WO2011105517A1 - 超低膨張ガラスの製造方法 - Google Patents
超低膨張ガラスの製造方法 Download PDFInfo
- Publication number
- WO2011105517A1 WO2011105517A1 PCT/JP2011/054192 JP2011054192W WO2011105517A1 WO 2011105517 A1 WO2011105517 A1 WO 2011105517A1 JP 2011054192 W JP2011054192 W JP 2011054192W WO 2011105517 A1 WO2011105517 A1 WO 2011105517A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tio
- cte
- glass
- zero
- sio
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/14—Other methods of shaping glass by gas- or vapour- phase reaction processes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
- G01N29/04—Analysing solids
- G01N29/07—Analysing solids by measuring propagation velocity or propagation time of acoustic waves
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N29/00—Investigating or analysing materials by the use of ultrasonic, sonic or infrasonic waves; Visualisation of the interior of objects by transmitting ultrasonic or sonic waves through the object
- G01N29/22—Details, e.g. general constructional or apparatus details
- G01N29/221—Arrangements for directing or focusing the acoustical waves
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/20—Doped silica-based glasses doped with non-metals other than boron or fluorine
- C03B2201/23—Doped silica-based glasses doped with non-metals other than boron or fluorine doped with hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
- C03B2201/42—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn doped with titanium
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2201/00—Glass compositions
- C03C2201/06—Doped silica-based glasses
- C03C2201/20—Doped silica-based glasses containing non-metals other than boron or halide
- C03C2201/23—Doped silica-based glasses containing non-metals other than boron or halide containing hydroxyl groups
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2291/00—Indexing codes associated with group G01N29/00
- G01N2291/04—Wave modes and trajectories
- G01N2291/042—Wave modes
- G01N2291/0423—Surface waves, e.g. Rayleigh waves, Love waves
Definitions
- the present invention relates to a method for producing ultra-low expansion glass, and more particularly to a method for producing TiO 2 —SiO 2 ultra-low expansion glass.
- Non-Patent Document 1 As a substrate material for photomask blanks and reflective optics for Extreme Ultraviolet Lithography (EUVL) systems, the coefficient of thermal expansion (CTE) is within 0 ⁇ 5 ppb / K at the desired temperature.
- ultra-low expansion glass There is a demand for ultra-low expansion glass [Non-Patent Document 1].
- TiO 2 —SiO 2 glass is one of the candidates [Non-Patent Documents 2 and 3]. Since the output of the light source is high, the specifications of the temperature at which the required coefficient of linear expansion (CTE) becomes zero, that is, the zero CTE temperature T (zero-CTE), are different at each stage of the mask substrate and mirror.
- a desired T is obtained by adjusting the TiO 2 concentration C (TiO 2 ) to 6-9 wt%.
- the conventional CTE measurement methods [Non-Patent Documents 4 and 5] do not have sufficient measurement accuracy, and the characteristics of the substrate surface are evaluated. Can not do it.
- the inventors of the present application Based on the experience of the Line-Focus-Beam Ultrasonic Material Characterization (LFB-UMC) system [Non-Patent Documents 6 and 7], the inventors of the present application have developed chemical properties, physical properties, and thermal properties.
- LFB-UMC Line-Focus-Beam Ultrasonic Material Characterization
- Non-Patent Document 10 we have established the basis of T (zero-CTE) measurement method for TiO 2 -SiO 2 ultra-low expansion (ULE) glass [Non-Patent Document 11-14], and made a prototype of homogeneous TiO 2 -SiO 2 ULE glass. Successful [Non Patent Literature 15].
- FIG. 1A is a cross section of a glass sample 14 having a linearly focused beam device (hereinafter referred to as an LFB device) 10 and striae 14P, and shows the principle of forming a V (z) curve.
- the LFB device 10 includes an LFB acoustic lens 12 and a ZnO film transducer 11 attached to the top surface thereof. Ultrasonic waves are generated by the high-frequency pulse applied to the transducer 11, converged in a wedge shape by the LFB acoustic lens 12, and irradiated to the sample surface 14 ⁇ / b> S through the water coupler.
- FIG. 1B shows an ultrasonic beam region 15 which is a measurement region W ⁇ D on the sample surface 14S.
- V W is the LSAW propagation distance in the focusing direction on the sample surface and is given by 2
- D is the effective beam width in the non-focusing direction. Therefore, the averaged velocity is measured in the measurement region where the LSAW propagates.
- V (z) curve for TiO 2 —SiO 2 ULE glass is shown in FIG. 2A.
- FIG. 2B is a spectrum distribution for the waveform of FIG. 2A obtained according to the V (z) curve analysis method [Non-Patent Document 6].
- V LSAW can be obtained by obtaining the interference period ⁇ z of the V (z) curve and substituting it into the equation (1).
- V w is the longitudinal wave speed of sound in water.
- An absolute value of V LSAW can be obtained by system calibration using a standard suitable for TiO 2 —SiO 2 ULE glass.
- V LSAW measurement repeatability is ⁇ 2 ⁇ ( ⁇ : standard deviation), within ⁇ 0.17 m / s ( ⁇ 0.005%) at 225 MHz, and within ⁇ 0.07 m / s ( ⁇ 0.002%) at 75 MHz. is there.
- the measurement area W ⁇ D is 280 ⁇ m and D is 900 ⁇ m for a 225 MHz device, W is 750 ⁇ m, and D is 1.4 mm for a 75 MHz device. Since the Rayleigh-type LSAW propagates with most of the energy concentrated within one wavelength below the sample surface, the resolution in the depth direction is approximately 15 ⁇ m at 225 MHz and approximately 44 ⁇ m at 75 MHz. 13].
- CTE characteristics are adjusted by C (TiO 2 ) [wt%], and there is a linear relationship from 0 wt% to 9 wt%.
- C (TiO 2 ) -0.0669 ⁇ V LSAW + 228.3
- T (zero-CTE) -2.67 ⁇ V LSAW + 8827 (3)
- T (zero-CTE) by LSAW velocity measurement is -2.67 ° C / (m / s), and the measurement reproducibility of ⁇ 0.17 m / s corresponds to the resolution of ⁇ 0.4 ° C.
- the CTE distribution within ⁇ 5 ppb / K required for UVL glass substrates for EUVL corresponds to the LSAW velocity distribution within ⁇ 1.15 m / s.
- J. Kushibiki and N. Chubachi “Material characterization by line-focus-beam acoustic microscope,” IEEE Trans. Sonics Ultrason., Vol. SU-32, pp. 189-212 (1985).
- J. Kushibiki, Y. Ono, Y. Ohashi, and M. Arakawa "Development of the line-focus-beam ultrasonic material characterization system," IEEE Trans. Ultrason., Ferroelect., Freq. Contr., Vol. 49, pp. 99-113 (2002).
- the object of the present invention is to solve such problems, have a high degree of freedom of control to achieve a desired T (zero-CTE), and can perform appropriate measurement regardless of the heat treatment conditions. It is an object of the present invention to provide a method for producing a TiO 2 —SiO 2 ultra-low expansion glass that can be easily fed back to the production of a glass having a T (zero-CTE) of 5%.
- the method for producing ultra-low expansion glass according to the present invention is as follows. (a) making a TiO 2 -SiO 2 glass ingot with a selected TiO 2 concentration; and (b) cutting a sample from the TiO 2 -SiO 2 glass ingot and measuring the OH concentration C (OH), the TiO 2 concentration C (TiO 2 ), and the fictive temperature TF ; (c) calculating zero CTE (thermal expansion coefficient) temperature T (zero-CTE) from measured C (OH), C (TiO 2 ), and T F ; (d) It is determined whether the difference ⁇ T between T (zero-CTE) and a predetermined target value is within a predetermined allowable range.
- the TiO 2 —SiO 2 glass ingot has a desired zero CTE temperature.
- a feedback process for correcting the production conditions of the TiO 2 -SiO 2 glass ingot based on the difference ⁇ T from the target value It is characterized by including.
- T the TiO 2 concentration C (TiO 2 ) but also the fictive temperatures T F and C (OH) are calculated as affecting T (zero-CTE), so T (zero- The degree of freedom of control of CTE) is high, manufacturing is easy, and T (zero-CTE) can be controlled even for samples having different virtual temperatures TF .
- A is a sectional view of an LFB ultrasonic device showing the principle of V (z) curve measurement
- B is a diagram showing an LFB measurement region at a certain defocus distance.
- A shows a typical V (z) curve measured at 225 MHz for a TiO 2 —SiO 2 glass sample
- B shows a spectrum distribution when the V (z) curve is analyzed by FFT.
- A shows the relationship between LSAW velocity and longitudinal wave velocity
- B shows the relationship between LSAW velocity and shear wave velocity
- C shows the relationship between LSAW velocity and density.
- TiO 2 -SiO 2 glass it shows the LSAW velocity and TiO 2 concentration relationship.
- A shows the relationship between longitudinal wave velocity and shear wave velocity
- B shows the relationship between longitudinal wave velocity and LSAW velocity
- C shows the relationship between longitudinal wave velocity and density
- D is The figure which shows the relationship between longitudinal wave sound velocity and CTE in 23 degreeC.
- A shows the relationship between fictive temperature and longitudinal sound velocity
- B shows the relationship between fictive temperature and shear wave velocity
- C shows the relationship between fictive temperature and LSAW velocity
- D shows The figure which shows the relationship between virtual temperature and a density
- E is a figure which shows the relationship between CTE in virtual temperature and 23 degreeC.
- Table 2 shows the sensitivity and resolution of acoustic characteristics for SiO 2 glass with respect to virtual temperature.
- A shows the relationship between fictive temperature and longitudinal wave speed
- B shows the relationship between fictive temperature and shear wave velocity
- C shows the relationship between fictive temperature and LSAW velocity.
- D is a figure which shows the relationship between virtual temperature and density
- E is a figure which shows the relationship between virtual temperature and zero CTE temperature
- F is a figure which shows the relationship between virtual temperature and CTE in 23 degreeC.
- Table 3 showing the sensitivity and resolution of the acoustic characteristics for TiO 2 —SiO 2 glass with respect to virtual temperature.
- Table 4 shows sensitivity and resolution with respect to changes in acoustic characteristics T (zero-CTE) for TiO 2 —SiO 2 glass.
- A is a diagram showing the relationship of ⁇ V L / ⁇ C (OH) to the fictive temperature
- B is a diagram showing the relationship of ⁇ V S / ⁇ C (OH) to the fictive temperature
- C is the relationship of ⁇ V LSAW / ⁇ C (OH) to the fictive temperature
- D is a diagram showing the relationship of ⁇ / ⁇ C (OH) to the virtual temperature
- E is a diagram illustrating the relationship of ⁇ T (zero-CTE) / ⁇ C (OH) to the virtual temperature
- F is ⁇ CTE / to the virtual temperature.
- C (OH) 1000 wtppm TiO 2 -SiO 2 glass
- A shows the relationship of T (zero-CTE) to LSAW velocity
- B shows the relationship of T (zero-CTE) to longitudinal wave velocity.
- FIG. The figure which shows the processing flow of a manufacturing and an evaluation method.
- CTE characteristics especially, zero CTE temperature ⁇ T (zero-CTE) ⁇ , which is the temperature at which CTE becomes zero
- chemical composition ratio TiO 2 concentration C (TiO 2 )
- impurity OH
- LSAW ky surface acoustic wave
- UMS Ultrasonic Microspectroscopy
- samples with different fictive temperatures were prepared by heat treatment at different temperatures using a high temperature electric furnace.
- OH concentration was measured by infrared spectroscopy for the prepared sample [Reference 1].
- the fictive temperature was measured from the relationship between longitudinal wave velocity, LSAW velocity, and zero CTE temperature.
- the OH concentration was 975 ⁇ 15 wtppm
- the fictive temperature was 873 ⁇ 7 ° C.
- Each measurement accuracy is ⁇ 1 wtppm, ⁇ 1 °C. Therefore, the samples C-7972 and C-7980 used for the measurement here can be handled with the OH concentration and the fictive temperature fixed.
- FIG. A shows the relationship between the LSAW speed and the longitudinal sound velocity
- B shows the relationship between the LSAW velocity and the transverse sound velocity
- C shows the relationship between the LSAW velocity and the density. It can be seen that the relationship between the acoustic characteristics is linear. As a result, the following formula was obtained for C-7972.
- V LSAW 0.6325 ⁇ V L -324.01
- V LSAW 57.85 ⁇ ⁇ - 123838.8
- V LSAW 0.8686 ⁇ V S + 153.26 (6)
- TiO 2 concentration was measured by a fluorescent X-ray analysis (XRF) method. Since the measured values by the XRF method vary depending on the system and measurement conditions used, calibration is performed using the sample used to determine the relationship between the XRF method and inductively coupled plasma optical emission spectrometry (ICP-OES) [Non-Patent Document 12]. It was. The measurement results are shown in FIG. As a result, the following formula was obtained.
- C (TiO 2 ) -0.0602 ⁇ V LSAW + 206.3 (7)
- FIG. 5 shows the relationship between the LSAW speed, the zero CTE temperature, and the CTE ⁇ CTE (23 ° C) [ppb / K] ⁇ at 23 ° C. From this result, the following equation was obtained.
- T (zero-CTE) -2.67 ⁇ V LSAW + 8827 (8)
- CTE (23 ° C) 4.33 ⁇ V LSAW -14310 (9)
- V LSAW -16.61 ⁇ C (TiO 2 ) + 3426.1 (10)
- V L -26.26 ⁇ C (TiO 2 ) + 5929.0 (11)
- V S -19.07 ⁇ C (TiO 2 ) + 3767.5
- n -0.287 ⁇ C (TiO 2 ) + 2199.8 (13)
- T (zero-CTE) 44.27 ⁇ C (TiO 2 ) -304.8
- CTE (23 ° C) -71.95 ⁇ C (TiO 2 ) + 533.7 (15) It is also possible to relate zero CTE temperature and acoustic characteristics as follows.
- T (zero-CTE) -1.69 ⁇ V L +9691 (16)
- T (zero-CTE) -2.32 ⁇ V S +8441 (17)
- T (zero-CTE) -154.2 ⁇ ⁇ + 338916.5 (18)
- Table 1 in FIG. 6 shows the sensitivity and resolution of the acoustic characteristics for TiO 2 concentration and CTE characteristics. It can be seen that the sound speeds (LSAW speed, longitudinal wave speed, and shear wave speed) all have high resolution with respect to TiO 2 concentration and zero CTE temperature.
- the characteristic temperature (strain point and annealing point) of each glass differs by performing heat treatment at 1050 ° C to 1200 ° C for ED-B and 900 ° C to 1100 ° C for C-7980. A virtual temperature sample was prepared.
- T A longitudinal wave acoustic velocity and density is increased, CTE in shear velocities and 23 ° C. is reduced.
- LSAW is a mode in which both the longitudinal wave and the transverse wave are coupled, but the characteristics of each other cancel each other and the speed change becomes small.
- T A 1200 ° C. in ED-B
- longitudinal wave acoustic velocity and density of T A 1050 ° C.
- T A 1100 ° C. is in C-7980, has become smaller than the value on the approximate line. This is considered to be because the relaxation time (the time ⁇ when the relaxation phenomenon occurs in the form of e ⁇ t / ⁇ with respect to the time t) is shortened at a high temperature, and the fictive temperature is lower than the heat treatment temperature.
- FIG. 8 shows the result of plotting other characteristics as a function of the longitudinal wave sound speed, assuming that the measured value of the longitudinal wave sound speed reflects the virtual temperature.
- the linearity was good including the data that was out of the linearity. This is because each characteristic reflects a virtual temperature change.
- FIG. 9 shows the result of illustrating each characteristic with respect to the virtual temperature using the equations (19) and (20) in the result of FIG. A to E respectively indicate longitudinal wave velocity, transverse wave velocity, LSAW velocity, density, and CTE at 23 ° C. with respect to the virtual temperature TF obtained from the longitudinal wave velocity VL . From these results, it can be seen that all the characteristics change linearly with respect to the virtual temperature in this temperature range. For ED-B, the following equation was obtained:
- V L 0.1371 ⁇ T F + 5798.62 (21)
- V S -0.0190 ⁇ T F + 3784.07
- V LSAW 0.0002 ⁇ T F + 3425.76
- ⁇ 0.0089 ⁇ T F + 2191.87
- CTE (23 ° C) -0.661 ⁇ T F + 1214.3
- V L 0.1527 ⁇ T F + 5782.90 (26)
- V S -0.0224 ⁇ T F + 3787.61 (27)
- V LSAW 0.0041 ⁇ T F + 3422.33 (28)
- ⁇ 0.0064 ⁇ T F + 2194.16 (29)
- CTE (23 ° C) -0.817 ⁇ T F + 1322.5 (30)
- Table 2 in FIG. 10 shows the sensitivity and resolution of the acoustic characteristics with respect to the virtual temperature. From this result, it can be seen that the resolution of longitudinal acoustic velocity is as high as 0.3 to 0.4 ° C with respect to the virtual temperature.
- the virtual temperature is conventionally evaluated by infrared spectroscopy or Raman spectroscopy, but the resolution is ⁇ 15 ° C. [reference document 7] and ⁇ 60 ° C. [reference document 8]. For this reason, the longitudinal sound velocity is 40 to 150 times higher than the conventional method and is extremely useful as a virtual temperature evaluation method.
- the fictive temperature TF can be obtained from the following equations (31) and (32) for the soot method sample and C-7972, respectively.
- T F (V L -5646.85) /0.1188 (31)
- T F (V L -5625.28) /0.1364 (32)
- FIG. 11 shows the results illustrating the characteristics with respect to the virtual temperature.
- a to F respectively indicate longitudinal wave velocity, transverse wave velocity, LSAW velocity, density, zero CTE temperature, and CTE at 23 ° C. with respect to the virtual temperature obtained from the longitudinal wave velocity. From this result, it can be seen that all the characteristics change linearly with respect to the virtual temperature in this temperature range. The following results were obtained for the soot method sample.
- V L 0.1188 ⁇ T F + 5646.85 (33)
- V S -0.0286 ⁇ T F + 3661.71 (34)
- V LSAW -0.0091 ⁇ T F + 3320.79 (35)
- ⁇ 0.0117 ⁇ T F + 2188.52 (36)
- T (zero-CTE) 0.26 ⁇ T F -241.4 (37)
- CTE (23 ° C) -0.55 ⁇ T F + 544.4 (38)
- the following relational expression was obtained for the C-7972 sample.
- V L 0.1364 ⁇ T F + 5625.28 (39)
- V S -0.0046 ⁇ T F + 3633.60 (40)
- V LSAW 0.0084 ⁇ T F + 3299.75 (41)
- ⁇ 0.0083 ⁇ T F + 2191.00 (42)
- T (zero-CTE) 0.35 ⁇ T F -309.4 (43)
- CTE (23 ° C) -0.70 ⁇ T F + 668.6 (44)
- TiO 2 —SiO 2 glass has a high longitudinal wave sound velocity resolution of 0.4 ° C. with respect to the virtual temperature, and is useful as a virtual temperature evaluation method.
- a to F represent longitudinal wave velocity, transverse wave velocity, LSAW velocity, density, zero CTE temperature, and CTE at 23 ° C. with respect to the virtual temperature obtained from the longitudinal wave velocity.
- the solid line is for SiO 2 glass and the dotted line is for TiO 2 —SiO 2 glass. From FIG. 14, the following equations were obtained for SiO 2 glass and TiO 2 —SiO 2 glass.
- Zero CTE temperature T (zero-CTE) of TiO 2 -SiO 2 glass depends on parameters such as TiO 2 concentration C (TiO 2 ), OH concentration C (OH), fictive temperature T F (glass structure freezing temperature) .
- the acoustic characteristics AP (LSAW velocity V LSAW , longitudinal wave velocity V L , transverse wave velocity V S , density ⁇ ) also depend on C (TiO 2 ), C (OH), and T F. Therefore, the relationship between these parameters can be expressed by the following equation.
- T (zero-CTE) f ⁇ C (TiO 2 ), C (OH), T F ⁇ (64)
- AP f ⁇ C (TiO 2 ), C (OH), T F ⁇ (65)
- Equations (21) to (30) and Equations (33) to (44) the virtual temperature dependence of acoustic characteristics and CTE characteristics varies depending on the TiO 2 concentration and OH concentration. Also, from the equations (53) to (63), their OH concentration dependency varies depending on the TiO 2 concentration and the fictive temperature. However, the OH concentration by the manufacturing process used to glass making, by the zero CTE temperature specifications and heat treatment process of requesting, TiO 2 concentration, since the virtual temperature comes determined, required specifications (TiO 2 concentration, fictive temperature, OH The relationship established in the vicinity of (concentration) may be derived from the above formula.
- V L -26.26 ⁇ C (TiO 2 ) + 0.1364 ⁇ T F -0.70 ⁇ C (OH) +5815.8 (66)
- V LSAW -16.61 ⁇ C (TiO 2 ) + 0.0084 ⁇ T F -0.65 ⁇ C (OH) +3422.2 (67)
- T (zero-CTE) 44.27 ⁇ C (TiO 2 ) + 0.35 ⁇ T F + 0.94 ⁇ C (OH) -628.3 (68)
- C (OH) 100 wtppm) (10), (11), (14), Eqs.
- V L -26.26 ⁇ C (TiO 2 ) + 0.1188 ⁇ T F -0.70 ⁇ C (OH) + 5815.8 + 6.1 + 9.5 (69)
- V LSAW -16.61 ⁇ C (TiO 2 ) -0.0091 ⁇ T F -0.65 ⁇ C (OH) + 3422.2 + 5.6-0.7 (70)
- T (zero-CTE) 44.27 ⁇ C (TiO 2 ) + 0.26 ⁇ T F + 0.94 ⁇ C (OH) -628.3-8.2 + 21.0 (71)
- TiO 2 concentration C (TiO 2 ) is the most basic parameter for controlling T (zero-CTE) of TiO 2 —SiO 2 glass.
- the OH concentration C (OH) depends on the production process of TiO 2 —SiO 2 glass. When manufactured by the direct synthesis method, it is about 500-2000 wtppm, and when manufactured by the soot method, it is about 50-200 wtppm.
- the virtual temperature TF can be controlled by heat treatment.
- the structure relaxation time is shortened, so that a large virtual temperature distribution is generated in the ingot and the virtual temperature is lower than the holding temperature during the heat treatment.
- the structure relaxation time becomes too long, which increases the cost industrially and is difficult to realize.
- the controllable range is a strain point of about ⁇ 100 ° C., which is one of glass characteristic temperatures.
- the coefficient of C (TiO 2 ) is 1 wt%
- TF is 1 ° C.
- C (OH) is the amount of change per 100 wtppm.
- T F Measured with accuracy of ⁇ 0.4 ° C by longitudinal wave sound velocity measurement.
- ⁇ C (TiO 2 ) ⁇ 0.02 wt%
- T F ⁇ 0.4 ° C
- C (OH): ⁇ 1 wtppm ⁇ on T (zero-CTE) is shown in the following table. Five.
- the zero CTE temperature and the acoustic characteristics depend only on C (TiO 2 ), and T (zero-CTE) can be evaluated from the acoustic characteristics (eg, V LSAW ).
- the strain point of the glass is 890 ° C.
- T F is about 20 ° C. lower than the strain point.
- T F 870 ° C.
- the TiO 2 concentration can be controlled in the range of 0.05-9 wt%.
- C (TiO 2 ) is 6wt% and 9wt%, T (zero-CTE) becomes -39 ° C and 94 ° C, respectively.
- T (zero-CTE in the range of -39 to 94 ° C -CTE) can be controlled.
- V LSAW and V L also change greatly, so that T (zero-CTE) can be evaluated by these measurements.
- longitudinal wave velocity VL is highly sensitive to virtual temperature TF . Therefore, if C (TiO 2 ) and C (OH) can be measured by another method (XRF method and FT-IR method), TF can be obtained by measuring VL . It is also useful for evaluating T (zero-CTE) due to TF changes.
- T F C Tf glass at about a strain point ⁇ 100 ° C.
- C (OH) C Tf glass
- T (zero-CTE) increases as TF increases
- the upper limit of T (zero-CTE) increases.
- a material with a high T (zero-CTE) is required. In this case, it is necessary to produce glass by a production process (soot method) that reduces C (OH).
- the longitudinal wave velocity and T (zero-CTE) The relationship is shown in FIG. 16B.
- V L -26.26 ⁇ C (TiO 2 ) + 0.1171 ⁇ T F -0.70 ⁇ C (OH) + 5815.8 + 6.6 + 16.4 (72)
- V LSAW -16.61 ⁇ C (TiO 2 ) -0.0108 ⁇ T F -0.65 ⁇ C (OH) + 3422.2 + 6.1-1.5 (73)
- T (zero-CTE) 44.27 ⁇ C (TiO 2 ) + 0.25 ⁇ T F + 0.94 ⁇ C (OH) -628.3-9.0 + 35.5 (74)
- An ultra-low expansion glass is obtained.
- FIG. 17 shows a flowchart of evaluation / analysis.
- Table 1 of FIG. 6 the sensitivity of the LSAW velocity V LSAW and the longitudinal wave velocity V L is high with respect to the change in T (zero-CTE) due to the change in the TiO 2 concentration, and the virtual temperature T F
- the sensitivity of V L is high, but the sensitivity of V LSAW is low.
- the glass development stage it is necessary to know the T (zero-CTE) of the produced glass and the distribution of the glass ingot (mainly due to changes in TiO 2 concentration).
- the problem of striae has been reduced, and if it is within the allowable range ( ⁇ V LSAW ⁇ 1.15 m / s), the glass manufacturing company is responsible for quality control and EUVL of the manufactured glass ingot.
- T zero-CTE
- the glass user needs to perform an acceptance test to confirm whether the glass material has the desired characteristics.
- Step S1 in a given manufacturing process conditions, to produce a TiO 2 -SiO 2 glass ingot.
- the manufacturing method determines whether to use the direct synthesis method or the soot method, for example, depending on the required zero CTE temperature range.
- Step S2 Heat treatment is performed under predetermined conditions. For example, a fictive temperature corresponding to the required zero CTE temperature is determined, and heat treatment conditions are determined.
- Step S3 A sample for evaluation is prepared from a glass ingot.
- C (OH) is generally measured with an FT-IR apparatus.
- C (TiO 2 ) is measured by a V LSAW or XRF apparatus.
- TF is measured by longitudinal sound velocity V L, FT-IR apparatus or Raman spectrometer.
- Step S5 A center value of T (zero-CTE) is calculated from the C (OH), C (TiO 2 ), and T F measured in Step S4 using a calibration curve. For example, if TiO 2 —SiO 2 glass is produced by a direct synthesis method, T (zero-CTE) is calculated from equation (68) using the measurement result of step S4. If it is produced by the soot method, it is calculated by equation (71).
- Step S6 Whether the difference ⁇ T between the calculated T (zero-CTE) and the target value is within a predetermined allowable range, and the V LSAW distribution ( ⁇ V LSAW ) measured in Step S4 satisfies ⁇ CTE ⁇ 5 ppb / K. Check if it is within the corresponding ⁇ 1.15 m / s. If both conditions are satisfied, the glass can be used as a glass for EUVL use in step S7. If either or both are not satisfied, the process proceeds to step S8, and the result is fed back to the glass manufacturing process conditions.
- Step S8 When ⁇ V LSAW is ⁇ 1.15 m / s or more, it is fed back to the glass manufacturing process conditions so as to produce a more homogeneous ingot.
- Specific manufacturing conditions for improving the homogeneity are described in this invention. The explanation is omitted because it is not intended.
- T zero-CTE
- T F T F
- C OH
- the first control method for example, if TiO 2 —SiO 2 glass is produced by a direct synthesis method, the value of TF and C (OH) in Equation (68) is not changed, and C ( Change TiO 2 ). Specifically, an instruction to change the TiO 2 concentration so as to be a value lower than the measured C (TiO 2 ) by ⁇ T / 44.27 is fed back to step S1. According to the second control method, the values of C (TiO 2 ) and C (OH) are not changed, and the instruction to control the heat treatment in step S2 to lower the virtual temperature TF by ⁇ T / 0.35 in equation (68). Is given to step S1.
- the values of C (TiO 2 ) and T F are not changed, and an instruction to adjust the manufacturing conditions so as to reduce C (OH) by ⁇ T / 0.94 is issued to Step S1.
- the case where the glass was produced by the direct synthesis method was described.
- feedback information can be obtained similarly using the formula (71). it can.
- Steps S1 to S3 at the time of glass development are performed in the same manner as at the time of glass development at the time of glass mass production .
- Step S4 C (OH), C (TiO 2 ), and T F are measured.
- V LSAW is measured at multiple points in the sample surface or by line scanning.
- Step S5 T (zero-CTE) is calculated from the C (OH), C (TiO 2 ), and T F measured in Step S4 using a calibration curve.
- Step S6 Check if it has the desired T (zero-CTE). It is checked whether the V LSAW distribution measured in step S4 is within ⁇ 1.15 m / s. If it is within ⁇ 1.15 m / s, it can be used as EUVL glass.
- Step S7 Using the T (zero-CTE) obtained in Step S5, the glass ingot is selected for a desired application.
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Pathology (AREA)
- Materials Engineering (AREA)
- Acoustics & Sound (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Glass Compositions (AREA)
- Glass Melting And Manufacturing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
C(TiO2) = -0.0669×VLSAW + 228.3 (2)
T(zero-CTE) = -2.67×VLSAW + 8827 (3)
(a) 選択したTiO2濃度のTiO2-SiO2ガラスインゴットを作製する過程と、
(b) 上記TiO2-SiO2ガラスインゴットからサンプルを切り出し、OH濃度C(OH)と、TiO2濃度C(TiO2)と、仮想温度TFを測定する過程と、
(c) 測定したC(OH)、C(TiO2)、TFからゼロCTE(熱膨張係数)温度T(zero-CTE)を計算する過程と、
(d) T(zero-CTE)と予め決めた目標値との差分ΔTが所定の許容範囲内であるか判定し、範囲内であれば上記TiO2-SiO2ガラスインゴットは所望のゼロCTE温度を有すると判定する過程と、
(e) 過程(d)で範囲内で無い場合、目標値との上記差分ΔTに基づいて上記TiO2-SiO2ガラスインゴットの作製条件を修正するフィードバック過程、
とを含むことを特徴とする。
TiO2-SiO2超低膨張ガラスの線膨張係数(Coefficient of Thermal Expansion: CTE)特性は、TiO2濃度により調整されるが、作製プロセスに依存して含まれるOH基、およびガラスの熱履歴(仮想温度TF)もCTE特性に少なからず影響を与える。このため、CTE特性(特に、CTEがゼロとなる温度であるゼロCTE温度{T(zero-CTE)})と化学組成比(TiO2濃度C(TiO2))、不純物(OH)濃度C(OH)、および仮想温度との間の関係を、超音波マイクロスペクトロスコピー(Ultasonic Microspectroscopy: UMS)技術により測定される音響特性(漏洩弾性表面波(LSAW)速度VLSAW、縦波音速VL、横波音速VS、および密度ρ)により調べた。
・直接合成法TiO2-SiO2超低膨張ガラス(C-7972, Corning社製, 市販品)
C(OH)は約1000 wtppm
・スート法TiO2-SiO2超低膨張ガラス(試作品)
C(OH)は約100 wtppm
・直接合成法SiO2ガラス(C-7980, Corning社製, 市販品)
C(OH)は約1000 wtppm
・スート法SiO2ガラス
(ED-B, 東ソー・クォーツ社製, 市販品)
C(OH)は0 wtppm
(a) TiO2濃度の影響
異なる複数のロットのC-7972インゴットから試料を用意した。試料は両面光学研磨されている。また、TiO2濃度がゼロであるC-7980も併せて用意した。
VLSAW = 0.6325×VL - 324.01 (4)
VLSAW = 57.85×ρ- 123838.8 (5)
VLSAW = 0.8686×VS + 153.26 (6)
C(TiO2) = -0.0602×VLSAW + 206.3 (7)
T(zero-CTE) = -2.67×VLSAW + 8827 (8)
CTE(23°C) = 4.33×VLSAW -14310 (9)
VLSAW = -16.61×C(TiO2) + 3426.1 (10)
VL = -26.26×C(TiO2) + 5929.0 (11)
VS = -19.07×C(TiO2) + 3767.5 (12)
n= -0.287×C(TiO2) + 2199.8 (13)
T(zero-CTE) = 44.27×C(TiO2)-304.8 (14)
CTE(23℃) = -71.95×C(TiO2) + 533.7 (15)
また、以下のように、ゼロCTE温度と音響特性間を関係づけることが可能である。
T(zero-CTE) = -1.69×VL +9691 (16)
T(zero-CTE) = -2.32×VS +8441 (17)
T(zero-CTE) = -154.2×ρ+ 338916.5 (18)
次に、仮想温度の影響について検討を行った。はじめに、TiO2-SiO2ガラスの基礎となるSiO2ガラスに対して検討を行う。次に、TiO2-SiO2ガラスに対して検討を行う。
(b-1) SiO2ガラス
試料をスート法により作製されたED-Bと直接合成法により作製されたC-7980から用意した。ED-BはOH濃度が0 wtppmであり、C-7980は約1000 wtppmである。
各ガラスの特性温度(歪点や徐冷点)を考慮し、ED-Bに対しては1050℃~1200℃、C-7980に対しては、900℃~1100℃として熱処理を行うことで異なる仮想温度の試料を作製した。
TF = (VL - 5798.6)/0.1371 (19)
TF = (VL - 5782.9)/0.1527 (20)
ED-Bに対しては、以下の式が得られた。
VS = -0.0190×TF + 3784.07 (22)
VLSAW = 0.0002×TF + 3425.76 (23)
ρ= 0.0089×TF + 2191.87 (24)
CTE(23℃) = -0.661×TF + 1214.3 (25)
また、C-7980に対しては以下の式が得られた。
VL = 0.1527×TF + 5782.90 (26)
VS = -0.0224×TF + 3787.61 (27)
VLSAW = 0.0041×TF + 3422.33 (28)
ρ= 0.0064×TF + 2194.16 (29)
CTE(23℃) = -0.817×TF + 1322.5 (30)
音響特性の仮想温度に対する感度と分解能を図10の表2に示す。この結果より、仮想温度に対して、縦波音速の分解能が0.3~0.4℃と高いことがわかる。仮想温度の評価は、従来、赤外分光法やラマン分光法により行われるが、分解能は±15℃[参考文献7]、±60℃[参考文献8]である。このため、縦波音速は、従来法よりも40~150倍分解能が高く、仮想温度評価法として極めて有用である。
スート法により作製したTiO2-SiO2ガラスおよび市販のC-7972を帯域溶融法により均質化したガラスインゴット[非特許文献15]から試料を用意した。スート法試料のOH濃度は90 wtppm、C-7972のOH濃度は953 wtppmであった。ここで用いた試料も、OH濃度は変化しないものとして取り扱う。
TF = (VL - 5646.85)/0.1188 (31)
TF = (VL - 5625.28)/0.1364 (32)
VL = 0.1188×TF + 5646.85 (33)
VS = -0.0286×TF + 3661.71 (34)
VLSAW = -0.0091×TF + 3320.79 (35)
ρ= 0.0117×TF + 2188.52 (36)
T(zero-CTE) = 0.26×TF - 241.4 (37)
CTE(23℃) = -0.55×TF+ 544.4 (38)
また、C-7972試料に対しては、以下の関係式が得られた。
VS = -0.0046×TF + 3633.60 (40)
VLSAW = 0.0084×TF + 3299.75 (41)
ρ= 0.0083×TF + 2191.00 (42)
T(zero-CTE) = 0.35×TF - 309.4 (43)
CTE(23℃) = -0.70×TF + 668.6 (44)
スート法試料
T(zero-CTE) = 2.20×VL - 12700 (45)
T(zero-CTE) = -9.15×VS + 33258 (46)
T(zero-CTE) = -28.72×VLSAW + 95138 (47)
T(zero-CTE) = 22.37×ρ- 49195 (48)
C-7972試料
T(zero-CTE) = 2.56×VL - 14688 (49)
T(zero-CTE) = -76.4×VS + 277253 (50)
T(zero-CTE) = 41.4×VLSAW - 136939 (51)
T(zero-CTE) = 41.8×ρ- 91893 (52)
仮想温度の変化に起因するゼロCTE温度の変化に対する音響特性の感度と分解能を図13の表4に示す。この場合、ゼロCTE温度に対して、縦波音速の分解能が非常に高いことがわかる。一方、 LSAW速度の分解能は縦波音速に比べて20倍程度低い。
図9におけるTiO2を含まないED-B {C(OH):0 wtppm}とC-7980の差分{C(OH):1000 wtppm}、および図11における同じTiO2濃度を有するスート法試料{C(OH):90 wtppm}とC-7972{C(OH):953 wtppm}の差分が、それぞれSiO2ガラス、TiO2-SiO2ガラスの音響特性、CTE特性におけるOH濃度の影響によるものである。SiO2ガラスとTiO2-SiO2ガラスに対して、100 wtppmあたりのOH濃度変化に対する音響特性とCTE特性の変化を仮想温度依存性として求めた結果を図14に示す。A~Fはそれぞれ縦波音速から求めた仮想温度に対する縦波音速、横波音速、LSAW速度、密度、ゼロCTE温度、23℃におけるCTEを示す。実線はSiO2ガラス、点線はTiO2-SiO2ガラスに対するものである。図14より、SiO2ガラスとTiO2-SiO2ガラスに対して、以下の式が得られた。
SiO2ガラス
ΔVL/ΔC(OH) = 1.56×10-3×TF - 1.57 (53)
ΔVS/ΔC(OH) = -0.35×10-3×TF + 0.35 (54)
ΔVLSAW/ΔC(OH) = 0.38×10-3×TF - 0.34 (55)
Δρ/ΔC(OH) = -0.25×10-3×TF + 0.23 (56)
ΔCTE(23°C)/ΔC(OH) = -15.7×10-3×TF + 10.8 (57)
TiO2-SiO2ガラス
ΔVL/ΔC(OH) = 2.04×10-3×TF - 2.50 (58)
ΔVS/ΔC(OH) = 2.79×10-3×TF - 3.26 (59)
ΔVLSAW/ΔC(OH) = 2.03×10-3×TF - 2.44 (60)
Δρ/ΔC(OH) = -0.39×10-3×TF + 0.29 (61)
ΔT(zero-CTE)/ΔC(OH) = 10.0×10-3×TF -7.9 (62)
ΔCTE(23°C)/ΔC(OH) = -18.1×10-3×TF + 14.4 (63)
音響特性やCTE特性のOH濃度依存性は仮想温度に依存している。また、その依存性(即ち、式(53)~(63)のTFの係数の絶対値)は、TiO2-SiO2ガラスのほうが、SiO2ガラスよりも大きいということがわかった。
以上の(a), (b), (c)から次のことが明らかである。TiO2-SiO2ガラスのゼロCTE温度T(zero-CTE)はTiO2濃度C(TiO2)、OH濃度C(OH)、仮想温度TF(ガラスの構造凍結温度)等のパラメータに依存する。また、音響特性AP (LSAW速度VLSAW, 縦波音速VL, 横波音速VS, 密度ρ)もC(TiO2)、C(OH)、TFに依存する。従ってこれらパラメータの関係を以下の式で表すことができる。
T(zero-CTE) = f{C(TiO2), C(OH), TF} (64)
AP = f{C(TiO2), C(OH), TF} (65)
このため、音響特性を測定することにより、C(TiO2)、C(OH)、TFを介して、T(zero-CTE)を評価することが可能である。
VL = -26.26×C(TiO2)+0.1364×TF -0.70×C(OH)+5815.8 (66)
VLSAW = -16.61×C(TiO2)+0.0084×TF -0.65×C(OH)+3422.2 (67)
T(zero-CTE) = 44.27×C(TiO2)+0.35×TF+0.94×C(OH)-628.3 (68)
同様に、スート法によるTiO2-SiO2ガラス(即ちC(TiO2) = 7 wt%, TF = 950(= 870+80)℃, C(OH) = 100 wtppmの近傍)に対し、式(10), (11), (14)、式(33), (35), (37)、及び式(58), (60), (62)を線形結合して以下の関係式を作ることができる。
VL= -26.26×C(TiO2)+0.1188×TF-0.70×C(OH)+5815.8+6.1+9.5 (69)
VLSAW=-16.61×C(TiO2)-0.0091×TF-0.65×C(OH)+3422.2+5.6-0.7 (70)
T(zero-CTE)=44.27×C(TiO2)+0.26×TF+0.94×C(OH)-628.3-8.2+21.0 (71)
ここで、C(TiO2)の係数は1 wt%、TFは1℃、C(OH)は100 wtppm当たりの変化量を表している。TF、C(OH)が上記の値と異なる場合、式(66), (67), (68), (69), (70), (71)の係数は変わってくる。
C(TiO2):蛍光X線分析(XRF)法により±0.02 wt%の精度で測定可能である。
C(OH):FT-IRを用いた赤外吸光分光法により±0.1% (±1 wtppm)の精度で測定可能である。
TF:縦波音速測定により、±0.4℃の精度で測定可能である。
このとき、各パラメータの不確かさ{C(TiO2):±0.02 wt%、TF:±0.4℃、C(OH):±1wtppm}が、T(zero-CTE)に与える影響は次の表5の通りである。
[制御方法1]
C(OH)=COHとTF=CTfを一定とし、C(TiO2)を変えることにより、T(zero-CTE)を所望の値に調整する。
T(zero-CTE) = f{C(TiO2), COH, CTf}
AP = f{C(TiO2), COH, CTf}
また、このとき、VLSAW、VLも大きく変化することから、これらの測定により、T(zero-CTE)を評価することが可能である。
C(TiO2)=CTiとC(OH)=COHを一定とし、TFを変えることにより、T(zero-CTE)を所望の値に調整する。
T(zero-CTE) = f{CTi, COH, TF }
AP = f{CTi, COH, TF}
・仮想温度TFにより、T(zero-CTE)を制御することが可能である。
・音響特性APの中で、縦波音速VLが仮想温度TFに対する感度が高い。このため、C(TiO2)、C(OH)を別の方法(XRF法およびFT-IR法)により測定できれば、VLを測定することによりTFを求めることができる。また、TF変化に起因するT(zero-CTE)の評価に有用である。
また、C(TiO2)、TFが高いほどT(zero-CTE)が高くなる。C(TiO2) = 9 wt%とし、TF = 970℃とした場合、T(zero-CTE)は128℃となる。
C(TiO2)=CTiとTF=CTfを一定とし、C(OH)を変える。C(OH)が少ないプロセスでガラスを製造することにより、より高いT(zero-CTE)のガラスを得ることができる。
T(zero-CTE) = f{CTi, C(OH), CTf}
AP = f{CTi, C(OH), CTf}
・C(OH)はガラスの製造プロセスに依存する。直接合成法により作製した場合には500- 2000 wtppm程度、スート法により作製した場合には50-200 wtppm程度である。
・前表5のように、C(OH)が音響特性やT(zero-CTE)に与える影響は小さい。
・C(OH)が少ないほど、ガラス特性温度(歪点)が高くなる。例えば、SiO2ガラスの場合、ガラス特性温度は次の表6のようになる。
・EUVLの量産段階においては、光源が高出力となるため、T(zero-CTE)の高い素材が必要である。この場合、C(OH)が少なくなる製造プロセス(スート法)によりガラスを作製する必要がある。
歪点は直接合成法よりも80(1050-970)℃高くなる。
音響特性やゼロCTE温度は、スート法TiO2-SiO2ガラス、即ちC(TiO2) = 7 wt%, TF = 950(= 870+80)℃, C(OH) = 100 wtppmの近傍では、式(69), (70), (71)を使うことができる。
TF = 870℃のとき、C(OH) =1000 wtppmからC(OH) = 100 wtppmになることにより、ゼロCTE温度は-8.2℃低下する。
歪点である950(= 870+80)℃におけるゼロCTE温度は、C(TiO2) = 7 wt%のときに17℃、C(TiO2) = 9 wt%のときに106℃となる。
歪点より100℃と高い1050(= 950 + 100)℃のときには、ゼロCTE温度は133℃となる。
歪点は直接合成法よりも140(1110-970)℃高くなる。
TF = 870℃のときの、C(OH) =1000 wtppmからC (OH) = 0 wtppmになることにより、ゼロCTE温度は-9.0℃低下する。
VL=-26.26×C(TiO2)+0.1171×TF-0.70×C(OH)+5815.8+6.6+16.4 (72)
VLSAW=-16.61×C(TiO2)-0.0108×TF-0.65×C(OH)+3422.2+6.1-1.5 (73)
T(zero-CTE)=44.27×C(TiO2)+0.25×TF+0.94×C(OH)-628.3-9.0+35.5 (74)
以上より、
C(TiO2):6-9 wt%、TF:770-1110℃、C(OH):0-2000 wtppmにおいて
-74℃~145℃のT(zero-CTE)を有するTiO2-SiO2超低膨張ガラスが得られる。
超低膨張ガラスのゼロCTE温度T(zero-CTE)の評価・解析手順をガラス開発時、ガラス量産時に分けて説明する。図17に評価・解析のフローチャートを示す。
図6の表1に示すように、TiO2濃度の変化に起因するT(zero-CTE)の変化に対しては、LSAW速度VLSAWと縦波音速VLの感度が高く、仮想温度TFの変化に起因するT(zero-CTE)の変化に対し.ては、VLの感度は高いが、VLSAWの感度は低いことを利用する。
ステップS1: 所定の製造プロセス条件において、TiO2-SiO2ガラスインゴットを作製する。製造方法は例えば要求されるゼロCTE温度の範囲により直接合成法を使用するか、あるいは スート法を使用するかを決める。
ステップS2:所定の条件で熱処理を行う。例えば要求されるゼロCTE温度に対応する仮想温度を決め、熱処理条件を決める。
ステップS3:ガラスインゴットから評価用サンプルを用意する。
ステップS4:C(OH) 、C(TiO2) 、TFを測定する。C(OH)は、一般的に、FT-IR装置により測定する。C(TiO2)は、VLSAWあるいはXRF装置により測定する。TFは縦波音速VLあるいはFT-IR装置あるいはラマン分光装置により測定する。
ステップS5:ステップS4で測定したC(OH) 、C(TiO2) 、TFより、検量線を用いて、T(zero-CTE)の中心値を算出する。例えばTiO2-SiO2ガラスが直接合成法で作製したものであれば、ステップS4の測定結果を使って式(68)からT(zero-CTE)を計算する。スート法により作製したものであれば、式(71)により計算する。
ステップS6:算出したT(zero-CTE)と目標値との差分ΔTが所定の許容範囲内であるか、及びステップS4で測定したVLSAW分布(ΔVLSAW)がΔCTE < ±5 ppb/Kに対応する±1.15 m/s以内であるか調べる。両条件が満足されていた場合、ステップS7でEUVL用途のガラスとして使用可能となる。いずれか一方又は両方が満足してない場合には、ステップS8に移りその結果をガラスの製造プロセス条件にフィードバックする。
ステップS8:ΔVLSAWが±1.15 m/s以上の場合には、より均質なインゴットを作製するようガラスの製造プロセス条件にフィードバックするが、均質性を高めるための具体的な製造条件はこの発明の趣旨でないので説明を省略する。測定されたT(zero-CTE)が例えば所望値よりΔT℃高かった場合、ΔTだけ低くなるようにCTEに影響を与える3つのパラメータC(TiO2)、TF、C(OH)のうちの2つの値を固定したまま残りの1つを変更する。その場合、前述の3つの制御方法のいずれかを使用することができる。
第2の制御方法によれば、C(TiO2)とC(OH)の値は変更せず、式(68)において仮想温度TFをΔT/0.35だけ下げるようステップS2の熱処理を制御する指示をステップS1に与える。
第3の制御方法によれば、C(TiO2)及びTFの値は変更せず、C(OH)をΔT/0.94だけ減らすよう製造条件を調整する指示をステップS1に出す。
以上の3つの例では直接合成法でガラスを作製した場合について述べたが、スート法により作製したTiO2-SiO2ガラスに対しては式(71)を使って同様にフィードバック情報を得ることができる。
ガラス開発時と同様に、ガラス開発時のステップS1~S3を行う。
ステップS4:C(OH) 、C(TiO2) 、TFを測定する。
試料面内の複数点において、あるいはラインスキャンによりVLSAWを測定する。
ステップS5:ステップS4で測定したC(OH) 、C(TiO2) 、TFより、検量線を用いて、T(zero-CTE)を算出する。
ステップS6:所望のT(zero-CTE)を有しているか確認する。ステップS4で測定したVLSAW分布が±1.15 m/s以内であるか調べる。±1.15 m/s以内であれば、EUVL用ガラスとして使用可能となる。±1.15 m/s以上の場合には、ステップS8でその結果をガラスの製造プロセス条件にフィードバックする。
ステップS7:ステップS5で求めたT(zero-CTE)を用いて、ガラスインゴットを所望の用途に選別する。
[1] K. M. Davis, A. Agarwal, M. Tomozawa, and K. Hirao, "Quantitative infrared spectroscopic measurement of hydroxyl concentrations in silica glass," J. Non-Cryst. Solids, Vol. 203, pp. 27-36 (1996).
[2] H. A. Bowman, R. M. Schoonover, and M. W. Jones, "Procedure for high precision density determinations by hydrostatic weighing," J. Res. Natl. Bur. Stand., Vol. 71C, pp. 179-198 (1967).
[3] M. Okaji, N. Yamada, and H. Moriyama, "Ultra-precise thermal expansion measurements of ceramic and steel gauge blocks with an interferometric dilatometer," Metrologia, Vol. 37, pp. 165-171 (2000).
[4] R. Bruckner, "Properties and structure of vitreous silica. I," J. Non-Cryst. Solids, Vol. 5, pp. 123-175 (1970).
[5] H. Kakiuchida, N. Shimodaira, E. H. Sekiya, K. Saito, and A. J. Ikushima, "Refractive index and density in F- and Cl-doped silica glasses," Appl. Phys. Lett., Vol. 86, 161907 (2005).
[6] J. E. Shelby, "Density of vitreous silica," J. Non-Cryst. Solids, Vol. 349, pp. 331-336 (2004).
[7] A. Agarwal, K. M. Davis, and M. Tomozawa, "A simple IR spectroscopic method for determining fictive temperature of silica glasses," J. Non-Cryst. Solids, Vol. 185, pp. 191-198 (1995).
[8] A. E. Geissberger and F. L. Galeener, "Raman studies of vitreous SiO2 versus fictive temperature," Phys. Rev. B, Vol. 28, pp. 3266-3271 (1983).
Claims (14)
- 超低膨張ガラスの製造方法であり、
(a) 選択したTiO2濃度のTiO2-SiO2ガラスインゴットを作製する過程と、
(b) 上記TiO2-SiO2ガラスインゴットからサンプルを切り出し、OH濃度C(OH)と、TiO2濃度C(TiO2)と、仮想温度TFを測定する過程と、
(c) 測定したC(OH)、C(TiO2)、TFからゼロCTE(熱膨張係数)温度T(zero-CTE)を計算する過程と、
(d) T(zero-CTE)と予め決めた目標値との差分ΔTが所定の許容範囲内であるか判定し、範囲内であれば上記TiO2-SiO2ガラスインゴットは所望のゼロCTE温度を有すると判定する過程と、
(e) 過程(d)で範囲内で無い場合、目標値との上記差分ΔTに基づいて上記TiO2-SiO2ガラスインゴットの作製条件を修正するフィードバック過程、
とを含む。 - 請求項1記載の製造方法において、上記過程(b) における上記C(OH)の測定は赤外分光法による測定である。
- 請求項1記載の製造方法において、上記過程(b) における上記C(TiO2)の測定は、上記サンプル上の漏洩弾性表面波速度VLSAWの測定、あるいは蛍光X線分析法による測定である。
- 請求項1記載の製造方法において、上記過程(b) における上記TFの測定は対応する縦波音速を測定する。
- 請求項1乃至4のいずれか記載の製造方法において、上記過程(c) は、a, b, c, dを予め決めた係数とすると、式T(zero-CTE)=aC(TiO2)+bTF +cC(OH)+dにより計算する。
- 請求項5記載の製造方法において、上記過程(e) は上記差分ΔTからΔT/aを求め、ΔT/aをC(TiO2)に対する修正量としてフィードバックする。
- 請求項5記載の製造方法において、上記過程(e) は上記差分ΔTからΔT/bを求め、ΔT/bをTFに対する修正量としてフィードバックする。
- 請求項5記載の製造方法において、上記過程(e) は上記差分ΔTからΔT/cを求め、ΔT/cをC(OH)に対する修正量としてフィードバックする。
- 請求項1乃至8のいずれか記載の製造方法において、上記過程(b) は上記サンプル上のLSAW速度分布ΔVLSAWを測定する過程を含み、上記過程(d) は測定したΔVLSAWが所定の範囲内であるか判定し、そうでなければ不良と判定する過程を含む。
- 請求項1記載の製造方法において作製されるTiO2-SiO2ガラスは、-74℃から145℃の範囲にゼロCTE 温度T(zero-CTE)を有する。
- 請求項10に記載のTiO2-SiO2ガラスは、C(TiO2)が0.05 wt%から9 wt%の範囲にある。
- 請求項11に記載のTiO2-SiO2ガラスは、C(TiO2)が6 wt%から9 wt%の範囲にある。
- 請求項10に記載のTiO2-SiO2ガラスは、C(OH)が0 wtppmから2000 wtppmの範囲にある。
- 請求項10に記載のTiO2-SiO2ガラスは、TFが770℃から1110℃の範囲にある。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/575,290 US20120289393A1 (en) | 2010-02-24 | 2011-02-24 | Method for Producing Ulta-Low-Expansion Glass |
JP2012501866A JP5742833B2 (ja) | 2010-02-24 | 2011-02-24 | 超低膨張ガラスの製造方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-038388 | 2010-02-24 | ||
JP2010038388 | 2010-02-24 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011105517A1 true WO2011105517A1 (ja) | 2011-09-01 |
Family
ID=44506919
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/054192 WO2011105517A1 (ja) | 2010-02-24 | 2011-02-24 | 超低膨張ガラスの製造方法 |
Country Status (3)
Country | Link |
---|---|
US (1) | US20120289393A1 (ja) |
JP (1) | JP5742833B2 (ja) |
WO (1) | WO2011105517A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102013002802A1 (de) | 2012-02-21 | 2013-08-22 | Asahi Glass Company, Ltd. | Verfahren zur Herstellung von Titandioxid-enthaltendem Quarzglas-Körper |
KR20140094451A (ko) * | 2013-01-22 | 2014-07-30 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Euv 리소그래피용 부재 및 그의 제조 방법, 및 티타니아 도핑 석영 유리 |
JP2014164053A (ja) * | 2013-02-22 | 2014-09-08 | Nippon Telegr & Teleph Corp <Ntt> | 光ファイバおよびその作製方法 |
JP2015010877A (ja) * | 2013-06-27 | 2015-01-19 | 日本電信電話株式会社 | 光ファイバの仮想温度の長手方向分布の評価方法 |
JP2016511211A (ja) * | 2013-02-11 | 2016-04-14 | ヘレウス・クアルツグラース・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンディット・ゲゼルシャフトHeraeus Quarzglas GmbH & Co. KG | EUVリソグラフィに使用されるミラー基板用のTiO2−SiO2ガラスのブランク及びその製造方法 |
JP2017507106A (ja) * | 2014-02-21 | 2017-03-16 | ショット アクチエンゲゼルシャフトSchott AG | 高均一性ガラスセラミック素子 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE112011102193T5 (de) * | 2010-06-30 | 2013-04-11 | Chuo Precision Industrial Co., Ltd. | Verfahren zur Messung der fiktiven Temperatur von optischem Glas |
EP3733616A4 (en) * | 2017-12-25 | 2021-09-15 | Agc Inc. | METHOD OF EVALUATING THE THERMAL EXPANSION PROPERTIES OF A SILICA GLASS BODY CONTAINING TITANIUM DIOXIDE, AND METHOD OF MANUFACTURING SILICA GLASS BODIES CONTAINING TITANIUM DIOXIDE |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005022954A (ja) * | 2003-04-03 | 2005-01-27 | Asahi Glass Co Ltd | TiO2を含有するシリカガラスおよびその製造法 |
JP2007182367A (ja) * | 2005-12-08 | 2007-07-19 | Shin Etsu Chem Co Ltd | チタニアドープ石英ガラス、euvリソグラフィ用部材、euvリソグラフィ用フォトマスク基板及びチタニアドープ石英ガラスの製造方法 |
WO2009101949A1 (ja) * | 2008-02-13 | 2009-08-20 | Tohoku University | シリカ・チタニアガラス及びその製造方法、線膨張係数測定方法 |
WO2009145288A1 (ja) * | 2008-05-29 | 2009-12-03 | 旭硝子株式会社 | TiO2を含有するシリカガラスおよびそれを用いたリソグラフィ用光学部材 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6291377B1 (en) * | 1997-08-21 | 2001-09-18 | Nikon Corporation | Silica glass and its manufacturing method |
TW200940472A (en) * | 2007-12-27 | 2009-10-01 | Asahi Glass Co Ltd | TiO2-containing silica glass |
-
2011
- 2011-02-24 JP JP2012501866A patent/JP5742833B2/ja active Active
- 2011-02-24 WO PCT/JP2011/054192 patent/WO2011105517A1/ja active Application Filing
- 2011-02-24 US US13/575,290 patent/US20120289393A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005022954A (ja) * | 2003-04-03 | 2005-01-27 | Asahi Glass Co Ltd | TiO2を含有するシリカガラスおよびその製造法 |
JP2007182367A (ja) * | 2005-12-08 | 2007-07-19 | Shin Etsu Chem Co Ltd | チタニアドープ石英ガラス、euvリソグラフィ用部材、euvリソグラフィ用フォトマスク基板及びチタニアドープ石英ガラスの製造方法 |
WO2009101949A1 (ja) * | 2008-02-13 | 2009-08-20 | Tohoku University | シリカ・チタニアガラス及びその製造方法、線膨張係数測定方法 |
WO2009145288A1 (ja) * | 2008-05-29 | 2009-12-03 | 旭硝子株式会社 | TiO2を含有するシリカガラスおよびそれを用いたリソグラフィ用光学部材 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102013002802A1 (de) | 2012-02-21 | 2013-08-22 | Asahi Glass Company, Ltd. | Verfahren zur Herstellung von Titandioxid-enthaltendem Quarzglas-Körper |
KR20140094451A (ko) * | 2013-01-22 | 2014-07-30 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Euv 리소그래피용 부재 및 그의 제조 방법, 및 티타니아 도핑 석영 유리 |
KR102178691B1 (ko) | 2013-01-22 | 2020-11-13 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Euv 리소그래피용 부재 및 그의 제조 방법, 및 티타니아 도핑 석영 유리 |
JP2016511211A (ja) * | 2013-02-11 | 2016-04-14 | ヘレウス・クアルツグラース・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンディット・ゲゼルシャフトHeraeus Quarzglas GmbH & Co. KG | EUVリソグラフィに使用されるミラー基板用のTiO2−SiO2ガラスのブランク及びその製造方法 |
KR101922765B1 (ko) * | 2013-02-11 | 2018-11-27 | 헤래우스 크바르츠글라스 게엠베하 & 컴파니 케이지 | EUV 리소그래피에서의 사용을 위한 미러 기판용 TiO2-SiO2 유리의 블랭크 및 그 생산을 위한 방법 |
JP2014164053A (ja) * | 2013-02-22 | 2014-09-08 | Nippon Telegr & Teleph Corp <Ntt> | 光ファイバおよびその作製方法 |
JP2015010877A (ja) * | 2013-06-27 | 2015-01-19 | 日本電信電話株式会社 | 光ファイバの仮想温度の長手方向分布の評価方法 |
JP2017507106A (ja) * | 2014-02-21 | 2017-03-16 | ショット アクチエンゲゼルシャフトSchott AG | 高均一性ガラスセラミック素子 |
JP7038473B2 (ja) | 2014-02-21 | 2022-03-18 | ショット アクチエンゲゼルシャフト | 高均一性ガラスセラミック素子 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2011105517A1 (ja) | 2013-06-20 |
US20120289393A1 (en) | 2012-11-15 |
JP5742833B2 (ja) | 2015-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5742833B2 (ja) | 超低膨張ガラスの製造方法 | |
US7124635B2 (en) | Evaluation method for coefficient of thermal expansion of ultra-low-expansion glass material | |
Kushibiki et al. | Development of the line-focus-beam ultrasonic material characterization system | |
JP5314901B2 (ja) | シリカ・チタニアガラス及びその製造方法、線膨張係数測定方法 | |
JP5626927B2 (ja) | 光学ガラスの仮想温度の測定方法 | |
Kushibiki et al. | Ultrasonic microspectroscopy characterization of silica glass | |
Vlasova et al. | High-sensitive absorption measurement in ultrapure quartz glasses and crystals using time-resolved photothermal common-pass interferometry and its possible prospects | |
Hrdina et al. | Characterization and characteristics of a ULE glass tailored for EUVL needs | |
Kushibiki et al. | A super-precise CTE evaluation method for ultra-low-expansion glasses using the LFB ultrasonic material characterization system | |
JP4560625B2 (ja) | 脈理を有する材料に対する超音波材料特性解析装置校正用標準試料の作製方法 | |
Arakawa et al. | Accurate calibration line for super-precise coefficient of thermal expansion evaluation technology of TiO2-doped SiO2 ultra-low-expansion glass using the line-focus-beam ultrasonic material characterization system | |
Edwards et al. | Improved precision of absolute thermal-expansion measurements for ULE glass | |
Stewart et al. | Infrared emission spectrum of silicon carbide heating elements | |
Kushibiki et al. | Development of an ultrasonic system for super-precise measurement of zero-CTE temperature of EUVL-grade TiO2-SiO2 ultra-low-expansion glasses | |
JP4825972B2 (ja) | 脈理を有する材料の漏洩弾性表面波速度と化学組成比および線膨張係数との関係を求める方法、およびその関係を使ったTiO2−SiO2ガラスのTiO2濃度測定方法および線膨張係数測定方法 | |
Kushibiki et al. | Evaluation of TiO2-SiO2 ultra-low-expansion glass fabricated by the soot method using the line-focus-beam ultrasonic material characterization system | |
Ohashi et al. | Improvement of velocity measurement accuracy of leaky surface acoustic waves for materials with highly attenuated waveform of the V (z) curve by the line-focus-beam ultrasonic material characterization system | |
Kushibiki et al. | Evaluation method of TiO/sub 2/-SiO/sub 2/ultra-low-expansion glasses with periodic striae using the LFB ultrasonic material characterization system | |
JP6372795B2 (ja) | 強化ガラスの表面特性の測定方法 | |
JP7238790B2 (ja) | チタニア含有シリカガラス体の熱膨張特性の評価方法およびチタニア含有シリカガラス体の製造方法 | |
Kushibiki et al. | Homogeneous TiO2–SiO2 Ultralow-Expansion Glass for Extreme Ultraviolet Lithography Evaluated by the Line-Focus-Beam Ultrasonic Material Characterization System | |
Kushibiki et al. | Precise evaluation of zero-CTE temperature of EUVL-grade TiO2-SiO2 ultra-low-expansion glass using the line-focus-beam ultrasonic material characterization system | |
Kushibiki | Development of Super-Precise Evaluation Method for | |
Wei | Acoustic properties of silica glass doped with fluorine | |
JP7050655B2 (ja) | セラミック材料またはガラス質材料の本体内の成分の濃度を測定する方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11747477 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012501866 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13575290 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11747477 Country of ref document: EP Kind code of ref document: A1 |