also, the excimer light resistance varied greatly depending on the part of the glass.

In Comparative Example 4, the light transmittance was sharply reduced by excimer light irradiation because it was F-free containing 900 wtppm of Cl.

Comparative Example 5 contained neither F nor Cl and contained an excess of OH groups of 300 wt ppm, so that the ultraviolet absorption edge shifted to longer wavelengths and the excimer light resistance was poor. .

In Comparative Example 6, since a + b was insufficient at 55 wtppm, the excimer light resistance was poor and the amount of distortion was large.

In Comparative Example 7, since the value of b / a was as small as 0.3, the Xe ₂ excimer lamp resistance was particularly poor. From the above, the effect of the silica glass optical material of the present invention is clear.

Continued on the front page F term (reference) 4G062 AA04 BB02 DA08 DB01 DC01 DD01 DE01 DF01 EA01 EA02 EA10 EB01 EB02 EC01 EC02 ED01 ED02 EE01 EE02 EF01 EG01 FA01 FA10 FB01 FC01 FD01 FE01 FF01 H01 G01 F01 G01 F01 G01 HH05 HH07 HH08 HH09 HH11 HH12 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ06 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM02 MM04 NN35

Claims (10)

[Claims] 1. A silica glass optical material for light from an excimer laser or an excimer lamp having a wavelength of 155 to 195 nm, which is ultra-high purity, has an OH group of 1 to 100 wt ppm, and H ₂ has a concentration of 5 × 10 5.
^{16 to} 5 × 10 ¹⁹ molecules / cm ³ , containing 10 to 10,000 wtppm of F, containing substantially no halogen other than F, Mo and W
Is 0.1 wtppb or less, and the refractive index fluctuation width Δ
A silica glass optical material, wherein n is 3 × 10 ^{−6 to} 3 × 10 ⁻⁷ . 2. The silica glass optical material according to claim 1, wherein the OH group concentration variation ΔOH is within 30 wtppm and the F concentration variation ΔF is within 50 wtppm. 3. The H ₂ concentration fluctuation width ΔH ₂ is 3 × 10 ¹⁷ molecules / cm 3
The silica glass optical material according to claim 1 or 2, wherein 4. 12~100wtppm an OH group, a H ₂ 3 × 10 ¹⁷ ~1
4. The silica glass optical material according to claim 1, which contains × 10 ¹⁹ molecules / cm ³ . 5. The silica glass optical material according to claim 1, which contains 10 to 380 wt ppm of F. 6. As impurities, Li, Na and K are each 5 wtp.
pb or less, Ca and Mg each less than 1 wtppb, Cr, Fe and Ni
6. The silica glass optical material according to claim 1, which is ultra-high purity containing 0.1 wtppb or less. 7. The concentration of oxygen-deficient defects producing a 7.6 eV absorption band is 1 × 10 ¹⁷ defects / cm ³ or less.
The silica glass optical material according to any of the above. 8. The method according to claim 1, wherein the Cl content is 10 wt ppm or less.
7. The silica glass optical material according to any one of items 7 to 7. 9. The silica glass optical material according to claim 1, which is used for an optical element having an optical path length of a light beam from an excimer laser or an excimer lamp of 30 mm or more. The 10. OH group 1～100Wtppm, the H ₂ 5 × 10 ¹⁶ ~
5 × 10 ¹⁹ molecules / cm ³ , and 50 to 10,000 wtppm of F,
10. The silica glass optical device according to claim 1, wherein when the amount of OH groups is a and the amount of F is b, the total amount of a and b is 100 wtppm or more, and b / a satisfies 1 to 1000. material.