CN1943013A - Liquid for immersion exposure and immersion exposure method - Google Patents

Abstract

The object of the present invention is to provide an immersion solution that has a refractive index greater than that of pure water, prevents the elution or dissolution of the photoresist film or its upper layer film components, and can suppress defects when the resist pattern is formed in the immersion solution exposure method. Liquid for exposure, and liquid immersion exposure method using the liquid. An exposure liquid for liquid immersion, which is used in a liquid immersion exposure device or a liquid immersion exposure method for exposing through a liquid filled between a lens of a projection optical system and a substrate, and is a liquid in the temperature range in which the liquid immersion exposure device operates , is a cyclic hydrocarbon compound containing an alicyclic hydrocarbon compound or a silicon atom in the ring structure.

Description

Liquid for immersion exposure and liquid immersion exposure method

technical field

The present invention relates to a liquid for immersion exposure and a method for immersion exposure. Specifically, in addition to these liquids and methods, it relates to a method for preparing the liquid for immersion exposure, a method for evaluating it as a liquid for immersion exposure, and a novel liquid composition. .

Background technique

In the manufacture of semiconductor elements, etc., a step-and-step or step-and-scan method is used in which the pattern of a reticle serving as a photomask is transferred to each shot area on a wafer coated with photoresist through a projection optical system projection exposure device.

The shorter the exposure wavelength used, the larger the numerical aperture of the projection optical system, and the higher the theoretical threshold of resolution of the projection optical system included in the projection exposure apparatus. Therefore, along with miniaturization of integrated circuits, the exposure wavelength used as the radiation wavelength used in the projection exposure apparatus becomes shorter year by year, and the numerical aperture of the projection optical system gradually increases.

In addition, when performing exposure, the depth of focus becomes important as well as the resolution. The theoretical thresholds of the resolution R and the depth of focus δ are expressed by the following mathematical expressions, respectively.

R＝k1·λ/NA (i)

δ=k2·λ/NA ² (ii)

Wherein, λ is the exposure wavelength, k1 and k2 are process parameters, and NA is the numerical aperture of the projection optical system, which is defined by the following formula (ii') when the refractive index of air is set to 1. That is, when the same resolution R is obtained, the one using radiation having a short wavelength can obtain a larger depth of focus δ.

NA = sin θ (θ = maximum incident angle of exposed light on the resist surface) (ii')

As mentioned above, until now, the miniaturization requirements of integrated circuits have been met by shortening the wavelength of the exposure light source and increasing the numerical aperture. Now, 1L1S (1 : 1 line and space) mass production of half-pitch 90nm nodes. However, it is considered difficult to achieve further miniaturization of the next-generation half-pitch 65nm node or 45nm node only by using an ArF excimer laser. Therefore, for these next-generation technologies, the use of short-wavelength light sources such as F ₂ excimer laser (wavelength 157nm) and EUV (wavelength 13nm) is being studied. However, the use of these light sources is technically difficult, and it is still difficult to use them.

In the exposure technique described above, a photoresist film is formed on the exposed wafer surface, and a pattern is transferred onto the photoresist film. In the conventional projection exposure apparatus, the space in which the wafer is arranged is filled with air or nitrogen gas having a refractive index of 1. At this time, when the space between the wafer and the lens of the projection exposure device is filled with a medium of refractive index n, it is reported that the theoretical threshold values of resolution R and depth of focus δ are expressed by the following mathematical formula.

R＝k1·(λ/n)/NA (iii)

δ=k2·nλ/NA ² (iv)

Here, NA is not the actual numerical aperture of the projection optical system, but represents a constant defined by the above formula (ii') (accurately, the numerical aperture NA' of the projection optical system is represented by NA'=nsinθ (n is the same as the above definition) ).

The above formula shows that by filling the liquid with refractive index n between the lens of the projection exposure device and the wafer, and setting an appropriate optical system, the threshold of resolution and the depth of focus can be made 1/n and n times respectively in theory. For example, in the ArF process, if water is used as the above-mentioned medium, the refractive index n of light with a wavelength of 193nm in water is n=1.44. Therefore, compared with the exposure with air or nitrogen as the medium, it is theoretically possible to design An optical system with a ratio R of 69.4% (R=k1·(λ/1.44)/NA) and a depth of focus of 144% (δ=k2·1.44λ/NA ² ).

The projection exposure method that shortens the effective wavelength of the radiation used for exposure in this way and can transfer a finer pattern is called immersion exposure, and it is considered to be suitable for the miniaturization of photolithography in the future, especially photolithography in units of several tens of nanometers. It is an essential technique, and its projection exposure apparatus is also known (see Patent Document 1).

Previously, in the liquid immersion exposure method, as a liquid filled between the lens and the substrate of the projection optical system, pure water was studied in the ArF excimer laser, and in the F ₂ excimer laser, because of its high transparency at 157nm For the reason, the use of fluorine-based inert liquids, etc. was studied.

Pure water is easy to obtain in semiconductor manufacturing plants, and there is no problem in terms of the environment. In addition, it is easy to adjust the temperature, and can prevent the thermal expansion of the substrate due to the heat generated during exposure. It is used as an immersion liquid for ArF (see Patent Document 2), and it has been adopted in mass production of devices at the 65nm half-pitch node. .

On the other hand, a liquid obtained by adding methanol or the like as an additive that reduces the surface tension of pure water and increases surface activity is also known (see Patent Document 3).

However, since pure water is used, the water permeates into the photoresist film, and the cross-sectional shape of the photoresist pattern becomes a T-tip shape, which sometimes deteriorates and the resolution decreases. In addition, due to the elution of water-soluble components such as photoacid generators, basic additives, and acids generated by exposure into the water that constitute the photoresist, it may also cause shape deterioration such as T-tip shape, resulting in resolution, focus, etc. Depth reduction, bridging defects, creating defects in the developed pattern, contaminating the lens surface. In addition, the elution of these components into the liquid also causes contamination of the liquid, making it difficult to reuse the liquid. Therefore, complicated refining treatment is frequently required.

Therefore, in order to block the photoresist film and water, there is a method of forming an upper layer film on the photoresist film, but there are insufficient light transmittance for exposure or mixing with the photoresist film. However, there is also the problem of complicated working hours. In addition, it has also been reported that CaF ₂ previously used in lens materials is corroded by water (Non-Patent Document 1), and therefore, there is also a problem that a coating material for coating the lens surface is required.

On the other hand, as shown in the above formula (iii), the resolution threshold is about 1.44 times that of ArF dry exposure, so it can be predicted that in the next generation technology of further miniaturization, especially the half-pitch below 45nm, its It becomes difficult to use.

As described above, in the next-generation liquid immersion exposure method for further miniaturization, a liquid having a refractive index higher than that of pure water at an exposure wavelength (for example, a wavelength of 193 nm, etc.) and having high translucency for light of these wavelengths is required. At the same time, the liquid needs to be a liquid that does not cause adverse effects on the photoresist film such as elution of additives from the photoresist film, dissolution of the resist film, and pattern deterioration, and that does not corrode the lens. At the same time, along with the increase in NA caused by the introduction of immersion exposure, the introduction of polarized light was studied as the exposure light. It is expected that this liquid will not bend the direction of polarization due to properties such as optical rotation, in addition to satisfying the above requirements.

As a method for achieving this object, for example, attempts have been made to increase the refractive index by dissolving various salts in water (Non-Patent Document 2). However, this method is difficult to control the concentration of the salt, and, like water, there are problems such as image development defects due to elution of water-soluble components, lens contamination, and the like.

On the other hand, fluorine-based inert liquids such as perfluoropolyether, which have been studied for _F2 exposure, have a small refractive index at, for example, 193 nm, so it is difficult to use it at this wavelength. In addition, due to the high refractive index at a wavelength of 589nm, organic bromides and iodides known so far as immersion exposure liquids for microscopes, for example, have poor light transmission at 193nm, and are not suitable for photoresist films. Poor stability.

Patent Document 1: Japanese Unexamined Patent Publication No. 11-176727

Patent Document 2: International Publication No. WO99/49504

Patent Document 3: Japanese Unexamined Patent Application Publication No. H10-303114

Non-Patent Document 1: NIKKEI MICRODEVICE April 2004 Issue p77

Non-Patent Document 2: Proc.SPIE Vol.5377(2004)p.273

Contents of the invention

The present invention is completed in order to solve the above problems, and the purpose is to provide a method of immersion exposure, which has a refractive index greater than that of pure water, has excellent light transmittance at the immersion exposure wavelength, and can prevent photoresist film The elution or dissolution of its upper layer film components (especially hydrophilic components) does not corrode the lens, and can suppress the defects when the resist pattern is formed. When it is used as a liquid for immersion exposure, it can suppress the deterioration of the pattern shape. A liquid for immersion exposure that forms a pattern with superior resolution and depth of focus, and the liquid is easy to reuse and refine, and an immersion exposure method using the same.

In addition, in addition to the liquid for liquid immersion exposure and the liquid immersion exposure method described above, the object of the present invention is to provide a method for preparing the liquid for liquid immersion exposure, a method for evaluating it as a liquid for liquid immersion exposure, and a novel liquid composition.

In order to solve the above-mentioned problems, it is necessary for the liquid for immersion exposure to have a high transmittance at an exposure wavelength that can be used for the purpose and to have a sufficiently high refractive index compared with water. On the other hand, it is generally known that the refractive index in the ultraviolet region of a liquid is related to the polarizability of molecules constituting the liquid. As a method to increase the polarizability, in general, elements such as sulfur, bromine, iodine, etc. that have n-electrons that are easily transferred, and carbon-carbon double bonds, carbon-carbon triple bonds, etc. Bonds, especially aromatic rings are effective. However, compounds containing these elements and molecular structures generally have strong absorption in the far ultraviolet region such as 193 nm, and cannot be used for this purpose. On the other hand, unsubstituted hydrocarbon compounds, cyanated hydrocarbon compounds, fluorinated hydrocarbon compounds, sulfonate compounds, some alcohols, etc. can be cited as compounds with low absorption in the far ultraviolet region, but these compounds generally have a refractive index lower than that of water. High, its refractive index is not much different from the current water.

On the other hand, the following formula (Lorentz-Lorenz formula) was proposed as a more accurate theoretical formula for the refractive index of liquid, and it was reported that the refractive index n of benzene could be accurately predicted using the following formula (J. Phy. Chem. .A., Vol.103, No.42, 1999 p8447).

N＝(1+4πNα ^eff ) ^0.5

In the above formula, N represents the number of molecules per unit volume, and the smaller the partial molar volume, the larger its value.

It can be predicted from the above formula that by introducing a highly absorbing functional group, even if α cannot be increased, the refractive index can be increased by increasing N. Based on the above description, various studies have been carried out on the molecular structure of the liquid, and it has been found that due to the compact structure, the high-density alicyclic hydrocarbon of the present invention, or the liquid containing silicon and having a cyclohydrocarbon skeleton, has both transparency and refraction. rate, and when used as a liquid for immersion exposure, it can prevent the elution or dissolution of the photoresist film or its upper layer film components (especially the hydrophilic components), and then solve the defects and lens defects when the resist pattern is formed. The problem of erosion and the like can be solved, and a pattern with better resolution and depth of focus can be formed, thereby completing the present invention.

That is, the liquid for liquid immersion exposure of the present invention is a liquid used in a liquid immersion exposure device or a liquid immersion exposure method that performs exposure through a liquid filled between a lens of a projection optical system and a substrate, and is characterized in that the liquid is used in an immersion exposure method. The temperature range in which the liquid exposure device works is a liquid, which is an alicyclic hydrocarbon compound or a cyclohydrocarbon compound containing silicon atoms in the ring structure.

In particular, the alicyclic hydrocarbon compound or the cyclic hydrocarbon compound containing silicon atoms in the ring structure is characterized in that: the radiation transmittance per 1 mm optical path at a wavelength of 193 nm is greater than or equal to 70%, and the refractive index of D rays is greater than or equal to 1.4, preferably 1.4 to 2.0.

The liquid immersion exposure method of the present invention is a liquid immersion exposure method in which the mask is illuminated by an exposure light beam, and the liquid filled between the lens of the projection optical system and the substrate is used to expose the substrate by the exposure light beam. It is characterized in that the liquid It is the liquid for the immersion exposure.

The immersion exposure method of the present invention uses an alicyclic hydrocarbon compound with high hydrophobicity and a high refractive index at the exposure wavelength or a cyclohydrocarbon compound containing silicon atoms in the ring structure as the liquid for immersion exposure, thereby preventing photoresist. The elution or dissolution of the etch film or its upper film components, especially the hydrophilic components, can solve the problems of defects and lens erosion when the resist pattern is formed. In addition, when it is used as a liquid for immersion exposure, it can suppress the pattern Deterioration of shape improves resolution and depth of focus.

Detailed ways

The alicyclic hydrocarbon compound or the cyclic hydrocarbon compound containing a silicon atom in the ring structure which can be used as the liquid for immersion exposure is preferably an alicyclic saturated hydrocarbon compound or a cyclic saturated hydrocarbon compound containing a silicon atom in the ring structure, respectively. If an unsaturated bond exists in the hydrocarbon compound, the exposure light beam is easily absorbed by the liquid for immersion exposure.

The alicyclic hydrocarbon compound which can be used as the liquid for immersion exposure or the cyclic hydrocarbon compound which contains a silicon atom in a ring structure is demonstrated by following formula (1-1) - formula (1-9).

In formula (1-1), R ¹ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine substitution group with 1 to 10 carbon atoms. Hydrocarbyl, -Si(R ⁹ ) ₃ base, or -SO ₃ R ¹⁰ base, n1, n2 each independently represent an integer of 1 to 3, a represents an integer of 0 to 10, when there are multiple R ¹ , the R ¹ can be the same or different, two or more R ¹ can be combined with each other to form a ring structure, R ⁹ and R ¹⁰ represent an alkyl group with 1 to 10 carbon atoms.

Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹ include methyl group, ethyl group, n-propyl group and the like. As an example of a ring structure formed by combining two or more R ¹ with each other, cyclopentyl, cyclohexyl and the like can be mentioned. Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms include cyclohexyl group, norbornyl group and the like. Examples of the fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms include a trifluoromethyl group and a pentafluoroethyl group. R ⁹ constituting the -Si(R ⁹ ) ₃ group and R ¹⁰ constituting the -SO ₃ R ¹⁰ group represent an alkyl group having 1 to 10 carbon atoms, and the alkyl group includes a methyl group, an ethyl group, etc. .

In the formula (1-1), the substituent R ¹ is preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms, A cyano group, a fluorine atom, or a fluorine-substituted saturated hydrocarbon group having 1 to 10 carbon atoms.

Among the above-mentioned substituents, since a higher refractive index can be obtained, there is less interaction with the resist, and it is difficult to cause defects caused by the elution of water-soluble components in the resist and corrosion of the lens material, so it is particularly Preferred are aliphatic saturated hydrocarbon groups having 1 to 10 carbon atoms and alicyclic saturated hydrocarbon groups having 3 to 14 carbon atoms.

In addition, preferred n1 and n2 are 1 to 3, particularly preferred n1 and n2 are 1 or 2, and preferred a is 0, 1 or 2. As a, especially when it is 0, since the refractive index becomes high at 193 nm, for example, it is especially preferable.

Specific examples of preferable alicyclic saturated hydrocarbon compounds represented by formula (1-1) are listed below. In addition, in this specification, the hydrogen atom bonded to the carbon atom which forms a ring in an alicyclic saturated hydrocarbon compound is abbreviate|omitted.

Specific examples of preferred cyano group-containing compounds represented by formula (1-1) are listed below.

Specific examples of preferred fluorine atom-containing compounds represented by formula (1-1) are listed below.

Specific examples of preferred fluorine-substituted saturated hydrocarbon compounds represented by formula (1-1) are listed below.

Among preferable compounds represented by formula (1-1), alicyclic saturated hydrocarbon compounds are preferable, and among them, compounds represented by the following formula (2-1) are exemplified as particularly preferable compounds.

In formula (2-1), R ¹ and a are the same as R ¹ and a of formula (1-1).

As a specific example in formula (2-1), can enumerate by above-mentioned (1-1-16), (1-1-19), (1-1-20), (1-1-21), (1 - compounds listed in 1-34), (1-1-35), (1-1-36), (1-1-37), (1-1-38), (1-1-39).

Among them, compounds without substituents are preferred because their refractive index at 193 nm is increased, for example. Particularly preferred examples in formula (2-1) include cis-decalin and trans-decalin.

In formula (1-2), A represents a single bond or a methylene group which may be substituted by an alkyl group having 1 to 10 carbon atoms or a group having 2 to 14 carbon atoms which may be substituted by an alkyl group having 1 to 10 carbon atoms. Alkylene group, ^R2 represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine-substituted hydrocarbon group with 1 to 10 carbon atoms, -Si (R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, R ⁷ represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine-substituted alkyl group with 1 to 10 carbon atoms , or -Si(R ⁹ ) ₃ groups, n3 represents an integer of 2 to 4, n4 represents an integer of 1 to 3, b represents an integer of 0 to 6, when there are multiple R ² or R ⁷ , the R ² can be The same or different, two or more ^R2 can combine with each other to form a ring structure, ^R9 and ^R10 represent an alkyl group with 1 to 10 carbon atoms.

Examples of the methylene group in A which may be substituted by an alkyl group having 1 to 10 carbon atoms or the alkylene group having 2 to 14 carbon atoms which may be substituted by an alkyl group having 1 to 10 carbon atoms include ethylene , n-propylene, etc.

R ² is the same as R ¹ in formula (1-1).

In the formula (1-2), the substituent R ² is preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms, A cyano group, a fluorine atom, or a fluorine-substituted saturated hydrocarbon group having 1 to 10 carbon atoms.

Among the above substituents, for the same reason as R ¹ in (1-1), an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms are preferable.

Preferred n3 is 2-4, particularly preferably 2 or 3; preferred n4 is 1-3, particularly preferably 1 or 2; preferred b is 0 or 1 or 2. As b, for example, since the refractive index increases at 193 nm, it is particularly preferably 0. Specific examples of preferred (1-2) are shown below.

Particularly preferable examples in formula (1-2) include 1,1,1-tricycloheptylmethane and 1,1,1-tricyclopentylmethane.

In formula (1-3), R ³ and R ⁴ represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or an aliphatic hydrocarbon group with 1 to 10 carbon atoms. A fluorine-substituted hydrocarbon group, ^-Si (R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, when there are multiple R 3 and R ⁴ , the R ³ and R ⁴ can be the same or different, two or More R ³ and R ⁴ can be alone or combined to form a ring structure, n5 and n6 represent an integer of 1 to 3, c and d represent an integer of 0 to 8, R ⁹ and R ¹⁰ represent 1 to 10 carbon atoms of alkyl.

R ³ and R ⁴ are the same as R ¹ in formula (1-1).

In the formula (1-3), the substituents ^R3 and ^R4 are preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms, from the viewpoint of excellent radiation transmittance at 193 nm. A hydrocarbon group, a cyano group, a fluorine atom, a fluorine-substituted saturated hydrocarbon group having 1 to 10 carbon atoms.

Among the above substituents, for the same reason as R ¹ in (1-1), an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms are preferable.

Preferred n5 and n6 are 1-3, particularly preferably 1 or 2, and c and d are 0 or 1 or 2. It is particularly preferred that both c and d are 0 due to the increased refractive index at, for example, 193 nm. Specific examples of preferred compounds (1-3) are shown below.

As a preferable example in formula (1-3), spiro[5.5]undecane is mentioned.

In (a), (b) and (c) of the formula (1-4), B represents a methylene group or an ethylene group, and ^R represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, and an aliphatic hydrocarbon group with 3 to 14 carbon atoms. Alicyclic hydrocarbon group, cyano group, hydroxyl group, fluorine atom, fluorine-substituted hydrocarbon group with 1 to 10 carbon atoms, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, when there are multiple R ⁵ groups, the R ⁵ can be the same or different, two or more R ⁵ can be combined to form a ring structure, e represents an integer of 0-10, n7 represents an integer of 1-3, R ⁹ and R ¹⁰ represent carbon atoms of 1-3 Alkyl of 10.

R ⁵ is the same as R ¹ in formula (1-1).

In the formula (1-4), the substituent R ⁵ is preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms, A cyano group, a fluorine atom, or a fluorine-substituted saturated hydrocarbon group having 1 to 10 carbon atoms.

Among the above substituents, for the same reason as R ¹ in (1-1), an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms are preferable.

Preferably c is 0 or 1 or 2, n7 is 1-3, particularly preferably 1 or 2. The case where e is 0 is particularly preferable because, for example, the refractive index increases at 193 nm. Examples of preferable compounds (1-4) are shown below.

Preferred compounds in formula (1-4) include compounds represented by formula (2-2) and formula (2-2').

In formulas (2-2) and (2-2'), R ⁵ is the same as R ⁵ in formula (1-4), and preferably i is 0, 1 or 2. For the same reason as a in (1-1), i is particularly preferably 0.

Specific examples of preferred compounds (2-2) and (2-2') include the compounds of the above-mentioned (1-4-1) to (1-4-6).

As a particularly preferable specific example, there may be mentioned pap-tetrahydrodicyclopentadiene.

In the formula (1-5), ^R6 represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine substitution group with 1 to 10 carbon atoms. Hydrocarbyl group, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, f represents an integer from 0 to 10, when there are multiple R ⁶ , the R ⁶ may be the same or different, R ⁹ and R ¹⁰ represent An alkyl group having 1 to 10 carbon atoms.

R ⁶ is the same as R ¹ in formula (1-1).

In the formula (1-5), the substituent R ⁶ is preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms, A cyano group, a fluorine atom, or a fluorine-substituted saturated hydrocarbon group having 1 to 10 carbon atoms.

Among the above-mentioned substituents, for the same reason as R ¹ in formula (1-1), an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms are preferable.

Preferred f is 1 or 2. In addition, the position of the substituent is preferably a bridgehead position.

Preferable examples of the formula (1-5) include compounds represented by the following formulas.

In the formula (1-6), R ⁸ and R ^8' represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or an aliphatic hydrocarbon group with 1 to 14 carbon atoms. 10 fluorine-substituted hydrocarbon groups, -Si(R ⁹ ) ₃ groups, or -SO ₃ R ¹⁰ groups, g and h represent integers from 0 to 6, n8 and n9 represent integers from 1 to 3, R ⁹ and R ¹⁰ represent An alkyl group having 1 to 10 carbon atoms.

R ⁸ and R ^8' are the same as R ¹ in formula (1-1).

In the formula (1-6), the substituents R ⁸ and R ^8' are preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms or an aliphatic saturated hydrocarbon group having 3 to 14 carbon atoms, from the viewpoint of excellent radiation transmittance at 193 nm. Cyclic saturated hydrocarbon group, cyano group, fluorine atom, fluorine-substituted saturated hydrocarbon group with 1 to 10 carbon atoms.

Among the above-mentioned substituents, for the same reason as R ¹ in formula (1-1), an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an alicyclic saturated hydrocarbon group having 3 to 14 carbon atoms are preferable.

Preferred g and h are 0, 1 or 2, n8 and n9 are 1-3, particularly preferably 1 or 2.

Specific examples of preferred compounds (1-6) are shown below.

Preferable examples of formula (1-6) include 5-silacyclo[4,4]nonane.

In formula (1-7), R ¹¹ and R ¹² represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or an aliphatic hydrocarbon group with 1 to 10 carbon atoms. fluorine-substituted hydrocarbon group, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, n10 and n11 each independently represent an integer of 1 to 3, j and k represent an integer of 0 to 6, when R ¹¹ and R When there are multiple ^{R 12} each, the R ¹¹ and R ¹² may be the same or different, two or more R ¹¹ may be combined to form a ring structure, or two or more R ¹² may be combined to form a ring structure, X represents a single bond, a divalent aliphatic hydrocarbon group with 2 to 10 carbon atoms, a divalent alicyclic hydrocarbon group with 3 to 14 carbon atoms, and R ⁹ and R ¹⁰ represent an alkyl group with 1 to 10 carbon atoms.

R ¹¹ and R ¹² are aliphatic hydrocarbon groups with 1 to 10 carbon atoms, alicyclic hydrocarbon groups with 3 to 14 carbon atoms, fluorine-substituted hydrocarbon groups with 1 to 10 carbon atoms, -Si(R ⁹ ) ₃ groups, or - The SO ₃ R ¹⁰ group is the same as the aliphatic hydrocarbon group, alicyclic hydrocarbon group, fluorine-substituted hydrocarbon group, -Si(R ⁹ ) ₃ group, and -SO ₃ R ¹⁰ group in formula (1-1).

In the formula (1-7), the substituents R ¹¹ and R ¹² are preferably an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms, an alicyclic group having 3 to 14 carbon atoms, from the viewpoint of excellent radiation transmittance at 193 nm. Saturated hydrocarbon group, cyano group, fluorine atom, fluorine-substituted saturated hydrocarbon group having 1 to 10 carbon atoms.

In addition, examples of the divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms in X include ethylene and propylene groups, and examples of the divalent alicyclic hydrocarbon group having 3 to 14 carbon atoms include cyclopentane-derived Divalent groups of alkane and cyclohexane, etc.

In formula (1-7), X is preferably a single bond. Specific examples of preferred compounds (1-7) are shown below.

Examples of preferable formula (1-7) include dicyclohexyl (dicyclohexyl) and dicyclopentyl (dicyclopentyl).

In the formula (1-8), ^R13 represents an alkyl group with 2 or more carbon atoms, an alicyclic hydrocarbon group with 3 or more carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine-substituted hydrocarbon group with 2 to 10 carbon atoms , -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, p represents an integer from 1 to 6, when there are multiple R ¹³ , the R ¹³ can be the same or different, two or more R ¹³ may be combined with each other to form a ring structure, and R ⁹ and R ¹⁰ represent an alkyl group with 1 to 10 carbon atoms.

Preferred R ¹³ is an alkyl group having 2 to 10 carbon atoms or an alicyclic hydrocarbon group having 3 to 14 carbon atoms, preferably p is 1 or 2, particularly preferably p is 1.

The above-mentioned alkyl group having 2 or more carbon atoms is preferably an alkyl group having 2 to 10 carbon atoms, and examples include methyl, ethyl, n-propyl and the like. The aforementioned alicyclic hydrocarbon group having 3 or more carbon atoms is preferably an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and examples thereof include cyclohexyl group, norbornyl group and the like. A fluorine-substituted hydrocarbon group with 2 to 10 carbon atoms, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group and a fluorine-substituted hydrocarbon group in formula (1-1), -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ groups are the same. The ring structure formed by combining two or more ^R13s includes cyclopentyl, cyclohexyl and the like.

Specific examples of preferred compounds in formula (1-8) are shown below.

In formula (1-9), R ¹⁴ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine substitution group with 1 to 10 carbon atoms. Hydrocarbon group, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, n12 represents an integer of 1 to 3, q represents an integer of 0 to 9, when there are multiple R ¹⁴ , the R ¹⁴ can be the same or can be Different, R ⁹ and R ¹⁰ represent an alkyl group having 1 to 10 carbon atoms.

R ¹⁴ is the same as R ¹ in formula (1-1). In addition, preferred R ¹⁴ is the same as preferred R ¹ . Preferred q is the same as a.

Specific examples of preferred compounds in formula (1-9) are shown below.

In formula (1-1)～formula (1-9), particularly preferred compound has the chemical structure shown in formula (1-1), formula (1-4), and these compounds are unsubstituted, or by the number of carbon atoms Compounds substituted with aliphatic saturated hydrocarbon groups having 1 to 10 carbon atoms and alicyclic saturated hydrocarbon groups having 3 to 14 carbon atoms, among which unsubstituted compounds are particularly preferred.

The above compound is a liquid at the temperature at which the liquid immersion exposure apparatus operates, and it is preferable that the refractive index is higher than that of pure water for the reasons of the above formulas (iii) and (iv).

Specifically, it is preferable that the refractive index is a value between water and the resist film (or upper layer film for immersion) before exposure, and is a value higher than that of water. At 25°C, the refraction at a wavelength of 193nm The index is 1.45 to 1.8, preferably in the range of 1.6 to 1.8, and the refractive index at 25° C. at a wavelength of 248 nm is 1.42 to 1.65, preferably in the range of 1.5 to 1.65. In addition, at 25° C., the refractive index at D-ray (wavelength: 589 nm) is not less than 1.4, preferably 1.4 to 2.0, and more preferably 1.40 to 1.65.

In addition, since changes in the refractive index due to changes in the use environment cause defocusing, the present compound is preferably a compound whose refractive index is not easily affected by temperature, pressure, and the like. It is expected that the temperature will change during use due to heat generated by light absorption of the lens or resist material, so it is particularly preferable that the temperature dependence of the refractive index is low. Specifically, the absolute value of the change rate dn/dT of the refractive index (n) due to temperature (T) is preferably within 5.0×10 ^-3 (°C ^-1 ), more preferably 7.0×10 ^-4 (°C ^-1 ) within.

In addition, from this viewpoint, the present compound preferably has a large specific heat value, specifically, the specific heat value is preferably 0.1 cal/g·°C or more, more preferably 0.30 cal/g·°C or more.

In addition, the above-mentioned compound preferably has a refractive index that is not easily affected by chromatic aberration, and preferably has a small wavelength dependence of the refractive index around the exposure wavelength.

In addition, as other characteristics, high light transmittance in the far ultraviolet region, viscosity, solubility of gases such as oxygen and nitrogen, contact angle with lenses, resist (or resist upper layer film), surface tension, flash point, etc. It is preferably within the following range. In addition, it is also desirable that the chemical interaction with the lens and the resist material is small. These characteristics are described in detail below.

The radiation transmittance at 193nm at 25°C is preferably equal to or greater than 70%, particularly preferably equal to or greater than 90%, and more preferably equal to or greater than 95%. At this time, if the transmittance is lower than 70%, heat generation due to heat energy generated by light absorption of the liquid tends to occur, and defocusing and deformation of the optical image due to changes in the refractive index due to temperature rise tend to occur. In addition, the amount of light reaching the resist film decreases due to the absorption of the liquid, causing a significant decrease in yield.

Regarding the viscosity, the viscosity at 20°C is 0.5 Pa·s or less, especially when used in an environment where the gap between the wafer and the lens material is 1 mm or less, preferably 0.01 Pa·s or less, particularly preferably 0.5 Pa·s or less 0.005 Pa·s. If the viscosity exceeds 0.5 Pa·s, it is difficult for the liquid to penetrate into the gap between the resist film (or the upper film for immersion) and the lens material, or it cannot be obtained. The step-and-scan method in which the stage on which the wafer is placed exposes the entire surface of the wafer is sufficient scanning speed as the exposure method, which causes a large decrease in yield. In addition, there is a tendency to cause a temperature rise caused by friction, which is easily affected by the temperature. Effects of changes in optical properties caused by changes. In addition, especially when the gap between the wafer and the lens material is 1 mm or less, the viscosity is preferably 0.01 Pa·s or less for the above reasons. At this time, by reducing the gap distance (thickness of the liquid film), it is possible to It is preferable to increase the transmittance of the liquid to make it difficult to be affected by liquid absorption.

In addition, when the viscosity is increased, bubbles (nanobubbles, microbubbles) are easily generated in the liquid, and the lifetime of the bubbles is prolonged, so it is not suitable.

In addition, regarding the solubility of gas in the liquid involved in the present invention, the solubility represented by the gas mole fraction in the liquid when the partial pressure of oxygen and nitrogen is at 25°C and the partial pressure is 1 atmosphere (atm) is preferably 0.5×10 ^-4 to 70 ×10 ^-4 , more preferably 2.5×10 ^-4 to 50×10 ^-4 , when the solubility of these gases is 0.5×10 ^-4 or less, the nanobubbles generated by the resist etc. are difficult to disappear, therefore, because Scattering of light by air bubbles tends to cause resist defects during pattern formation. In addition, if it is 70×10 ^-4 or more, surrounding gas is absorbed during exposure, and it is easy to be affected by changes in optical characteristics due to gas absorption.

In addition, the contact angle between the liquid of the present invention and _the resist (or the upper layer film for liquid immersion) is preferably 20° to 90°, and more preferably 50° to 80°. The contact angle of the material is preferably equal to or less than 90°, more preferably equal to or less than 80°. If the contact angle of the liquid of the present invention and the resist (or immersion liquid upper layer film) before exposure is less than or equal to 20 °, the liquid is difficult to immerse into the gap. In the exposure mode, the liquid tends to scatter into the film. On the other hand, if the contact angle of the liquid of the present invention and the resist (or immersion upper layer film) before exposure is greater than or equal to 90°, it is easy to absorb gas at the resist (or upper layer film) interface with unevenness, and it is easy to Bubbles are produced. Such a phenomenon is described in ImmersionLithography Modeling 2003 Year-End Report (International SEMATECH).

In addition, if the contact angle of the liquid of the present invention with the lens material exceeds 90°, there is a tendency for air bubbles to be generated between the lens surface and the liquid.

In addition, especially when it is used in an exposure apparatus of a step-and-scan method in which immersion is carried out by partial immersion in the same way as currently used in water immersion exposure, scattering of liquid during scanning becomes a problem. Therefore, the liquid of the present invention Preferably the surface tension is high. Specifically, the surface tension at 20° C. is preferably 5 dyn/cm to 90 dyn/cm, more preferably 20 dyn/cm to 80 dyn/cm.

When the contact angle of the liquid of the present invention with the resist surface is not suitable, the contact angle can be improved by using an appropriate immersion liquid upper layer film. In particular, since the liquid of the present invention has low polarity, the contact angle can be increased by using a high-polarity upper layer film.

The elution of resist components such as photoacid generators and basic components by this liquid not only causes defects in the pattern forming performance of the resist, adversely affects profile deterioration, etc., but also causes contamination of the liquid itself, such as becoming Causes such as changes in the optical properties of the liquid or erosion of the lens. In addition, it becomes difficult to reuse the liquid, and frequent liquid purification is required. Therefore, it is preferable that there is little contamination by elution of the liquid. The amount of elution can be evaluated by a method using HPLC or the like, but, more precisely, the absorbance at 193 nm is very sensitive to the incorporation of components in the resist, so it can be evaluated by following the change of the latter. As a specific requirement for the liquid, the change in absorbance per 1 cm after immersion for 180 seconds (absorbance after immersion - absorbance before immersion) in the immersion test using "change in absorbance when resist is in contact" in the evaluation method described later is less than equal to 0.05, preferably less than or equal to 0.02, more preferably less than or equal to 0.005.

The liquid of the present invention is preferably a compound with a low risk of explosion, ignition, ignition, etc. in the use environment. Specifically, the flash point is preferably equal to or greater than 25°C, more preferably equal to or greater than 50°C, and the flash point is preferably equal to or greater than 180°C, and more preferably equal to or greater than 230°C. In addition, the vapor pressure at 25° C. is preferably equal to or less than 50 mmHg, more preferably equal to or less than 5 mmHg.

In addition, it is preferably a compound with low harmfulness to the human body and the environment. Specifically, with regard to the harmfulness to the human body, compounds with low acute toxicity and no carcinogenicity, mutagenicity, teratogenicity, reproductive toxicity, etc. are preferred. Specifically, the allowable concentration is preferably greater than or equal to 30 ppm, more preferably greater than or equal to 70 ppm, and is preferably a liquid with a negative Ames test result. With regard to the harmfulness to the environment, it is preferable to have no residual or eco-accumulative compounds.

In addition, the liquid of the present invention preferably has a purity of 95.0% by weight or more, particularly preferably 99.0% by weight or more, more preferably 99.9% by weight or more, as measured by gas chromatography.

It is preferable that the proportion of compounds containing olefins, compounds containing aromatic rings, compounds containing sulfur (sulfide, sulfoxide, sulfone structure), halogen, carbonyl, ether groups, etc., which have a large absorbance at exposure wavelengths such as 193 nm, be less than 0.01 wt. %, particularly preferably less than 0.001% by weight.

In addition, the liquid composed of this compound is used in the manufacturing process of semiconductor integrated circuits, so it is preferable that the metal or metal salt content is low, specifically, the metal content is 100 ppb or less, preferably 10 ppb or less, more preferably 1.0 ppb or less. If the metal content exceeds 100 ppb, metal ions or metal components may adversely affect the resist film or the like and contaminate the wafer.

Examples of the metal include at least one metal selected from Li, Na, K, Mg, Cu, Ca, Al, Fe, Zn, and Ni. These metals can be measured by atomic absorption method.

In addition, the oxygen concentration in the liquid is 100 ppm or less (100 μg/ml), preferably 10 ppm or less, more preferably 2 ppm or less. In addition, especially at the time of exposure, it is preferably equal to or less than 1 ppm, and more preferably equal to or less than 10 ppb. If the oxygen concentration exceeds 100 ppm, there is a tendency for the transmittance to decrease due to an oxidation reaction by dissolved oxygen or the like. In addition, even if no oxidation reaction occurs, if oxygen is dissolved, for example, as shown in Examples, the absorbance of the liquid decreases according to the concentration of dissolved oxygen due to the absorption of dissolved oxygen and ozone generated when irradiating oxygen to radiation. In addition, if the liquid is exposed in the presence of oxygen, the generated ozone will oxidize the liquid and accelerate the deterioration of the liquid.

In addition, especially in the case of polarized light exposure, if the liquid is optically active, the optical contrast will be lowered, so the present liquid is preferably a liquid that does not have optical activity. Specifically, the compound constituting the present liquid is preferably a compound without optical activity (not optically active), and when the compound constituting the liquid is a compound having optical activity (optical activity), it preferably contains an equivalent amount of optical isomers ( as a racemate), the liquid as a whole is not optically active.

The compounds of the present invention can be obtained as commercially available compounds, or can be produced from available raw materials by various known synthetic methods. Hereinafter, the production method of the present compound will be described by giving specific examples.

For example, for the compound represented by the formula (2-1), it is possible to use a suitable catalyst to use contact hydrogenation to produce dry distillation oil from coal coke ovens, petroleum contact reforming oil and flow contact cracking oil, as well as in ethylene. Manufactured by nuclear hydrogenation of naphthalene or naphthalene derivatives contained in naphtha cracking oil, etc., which are produced by-products.

In addition to naphthalene and alkylnaphthalene, the above-mentioned contact reforming oil, mobile reforming oil, and naphtha decomposition oil also contain benzene, alkylbenzene, phenanthrene, anthracene, other polycyclic aromatics and their derivatives, benzene Sulfur-containing compounds such as thiophene and its derivatives, nitrogen-containing compounds such as pyridine and its derivatives, naphthalene and naphthalene derivatives as raw materials can be obtained by separating and purifying these mixtures.

Among naphthalene and naphthalene derivatives used in the production of the above-mentioned compound (2-1), it is preferable that the content of the above-mentioned sulfur-containing compound is low. In this case, the content of the sulfur-containing compound is preferably equal to or less than 100 ppm, more preferably equal to or less than 50 ppm. If the content of the sulfur-containing compound exceeds 100ppm, the sulfur-containing compound will cause catalyst poisoning during contact hydrogenation and hinder the progress of the nuclear hydrogenation reaction. In addition, the compound (2-1) is mixed with sulfur-containing When impurities cannot be removed by purification, the transmittance of the liquid of the present invention at exposure wavelengths such as 193 nm will decrease.

In addition, when producing cis-decalin or trans-decalin and mixtures thereof in compound (2-1), it is particularly preferable that the purity of naphthalene as a raw material is high, preferably the purity of naphthalene is greater than or equal to 99.0%, particularly preferably The purity of naphthalene is greater than or equal to 99.9%. At this time, when the content of sulfur-containing compounds, etc. The difficult-to-separate hydrocarbon compound, the purity control of decahydronaphthalene becomes difficult.

In addition, as catalysts for the catalytic hydrogenation, sulfides such as cobalt molybdenum, nickel molybdenum, nickel tungsten, etc. can be used in addition to noble metal catalysts such as nickel, platinum, rhodium, ruthenium, iridium, and palladium. Among them, nickel-based catalysts are preferred in view of their catalytic activity and cost.

In addition, these metal catalysts are preferably supported on a suitable carrier for use. At this time, by making the catalyst highly dispersed on the carrier, the reaction rate of hydrogenation is improved. In addition, it can prevent the deterioration of the active center under high temperature and high pressure conditions, and improve the performance of the catalyst. Poison resistance.

As the carrier, SiO ₂ , γ-Al ₂ O ₃ , Cr ₂ O ₃ , TiO ₂ , ZrO ₂ , MgO, ThO ₂ , diatomaceous earth, activated carbon, and the like can be preferably used.

In addition, as the method of the above-mentioned contact hydrogenation, a gas-phase method not using a solvent and a liquid-phase method in which a raw material is dissolved in an appropriate solvent and reacted can be utilized. Among them, the gas phase method is preferable because it is excellent in cost and reaction speed.

When the gas phase method is used, nickel, platinum, or the like is preferable as the catalyst. The larger the amount of the catalyst used, the higher the reaction rate, but it is not preferable from the viewpoint of cost. Therefore, in order to complete the reaction by increasing the reaction rate, it is preferable to reduce the amount of the catalyst and perform the reaction under conditions of high temperature and high hydrogen pressure. Specifically, it is preferable to carry out the reaction at a catalyst amount of 0.01 to 10 parts by weight relative to the raw material naphthalene (naphthalene derivative), a hydrogen pressure of 5 to 15 MPa, and a reaction temperature of about 100°C to 400°C.

In addition, the target product can also be obtained under mild conditions by using, for example, the method described in Patent Document (JP-A-2003-160515) to remove naphthalene from the intermediate tetralin using a nickel, platinum, or palladium-based catalyst.

In the above reaction, the reaction conversion rate is preferably equal to or greater than 90%, more preferably equal to or greater than 99%.

After the above reaction, it is preferable to perform appropriate purification to remove impurities such as unreacted raw materials and catalysts.

As the above-mentioned purification method, purification methods such as rectification, water washing, concentrated sulfuric acid washing, filtration, and crystallization, and combinations thereof can be utilized. Among them, rectification is preferable because it is effective for removal of non-volatile catalyst-derived metals and other metals, and removal of both raw material-derived components. In addition, in order to remove metals derived from the catalyst, it is preferable to perform a demetallization treatment corresponding to the catalyst.

Tetrahydrodicyclopentadiene in the above-mentioned compounds can be obtained by the following steps: Dicyclopentadiene (outer (exo), inner (endo) mixture) or internal dicyclopentadiene is hydrogenated, and the resulting tetrahydrodicyclopentadiene is purified by distillation and other methods. When exoisomers are to be selectively obtained from dicyclopentadiene, the hydrogenation reaction described above is carried out by isomerizing dicyclopentadiene isomer mixtures using an appropriate catalyst to selectively obtain exoisomers , or using a suitable catalyst to isomerize the internal (internal, external mixing) tetrahydrodicyclopentadiene obtained by the hydrogenation of the internal (internal and external mixing) dicyclopentadiene, thereby selectively obtaining the external Tetrahydrodicyclopentadiene.

The above-mentioned dicyclopentadiene is generally produced by dimerizing cyclopentadiene contained in a large amount in the so-called C ₅ fraction among thermal decomposition products of naphtha. The dicyclopentadiene contains, for example, 5-isopropenylnorbornene and other hydrocarbon components derived from the _C5 fraction as impurities. If these compounds are contained, after hydrogenation and isomerization, hydrocarbon products derived from these impurities will remain. This makes the purification of the final product tetrahydrodicyclopentadiene difficult. Therefore, it is preferable to use what has been highly purified in advance by means of purification or the like. The purity at this time is preferably equal to or greater than 95% by weight, more preferably equal to or greater than 97% by weight.

In addition, the above-mentioned dicyclopentadiene preferably has a low content of sulfur-containing components that cause hydrogenation reaction catalyst poisoning. Specifically, the content of sulfur-containing components in dicyclopentadiene is preferably 500 ppb or less, more preferably 50 ppb or less. If the amount of sulfur-containing components is 500 ppb, it will easily hinder the hydrogenation reaction in the subsequent process.

The so-called sulfur-containing components here refer to the total amount of sulfur element present in the form of inorganic or organic compounds such as free sulfur, elemental sulfur, hydrogen sulfide, mercaptans, disulfides, thiophene, etc. Gas chromatography with a luminescence detector (SCD) was used for analysis. This sulfur fraction can be removed, for example, by the method of JP-A-2001-181217. This hydrogenation of dicyclopentadiene can be performed using a known carbon-carbon double bond hydrogenation catalyst. This hydrogenation can be performed, for example, by the methods disclosed in JP-A-60-209536 and JP-A-2004-123762. Tetrahydrodicyclopentadiene can be produced by distillation after the above-mentioned hydrogenation. For example, in order to selectively produce exosomes, methods of isomerization using various Lewis acids are known. This isomerization can be performed by the method using aluminum halide, sulfuric acid, etc. as a Lewis acid, for example (JP-A-2002-255866). In this reaction, it is known that adamantane is produced as a by-product, but when a large amount of adamantane exists, the transmittance at 193 nm decreases, so the amount of adamantane coexisting in the final liquid must be 0.5% by weight or less, preferably 0.5% by weight or less. 0.1% by weight or less, more preferably 0.05% by weight or less. This adamantane can be removed by appropriately setting the conditions of the above-mentioned isomerization reaction or various known purification methods.

Hereinafter, specific examples of the structure and physical property values of preferable liquids for liquid immersion exposure are shown in Table 1.

Table 1

In addition, various physical property data of trans-decalin and penta-tetrahydrodicyclopentadiene are shown in Table 2.

Table 2 Physical item Physical value project condition unit cis-decalin H-Tetrahydrodicyclopentadiene boiling point 760mmHg ℃ 187.31 185 melting point 760mmHg ℃ -30.382 -79 proportion 20℃(/4℃) - 0.86969 0.93 Refractive index 194.227nm - 1.631 1.649 589nm - 1.46932 1.49 Refractive Index Temperature Dependence Dn/dT 194.227nm - -0.00056 -0.000056 Refractive index pressure dependence dn/dP - - 5× ^10-10 - Dielectric constant 20°C - 2.172 - Dipole moment - D. 0 - Viscosity coefficient 20°C CP 2.128 2.86 Surface Tension 20°C dyn/cm 29.89 - Specific heat (constant pressure) 20°C cal/deg.mol 54.61 48.5 Critical temperature - ℃ 413.8 - critical pressure - atm 27 - vapor pressure 25°C mmHg 0.78 - Thermal conductivity 62.8°C (D), 30°C (W) cal/cm.s.deg 0.000256 - Flash point - ℃ 58 55 ignite - ℃ 262 - oxygen solubility Partial pressure 1atm ppm 274 220 Cyanide solubility Partial pressure 1atm ppm 113 96

In Table 2, the values of oxygen solubility and nitrogen solubility are values at a partial pressure of 1 atmosphere, and the unit is ppm.

The liquid for immersion exposure of the present invention has a structure selected from the above-mentioned formulas (1-1) to (1-9), so for example, the absorbance at 193 nm is small, which is suitable, but the absorbance in this wavelength range is easily affected by trace impurities. Impact. In addition, when an alkali component exists in these liquids, even a very small amount will have a great influence on the resist profile. These impurities can be removed by refining the above-mentioned liquid by an appropriate method. For example, for saturated hydrocarbon compounds having the structure of (1-1)-(1-5), (1-7)-(1-9), it can be washed with concentrated sulfuric acid, washed with water, washed with alkali, purified by silica gel column, purified Distillation, permanganate treatment under alkaline conditions and their combination for refining.

Specifically, appropriate purification can be performed by, for example, repeated washing with concentrated sulfuric acid until the coloring of concentrated sulfuric acid disappears, then washing with water and washing with alkali to remove concentrated sulfuric acid, washing with water, drying, and then performing rectification.

In addition, depending on the compound, impurities can be removed more efficiently by treating with permanganate under alkaline conditions before preliminary treatment.

In the above-mentioned refining operation, concentrated sulfuric acid washing is effective for the removal of aromatic compounds with large absorption at 193nm and compounds with carbon-carbon unsaturated bonds. In addition, it is also effective for the removal of trace amounts of basic compounds and is preferred. refining method. This treatment is preferably carried out by selecting the optimum stirring method, temperature range, treatment time, and treatment times according to the refined compound.

Specifically, the higher the temperature, the higher the efficiency of impurity removal, but at the same time, impurities that lead to absorption are easily generated due to side reactions. A preferred treatment temperature is -20°C to 40°C, and a particularly preferred treatment temperature is -10°C to 20°C.

The longer the treatment time, the further the reaction with the above-mentioned aromatic compounds and impurities having carbon-carbon unsaturated bonds, the higher the removal efficiency of the above-mentioned impurities, but there is a tendency to increase the amount of impurities that cause absorption due to side reactions.

When refining by the above-mentioned concentrated sulfuric acid treatment, in order to completely remove the acidic impurities derived from concentrated sulfuric acid and the sulfonic acid components generated by the concentrated sulfuric acid treatment remaining in the liquid of the present invention after treatment, it is preferable to carry out alkali washing, pure water washing and Drying process for removing moisture.

In addition, by rectifying after washing with concentrated sulfuric acid, impurities causing absorption can be removed more efficiently.

This rectification is preferably performed using a distillation column having a theoretical plate number equal to or greater than the theoretical plate number required for the separation, based on the difference in boiling point between the impurities to be removed and the liquid of the present invention. From the viewpoint of removing impurities, the preferred number of theoretical plates is 10 to 100. When the number of theoretical plates is increased, equipment and manufacturing costs will increase. Therefore, by combining with other refining methods, a lower number of plates than the above can be used. Refined. A particularly preferable number of theoretical plates is 30-80.

In addition, this rectification is preferably carried out under appropriate temperature conditions. As the distillation temperature rises, the effect of reducing absorption tends to decrease due to the oxidation reaction of the compound or the like. The preferred distillation temperature is 30°C to 120°C, and the particularly preferred distillation temperature is 30°C to 80°C.

In order to carry out the distillation in the above-mentioned temperature range, it is preferable to carry out this rectification under reduced pressure as necessary.

The above-mentioned purification treatment is preferably performed under an inert gas atmosphere such as nitrogen or argon. In this case, the oxygen concentration and the organic component concentration in the inert gas are preferably low. A preferable oxygen concentration is equal to or less than 1000 ppm, more preferably equal to or less than 10 ppm, and particularly preferably equal to or less than 1 ppm.

In addition, among the above-mentioned treatments, the treatment with permanganate is particularly effective for the removal of non-aromatic compounds containing carbon-carbon unsaturated bonds, but for compounds with tertiary carbons, it is easy to cause oxidation reactions of tertiary carbons, so It is suitable for the purification of compounds without tertiary carbon.

In addition, from the viewpoint of preventing side reactions, the treatment is preferably performed at a low temperature of room temperature or lower.

As specific examples, decahydronaphthalene (cis-trans mixture: manufactured by Aldrich), trans-decalin (manufactured by Tokyo Chemical Industry Co., Ltd.), and purified trans-decalin purified by the method shown in Example 1 described later Hydronaphthalene (1), bicyclohexyl, isopropyl cyclohexane, cyclooctane, cycloheptane, adopt the method shown in Example 2 to carry out the refined trans-decalin (2) after refining, adopt implementation The method shown in example 3 has carried out the purified epsilon-tetrahydrodicyclopentadiene (1) after refining, the method shown in embodiment 4 has carried out the refined epsilon-tetrahydrodicyclopentadiene (2) after the refining ), adopting the method shown in Example 5 to carry out the trans-decalin (3) after the refining of the refinement, adopting the method shown in Example 6 to carry out the refined epi-tetrahydrodicyclopentadiene ( 3), adopt the method shown in embodiment 7 to carry out the measurement result of the refractive index and transmittance of refined dicyclohexyl, isopropyl cyclohexane, cyclooctane, cycloheptane after refining are shown in table 3 and table 4. In addition, acetonitrile as a reference liquid, pure water as a liquid for immersion exposure, and diiodomethane were used as comparative examples.

Regarding the refractive index, the refractive index in the ultraviolet range was measured for cis, trans-decalin, and purified trans-decalin, dicyclohexyl, isopropylcyclohexane, cyclooctane, cycloheptane, and acetonitrile. As a measurement device, a goniospectrospectrometer type 1 UV-VIS-IR manufactured by Moller-Wedel Co. was used, and the measurement method was the minimum deflection angle method at a measurement temperature of 25°C.

Transmittance was performed using Assay A or Assay B. Determination method A is determined by the following steps: In a glove box with nitrogen atmosphere controlled at an oxygen concentration of less than or equal to 0.5ppm, liquid sampling is carried out in a polytetrafluoroethylene capped pool with an optical path of 10 mm, using JASCO Corporation Manufactured JASCO-V-550 is measured using the above-mentioned cell with air as a reference. The values in the table are calculated and converted to optical distance 1mm after calculating the reflection of the calibration cell.

Measurement method B is carried out in a glove box with nitrogen atmosphere controlled at an oxygen concentration of less than or equal to 0.5ppm, in a covered quartz cell made of polytetrafluoroethylene (for measurement: optical path 50mm, reference: optical path 10mm). sampling. Using the above-mentioned cell, the measurement was performed using JASCO-V-550 manufactured by JASCO Corporation, with a cell with an optical path length of 50 mm as a sample and a cell with an optical path length of 10 mm as a reference. The value of this measurement is made into the absorbance per optical path 40mm. The values in the table are converted into values per 1mm optical path according to the values.

table 3 wavelength(nm) Refractive index Decalin (cis, trans-mixture) Refined trans-decalin(1) Refined back-tetrahydrodicyclopentane (1) Refined dicyclohexyl Refined isopropylcyclohexane Refined cyclooctane Refined Cycloheptane Acetonitrile pure water 589 1.475 1.469 1.49 1.479 1.44 1.458 1.445 1.344 1.332 486.269 1.477 1.48 1.4926 - - - - 1.345 - 388.975 1.4989 - - - - - - 1.353 - 312.657 1.501 - 1.5228 - - 1.4893 1.475 1.366 - 289.444 1.517 - - - - 1.518 1.5035 1.386 - 253.728 1.539 - 1.5547 - - - - 1.403 - 226.572 1.568 - - - - - - 1.414 - 214.506 1.586 - 1.6014 - - 1.561 1.545 1.428 - 194.227 1.637 1.6315 1.6492 1.6384 1.5826 - - 1.441 1.433

Table 4 Transmittance (193nm:mm ^-1 )(%) Refractive index (193nm) Refractive index (589nm) Assay A Assay B Decalin (cis and trans mixture) 73.5 - 1.64 1.48 Trans-decalin (Tokyo Chemicals) less than or equal to 10 - - 1.48 Refined trans-decalin(1) 93.4 - 1.63 1.48 Refined trans-decalin(2) 96.8 - 1.63 1.48 Refined trans-decalin(3) - 99.5 1.63 1.48 H-Tetrahydrodicyclopentadiene less than or equal to 10 - - 1.49 Refined Na-tetrahydrodicyclopentadiene (1) 87.7 - 1.65 1.49 Refined Na-Tetrahydrodicyclopentadiene (2) 97.5 - 1.65 1.49 Refined Na-tetrahydrodicyclopentadiene (3) - 99.6 1.65 1.49 Refined bicyclohexyl 97.3 - 1.64 1.48 Refined isopropylcyclohexane 76.3 - 1.59 1.44 Refined cyclooctane 70.2 - - 1.46 Refined Cycloheptane 71 - - 1.44 Acetonitrile 91.8 - 1.44 1.34 pure water 94 - 1.44 1.34 Diiodomethane less than or equal to 10 - - 1.7

As shown in Table 3 and Table 4, the wavelength dependence of the refractive index is that as the wavelength decreases, the refractive index increases. The liquid of the present invention in the above table has a high refractive index of 1.58 or more at 193nm, for example.

In addition, the compounds of the present invention are low-polar compounds, so they have high solubility in gases such as oxygen and nitrogen. Therefore, it is easily affected by the dissolution of these gases, such as the absorption of dissolved oxygen or the absorption of ozone generated by photoexcitation of dissolved oxygen when placed in an atmospheric atmosphere, or the oxidation reaction related to dissolved oxygen. Tendency to decrease transmittance. Therefore, these compounds are preferably degassed and stored in an inert gas with little absorption such as nitrogen or argon. Specifically, the treatment is performed so that the oxygen concentration in the storage liquid is equal to or less than 100 ppm, more preferably equal to or less than 10 ppm. In addition, when deoxidation cannot be performed before exposure, it is particularly preferably equal to or less than 1 ppm, more preferably equal to or less than 10 ppb.

A liquid immersion exposure method using the liquid for liquid immersion exposure of the present invention will be described below.

The liquid for immersion exposure of the present invention is preferably stored in an inert gas as described above, and as the container at this time, it is preferable to use a container component or a cover component of the container (for example, a plasticizer mixed in plastic, etc.) that will not be washed. Store in a detached container. Examples of preferred containers include glass, metal (such as SUS), pottery, PTFE (polytetrafluoroethylene), PFEP (perfluoroethylene propylene copolymer), ECTFE (ethylene-chlorotrifluoroethylene copolymer) ), PTFE/PDD (polytetrafluoroethylene-perfluorodioxene copolymer), PFA (perfluoroalkoxyalkane), ETFE (ethylene-tetrafluoroethylene copolymer), PVDF (polyvinylidene fluoride), Fluoroplastic containers such as PVF (polyvinyl fluoride) and PCTFE (polychlorotrifluoroethylene) are preferred, but glass and fluororesin containers are particularly preferable.

In addition, as an example of a preferred container lid, for example, a lid that is made of polyethylene and does not contain a plasticizer, the material is glass, metal (such as SUS), pottery, PTFE (polytetrafluoroethylene), PFEP (full teflon) Fluoroethylene propylene copolymer), ECTFE (ethylene-chlorotrifluoroethylene copolymer), PTFE/PDD (polytetrafluoroethylene-perfluorodioxene copolymer), PFA (perfluoroalkoxyalkane), ETFE ( Ethylene-tetrafluoroethylene copolymer), PVDF (polyvinylidene fluoride), PVF (polyvinyl fluoride), PCTFE (polychlorotrifluoroethylene) and other fluororesin caps.

In addition, the piping used for infusing the liquid from the container to the exposure machine is preferably the same piping as described above that does not cause elution, and glass, metal, pottery, etc. are exemplified as preferable piping materials.

When the liquid for immersion exposure of the present invention is used for immersion exposure, fine particles and air bubbles (microbubbles) cause pattern defects and the like, and therefore, it is preferable to remove the fine particles and dissolved gas generating air bubbles before exposure.

As a method of removing fine particles, a method of filtering using an appropriate filter is mentioned. As the filter, it is preferable to use a filter that has a high particle removal efficiency and does not change its absorption at the exposure wavelength due to elution during filtration. As a preferable filter material, for example, glass, metal (such as SUS, silver) and metal oxide, PTFE (polytetrafluoroethylene), PFEP (perfluoroethylene propylene copolymer), ECTFE (ethylene-chlorotrifluoroethylene copolymer), PTFE/PDD (polytetrafluoroethylene-perfluorodioxene copolymer), PFA (perfluoroalkoxyalkane), ETFE (ethylene-tetrafluoroethylene copolymer), PVDF (polyvinylidene fluoride ), PVF (polyvinyl fluoride), PCTFE (polychlorotrifluoroethylene) and other fluororesins. In addition, it is also preferable to use materials selected from the above-mentioned preferred materials for the filter with respect to the material of peripheral parts such as the casing, core, holder, and plug of the filter.

Examples of methods for removing dissolved gas include reduced-pressure degassing, ultrasonic degassing, degassing using a gas-permeable membrane, and degassing using various degassers.

The liquid for immersion exposure of the present invention is a part of the optical system during exposure, and thus is preferably used in an environment that does not affect changes in optical properties such as the refractive index of the liquid. For example, it is preferably used in an environment where the temperature, pressure, etc. that affect the optical properties of the liquid are kept constant. For example, the temperature is preferably controlled within the range of ±0.1°C, more preferably within the range of ±0.01°C.

In addition, the liquid immersion exposure using the liquid of the present invention can also be carried out in the air atmosphere. As mentioned above, the solubility of oxygen in the liquid of the present invention is high, which may affect the absorption characteristics at the exposure wavelength. Exposure is performed in an inert gas that has little absorption and does not cause a chemical reaction with the liquid. As this inert gas preferable, nitrogen gas, argon gas, etc. are mentioned, for example.

In addition, from the viewpoint of preventing changes in the absorption characteristics of the liquid at the exposure wavelength due to contamination by organic components in the air, it is preferable to control the concentration of organic components in the atmosphere used to be below a certain level. As the method of controlling the concentration of the organic component, there may be mentioned the method of using the above-mentioned high-purity inert gas atmosphere, a filter for adsorbing the organic component, various gas purification tubes (apparatus), and the like. For concentration control, it is preferable to periodically analyze the surrounding atmosphere, for which various analysis methods using gas chromatography, for example, can be used.

As the liquid supply method of the immersion liquid in the exposure area, the mooving pool method, the seimming stage method, and the Local Fill method (local immersion method) are known (refer to the academic seminar on immersion liquid exposure technology (held on May 27, 2004) Seminar materials), the partial immersion method is preferable because the amount of liquid used for immersion exposure is small.

As the final (objective lens) lens material for immersion exposure using this liquid, current CaF ₂ or fused silica is preferable because of its optical properties. As other preferred lens materials, for example, fluorine salts of high-period alkaline earth metals M and salts represented by the general formula Ca _x M _1-x F ₂ , oxides of alkaline earth metals such as CaO, SrO, and BaO, etc., are preferred. For materials, the refractive index of the lens is higher than that of CaF ₂ (n@193nm=1.50) and fused silica (n@193nm=1.50). Therefore, it is especially important when designing and processing high NA lenses with a numerical aperture exceeding 1.5. preferred.

Since there is very little elution of resist components, the liquid of the present invention can be reused after use. When using a resist (or resist upper layer film) that can ignore the influence of elution of the resist film during exposure, the liquid of the present invention can be reused without purification, but at this time, it is preferable to After degassing, filtering and other treatment, it can be reused. From the viewpoint of simplification of the process, it is preferable to perform these treatments in-line.

In addition, in use, even if the level of elution from the above-mentioned resist film can be ignored in one use, when the number of uses exceeds a certain number of times, it can be predicted that the physical properties of the liquid will deteriorate due to the influence of accumulated impurities. Therefore, it is preferable to recover and refine after using a certain number of times.

As the purification method, methods such as water washing treatment, acid washing, alkali washing, rectification, purification using an appropriate filter (packed column), filtration, etc., and the above-mentioned liquid purification method of the present invention or by A method resulting from a combination of these refining methods. Among them, purification by water washing treatment, alkali washing, acid washing, rectification, or a combination of these refining methods is preferable.

The above-mentioned alkali washing is effective for removing the acid generated by exposure eluting in the liquid of the present invention, and acid washing is effective for removing the alkaline components in the resist eluting in the liquid of the present invention. Water washing treatment The liquid of the present invention is effective in removing eluents such as photoacid generators, basic additives, acids generated during exposure, and the like in the resist film.

For rectification, in addition to being effective for removing low-volatile compounds among the above-mentioned additives, it is also effective for removing hydrophobic components generated by decomposition of protective groups in resists during exposure.

The liquids for liquid immersion exposure represented by the formulas (1-1) to (1-9) can be used alone or in combination. A preferable example is the case of single use. By using it alone, it is easy to set the immersion exposure conditions.

In addition, the liquid of the present invention can be used in admixture with liquids other than the present invention as needed, so that optical properties such as refractive index and transmittance, contact angle, specific heat, viscosity, expansion rate and other physical properties can be adjusted to desired values.

As liquids other than the present invention used for this purpose, in addition to other solvents capable of immersion exposure, various defoamers, surfactants, etc. can be used, and are effective for reducing air bubbles and controlling surface tension.

The liquid immersion exposure is performed using the liquid for liquid immersion exposure mentioned above.

A photoresist is coated on a substrate to form a photoresist film. As the substrate, for example, a silicon wafer, a wafer coated with aluminum, or the like can be used. In addition, in order to maximize the potential of the resist film, an organic or inorganic antireflection film can be formed in advance on the substrate to be used, as disclosed in, for example, JP-A-6-12452.

The photoresist used is not particularly limited, and can be appropriately selected according to the purpose of use of the resist. Examples of the resin component of the photoresist include acid-dissociable group-containing polymers. The acid dissociative group is preferably not decomposed by exposure, and it is particularly preferred that the decomposed product is volatilized under exposure conditions and is not eluted in the liquid of the present invention. Examples of these polymers include resins containing alicyclic groups, lactone groups, derivatives thereof, and the like in polymer side chains, resins containing hydroxystyrene derivatives, and the like.

A photoresist using a resin having an alicyclic group, a lactone group, and derivatives thereof in a polymer side chain is particularly preferable. These photoresists have a chemical structure similar to that of an alicyclic hydrocarbon compound or a cyclic hydrocarbon compound containing a silicon atom in a ring structure, and thus are excellent in affinity with the liquid for immersion exposure of the present invention. In addition, the photoresist film is neither eluted nor dissolved.

Examples of photoresists include chemically amplified positive or negative resists containing acid-dissociable group-containing polymers as resin components, acid generators, acid diffusion control agents and other additives.

When using the liquid for immersion exposure of the present invention, a positive resist is particularly preferred. For chemically amplified positive resists, the acid-dissociable organic groups in the polymer are dissociated under the action of the acid generated from the acid generator by exposure to generate, for example, carboxyl groups. As a result, the exposure of the resist The solubility of the site to the alkali developing solution is improved, and the exposed site is dissolved and removed by the alkaline developing solution, whereby a positive resist pattern is obtained.

The photoresist film is formed by the following process: for example, the resin composition for forming the photoresist film is dissolved in a suitable solvent at a solid content concentration of 0.1 to 20% by weight, and then, for example, is filtered through a filter having a pore size of about 30 nm. filter to prepare a solution, apply the resist solution on a substrate by an appropriate coating method such as spin coating, cast coating, and roll coating, and perform prebaking (hereinafter referred to as "PB") to volatilize the solvent. . In addition, at this time, a commercially available resist solution can be used as it is. The photoresist film preferably has a higher refractive index than the immersion upper layer film and the liquid for immersion exposure. Specifically, it is preferable that the photoresist film has a refractive index n _RES greater than or equal to 1.65. In particular, when NA is equal to or greater than 1.3, n _RES is preferably greater than 1.75. In this case, it is possible to prevent a decrease in the contrast of exposure light due to an increase in NA.

In addition, in the liquid immersion exposure method, an upper layer film for liquid immersion can be further formed on the photoresist film.

As the upper layer film for immersion, as long as it can form a protective film on the photoresist film without causing sufficient transmittance and mixing with the photoresist film for the wavelength of the exposure light, and maintains a stable film. A film that does not elute in the above liquid used for immersion exposure and can be peeled off before development can be used. In this case, it is preferable that the upper layer film is easily dissolved in alkaline solution as a developing solution, since it will be peeled off during development.

Preferably, the side chain has at least one hexafluoromethanol group and carboxyl group as a substituent for imparting alkali solubility.

The upper layer film for liquid immersion preferably has the function of preventing multiple interference at the same time. In this case, the refractive index n _oc of the upper layer film for liquid immersion is preferably expressed in the following formula.

n _oc ＝(n _1q ×n _RES ) ^0.5

Here, n _1q and n _RES represent the refractive index of the liquid for immersion exposure and the refractive index of the resist film, respectively.

Specifically, n _oc is preferably in the range of 1.6 to 1.9.

The liquid immersion upper layer film can be formed by dissolving the resin composition for the liquid immersion upper layer film in a solvent that is not mixed with the resist film at a solid content concentration of 0.01 to 10%, and then using Apply the same method on the resist film and perform pre-baking.

Using the liquid for immersion exposure of the present invention as a medium, 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, followed by developing to form resist pattern. This step is a step of performing immersion exposure, baking at a predetermined temperature, and then developing.

The radiation used for immersion exposure can be selected and used, for example, visible light; ultraviolet rays such as g-rays and i-rays; Ultraviolet rays; X-rays such as synchrotron radiation; and various types of radiation such as charged particle rays such as electron rays. ArF excimer laser light (wavelength 193 nm) or KrF excimer laser light (wavelength 248 nm) is particularly preferable.

In addition, in order to improve the resolution, pattern shape, developability, etc. of the resist film, it is preferable to perform baking (hereinafter referred to as "PEB") after exposure. The firing temperature is appropriately adjusted depending on the resist to be used, and is usually about 30 to 200°C, preferably 50 to 150°C.

Next, the photoresist film is developed with a developing solution and washed to form a desired resist pattern.

Example

In order to evaluate the liquid for immersion exposure of the present invention, a resist film was formed using the radiation-sensitive composition shown below. In addition, an upper layer film for immersion shown below was formed on a part thereof. The characteristics (elution test, film solubility test, pattern formation evaluation) as a liquid for immersion exposure were measured using this resist film for evaluation.

Reference example 1

The resin used for the radiation-sensitive resin composition was prepared by the following method.

39.85g (40 mol%) of compound (S1-1), 27.47g (20 mol%) of compound (S1-2), 32.68g (40 mol%) of compound (S1-3) were dissolved in 200g of 2-butanone 4.13 g of methyl azobisisovalerate was further added to prepare a monomer solution, and a 1000-ml three-necked flask into which 100 g of 2-butanone was charged was purged with nitrogen for 30 minutes. After nitrogen purging, the reactor was heated to 80° C. while stirring, and the above-mentioned monomer solution prepared in advance was added dropwise over 3 hours using a dropping funnel. The polymerization reaction was carried out for 5 hours with the initiation of the polymerization as the start of dropping. After the polymerization is completed, the polymerization solution is cooled to 30° C. or less by water cooling, put into 2000 g of methanol, and the precipitated white powder is filtered. The filtered white powder was washed twice on the slurry with 400 g of methanol, filtered, and dried at 50° C. for 17 hours to obtain a white powder polymer (75 g, yield 75% by weight). The molecular weight of this polymer is 10300, and the result of ¹³ C-NMR analysis is the repeating unit represented by compound (S1-1), compound (S1-2), and compound (S1-3), and the content ratio of each repeating unit is 42.3:20.3 : 37.4 (mol%) copolymer. This polymer was made into resin (A-1).

Reference example 2

The resin used for the radiation-sensitive resin composition was prepared by the following method.

53.92g (50 mol%) of compound (S2-1), 10.69g (10 mol%) of compound (S2-2), 35.38g (40 mol%) of compound (S2-3) were dissolved in 187g of 2-butanone And obtain monomer solution (1), prepare the dimethyl 2 of 3.37g, the solution (2) that 2 '-azobis (2-methylpropionate) is dissolved in the 2-butanone that obtains of 64g, then 28.77g of the monomer solution (1) and 4.23g of the solution (2) prepared in advance were put into a 1000ml three-necked flask containing 15g of 2-butanone, and nitrogen was purged by a decompression replacement method. After nitrogen purging, the reactor was heated to 80° C. while stirring, and after 15 minutes, 258.98 g of monomer solution (1) and 24.64 g of solution (2) were added dropwise over 3 hours using an infusion pump. After the dripping was completed, stirring was continued for 4 hours. After the polymerization is completed, the polymerization solution is cooled to 30° C. or less by standing for cooling. After the reaction, the solution was left to cool, cooled to less than or equal to 30° C., put into 4000 g of isopropanol, and filtered out the white powder. The filtered white powder was washed twice on the slurry with 2000 g of isopropanol, filtered, and dried at 60° C. for 17 hours to obtain a white powder polymer (85 g, yield 85% by weight). The Mw of this polymer was 7600. As a result of ¹³ C-NMR analysis, there were repeating units represented by compound (S2-1), compound (S2-2), and compound (S2-3), and the content ratio of each repeating unit was 53.1: 8.5:38.4 (mol%) copolymer. This polymer was made into resin (A-2).

Reference example 3

The resin for forming the upper layer film for immersion liquid was produced by the following method.

Dissolve 50g of compound (S3-1), 5g of compound (S3-2), 25g of compound (S3-3), 20g of compound (S3-4) and 6.00g of methyl azobisisovalerate in 200g of methyl ethyl ketone, ready to become Monomer solution of homogeneous solution. Next, nitrogen purging was performed for 30 minutes in a 1000 ml three-necked flask into which 100 g of methyl ethyl ketone had been charged. After nitrogen purging, the flask was heated to 80° C. while stirring, and the previously prepared monomer solution was added dropwise at a rate of 10 ml/5 minutes using a dropping funnel. Polymerization was performed for 5 hours with the start of the dropwise addition taken as the point in time at which the polymerization started. After the polymerization, the reaction solution was cooled to 30° C. or less, and then, the reaction solution was poured into 2000 g of heptane, and the precipitated white powder was filtered. The operation of mixing the filtered white powder with 400 g of heptane, forming a slurry, and stirring was repeated twice, washed, filtered, and dried at 50° C. for 17 hours to obtain a white powder resin (E-1) (89 g, yield 89 wt. %). Mw of resin (E-1) was 7300.

Reference example 4

The resin for forming the upper layer film for immersion liquid was produced by the following method.

As a monomer, except that 70 g of compound (S4-1), 20 g of compound (S4-2) and 10 g of compound (S4-3) were used, resin (E-2) (88 g of white powder) was obtained in the same manner as in Reference Example 3. , Yield 88% by weight). The Mw of the resin (E-2) was 6800.

Reference example 5

A radiation-sensitive resin composition was obtained by the following method.

The resins, acid generators, acid diffusion controllers, and solvents shown in Table 5 were mixed to form a uniform solution, and then filtered through a membrane filter with a pore size of 200 nm to prepare radiation-sensitive resin compositions (F1 to F3). In Table 5, "part" is based on weight.

In addition, the acid generator (B), acid diffusion controller (C), and solvent (D) used are shown below.

Acid generator (B)

B-1: 4-Nafluoro-n-butylsulfonyloxyphenyl·diphenylsulfonium nonafluoro-n-butanesulfonate

B-2: Triphenylsulfonium nonafluorobutanesulfonate

Acid diffusion controller (C)

C-1: 2-Phenylbenzimidazole

solvent (D)

D-1: Propylene glycol monomethyl ether acetate

table 5 Radiation sensitive resin composition Resin (A) (parts) Acid generator (B) (part) Acid diffusion control agent (C) (part) Solvent (D) (parts) F-1 A-1(100) B-1(2.5) C-1(0.2) D-1(750) F-2 A-1(100) B-1(2.5) C-1(0.2) D-1(750) F-3 A-1(100) B-1(2.5) C-1(0.2) D-1(750)

Reference example 6

The upper film composition for immersion was prepared by the following method.

The resins and solvents shown in Table 6 were mixed to form a homogeneous solution, and then filtered through a membrane filter with a pore size of 200 nm to prepare upper membrane compositions (G1 and G2) for immersion. In Table 6, n-BuOH represents n-butanol, and "parts" are based on weight.

Table 6 Upper film composition Resin (E) (parts) Solvent (parts) G-1 E-1(1) n-BuOH(99) G-2 E-2(1) n-BuOH(99)

Reference example 7

The resist films (H-1 to H-5) for evaluation were produced by the following method.

On an 8-inch silicon wafer, the lower layer anti-reflection film ARC29 (manufactured by Blu-Wase Corporation) was coated by spin coating and PB (90°C, 60 seconds) to form a coating film with a film thickness of 77nm. Next, using the radiation-sensitive resin composition shown in Table 7, a resist film (205 nm in film thickness) was formed (H-1 to H-3).

In addition, after forming a resist film (film thickness: 205 nm) using the radiation-sensitive resin composition by the same method as above, on the resist film, spin coating, PB (130° C., 90 seconds) were applied to the resist film shown in Table 7. The upper layer film composition for the immersion solution shown was used to form an upper layer film with a film thickness of 32 nm (H-4 and H-5).

Table 7 Resist film Radiation sensitive resin composition Upper film composition H-1 F-1 - H-2 F-2 - H-3 F-3 - H-4 F-1 G-1 H-5 F-1 G-2

Example 1

Commercially available trans-decalin (trans-decalin) was purified by the following method to obtain a liquid for immersion exposure.

100ml of commercially available trans-decalin (manufactured by Tokyo Chemical Industry Co., Ltd., the transmittance at 193nm converted to 1mm optical path is less than or equal to 10%) is put into a 200ml eggplant-shaped flask with a glass-coated stirring piece, and 20ml concentrated sulfuric acid (product of Wako Pure Chemical Industries), set the rotation speed of the stirring plate to 500-1000 rpm, and stirred at 25° C. for 20 minutes. Then, concentrated sulfuric acid was removed by liquid separation, and the above operation was performed three times. Then, the separated organic layer was washed once with 50 ml of deionized water and washed three times with saturated aqueous sodium bicarbonate solution. Then, the organic layer was washed 3 times with pure water. It was confirmed at this time point that the pH showed 7 (neutral). Then, carry out drying with magnesium sulfate, adopt decantation to remove magnesium sulfate after drying, under pressure 10mmHg, utilize the distillation apparatus equipped with the Wedman type rectification tower of long 20cm to carry out vacuum distillation, reclaim 16 parts of 10ml fractions. Measure the absorbance of each fraction at 193nm (measurement conditions adopt the conditions of the above-mentioned measurement method A), convert into 12 fractions with a transmittance greater than or equal to 93% of the optical path of 1mm, and prepare a total of 120ml Trans-decalin with transmittance greater than or equal to 90%. In addition, each fraction was saturated with nitrogen, degassed under reduced pressure, and stored in a nitrogen-substituted glass container. After sealing in the container, the purity of the compound was analyzed by gas chromatography, and the purity (hereinafter referred to as "GC purity") was 99.92%. The refined trans-decalin obtained by the method of Example 1 is called the refined trans-decalin (1).

In addition, commercially available trans, cis-mixed decahydronaphthalene and commercially available cis-decalin were refined by the above method.

Example 2

Under a nitrogen atmosphere, sulfuric acid treatment was carried out in the same manner as in Example 1. Then, the same method as in Example 1 was used to refine commercially available trans-decalin (manufactured by Tokyo Chemical Industry Co., Ltd.; the transmittance at 193 nm converted to an optical path of 1 mm is less than or equal to 10%) to obtain a trans-decalin converted to an optical path of 1 mm. The transmittance of liquid is 96.8%. The dissolved oxygen and dissolved nitrogen concentrations of this liquid were analyzed by gas chromatography (detector TCD), and the dissolved oxygen concentration was less than 1 ppm (below the detection limit), and the dissolved nitrogen concentration was 119 ppm. In addition, the metal content of Li, Na, K, Mg, Cu, Ca, Al, Fe, Mn, Sn, Zn, Ni was measured by atomic absorption method, Ca was 1ppb, Zn was 6ppb, and other metals were less than 1ppb (below detection limit). The refined trans-decalin obtained by the method of Example 2 is called the refined trans-decalin (2).

This liquid has a small metal component, and can be used not only as a liquid for immersion exposure but also in optical devices used in the visible light region, and the like.

In addition, the purified trans-decalin (2) obtained in the above Example 2 was placed in the air to reach the air saturation state, and the transmittance at 193 nm was measured. The results are shown in Table 8.

Table 8 Oxygen concentration (μg/ml) Transmittance (%) (1mm) Refined trans-decalin(2) Less than 1 96.8 air saturated trans-decalin 61 74.8 Pure water (air saturated) 7 96.3

As shown in Table 8, it was confirmed that the transmittance increased when the oxygen concentration was not saturated.

In addition, the change in transmittance caused by contact with the resist film was measured by the following method.

In a nitrogen glove box with nitrogen replacement and oxygen concentration controlled at less than or equal to 10ppm, place the liquid on the silicon wafers with the resist films H-1 and H-4 for 3 minutes, so that the thickness of the liquid film reaches 0.8mm, and measure Change in transmittance at 193nm. Pure water was used as a comparative example. The results are shown in Table 9.

Table 9 before dipping After dipping in H1 After soaking in H4 Refined trans-decalin(2) 96.6% 96.8% 96.7% pure water 98.0% 97.1% 96.0%

As shown in Table 9, the transmittance of the purified trans-decalin (2) hardly changed even when it was in contact with the resist film.

The solubility of the acid generator in the purified trans-decalin (2) was measured by the following method.

Using triphenylsulfonium nonafluoro-n-butanesulfonate as an acid generator, add a predetermined amount of the acid generator to 100 ml of purified trans-decalin, stir for 1 hour, and check whether it is completely dissolved by visual inspection. Solubility was studied. Pure water was used as a comparative example. The results are shown in Table 10.

Table 10 liquid water (100ml) trans-decalin Solubility of nonafluorobutane sulfonic acid 50g Less than or equal to 0.5mg

As shown in Table 10, the acid generator was hardly dissolved in the purified trans-decalin (2).

Example 3

A liquid for immersion exposure was prepared by purifying commercially available penta-tetrahydrodicyclopentadiene by the following method.

Put 100 ml of commercially available Na-tetrahydrodicyclopentadiene (manufactured by Tokyo Chemical Industry Co., Ltd., the transmittance at 193 nm converted to 1 mm optical path is less than or equal to 10%) into a 200 ml eggplant-shaped flask with a glass-coated stirring plate , After cooling the internal temperature to 5°C with an ice-water bath, add 20ml of concentrated sulfuric acid (Wako Pure Chemical Products), set the rotation speed of the stirring plate to 500-1000rpm, and stir at 25°C for 20 minutes. Then, the concentrated sulfuric acid was removed by liquid separation, and the above operation was carried out 3 times. Then, the separated organic layer was washed once with 50 ml of deionized water and washed three times with saturated aqueous sodium bicarbonate solution. The organic layer was then washed 3 times with pure water. It was confirmed that the pH at this time showed 7 (neutral). Then, the organic layer was dried using magnesium sulfate, and the magnesium sulfate was removed by decantation. The 91 ml of the liquid obtained at this time was bubbled with nitrogen for 30 minutes, and the transmittance at 193 nm was measured (the measurement conditions used the conditions described in the above text). The result was 87.7% when converted to a 1 mm optical path. In addition, after saturating and degassing this liquid nitrogen, it stored in the glass container which replaced with nitrogen. The GC purity of the compound sealed in the container was 99.94%. The refined pap-tetrahydrodicyclopentadiene obtained by the method of Example 3 is called the refined pap-tetrahydrodicyclopentadiene (1).

Example 4

Under a nitrogen atmosphere, sulfuric acid treatment was carried out in the same manner as in Example 1. Then use the same method as in Example 3 to refine commercially available P-tetrahydrodicyclopentadiene, and then use the same method as in Example 2 to carry out vacuum distillation under a nitrogen atmosphere to obtain a 1mm optical path The transmittance is 97.5% liquid. Analyze the dissolved oxygen and dissolved nitrogen concentration of this liquid by gas chromatography (detector TCD), the dissolved oxygen concentration is lower than 1ppm (below the detection limit), and the dissolved nitrogen concentration is 100ppm. The refined pap-tetrahydrodicyclopentadiene obtained by the method of Example 4 is called the refined pap-tetrahydrodicyclopentadiene (2).

Example 5

In addition to using nitrogen refined by a nitrogen refiner, all operations are carried out in a glove box with a nitrogen concentration controlled to be less than or equal to 0.5ppm, and the degree of reduced pressure is controlled so that the steam temperature is less than or equal to 50°C for vacuum distillation. Adoption and implementation The same method as Example 1 was used to refine commercially available trans-decalin (Tokyo Chemical Products). Based on the absorbance value measured by the above-mentioned measurement method B, the transmittance per 1 mm optical path of the purified compound was calculated, and the result was T=99.5%. The oxygen concentration at this time was measured by GC (detector TCD). As a result, the oxygen concentration was less than 1 ppm, and the nitrogen concentration was 119 ppm. In addition, the GC purity was 99.92%. The refined trans-decalin obtained by the method of Example 5 is called the refined trans-decalin (3).

Example 6

In addition to using nitrogen refined by a nitrogen refiner, all operations are carried out in a glove box with a nitrogen concentration controlled to be less than or equal to 0.5ppm, and the degree of reduced pressure is controlled so that the steam temperature is less than or equal to 50°C for vacuum distillation. Adoption and implementation The same method of Example 3 carried out the purification of commercially available keto-tetrahydrodicyclopentadiene (Tokyo Chemical Products). Based on the absorbance value measured by the above-mentioned measurement method B, the transmittance per 1 mm optical path of the purified compound was calculated, and the result was T=99.6%. The oxygen concentration at this time was measured by GC (detector TCD), and it was found that the oxygen concentration was less than 1 ppm and the nitrogen concentration was 100 ppm. In addition, the GC purity was 97.80%. The refined pap-tetrahydrodicyclopentadiene obtained by the method of Example 6 is called the refined pap-tetrahydrodicyclopentadiene (3).

Example 7

Commercially available dicyclohexyl, isopropylcyclohexane, cyclooctane, and cycloheptane were purified by sulfuric acid treatment in the same manner as in Example 3 to obtain a liquid for immersion exposure.

In the above examples, the following conditions were used for the GC purity analysis.

Agilent Technology's GC6850 (column Agilent Technology HP-1 (non-polar type) detector FID) was used for determination. The measurement is carried out under the conditions that the injection port temperature is 250°C, the column temperature is 70°C-300°C (temperature rising method), and the carrier gas is helium. The purity was determined from the area ratio, taking the total peak area of FID as 100%.

Embodiment 8～Example 22 and Comparative Example 1～Comparative Example 2

Using the above-mentioned resist film for evaluation, the elution test, film solubility test, pattern formation evaluation (immersion pattern formation evaluation, immersion exposure evaluation using a two-beam interference exposure machine), and the change in absorbance when the resist is in contact ( or contamination) evaluated the liquid for immersion exposure of the present invention. The results are shown in Tables 11 to 14. In addition, the wavelength dependence of the refractive index is shown in Table 3, and there is a correlation in which the refractive index value increases as the wavelength decreases. Therefore, the refractive index at a short wavelength can be predicted by measuring the refractive index at D-rays (wavelength: 589 nm). In particular, since the liquid for immersion exposure of the present invention has a chemically similar structure to decahydronaphthalene shown in Table 1, it can be predicted from the refractive index of D-rays (wavelength: 589 nm). The refractive index at D-ray (wavelength 589 nm) is therefore shown. Both show higher values than the refractive index of pure water.

In addition, the liquids for immersion exposure shown in Examples 8 to 13 were purified according to Example 1, and the liquids for immersion exposure shown in Examples 14 to 22 were purified according to the method of Example 1.

(1) Elution test

After immersing the wafer coated with the above-mentioned resist film for evaluation in 300 ml of the liquid for immersion exposure shown in Table 11 for 30 seconds, the wafer was taken out, and HPLC (manufactured by Shimadzu Corporation, column Inertsil ODS-3 (inner diameter) 10mm×length 250mm), elution solvent: acetonitrile/water=80/20, detector: UV@205nm, 220nm, 254nm, sample injection volume 4μm) to determine whether there are impurities remaining in the liquid for immersion exposure. At this time, when impurities above the detection limit were confirmed by any detector, the elution test result was marked as ×, and when no impurity above the detection limit was confirmed, the elution test result was marked as ○.

(2) Solubility test of film

After measuring the initial film thickness of the wafer coated with the resist film for evaluation, the film thickness was measured again after immersion in 300 ml of the liquid for immersion exposure shown in Table 11 for 30 seconds. At this time, if the decrease in film thickness is within 0.5% of the initial film thickness, it is judged that the liquid for immersion exposure does not dissolve the resist film, and it is marked as "○", and if it is more than 0.5%, it is judged as immersion exposure Use a liquid to dissolve the resist film, and mark it as "×".

(3) Pattern formation evaluation test

Pattern Formation Evaluation Test (1)

For the wafer coated with the above-mentioned resist film for evaluation, use an ArF projection exposure apparatus S306C (manufactured by Nicon Co., Ltd.) to expose under the optical conditions of NA: 0.78, δ: 0.85, and 2/3Ann (exposure amount: 30mJ /cm ² ), and then perform PEB (130°C, 90 seconds) on a CLEAN TRACK ACT8 hot plate, and perform paddle stirring development with the LD nozzle of this CLEAN TRACK ACT8 (developing liquid composition: 2.38% by weight tetrahydroxide Ammonium Hydrogen Aqueous Solution) (60 seconds), rinsed with ultrapure water, and then spin-dried by centrifugation at 4000 rpm for 15 seconds (substrate A after development). Then, after immersing the developed substrate A formed by the above-mentioned pattern in the liquid for immersion exposure shown in Table 11 for 30 seconds, PEB, development, and rinsing were carried out in the same manner as above, and the developed substrate B was obtained. . The pattern corresponding to the mask pattern of 90 nm line and 90 nm space was observed with the scanning electron microscope (manufactured by Hitachi Instrument Co., Ltd.) S-9360 with respect to the board|substrate A and B after image development. At this time, when a good rectangular resist pattern of the same shape was obtained for the substrates A and B after development was visually observed, "◯" was marked, and when a good pattern was not obtained, "x" was marked. "-" indicates that no evaluation was performed.

Pattern Formation Evaluation Test (2)

The wafer exposed under the same conditions as in the pattern formation evaluation test (1) was immersed in the liquid for immersion exposure for 30 seconds, PEB, developed, and rinsed by the same method as above, and the developed substrate C was obtained. . At this time, when a good rectangular resist pattern of the same shape was obtained for the substrates A and C, it was marked as "◯", and when a good shape pattern was not obtained, it was marked as "×". "-" indicates that no evaluation was performed.

(4) Contact angle measurement test

Using Mode IDSA10L2E manufactured by Kruss, the contact angles of trans-decalin on the above-mentioned resist films H2, H4, H5, and quartz glass were measured (measurement method Elipse (tangentl) method). The results are shown in Table 12.

(5) Exposure test using two-beam interference

Except that the film thickness of the lower layer antireflection film was 29 nm, and the resist film thickness was 100 nm (for 45 nm) and 60 nm (for 30 nm), the evaluation film prepared by the same method as the resist film H2 was coated. The wafer of the resist film is between the lens and the wafer of a simple exposure device for two-beam interference type ArF immersion (for 45nm 1L/1S manufactured by Canon, for 35nm 1L/1S manufactured by Nicon Corporation, and for TE polarized light exposure). Insert the above-mentioned liquid for immersion exposure after refining into the space (gap 0.7mm) for exposure, then remove the liquid for immersion exposure on the wafer by air drying, and perform PEB (115°C, 90 seconds) on the wafer with a CLEAN TRACK ACT8 hot plate ), using the LD nozzle of the CLEAN TRACK ACT8 to perform paddle-type agitation and development (composition of the developer: 2.38% by weight tetrahydroammonium hydroxide aqueous solution) (60 seconds), rinse with ultrapure water, and scan through a scanning electron microscope ( The pattern was observed on the developed substrate using Hitachi Scientific Instruments Co., Ltd. S-9360. At this time, the case where a good resist pattern of L/S (1L/1S) of the desired size was obtained was marked as "◯", and the case where a good pattern was not obtained was marked as "×". The results are shown in Table 13.

(6) Absorbance change (or contamination) when resist is in contact

Use a pipette made of glass to add liquid (deionized water or refined trans-decalin (2) (other batches of products refined in the same way as in Example 2) to a petri dish with a diameter of 6 cm. At this time , adjust the liquid volume so that the film thickness of the liquid just reaches 1mm. Then, cover the top of the petri dish with a silicon wafer that has been coated with photoresist (H1, H4). Then, the wafer and the petri dish are turned upside down to become The state where the liquid is immersed in the photoresist film. At this time, the petri dish and the wafer are fully sealed so that the liquid does not leak from between the two, and attention is paid to keeping the wafer level so that the photoresist is on the entire part covered with the petri dish. The etching agent is evenly soaked by the liquid. Then dip with the prescribed dipping time, and the wafer and the petri dish are turned upside down again. Collect the liquid after these series of operations, and adopt the method of embodiment B to carry out the absorbance measurement of 193.4nm, according to the determination The absorbance per 1 cm absorbance was calculated. In addition, the above series of operations were performed in a nitrogen-filled glove box at 23° C. The results are shown in Table 14.

Table 11 Liquid for immersion exposure Resist film Elution test results Membrane Solubility Test Pattern formation evaluation test name Refractive index 193nm 589nm test (1) test (2) Example 8 cis-decalin 1.64 1.48 H1 ○ ○ ○ ○ 9 cis-decalin 1.64 1.48 H2 ○ ○ ○ ○ 10 cis-decalin 1.64 1.48 H3 ○ ○ ○ ○ 11 cis-decalin 1.64 1.48 H4 ○ ○ ○ ○ 12 cis-decalin 1.64 1.48 H5 ○ ○ ○ ○ 13 trans-decalin - 1.47 H1 ○ ○ ○ ○ 14 spiro[5.5]undecane - 1.48 H1 ○ ○ ○ ○ 15 H-Tetrahydrodicyclopentadiene 1.65 1.49 H1 ○ ○ ○ ○ 16 5-Sicyclo[4.4]nonane - 1.49 H1 ○ ○ ○ ○ 17 1-Ethyladamantane - 1.50 H1 ○ ○ ○ ○ 18 1,1,1-Tricycloheptylmethane - 1.51 H1 ○ ○ ○ ○ 19 Bicyclohexyl 1.64 1.48 H1 ○ ○ ○ ○ 20 Isopropylcyclohexane 1.59 1.44 H1 ○ ○ ○ ○ twenty one Cyclooctane - 1.46 H1 ○ ○ ○ ○ twenty two Cycloheptane - 1.44 H1 ○ ○ ○ ○ comparative example 1 pure water 1.44 1.34 H1 x ○ ○ ×(T-top shape) 2 Diiodomethane - - H1 x x ×(membrane dissolved) ×(membrane dissolved)

Table 12 Resist film contact angle (degrees) H2 twenty three H4 63.5 H5 64 Quartz glass less than or equal to 10

Table 13 liquid for immersion half spacing Photosensitive (Ecd)mJ/cm ² pattern shape Refined trans-decalin(1) 45nm 27.1 ○ Refined trans-decalin(1) 35nm - ○ Refined trans-decalin(2) 45nm 22.7 ○ Refined trans-decalin(2) 35nm - ○ Refined Na-tetrahydrodicyclopentadiene (1) 45nm 28.6 ○ Refined Na-tetrahydrodicyclopentadiene (1) 35nm - ○ Refined Na-Tetrahydrodicyclopentadiene (2) 45nm twenty three ○ Refined Na-Tetrahydrodicyclopentadiene (2) 35nm - ○ Isopropylcyclohexane 45nm - ○ Isopropylcyclohexane 35nm - no resolution Cyclooctane 45nm - ○ Cyclooctane 35nm - no resolution water 45nm - T-Tip Shape

Table 14 chip Dipping time (seconds) Absorbance at 193nm before dipping Absorbance at 193nm after dipping change in absorbance pure water H1 30 0.0838 0.2169 0.1331 180 0.2577 0.1739 H4 30 0.0917 0.0079 180 0.2298 0.1460 Refined trans-decalin(2) H1 30 0.1421 0.1414 -0.0007 180 0.1397 -0.0024 H4 30 0.1417 -0.0004 180 0.1421 0

As shown in Table 11, the liquid for immersion exposure of the present invention has a higher refractive index than pure water and has chemical structures shown in formulas (1-1) to (1-9), so it exhibits excellent resolution, Moreover, it does not dissolve the resist film alone or the resist film forming the upper layer film, does not elute the film components, and does not deform the shape of the resist pattern formed. In addition, as shown in Table 14, it can be seen that the absorbance of purified decahydronaphthalene does not change after extraction at an immersion time of 180 seconds.

In addition, it was found that as an evaluation method of the liquid for immersion exposure, the liquid for immersion exposure is brought into contact with the photoresist film formed on the substrate under a nitrogen atmosphere, and the absorbance at 193 nm of the liquid before and after contact is measured. Changes and comparisons make it possible to evaluate the degree of contamination of the liquid for immersion exposure.

The liquid for immersion exposure of the present invention is an alicyclic hydrocarbon compound or a cyclic hydrocarbon compound containing a silicon atom in the ring structure, so that the photoresist film will not be dissolved during the immersion exposure, and the resolution, image development, etc. can be formed. Excellent resist pattern, very suitable for manufacturing semiconductor devices that are expected to be further miniaturized in the future.

claims

(Amended in accordance with Article 19 of the Treaty)

1. A liquid for liquid immersion exposure, the liquid is used in a liquid immersion exposure device or a liquid immersion exposure method for exposing through the liquid filled between the lens of the projection optical system and the substrate, characterized in that: the liquid is placed in the above liquid immersion exposure device The working temperature range is a liquid, the liquid contains alicyclic hydrocarbon compounds or cyclic hydrocarbon compounds containing silicon atoms in the ring structure, and the above-mentioned alicyclic hydrocarbon compounds or cyclic hydrocarbon compounds containing silicon atoms in the ring structure are per The radiation transmittance of 1mm optical path is greater than or equal to 70%, and the refractive index of D rays is greater than or equal to 1.4.

2. The liquid for immersion exposure according to claim 1, characterized in that: the alicyclic hydrocarbon compound or the cyclohydrocarbon compound containing silicon atoms in the ring structure is selected from the following formula (1-1) to formula ( at least 1 compound of 1-9),

In formula (1-1), R ¹ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a fluorine atom, or a fluorine-substituted hydrocarbon group with 1 to 3 carbon atoms, n1, n2 each independently represent an integer of 1 to 3, and a represents an integer of 0 to 10. When there are multiple ^R1s , the ^R1s may be the same or different, and two or more ^R1s may be combined to form a ring structure ,

In formula (1-2), A represents a single bond or a methylene group which may be substituted by an alkyl group having 1 to 10 carbon atoms or a group having 2 to 14 carbon atoms which may be substituted by an alkyl group having 1 to 10 carbon atoms. An alkylene group, R ² represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a fluorine atom, or a fluorine-substituted hydrocarbon group with 1 to 3 carbon atoms, R ⁷ represents a hydrogen atom, An alkyl group with 1 to 10 carbon atoms, a fluorine atom, or a fluorine-substituted alkyl group with 1 to 3 carbon atoms. When there are multiple ^R7 , the ^R7 can be the same or different. Two or more R7 ⁷ can be combined with each other to form a ring structure, n3 represents an integer of 2 to 4, n4 represents an integer of 1 to 3, b represents an integer of 0 to 6, when there are multiple ^R2 , the ^R2 can be the same or different, 2 One or more ^R2 can combine with each other to form a ring structure,

In formula (1-3), ^R3 and ^R4 represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a fluorine atom, or a fluorine-substituted hydrocarbon group with 1 to 3 carbon atoms , when there are multiple ^R3 and ^R4 , the ^R3 and ^R4 can be the same or different, two or more ^R3 and ^R4 can be alone or combined to form a ring structure, n5 and n6 represents an integer from 1 to 3, c and d represent an integer from 0 to 8,

In (a), (b) and (c) of the formula (1-4), B represents a methylene group or an ethylene group, and ^R represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, and an aliphatic hydrocarbon group with 3 to 14 carbon atoms. Alicyclic hydrocarbon group, fluorine atom, or fluorine-substituted hydrocarbon group with 1 to 3 carbon atoms, e represents an integer of 0 to 10, n7 represents an integer of 1 to 3, when there are multiple R ⁵ , the R ⁵ can be the same or Can be different, 2 or more R ⁵ can combine with each other to form a ring structure,

In formula (1-5), R ⁶ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a fluorine atom, or a fluorine-substituted hydrocarbon group with 1 to 3 carbon atoms, and f represents An integer of 0 to 10, when there are multiple R ⁶ , the R ⁶ may be the same or different,

In formula (1-6), R ⁸ and R ^8' represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a fluorine atom, or a fluorine substitution with 1 to 3 carbon atoms Hydrocarbyl, g and h respectively represent an integer of 0 to 6, n8 and n9 represent an integer of 1 to 3,

In formula (1-7), R ¹¹ and R ¹² represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a fluorine atom, or a fluorine-substituted hydrocarbon group with 1 to 3 carbon atoms , n10 and n11 each independently represent an integer of 1 to 3, j and k represent an integer of 0 to 6, when there are multiple ^R11 and ^R12 , the ^R11 and ^R12 can be the same or different, two Or more R ¹¹ can be combined to form a ring structure, or two or more R ¹² can be combined to form a ring structure, X represents a single bond, a divalent aliphatic hydrocarbon group with 2 to 10 carbon atoms, and a carbon number 3-14 divalent alicyclic hydrocarbon groups,

In formula (1-8), R ¹³ represents an alkyl group with 2 or more carbon atoms, an alicyclic hydrocarbon group with 3 or more carbon atoms, a fluorine atom, or a fluorine-substituted hydrocarbon group with 2 to 3 carbon atoms, and p represents 1 An integer of ~6, when there are multiple R ^13s , the R ^13s may be the same or different, and two or more R ^13s may combine with each other to form a ring structure,

In formula (1-9), ^R14 represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a fluorine atom, or a fluorine-substituted hydrocarbon group with 1 to 3 carbon atoms, and n12 represents An integer of 1 to 3, q represents an integer of 0 to 9, and when there are a plurality of R ¹⁴ , the R ¹⁴ may be the same or different.

3. The liquid for immersion exposure according to claim 2, wherein the compound represented by the above formula (1-1) is represented by the following formula (2-1), and the compound represented by the above formula (1-4) The compound is represented by the following formula (2-2),

In formula (2-1), R ¹ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a fluorine atom, or a fluorine-substituted hydrocarbon group with 1 to 3 carbon atoms, and a represents An integer of 0 to 10. When there are multiple ^R1s , the ^R1s may be the same or different, and two or more ^R1s may combine with each other to form a ring structure,

In formula (2-2), R ⁵ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a fluorine atom, or a fluorine-substituted hydrocarbon group with 1 to 3 carbon atoms, and i represents An integer of 0 to 2. When there are multiple ^R5s , the ^R5s may be the same or different, and two or more ^R5s may combine with each other to form a ring structure.

4. The liquid for immersion exposure according to claim 1, characterized in that: when the thickness of the liquid film is 1 mm, and the liquid is contacted on the photoresist film for 180 seconds under a nitrogen atmosphere, the difference between before and after contact is The absorbance change of the liquid per 1cm optical path at 193nm is less than or equal to 0.05.

5. The liquid for immersion exposure according to claim 1, characterized in that it contains not less than 95% by weight of the alicyclic hydrocarbon compound or a ring containing a silicon atom in the ring structure relative to the entire liquid for immersion exposure. Hydrocarbons.

6. The liquid for immersion exposure according to claim 1, characterized in that the dissolved oxygen content of the liquid is less than or equal to 2 ppm.

7. The liquid for immersion exposure according to claim 1, characterized in that the total amount of metal contained in the liquid is less than or equal to 10 ppb.

8. The liquid for immersion exposure according to claim 7, wherein the metal is at least one metal selected from lithium, sodium, potassium, magnesium, copper, calcium, aluminum, iron, zinc, and nickel.

9. The liquid for immersion exposure according to claim 1, characterized in that the viscosity of the liquid at 25°C is less than or equal to 0.01 Pa·s.

10. The liquid for immersion exposure according to claim 1, characterized in that the refractive index at a wavelength of 193 nm is greater than or equal to 1.63.

11. The liquid for immersion exposure according to claim 10, characterized in that the radiation transmittance per 1 mm optical path at a wavelength of 193 nm is greater than or equal to 95%.

12. The liquid for immersion exposure according to claim 3, characterized in that the compound represented by the above formula (2-1) is trans-decalin, and the radiation transmittance per 1 mm optical path at a wavelength of 193 nm is greater than or equal to 95%, dissolved oxygen is less than or equal to 2ppm.

13. The liquid for immersion exposure according to claim 12, characterized in that it is a liquid with a purity of 95% by weight or higher obtained by washing and distilling trans-decalin raw material with concentrated sulfuric acid in a nitrogen atmosphere.

14. The liquid for immersion exposure according to claim 3, characterized in that the compound represented by the above formula (2-2) is N-tetrahydrodicyclopentadiene, and the radiation transmission per 1 mm optical path at a wavelength of 193 nm is The rate is greater than or equal to 95%, and the amount of dissolved oxygen is less than or equal to 2ppm.

15. The liquid for immersion exposure according to claim 14, which is characterized in that it is obtained by washing and distilling the raw material of Na-tetrahydrodicyclopentadiene with concentrated sulfuric acid under a nitrogen atmosphere, and the purity is greater than or equal to 95% by weight. liquid.

16. The method for producing the liquid for immersion exposure according to claim 1, characterized in that it comprises subjecting the liquid containing the alicyclic hydrocarbon compound or the cyclohydrocarbon compound containing silicon atoms in the ring structure to concentrated sulfuric acid under a nitrogen atmosphere. At least one process of washing and distillation.

17. Liquid immersion exposure method. The liquid immersion exposure method is to illuminate a mask with an exposure light beam, and expose the substrate with the above-mentioned exposure light beam through the liquid filled between the lens of the projection optical system and the substrate, characterized in that the above-mentioned liquid is The liquid for immersion exposure according to claim 1.

18. The liquid immersion exposure method according to claim 17, characterized in that: an upper layer film for immersion liquid is formed on the surface of the resist film on the above-mentioned substrate, and the upper layer film for liquid immersion contains a soluble alkali developing solution, and The upper film for immersion of the resin component insoluble in the liquid for immersion exposure according to claim 1 has at least one of a hexafluoromethanol group and a carboxyl group as a substituent for imparting alkali solubility.

19. Method for evaluating the degree of contamination of a liquid for immersion exposure, the method for evaluating the degree of contamination used in an immersion exposure device or method for exposing with a liquid filled between a lens and a substrate of a projection optical system degree of contamination of liquids when used for immersion exposure,

It is characterized in that: the liquid for immersion exposure is brought into contact with the photoresist film formed on the above-mentioned substrate under nitrogen atmosphere, and the change of absorbance of the above-mentioned liquid at a wavelength of 193nm before and after contact is measured and compared, thereby evaluating The degree of contamination of the liquid used for immersion exposure.

20. Liquid immersion exposure composition, characterized in that it contains more than or equal to 95% by weight of the compound represented by the following formula (2-1) or the following formula (2-2), and the amount of dissolved oxygen is less than or equal to 2 ppm,

In formula (2-1), R ¹ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a fluorine atom, or a fluorine-substituted hydrocarbon group with 1 to 3 carbon atoms, and a represents An integer of 0 to 10. When there are multiple ^R1s , the ^R1s may be the same or different, and two or more ^R1s may combine with each other to form a ring structure,

In formula (2-2), R ⁵ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a fluorine atom, or a fluorine-substituted hydrocarbon group with 1 to 3 carbon atoms, and i represents An integer of 0 to 2. When there are multiple ^R5s , the ^R5s may be the same or different, and two or more ^R5s may combine with each other to form a ring structure.

21. The liquid composition as claimed in claim 20, characterized in that the total amount of metal contained in the liquid composition is less than or equal to 10 ppb.

22. The liquid composition according to claim 20, characterized in that the compound represented by the above formula (2-1) is trans-decalin, and the radiation transmittance per 1 mm optical path at a wavelength of 193 nm is greater than or equal to 95%. .

23. The liquid composition according to claim 20, characterized in that the compound represented by the above formula (2-2) is N-tetrahydrodicyclopentadiene, and the radiation transmittance per 1mm optical path at a wavelength of 193nm is greater than Equal to 95%.

24. The liquid composition according to claim 20, characterized in that: the compound represented by the above formula (2-1) or formula (2-2) is treated by at least one method of washing with concentrated sulfuric acid and distillation under a nitrogen atmosphere. Refined.

Claims (25)

1. A liquid for liquid immersion exposure, the liquid is used in a liquid immersion exposure device or a liquid immersion exposure method for exposing through the liquid filled between the lens of the projection optical system and the substrate, characterized in that: the liquid is placed in the above liquid immersion exposure device The operating temperature range is a liquid containing alicyclic hydrocarbon compounds or cyclic hydrocarbon compounds containing silicon atoms in the ring structure. 2. The liquid for immersion exposure according to claim 1, characterized in that: the radiation transmittance of the alicyclic hydrocarbon compound or the cyclohydrocarbon compound containing silicon atoms in the ring structure at a wavelength of 193 nm per 1 mm optical path is greater than or equal to 70%, the refractive index of D rays is greater than or equal to 1.4. 3. The liquid for immersion exposure according to claim 2, characterized in that: the alicyclic hydrocarbon compound or the cyclohydrocarbon compound containing silicon atoms in the ring structure is selected from the following formula (1-1) to formula ( at least 1 compound of 1-9),

In formula (1-1), R ¹ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine substitution group with 1 to 10 carbon atoms. Hydrocarbyl, -Si(R ⁹ ) ₃ base, or -SO ₃ R ¹⁰ base, n1, n2 each independently represent an integer of 1 to 3, a represents an integer of 0 to 10, when there are multiple R ¹ , the R ¹ can be the same or different, two or more ^R1 can be combined with each other to form a ring structure, ^R9 and ^R10 represent an alkyl group with 1 to 10 carbon atoms, In formula (1-2), A represents a single bond or a methylene group which may be substituted by an alkyl group having 1 to 10 carbon atoms or a group having 2 to 14 carbon atoms which may be substituted by an alkyl group having 1 to 10 carbon atoms. Alkylene group, ^R2 represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine-substituted hydrocarbon group with 1 to 10 carbon atoms, -Si (R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, R ⁷ represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine-substituted alkyl group with 1 to 10 carbon atoms , or -Si(R ⁹ ) ₃ group, when there are multiple R ^7s , the R ^7s can be the same or different, and two or more R ^7s can combine with each other to form a ring structure, n3 represents an integer of 2 to 4 , n4 represents an integer of 1 to 3, b represents an integer of 0 to 6, when there are multiple R ² , the R ² can be the same or different, and two or more R ² can be combined to form a ring structure, R ⁹ and R ¹⁰ represent an alkyl group with 1 to 10 carbon atoms, In formula (1-3), R ³ and R ⁴ represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or an aliphatic hydrocarbon group with 1 to 10 carbon atoms. A fluorine-substituted hydrocarbon group, ^-Si (R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, when there are multiple R 3 and R ⁴ , the R ³ and R ⁴ can be the same or different, two or More R ³ and R ⁴ can be alone or combined to form a ring structure, n5 and n6 represent an integer of 1 to 3, c and d represent an integer of 0 to 8, R ⁹ and R ¹⁰ represent 1 to 10 carbon atoms the alkyl,

In (a), (b) and (c) of the formula (1-4), B represents a methylene group or an ethylene group, and ^R represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, and an aliphatic hydrocarbon group with 3 to 14 carbon atoms. Alicyclic hydrocarbon group, cyano group, hydroxyl group, fluorine atom, fluorine-substituted hydrocarbon group with 1 to 10 carbon atoms, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, e represents an integer of 0 to 10, n7 Represents an integer of 1 to 3. When there are multiple ^R5s , the ^R5s can be the same or different. Two or more ^R5s can be combined to form a ring structure. ^R9 and ^R10 represent carbon atoms of 1 to 10. 10 alkyl,

In the formula (1-5), ^R6 represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine substitution group with 1 to 10 carbon atoms. Hydrocarbyl group, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, f represents an integer from 0 to 10, when there are multiple R ⁶ , the R ⁶ may be the same or different, R ⁹ and R ¹⁰ represent An alkyl group with 1 to 10 carbon atoms,

In the formula (1-6), R ⁸ and R ^8' represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or an aliphatic hydrocarbon group with 1 to 14 carbon atoms. 10 fluorine-substituted hydrocarbon groups, -Si(R ⁹ ) ₃ groups, or -SO ₃ R ¹⁰ groups, g and h represent integers from 0 to 6, n8 and n9 represent integers from 1 to 3, R ⁹ and R ¹⁰ represent An alkyl group with 1 to 10 carbon atoms,

In formula (1-7), R ¹¹ and R ¹² represent an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or an aliphatic hydrocarbon group with 1 to 10 carbon atoms. fluorine-substituted hydrocarbon group, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, n10 and n11 each independently represent an integer of 1 to 3, j and k represent an integer of 0 to 6, when R ¹¹ and R When there are multiple ^{R 12} each, the R ¹¹ and R ¹² may be the same or different, two or more R ¹¹ may be combined to form a ring structure, or two or more R ¹² may be combined to form a ring structure, X represents a single bond, a divalent aliphatic hydrocarbon group with 2 to 10 carbon atoms, a divalent alicyclic hydrocarbon group with 3 to 14 carbon atoms, ^R9 and ^R10 represent an alkyl group with 1 to 10 carbon atoms,

In the formula (1-8), ^R13 represents an alkyl group with 2 or more carbon atoms, an alicyclic hydrocarbon group with 3 or more carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, a fluorine-substituted hydrocarbon group with 2 to 10 carbon atoms , -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, p represents an integer from 1 to 6, when there are multiple R ¹³ , the R ¹³ can be the same or different, two or more R ¹³ can be combined with each other to form a ring structure, R ⁹ and R ¹⁰ represent an alkyl group with 1 to 10 carbon atoms,

In formula (1-9), R ¹⁴ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine substitution group with 1 to 10 carbon atoms. Hydrocarbon group, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, n12 represents an integer of 1 to 3, q represents an integer of 0 to 9, when there are multiple R ¹⁴ , the R ¹⁴ can be the same or can be Different, R ⁹ and R ¹⁰ represent an alkyl group having 1 to 10 carbon atoms. 4. The liquid for immersion exposure according to claim 3, wherein the compound represented by the above formula (1-1) is represented by the following formula (2-1), and the compound represented by the above formula (1-4) The compound is represented by the following formula (2-2), In formula (2-1), R ¹ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine substitution group with 1 to 10 carbon atoms. Hydrocarbon group, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, a represents an integer from 0 to 10, when there are multiple R ^1s , the R ^1s can be the same or different, 2 or more R ¹ can combine with each other to form a ring structure, R ⁹ and R ¹⁰ represent an alkyl group with 1 to 10 carbon atoms, In formula (2-2), R ⁵ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine substitution group with 1 to 10 carbon atoms. Hydrocarbon group, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, i represents an integer from 0 to 2, when there are multiple R ⁵ , the R ⁵ can be the same or different, 2 or more R ⁵ may combine with each other to form a ring structure, and R ⁹ and R ¹⁰ represent an alkyl group having 1 to 10 carbon atoms. 5. The liquid for immersion exposure according to claim 1, characterized in that: when the thickness of the liquid film is 1 mm, and the liquid is contacted on the photoresist film for 180 seconds under a nitrogen atmosphere, the difference between before and after contact is The absorbance change of the liquid per 1cm optical path at 193nm is less than or equal to 0.05. 6. The liquid for immersion exposure according to claim 1, characterized in that it contains not less than 95% by weight of the alicyclic hydrocarbon compound or a cyclohydrocarbon containing a silicon atom in the ring structure relative to the entire liquid for immersion exposure. compound. 7. The liquid for immersion exposure according to claim 1, characterized in that the dissolved oxygen content of the liquid is less than or equal to 2 ppm. 8. The liquid for immersion exposure according to claim 1, characterized in that the total amount of metal contained in the liquid is less than or equal to 10 ppb. 9. The liquid for immersion exposure according to claim 8, wherein the metal is at least one metal selected from the group consisting of lithium, sodium, potassium, magnesium, copper, calcium, aluminum, iron, zinc and nickel. 10. The liquid for immersion exposure according to claim 1, characterized in that the viscosity of the liquid at 25°C is less than or equal to 0.01 Pa·s. 11. The liquid for immersion exposure according to claim 1, characterized in that the refractive index at a wavelength of 193 nm is greater than or equal to 1.63. 12. The liquid for immersion exposure according to claim 11, characterized in that the radiation transmittance per 1 mm optical path at a wavelength of 193 nm is greater than or equal to 95%. 13. The liquid for immersion exposure according to claim 4, characterized in that the compound represented by the above formula (2-1) is trans-decalin, and the radiation transmittance per 1 mm optical path at a wavelength of 193 nm is greater than or equal to 95%, dissolved oxygen is less than or equal to 2ppm. 14. The liquid for immersion exposure according to claim 13, characterized in that it is a liquid with a purity greater than or equal to 95% by weight obtained by washing and distilling trans-decalin raw material with concentrated sulfuric acid in a nitrogen atmosphere. 15. The liquid for immersion exposure according to claim 4, characterized in that the compound represented by the above formula (2-2) is N-tetrahydrodicyclopentadiene, and the radiation transmission per 1 mm optical path at a wavelength of 193 nm is The rate is greater than or equal to 95%, and the amount of dissolved oxygen is less than or equal to 2ppm. 16. The liquid for immersion exposure according to claim 15, which is characterized in that it is obtained by washing and distilling the raw material of Na-tetrahydrodicyclopentadiene with concentrated sulfuric acid under a nitrogen atmosphere, and the purity is greater than or equal to 95% by weight. liquid. 17. The method for producing the liquid for immersion exposure according to claim 1, characterized in that it comprises subjecting the liquid containing the alicyclic hydrocarbon compound or the cyclohydrocarbon compound containing silicon atoms in the ring structure to concentrated sulfuric acid under a nitrogen atmosphere. At least one process of washing and distillation. 18. Liquid immersion exposure method, the liquid immersion exposure method is to illuminate the mask with an exposure light beam, and expose the substrate with the above-mentioned exposure light beam through the liquid filled between the lens of the projection optical system and the substrate, characterized in that the above-mentioned liquid is The liquid for immersion exposure according to claim 1. 19. The liquid immersion exposure method according to claim 18, characterized in that an upper layer film for immersion liquid is formed on the surface of the resist film on the above-mentioned substrate, and the upper layer film for liquid immersion contains a soluble alkali developing solution, and The upper film for immersion of the resin component insoluble in the liquid for immersion exposure according to claim 1 has at least one of a hexafluoromethanol group and a carboxyl group as a substituent for imparting alkali solubility. 20. A method for evaluating the degree of contamination of liquid for immersion exposure, the method for evaluating the degree of contamination used in an immersion exposure device or method for immersion exposure that performs exposure with a liquid filled between a lens and a substrate of a projection optical system degree of contamination of liquids when used for immersion exposure, It is characterized in that: the liquid for immersion exposure is brought into contact with the photoresist film formed on the above-mentioned substrate under nitrogen atmosphere, and the change of absorbance of the above-mentioned liquid at a wavelength of 193nm before and after contact is measured and compared, thereby evaluating The degree of contamination of the liquid used for immersion exposure. 21. The liquid composition for immersion exposure, characterized in that it contains more than or equal to 95% by weight of the compound represented by the following formula (2-1) or the following formula (2-2), and the amount of dissolved oxygen is less than or equal to 2 ppm,

In formula (2-1), R ¹ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine substitution group with 1 to 10 carbon atoms. Hydrocarbon group, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, a represents an integer from 0 to 10, when there are multiple R ^1s , the R ^1s can be the same or different, 2 or more R ¹ can combine with each other to form a ring structure, R ⁹ and R ¹⁰ represent an alkyl group with 1 to 10 carbon atoms, In formula (2-2), R ⁵ represents an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 14 carbon atoms, a cyano group, a hydroxyl group, a fluorine atom, or a fluorine substitution group with 1 to 10 carbon atoms. Hydrocarbon group, -Si(R ⁹ ) ₃ group, or -SO ₃ R ¹⁰ group, i represents an integer from 0 to 2, when there are multiple R ⁵ , the R ⁵ can be the same or different, 2 or more R ⁵ may combine with each other to form a ring structure, and R ⁹ and R ¹⁰ represent an alkyl group having 1 to 10 carbon atoms. 22. The liquid composition according to claim 21, characterized in that the total amount of metal contained in the liquid composition is less than or equal to 10 ppb. 23. The liquid composition according to claim 21, characterized in that the compound represented by the above formula (2-1) is trans-decalin, and the radiation transmittance per 1 mm optical path at a wavelength of 193 nm is greater than or equal to 95%. . 24. The liquid composition according to claim 21, characterized in that the compound represented by the above formula (2-2) is N-tetrahydrodicyclopentadiene, and the radiation transmittance per 1mm optical path at a wavelength of 193nm is greater than Equal to 95%. 25. The liquid composition according to claim 21, characterized in that: the compound represented by the above formula (2-1) or formula (2-2) is treated by at least one method of washing with concentrated sulfuric acid and distillation under a nitrogen atmosphere. Refined.