JPH05164692A - Judging method of polymerization degree of resist and judging apparatus thereof - Google Patents

Abstract

PURPOSE:To detect the polymerization degree of a resist formed on a substrate at real time without breaking the resist. CONSTITUTION:Infrared rays projected from an infrared irradiating device 1 are condensed by a first concave mirror 2 and cast to a substrate 3 on a reflecting mirror 4. A resist is applied to the substrate 3. The reflecting light is guided to a vacuum thermocouple 8 via a second concave mirror 5, a prism 6 and a third concave mirror 7. The detected values of infrared rays of the wave number, i.e., 805cm<-1>, 1170cm<-1> before and after the resist is set are compared with each other, thereby to detect when the polymerization of the resist is finished. According to this method, hardening of the resist can be detected at real time without breaking the resist. Moreover, if this apparatus is built in a belt conveyor, the apparatus can be utilized as a line sensor.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for judging the degree of polymerization of resist used in the production of color filters for liquid crystals and a judging apparatus therefor.

[0002]

2. Description of the Related Art In recent years, liquid crystal displays have been used for display on televisions and the like due to the progress of colorization of liquid crystal display devices by adopting color filters. In the manufacture of conventional color filters used in such liquid crystal display devices, pigments are deposited by photolithography and vacuum deposition to display a required color tone on a required portion. As another manufacturing method, a transparent electrode is formed on a transparent glass, a voltage is applied to the transparent electrode, and the transparent glass is immersed in a liquid in which a pigment is dispersed. There is an electrodeposition method that attaches a pigment to. Another manufacturing method is a pigment dispersion method in which a pigment is dispersed in a resist to coat a resist which has already been colored on transparent glass, and a desired pattern is formed by exposure and development steps. The picture element of the conventional color filter for liquid crystal is manufactured by any of the above methods.

Among these color filter manufacturing methods, the color filter manufacturing method by the pigment dispersion method relating to the present invention will be described in more detail. The material used is one in which a pigment is dispersed in a resin (solvent-soluble type), and a polymerizable monomer and a photopolymerization initiator are added to form a resist. The color filter manufacturing process by the pigment dispersion method is based on the following photolithography method. First, the resist prepared as described above is uniformly applied onto a glass substrate. After that, pre-baking is performed to evaporate the solvent contained in the resist. Next,
In order to prevent deterioration of exposure sensitivity due to oxygen desensitization at the time of exposure, an oxygen barrier film is uniformly applied and dried by heating. After drying the oxygen barrier film, the temperature of the glass substrate is returned to room temperature (about 24 ° C.). The patterning required for the color filter is performed by an exposure process using a mask. Since the resist used in the pigment dispersion method is generally a negative type, the portion irradiated with UV light remains. After completion of the exposure step, baking (temperature is around 100 ° C.) called polymerization accelerating heating is performed in order to accelerate the polymerization reaction of the resist. After that, the oxygen barrier film is removed by washing with pure water, and then a pixel pattern of the color filter is formed by development. After patterning, the resist is heated at a high temperature (around 200 ° C.) by post-baking to promote the thermal polymerization reaction of the resist to increase the adhesive force with the glass substrate and increase the polymerization degree of the resist to increase the developing solution and other Improves corrosion resistance to organic solvents. The above steps may be repeated for the number of colors required for the color filter.

[0004]

However, with such a conventional method, the degree of polymerization of the resist cannot be directly grasped. Therefore, for example, when the heating device used in the baking process is temporarily broken, the resist polymerization reaction is sent to the pattern formation process of the next pixel in a state where the polymerization reaction of the resist is not completed, and the expansion and peeling of the picture elements occur during development, Alternatively, there is a problem that peeling occurs due to contact with an organic solvent such as acetone.

Further, if it is desired to know the degree of the polymerization reaction of such a resist, Fourier transform infrared spectroscopic analysis was carried out, but in this case, the resist had to be scraped off from the glass substrate for analysis. A part of the resist film applied to the glass substrate was damaged.

The present invention solves such a problem, without destroying the resist applied on the glass substrate,
It is an object of the present invention to provide a method and an apparatus for judging the degree of polymerization of a resist, which allows the degree of progress of the polymerization reaction to be known in real time.

[0007]

In order to solve this problem, the present invention relates to the C = C bond contained in the acrylic group contained in the resist, which is one of the infrared absorption spectra of the resist to be inspected. Infrared absorption wavelength 800-82
Infrared spectrum intensity A (C = C) appearing at 0 nm, or CH ₂ ═CH of acrylic group contained in the resist
Associated with the above, at least one of the infrared absorption spectrum intensities A (CH ₂ = CH) appearing in the infrared absorption wavelengths 1170 to 1180 nm is extracted, and is the infrared absorption spectrum intensity A immediately after coating the resist on the substrate.
₀ (C = C), A ₀ (CH ₂ = CH), and the infrared absorption spectrum intensity A ₁ (C = C) after a preset curing process for terminating the resist polymerization reaction.
The ratio of A ₁ (CH ₂ = CH) was calculated from (Equation 3) and (Equation 4), respectively, and the termination of the polymerization reaction of the resist was completed when Ψ and Φ reached the preset values Ψ ₀ and Φ _0. The degree of polymerization of the resist is determined according to the determination.

[0008]

[Equation 3]

[0009]

[Equation 4]

Further, an infrared irradiating means, a condensing means for condensing infrared rays from the infrared irradiating means, and a substrate which is provided on the converging surface of the condensing means and has a resist coated on the surface to be inspected From the reflecting mirror to be installed and the infrared rays which are condensed by the condensing means and are reflected on the substrate and then spread out, C
= C, the infrared spectrum intensity A (C = C), which appears in the infrared absorption wavelength 800 to 820 nm, or CH
Infrared absorption wavelengths 1170 to 11 due to the influence of ₂ = CH group
Infrared absorption spectrum intensity A (CH ₂
= CH) for extracting at least one of the above, a detecting means for converting the spectrum intensity extracted by the extracting means into an electric signal, and a spectrum intensity A ₀ (i) immediately after the resist is applied to the substrate. C =
C), A ₀ (CH ₂ = CH) and the spectral intensities A ₁ (C = C), A ₁ (CH ₂ = CH) after a preset curing process for terminating the resist polymerization reaction.
The ratio of is calculated by (Equation 3) and (Equation 4), respectively, and Ψ,
The calculation means is provided for determining the end of the polymerization reaction of the resist when Φ reaches preset values Ψ ₀ and Φ ₀ .

In addition, an infrared irradiating means, a condensing means for condensing infrared rays from the infrared irradiating means, and a surface of an object to be inspected installed on a condensing surface of the condensing means are coated with a resist. The infrared absorption wavelength 800 due to the influence of C = C from the substrate and the infrared rays that have spread after passing through the substrate.
Infrared spectrum intensity A (C =
C), or an extraction means for extracting at least one of the infrared absorption spectrum intensities A (CH ₂ = CH) appearing in the infrared absorption wavelengths 1170 to 1180 nm due to the influence of the CH ₂ ═CH group, and the spectrum intensity extracted by the extraction means. Of the spectrum intensity immediately after the resist is applied to the substrate and the detection means for converting
₀ (C = C), A ₀ (CH ₂ = CH) and spectral intensities A ₁ (C = C), A ₁ (CH ₂ = CH) after a preset curing process for curing this resist. ) Are calculated by (Equation 3) and (Equation 4), respectively, and an arithmetic means for determining the end of the polymerization reaction of the resist when Ψ, Φ reach preset values Ψ ₀ , Φ ₀ are provided. It was done like this.

[0012]

The present invention has the above-mentioned structure and is applied on a substrate.
Irradiated the resist with infrared rays and passed through the resist layer
Reflects infrared rays with a reflector and absorbs infrared rays from the resist
Infrared absorption wavelength 8 due to the effect of C = C in the spectrum
Infrared spectrum intensity A (C
= C), or CH₂= Infrared absorption due to the influence of CH group
Infrared absorption spectrum appearing at wavelengths 1170 to 1180 nm
Torr strength A (CH ₂= CH) at least one of
To ring. And immediately after applying the resist to the substrate
A of each spectrum intensity₀(C = C), A
₀(CH₂= CH) and for hardening this resist in advance
Spectral intensity A after going through the set curing process
₁(C = C), A₁(CH₂= CH) ratio (number)
3), calculated by (Equation 4), Ψ, Φ are preset values
Ψ₀, Φ₀Then the polymerization reaction of the resist was completed.
To determine. Whether the resist polymerization reaction has ended
Value Ψ set in advance to determine whether₀, Φ₀Is next
To decide. For example, Fourier transform infrared spectroscopy
Infrared of resist applied to the substrate to be inspected
Examine the absorption spectrum. Progress of resist polymerization reaction
As the solvent evaporates and the constituents react,
The absorption spectrum changes (for example, "infrared absorption spectrum
Tor-Theory and Application- ", Domain Committee of Chemistry, ed.
Nankodo, pages 27-47). Polymerization of resist
Observe the change in infrared absorption spectrum with the progress of reaction,
Select the infrared absorption spectrum intensity for a specific wave number. Previous
The infrared absorption spectrum intensity selected as described above,
For example, calculation such as taking the sum of them is performed. Resist
The relationship between the degree of polymerization of
To read. To determine the degree of polymerization of the resist,
Organic solvents such as NMP and NMP (N-Methyl-Pyrrolidinone)
It can be judged by conducting a chemical resistance test with
It For example, the degree of polymerization of the resist determined as described above
The value that represents the
If you haven't released it, you can check it. In this way
Map the degree of polymerization of the created resist and the above calculation results.
If this is done, the degree of polymerization of the resist can be promptly calculated from the calculation results.
Can be determined. The present invention has the above-mentioned configuration.
Therefore, the resist applied to the substrate of the inspected object
If the infrared absorption spectrum is known in advance,
The degree of polymerization of the resist can be determined by the above method.

As described above, since the resist coated on the substrate to be inspected is irradiated with infrared rays and the degree of polymerization of the resist is determined from the infrared absorption spectrum, the resist coated on the substrate is destroyed in real time. The degree of polymerization of the resist can be detected.

Further, the resist coated on the substrate is irradiated with infrared rays, the infrared rays passing through the resist layer are reflected by a reflecting mirror, and the absorption spectrum of the transmitted light is detected in the same manner as described above, whereby the degree of polymerization of the resist is determined. Can be detected.

[0015]

EXAMPLES A method for determining the degree of polymerization of a resist and an apparatus for determining the degree of polymerization of a resist according to an example of the present invention will be described below with reference to the drawings, when the degree of polymerization of pixels of a color filter prepared by a pigment dispersion method is used. explain.

(Embodiment 1) FIG. 1 shows the structure of a resist polymerization degree determining apparatus according to Embodiment 1 of the present invention. As shown in FIG. 1, the infrared rays emitted from the infrared irradiation device 1 are condensed by the first concave mirror 2. Since infrared rays are absorbed by the glass, the first concave mirror 2 is formed by depositing a metal such as aluminum on the incident surface of the infrared rays. Reference numeral 3 is a glass substrate coated with a resist which is an object to be inspected, and 4 is a reflecting mirror on which the glass substrate 3 is installed. The glass substrate 3 is placed on the reflecting mirror 4 so that a resist (not shown) serves as an incident surface of infrared rays,
The infrared focal point of the first concave mirror 2 is the glass substrate 3
It is adjusted to be between the upper resist layer (not shown) and the reflecting surface of the reflecting mirror 4. The reflecting mirror 4 is formed by depositing a metal such as aluminum on the incident surface of infrared rays. The second concave mirror 5 collimates the infrared rays again. The prism 6 is the second concave mirror 5
The infrared rays that have become parallel light are decomposed into spectra.
The third concave mirror 7 collects the infrared rays that have passed through the prism 6 and decomposed into spectra. Since infrared rays are absorbed by glass, the third concave mirror 7 is formed by depositing a metal such as aluminum on the incident surface of infrared rays. Reference numeral 8 is a vacuum thermocouple and prism 6
Then, the spectrum intensity of each wave number of the infrared rays condensed by the third concave mirror 7 after being decomposed into a spectrum is converted into an electric signal. The vacuum thermocouple 8 amplifies the electric signal of the spectrum intensity of each wave number by the signal amplifier 9, and the analog / digital converter 1
Digitize with 0. 11 is a computing device, of the electrical signals of the spectral intensity of each wave number that has been digitized by an analog / digital converter 10, the wave number 805cm ^-1 and 1170cm ^-1
Infrared intensity electrical signals A (805), A (1170)
Sample at least one of Where wave number 8
05 cm ^-1 is included in the acrylic group of the resist (C = C)
Infrared absorption region related to binding, wave number 1170 cm ^-1
Corresponds to the infrared absorption region related to CH ₂ ═CH of the acrylic group contained in the resist.

The infrared absorption spectrum intensities A ₀ (805) and A ₀ immediately after coating the resist on the substrate, respectively.
(1170) and the infrared absorption spectrum intensities A ₁ (805) and A ₁ (1170) after a preset curing process for terminating the polymerization reaction of this resist are respectively expressed by (Equation 5) and (Equation 5) Calculate according to 6). The degree of progress of the polymerization reaction of the resist is performed by the following method. When sampling wave number 805 cm ^-1 , ψ is ψ ₀ = 0.6
At the time of 6, when the wave number of 1170 cm ⁻¹ is sampled, it is assumed that the polymerization reaction of the resist is completed when φ becomes φ ₀ = 0.70. When both the wave number of 805 cm ^-1 and the wave number of 1170 cm ^-1 are used, it is assumed that the polymerization reaction of the resist ends when ψ and φ reach 0.66 and 0.70, respectively. Then, the device of the first embodiment has ψ and φ.
Is provided with a means for notifying that the resist polymerization reaction has ended.

[0018]

[Equation 5]

[0019]

[Equation 6]

The operation of the resist polymerization degree determining device configured as described above will be described below with reference to FIGS. 1, 3, 4, and 5.

First, a method of judging the degree of polymerization of the resist will be described. As the resist, a colored resist CRY manufactured by Fuji Hunt Electronics Technology Co., Ltd. was used.

FIG. 3 shows a change in infrared absorption spectrum of the resist as the process progresses. Further, FIG. 4 compares the infrared absorption spectra of the case where the baking is performed at 200 ° C. for 15 minutes and the case of baking for 30 minutes in the post-baking step which is the final step. Further, it can be seen from FIG. 3 that in the infrared absorption spectrum, the infrared absorption spectrum intensities at wave numbers 805 cm ⁻¹ and 1170 cm ⁻¹ change with the progress of the polymerization reaction of the resist. Especially in the post-baking step, the progress of the polymerization reaction due to thermal polymerization is remarkable. Here, the wave number 805 cm ⁻¹ is an infrared absorption region related to the (C═C) bond contained in the acrylic group of the resist, and the wave number 1
170 cm ^-1 corresponds to the infrared absorption region related to the acrylic group CH ₂ = CH group of the resist. Furthermore, FIGS.
It can be seen that there is no change in the infrared absorption spectrum after 15 minutes of baking at 0 ° C.

FIG. 5, of the infrared absorption spectrum that varies with the progress of the resist of the polymerization reaction, there is shown the wavenumber 805cm ^-1 and 1170cm ^-1 which were selected as described above. A ₀ (805) and A ₀ (1) are the infrared absorption spectrum intensities immediately after coating the resist on the substrate.
170) and the infrared absorption spectrum intensities A ₁ (805) and A ₁ (1170) after a preset process for ending the polymerization reaction of the resist are sampled. Then, from a change in the infrared absorption spectrum at a wavenumber of 805cm ^-1 (5), calculating the change in the infrared absorption spectrum at a wavenumber of 1170cm ^-1 from (6). The changes in ψ and φ thus obtained are shown in FIG.

From FIG. 5, when the post-baking temperature is 200 ° C., the value of ψ is ψ ₀ when the heating time exceeds 15 minutes.
= 0.66, the value of φ is constant at φ ₀ = 0.70, and it can be seen that the resist polymerization reaction is completed. Further, even when the post-baking temperature is 200 ° C., when the heating time is 10 minutes, the value of ψ is 0.74, which is larger than ψ ₀ = 0.66, and the value of φ is 0.83, which is larger than φ ₀ = 0.70. Therefore, the polymerization reaction has not been completed.

This will be described with reference to (Table 1).
(Table 1) shows that after the resist polymerized as described above was immersed in an organic solvent left at room temperature of 24 ° C. for 40 minutes,
It is the result of examining the change in appearance. From the results of (Table 1),
The value of ψ calculated from (Equation 5) becomes ψ ₀ = 0.66,
When the value of φ calculated from (Equation 6) becomes φ ₀ = 0.70, it can be judged that the polymerization reaction of the resist is completed.

[0026]

[Table 1]

A method of determining the degree of polymerization of resist by the apparatus for determining degree of polymerization of resist of the present invention will be described with reference to FIG. The infrared light emitted from the infrared irradiation device 1 is
It is condensed by the first concave mirror 2. The glass substrate 3 coated with a resist, which is an object to be inspected, is installed on the reflecting mirror 4 so that a resist (not shown) serves as an incident surface of infrared rays.
The infrared focal point of the first concave mirror 2 is the glass substrate 3
It is adjusted so as to be between the upper resist (not shown) and the reflecting surface of the reflecting mirror 4. In this way, the infrared rays pass through the resist and are reflected by the reflecting mirror 4. At this time, since a part of infrared rays is absorbed by the resist, an infrared absorption spectrum of the resist can be obtained by examining the reflected infrared rays. Further, infrared rays are absorbed by the glass substrate, but some of them are reflected in the resist film, so that an infrared absorption spectrum can be obtained. The reflected light of infrared rays described above is collimated by the second concave mirror 5,
The prism 6 decomposes the spectrum. Further, the third concave mirror 7 collects infrared rays, and the vacuum thermocouple 8 converts the spectrum intensity of each wave number of the infrared absorption spectrum into an electric signal. Further, the electric signal is amplified by the signal amplifier 9 and digitized by the analog / digital converter 10. Arithmetic unit 11
In, among the electric signals of the spectral intensity of each wave number that has been digitized by an analog / digital converter 10, the wave number 805cm ^-1 was set as described above, the electric signal of the infrared absorption spectrum intensity of 1170cm ^-1 A (805) , A (1170)
Sample at least one of Then, the infrared absorption spectrum intensities A ₀ (805) and A ₀ (1170) immediately after the resist is applied to the substrate, and the infrared rays after a preset process for terminating the polymerization reaction of the resist Absorption spectrum intensity A ₁ (8
05), the ratio with A ₁ (1170) is (Equation 5), (Equation 6)
Calculate from The degree of progress of the polymerization reaction of the resist is determined by the method described below. When sampling wave number 805 cm ^-1 , when ψ reaches 0.66, wave number 117
When sampling 0 cm ⁻¹ , it is assumed that the resist polymerization reaction is completed when φ becomes 0.70. When both the wave number of 805 cm ^-1 and the wave number of 1170 cm ^-1 are used, it is assumed that the polymerization reaction of the resist ends when ψ and φ reach 0.66 and 0.70, respectively. Then, it is assumed that the polymerization reaction of the resist ends when ψ and φ reach preset values. Then, a means is provided for notifying that the polymerization reaction of the resist is completed when ψ and φ reach preset values.

In the present embodiment, an example using a colored resist (manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was explained, but the progress of the polymerization reaction and the change of the infrared absorption spectrum were changed in the same manner for other resists. You can look it up.

As described above, according to this embodiment, the infrared absorption spectrum can be detected in the state where the resist is formed on the glass substrate, and when the color filter is formed by the resist, the resist film is not damaged in real time. The degree of cure can be determined by.

(Second Embodiment) A second embodiment of the present invention will be described below with reference to the drawings.

FIG. 4 shows the degree of polymerization of resist in Example 2 of the present invention.
The structure of a determination apparatus is shown. As shown in the figure,
The infrared rays emitted from the table 12 are reflected by the first concave mirror 13.
Is collected. Since infrared rays are absorbed by glass,
The first concave mirror 13 is a metal such as aluminum on the incident surface of infrared rays.
Is vapor-deposited. The glass substrate 14 has a resist layer (not shown).
Is installed so that it becomes the incident surface of infrared rays, and the first concave
The focus position of infrared rays by the surface mirror 13 is on the glass substrate 14.
The position is adjusted so as to be within the resist layer (not shown). 1
Reference numeral 5 is a second concave mirror for converting infrared rays into parallel rays again. 16
Is a prism, and collimated by the second concave mirror 15
Break infrared into spectra. 17 is a third concave mirror
Infrared light that has passed through the prism 16 and has been decomposed into spectra
Focus the line. Since infrared rays are absorbed by glass,
The third concave mirror 17 is a metal such as aluminum on the incident surface of infrared rays.
Is vapor-deposited. 18 is a vacuum thermocouple and is a prism 16
Infrared collected by the third concave mirror after being decomposed into spectra
Converts the spectral intensity of each wave number of the line into an electrical signal. true
The air thermocouple 18 transmits the electric signal of the spectrum intensity of each wave number.
It is amplified by the No. amplifier 19 and is converted by the analog / digital converter 20.
Digitize. 21 is an arithmetic unit, which is an analog / digital
Spectrum strength of each wave number digitized by the converter 22
Of the electrical signal of the degree, wave number 805cm set as described above
^-1, 1170 cm ^-1Electrical signal A (80
5), sampling at least one of A (1170)
To do. Then, the resist polymerization degree determination device of the present embodiment,
Infrared absorption of each resist just after applying it to the substrate
Spectral intensity A₀(805), A₀(1170)
And a preset setting to complete the polymerization reaction of this resist.
Infrared absorption spectrum intensity A after going through a defined process
₁(805), A₁From (1170), ψ according to (Equation 5)
Is calculated by (Equation 6), ψ is 0.66, and φ is
The polymerization reaction of the resist was completed when it reached 0.70.
It is equipped with a means to announce that. The above is the actual one shown in FIG.
The configuration is the same as that of the first embodiment.

The difference from the first embodiment is that the second concave mirror 15 is provided so as to face the substrate 14 to be inspected, which is coated with a resist, and the infrared absorption spectrum of infrared rays passing through the resist film is detected. This is the point where the reflection mirror 4 is omitted. The operation of the resist polymerization degree determining apparatus of the second embodiment having this configuration is the same as that of the first embodiment.

As described above, the resist polymerization degree determining apparatus according to the second embodiment can determine the degree of curing in real time without damaging the resist applied to the substrate.

In Example 1, it was determined that the polymerization reaction of the resist was completed because the values of (Equation 5) and (Equation 6) were 0.66 and 0.70, respectively. Varies depending on the type of resist that is the object to be inspected and the type of organic solvent used in the chemical resistance test.

Further, in Example 1, the infrared spectrum intensity A appearing at an infrared absorption wavelength of 800 to 820 nm in relation to the C = C bond contained in the acrylic group of the resist.
(C = C) and at least one of the infrared absorption spectrum intensities appearing in the infrared absorption wavelength of 1170 to 1180 nm related to the CH ₂ ═CH group of the acrylic group of the resist was extracted, but the acrylic group CH ₂ ═CH of the resist was extracted. Infrared absorption spectral intensities appearing at infrared absorption wavelengths of 1400 to 1430 nm related to the base may be extracted.

Although the prism 7 is used as the spectroscopic means in the first embodiment, the prism 7 may be a crystal plate made of alkali halide or the like.

Although the vacuum thermocouple 9 is used as the detecting means in the first embodiment, a photoconductive cell, a bolometer, a pneumatic, or the like may be used instead of the vacuum thermocouple 9.

Although the substrate is fixed in the first embodiment, the inspection can be performed while moving the substrate.

Further, in the first embodiment, the concave mirror is used as the means for condensing infrared rays or for making parallel rays, but a plurality of lenses may be used.

In Example 2, it was judged that the polymerization reaction of the resist was completed because the values of (Equation 5) and (Equation 6) were 0.66 and 0.70, respectively. Varies depending on the type of resist to be inspected and the organic solvent used in the chemical resistance test.

Further, in Example 2, the infrared spectrum intensity A appearing at an infrared absorption wavelength of 800 to 820 nm in relation to the C = C bond contained in the acrylic group of the resist.
(C = C) and at least one of the infrared absorption spectrum intensities appearing at infrared absorption wavelengths 1170 to 1180 nm related to the acrylic group CH ₂ ═CH group of the resist was extracted, but the acrylic group CH ₂ ═CH group of the resist was extracted. The infrared absorption spectrum intensity appearing in the infrared absorption wavelengths of 1400 to 1430 nm may be extracted.

Although the prism 17 is used as the spectroscopic means in the second embodiment, a crystal plate made of alkali halide or the like may be used instead of the prism 17.

In the second embodiment, the vacuum thermocouple 18 is used as the detecting means, but a photoconductive cell, a bolometer, a pneumatic or the like may be used instead of the vacuum thermocouple 18.

In the second embodiment, the example in which the substrate is fixed has been described, but it is also possible to perform the inspection while moving the substrate.

Further, in the second embodiment, the concave mirror is used as the means for condensing the infrared rays or converting them into parallel rays, but a plurality of lenses may be used.

[0046]

As is apparent from the above description of the embodiments, according to the present invention, the resist coated on the substrate is irradiated with infrared rays to reflect the light from the resist layer or the transmitted light from the resist layer. The degree of polymerization of the resist is determined by detecting the infrared absorption spectrum. Therefore, when the resist polymerization degree determination device according to the present invention is used, the polymerization degree can be determined in real time without damaging the resist film applied on the substrate.

Further, in determining the degree of polymerization, the degree of polymerization can be determined by using reflected light even when a resist, which is an object to be inspected, is applied to a glass substrate having a high infrared absorption rate.

Further, it is sufficient to irradiate the substrate coated with the resist as the inspection object with infrared rays and detect the infrared absorption spectrum of the resist from the reflected light from the resist layer or the transmitted light from the resist layer. It can also be used as an in-line sensor by incorporating it.

[Brief description of drawings]

FIG. 1 is a diagram showing a schematic configuration of a resist polymerization degree determining apparatus according to a first embodiment of the present invention.

FIG. 2 is a diagram showing a schematic configuration of a resist polymerization degree determination device of the second embodiment.

FIG. 3 is a diagram showing a change in infrared absorption spectrum accompanying the curing reaction of the resist.

FIG. 4 is a view showing a change in infrared absorption spectrum of the resist due to post-baking.

[Fig. 5] Wave number 805 cm ^-1 , 1170 cm accompanying the curing reaction
^-1 Diagram showing changes in infrared absorption spectrum intensity ratio

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Infrared irradiation device 2 First concave mirror 3 Substrate coated with resist 4 Reflective mirror 5 Second concave mirror 6 Prism 7 Third concave mirror 8 Vacuum thermocouple

Claims (3)

[Claims] 1. An infrared absorption wavelength range of 800 to 82 in relation to the C═C bond contained in the acrylic group contained in the resist in the infrared absorption spectrum of the resist as the inspection object.
Infrared spectrum intensity A (C = C) appearing at 0 nm, or CH ₂ ═CH of acrylic group contained in the resist
Associated with the above, at least one of the infrared absorption spectrum intensities A (CH ₂ = CH) appearing in the infrared absorption wavelengths 1170 to 1180 nm is extracted, and is the infrared absorption spectrum intensity A immediately after coating the resist on the substrate.
₀ (C = C), A ₀ (CH ₂ = CH), and the infrared absorption spectrum intensity A ₁ (C = C) after a preset curing process for terminating the resist polymerization reaction.
The ratio of A ₁ (CH ₂ = CH) was calculated from (Equation 1) and (Equation 2), respectively, and the termination of the polymerization reaction of the resist was completed when Ψ and Φ reached the preset values Ψ ₀ and Φ _0. Judgment method of resist polymerization degree. [Equation 1] [Equation 2] 2. An infrared irradiating means, a condensing means for condensing infrared rays emitted from the infrared irradiating means, and a substrate provided on the condensing surface of the condensing means and having a surface coated with a resist. In relation to the C = C bond contained in the acrylic group contained in the resist, the infrared absorption wavelength range from 800 to 820 nm At least 1 of the infrared spectrum intensity A (C = C) appearing in the above, or the infrared absorption spectrum intensity A (CH ₂ = CH) appearing at infrared absorption wavelengths 1170 to 1180 nm related to CH ₂ ═CH of the acrylic group contained in the resist. 2. An extraction unit for extracting one of the two, and a detection unit for converting the infrared absorption spectrum intensity extracted by the extraction unit into an electric signal. An apparatus for determining the degree of polymerization of resist, which is provided with a calculation means for determining the end of the polymerization reaction of the resist by the method described. 3. An infrared irradiating means, a condensing means for condensing infrared rays from the infrared irradiating means, and a resist which is a test object installed on a condensing surface of the condensing means, is coated with a resist. And the C contained in the acrylic group contained in the resist from the infrared rays spread after passing through the substrate.
Infrared spectrum intensity A (C = C) that appears in the infrared absorption wavelength of 800 to 820 nm in relation to the ═C bond, or in the infrared absorption wavelength of 1170 to 1180 nm that relates to the CH ₂ ═CH bond of the acrylic group contained in the resist. The method according to claim 1, comprising extraction means for extracting at least one of the infrared absorption spectrum intensities A (CH ₂ = CH), and detection means for converting the infrared absorption spectrum intensities extracted by the extraction means into an electric signal. An apparatus for judging the degree of polymerization of resist, which is provided with a calculating means for judging the end of the polymerization reaction of the resist.