JP2009023967A - Method for producing alicyclic saturated hydrocarbon compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an alicyclic saturated hydrocarbon compound by using a purification method of using an adsorbent, removing impurities contained in the alicyclic saturated hydrocarbon compound suitable as a liquid immersion light exposure and excellent in transmittance at 193 nm, in a good efficiency, and having good reproducibility and a stable optical property. <P>SOLUTION: This alicyclic saturated hydrocarbon compound having ≥99% mean value of transmittance per 1 mm optical path length of the liquid at 193 nm with ≤0.1 3σ values is produced by bringing 1,1'-bicyclohexyl, exo-tetrahydrodicyclopentadiene or trans-decahydronaphthalene becoming a raw material, into contact with an adsorbent in an inert gas atmosphere having ≤0.1 vol.% oxygen concentration and ≤1 vol. ppm hydrocarbon concentration. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an alicyclic saturated hydrocarbon compound, and more particularly to a production method capable of improving the transmittance for use in an immersion exposure apparatus or an immersion exposure method.

Stepper-type or step-and-scan projection exposure that transfers a reticle pattern as a photomask to each shot area on a photoresist-coated wafer via a projection optical system when manufacturing semiconductor elements, etc. The device is in use.
The theoretical limit value of the resolution of the projection optical system provided in the projection exposure apparatus becomes higher as the exposure wavelength used is shorter and the numerical aperture of the projection optical system is larger. For this reason, with the miniaturization of integrated circuits, the exposure wavelength, which is the wavelength of radiation used in the projection exposure apparatus, has become shorter year by year, and the numerical aperture of the projection optical system has also increased.
As described above, in the field of manufacturing semiconductor devices and the like, conventionally, the exposure light source has been shortened in wavelength and the numerical aperture has been increased to meet the demand for miniaturization of an integrated circuit. At present, an ArF excimer laser (wavelength: 193 nm) is used as an exposure light source. ) Using 1L1S (1: 1 line and space) half pitch 90 nm node is under study. However, it is said that it is difficult to achieve the next generation half pitch 65 nm node or 45 nm node, which is further miniaturized, only by using an ArF excimer laser. Thus, for these next-generation technologies, the use of short-wavelength light sources such as F ₂ excimer laser (wavelength 157 nm), EUV (wavelength 13 nm), etc. is being studied. However, the use of these light sources is technically difficult and is still difficult to use.

In the above exposure technique, a photoresist film is formed on the exposed wafer surface, and a pattern is transferred to the photoresist film. In a conventional projection exposure apparatus, a space in which a wafer is placed is filled with air or nitrogen having a refractive index of 1.
Theoretically, the limit value of resolution and the depth of focus are increased to 1 / n and n times, respectively, by filling a liquid of refractive index n between the lens of the projection exposure apparatus and the wafer and setting an appropriate optical system. Is possible. For example, in the ArF process, when water is used as the liquid filled between the lens and the wafer, the refractive index n of water having a wavelength of 193 nm in water is n = 1.44. In comparison, it is theoretically possible to design an optical system with a resolution of 69.4% and a focal depth of 144%.
A projection exposure method capable of shortening the effective wavelength of radiation for exposure and transferring a finer pattern is referred to as immersion exposure, and for future miniaturization of lithography, particularly lithography of several tens of nanometers, It is considered an essential technology.

In the immersion exposure method, the applicant of the present invention has a refractive index larger than that of pure water conventionally used as a liquid for immersion exposure, and has excellent transparency, and a photoresist film or its upper layer film component (especially hydrophilic layer). Liquid) that can prevent elution and dissolution of the active ingredient), suppress the defects during resist pattern generation without eroding the lens, and can form patterns with better resolution and depth of focus when used as an immersion liquid. As a result of investigating various compounds for the purpose of providing immersion exposure liquids, we have filed applications for alicyclic saturated hydrocarbon compounds that have low absorption in the far ultraviolet region and have a high refractive index suitable as immersion exposure liquids. (Patent Document 1).
However, when an alicyclic saturated hydrocarbon compound synthesized by a known method or available on the market is used as a liquid for immersion exposure, it generally has a large absorption in the far ultraviolet region. There are cases where problems such as degradation of throughput due to decrease in throughput due to reduction, optical image defocus and distortion due to refractive index fluctuation due to heat generation of liquid due to light absorption of liquid, degradation of pattern shape, etc. due to defocus of optical image there were.

Absorption in the far-ultraviolet region is a compound having a carbon-carbon unsaturated bond or an aromatic ring, which has a large influence on the transmittance even in a very small amount, and a compound having a functional group such as a carbonyl group or a hydroxyl group as impurities. The alicyclic saturated hydrocarbon compound is considered to be slightly present, and therefore includes a plurality of sulfuric acid washing treatment steps having different treatment temperatures, and at least the final sulfuric acid washing treatment step has a treatment temperature higher than that of the washing treatment step. The present inventors have already proposed a method characterized by processing at a processing temperature lower than the processing temperature of the previous processing step (Patent Document 2). Moreover, the method of refine | purifying an alicyclic saturated hydrocarbon compound using an adsorbent is disclosed (patent documents 3 and 4).
However, even with the above purification method, there are problems that the transmittance at 193 nm of the alicyclic saturated hydrocarbon compound is not sufficiently improved, and the man-hours are complicated. For example, in the method of Patent Document 3, the transmittance at 193 nm cannot be increased to 99% or more per 1 mm of the optical path length. Further, the method of Patent Document 4 has a problem that two kinds of adsorbents must be used to increase the transmittance. Furthermore, the methods of Patent Document 3 and Patent Document 4 have a problem that when an attempt is made to industrially manufacture a liquid for immersion exposure, an alicyclic saturated hydrocarbon compound cannot be efficiently treated with an adsorbent. In industrialization, there has been a demand for a method for producing a liquid for immersion exposure that has good reproducibility and stable optical properties.
WO2005 / 114711 Japanese Patent Application No. 2006-329265 WO2005 / 119371 WO2006 / 115268

  The present invention has been made to cope with such problems, and is a purification method using an adsorbent, and is contained in an alicyclic saturated hydrocarbon compound suitable as an immersion exposure liquid excellent in transmittance at 193 nm. It is an object of the present invention to provide a method for producing a liquid for immersion exposure that efficiently removes impurities, is reproducible, and has stable optical properties.

Various studies were made on the removal of impurities contained in the alicyclic saturated hydrocarbon compound efficiently and reproducibly with a refining method using an adsorbent.
In the purification method using an adsorbent, not only the type of adsorbent, but also the atmosphere during purification is an important factor that determines the purification capability of the adsorbent. For example, in the case of purification in the atmosphere, oxygen contained in the atmosphere dissolves in the liquid, thereby deteriorating the transmittance at 193 nm. Therefore, a deoxygenation step is required after purification using an adsorbent. Further, impurities contained in the atmosphere are also dissolved in the liquid and adsorbed by the adsorbent, which may cause a reduction in the purification capacity of the adsorbent. By making the atmosphere at the time of purification inert gas, there is no need for a deoxygenation step after purification, and even if the purification treatment is performed multiple times, the variation in transmittance at 193 nm is smaller than when performed in the atmosphere. I found out that I can do it.
The present invention has been made based on the above findings. That is, in the method for producing an alicyclic saturated hydrocarbon compound of the present invention, an average of transmittance per 1 mm of optical path length of a liquid at a wavelength of 193 nm is obtained by bringing an alicyclic saturated hydrocarbon compound as a raw material into contact with an adsorbent. A method for producing an alicyclic saturated hydrocarbon compound having a value of 99% or more and a 3σ value of 0.1 or less, wherein the alicyclic saturated hydrocarbon compound used as a raw material is the above in an inert gas atmosphere It includes a step of contacting with an adsorbent.
The inert gas has an oxygen concentration of 0.1% by volume or less and a hydrocarbon concentration of 1 volume ppm or less.
The alicyclic saturated hydrocarbon compound is at least one alicyclic saturated hydrocarbon compound selected from 1,1′-bicyclohexyl, exo-tetrahydrodicyclopentadiene, and trans-decahydronaphthalene. It is characterized by.
The adsorbent is at least one adsorbent selected from alumina, silica alumina, and zeolite.
In the combination of the alicyclic saturated hydrocarbon compound and the adsorbent, when the alicyclic saturated hydrocarbon compound is 1,1′-bicyclohexyl or exo-tetradicyclopentadiene, the adsorbent is silica alumina and It is at least one adsorbent selected from zeolite, and in the case of trans-decahydronaphthalene, it is characterized by being at least one adsorbent selected from alumina, silica alumina and zeolite.
The purity of the alicyclic saturated hydrocarbon compound used as the raw material by gas chromatography (hereinafter abbreviated as GC purity) is 99% by mass or more.

Since the production method of the present invention includes a step of bringing the raw material alicyclic saturated hydrocarbon compound into contact with the adsorbent in an inert gas atmosphere, a deoxygenation step after purification is not required, and a very small amount of impurities can be efficiently obtained. Can be removed. Further, even if the purification treatment is performed a plurality of times, the variation in transmittance at 193 nm can be made smaller than that in the case of being performed in the atmosphere.
By using an alicyclic saturated hydrocarbon compound purified by this production method, heat generation due to light absorption can be suppressed, and defocusing, distortion, or defocusing of the optical image due to refractive index variation. Problems such as resolution and pattern shape deterioration due to the above can be suppressed.

The alicyclic saturated hydrocarbon compound produced by the production method of the present invention has a light transmittance at a wavelength of 193 nm of 99% or more per 1 mm of the optical path length of the liquid.
Between the transmittance T per 1 mm of the optical path length and the absorbance A per 1 cm of the optical path length,

T (%) = 100 × 10 ^{−0.1 A}

Therefore, a transmittance of 99% or more per 1 mm of the optical path length corresponds to an absorbance of 0.0437 or less per 1 cm of the optical path length.
In the production method of the present invention, the transmittance is a value expressed as an average value of a plurality of measurement results. Further, the 3σ value is 0.1 or less. Here, the σ value is a standard deviation of the measurement sample calculated on the assumption that the measured value of transmittance has a normal distribution. Preferably, the number of measurements is a statistical value of 5 or more.
When the average value of transmittance and the 3σ value are within the above ranges, heat generation due to light absorption can be suppressed, and the resolution and pattern due to defocusing or distortion of the optical image due to refractive index fluctuations, or defocusing of the optical image. Problems such as shape deterioration can be suppressed with good reproducibility.

The contact between the alicyclic saturated hydrocarbon compound as the raw material and the adsorbent is performed by immersing the adsorbent in the raw material compound for an appropriate time, stirring the adsorbent and the raw material compound for an appropriate time, and adsorbing the adsorbent to the column. A column chromatography method in which the raw material compound is allowed to pass through is packed.
The contact with the adsorbent is preferably performed a plurality of times. Specific examples include a method in which an adsorbent is immersed or adsorbed and filtered in a raw material compound for an appropriate time, and then the adsorbent is immersed or adsorbed and filtered in place of a new adsorbent, and a method using a plurality of columns. The plurality of columns are preferably used by preparing two or more unused columns and connecting them in series. The column shape may be the same or different. It is preferable to use two or more columns packed with the same adsorbent because of easy quality control of the adsorbent. This is because when a plurality of adsorbents are used, as much effort is required for quality control as the number of adsorbent types.

The column is a container filled with an adsorbent. Preferably, it is a cylindrical container having openings at both ends, and is a container in which an alicyclic saturated hydrocarbon compound as a raw material is introduced from one opening and the purified product can be recovered from the other opening. The packing ratio (100ρ _b / ρ _p ) calculated from the particle density (ρ _p (g / cm ³ )) and bulk density (ρ _b (g / cm ³ )) of the adsorbent packed in the column is 15% or more. Is preferred. The particle density ρ _p can be measured using a pycnometer, and the bulk density ρ _b (g / cm ³ ) can be calculated as the mass of the adsorbent per unit volume when an adsorbent is placed in the column.

The adsorbent that can be used in the present invention is alumina, silica alumina, zeolite, or an oxide obtained by combining these.
Alumina is an oxide whose composition formula is represented by Al ₂ O ₃ . Silica alumina is called amorphous silica-alumina, and zeolite is called crystalline aluminosilicate.
When the adsorbent that can be used in the present invention is evaluated by the following method, the ratio between the absorbance after contacting with the adsorbent and the absorbance of the alicyclic saturated hydrocarbon compound before contacting with the adsorbent is 1.1 or less can be used.
<Evaluation method>
30 ml of alicyclic saturated hydrocarbon compound of 0.0437 or less per 1 cm of optical path length of liquid at a wavelength of 193 nm is put in a glass container, and 1.5 g of adsorbent is added to this alicyclic saturated hydrocarbon compound to form nitrogen. Let stand at 25 ° C. for 72 hours under atmosphere. The absorbance (A) before contact with the adsorbent and the absorbance (B) after contact are measured with light having a wavelength of 193 nm, and the absorbance ratio (B / A) is calculated.

  For use in the present invention, the adsorbent is preferably calcined before use at a temperature of 200-500 ° C, preferably 250-500 ° C. In the case of firing below 200 ° C. or unfired, the above evaluation value cannot be achieved.

In the production method of the present invention, an alicyclic saturated hydrocarbon compound as a raw material is brought into contact with the adsorbent in an inert gas atmosphere.
The inert gas that can be used in the present invention refers to a gas that does not decrease the transmittance of the compound at 193 nm by contact with an alicyclic saturated hydrocarbon compound at 25 ° C. under atmospheric pressure.
Examples of the inert gas include noble gases such as helium and argon, nitrogen gas, and the like. Nitrogen gas is preferred because of its ease of industrial use.
Moreover, it is preferable that the said inert gas does not contain the component used as the factor which reduces the transmittance | permeability of an alicyclic saturated hydrocarbon compound. Examples of components that lower the transmittance include oxygen and hydrocarbons (particularly unsaturated hydrocarbons).
In the production method of the present invention, an inert gas having an oxygen concentration of 0.1 volume% or less and a hydrocarbon concentration of 1 volume ppm or less, particularly an oxygen concentration of 0.1 volume% or less, and a hydrocarbon concentration of 1 volume ppm or less. Nitrogen gas is preferred. By contacting the adsorbent with an alicyclic saturated hydrocarbon compound as a raw material in an atmosphere of nitrogen gas having an oxygen concentration of 0.1 vol% or less and a hydrocarbon concentration of 1 vol ppm or less, the average value of the transmittance Is 99% or more, and an alicyclic saturated hydrocarbon compound having a 3σ value of 0.1 or less is obtained.
The oxygen concentration can be measured by atmospheric pressure ionization mass spectrometry, and the hydrocarbon concentration can be measured by gas chromatography with a flame ionization detector.

In the purification method using the adsorbent, the alicyclic saturated hydrocarbon compound used as a raw material is at least one fat selected from 1,1′-bicyclohexyl, exo-tetrahydrodicyclopentadiene, and trans-decahydronaphthalene. A cyclic saturated hydrocarbon compound is preferable because the transmittance is easily set to 99% / mm or more by the production method of the present invention.
Moreover, it is preferable that GC purity before making the alicyclic saturated hydrocarbon compound used as a raw material contact an adsorbent is 99 mass% or more. The GC purity can be measured with an Agilent 6890 gas chromatography system, a column (TC1701), a carrier gas (helium), and a detector (TCD).

The combination of the alicyclic saturated hydrocarbon compound and the adsorbent is such that when the alicyclic saturated hydrocarbon compound is 1,1′-bicyclohexyl or exo-tetrahydrodicyclopentadiene, the adsorbent is silica alumina, zeolite, or these This mixture is preferable because the impurities contained in the alicyclic hydrocarbon compound as a raw material can be efficiently removed.
Further, when the alicyclic saturated hydrocarbon compound is trans-decahydronaphthalene, the impurities contained in the alicyclic hydrocarbon compound from which alumina, silica alumina, zeolite, or a mixture thereof is used as a raw material can be efficiently removed. It is preferable because it can be removed.

Since the alicyclic saturated hydrocarbon compound produced by the method of the present invention has little elution of volatile impurities, particularly the resist components, the optical properties are recovered with good reproducibility by performing recovery and purification by a simple method. Can be reused.
As a purification method in the case of reusing, a method such as washing with water, acid washing (sulfuric acid washing), alkali washing, precision distillation, purification using an appropriate filter (packed column), filtration, etc., and the above-described method of the present invention Examples thereof include a purification method or a method using a combination of these purification methods. Among these, it is preferable to carry out purification by the purification treatment, water washing treatment, alkali washing, acid washing, precision distillation, oxide adsorption or a combination of these purification methods according to the method of the present invention.
The above alkali cleaning removes the acid generated by the exposure eluted in the immersion exposure liquid, the acid cleaning removes the basic components in the resist eluted in the immersion exposure liquid, and the water washing process elutes in the immersion exposure liquid. It is effective for removal of a photoacid generator, a basic additive, and an eluate such as an acid generated during exposure in the resist film.
The method for producing an alicyclic saturated hydrocarbon compound disclosed in the present invention is also effective in the above recovery and purification, and is caused by the decomposition of an acid-dissociable protecting group in a resin or irradiation of a liquid with radiation by this method. Since removal of impurities having carbon and carbon unsaturated bonds, which are photoreaction products, can be effectively performed, fluctuations in transmittance can be prevented.
In addition, precision distillation can be performed at the time of purification. Precision distillation is effective for removing low-volatile compounds among the above additives, and is effective for removing hydrophobic components generated by the decomposition of protecting groups in the resist during exposure.

The photoresist film or the photoresist film on which the upper layer film for immersion is formed is irradiated with radiation through a mask having a predetermined pattern using the alicyclic saturated hydrocarbon compound produced in the present invention as a medium, and then developed. Thus, a resist pattern can be formed.
The radiation used for immersion exposure depends on the photoresist film used and the combination of the photoresist film and the upper layer film for immersion, for example, visible rays; ultraviolet rays such as g rays and i rays; Various types of radiation such as ultraviolet rays; X-rays such as synchrotron radiation; and charged particle beams such as electron beams can be selectively used. In particular, an ArF excimer laser (wavelength 193 nm) or a KrF excimer laser (wavelength 248 nm) is preferable.

Examples are shown below. In addition, in a glove box with a nitrogen atmosphere controlled to have a light absorbance of 0.5 ppm or less, liquids were sampled in cells with optical path lengths of 1 cm and 2 cm with a lid made of polytetrafluoroethylene, and JASCO-V7100 manufactured by JASCO Corporation was used. The absorbance was measured using the cell containing the liquid as a sample and air as a reference, and the difference between the two was defined as the absorbance per 1 cm. The measurement temperature is 23 ° C. Based on this value, the transmittance per mm was calculated according to Lambert Beer's law. If the transmitted light intensity of the sample is l ₀ and the transmitted light intensity of the reference is l, the absorbance is expressed as log ₁₀ (l ₀ / l). The values in the table shown in each example are values obtained by correcting the reflection of the cells by calculation.

The following adsorbents were used. Each adsorbent was used after baking at 500 ° C. for 3 hours.
Silica alumina: N633L, manufactured by JGC
Zeolite-1: HSZ-341NHA manufactured by Tosoh Corporation
Zeolite-2: manufactured by Tosoh Corporation, F-9
Alumina: Sumitomo Chemical Co., Ltd., KHD-12

Example 1
In an atmosphere of nitrogen (oxygen concentration 50 ppm, hydrocarbon concentration 0.1 ppm), after adsorption filtration using 4 g of silica alumina to 100 ml of 1,1′-bicyclohexyl having a GC purity of 99.9% by mass, 193 nm The transmittance was measured and was 95.50% / mm.
The adsorbed and filtered liquid was newly adsorbed and filtered using 1 g of silica alumina, and the transmittance at 193 nm was measured to be 99.54% / mm.
The average transmittance of 5 lots obtained by carrying out this purification step 5 times in total was 99.54% / mm, and 3σ was 0.044% / mm.

Example 2
In an atmosphere of nitrogen (oxygen concentration 50 ppm, hydrocarbon concentration 0.1 ppm), after adsorption filtration using 5 g of zeolite-2 against 100 ml of 1,1′-bicyclohexyl having a GC purity of 99.9% by mass, The transmittance at 193 nm was measured and found to be 95.75% / mm.
The adsorption-filtered liquid was newly adsorbed and filtered using 2 g of zeolite-2, and the transmittance at 193 nm was measured. As a result, it was 99.54% / mm.
The average transmittance of 5 lots obtained by carrying out this purification step 5 times in total was 99.54% / mm, and 3σ was 0.045% / mm.

Example 3
In an atmosphere of nitrogen (oxygen concentration 50 ppm, hydrocarbon concentration 0.1 ppm), after adsorption filtration using 5 g of zeolite-1 against 100 ml of exo-tetradicyclopentadiene having a GC purity of 99.9% by mass, 193 nm The transmittance was measured and found to be 97.61% / mm.
The adsorption-filtered liquid was newly adsorbed and filtered using 5 g of zeolite-1, and the transmittance at 193 nm was measured. As a result, it was 99.75% / mm.
The average transmittance of 5 lots obtained by carrying out this purification step 5 times in total was 99.75% / mm, and 3σ was 0.056% / mm.

Example 4
Under an atmosphere of nitrogen (oxygen concentration 50 ppm, hydrocarbon concentration 0.1 ppm), after adsorption filtration using 5 g of zeolite-1 against 100 ml of trans-decahydronaphthalene having a GC purity of 99.9% by mass, The transmittance was measured and found to be 91.20% / mm.
The adsorption-filtered liquid was newly adsorbed and filtered using 5 g of zeolite-1, and the transmittance at 193 nm was measured and found to be 98.70% / mm.
Further, the liquid was adsorbed and filtered using 5 g of zeolite-1 and the transmittance at 193 nm was measured and found to be 99.11% / mm.
The average transmittance of 5 lots obtained by carrying out this purification step 5 times in total was 99.10% / mm, and 3σ was 0.039% / mm.

Example 5
In an atmosphere of nitrogen (oxygen concentration: 50 ppm, hydrocarbon concentration: 0.1 ppm), after performing adsorption filtration using 5 g of alumina with respect to 100 ml of trans-decahydronaphthalene having a GC purity of 99.9% by mass, the transmittance at 193 nm Was measured and found to be 91.40% / mm.
The adsorption-filtered liquid was newly adsorbed and filtered using 5 g of alumina, and the transmittance at 193 nm was measured and found to be 98.50% / mm.
Further, the liquid was adsorbed and filtered using 5 g of zeolite-1 and measured for transmittance at 193 nm. As a result, it was 99.07% / mm.
The average transmittance of 5 lots obtained by carrying out this purification step 5 times in total was 99.06% / mm, and 3σ was 0.052% / mm.

Comparative Example 1
Under atmospheric pressure, adsorption filtration was performed using 5 g of silica alumina to 100 ml of 1,1′-bicyclohexyl having a GC purity of 99.9% by mass, followed by deoxygenation by nitrogen bubbling and measuring the transmittance at 193 nm. As a result, it was 96.24% / mm.
The adsorbed and filtered liquid was newly adsorbed and filtered using 5 g of silica alumina, deoxygenated by nitrogen bubbling, and the transmittance at 193 nm was measured. As a result, it was 98.89% / mm.
Further, this liquid was adsorbed and filtered using 5 g of silica alumina, deoxygenated by nitrogen bubbling, and the transmittance at 193 nm was measured. As a result, it was 99.34% / mm.
The average transmittance of 5 lots obtained by carrying out this purification step 5 times in total was 99.42% / mm, and 3σ was 0.318% / mm.

Comparative Example 2
In the atmosphere, adsorption filtration was performed using 5 g of zeolite-1 with respect to 100 ml of trans-decahydronaphthalene having a GC purity of 99.9% by mass, followed by deoxygenation by nitrogen bubbling, and the transmittance at 193 nm was measured. However, it was 88.31% / mm.
The adsorbed and filtered liquid was newly adsorbed and filtered using 5 g of zeolite-1, deoxygenated by nitrogen bubbling, and the transmittance at 193 nm was measured. As a result, it was 95.38% / mm.
Further, the liquid was adsorbed and filtered with 5 g of zeolite-1 and then deoxygenated by nitrogen bubbling. The transmittance at 193 nm was measured and found to be 98.12% / mm.
Further, this liquid was adsorbed and filtered using 5 g of zeolite-1 again, deoxygenated by nitrogen bubbling, and the transmittance at 193 nm was measured. As a result, it was 99.03% / mm.
The average transmittance of 5 lots obtained by carrying out this purification step 5 times in total was 98.96% / mm, and 3σ was 0.343% / mm.

  From Examples 1-5 and Comparative Examples 1-2, 1,1′-bicyclohexyl, exo-tetradicyclopentadiene, trans-decahydronaphthalene was brought into contact with an adsorbent in an inert gas atmosphere to obtain 193 nm. As compared with the comparative example in which the same operation was performed in the atmosphere, the transmittance in the liquid crystal was 99% / mm or more, and the variation in the transmittance of the liquid obtained was reduced, and the number of contact processes was reduced, and the deoxygenation process I could omit it.

  In the method for producing an alicyclic saturated hydrocarbon compound of the present invention, the average value of the transmittance per 1 mm of the optical path length of a liquid at a wavelength of 193 nm is obtained by bringing the alicyclic saturated hydrocarbon compound as a raw material into contact with an adsorbent. 99% or more and a method for producing an alicyclic saturated hydrocarbon compound having a 3σ value of 0.1 or less, the alicyclic saturated hydrocarbon compound used as a raw material in the inert gas atmosphere. In this way, the liquid contained in the alicyclic saturated hydrocarbon compound can be efficiently removed, and the liquid for immersion exposure having good reproducibility and stable optical properties can be produced. Therefore, it can be used very suitably as a liquid used in immersion exposure, which is an essential technique for manufacturing semiconductor devices that are expected to be further miniaturized in the future.

Claims (8)

By bringing the alicyclic saturated hydrocarbon compound as a raw material into contact with the adsorbent, the average value of the transmittance per 1 mm of the optical path length of the liquid at a wavelength of 193 nm is 99% or more, and the 3σ value is 0.1 or less. A method for producing an alicyclic saturated hydrocarbon compound comprising:
The manufacturing method of the alicyclic saturated hydrocarbon compound characterized by including the process of making the alicyclic saturated hydrocarbon compound used as the said raw material contact with the said adsorption agent in inert gas atmosphere.   2. The alicyclic saturated hydrocarbon compound according to claim 1, wherein the inert gas has an oxygen concentration of 0.1 vol% or less and a hydrocarbon concentration of 1 vol ppm or less. Production method.   The alicyclic saturated hydrocarbon compound is at least one alicyclic saturated hydrocarbon compound selected from 1,1′-bicyclohexyl, exo-tetrahydrodicyclopentadiene, and trans-decahydronaphthalene. A method for producing an alicyclic saturated hydrocarbon compound according to claim 1 or 2.   4. The method for producing an alicyclic saturated hydrocarbon compound according to claim 1, wherein the adsorbent is at least one adsorbent selected from alumina, silica alumina, and zeolite. .   5. The alicyclic saturated hydrocarbon compound is 1,1′-bicyclohexyl, and the adsorbent is at least one adsorbent selected from silica alumina and zeolite. The manufacturing method of alicyclic saturated hydrocarbon compound of description.   5. The alicyclic saturated hydrocarbon compound is exo-tetradicyclopentadiene, and the adsorbent is at least one adsorbent selected from silica alumina and zeolite. Of producing an alicyclic saturated hydrocarbon compound.   The method for producing an alicyclic saturated hydrocarbon compound according to claim 3, wherein the alicyclic saturated hydrocarbon compound is trans-decahydronaphthalene.   The alicyclic saturated hydrocarbon compound according to any one of claims 1 to 7, wherein the purity of the alicyclic hydrocarbon compound as the raw material by gas chromatography is 99% by mass or more. Production method.