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

Abstract

Disclosed is a liquid for immersion exposure having a high refractive index which enables to prevent elution or dissolution of a photoresist film component or a film component of an upper layer of the photoresist film and suppress defects during resist pattern formation in immersion exposure methods. Also disclosed is an immersion exposure method using such a liquid. Specifically disclosed is a liquid used in an immersion exposure apparatus or an immersion exposure method wherein exposure is performed through a liquid filled in the space between a lens of a projection optical system and a substrate. This liquid is in a liquid state within the temperature range at which the immersion exposure apparatus is operated, and is composed of an alicyclic hydrocarbon compound or a cyclic hydrocarbon compound containing a silicon atom in the ring structure.

Description

Immersion exposure liquid and immersion exposure method

Technical field

The present invention relates to immersion exposure liquid and immersion exposure methods, in detail, other than these liquid and method, are related to the immersion exposure preparation method of liquid, the evaluation method as immersion exposure liquid, new liquid composition.

Background technique

When manufacturing semiconductor element etc., use the substep type for each shooting area being transferred to as the pattern of the graticule of photomask on the chip for being coated with photoresist or the projection aligner of step-scan mode through projection optical system.

The exposure wavelength used is shorter, and the numerical aperture of projection optical system is bigger, and the Threshold of the resolution ratio for the projection optical system that projection aligner has is higher.Therefore, with the miniaturization of integrated circuit, the exposure wavelength used in projection aligner as radioactive ray wavelength shortens year by year, and the numerical aperture of projection optical system is also gradually increased.

In addition, when exposure is made, the depth of focus also becomes important in the same manner as resolution ratio.The Threshold of resolution ratio R and depth of focus δ are indicated with following mathematical expression respectively.

R=k1 λ/NA (i)

δ=k2 λ/NA²   (ii)

Wherein, λ is exposure wavelength, and k1, k2 are technological parameters, and NA is the numerical aperture of projection optical system, when the refractive index of air is set as 1, following formula (ii ') definition.That is, having used a side of the radioactive ray with short wavelength that can obtain big depth of focus δ when obtaining identical resolution ratio R.

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

As described above, so far, pass through the increase of the short wavelengthization of exposure light source, numerical aperture, constantly meet the miniaturization requirement of integrated circuit, now, the mass production for the half spacing 90nm node of 1L1S (1: 1 line and space) for having used ArF excimer laser (wavelength 193nm) as exposure light source is being studied.However, for the half spacing 65nm node of the next generation or 45nm node that further miniaturize, it is believed that only be difficult to reach by using ArF excimer laser.Therefore, for these next-generation technologies, F is being studied₂The use of the short wavelength light sources such as excimer laser (wavelength 157nm), EUV (wavelength 13nm).However, technical difficulty is high for the use of these light sources, now also in the situation for using difficulty.

In above-mentioned exposure technique, photoresist is formed in the wafer surface of exposure, transfers pattern on the photoresist.In pervious projection aligner, the space configured with chip is refracted the air that rate is 1 or nitrogen is full of.At this point, when being full of the space between chip and the lens of projection aligner with the medium of refractive index n, it was reported that the theoretical threshold values of resolution ratio R, depth of focus δ are indicated with following mathematical expression.

R=k1 (λ/n)/NA (iii)

δ=k2n λ/NA²     (iv)

Wherein, NA is not the numerical aperture of actual projection optical system, indicate the constant (accurately saying, numerical aperture NA ' NA '=nsin θ (n is as defined above) of projection optical system is indicated) defined with above-mentioned formula (ii ').

Above formula indicates to set optical system appropriate by the liquid for being full of refractive index n between the lens and chip of projection aligner, can theoretically make the threshold values and depth of focus 1/n, n times of resolution respectively.Such as, in ArF technique, if using water as above-mentioned medium, the refractive index n of the light of wavelength 193nm in water is n=1.44, therefore, compared with when using air or nitrogen as the exposure of medium, it can theoretically design that resolution R reaches 69.4% (R=k1 (λ/1.44)/NA), the depth of focus reaches 144% (δ=k21.44 λ/NA²) optical system.

The effective wavelength for the radioactive ray that such shortening is used to expose, the exposure method that more fine pattern can be transferred is known as immersion exposure, miniaturization for photoengraving from now on, especially count the photoengraving of 10nm unit, it is considered as required technology, projection aligner is also known (referring to patent document 1).

In the past, in immersion exposure method, as the liquid being full of between the lens and substrate of projection optical system, pure water is had studied in ArF excimer laser, in F₂In excimer laser, for the high reason of the transparency under 157nm, the use of fluorine class inert fluid etc. is had studied.

It for pure water, is easy to get in semiconductor fabrication factory, also there is no problem in the environment.In addition, being easy to carry out temperature adjusting, the thermal expansion of thermally-induced substrate by generating in exposure can be prevented, is used as ArF with immersion liquid liquid (referring to patent document 2), is used in the mass production of the device of half spacing node of 65nm really.

On the other hand, it is also known that addition methanol etc. is as the surface tension for reducing pure water, while the liquid (reference patent document 3) that the additive for increasing surface-active power obtains.

However, water saturates are in photoresist, and the cross sectional shape for generating photoresist pattern sometimes becomes the shape deterioration of T- end shape, and resolution ratio reduces due to using pure water.In addition, it is eluted in water due to the light acid propellant of composition photoresist, alkalinity additive, by water soluble ingredients such as the acid of exposure generation, it can also cause the shapes such as T- end shape to deteriorate sometimes, generate resolution ratio, the reduction of the depth of focus, bridge defects, defect is generated in pattern after imaging, pollutes lens surface.In addition, these ingredients are eluted in liquid the pollution that can cause liquid simultaneously, it is difficult to carry out the recycling of liquid.Therefore, complicated refinement treatment is continually needed.

Therefore, the case where in order to separate photoresist and water, there is the method for forming upper layer film on photoresist, but existing for enough translucency of exposure or be not enough with the Combination of photoresist etc., the problem of complicating there is also working hour.In addition, it is also reported that the CaF used in lens material in the past₂By water erosion (non-patent literature 1), therefore, the problem of also creating the coating material for needing coat lens surface.

On the other hand, as shown in above-mentioned formula (iii), the threshold values of resolution ratio is about 1.44 times of ArF dry type exposure, so as to predict: further miniaturizeing, in especially half spacing 45nm next-generation technology below, use is become difficult.

As described above, needing the refractive index at exposure wavelength (such as wavelength 193nm etc.) to be greater than pure water, the liquid high for the translucency of the light of these wavelength in the next-generation immersion exposure method further miniaturizeing.Also needing the liquid simultaneously is the adverse effect that will not cause additive from photoresist membrane elution, the dissolution of etchant resist, deterioration of pattern etc. to photoresist, and will not corrode the liquid of lens.Simultaneously with the high NAization as caused by introducing immersion exposure, the light as exposure has studied the introducing of polarised light, expects that the liquid is to meet other than above-mentioned requirements, such as do not make the curved liquid of direction of polarized light using properties such as optical activities.

As reaching the method for the purpose, for example, having attempted various salt being dissolved in water and having improved refractive index (non-patent literature 2).However, this method is difficult to carry out the concentration control of salt, in addition, and water similarly, the presence of imaging defect, lens caused by the elution as water soluble ingredient pollution the problems such as.

On the other hand, in F₂The fluorine class inert fluids such as the perfluoropolyether that exposure is studied in, such as refractive index at 193 nm are small, and therefore, it is difficult to use at that wavelength.In addition, immersion exposure liquid due to the high refractive index at wavelength 589nm and as microscope and up to the present well known organic bromide, iodide, such as translucency at 193 nm are poor and poor for the stability of photoresist.

Patent document 1: Japanese Laid-Open Patent Publication 11-176727 bulletin

Patent document 2: International Publication WO99/49504 bulletin

Patent document 3: Japanese Laid-Open Patent Publication 10-303114 bulletin

Non-patent literature 1:NIKKEI MICRODEVICE in April, 2004 p77

Non-patent literature 2:Proc.SPIE Vol.5377 (2004) is p.273

Summary of the invention

The present invention was completed to solve the above problem, one kind is designed to provide in immersion exposure method, refractive index is greater than pure water, there is excellent translucency under the immersion exposure wavelength, it can prevent the elution or dissolution of photoresist or its upper layer film ingredient (especially hydrophilic composition), do not corrode lens, it is able to suppress defect when corrosion-resisting pattern generates, when being used as immersion exposure liquid, it is able to suppress the deterioration of pattern form, form resolution ratio and the superior pattern of the depth of focus, and liquid is easy to recycling and the immersion exposure liquid refined and the immersion exposure method for having used the liquid.

In addition, the object of the invention is also to provide preparation method, the evaluation methods as immersion exposure liquid, new liquid composition that the immersion exposure uses liquid other than above-mentioned immersion exposure liquid and immersion exposure method.

In order to solve the above problems, there is high transmissivity under the exposure wavelength that can be used in this purpose, and it is condition that immersion exposure liquid must meet that refractive index is sufficiently high compared with water.On the other hand, it is generally known that the refractive index of the ultraviolet region of liquid is related with the molecular polarizability of liquid is constituted.As the method for improving polarizability, the element with the n electronics for being easy migration such as sulphur, bromine, iodine is in general introduced into molecule and introduces carbon-to-carbon double bond, the carbon-carbon triple bond with the pi-electron for being relatively easy migration, especially aromatic rings is effective.However, the generally far ultraviolet region such as in 193nm of the compound containing these elements and molecular structure has strong absorb, it is impossible to be used in this purpose.On the other hand, as absorbing small compound for far ultraviolet region, non-substituted hydrocarbon compound, cyanalation hydrocarbon compound, fluorinated hydrocarbon compound, sulfonate compound, a part of alcohol etc. can be enumerated, but the general refractive index of these compounds is higher than water, refractive index and present water difference are little.

On the other hand, as the more accurate theoretical formula of the refractive index of liquid, following formula (Lorentz-Lorenz formula) is proposed, report the result (J.Phy.Chem.A. that the refractive index n of benzene can be accurately predicted using following formula, Vol.103, No.42,1999 p8447).

N=(1+4 π N α^eff)^0.5

In above formula, N indicates the molecular number in unit volume, and part molal volume is smaller, and value is bigger.

It can be predicted by above-mentioned formula: by introducing the functional group of high-selenium corn, even if α cannot be improved, but also can be improved refractive index by increasing N.Based on above description, various researchs have been carried out to the molecular structure of liquid, as a result, it has been found that: due to compact structure, the high alicyclic of the invention of density or containing silicon and with cyclic hydrocarbon skeleton liquid have both the transparency and refractive index, and when being used as immersion exposure liquid, it can prevent the elution or dissolution of photoresist or its upper layer film ingredient (especially hydrophilic composition), the problems such as erosion of defect, lens when solution corrosion-resisting pattern generates in turn, it is capable of forming resolution ratio and the superior pattern of the depth of focus, thereby completing the present invention.

I.e., the immersion exposure of the invention liquid used in the immersion exposure device or immersion exposure method that liquid is that the liquid being full of between the lens and substrate by projection optical system is exposed, it is characterized by: the liquid immersion exposure device work within the temperature range of be liquid, be alicyclic hydrocarbon compound or in ring structure containing the cyclic hydrocarbon compound of silicon atom.

Particularly, alicyclic hydrocarbon compound or contain the cyclic hydrocarbon compound of silicon atom in ring structure, it is characterised in that: it is more than or equal to 1.4 preferably 1.4~2.0 that the radioactive ray transmissivity of every 1mm light path, which is more than or equal to the refractive index of 70%, D ray, at wavelength 193nm.

Immersion exposure method of the invention, it is to illuminate exposure mask with exposing light beam, by the liquid being full of between the lens and substrate of projection optical system, the immersion exposure method that substrate is exposed using exposing light beam, it is characterised in that: aforesaid liquid is the immersion exposure liquid.

Immersion exposure method of the invention uses hydrophobicity is high, is at the exposure wavelength the alicyclic hydrocarbon compound of high refractive index or contains silicon atom in ring structure cyclic hydrocarbon compound as immersion exposure liquid, so as to prevent photoresist or its upper layer film ingredient, the especially elution or dissolution of hydrophilic composition, it is able to solve defect, the erosion problem of lens when corrosion-resisting pattern generates, in addition, when being used as immersion exposure liquid, it is able to suppress the deterioration of pattern form, improves resolution ratio and the depth of focus.

Specific embodiment

Can be used as the alicyclic hydrocarbon compound of immersion exposure liquid or the cyclic hydrocarbon compound in ring structure containing silicon atom is preferably respectively alicyclic ring saturated hydrocarbon compound or the ring filling hydrocarbon compound in ring structure containing silicon atom.If there are unsaturated bond in hydrocarbon compound, exposing light beam is easy by immersion exposure liquid absorption.

For can be used as the alicyclic hydrocarbon compound of immersion exposure liquid or in ring structure containing the cyclic hydrocarbon compound of silicon atom, it is illustrated by following formula (1-1)~formula (1~9).

In formula (1-1), R¹Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, n1, n2 each independently represent 1~3 integer, and a indicates 0~10 integer, when there are multiple R¹When, the R¹It can be the same or different, 2 or more R¹Ring structure, R can be bound to each other to form⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

As R¹In carbon atom number 1~10 aliphatic alkyl, methyl, ethyl, n-propyl etc. can be enumerated.As 2 or more R¹It is bound to each other to form the example of ring structure, cyclopenta, cyclohexyl etc. can be enumerated.As the alicyclic hydrocarbon radical of carbon atom number 3~14, cyclohexyl, norborny (norbornyl) etc. can be enumerated.As the fluorine substituted hydrocarbon radical of carbon atom number 1~10, trifluoromethyl, pentafluoroethyl group etc. can be enumerated.As composition-Si (R⁹)₃The R of base⁹And composition-SO₃R¹⁰The R of base¹⁰, indicate that the alkyl of carbon atom number 1~10 can enumerate methyl, ethyl etc. as the alkyl.

In formula (1-1), as substituent R¹, from the viewpoint of the radioactive ray transmissivity of 193nm is excellent, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, the alicyclic ring saturated hydrocarbyl of carbon atom number 3~14, cyano, fluorine atom, carbon atom number 1~10 fluorine replace saturated hydrocarbyl.

In above-mentioned substituent group, since higher refractive index can be obtained, it is few with the interaction of resist, it is difficult to cause by the defect of the elution generation of the water soluble ingredient in resist, to the erosion of lens material, thus the alicyclic saturated hydrocarbon base of the sturated aliphatic hydrocarbon base of particularly preferably carbon atom number 1~10, carbon atom number 3~14.

Additionally, it is preferred that n1, n2 be 1~3, particularly preferred n1, n2 be 1 or 2, preferred a be 0,1 or 2.As a, the refractive index especially in the case where it is 0, such as at 193 nm increases, thus particularly preferably.

It is exemplified below the specific example of preferred alicyclic ring saturated hydrocarbon compound shown in formula (1-1).It should be noted that in the present specification, the hydrogen atom in alicyclic ring saturated hydrocarbon compound in conjunction with the carbon atom for forming ring is omitted.

It is exemplified below shown in formula (1-1) the preferably specific example of the compound containing cyano.

It is exemplified below shown in formula (1-1) the preferably specific example of the compound containing fluorine atom.

It is exemplified below the specific example that preferred fluorine shown in formula (1-1) replaces saturated hydrocarbon compound.

In the preferred compound shown in formula (1-1), preferred alicyclic ring saturated hydrocarbon compound, wherein as particularly preferred compound, following formula (2-1) compound represented can be enumerated.

In formula (2-1), R¹With the R of a and formula (1-1)¹It is identical with a.

As the specific example in formula (2-1), the compound as cited by above-mentioned (1-1-16), (1-1-19), (1-1-20), (1-1-21), (1-1-34), (1-1-35), (1-1-36), (1-1-37), (1-1-38), (1-1-39) can be enumerated.

Wherein, the refractive index of the compound without substituent group for example at 193 nm increases, thus preferably, as more preferred example in formula (2-1), cis- decahydronaphthalenes, trans- decahydronaphthalenes can be enumerated.

In formula (1-2), A indicates singly-bound or can be by the alkyl-substituted methylene of carbon atom number 1~10 or can be by the alkylidene of the alkyl-substituted carbon atom number 2~14 of carbon atom number 1~10, R²Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, R⁷Indicate hydrogen atom, the alkyl of carbon atom number 1~10, cyano, hydroxyl, fluorine atom, carbon atom number 1~10 fluorine replace alkyl or-Si (R⁹)₃Base, n3 indicate that 2~4 integer, n4 indicate 1~3 integer, and b indicates 0~6 integer, when there are multiple R²Or R⁷When, the R²It can be the same or different, 2 or more R²Ring structure, R can be bound to each other to form⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

By the alkyl-substituted methylene of carbon atom number 1~10 or ethylidene, sub- n-propyl etc. can can be enumerated by the alkylidene of the alkyl-substituted carbon atom number 2~14 of carbon atom number 1~10 as in A.

R²With the R of formula (1-1)¹It is identical.

In formula (1-2), as substituent R², from the viewpoint of the radioactive ray transmissivity of 193nm is excellent, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, the alicyclic ring saturated hydrocarbyl of carbon atom number 3~14, cyano, fluorine atom, carbon atom number 1~10 fluorine replace saturated hydrocarbyl.

In above-mentioned substituent group, for R in (1-1)¹The alicyclic saturated hydrocarbon base of identical reason, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, carbon atom number 3~14.

Preferred n3 is 2~4, particularly preferably 2 or 3, and preferred n4 is 1~3, particularly preferably 1 or 2, and preferred b is 0 or 1 or 2.As b, since refractive index for example at 193 nm increases, thus particularly preferably 0.The specific example of preferred (1-2) described below.

As more preferred example in formula (1-2), 1,1,1- tri- suberyl methane, 1,1,1- tri- cyclopenta methane can be enumerated.

In formula (1-3), R³And R⁴Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base works as R³And R⁴When being individually present multiple, the R³And R⁴It respectively identical can also be different, 2 or more R³And R⁴Respectively individually or it can be bound to each other to form ring structure, n5 and n6 indicate that 1~3 integer, c and d indicate 0~8 integer, R⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

R³And R⁴With the R of formula (1-1)¹It is identical.

In formula (1-3), as substituent R³And R⁴From the viewpoint of the radioactive ray transmissivity of 193nm is excellent, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, the alicyclic ring saturated hydrocarbyl of carbon atom number 3~14, cyano, fluorine atom, carbon atom number 1~10 fluorine replace saturated hydrocarbyl.

In above-mentioned substituent group, for R in (1-1)¹The alicyclic saturated hydrocarbon base of identical reason, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, carbon atom number 3~14.

Preferred n5 and n6 is 1~3, particularly preferably 1 or 2, and c and d are 0 or 1 or 2.Since refractive index for example at 193 nm increases, thus both particularly preferably c and d is 0.The specific example of preferred compound (1-3) described below.

As preferred example in formula (1-3), spiral shell [5.5] hendecane can be enumerated.

In (a) of formula (1-4), (b), (c), B indicates methylene or ethylidene, R⁵Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, when there are multiple R⁵When, the R⁵It can be the same or different, 2 or more R⁵It can be bound to each other to form ring structure, e indicates that 0~10 integer, n7 indicate 1~3 integer, R⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

R⁵With the R of formula (1-1)¹It is identical.

In formula (1-4), as substituent R⁵, from the viewpoint of the radioactive ray transmissivity of 193nm is excellent, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, the alicyclic ring saturated hydrocarbyl of carbon atom number 3~14, cyano, fluorine atom, carbon atom number 1~10 fluorine replace saturated hydrocarbyl.

In above-mentioned substituent group, for the R with (1-1)¹The alicyclic ring saturated hydrocarbyl of identical reason, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, carbon atom number 3~14.

Preferred c is 0 or 1 or 2, and n7 is 1~3, particularly preferably 1 or 2.Since refractive index for example at 193 nm increases, thus particularly preferably e be 0 the case where.The example of preferred compound (1-4) described below.

It, can be with enumeration (2-2), formula (2-2 ') compound represented as preferred compound in formula (1-4).

In formula (2-2), (2-2 '), R⁵With the R in formula (1-4)⁵Identical, preferred i is 0,1 or 2.For the reason identical as a in (1-1), particularly preferred i is 0.

As preferred compound (2-2), the specific example of (2-2 '), the compound of above-mentioned (1-4-1)~(1-4-6) can be enumerated.

As particularly preferred specific example, extension-tetrahydro-dicyclopentadiene can be enumerated.

In formula (1-5), R⁶Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, f indicates 0~10 integer, when there are multiple R⁶When, the R⁶It can be the same or different, R⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

R⁶With the R of formula (1-1)¹It is identical.

In formula (1-5), as substituent R⁶, from the viewpoint of the radioactive ray transmissivity of 193nm is excellent, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, the alicyclic ring saturated hydrocarbyl of carbon atom number 3~14, cyano, fluorine atom, carbon atom number 1~10 fluorine replace saturated hydrocarbyl.

In above-mentioned substituent group, for the R with formula (1-1)¹The alicyclic saturated hydrocarbon base of identical reason, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, carbon atom number 3~14.

Preferred f is 1 or 2.In addition, the preferred end of the bridge position in the position of substituent group.

As preferred example in formula (1-5), following formula compound represented can be enumerated.

In formula (1-6), R⁸And R^8’Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, g and h respectively indicate 0~6 integer, and n8 and n9 indicate 1~3 integer, R⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

R⁸And R^8’With the R of formula (1-1)¹It is identical.

In formula (1-6), as substituent R⁸And R^8’, from the viewpoint of the radioactive ray transmissivity of 193nm is excellent, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, the alicyclic ring saturated hydrocarbyl of carbon atom number 3~14, cyano, fluorine atom, carbon atom number 1~10 fluorine replace saturated hydrocarbyl.

In above-mentioned substituent group, for R in formula (1-1)¹The alicyclic saturated hydrocarbon base of identical reason, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, carbon atom number 3~14.

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

The specific example of preferred compound (1-6) described below.

As preferred example in formula (1-6), 5- silicon ring [4,4] nonane can be enumerated.

In formula (1-7), R¹¹And R¹²Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, n10, n11 each independently represent 1~3 integer, and j, k indicate 0~6 integer, work as R¹¹And R¹²When being individually present multiple, the R¹¹And R¹²It can be the same or different, 2 or more R¹¹Ring structure or 2 or more R can be bound to each other to form¹²Can be bound to each other to form ring structure, X indicate singly-bound, the aliphatic alkyl of the divalent of carbon atom number 2~10, carbon atom number 3~14 divalent alicyclic hydrocarbon radical, R⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

R¹¹And R¹²The aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base and aliphatic alkyl, alicyclic hydrocarbon radical, fluorine substituted hydrocarbon radical ,-Si (R in formula (1-1)⁹)₃Base ,-SO₃R¹⁰Base phase is same.

In formula (1-7), as substituent R¹¹And R¹², from the viewpoint of the radioactive ray transmissivity of 193nm is excellent, preferably the sturated aliphatic hydrocarbon base of carbon atom number 1~10, the alicyclic ring saturated hydrocarbyl of carbon atom number 3~14, cyano, fluorine atom, carbon atom number 1~10 fluorine replace saturated hydrocarbyl.

In addition, the aliphatic alkyl of the divalent of the carbon atom number 2~10 as X, can enumerate ethylidene, propylidene, the alicyclic hydrocarbon radical of the divalent as carbon atom number 3~14 can be enumerated from pentamethylene, divalent group of hexamethylene etc..

In formula (1-7), X is preferably singly-bound.The specific example of preferred compound (1-7) described below.

As the example of preferred formula (1-7), dicyclohexyl (dicyclohexyl), Bicvclopentyl (dicyclopentyl) can be enumerated.

In formula (1-8), R¹³Indicate alkyl of the carbon atom number more than or equal to 2, alicyclic hydrocarbon radical of the carbon atom number more than or equal to 3, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 2~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, p indicates 1~6 integer, when there are multiple R¹³When, the R¹³It can be the same or different, 2 or more R¹³Ring structure, R can be bound to each other to form⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

Preferred R¹³It is the alicyclic hydrocarbon radical of the alkyl of carbon atom number 2~10, carbon atom number 3~14, preferred p is 1 or 2, and particularly preferred p is 1.

The alkyl of alkyl preferred carbon atom number 2~10 of the above-mentioned carbon atom number more than or equal to 2, can enumerate methyl, ethyl, n-propyl etc..The alicyclic hydrocarbon radical of alicyclic hydrocarbon radical preferred carbon atom number 3~14 of the above-mentioned carbon atom number more than or equal to 3, can enumerate cyclohexyl, norborny etc..Fluorine substituted hydrocarbon radical, the-Si (R of carbon atom number 2~10⁹)₃Base or-SO₃R¹⁰Base and fluorine substituted hydrocarbon radical ,-Si (R in formula (1-1)⁹)₃Base or-SO₃R¹⁰Base phase is same.2 or more R¹³The ring structure being bound to each other to form can enumerate cyclopenta, cyclohexyl etc..

The specific example of preferred compound in formula (1-8) described below.

In formula (1-9), R¹⁴Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, n12 indicate 1~3 integer, and q indicates 0~9 integer, when there are multiple R¹⁴When, the R¹⁴It can be the same or different, R⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

R¹⁴With the R in formula (1-1)¹It is identical.Additionally, it is preferred that R¹⁴With preferred R¹It is identical.Preferred q is identical as a.

The specific example of preferred compound in formula (1-9) described below.

In formula (1-1)~formula (1-9), particularly preferred compound is with chemical structure shown in formula (1-1), formula (1-4), and these compounds are compounds that is non-substituted or being replaced by the alicyclic ring saturated hydrocarbyl of the sturated aliphatic hydrocarbon base of carbon atom number 1~10, carbon atom number 3~14, wherein particularly preferably non-substituted compound.

Above compound is liquid at a temperature of immersion exposure device works, and the reasons why for above-mentioned (iii) formula, (iv) formula, preferred index is higher than pure water.

Specifically, preferred index is the value between the etchant resist (or immersion liquid upper layer film) before water and exposure, it and is higher value compared with water, at 25 DEG C, refractive index under wavelength 193nm is 1.45~1.8, preferably 1.6~1.8 range, at 25 DEG C, refractive index under wavelength 248nm is 1.42~1.65, preferably 1.5~1.65 range.In addition, the refractive index under D ray (wavelength 589nm) is more than or equal to 1.4 preferably 1.4~2.0, more preferably 1.40~1.65 range at 25 DEG C.

In addition, the variations in refractive index caused by the variation of use environment is as due to defocusing, this compound is preferably compound of the refractive index not vulnerable to influences such as temperature, pressure.It can predict that the light absorption bring due to lens, anticorrosive additive material is generated heat, temperature can change when in use, therefore the temperature dependency of particularly preferably refractive index is low.Specifically, the absolute value of the change rate dn/dT for the refractive index (n) that temperature (T) generates is preferably 5.0 × 10^-3(℃^-1) within, more preferably 7.0 × 10^-4(℃^-1) within.

In addition, preferably the specific heat of this compound is big value from this viewpoint, in particular, the value of specific heat is preferably greater than or equal to 0.1cal/g DEG C, more preferably greater than it is equal to 0.30cal/g DEG C.

In addition, the influence that above compound preferably its refractive index is not generated vulnerable to color difference, preferably small in the wavelength dependency of the refractive index on exposure wavelength periphery.

In addition, as other characteristics, translucency in far ultraviolet region is high, the solubility of the gases such as viscosity, oxygen, nitrogen, with lens, resist (or resistant upper layer film) contact angle, surface tension, flash-point etc. preferably in following ranges, furthermore, also it is desirable to small with the chemical interaction of lens, anticorrosive additive material.These characteristics described in detail below.

The transmissivity of radioactive ray transmissivity preferred light path 1mm at 25 DEG C under 193nm is more than or equal to 70%, is especially preferred more than equal to 90%, is further preferably greater than equal to 95%.At this point, easily causing the fever as caused by the thermal energy of the light absorption generation of liquid if transmissivity is lower than 70%, being easy to produce defocusing and deforming for refraction index changing bring optical image caused by being risen by temperature.In addition, due to the absorption of liquid, the reason of becoming the light quantity reduction for reaching etchant resist, yield is caused to be greatly reduced.

For viscosity, 20 DEG C of viscosity is, especially when being equal to 0.01Pas in use, being preferably less than in the environment that the gap between chip and lens material is less than or equal to 1mm, to be particularly preferably less than or equal to 0.005Pas less than or equal to 0.5Pas.If viscosity is more than 0.5Pas, liquid is difficult to the gap immersed between etchant resist (or immersion liquid upper layer film) and lens material, or it cannot obtain when using local immersion method as the supply method of immersion liquid liquid, enough scanning speeds when being used as Exposure mode in the way of the step-scan for carrying out blanket exposure to chip by the objective table of mobile bearing wafer, cause being greatly reduced for yield, in addition, there is also the tendency for being easy to produce the rising of the temperature caused by rubbing, it is easy to be influenced by the changes in optical properties as caused by temperature change.In addition, in the case that gap especially between chip and lens material is less than or equal to 1mm, for the above reasons, viscosity, which is preferably less than, is equal to 0.01Pas, at this point, can be improved the transmissivity of liquid by the distance (thickness of liquid film) for reducing gap, it can be allowed to be difficult to the influence by liquid absorption, thus be suitable.

In addition, be easy to produce in liquid when viscosity increases and generate bubble (nanometer bubble, microvesicle), in addition, the service life of the bubble extends, thus it is improper.

In addition, the solubility for gas in liquid of the present invention, with oxygen and nitrogen 25 DEG C, partial pressure be 1 atmospheric pressure (atm) when liquid in the solubility of gas molar fraction representation be preferably 0.5 × 10^-4~70 × 10^-4, further preferably 2.5 × 10^-4~50 × 10^-4, when the solubility of these gases is less than or equal to 0.5 × 10^-4When, it is difficult to disappear by the nanometer bubble of the generations such as resist, therefore, because light caused by bubble scatters, the defect of resist is easy to produce in pattern formation.In addition, if it is being more than or equal to 70 × 10^-4, the gas of surrounding can be absorbed in exposure, being easy changes in optical properties caused by by being absorbed by gas is influenced.

In addition, the contact angle between liquid of the invention and resist (or immersion liquid upper layer film) is preferably 20 °~90 °, and further preferably 50 °~80 °, in addition, with quartz glass or CaF₂The contact angle of equal lens materials, which is preferably less than, is equal to 90 °, is more preferably less than equal to 80 °.If the contact angle of the resist (or immersion liquid upper layer film) before liquid and exposure of the invention is less than or equal to 20 °, liquid is difficult to immerse gap, in addition, liquid is easy to disperse into film when the combination in the way of above-mentioned local immersion method and step-scan is as when Exposure mode.On the other hand, if the contact angle of the resist (perhaps immersion liquid upper layer film) before liquid and exposure of the invention, which is more than or equal to 90 °, is having the easy absorption gas in indent and convex resist (or upper layer film) interface, it is easy to produce bubble.Such phenomenon is recorded in 2003 Year-End Report (InternationalSEMATECH) of ImmersionLithography Modeling.

In addition, there are the tendencies for generating bubble between lens surface and liquid if the contact angle of liquid and lens material of the invention is more than 90 °.

In addition, especially when for similarly exposure device in such a way that local immersion method carries out the step-scan of immersion liquid used in the immersion exposure of present water, liquid when scanning disperses as problem, therefore the preferred surface tension of liquid of the invention is high.In particular, 20 DEG C of surface tension is preferably 5dyn/cm~90dyn/cm, further preferably 20dyn/cm~80dyn/cm.

When the contact angle of liquid of the invention and resist surface is improper, contact angle can be improved by using immersion liquid upper layer film appropriate.Especially because liquid of the invention is low polarity, thus contact angle can be improved by using highly polar upper layer film.

The elution of the resist ingredient of light acid propellant, the alkaline components that the liquid generates etc. not only can generate defect to the patternability of resist, adverse effect is generated to profile degradation etc., but also the pollution for causing liquid itself, such as the optical characteristics as liquid variation or lens erosion etc. reason.In addition, therefore the recycling of liquid becomes difficult, need frequently to carry out liquid purification.It is therefore preferable that the pollution as caused by the elution of liquid is few.It can use the method evaluation elution amount using HPLC etc., still, more precisely, the absorbance under 193nm is very sensitive for being mixed into for the ingredient in resist, therefore can evaluate by tracking the variation of the latter.As the requirement particularly for liquid, use the absorbance change (absorbance before absorbance-dipping after dipping) of every 1cm after impregnating 180 seconds in the immersion test of " absorbance change when resist contacts " for less than or equal to 0.05 in aftermentioned evaluation method, preferably less than it is equal to 0.02, is further preferably less than equal to 0.005.

Liquid of the invention is preferably the low compound of risk such as explode, catch fire under use environment, igniting.In particular, flash-point is preferably greater than to be equal to 25 DEG C, further preferably greater than it is equal to 50 DEG C, burning point is preferably greater than to be equal to 180 DEG C, is further preferably greater than equal to 230 DEG C.In addition, 25 DEG C of vapour pressure, which is preferably less than, is equal to 50mmHg, further preferably less than it is equal to 5mmHg.

Additionally, it is preferred that it is low to the harmfulness of human body, environment, in particular, about the harmfulness for human body, preferably acute toxicity is low, without the compound of carcinogenicity, anisotropic, the abnormalities, genotoxicity of rush of mutagens etc..In particular, acceptable concentration is preferably greater than to be equal to 30ppm, further preferably greater than it is equal to 70ppm, preferably Salmonella reversion test result is negative liquid.About the harmfulness for environment, preferably without residual, the cumulative compound of ecology.

In addition, liquid of the invention is particularly preferably greater than to be equal to 99.0 weight % more than or equal to 95.0 weight % preferably by the purity of gas Chromatographic Determination, further preferred purity is more than or equal to 99.9 weight %.

The big compound containing alkene of absorbance, the compound containing aromatic rings, the ratio of compound etc. containing sulphur (sulfide, sulfoxide, sulfone structure), halogen, carbonyl, ether are lower than 0.01 weight %, especially preferably less than 0.001 weight % preferably especially under the exposure wavelengths such as 193nm.

In addition, the liquid being made of this compound is for semiconductor integrated circuit manufacturing process, therefore preferably, metal or metal salt content are low, in particular, tenor is preferably less than to be equal to 10ppb less than or equal to 100ppb, are further preferably less than equal to 1.0ppb.If tenor is more than 100ppb, metal ion or metal component may bring adverse effect to etchant resist etc., pollute chip.

As metal, at least one kind of metal selected from Li, Na, K, Mg, Cu, Ca, Al, Fe, Zn, Ni can be enumerated.These metals can be measured by atom light absorption method.

In addition, the oxygen concentration in the liquid is preferably less than to be equal to 10ppm less than or equal to 100ppm (100 μ g/ml), more preferably less than it is equal to 2ppm.It is equal to 1ppm in addition, being especially preferably less than in exposure, is further preferably less than equal to 10ppb.If oxygen concentration is more than 100ppm, there is transmissivity downward trend caused by being easy to produce oxidation reaction as caused by dissolved oxygen etc..In addition, if dissolution is aerobic, such as shown in the Examples, due to the absorption of dissolved oxygen and the ozone generated when irradiating radioactive ray to oxygen, according to dissolved oxygen concentration, the absorbance of liquid is reduced even if not causing oxidation reaction etc..In addition, the ozone meeting oxidation liquid of generation accelerates the deterioration of liquid if lower exposure liquid coexists in oxygen.

In addition, if having optical activity, will lead to optical contrast's reduction especially when carrying out polarised light exposure, therefore, this liquid is preferably the liquid without optical activity.Specifically, the compound of structure cost liquid is preferably the compound for not having optical activity (without optical activity), when the compound for constituting liquid is that have the compound of optical activity (optical activity), the optical isomer (as raceme presence) of equivalent is preferably comprised, liquid does not have optical activity integrally.

The compound of the present invention can be obtained with commercially available compound, or can be manufactured by known various synthetic methods by the raw material that can be obtained.Hereinafter, being illustrated by enumerating specific example to the preparation method of this compound.

Such as, for formula (2-1) compound represented, naphthalene contained by oil etc. or naphthalene derivatives progress nuclear hydrogenation can be decomposed using the stone brain that contact hydrogenation decomposes oil and the manufacture by-product in ethylene to the empyreumatic oil, petroleum-type contact reforming oil and flowing contact that originate from coal coking furnace and manufactured by using catalyst appropriate.

It is decomposed in oil in above-mentioned contact reforming oil, flowing reformate, stone brain, other than naphthalene, alkylnaphthalene, also containing nitrogenous compounds such as sulfur-containing compounds, the pyridine and its derivatives such as benzene, alkylbenzene, phenanthrene, anthracene, other Ppolynuclear aromatics and its derivative, benzothiophene and its derivative, naphthalene and naphthalene derivatives as raw material can be obtained and carrying out separation and purification in the mixture by these.

In the naphthalene and naphthalene derivatives for manufacturing above compound (2-1), preferably the content of sulfur-containing compound is low among the above.At this point, the content of sulfur-containing compound, which is preferably less than, is equal to 100ppm, further preferably less than it is equal to 50ppm.If the content of sulfur-containing compound is more than 100ppm, the catalyst poisoning when sulfur-containing compound can cause contact to hydrogenate, harm the progress of nuclear hydrogenation reaction, furthermore, the sulfur-containing impurities from the sulfur-containing compound are mixed into compound (2-1), when cannot remove by purification, decrease in transmission of the fluid present invention under the exposure wavelengths such as 193nm can be caused.

In addition, when the cis- decahydronaphthalenes or trans- decahydronaphthalenes and its mixture in manufacture compound (2-1), particularly preferable as the purity is high of the naphthalene of raw material, the preferably purity of naphthalene is more than or equal to 99.0%, and the purity of particularly preferred naphthalene is more than or equal to 99.9%.At this time, when the content of sulfur-containing compound as impurity etc. is high, other than it can cause the above problem, when containing other naphthalene derivatives, aromatic compound and its derivative as impurity, generate these impurity carry out plus hydrogen obtain be difficult to isolated hydrocarbon compound, the Pureness control of decahydronaphthalenes becomes difficult.

In addition, the catalyst as contact hydrogenation can also use the sulfide of cobalt molybdenum, nickel molybdenum, nickel tungsten etc. in addition to precious metal based catalysts such as nickel class, platinum, rhodium, ruthenium, iridium, palladiums.Wherein, it is contemplated that its catalytic activity, cost, preferably nickel class catalyst.

It is used in addition, these metallic catalysts are preferably supported on carrier appropriate, at this time, by being highly dispersed at catalyst on carrier, the reaction speed of hydrogenation is improved, furthermore, it especially prevents the activated centre under high temperature, condition of high voltage from deteriorating, and improves the resistance for catalyst poisoning.

As the carrier, it is preferable to use SiO₂、γ-Al₂O₃、Cr₂O₃、TiO₂、ZrO₂、MgO、ThO₂, diatomite, active carbon etc..

In addition, the method as above-mentioned contact hydrogenation, can use the vapor phase method without using solvent and the liquid phase method for reacting dissolution of raw material in appropriate solvent.Wherein, due to excellent in terms of cost and reaction speed, thus preferred vapor phase method.

When using vapor phase method, as catalyst, preferably nickel, platinum etc..The amount of the catalyst used is more, and reaction speed is higher, but from the aspect of cost, not preferably.Therefore, terminate reaction, preferably reduction catalytic amount, reacted under conditions of temperature and high hydrogen pressure.It is specifically preferably that 0.01~10 parts by weight, hydrogen pressure are 5~15MPa, are reacted under reaction temperature is 100 DEG C~400 DEG C or so relative to raw naphthalene material (naphthalene derivatives) in catalytic amount.

In addition, using the method for nickel or platinum, palladium series catalyst by removing naphthalene in intermediate tetrahydronaphthalene is used, can also obtain target product under mild conditions using the method recorded in such as patent document (special open 2003-160515).

In above-mentioned reaction, reaction conversion ratio is preferably greater than to be equal to 90%, is further preferably greater than equal to 99%.

After above-mentioned reaction, preferably by carrying out purification appropriate, the impurity such as unreacting material, catalyst are removed.

As above-mentioned refining methd, refining methds and the their combinations such as rectifying, washing, concentrated sulfuric acid washing, filtering, partial crystallization can use.Wherein, the removal of both ingredients for the removal of the non-volatile metal and other metals from catalyst, from raw material is effective, thus preferred rectifying.In addition, preferably carrying out demetalization processing corresponding with catalyst to remove the metal for being originated from catalyst.

Tetrahydro-dicyclopentadiene in above compound can be made through the following steps: the dicyclopentadiene useful to the starting monomer for being known as optical lens, optical thin film resin (outer (exo), interior (endo) mixture) or interior dicyclopentadiene carry out adding hydrogen under suitable condition, the tetrahydro-dicyclopentadiene as obtained by the methods of distillation purification.When selectively obtaining outer isomers in by dicyclopentadiene, by carrying out isomerization to dicyclopentadiene isomer mixture using catalyst appropriate, to selectively obtain ectosome, carry out above-mentioned hydrogenation reaction, or using catalyst appropriate to the dicyclopentadiene by interior (inside and outside mixing) to add hydrogen to obtain interior (interior, outer mixing) tetrahydro-dicyclopentadiene progress isomerization, so as to selectively obtain outer tetrahydro-dicyclopentadiene.

Above-mentioned dicyclopentadiene generally passes through the so-called C in the thermal decomposition product to naphtha₅The cyclopentadiene largely contained in fraction carries out dimerization and manufactures.The dicyclopentadiene such as isopropenylnorbornene containing 5- etc. is originated from C₅The hydrocarbon ingredient of fraction, if containing these compounds, after adding hydrogen, isomerization, can remain the hydrocarbon products from these impurity, so that the purification of final product tetrahydro-dicyclopentadiene becomes difficult as impurity.It is therefore preferable that using the substance for first passing through the methods of purification high purity in advance.Purity at this time is preferably greater than to be equal to 95 weight %, is further preferably greater than equal to 97 weight %.

In addition, the content for the sulfur-bearing ingredient that above-mentioned dicyclopentadiene preferably for example causes catalyst for hydrogenation to be poisoned is few, in particular, sulfur-bearing ingredient present in dicyclopentadiene, which is preferably less than, is equal to 500ppb, further preferably less than it is equal to 50ppb.If the amount of sulfur-bearing ingredient is 500ppb, it is easy to harm the hydrogenation reaction of subsequent handling.

Here so-called sulfur-bearing ingredient, the total amount of element sulphur existing for referring in the form of the inorganic or organic compound by free sulphur, elemental sulfur, hydrogen sulfide, thio-alcohol, disulfides, thiophene can be analyzed using the gas-chromatography etc. for having sulfur chemiluminescent detector (SCD).The sulphur fraction can for example be removed by the method for special open 2001-181217.The dicyclopentadiene adds hydrogen that can carry out using the hydrogenation catalyst of well known carbon-to-carbon double bond.It should add hydrogen that can carry out for example, by method disclosed in tekiaki 60-209536, special open 2004-123762.After above-mentioned plus hydrogen, tetrahydro-dicyclopentadiene can be made by carrying out distillation, such as ectosome is selectively made, it is known that the method for carrying out isomerization using various lewis acids.This isomerization such as can by using aluminum halide, sulfuric acid as lewis acidic method carry out (special open 2002-255866).In the present reaction, it is known as by-product and generates adamantane, but when largely there are when adamantane, transmissivity decline under 193nm, thus the amount of the adamantane coexisted in final liquid must be made less than or equal to 0.5 weight %, preferably less than it is equal to 0.1 weight %, is further preferably less than equal to 0.05 weight %.The adamantane can be removed by the condition or various well known refining methds for suitably setting above-mentioned isomerization reaction.

Hereinafter, the structure of preferred immersion exposure liquid and the specific example of physics value are shown in table 1.

Table 1

In addition, trans- decahydronaphthalenes, the various physical datas of extension-tetrahydro-dicyclopentadiene are shown in table 2.

Table 2

Physical property project			Physics value
					Project	Condition	Unit	Cis- decahydronaphthalenes	Extension-tetrahydro-dicyclopentadiene
Boiling point	760mmHg	℃	187.31	185
					Fusing point	760mmHg	℃	-30.382	-79
Specific gravity	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 dependency dn/dP	-	-	5×10-10		-
				Dielectric constant		20℃	-	2.172	-
Dipole moment	-	D	0		-
				Viscosity		20℃	cP	2.128	2.86
Surface tension	20℃	dyn/cm	29.89		-
				Specific heat (level pressure)		20℃	cal/deg.mol	54.61	48.5
Critical-temperature	-	℃	413.8		-
				Critical pressure		-	atm	27	-
Vapour pressure	25℃	mmHg	0.78		-
				Pyroconductivity		62.8 DEG C (D), 30 DEG C (W)	cal/cm.s.deg	0.000256	-
Flash-point	-	℃	58		55
				Burning point		-	℃	262	-
Oxygen solubility	Divide 1atm	ppm	274		220
				Cyanogen solubility		Divide 1atm	ppm	113	96

In table 2, the value of oxygen solubility and nitrogen solubility is value when dividing 1 atmospheric pressure, and unit is ppm.

Immersion exposure of the invention has the structure selected from above-mentioned formula (1-1)~(1-9) with liquid, thus absorbance for example at 193 nm is small, is suitable, but the absorbance of the wave-length coverage is easy to be influenced by trace impurity.In addition, when, there are when alkali composition, even if very micro, big influence can be also generated to Resist profile in these liquid.These impurity can be removed and refining aforesaid liquid using method appropriate.Such as, for the saturated hydrocarbon compound of the structure with (1-1)~(1-5), (1-7)~(1-9), it can be handled by the permanganate under the conditions of concentrated sulfuric acid washing, washing, neutralizing treatment, silicagel column purification, rectifying, alkali and their combination is refined.

In particular, for example purification appropriate can be carried out through the following steps: be repeated concentrated sulfuric acid washing until the concentrated sulfuric acid decoloration then the concentrated sulfuric acid is removed by washing, neutralizing treatment, and then after being washed, being dried, carry out rectifying.

In addition, before carrying out pre-processing, by being handled under alkaline condition using permanganate, can more efficiently remove impurity because of the difference of compound.

In above-mentioned purification operations, it, in addition, being also effective for the removal of micro alkali compounds, is preferred refining methd that the concentrated sulfuric acid, which is washed for absorbing big aromatic compound at 193 nm, the removal of the compound with carbon-to-carbon unsaturated bond is effective.The processing preferably according to the compound of purification, selects optimal stirring means, temperature range, processing time, number of processes to be handled.

In particular, temperature is higher, the efficiency that impurity removes is higher, but simultaneously because side reaction is easy to generate the impurity for leading to absorb.Preferred treatment temperature is -20 DEG C~40 DEG C, and particularly preferred treatment temperature is -10 DEG C~20 DEG C.

It is longer to handle the time, with above-mentioned aromatic compound, the impurity with carbon-to-carbon unsaturated bond react further progress, the removal efficiency of above-mentioned impurity is higher, but the production quantity increased trend of the impurity for causing to absorb generated there are side reaction.

When being refined using above-mentioned dense sulfuric acid treatment, in order to completely remove after processing the remaining acid impurities from the concentrated sulfuric acid, the sulfonic acid composition generated by dense sulfuric acid treatment in liquid of the invention, preferably progress neutralizing treatment, pure water and for dewatered drying process.

In addition, can more efficiently remove the impurity for leading to absorb by carrying out rectifying after the concentrated sulfuric acid washs.

The rectifying preferably according to the boiling-point difference for the impurity and fluid present invention that should be removed, is carried out using the destilling tower with theoretical cam curve more than theoretical cam curve needed for the separation.From the viewpoint of removing impurity, preferred theoretical cam curve is 10~100, when improving theoretical cam curve, since equipment, manufacturing cost improve, by combining with other refining methds, can be refined with than the above-mentioned lower number of plates.Particularly preferred theoretical cam curve is 30~80.

In addition, the rectifying preferably carries out under the appropriate temperature conditions.Vapo(u)rizing temperature increases, and there are the tendencies that the reducing effect of absorption reduces by oxidation reaction of compound etc..Preferred vapo(u)rizing temperature is 30 DEG C~120 DEG C, and particularly preferred vapo(u)rizing temperature is 30 DEG C~80 DEG C.

In order to carry out the distillation in above-mentioned temperature range, the rectifying is preferably carried out under reduced pressure as needed.

Above-mentioned refinement treatment preferably carries out under the inert gas atmospheres such as nitrogen or argon.At this point, it is preferred that oxygen concentration, organic principle concentration in inert gas are low.Preferred oxygen concentration is further preferably less than to be equal to 10ppm less than or equal to 1000ppm, is particularly preferably less than or equal to 1ppm.

In addition, in the process above, especially effective using removal of the processing of permanganate for the compound containing carbon-to-carbon unsaturated bond of non-aromatic, but for tertiary carbon compound, the oxidation reaction for easily causing tertiary carbon is consequently adapted to the purification without tertiary carbon compound.

In addition, the processing preferably carries out in a low temperature of being less than or equal to room temperature from the viewpoint of preventing side reaction.

As specific example, it is (suitable, anti- mixture: Aldrich manufacture) decahydronaphthalenes, trans- decahydronaphthalenes (Tokyo is melted into company's manufacture), trans- decahydronaphthalenes (1) after the purification refined using method shown in aftermentioned embodiment 1, dicyclohexyl, isopropyl cyclohexane, cyclooctane, cycloheptane, trans- decahydronaphthalenes (2) after the purification refined using method shown in embodiment 2, extension-tetrahydro-dicyclopentadiene (1) after the purification refined using method shown in embodiment 3, extension-tetrahydro-dicyclopentadiene (2) after the purification refined using method shown in embodiment 4, trans- decahydronaphthalenes (3) after the purification refined using method shown in embodiment 5, extension-four after the purification refined using method shown in embodiment 6 The measurement result of dicyclohexyl, isopropyl cyclohexane, cyclooctane, the refractive index of cycloheptane after hydrogen dicyclopentadiene (3), the purification refined using method shown in embodiment 7 and transmissivity is shown in table 3 and table 4.In addition, using the pure water of liquid, diiodomethane as comparative example used as the acetonitrile of reference fluid, as immersion exposure.

For refractive index, the refractive index in ultraviolet range is measured for trans- decahydronaphthalenes, dicyclohexyl, isopropyl cyclohexane, cyclooctane, cycloheptane, the acetonitrile after suitable, trans- decahydronaphthalenes and purification.The 1 type UV-VIS-IR of angle measurement spectrometer that measurement device is manufactured using MOLLER-WEDEL company, measuring method are measured using minimum deflection horn cupping, under 25 DEG C of measuring temperature.

Transmissivity is carried out using measuring method A or measuring method B.Measuring method A is measured through the following steps: in oxygen concentration control in the glove box of the nitrogen atmosphere less than or equal to 0.5ppm, the sampling of liquid is carried out in the pond of the light path 10mm of the capping of polytetrafluoroethylene (PTFE), the JASCO-V-550 manufactured using Japanese light splitting company, using above-mentioned pond, it is measured using air as reference.Value in table be by calculate correction pond reflection after, the value of light path 1mm is converted into according to the value.

Measuring method B is that the sampling of liquid is carried out in the capping quartz cell (measurement is used: light path 50mm, reference: light path 10mm) of polytetrafluoroethylene (PTFE) in oxygen concentration control in the glove box of the nitrogen atmosphere less than or equal to 0.5ppm.Using above-mentioned pond, using the pond of light path 10mm as reference, it is measured by the JASCO-V-550 that Japanese light splitting company manufactures using the pond of light path 50mm as sample.Using the value of this measurement as the absorbance of every light path 40mm.Value in table is that the value of every 1mm light path is converted into according to the value.

Table 3

Wavelength (nm)	Refractive index
										Decahydronaphthalenes (suitable, trans- mixture)	Trans- decahydronaphthalenes (1) after purification	The bicyclic pentane of extension-tetrahydro (1) after purification	Dicyclohexyl after purification	Isopropyl cyclohexane after purification	Cyclooctane after purification	Cycloheptane after purification	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

	Transmissivity (193nm:mm-1) (%)		Refractive index (193nm)	Refractive index (589nm)
					Measuring method A	Measuring method B
	Decahydronaphthalenes (suitable, anti-mixture)	73.5					-	1.64	1.48
Trans- decahydronaphthalenes (Tokyo chemical conversion product)			Less than or equal to 10	-	-	1.48
	Trans- decahydronaphthalenes (1) after purification	93.4					-	1.63	1.48
Trans- decahydronaphthalenes (2) after purification			96.8	-	1.63	1.48
	Trans- decahydronaphthalenes (3) after purification	-					99.5	1.63	1.48
Extension-tetrahydro-dicyclopentadiene			Less than or equal to 10	-	-	1.49
	Extension-tetrahydro-dicyclopentadiene (1) after purification	87.7					-	1.65	1.49
Extension-tetrahydro-dicyclopentadiene (2) after purification			97.5	-	1.65	1.49
	Extension-tetrahydro-dicyclopentadiene (3) after purification	-					99.6	1.65	1.49
Dicyclohexyl after purification			97.3	-	1.64	1.48
	Isopropyl cyclohexane after purification	76.3					-	1.59	1.44
Cyclooctane after purification			70.2	-	-	1.46
	Cycloheptane after purification	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 dependency of refractive index is as wavelength reduces, and refractive index increases, and the liquid of the invention in above-mentioned table for example has the high refractive index more than or equal to 1.58 at 193 nm.

In addition, the compound of the present invention is low polar compound, therefore the solubility of the gases such as oxygen, nitrogen is high.Therefore, it is easy to be influenced by the dissolution of these gases, such as when being placed under air atmosphere, there is the tendency of the decrease in transmission of such as 193nm in absorption due to dissolved oxygen or light excitation dissolved oxygen and the absorption of ozone generated or oxidation reaction relevant to dissolved oxygen etc..Therefore, these compounds are preferably de-gassed, and are saved in inertia such as nitrogen, argon and absorbing in few gas.In particular, it is preferred that make save liquid in oxygen concentration less than or equal to 100ppm, further preferably less than equal to 10ppm and handled.In addition, being particularly preferably less than or equal to 1ppm when not can be carried out deoxidation before exposure, further preferably less than it is equal to 10ppb.

The immersion exposure method for having used immersion exposure liquid of the invention is described below.

Immersion exposure of the invention is saved in inert gas preferably as described above with liquid, as container at this time, is preferably saved with the container that the lid ingredient (for example, the plasticizer etc. of mixture in plastics) of container component or container will not elute.Example as preferred container, such as can enumerate material is glass, metal (such as SUS), pottery, PTFE (polytetrafluoroethylene (PTFE)), PFEP (fluorinated ethylene propylene copolymer), ECTFE (ethylene-chlorotrifluoro-ethylene copolymer), PTFE/PDD (two cyclopentadienyl copolymer of polytetrafluoroethylene (PTFE)-perfluor), PFA (perfluoroalkoxyalkane), ETFE (ethylene-tetrafluoroethylene copolymer), PVDF (Kynoar), PVF (polyvinyl fluoride), the container of the fluororesin such as PCTFE (polychlorotrifluoroethylene), but particularly preferred material is glass, the container of fluororesin.

In addition, the example of lid as preferred container, such as can enumerate material is polyethylene and the not lid of plasticizer-containing, material is glass, metal (such as SUS), pottery, PTFE (polytetrafluoroethylene (PTFE)), PFEP (fluorinated ethylene propylene copolymer), ECTFE (ethylene-chlorotrifluoro-ethylene copolymer), PTFE/PDD (two cyclopentadienyl copolymer of polytetrafluoroethylene (PTFE)-perfluor), PFA (perfluoroalkoxyalkane), ETFE (ethylene-tetrafluoroethylene copolymer), PVDF (Kynoar), PVF (polyvinyl fluoride), the lid of the fluororesin such as PCTFE (polychlorotrifluoroethylene).

In addition, the piping used when for being infused from container to exposure machine, the piping preferably similar to the above for not causing elution can enumerate glass, metal, pottery etc. as the material being preferably piped.

Immersion exposure liquid of the invention, when being used for immersion exposure, particle, bubble (microvesicle) lead to defect of pattern etc., thus preferably remove particle before exposure and generate the dissolved gas of bubble.

As the method for removing particle, the method being filtered using filter appropriate can be enumerated.As filter, the preferably removal efficiency of particle is high, and has used the filter of the material of Change of absorption under exposure wavelength caused by elution when without filtering.As preferred filter material, such as the fluororesin such as glass, metal (such as SUS, silver) and metal oxide, PTFE (polytetrafluoroethylene (PTFE)), PFEP (fluorinated ethylene propylene copolymer), ECTFE (ethylene-chlorotrifluoro-ethylene copolymer), PTFE/PDD (two cyclopentadienyl copolymer of polytetrafluoroethylene (PTFE)-perfluor), PFA (perfluoroalkoxyalkane), ETFE (ethylene-tetrafluoroethylene copolymer), PVDF (Kynoar), PVF (polyvinyl fluoride), PCTFE (polychlorotrifluoroethylene) can be enumerated.In addition, for the material of the circumferential components such as the shell of filter, core, bracket, plug, the material that is preferably also selected from the preferred material of above-mentioned filter.

As the removing method of dissolved gas, such as decompression degassing method can be enumerated, ultrasonic wave degassing method, utilize degassing method, the degassing method for having used various degassers of gas-premeable film etc..

Immersion exposure of the invention with liquid in exposure is a part of optical system, thus preferably uses in the environment of the variation of the optical properties such as refractive index on liquid does not influence.For example, it is preferable to be used in the case where making the constant environment such as the temperature, the pressure that influence optics of liquids characteristic.Such as temperature, it is preferably controlled in ± 0.1 DEG C, more preferably control is in the range of ± 0.01 DEG C.

In addition, the immersion exposure of liquid of the invention is used, it can also be carried out under air atmosphere, as described above, solubility of the oxygen in liquid of the invention is high, sometimes influence exposure wavelength under absorption characteristic, therefore preferably at the exposure wavelength absorb less, will not cause to be exposed with the inert gas of the chemical reaction of liquid.As the preferred inert gas, such as nitrogen, argon gas can be enumerated etc..

In addition, from the viewpoint of preventing as caused by the organic principle in air liquid caused by pollution at the exposure wavelength absorption characteristic variation, preferably by the organic principle concentration control in atmosphere used below certain level.As the control method of the organic principle concentration, the above-mentioned inert gas atmosphere using high-purity and filter, the method for various gas purification pipes (device) etc. using absorption organic principle can be enumerated.For concentration control, the analysis of surrounding atmosphere is preferably periodically carried out, can for example use the various analysis methods that gas-chromatography is utilized thus.

The liquid supply method of immersion liquid as exposure area, known mooving pool method, seimming stage method, Local Fill method (local immersion liquid mode) (referring to special scientific seminar's immersion exposure technology (on May 27th, 2004 holds) scientific seminar's data), since the usage amount of the immersion exposure liquid of local immersion method is few, thus preferably.

As final (object lens) lens material for the immersion exposure that this liquid is utilized, due to its optical characteristics it is preferred that existing CaF₂Or fused silica.As other preferred lens materials, the villiaumite and general formula Ca of preferably for example high period alkaline-earth metal M_xM_1-xF₂Oxide of alkaline-earth metals such as the salt of expression, CaO, SrO, BaO etc., when using the material, with CaF₂(n@193nm=1.50), fused silica (n@193nm=1.50) are compared, and the refractive index of lens improves, therefore, particularly preferred when design, processing numerical aperture are more than the lens of 1.5 high NA.

Since the considerably less thus of the invention liquid of the elution of resist ingredient can recycle after use.When used can ignore that exposure when by the influence of the elution of etchant resist etc. resist (or resistant upper layer film) when, liquid of the invention can be recycled without purification, but it is preferably recycled after having carried out the processing such as degassing, filtering at this time.From the perspective of the chemical industry sequence that conforms to the principle of simplicity, these processing are preferably carried out online.

In addition, when in use, even being can ignore that in 1 use by the level of the elution of above-mentioned etchant resist etc., but when access times are more than certain number, it can predict: due to the influence of the impurity of savings, the physical property of liquid can change, it is therefore preferable that being recycled, being refined after a certain number of uses.

As the refining methd, the refining methd of the methods of washing process, acid elution, neutralizing treatment, rectifying, the purification for having used filter appropriate (packed column), filtering and liquid present invention as described above can be enumerated or combine the method generated by these refining methds.Wherein, it is refined preferably by the combination of washing process, neutralizing treatment, acid elution, rectifying or these refining methds.

Above-mentioned neutralizing treatment is effective for the removing for eluting the acid generated by exposure in fluid present invention, acid elution is that effectively, washing process is effective for the removal for eluting the eluates such as the acid generated when the light acid propellant in the etchant resist in liquid of the invention, alkalinity additive, exposure for the removal for eluting the alkaline components in the resist in fluid present invention.

For rectifying, other than the removal effectively for the low voc compounds in above-mentioned additive, for remove expose when by the protecting group in resist decomposition generate hydrophobic combination be also effective.

Immersion exposure shown in formula (1-1)~formula (1-9) can be respectively used alone with liquid, can be also used in mixed way.The case where preferred example is single use.By being used alone, it is easy setting immersion exposure condition.

In addition, liquid of the invention can be used in mixed way as needed with the liquid other than the present invention, the physics values such as the optical characteristic value such as refractive index, transmissivity, contact angle, specific heat, viscosity, expansion rate can be made to reach desired value in this way.

As the liquid other than the present invention for this purpose, other than other are capable of the solvent of immersion exposure, additionally it is possible to use various defoaming agents, surfactant etc., be effective for the reduction of bubble, the control of surface tension.

Immersion exposure is carried out with liquid using above-mentioned immersion exposure.

The painting photoresist on substrate and form photoresist.Substrate is able to use such as silicon wafer, the chip being coated with aluminium.In addition, as such as fairness 6-12452 bulletin etc. is open, the antireflection film of organic or inorganic can be formed on used substrate in advance in order to play the potential of etchant resist to the maximum extent.

Photoresist used is not particularly limited, and can in time be selected according to the use purpose of resist.As the resin component of photoresist, the macromolecule of the group containing acid dissociation can be enumerated.The acid dissociation group is not preferably decomposed because of exposure, and product volatilizees under conditions of exposure after the particularly preferred decomposition, is not eluted in fluid present invention.As these high molecular examples, resin of the polymer side chain containing alcyl, lactone group and their derivative etc., resin comprising hydroxy styrenes derivative etc. etc. can be enumerated.

Particularly preferably use the photoresist of resin of the polymer side chain containing alcyl, lactone group and their derivative.These photoresists contain the chemical structure that with alicyclic hydrocarbon compound or the cyclic hydrocarbon compound of silicon atoms is similar in ring structure, thus excellent with the compatibility of immersion exposure liquid of the invention.In addition, not making photoresist membrane elution, will not make it dissolve.

As the example of photoresist, it can enumerate and contain the macromolecule comprising acid dissociation group as positive or negative type resists of chemical amplifying type of additives such as resin component, acid-producing agent, acid diffusion controlling agent etc..

When using immersion exposure liquid of the invention, particularly preferred positive-workingresist.For chemical amplification type positive resist, under the action of the acid generated by exposure by acid-producing agent, acid dissociation organic group dissociation in polymer, generate such as carboxyl, its result, the dissolubility of alkali imaging liquid is improved at the exposure position of resist, which is dissolved and removed by alkali imaging liquid, obtains eurymeric corrosion-resisting pattern.

Photoresist is formed by following procedure: for example the resin combination for being used to form photoresist being dissolved in solvent appropriate with the solid component concentration of 0.1~20 weight %, then, such as it is filtered by the filter of aperture 30nm or so and modulates solution, utilize the coating method appropriate such as spin coating, cast coat, roller coating, the resist solution is coated on substrate, carrying out preroast (hereinafter referred to as " PB ") makes solvent volatilize.In addition, can directly use commercially available resist solution at this time.It is high refractive index that the photoresist, which preferably compares immersion liquid upper layer film and immersion exposure with liquid, specifically the refractive index n of preferred photoresist_RESFor more than or equal to 1.65.Especially when NA is more than or equal to 1.3, n_RESPreferably greater than 1.75, at this point, can prevent the contrast of the increase bring exposure light of NA from declining.

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

As immersion liquid upper layer film; as long as can be formed on photoresist protective film without cause permeability enough for the wavelength of exposure light and with the mixing of photoresist; furthermore; maintain stable envelope without eluting in the aforesaid liquid that uses in immersion exposure; and the film that can be removed before imaging, it will be able to use.At this point, the upper layer film if it is being easy to be dissolved in the film of the lye as imaging liquid, is stripped in imaging, thus preferably.

It is preferred that side chain has resin of at least one group of hexafluoro methanol-based and carboxyl as the substituent group for assigning alkali-soluble.

The immersion liquid upper layer film preferably has the function of preventing multi interference simultaneously, at this point, the refractive index n of the immersion liquid upper layer film_ocMathematical expression preferably as shown below.

n_oc=(n_1q×n_RES)^0.5

Wherein, n_1q、n_RESRespectively indicate the refractive index of immersion exposure liquid, the refractive index of etchant resist.

In particular, n_ocPreferably 1.6~1.9 range.

Above-mentioned immersion liquid upper layer film can be formed by following procedure: be dissolved in immersion liquid upper layer film in the solvent not mixed with etchant resist with resin combination with 0.01~10% solid component concentration, same method is coated on etchant resist when then using with photoresist formation, carries out preroast.

It uses liquid as medium using immersion exposure of the invention, to the photoresist or forms the photoresist of immersion liquid upper layer film by the exposure mask with predetermined pattern and irradiate radioactive ray, then imaged, to form corrosion-resisting pattern.The process is to carry out immersion exposure, the process imaged after being roasted at an established temperature.

For the radioactive ray of immersion exposure, can select to use such as visible light according to the combination of photoresist and photoresist and immersion liquid upper layer film used；The ultraviolet lights such as g ray, i ray；The far ultraviolets such as excimer laser；The X-rays such as synchrotron radioactive ray；Various radioactive ray as the charged particle rays such as electron ray.Particularly preferred ArF excimer laser (wavelength 193nm) or KrF excimer laser (wavelength 248nm).

In addition, preferably being roasted (hereinafter referred to as " PEB ") after exposure in order to improve the resolution ratio of etchant resist, pattern form, resulting visualization etc..The maturing temperature is suitably adjusted according to resist used etc., usually 30~200 DEG C or so, preferably 50~150 DEG C.

Then, photoresist is imaged with imaging liquid, is washed, form desired corrosion-resisting pattern.

Embodiment

In order to evaluate immersion exposure liquid of the invention, etchant resist is formed using radiation-ray sensitive composition as shown below.In addition, forming immersion liquid upper layer film as shown below on part of it.Use etchant resist measurement as the characteristic of immersion exposure liquid using the evaluation (elution test, the dissolubility test of film, pattern form evaluation).

Reference example 1

It is prepared by the following method the resin for radiation sensitive resin composition.

39.85g (40 moles of %) compound (S1-1), 27.47g (20 moles of %) compound (S1-2), 32.68g (40 moles of %) compound (S1-3) are dissolved in the 2- butanone of 200g, further put into 4.13g azo diisoamyl acid methyl esters, prepare monomer solution, the nitrogen carried out 30 minutes to the three-necked flask of the 1000ml for the 2- butanone for having put into 100g purifies.After nitrogen purification, one side stirred autoclave is heated to 80 DEG C on one side, and using dropping funel, cut-and-dried above-mentioned monomer solution was added dropwise with 3 hours.With dropping liquid initially as the polymerization time started, 5 hours polymerization reactions are carried out.After polymerization, polymeric solution is put into the methanol of 2000g by cooling by water to less than equal to 30 DEG C, filters the white powder of precipitation.Using 400g methanol, filtered after being washed 2 times on slurries to the white powder of filtering, it is 17 hours dry at 50 DEG C, the polymer (75g, 75 weight % of yield) of white powder is made.The polymer molecular weight is 10300,¹³C-NMR analysis the result is that compound (S1-1), compound (S1-2), repetitive unit shown in compound (S1-3), the containing ratio of each repetitive unit are the copolymer of 42.3: 20.3: 37.4 (mole %).Using the polymer as resin (A-1).

Reference example 2

It is prepared by the following method the resin for radiation sensitive resin composition.

By 53.92g (50 moles of %) compound (S2-1), 10.69g (10 moles of %) compound (S2-2), 35.38g (40 moles of %) compound (S2-3) is dissolved in the 2- butanone of 187g and obtains monomer solution (1), prepare the dimethyl 2 of 3.37g, 2 '-azos two (2 Methylpropionic acid ester) are dissolved in the solution (2) that the 2- butanone of 64g obtains, again by cut-and-dried 28.77g monomer solution (1), 4.23g solution (2) investment is placed in the three-necked flask of the 1000ml of the 2- butanone of 15g, then nitrogen purification is carried out using decompression displacement method.After nitrogen purification, one side stirred autoclave is heated on one side after 80 DEG C, 15 minutes, using infusion pump, with 3 hours instillation 258.98g monomer solutions (1), 24.64g solution (2).After dropping liquid, it is stirred for 4 hours.After polymerization, polymeric solution is cooled to by placing less than or equal to 30 DEG C.After reaction, solution is cooled to less than or equal to 30 DEG C, puts into 4000g isopropanol, filter the white powder of precipitation by placing cooling.Using 2000g isopropanol, after being washed 2 times on slurries to the white powder of filtering, it is filtered, it is 17 hours dry at 60 DEG C, the polymer (85g, 85 weight % of yield) of white powder is made.The Mw of the polymer is 7600,¹³C-NMR analysis the result is that compound (S2-1), compound (S2-2), repetitive unit shown in compound (S2-3), the containing ratio of each repetitive unit are the copolymer of 53.1: 8.5: 38.4 (mole %).Using the polymer as resin (A-2).

Reference example 3

It is prepared by the following method the resin to form immersion liquid upper layer film.

50g compound (S3-1), 5g compound (S3-2), 25g compound (S3-3), 20g compound (S3-4) and 6.00g azo diisoamyl acid methyl esters are dissolved in 200g methyl ethyl ketone, prepare the monomer solution for becoming homogeneous solution.Then, the nitrogen for having the three-necked flask of the 1000ml of 100g methyl ethyl ketone to carry out to investment 30 minutes purifies.After nitrogen purification, flask being stirred on one side, is heated to 80 DEG C on one side, using dropping funel, the above-mentioned monomer solution modulated in advance was added dropwise with 10ml/5 minutes speed.Polymerization sart point in time is begun as to be added dropwise, carries out polymerization in 5 hours.After polymerization, reaction solution is cooled to less than or equal to 30 DEG C, then, which is put into 2000g heptane, filters the white powder of precipitation.It is repeated 2 times the operation that the white powder of filtering is mixed to 400g heptane, formed slurries, stirring, is filtered after washing, it is 17 hours dry at 50 DEG C, it is made white powder resin (E-1) (89g, 89 weight % of yield).The Mw of resin (E-1) is 7300.

Reference example 4

The resin for forming immersion liquid upper layer film is made using the following method.

As monomer, other than using 70g compound (S4-1), 20g compound (S4-2) and 10g compound (S4-3), the resin (E-2) (88g, 88 weight % of yield) of white powder is made in the same manner as reference example 3.The Mw of resin (E-2) is 6800.

Reference example 5

Radiation sensitive resin composition is obtained using following methods.

Resin shown in mixture table 5, acid-producing agent, acid diffusion controlling agent, solvent are filtered after forming homogeneous solution using the molecular filter of aperture 200nm, are modulated radiation sensitive resin composition (F1~F3).In table 5, " part " is weight basis.

In addition, acid-producing agent (B) used described below, acid diffusion controlling agent (C), solvent (D).

Acid-producing agent (B)

Nine fluorine normal-butyl oxyphenyl diphenyl sulfonium of B-1:4-, nine fluorine n-butanesulfonic acid salt

B-2: nine fluorine n-butanesulfonic acid salt of triphenylsulfonium

Acid diffusion controlling agent (C)

C-1:2- phenylbenzimidazol

Solvent (D)

D-1: propylene glycol methyl ether acetate

Table 5

Radiation sensitive resin composition	Resin (A) (part)	Acid-producing agent (B) (part)	Acid diffusion controlling agent (C) (part)	Solvent (D) (part)
					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

It is prepared by the following method immersion liquid upper layer film composition.

Resin shown in table 6, solvent are mixed, after forming homogeneous solution, are filtered using the molecular filter of aperture 200nm, modulates immersion liquid with upper layer film composition (G1 and G2).In table 6, n-BuOH indicates n-butanol, and " part " is weight basis.

Table 6

Upper layer film composition	Resin (E) (part)	Solvent (part)
			G-1	E-1(1)	n-BuOH(99)
G-2	E-2(1)	n-BuOH(99)

Reference example 7

It is prepared by the following method evaluation etchant resist (H-1~H-5).

On 8 inch silicon wafers, the coating of lower layer reflection preventing film ARC29 (manufacture of one ワ サ イ エ Application ス company of Block Le) is carried out using spin coating, (90 DEG C, 60 seconds) of PB, after forming the film of film thickness 77nm, under identical condition using radiation sensitive resin composition shown in table 7, formed etchant resist (film thickness 205nm) (H-1~H-3).

In addition, using method similar to the above, after forming etchant resist (film thickness 205nm) using radiation sensitive resin composition, on the etchant resist, immersion liquid shown in table 7 is formed to the upper layer film (H-4 and H-5) of film thickness 32nm using spin coating, PB (130 DEG C, 90 seconds) with upper layer film composition.

Table 7

Etchant resist	Radiation sensitive resin composition	Upper layer 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

Embodiment 1

Commercially available trans- naphthalane (trans- decahydronaphthalenes), obtained immersion exposure liquid are refined using following methods.

By the commercially available trans- decahydronaphthalenes of 100ml, (Tokyo is melted into company's manufacture, the transmissivity for being converted into the 193nm of 1mm light path is in the 200ml eggplant type flask for the stirring sheet for being placed with glass coating less than or equal to 10%) investment, add the concentrated sulfuric acid (He Guangchun medicine product) of 20ml, the rotation speed of stirring sheet is set as 500~1000rpm, is stirred 20 minutes at 25 DEG C.Then, the concentrated sulfuric acid is removed by liquid separation, carries out 3 aforesaid operations.Then, the organic layer that 1 separation is washed with 50ml deionized water, is washed 3 times with saturated sodium bicarbonate aqueous solution.Then, with pure water organic layer 3 times.Confirmation pH shows 7 (neutrality) at the time point.Then, be dried with magnesium sulfate, magnesium sulfate removed using decantation after dry, at pressure 10mmHg, using defending equipped with long 20cm the distilling apparatus of gate rectifying column is evaporated under reduced pressure, recycle the fraction of 16 parts of 10ml.Measure the absorbance (condition that determination condition uses said determination method A) of each fraction at 193 nm, it is 12 parts that the transmissivity of 1mm light path, which is converted into, as the fraction more than or equal to 93%, and the transmissivity for being converted into 1mm light path of total 120ml is made as the trans- decahydronaphthalenes more than or equal to 90%.In addition, being saturated each fraction nitrogen and carrying out decompression degassing, it is stored in the glass container for having carried out nitrogen displacement.After enclosed container, by the purity of gas chromatographic analysis compound, purity (hereinafter referred to as " GC purity ") is 99.92%.Trans- decahydronaphthalenes (1) after refining will be known as using the trans- decahydronaphthalenes after refining made from the method for embodiment 1.

In addition, refining commercially available anti-, cis- mixing decahydronaphthalenes and commercially available cis- decahydronaphthalenes using the above method.

Embodiment 2

In a nitrogen atmosphere, sulfuric acid treatment is carried out using method same as Example 1.Then method same as Example 1 is used, carrying out commercially available trans- decahydronaphthalenes, (Tokyo is melted into company's manufacture；The transmissivity for being converted into the 193nm of light path 1mm is that the liquid for being converted into that the transmissivity of 1mm light path is 96.8% is made less than or equal to purification 10%).The dissolved oxygen and dissolution nitrogen concentration of this liquid are analyzed using gas chromatography (detector TCD), dissolved oxygen concentration is lower than 1ppm (below detection limit), and dissolution nitrogen concentration is 119ppm.In addition, measuring the tenor of Li, Na, K, Mg, Cu, Ca, Al, Fe, Mn, Sn, Zn, Ni of this liquid using atom light absorption method, Ca 1ppb, Zn 6ppb, other metals are lower than 1ppb (being lower than detection limit).Trans- decahydronaphthalenes (2) after refining will be known as using the trans- decahydronaphthalenes after refining made from the method for embodiment 2.

The metal component of the liquid is few, is not only used as immersion exposure liquid, additionally it is possible to the Optical devices etc. for using in visible light region.

In addition, the trans- decahydronaphthalenes (2) after purification obtained in above-described embodiment 2 is placed in air, reach saturation of the air state, measures the transmissivity under 193nm.As a result it is shown in table 8.

Table 8

	Oxygen concentration (μ g/ml)	Transmissivity (%) (1mm)
			Trans- decahydronaphthalenes (2) after purification	Less than 1	96.8
Trans- decahydronaphthalenes after the saturation of the air	61	74.8
			Pure water (saturation of the air)	7	96.3

As shown in table 8, when may validate that oxygen concentration is not saturated, transmissivity is improved.

In addition, using the variation of following methods measurement transmissivity as caused by being contacted with etchant resist.

Nitrogen displacement, oxygen concentration control are being carried out in the nitrogen glove box less than or equal to 10ppm, is being placed liquid 3 minutes on the silicon wafer for foring etchant resist H-1, H-4, the thickness of liquid film is made to reach 0.8mm, measure the variation of the transmissivity under 193nm.Use pure water as comparative example.As a result it is shown in table 9.

Table 9

	Before dipping	After being impregnated in H1	After being impregnated in H4
				Trans- decahydronaphthalenes (2) after purification	96.6%	96.8%	96.7%
Pure water	98.0%	97.1%	96.0%

As shown in table 9, even if contacting with etchant resist, the transmissivity of the trans- decahydronaphthalenes (2) after purification has almost no change.

Acid-producing agent is measured for the solubility of the trans- decahydronaphthalenes (2) after purification using following methods.

Use nine fluorine n-butanesulfonic acid salt of triphenylsulfonium as acid-producing agent, the acid-producing agent of specified amount is added into the trans- decahydronaphthalenes after 100ml purification, is stirred 1 hour, whole dissolutions are confirmed whether by range estimation, solubility is studied.Use pure water as comparative example.As a result shown in table 10.

Table 10

Liquid	Water (100ml)	Trans- decahydronaphthalenes
			Nine fluorine butane sulfonic acid solubility	50g	Less than or equal to 0.5mg

As shown in table 10, acid-producing agent is almost not dissolved in the trans- decahydronaphthalenes (2) after purification.

Embodiment 3

Commercially available extension-tetrahydro-dicyclopentadiene is refined by using following methods, so that immersion liquid exposure liquid be made.

By the commercially available extension-tetrahydro-dicyclopentadiene of 100ml, (Tokyo is melted into company's manufacture, the transmissivity for being converted into the 193nm of 1mm light path is in the 200ml eggplant type flask for the stirring sheet for being placed with glass coating less than or equal to 10%) investment, after internal temperature is cooled to 5 DEG C with ice-water bath, the concentrated sulfuric acid (He Guangchun medicine product) of 20ml is added, the rotation speed of stirring sheet is set as 500~1000rpm, is stirred 20 minutes at 25 DEG C.Then the concentrated sulfuric acid is removed by liquid separation, carries out 3 aforesaid operations.Then, it is washed organic layer 1 time of separation with 50ml deionized water, is washed 3 times with saturated sodium bicarbonate aqueous solution.Then 3 organic layers of pure water are used.The pH of confirmation at this time shows 7 (neutrality).Then, using the dry organic layer of magnesium sulfate, magnesium sulfate is removed by decantation.30 minutes nitrogen gas foamings are carried out to the 91ml liquid obtained at this time, measure the transmissivity (determination condition uses above-mentioned condition described herein) under 193nm, being as a result converted into 1mm light path is 87.7%.In addition, being stored in the glass container by nitrogen displacement after so that this liquid nitrogen is saturated and is de-gassed.The GC purity of compound after enclosed container is 99.94%.Extension-tetrahydro-dicyclopentadiene (1) after refining will be known as using extension-tetrahydro-dicyclopentadiene after refining made from the method for embodiment 3.

Embodiment 4

In a nitrogen atmosphere, sulfuric acid treatment is carried out using method same as Example 1.Then method same as Example 3 is used, commercially available extension-tetrahydro-dicyclopentadiene is refined, then use method same as Example 2, is evaporated under reduced pressure in a nitrogen atmosphere, so that the liquid for being converted into that the transmissivity of 1mm light path is 97.5% be made.The dissolved oxygen of this liquid is analyzed by gas-chromatography (detector TCD) and dissolution nitrogen concentration, dissolved oxygen concentration are lower than 1ppm (below detection limit), and dissolution nitrogen concentration is 100ppm.Extension-tetrahydro-dicyclopentadiene (2) after refining will be known as using extension-tetrahydro-dicyclopentadiene after refining made from the method for embodiment 4.

Embodiment 5

In addition to using the nitrogen refined by nitrogen refiner, all operationss are carried out in the glove box less than or equal to 0.5ppm in nitrogen concentration control, and controlling degree of decompression makes vapor (steam) temperature, thus outside being evaporated under reduced pressure, the purification of commercially available trans- decahydronaphthalenes (Tokyo chemical conversion product) be carried out using method same as Example 1 less than or equal to 50 DEG C.Based on the absorbance value using said determination method B measurement, the transmissivity of the every 1mm light path of compound after refining is calculated, as a result T=99.5%.By the oxygen concentration of GC (detector TCD) measurement at this time, as a result oxygen concentration is lower than 1ppm, nitrogen concentration 119ppm.In addition, GC purity is 99.92%.Trans- decahydronaphthalenes (3) after refining will be known as using the trans- decahydronaphthalenes after refining made from the method for embodiment 5.

Embodiment 6

In addition to using the nitrogen refined by nitrogen refiner, all operationss are carried out in the glove box less than or equal to 0.5ppm in nitrogen concentration control, and controlling degree of decompression makes vapor (steam) temperature, thus outside being evaporated under reduced pressure, the purification of commercially available extension-tetrahydro-dicyclopentadiene (Tokyo chemical conversion product) be carried out using method same as Example 3 less than or equal to 50 DEG C.Based on the absorbance value using said determination method B measurement, the transmissivity of the every 1mm light path of compound after refining is calculated, as a result T=99.6%.By the oxygen concentration of GC (detector TCD) measurement at this time, as a result oxygen concentration is lower than 1ppm, nitrogen concentration 100ppm.In addition, GC purity is 97.80%.Extension-tetrahydro-dicyclopentadiene (3) after refining will be known as using extension-tetrahydro-dicyclopentadiene after refining made from the method for embodiment 6.

Embodiment 7

By carrying out sulfuric acid treatment similarly to Example 3, so that commercially available dicyclohexyl, isopropyl cyclohexane, cyclooctane, cycloheptane are refined, obtained immersion exposure liquid.

In the above-described embodiments, GC purity analysis uses the following conditions.

It is measured using the GC6850 (column Agilent Technology HP-1 (nonpolar type) detector FID) of Agilent Technology.In 250 DEG C of inlet temperature, 70 DEG C~300 DEG C of column temperature (temperature-raising method), carrier gas is to carry out under conditions of helium for measurement.Purity is to be acquired using the total peak area of FID as 100% by area ratio.

8~embodiment of embodiment 22 and 1~comparative example of comparative example 2

Using above-mentioned evaluation etchant resist, absorbance change (or pollution) the evaluation immersion exposure liquid of the invention when evaluating (dipping pattern is formed evaluation, evaluated using the immersion exposure of two-beam interference exposure machine), resist contact is formed by elution test, the dissolubility test of film, pattern.As a result 1~table 14 shown in table 1.In addition, the wavelength dependency of refractive index is as shown in table 3, exist with wavelength shortening and the correlation of refractive index value raising.Therefore, by the refractive index under measurement D ray (wavelength 589nm), the refractive index under short wavelength can be predicted.Especially because immersion exposure of the invention has the structure being chemically similar with decahydronaphthalenes shown in table 1 with liquid, it is thus possible to be predicted by the refractive index of D ray (wavelength 589nm).Therefore illustrate the refractive index under D ray (wavelength 589nm).All show value more higher than the refractive index of pure water.

In addition, immersion exposure shown in embodiment 8~13 with liquid is refined according to embodiment 1, immersion exposure shown in embodiment 14~22 with liquid is refined according to the method for embodiment 1.

(1) elution test

After the chip for being coated with above-mentioned evaluation etchant resist is impregnated 30 seconds in the immersion exposure liquid shown in the table 11 of 300ml, take out chip, using HPLC, (Shimadzu Seisakusho Ltd. is manufactured, column Inertsil ODS-3 (internal diameter 10mm × long 250mm), eluting solvent: acetonitrile/water=80/20, detector: UV@205nm, 220nm, 254nm, 4 μm of sample injection rate) whether there is or not the impurity in the immersion exposure liquid of remaining for measurement.At this point, be denoted as elution test result when with more than any one detector confirmation detection limit impurity ×, when not having to confirm the impurity of detection limit or more, elution test result is denoted as zero.

(2) dissolubility test of film

After the initial film thickness for measuring the chip for being coated with above-mentioned evaluation etchant resist, after impregnating 30 seconds in the immersion exposure liquid shown in the table 11 of 300ml, film thickness measuring is carried out again.At this point, if it is 0.5% or more, being judged as that immersion exposure liquid dissolves etchant resist if the reduction amount of film thickness within the 0.5% of initial film thickness, is judged as that immersion exposure does not dissolve etchant resist with liquid, is denoted as "○", being denoted as "×".

(3) pattern forms evaluation test

Pattern forms evaluation test (1)

For being coated with the chip of above-mentioned evaluation etchant resist, with ArF projection aligner S306C (ニ U Application (strain) society manufactures), in NA:0.78, δ: 0.85, being exposed (light exposure 30mJ/cm under the optical condition of 2/3Ann²), then, PEB (130 DEG C, 90 seconds) are carried out with CLEAN TRACK ACT8 hot plate, oar blade type stirring imaging (imaging liquid ingredient: 2.38 weight % hydroxide tetrahydro aqueous ammoniums) (60 seconds) is carried out with the LD nozzle of the CLEAN TRACK ACT8, it is rinsed with ultrapure water, then, with the centrifugal dehydration of 4000rpm progress 15 seconds, to rotarily dry (imaging metacoxal plate A).Then, after the imaging metacoxal plate A above-mentioned pattern formed impregnates 30 seconds in the immersion exposure liquid shown in table 11, PEB, imaging, flushing are carried out using method similar to the above, imaging metacoxal plate B is made.Using scanning electron microscope (manufacture of Hitachi's tester (strain) society) S-9360 to imaging metacoxal plate A and B observation be equivalent to 90nm line, the space 90nm mask pattern pattern.At this point, the occasion for the good rectangle corrosion-resisting pattern that same shape can be obtained for imaging metacoxal plate A and B is denoted as "○" by visual observation, it is impossible to which the occasion for obtaining good pattern is denoted as "×"."-" expression is not evaluated.

Pattern forms evaluation test (2)

The chip exposed in the case where forming evaluation test (1) the same terms with pattern is impregnated 30 seconds in immersion exposure liquid, PEB, imaging, flushing are carried out using method same as described above, imaging metacoxal plate C is made.At this point, the occasion that the good rectangle corrosion-resisting pattern of same shape can be obtained for substrate A and C is denoted as "○" by visual observation, the occasion that cannot obtain excellent in shape pattern is denoted as "×"."-" expression is not evaluated.

(4) contact angle determination is tested

The Mode IDSA10L2E manufactured using Kruss, measures contact angle (measuring method Elipse (tangentl) method) of the trans- decahydronaphthalenes on above-mentioned etchant resist H2, H4, H5, quartz glass.As a result shown in table 12.

(5) light exposure test of two-beam interference has been used

Film thickness 29nm in addition to making lower layer reflection preventing film, make resist film thickness 100nm (for 45nm), other than 60nm (being used for 30nm), for being coated with the chip of the evaluation etchant resist using method identical with etchant resist H2 production, in two-beam interference type ArF immersion liquid, with Simple exposure device, (45nm1L/1S that Canon manufactures is used, the 35nm1L/1S of ニ U Application (strain) society manufacture is used, TE polarised light exposure use) lens, (gap 0.7mm) is inserted into immersion exposure liquid after above-mentioned purification between chip, it is exposed, then, by being air-dried the immersion exposure liquid removed on chip, (115 DEG C of PEB are carried out to this chip with CLEAN TRACK ACT8 hot plate, 90 seconds), with the CLEA The LD nozzle of N TRACK ACT8 carries out oar blade type stirring imaging (imaging liquid ingredient: 2.38 weight % hydroxide tetrahydro aqueous ammoniums) (60 seconds), it is rinsed with ultrapure water, pattern is observed to imaging metacoxal plate by scanning electron microscope (manufacture of Hitachi's tester (strain) society) S-9360.At this point, the occasion of the good corrosion-resisting pattern for the L/S (1L/1S) for obtaining desired size is denoted as "○", it is impossible to which the occasion for obtaining good pattern is denoted as "×".As a result shown in table 13.

(6) absorbance change (or pollution) when resist contacts

Liquid (the trans- decahydronaphthalenes (2) (other batch products refined using method same as Example 2) after deionized water or purification is added into the culture dish of diameter 6cm using the pipette of glass system.The film thickness of liquid is set to be right up to 1mm at this point, adjusting liquid measure.Then, the top of culture dish is covered with the silicon wafer for being coated with photoresist (H1, H4).Then, chip and culture dish are reversed up and down, becomes the state for making liquid infiltration in photoresist.Sufficiently closely sealed culture dish and chip leak out liquid between the two at this time, and pay attention to keeping chip holding horizontal so that in the upper photoresist in entire part covered with culture dish equably by liquid infiltration.Then it is impregnated with defined dip time, reverses chip and culture dish up and down.Liquid after collecting these sequence of operations is carried out the absorbance measurement of 193.4nm using the method for embodiment B, the absorbance of every 1cm absorbance is calculated according to measured value.In addition, carrying out above-mentioned sequence of operations in the glove box full of nitrogen at 23 DEG C.As a result shown in table 14.

Table 11

		Immersion exposure liquid			Etchant resist	Elution test result	The dissolubility test of film	Pattern forms evaluation test
										Title	Refractive index
		193nm	589nm	It tests (1)									It tests (2)
								Embodiment	8		Cis- decahydronaphthalenes	1.64		1.48	H1	○	○	○	○
9	Cis- decahydronaphthalenes	1.64	1.48	H2	○	○	○			○
									10		Cis- decahydronaphthalenes	1.64	1.48	H3	○	○	○	○
11	Cis- decahydronaphthalenes	1.64	1.48	H4	○	○	○			○
									12		Cis- decahydronaphthalenes	1.64	1.48	H5	○	○	○	○
13	Trans- decahydronaphthalenes	-	1.47	H1	○	○	○			○
									14		Spiral shell [5.5] hendecane	-	1.48	H1	○	○	○	○
15	Extension-tetrahydro-dicyclopentadiene	1.65	1.49	H1	○	○	○			○
									16		5- silicon ring [4.4] nonane	-	1.49	H1	○	○	○	○
17	1- ethyl adamantane	-	1.50	H1	○	○	○			○
									18		1,1,1- tri- suberyl methane	-	1.51	H1	○	○	○	○
19	Dicyclohexyl	1.64	1.48	H1	○	○	○			○
									20		Isopropyl cyclohexane	1.59	1.44	H1	○	○	○	○
21	Cyclooctane	-	1.46	H1	○	○	○			○
									22		Cycloheptane	-	1.44	H1	○	○	○	○
Comparative example	1	Pure water	1.44	1.34	H1	×	○			○									× (T- end shape)
								2	Diiodomethane		-	-	H1	×	×	× (film dissolution)	× (film dissolution)

Table 12

Etchant resist	Contact angle (degree)
		H2	23
H4	63.5
		H5	64
Quartz glass	Less than or equal to 10

Table 13

Immersion liquid liquid	Half spacing	Photosensitive (Ecd) mJ/cm2	Pattern form
				Trans- decahydronaphthalenes (1) after purification	45nm	27.1	○
Trans- decahydronaphthalenes (1) after purification	35nm	-	○
				Trans- decahydronaphthalenes (2) after purification	45nm	22.7	○
Trans- decahydronaphthalenes (2) after purification	35nm	-	○
				Extension-tetrahydro-dicyclopentadiene (1) after purification	45nm	28.6	○
Extension-tetrahydro-dicyclopentadiene (1) after purification	35nm	-	○
				Extension-tetrahydro-dicyclopentadiene (2) after purification	45nm	23	○
Extension-tetrahydro-dicyclopentadiene (2) after purification	35nm	-	○
				Isopropyl cyclohexane	45nm	-	○
Isopropyl cyclohexane	35nm	-	There is no exploring
				Cyclooctane	45nm	-	○
Cyclooctane	35nm	-	There is no exploring
				Water	45nm	-	T- end shape

Table 14

	Chip	Dip time (second)	193nm absorbance before dipping	193nm absorbance after dipping	The variation of 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
				Trans- decahydronaphthalenes (2) after purification	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, immersion exposure liquid of the invention is bigger than the refractive index of pure water, with chemical structure shown in formula (1-1)~formula (1-9), thus it is shown that excellent resolution ratio, and the etchant resist of insoluble etchant resist monomer or formation upper layer film, film component is not eluted, the corrosion-resisting pattern shape distortion generated is not also made.In addition, as shown in Table 14, the absorbance after the decahydronaphthalenes after purification was extracted at dip time 180 seconds does not change.

In addition we know: the evaluation method as immersion exposure liquid, contact immersion exposure with liquid with the photoresist formed on substrate, it measures the absorbance change contacted the preceding aforesaid liquid with after contact at 193 nm and is compared, so as to evaluate the dustiness of immersion exposure liquid.

Immersion exposure of the invention with liquid be alicyclic hydrocarbon compound or in ring structure containing the cyclic hydrocarbon compound of silicon atom, photoresist will not be thus dissolved in immersion exposure, it is capable of forming the excellent corrosion-resisting pattern such as resolution ratio, resulting visualization, manufacture is highly suitable for and expects to miniaturize the semiconductor device further developed from now on.

Claims

(according to the 19th article of modification of treaty)

1, immersion exposure liquid, the immersion exposure device or immersion exposure method that the liquid that the liquid is used to be full of between lens and substrate by projection optical system is exposed, it is characterized by: the liquid is liquid within the temperature range of above-mentioned immersion exposure device works, the liquid is comprising alicyclic hydrocarbon compound or contains the cyclic hydrocarbon compound of silicon atom in ring structure, the radioactive ray transmissivity of above-mentioned alicyclic hydrocarbon compound or cyclic hydrocarbon compound every 1mm light path at wavelength 193nm in ring structure containing silicon atom is more than or equal to 70%, the refractive index of D ray is more than or equal to 1.4.

2, immersion exposure liquid described in claim 1, it is characterised in that: the alicyclic hydrocarbon compound or the cyclic hydrocarbon compound in ring structure containing silicon atom are at least one kind of compounds selected from following formula (1-1)~formula (1-9),

In formula (1-1), R¹Indicate that the fluorine substituted hydrocarbon radical of the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, n1, n2 each independently represent 1~3 integer, a indicates 0~10 integer, when there are multiple R¹When, the R¹It can be the same or different, 2 or more R¹It can be bound to each other to form ring structure,

In formula (1-2), A indicates singly-bound or can be by the alkyl-substituted methylene of carbon atom number 1~10 or can be by the alkylidene of the alkyl-substituted carbon atom number 2~14 of carbon atom number 1~10, R²Indicate the fluorine substituted hydrocarbon radical of the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, R⁷Indicate that the fluorine of hydrogen atom, the alkyl of carbon atom number 1~10, fluorine atom or carbon atom number 1~3 replaces alkyl, when there are multiple R⁷When, the R⁷It can be the same or different, 2 or more R⁷It can be bound to each other to form ring structure, n3 indicates that 2~4 integer, n4 indicate 1~3 integer, and b indicates 0~6 integer, when there are multiple R²When, the R²It can be the same or different, 2 or more R²It can be bound to each other to form ring structure,

In formula (1-3), R³And R⁴The fluorine substituted hydrocarbon radical for indicating the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, works as R³And R⁴When being individually present multiple, the R³And R⁴It respectively identical can also be different, 2 or more R³And R⁴Respectively individually or it can be bound to each other to form ring structure, n5 and n6 indicate that 1~3 integer, c and d indicate 0~8 integer,

In (a) of formula (1-4), (b), (c), B indicates methylene or ethylidene, R⁵Indicate that the fluorine substituted hydrocarbon radical of the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, e indicate 0~10 integer, n7 indicates 1~3 integer, when there are multiple R⁵When, the R⁵It can be the same or different, 2 or more R⁵It can be bound to each other to form ring structure,

In formula (1-5), R⁶Indicate the fluorine substituted hydrocarbon radical of the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, f indicates 0~10 integer, when there are multiple R⁶When, the R⁶It can be the same or different,

In formula (1-6), R⁸And R^8’Indicating that the fluorine substituted hydrocarbon radical of the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, g and h respectively indicate 0~6 integer, n8 and n9 indicate 1~3 integer,

In formula (1-7), R¹¹And R¹²Indicate that the fluorine substituted hydrocarbon radical of the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, n10, n11 each independently represent 1~3 integer, j, k indicate 0~6 integer, work as R¹¹And R¹²When being individually present multiple, the R¹¹And R¹²It can be the same or different, 2 or more R¹¹Ring structure or 2 or more R can be bound to each other to form¹²Can be bound to each other to form ring structure, X indicate singly-bound, the divalent aliphatic alkyl of carbon atom number 2~10, carbon atom number 3~14 divalent alicyclic hydrocarbon radical,

In formula (1-8), R¹³Indicate the fluorine substituted hydrocarbon radical of alkyl of the carbon atom number more than or equal to 2, alicyclic hydrocarbon radical of the carbon atom number more than or equal to 3, fluorine atom or carbon atom number 2~3, p indicates 1~6 integer, when there are multiple R¹³When, the R¹³It can be the same or different, 2 or more R¹³It can be bound to each other to form ring structure,

In formula (1-9), R¹⁴Indicate that the fluorine substituted hydrocarbon radical of the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, n12 indicate 1~3 integer, q indicates 0~9 integer, when there are multiple R¹⁴When, the R¹⁴It can be the same or different.

3, immersion exposure liquid as claimed in claim 2, it is characterized by: above-mentioned formula (1-1) compound represented is indicated by following formula (2-1), above-mentioned formula (1-4) compound represented is indicated by following formula (2-2)

In formula (2-1), R¹Indicate the fluorine substituted hydrocarbon radical of the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, a indicates 0~10 integer, when there are multiple R¹When, the R¹It can be the same or different, 2 or more R¹It can be bound to each other to form ring structure,

In formula (2-2), R⁵Indicate the fluorine substituted hydrocarbon radical of the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, i indicates 0~2 integer, when there are multiple R⁵When, the R⁵It can be the same or different, 2 or more R⁵Ring structure can be bound to each other to form.

4, immersion exposure liquid described in claim 1, it is characterized by: make liquid film with a thickness of 1mm, make the liquid when contacting 180 seconds on photoresist in a nitrogen atmosphere, before contact with contact after liquid every 1cm light path at 193 nm absorbance change less than or equal to 0.05.

5, immersion exposure liquid described in claim 1, it is characterised in that: relative to whole immersion exposure liquid, the cyclic hydrocarbon compound of silicon atom is contained containing the alicyclic hydrocarbon compound more than or equal to 95 weight % or in ring structure.

6, immersion exposure liquid described in claim 1, it is characterised in that: the dissolved oxygen content of the liquid is less than or equal to 2ppm.

7, immersion exposure liquid described in claim 1, it is characterised in that: the total metal content that the liquid contains is less than or equal to 10ppb.

8, immersion exposure liquid as claimed in claim 7, it is characterised in that: the metal is at least one kind of metal for being selected from lithium, sodium, potassium, magnesium, copper, calcium, aluminium, iron, zinc, nickel.

9, immersion exposure liquid described in claim 1, it is characterised in that: viscosity of the liquid at 25 DEG C is less than or equal to 0.01Pas.

10, immersion exposure liquid described in claim 1, it is characterised in that: the refractive index at wavelength 193nm is more than or equal to 1.63.

11, immersion exposure liquid described in any one of claim 10, it is characterised in that: the radioactive ray transmissivity of every 1mm light path is more than or equal to 95% at wavelength 193nm.

12, immersion exposure liquid as claimed in claim 3, it is characterized by: above-mentioned formula (2-1) compound represented is trans- decahydronaphthalenes, the radioactive ray transmissivity of every 1mm light path is more than or equal to 95% at wavelength 193nm, and dissolved oxygen content is less than or equal to 2ppm.

13, immersion exposure liquid described in claim 12, it is characterised in that: be the liquid that the purity as obtained from carrying out concentrated sulfuric acid washing and distillation to trans- decahydronaphthalenes raw material is more than or equal to 95 weight % in a nitrogen atmosphere.

14, immersion exposure liquid as claimed in claim 3, it is characterized by: above-mentioned formula (2-2) compound represented is extension-tetrahydro-dicyclopentadiene, the radioactive ray transmissivity of every 1mm light path is more than or equal to 95% at wavelength 193nm, and dissolved oxygen content is less than or equal to 2ppm.

15, immersion exposure liquid described in claim 14, it is characterised in that: be the liquid that the purity as obtained from carrying out concentrated sulfuric acid washing and distillation to extension-tetrahydro-dicyclopentadiene raw material is more than or equal to 95 weight % in a nitrogen atmosphere.

16, the manufacturing method of immersion exposure liquid described in claim 1, it is characterised in that: at least one process of concentrated sulfuric acid washing and distillation is carried out including the liquid in a nitrogen atmosphere to the cyclic hydrocarbon compound comprising above-mentioned alicyclic hydrocarbon compound or in ring structure containing silicon atom.

17, immersion exposure method, the immersion exposure method is to illuminate exposure mask with exposing light beam, by the liquid being full of between the lens and substrate of projection optical system, make base plate exposure with above-mentioned exposing light beam, it is characterised in that: aforesaid liquid is immersion exposure liquid described in claim 1.

18, immersion exposure method described in claim 17, it is characterized by: the film surface against corrosion on aforesaid substrate forms immersion liquid upper layer film, the immersion liquid is to have at least one group of hexafluoro methanol-based and carboxyl as the substituent group for assigning the alkali-soluble containing the immersion liquid upper layer film for dissolving in alkali imaging liquid and the resin component insoluble in immersion exposure liquid described in claim 1 with upper layer film.

19, the dustiness evaluation method of immersion exposure liquid, the dustiness when immersion exposure that the dustiness evaluation method is used to evaluate liquid used in the immersion exposure device being exposed by the liquid being full of between the lens and substrate of projection optical system or immersion exposure method uses

It is characterized by: contacting immersion exposure with liquid with the photoresist formed on aforesaid substrate, it measures the absorbance change contacted the preceding aforesaid liquid with after contact at wavelength 193nm and is compared, to evaluate the dustiness of immersion exposure liquid.

20, immersion exposure liquid composition, it is characterised in that: containing the following formula (2-1) or following formula (2-2) compound represented for being more than or equal to 95 weight %, dissolved oxygen content is less than or equal to 2ppm,

In formula (2-1), R¹Indicate the fluorine substituted hydrocarbon radical of the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, a indicates 0~10 integer, when there are multiple R¹When, the R¹It can be the same or different, 2 or more R¹It can be bound to each other to form ring structure,

In formula (2-2), R⁵Indicate the fluorine substituted hydrocarbon radical of the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, fluorine atom or carbon atom number 1~3, i indicates 0~2 integer, when there are multiple R⁵When, the R⁵It can be the same or different, 2 or more R⁵Ring structure can be bound to each other to form.

21, liquid composition described in claim 20, it is characterised in that: the total metal content that the liquid composition contains is less than or equal to 10ppb.

22, liquid composition described in claim 20, it is characterised in that: above-mentioned formula (2-1) compound represented is trans- decahydronaphthalenes, and the radioactive ray transmissivity of every 1mm light path is more than or equal to 95% at wavelength 193nm.

23, liquid composition described in claim 20, it is characterised in that: above-mentioned formula (2-2) compound represented is extension-tetrahydro-dicyclopentadiene, and the radioactive ray transmissivity of every 1mm light path is more than or equal to 95% at wavelength 193nm.

24, liquid composition described in claim 20, it is characterised in that: at least one kind of method washed and distilled using the concentrated sulfuric acid in a nitrogen atmosphere refines above-mentioned formula (2-1) or formula (2-2) compound represented.

Claims (25)

1, immersion exposure liquid, the immersion exposure device or immersion exposure method that the liquid that the liquid is used to be full of between lens and substrate by projection optical system is exposed, it is characterized by: the liquid is liquid within the temperature range of above-mentioned immersion exposure device works, the liquid is comprising alicyclic hydrocarbon compound or contains the cyclic hydrocarbon compound of silicon atom in ring structure.

2, immersion exposure liquid described in claim 1, it is characterized by: the refractive index that the radioactive ray transmissivity of the alicyclic hydrocarbon compound or the cyclic hydrocarbon compound in ring structure containing silicon atom every 1mm light path at wavelength 193nm is more than or equal to 70%, D ray is more than or equal to 1.4.

3, immersion exposure liquid as claimed in claim 2, it is characterised in that: the alicyclic hydrocarbon compound or the cyclic hydrocarbon compound in ring structure containing silicon atom are at least one kind of compounds selected from following formula (1-1)~formula (1-9),

In formula (1-1), R¹Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, n1, n2 each independently represent 1~3 integer, and a indicates 0~10 integer, when there are multiple R¹When, the R¹It can be the same or different, 2 or more R¹Ring structure, R can be bound to each other to form⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10,

In formula (1-2), A indicates singly-bound or can be by the alkyl-substituted methylene of carbon atom number 1~10 or can be by the alkylidene of the alkyl-substituted carbon atom number 2~14 of carbon atom number 1~10, R²Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, R⁷Indicate hydrogen atom, the alkyl of carbon atom number 1~10, cyano, hydroxyl, fluorine atom, carbon atom number 1~10 fluorine replace alkyl or-Si (R⁹)₃Base, when there are multiple R⁷When, the R⁷It can be the same or different, 2 or more R⁷It can be bound to each other to form ring structure, n3 indicates that 2~4 integer, n4 indicate 1~3 integer, and b indicates 0~6 integer, when there are multiple R²When, the R²It can be the same or different, 2 or more R²Ring structure, R can be bound to each other to form⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10,

In formula (1-3), R³And R⁴Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base works as R³And R⁴When being individually present multiple, the R³And R⁴It respectively identical can also be different, 2 or more R³And R⁴Respectively individually or it can be bound to each other to form ring structure, n5 and n6 indicate that 1~3 integer, c and d indicate 0~8 integer, R⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10,

In (a) of formula (1-4), (b), (c), B indicates methylene or ethylidene, R⁵Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, e indicate 0~10 integer, and n7 indicates 1~3 integer, when there are multiple R⁵When, the R⁵It can be the same or different, 2 or more R⁵Ring structure, R can be bound to each other to form⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10,

In formula (1-5), R⁶Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, f indicates 0~10 integer, when there are multiple R⁶When, the R⁶It can be the same or different, R⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10,

In formula (1-6), R⁸And R^8’Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, g and h respectively indicate 0~6 integer, and n8 and n9 indicate 1~3 integer, R⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10,

In formula (1-7), R¹¹And R¹²Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, n10, n11 each independently represent 1~3 integer, and j, k indicate 0~6 integer, work as R¹¹And R¹²When being individually present multiple, the R¹¹And R¹²It can be the same or different, 2 or more R¹¹Ring structure or 2 or more R can be bound to each other to form¹²Can be bound to each other to form ring structure, X indicate singly-bound, the divalent aliphatic alkyl of carbon atom number 2~10, carbon atom number 3~14 divalent alicyclic hydrocarbon radical, R⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10,

In formula (1-8), R¹³Indicate alkyl of the carbon atom number more than or equal to 2, alicyclic hydrocarbon radical of the carbon atom number more than or equal to 3, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 2~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, p indicates 1~6 integer, when there are multiple R¹³When, the R¹³It can be the same or different, 2 or more R¹³Ring structure, R can be bound to each other to form⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10,

In formula (1-9), R¹⁴Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, n12 indicate 1~3 integer, and q indicates 0~9 integer, when there are multiple R¹⁴When, the R¹⁴It can be the same or different, R⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

4, immersion exposure liquid as claimed in claim 3, it is characterized by: above-mentioned formula (1-1) compound represented is indicated by following formula (2-1), above-mentioned formula (1-4) compound represented is indicated by following formula (2-2)

In formula (2-1), R¹Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, a indicates 0~10 integer, when there are multiple R¹When, the R¹It can be the same or different, 2 or more R¹Ring structure, R can be bound to each other to form⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10,

In formula (2-2), R⁵Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, i indicates 0~2 integer, when there are multiple R⁵When, the R⁵It can be the same or different, 2 or more R⁵Ring structure, R can be bound to each other to form⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

5, immersion exposure liquid described in claim 1, it is characterized by: make liquid film with a thickness of 1mm, make the liquid when contacting 180 seconds on photoresist in a nitrogen atmosphere, before contact with contact after liquid every 1cm light path at 193 nm absorbance change less than or equal to 0.05.

6, immersion exposure liquid described in claim 1, it is characterised in that: relative to whole immersion exposure liquid, containing being more than or equal to alicyclic hydrocarbon compound described in 95 weight % or contain the cyclic hydrocarbon compound of silicon atom in ring structure.

7, immersion exposure liquid described in claim 1, it is characterised in that: the dissolved oxygen content of the liquid is less than or equal to 2ppm.

8, immersion exposure liquid described in claim 1, it is characterised in that: the total metal content that the liquid contains is less than or equal to 10ppb.

9, immersion exposure liquid according to any one of claims 8, it is characterised in that: the metal is at least one kind of metal for being selected from lithium, sodium, potassium, magnesium, copper, calcium, aluminium, iron, zinc, nickel.

10, immersion exposure liquid described in claim 1, it is characterised in that: viscosity of the liquid at 25 DEG C is less than or equal to 0.01Pas.

11, immersion exposure liquid described in claim 1, it is characterised in that: the refractive index at wavelength 193nm is more than or equal to 1.63.

12, immersion exposure liquid described in claim 11, it is characterised in that: the radioactive ray transmissivity of every 1mm light path is more than or equal to 95% at wavelength 193nm.

13, immersion exposure liquid as claimed in claim 4, it is characterized by: above-mentioned formula (2-1) compound represented is trans- decahydronaphthalenes, the radioactive ray transmissivity of every 1mm light path is more than or equal to 95% at wavelength 193nm, and dissolved oxygen content is less than or equal to 2ppm.

14, immersion exposure liquid described in claim 13, it is characterised in that: be the liquid that the purity as obtained from carrying out concentrated sulfuric acid washing and distillation to trans- decahydronaphthalenes raw material is more than or equal to 95 weight % in a nitrogen atmosphere.

15, immersion exposure liquid as claimed in claim 4, it is characterized by: above-mentioned formula (2-2) compound represented is extension-tetrahydro-dicyclopentadiene, the radioactive ray transmissivity of every 1mm light path is more than or equal to 95% at wavelength 193nm, and dissolved oxygen content is less than or equal to 2ppm.

16, immersion exposure liquid described in claim 15, it is characterised in that: be the liquid that the purity as obtained from carrying out concentrated sulfuric acid washing and distillation to extension-tetrahydro-dicyclopentadiene raw material is more than or equal to 95 weight % in a nitrogen atmosphere.

17, the manufacturing method of immersion exposure liquid described in claim 1, it is characterised in that: at least one process of concentrated sulfuric acid washing and distillation is carried out including the liquid in a nitrogen atmosphere to the cyclic hydrocarbon compound comprising above-mentioned alicyclic hydrocarbon compound or in ring structure containing silicon atom.

18, immersion exposure method, the immersion exposure method is to illuminate exposure mask with exposing light beam, by the liquid being full of between the lens and substrate of projection optical system, make base plate exposure with above-mentioned exposing light beam, it is characterised in that: aforesaid liquid is immersion exposure liquid described in claim 1.

19, immersion exposure method described in claim 18, it is characterized by: the film surface against corrosion on aforesaid substrate forms immersion liquid upper layer film, the immersion liquid is to have at least one group of hexafluoro methanol-based and carboxyl as the substituent group for assigning the alkali-soluble containing the immersion liquid upper layer film for dissolving in alkali imaging liquid and the resin component insoluble in immersion exposure liquid described in claim 1 with upper layer film.

20, the dustiness evaluation method of immersion exposure liquid, the dustiness when immersion exposure that the dustiness evaluation method is used to evaluate liquid used in the immersion exposure device being exposed by the liquid being full of between the lens and substrate of projection optical system or immersion exposure method uses

It is characterized by: contacting immersion exposure with liquid with the photoresist formed on aforesaid substrate, it measures the absorbance change contacted the preceding aforesaid liquid with after contact at wavelength 193nm and is compared, to evaluate the dustiness of immersion exposure liquid.

21, immersion exposure liquid composition, it is characterised in that: containing the following formula (2-1) or following formula (2-2) compound represented for being more than or equal to 95 weight %, dissolved oxygen content is less than or equal to 2ppm,

In formula (2-1), R¹Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, a indicates 0~10 integer, when there are multiple R¹When, the R¹It can be the same or different, 2 or more R¹Ring structure, R can be bound to each other to form⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10,

In formula (2-2), R⁵Indicate the aliphatic alkyl of carbon atom number 1~10, the alicyclic hydrocarbon radical of carbon atom number 3~14, cyano, hydroxyl, fluorine atom, the fluorine substituted hydrocarbon radical of carbon atom number 1~10 ,-Si (R⁹)₃Base or-SO₃R¹⁰Base, i indicates 0~2 integer, when there are multiple R⁵When, the R⁵It can be the same or different, 2 or more R⁵Ring structure, R can be bound to each other to form⁹And R¹⁰Indicate the alkyl of carbon atom number 1~10.

22, liquid composition described in claim 21, it is characterised in that: the total metal content that the liquid composition contains is less than or equal to 10ppb.

23, liquid composition described in claim 21, it is characterised in that: above-mentioned formula (2-1) compound represented is trans- decahydronaphthalenes, and the radioactive ray transmissivity of every 1mm light path is more than or equal to 95% at wavelength 193nm.

24, liquid composition described in claim 21, it is characterised in that: above-mentioned formula (2-2) compound represented is extension-tetrahydro-dicyclopentadiene, and the radioactive ray transmissivity of every 1mm light path is more than or equal to 95% at wavelength 193nm.

25, liquid composition described in claim 21, it is characterised in that: at least one kind of method washed and distilled using the concentrated sulfuric acid in a nitrogen atmosphere refines above-mentioned formula (2-1) or formula (2-2) compound represented.