The present invention relates to glass used in optical applications, such as a lens, a prism and a photomask. In particular, it relates to a method of measuring the fictive temperature that has an effect on the refractive index, the transmittance, the resistance to ultraviolet rays and the expansion coefficient of optical glass.
For example, silica glass has three major advantages of an extremely high transmittance, a high heat resistance and an extremely low metal impurity content and is an indispensable material for semiconductor devices and optical communication cables. Besides, silica-titania (TiO2—SiO2) glass is drawing attention as ultra-low expansion glass used as a substrate material of photomask blanks and reflective optics for extreme ultraviolet lithography (EUVL) systems. The silica glass is generally classified into two types: fused silica glass fabricated by melting a natural crystal powder, and synthetic glass fabricated by chemical synthesis. The fused silica glass can be fabricated in an electric melting method (Type I) that involves electrically melting the natural crystal powder or in a flame melting method (Type II) that involves melting the natural crystal powder in oxyhydrogen flame. The synthetic silica glass can be fabricated by a direct method (Type III) that involves directly depositing fine particles of silica glass by hydrolysis of silicon tetrachloride (SiCl4), octamethylcyclotetrasiloxane (C8H24O4Si4) or the like in oxyhydrogen flame, a plasma method (Type IV) that uses induced plasma of Ar or O2 instead of the oxyhydrogen flame for synthesis, a soot method that involves producing a lump of soot of silica by thermal decomposition of silicon tetrachloride (SiCl4) or the like and then burning the lump of soot, or a sol-gel method that involves producing a gel by hydrolysis and condensation polymerization in a solution containing silicon alkoxide, such as Si(OC2H5)4, water, an alcohol and hydrochloric acid, drying the gel and then heating the gel to cause vitrification.
The synthetic silica glass, which has a low metal impurity content of 10 ppb or less, is used in optical applications, such as a lens, a prism and a photo mask. In general, the optical applications require glass that has a high uniformity of the refractive index and a high transmittance and is free of defects which cause light scattering. Glass used for a lens of a reduction projection exposure system (a stepper) is additionally required to have a high resistance to ultraviolet rays, that is, to be less likely to change in refractive index and decrease in transmittance when the glass is irradiated with ultraviolet rays. The refractive index, the transmittance and the resistance to ultraviolet rays of the synthetic silica glass and the silica-titania glass vary with the concentrations of hydroxyl (OH) and other impurities, or F and Ti as additives added to the glasses in the production process. The concentration of OH trapped in the production process is typically 500 to 2000 [wtppm] for the synthetic silica glass fabricated in the direct method (Type III) and 50 to 200 [wtppm] for the synthetic silica glass fabricated by a vapor-phase axial deposition (VAD) method, which is a kind of soot method, so that it is essential not only to control the concentration of the additives but also to control the OH concentration and other impurities during production.
It is also known that the refractive index, the transmittance and the resistance to ultraviolet rays of the synthetic silica glass are substantially affected by the fictive temperature of the silica glass. Similarly, the temperature at which the expansion coefficient of the silica-titania glass is 0 is also affected by the fictive temperature. Therefore, just controlling the concentrations of the additives and the impurities is not enough, and the fictive temperature needs to be controlled and evaluated. Thus, there is a demand for a method of precisely measuring the fictive temperature that can be introduced into a manufacturing line.
Known methods of measuring the fictive temperature include a method based on the Raman spectroscopic analysis and a method based on the infrared spectroscopic analysis. Non-patent literature 1 discloses a well-known method of measuring the fictive temperature based on the infrared spectroscopic analysis. Non-patent literature 2 discloses a well-known method of measuring the fictive temperature based on the Raman spectroscopic analysis.
Furthermore, as reported in Non-patent literatures 3 and 5, there are known methods of determining the fictive temperature from measurement values of the density of the synthetic silica glass according to the relationship between the density and the fictive temperature.
However, all the conventional fictive temperature measuring methods described above have the following disadvantages:
(1) the measurement precision of the fictive temperature is inadequate, ±15° C. for the infrared spectroscopic analysis and about ±60° C. for the Raman spectroscopic analysis;
(2) the methods need a sample used for measurement of the fictive temperature separately prepared and thus are difficult to introduce into the manufacturing line;
(3) the methods can hardly measure the fictive temperature distribution over the substrate surface; and
(4) the methods yield only the average value for the sample in the case of the density-based fictive temperature evaluation.
Furthermore, the present inventors have already investigated the relationship between the density of the synthetic silica glass and the longitudinal wave velocity, found that there is a linear relationship between them, and reported in Non-patent literature 4 that there is a linear relationship between the longitudinal wave velocity and the fictive temperature determined from the density according to the relationship between the fictive temperature and the density reported in Non-patent literature 3.
In Non-patent literature 3, it is reported that the slope of the dependence of the density on the fictive temperature varies with the chlorine concentration. On the other hand, in Non-patent literature 5, it is reported that the slope of the dependence of the density on the fictive temperature does not vary with the OH concentration. Further investigation has shown that the relationship between the fictive temperature and the density varies in coefficient with the OH concentration of the silica glass, and it is difficult to incorporate density measurement into the manufacturing line. Thus, the present invention has been devised.
An object of the present invention is to overcome the disadvantages of conventional methods of measuring the fictive temperature of optical glass and to provide a method of measuring the fictive temperature of optical glass with higher precision than conventional.
A method of measuring a fictive temperature of optical glass according to a first aspect of the present invention comprises:
(1-A) a step of performing a heat treatment at different temperatures for a plurality of calibration-line forming glass samples having a same composition;
(1-B) a step of measuring any one of a longitudinal wave velocity, an leaky surface acoustic wave (LSAW) velocity and a shear wave velocity of the samples obtained in said step (1-A) as an acoustic property AP1;
(1-C) a step of determining an approximate straight line formula:
T
f
=a×AP1+b
that expresses a relationship between a fictive temperature and the acoustic property AP1 measured in said step (1-B) on an assumption that said heat treatment temperature is the fictive temperature, provided that Tf denotes the fictive temperature, and a and b denote constant; and
(1-D) a step of measuring the acoustic property AP1 of an optical glass sample to be measured having the same composition as said calibration-line forming glass samples and determining the fictive temperature Tf by calculation according to said approximate straight line formula.
A method of measuring a fictive temperature of optical glass according to a second aspect of the present invention comprises:
(2-A) a step of performing a heat treatment at different temperatures for a plurality of calibration-line forming glass samples having a same composition;
(2-B) a step of measuring any one of a longitudinal wave velocity, an LSAW velocity and a shear wave velocity of the samples obtained in said step (2-A) as a first acoustic property AP1 and another of the velocities as a second acoustic property AP2;
(2-C) a step of determining a first approximate straight line formula:
T
f
=a×AP1+b
that approximates a relationship between a fictive temperature and said first acoustic property AP1 on an assumption that said heat treatment temperature is the fictive temperature, provided that Tf denotes the fictive temperature, and a and b denote constants;
(2-D) a step of determining a second approximate straight line formula:
T
f
=c×AP2+d
that expresses a relationship between the fictive temperature Tf determined in said step (2-C) and said second acoustic property AP2, provided that c and d denote constants; and
(2-E) a step of measuring the second acoustic property AP2 of an optical glass sample to be measured having the same composition as said calibration-line forming glass samples and determining the fictive temperature Tf from the measured second acoustic property AP2 according to said second approximate straight line formula.
The present invention provides a method of measuring the fictive temperature of optical glass that can measure the fictive temperature with higher precision than conventional methods of measuring the fictive temperature by one or more orders of magnitude, can measure the fictive temperature of the material in the production line, and can measure the in-plane distribution of the fictive temperature of the sample to be measured.
Of course, the basic principle of the “method of measuring the fictive temperature” according to the present invention can be applied not only to the synthetic silica but also to synthetic silica glass with the properties improved by an appropriate additive (fluorine, germanium, phosphorus, boron or the like), synthetic silica glass containing residual impurities (OH, chlorine or the like), fused silica glass, TiO2—SiO2 glass which is ultra-low expansion glass, and other popular glass materials (such as borosilicate glass and soda lime glass).
In the following, measurement of the fictive temperature of synthetic silica glass as optical glass will be first described.
Table 1 shown in
The samples shown in Table 1 were subjected to a heat treatment in the atmosphere with a high temperature electric furnace. First, to eliminate the thermal history of the samples, each sample was heated to a temperature about 50° C. higher than the annealing point and then held at the temperature for 5 hours (in the following, “hour” will be represented by “h”). Then, the temperature was decreased to a desired heat-treatment temperature TA at a temperature decreasing rate of 5 to 10° C./h, the samples were held at the temperature for a long time to allow for the structural relaxation time of the samples, and then, the samples were cooled in the furnace by turning off the heater. In order to narrow the distribution of the fictive temperature during the heat treatment, each sample was sandwiched between two fused silica glass plates having a size of 70 mm×70 mm×10 mm in the furnace. The four samples of #1 were held at 1050° C., 1100° C., 1150° C. and 1200° C., respectively, and the four samples of #2 were held at 900° C., 1000° C., 1050° C. and 1100° C., respectively.
After the heat treatment, the samples were reformed to be 50 mm×35 mm×10 mm, and the both surfaces having a size of 50 mm×35 mm were optically polished.
The LSAW velocity of the fabricated samples was measured with a line-focus-beam ultrasonic material characterization (LFB-UMC) system at an ultrasonic frequency of 225 MHz. The principle and method of measuring the LSAW velocity is described in detail in Reference literatures 2 and 3. In addition, with a plane-wave ultrasonic material characterization (PW-UMC) system, the longitudinal wave velocity and the shear wave velocity were measured at ultrasonic frequencies of 50 to 250 MHz. The principle and method of measuring the longitudinal wave velocity and the shear wave velocity are described in detail in Reference literature 4. Furthermore, the density ρ was measured according to the Archimedes principle. The measurement was performed based on Reference literature 5. The LSAW velocity measured with the LFB-UMC system varies with the measuring system (the LFB ultrasonic device, in particular) and the measurement frequency, and therefore, the system was calibrated with a standard sample whose longitudinal wave velocity, shear wave velocity and density had already been measured (Reference literature 6).
As reported in Non-patent literature 3, there is a linear relationship between the fictive temperature and the density of the synthetic silica glass.
Table 2 in
The slope of the dependence of the acoustic properties on the fictive temperature is due to the difference in OH concentration and differs between the synthetic silica glasses of #1 and #2 as shown in
T
f
=a×V
L
+b (1)
In this formula, “a” and “b” denote constants determined by the OH concentration of the synthetic silica glass, and the constants a and b of the approximate straight line assume the following values for the data of the samples of #1 and #2 shown in
Sample #1: a=7.294, b=−42295
Sample #2: a=6.549, b=−37871
As can be seen from the above description, if any one of the longitudinal wave velocity, the LSAW velocity and the shear wave velocity, for example, the longitudinal wave velocity, is adopted as the acoustic property, and the approximate straight line expressed by the formula (1) shown in
Although the longitudinal wave velocity is advantageous in that it is highly sensitive to the fictive temperature, measurement of the longitudinal wave velocity involves measuring the thickness of the sample and therefore requires polishing of both surfaces of the sample. Furthermore, to measure the in-plane thickness distribution takes time and effort. To the contrary, the LSAW velocity is convenient in that measurement of the LSAW velocity does not require measurement of the thickness of the sample and therefore can be achieved by polishing only one surface of the sample, and the in-plane distribution thereof can be easily measured. However, as can be seen from
According to the second embodiment, first, for the longitudinal wave velocity, which is sensitive to the fictive temperature, the approximate straight line formula (1) that expresses the relationships between the fictive temperature and the longitudinal wave velocity shown in
T
f
=c×V
LSAW
+d (2)
In this formula, “c” and “d” denote constants determined by the OH concentration of the synthetic silica glass, and the constants c and d in the formula (2) assume the following values for the samples of #1 and #2.
Sample #1: c=144, d=−4.922×105
Sample #2: c=187, d=−6.395×105
With the approximate straight line formula (2) determined in this way, the fictive temperature Tf of the sample to be measured can be calculated from a measurement of the LSAW velocity VLSAW of the sample. In the case of measuring the in-plane distribution of the fictive temperature, the fictive temperature at each point in the plane may be determined from the measurement of the LSAW velocity VLSAW at the point according to the approximate straight line formula (2) expressing the relationships shown in
The LSAW velocity VLSAW(x, y) at a point (x, y) on the surface of the sample to be measured and the LSAW velocity VLSAW-Std and the longitudinal wave velocity VL-Std of a standard sample are measured, and a precise value Tf(VL-Std) of the fictive temperature of the standard sample is determined from the longitudinal wave velocity VL-Std according to the formula (1). In addition, the fictive temperature Tf(VLSAW-Std) of the standard sample and the fictive temperature distribution Tf{VLSAW(x, y)} in the surface of the sample are determined from the LSAW velocities VLSAW-Std and VLSAW(x, y). Provided that
ΔTf(x,y)=Tf{VLSAW(x,y)}−Tf(VLSAW-Std) (3)
the fictive temperature Tf(x, y) at the point (x, y) on the sample to be measured can be determined according to the following formula.
T
f(x,y)=Tf(VL-Std)+ΔTf(x,y) (4)
Furthermore, calibration using the longitudinal wave velocity of the sample is also possible. The longitudinal wave velocity VL-C and the LSAW velocity VLSAW-C at the center of the sample and the LSAW velocity VLSAW(x, y) at the point (x, y) on the surface of the sample are measured. A precise value Tf(VL-C) of the fictive temperature at the center of the sample is determined from the longitudinal wave velocity VL-c according to the formula (1). Furthermore, the fictive temperature Tf(VLSAW-C) at the center of the sample and the fictive temperature distribution Tf{VLSAW(x, y)} in the plane of the sample are determined from the LSAW velocities VLSAW-C and VLSAW(x, y) according to the formula (2). From these values, provided that
ΔTf(x,y)=Tf{VLSAW(x,y)}−Tf(VLSAW-C) (5)
the in-plane distribution Tf(x, y) of the fictive temperature on the surface of the sample can be determined according to the following formula (6).
T
f(x,y)=Tf(VL-C)×ΔT(x,y) (6)
Similarly, the fictive temperature can also be calculated from the shear wave velocity of the sample to be measured according to the approximate straight line formula that expresses the relationships between the shear wave velocity and the fictive temperature shown in
In
In Non-patent literature 5, the dependences of the density ρ and the fictive temperature Tf on the OH concentration were investigated. This investigation has revealed that the absolute value of the density varies with the OH concentration but has not led to a recognition that the slope of the density with respect to the fictive temperature varies. Consequently, the measurement error is significant if the fictive temperature is determined from the measurement of the density ρ according to the conventionally known relationship.
In
For the synthetic silica glass produced under standard manufacturing conditions, the concentrations of impurities, such as OH and chlorine, and the concentrations of additives, such as F and Ti, are known and can be considered as varying less significantly.
Therefore, in the case of the synthetic silica glass fabricated in the standard fabrication process as described above, the fictive temperature can be determined according to the formula (1) simply by measuring the longitudinal wave velocity of the sample to be measured as described in the first embodiment. In general, the longitudinal wave velocity can be determined from the propagation time of the longitudinal wave propagating in the sample to be measured in the thickness direction and the thickness of the sample to be measured. The resolution of the longitudinal wave velocity to the fictive temperature is high. Although parallel polishing of the top surface and the bottom surface of the sample to be measured is needed to measure the longitudinal wave velocity, the polishing requirements on the sample to be measured can be relaxed by decreasing the measurement ultrasonic frequency (to about 10 MHz or lower), and the measurement can be incorporated into a mass production process.
As described above, although the LSAW velocity is less sensitive to the fictive temperature than the longitudinal wave velocity, the LSAW velocity can be measured by performing calibration using the standard sample if the surface of the sample to be measured is flat. In addition, the LFB device used for the measurement of the LSAW velocity can be easily moved along the sample surface, the two-dimensional distribution, that is, the fictive temperature distribution over the sample surface can be measured. In particular, the measurement of the LSAW velocity can be incorporated an early stage a stable mass production line.
The sensitivity of the shear wave velocity to the fictive temperature is lower than that of the longitudinal wave velocity, and the measuring ultrasonic device needs to be bonded to the sample to be measured in order to measure the shear wave velocity. Accordingly, the shear wave velocity is useful in the research and development but is more difficult to introduce into a mass-production line than the LSAW velocity.
Silica-Titania Glass
In the foregoing, a method of measuring the fictive temperature of the synthetic silica glass has been described as an example. In the following, an application of the measurement principle described above to measurement of the fictive temperature of the silica-titania glass will be briefly described.
The present invention was applied to the TiO2—SiO2 ultra-low expansion glass. The commercially available TiO2—SiO2 ultra-low expansion glass was subjected to a homogenization processing and then to a heat treatment at temperatures of 900° C. to 1100° C., as with the SiO2 glass. The TiO2 concentration of the sample used was measured by the fluorescent X-ray analysis (Reference literature 8) and the resultant concentration was 7.02 to 7.14 wt %. The longitudinal wave velocity of the TiO2—SiO2 ultra-low expansion glass depends on the TiO2 concentration, the fictive temperature and the OH concentration and therefore was corrected to the value at 7.00 wt % according to the relationship between the TiO2 concentration and the longitudinal wave velocity (Reference literature 9).
a=7.388, b=−41567
[Flowchart of Fictive Temperature Measurement]
In the following, based on the first and second embodiments described above, a basic procedure of evaluating the fictive temperature of the synthetic silica glass according to the present invention will be described with reference to the flowchart shown in
Step S1: A heat treatment is performed at different temperatures for a plurality of synthetic silica glass samples having the same composition as the sample to be measured to produce calibration-line forming samples having different fictive temperatures.
Step S2: As an acoustic property AP1, any one of the longitudinal wave velocity, the LSAW velocity and the shear wave velocity for the plurality of calibration-line forming samples produced in Step S1 is measured.
Step S3: From the result of the measurement in Step S2, the relationship between the fictive temperature and the acoustic property AP1 is determined in the form of an approximate straight line formula, provided that the heat treatment temperature TA is the fictive temperature Tf in the range where there is a linear relationship between the heat treatment temperature TA and the acoustic property AP1. In the case where the longitudinal wave velocity VL is used as the acoustic property AP1, the formula (1) results.
Step S4: The acoustic property AP1 of the sample to be measured is measured.
Step S5: The fictive temperature is calculated by substituting the measured acoustic property AP1 into the approximate straight line formula.
Steps S1, S2 and S3 are the same as those in the case of the first embodiment except that, in Step S2, another one of the longitudinal wave velocity, the LSAW velocity and the shear wave velocity is measured as an acoustic property AP2 in addition to the acoustic property AP1. The procedure from Step S3 is as follows.
Step S3A: Another approximate straight line formula that expresses a relationship between the fictive temperature Tf determined from the acoustic property AP1 in Step S3 and the acoustic property AP2 measured in Step S2 is determined. In the case where the LSAW velocity is used as the acoustic property AP2, the formula (2) results.
Step S4′: The acoustic property AP2 of the sample to be measured is measured.
Step S5′: The fictive temperature is determined from the measured acoustic property AP2 according to the approximate straight line formula determined in Step S3A.
If the approximate straight line formula (1) or (2) for the calibration-line forming samples fabricated under the same conditions as the sample to be measured is known in advance, the fictive temperature can be determined in Steps S4 and S5 or Steps S4′ and S5′.
According to the present invention, the fictive temperature and the distribution of the fictive temperature of optical glass can be determined with higher precision than conventional and, therefore, glass manufacturers can evaluate the fictive temperature of the fabricated glass, the distribution of the fictive temperature, and the glass fabrication process. The result of the evaluation can be used to improve process conditions for fabricating glass having the fictive temperature and the distribution thereof controlled so as to have desired properties (optical properties, for example).
Number | Date | Country | Kind |
---|---|---|---|
2010-149961 | Jun 2010 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/JP2011/065053 | 6/30/2011 | WO | 00 | 12/18/2012 |