CN100440431C - Immersion liquid for immersion exposure process and resist pattern forming method using such immersion liquid - Google Patents

Abstract

An immersion fluid for use in liquid immersion lithography in which a resist film is exposed to light via a fluid. The fluid is transparent to the exposure light used in the liquid immersion lithography and comprises a fluorine-based liquid having a boiling point of 70 to 270 DEG C. A method of forming resist patter includes a step of placing the immersion fluid directly on the resist film or a protective film deposited on the resist film. The present invention prevents alteration of resist film and other films as well as alteration of the fluid during liquid immersion lithography and enables high resolution resist patterning using liquid immersion lithography.

Description

Immersion liquid for immersion exposure process and use the resist pattern formation method of this maceration extract

Technical field

The present invention relates to be suitable for the liquid (below be designated as maceration extract) of liquid for immersion exposure process and the resist pattern formation method of using this maceration extract, this maceration extract is in immersion exposure (Liquid Immersion Lithography) technology, wherein arrive on the above-mentioned at least resist film in path of resist film at the light of offset printing exposure, Jie is under the state of the liquid of the big given thickness of refractive index ratio air, above-mentioned resist film is exposed, thus the formation of the resolution of raising resist pattern.

Background technology

In the manufacturing of the fine structure of various electronic installations such as semiconductor device, liquid-crystal apparatus, usually use the offset printing method, but, the resist pattern in the offset printing operation is also required to become more meticulous along with the becoming more meticulous of apparatus structure.

At present, adopt the offset printing method,, can form the meticulous resist pattern of the about 90nm of live width, will require to form meticulousr pattern from now on for example in most advanced field.

In order to form this pattern meticulousr than 90nm, the exploitation of exposure device and its corresponding resist becomes the 1st main points.In exposure device, the increase of the short wavelengthization of optical source wavelengths such as F2 laser, EUV (extreme ultraviolet light), electron ray, X ray and the pinhole number (NA) of lens etc. generally is the main points of exploitation.

But the short wavelengthization of optical source wavelength needs expensive novel exposure device, and in high NAization, because there are trade-off relation in the resolution and the depth of focus width of cloth, even improve resolution, the problem that also exists the depth of focus width of cloth to reduce.

Recently, as the lithographic printing that can address this problem, reported the such method of immersion exposure (Liquid Immersion Lithography) method (for example, non-patent literature 1 (J.Vac.Sci.Technol.B (1999) 17 (6) p3306-3309), non-patent literature 2 (J.Vac.Sci.Technol.B (2001) 19 (6) p2353-2356), non-patent literature 3 (Proceedings of SPIE Vol.4691 (2002) p459-465)).This method is when exposure, and Jie is at aqueous (maceration extracts) such as the pure water of given thickness or fluorine-containing inert fluids on the above-mentioned at least resist film between the resist film on lens and the substrate.In the method, with the bigger liquid of refractive index (n), for example displacement such as pure water was the exposure light path space of inert gases such as air or nitrogen in the past, even use the light source of identical exposure wavelength, during also with the light source that uses short wavelength more or the same when using high NA lens, when reaching high resolution, the depth of focus width of cloth can not reduce.

If use this immersion exposure, use the lens of in existing device, installing, can realize forming the resist pattern that high resolution is better and the depth of focus is also good, thereby receive very big concern with low cost.

Summary of the invention

; in above-mentioned liquid for immersion exposure process; as the maceration extract that uses; inertia water and perfluor ethers such as pure water and deionized water have been proposed; be expected to be much accounted of from the consideration inertia water such as easiness of cost and operation; but because resist film directly contacts with maceration extract, so resist film is subjected to the invasion and attack of liquid when exposure.Therefore, need checking whether can former state fixedly be suitable for the resist composition that in the past used.

Now habitual resist composition, be from have to the transparency of exposure light this most important must characteristic, discussed possible resin widely and the composition established.Following content has been discussed in experiments such as the inventor: promptly, among the resist composition of this present proposition, under intact composition or by composition is done some adjustment, whether can obtain having the resist composition of the characteristic that is suitable for immersion exposure.The result distinguishes, has the resist composition that can expect in practicality.Also confirm on the other hand: even the resist composition of sufficient pattern resolving power takes place to be can not get by cause rotten of liquid in immersion exposure, in the lithographic printing that is undertaken by the exposure of air layer usually, the material that demonstrates meticulous and high resolving power also exists in a large number.Such resist composition is to consume many exploiting natural resources and the composition established, it is composition to the various resist excellents such as the transparency, video picture, storage stability of exposure light, in such resist composition, exist many only for the material of the patience difference of maceration extract.

Even use the above-mentioned occasion that is suitable for the resist film of immersion exposure, when carrying out immersion exposure, compare with exposure by air layer, confirmed the fact that quality and non-defective unit yield reduce to a certain degree.

The immersion exposure of above-mentioned existing resist film is fitted property, is to estimate according to following analysis to the immersion exposure method.

Promptly, when estimating the resist pattern formation performance that adopts immersion exposure, if can confirm the performance of the optical system of (i) immersion exposure method, (ii) resist film is for the influence of maceration extract, (iii) rotten this 3 point of the resist film that causes of maceration extract, it is fully necessary then being judged as.

Performance about the optical system of (i), if for example imagination sinks to the photo of surperficial resistance to water in the water with photographic plate, situation to its surface irradiation pattern light then can be clear and definite: if the optical transmission loss that does not reflect at the interface on the water surface and water and photographic plate surface etc., then problem does not take place in the back, and this does not have query on principle.Optical transmission loss under this situation can easily solve by suitableization of the incident angle of exposure light.Therefore, when the material as exposure object is resist film, be photo use light sensitive plate the time, or during the imaging silk screen, if they are inertia to maceration extract, if not influenced by maceration extract, do not influence maceration extract yet, can think that then the performance of optical system does not change.Therefore, about this point, needn't confirm experiment again.

Resist film (ii) specifically is composition stripping in liquid of resist film for the influence of maceration extract, and liquid refractive index is changed.If liquid refractive index changes, then the optical resolution of pattern exposure is changed, and this need not experimentize, and is definite theoretically.About this point, only resist film is immersed in the occasion in the liquid, if can confirm the composition stripping, the composition of maceration extract changes, perhaps variations in refractive index then is fully, does not in fact need irradiation pattern light, resolution is confirmed in video picture.

In contrast, resist film irradiation pattern light in liquid, video picture, the occasion of affirmation resolving power, enable promptly to confirm whether resolving power is good, whether whether rotten influential to resolving power, the going bad of anticorrosive additive material that can not distinguish maceration extract influence resolving power or this two aspect.

About because the resist film that (iii) maceration extract causes rotten makes the problem of resolving power deterioration, adopt following evaluation test promptly enough: ", checking the resolving power of resulting resist pattern " in the laggard processing of maceration extract shower on resist film of being about to that expose; video picture then.And, in this evaluation method,, soak more too harshness of condition as liquid to the direct spraying liquid of resist film.About this point, the occasion of the test that under the thorough impregnation state, exposes, whether have by the rotten influence that brings of maceration extract, resist composition by maceration extract cause rotten whether be reason or whether since both sides' influence to make that resolving power changes all indeterminate.

Above-mentioned phenomenon (ii) and (iii) is the phenomenon of one in the table, can hold by the degree of metamorphism that is caused by liquid of confirming resist film.

Based on such analysis, by " being about to the processing of maceration extract (pure water) shower on resist film in that exposure is laggard; video picture then; check the resolving power of resulting resist pattern " this evaluation test (below be designated as " evaluation test 1 "), confirms the above-mentioned immersion exposure adaptability of the resist film of proposition in the past.Moreover, use the interference light that obtains by prism to replace the pattern light of exposure by employing, sample is placed to liquid soaks state, " the 2 beam interference exposure method " of the formation that makes it to expose, the evaluation test of the manufacturing process that simulation is actual (below be designated as " evaluation test 2 ") is confirmed.And, about the relation of resist film and maceration extract, by confirming as the evaluation test of the quartz crystal method (based on adopting quartzy balance: the weight change that Quarts Crystal Microbalance obtains detects the film thickness measuring of thickness) of the method for the Thickness Variation of measuring denier (below be designated as " evaluation test 3 ").

As mentioned above, when coming of new is suitable for the resist film of immersion exposure, really need many exploiting natural resources, on the other hand, among the resist composition that proposes now, under intact composition, or by composition is done some adjustment, though deterioration a little takes place on the quality, but confirm: there is resist composition with the characteristic that is suitable for immersion exposure, on the other hand, even in immersion exposure, generation is by going bad that maceration extract (pure water) causes, and can not get the resist film of sufficient pattern resolving power, in the lithographic printing of the exposure by air layer usually, demonstrate existing of meticulous and high resolving power also morely.

The present invention finishes in view of described prior art problems, its problem provides a kind of technology, the resist film that the existing resist composition of establishing by consuming many exploiting natural resources can be obtained is applicable to immersion exposure, problem specifically of the present invention is: as the maceration extract of immersion exposure method use, do not make water, and use the exposure optical transparency, volatilization under the temperature conditions of exposure process is few, and liquid with characteristic that the resist film after the exposure removes easily, prevent going bad of resist film and going bad of use liquid self in the immersion exposure thus simultaneously, can form the high resolution resist pattern that has used immersion exposure.

In order to solve above-mentioned problem, immersion liquid for immersion exposure process of the present invention is characterised in that by the exposure optical transparency that above-mentioned exposure technology is used, its boiling point is that 70-270 ℃ fluorinated solvent constitutes.

In addition, resist pattern of the present invention forms method feature and is, has been to use the resist pattern formation method of liquid for immersion exposure process, comprises following operation: the operation that forms photoresist film on substrate at least; Will be by the exposure optical transparency that above-mentioned exposure technology is used, its boiling point is that the maceration extract of 70-270 ℃ fluorinated liquid formation directly is configured in the operation on the above-mentioned resist film; By above-mentioned maceration extract optionally with the operation of above-mentioned resist film exposure; The operation of the above-mentioned resist film of heat treated as required; Then, with above-mentioned resist film video picture, form the operation of resist pattern.

In addition, the 2nd resist pattern of the present invention forms method feature and is, has been to use the resist pattern formation method of liquid for immersion exposure process, comprises following operation: the operation that forms photoresist film on substrate at least; On above-mentioned resist film, form the operation of diaphragm; Will be by the exposure optical transparency that above-mentioned exposure technology is used, its boiling point is that the maceration extract of 70-270 ℃ fluorinated liquid formation directly is configured in the operation on the said protection film; By above-mentioned maceration extract and diaphragm optionally with the operation of above-mentioned resist film exposure; The operation of the above-mentioned resist film of heat treated as required; Then, with above-mentioned resist film video picture, form the operation of resist pattern.

Moreover, in the above-described configuration, liquid for immersion exposure process is the technology of preferred following formation therein: on the above-mentioned at least resist film that makes the path till lithographic printing exposure light arrives resist film, Jie exposes under the state of the liquid of the big given thickness of refractive index ratio air, thereby the resolution of resist pattern is improved.

According to the present invention, use habitual any resist composition to constitute resist film, the bad phenomenon such as fluctuating, wire drawing phenomenon that does not all have surface checking, the pattern of T-pointed shapeization, the resist pattern of resist pattern in immersion exposure process can access highly sensitive, resist pattern profile proterties excellence, resist pattern that precision is high.In addition, on resist film, form diaphragm, the occasion of maceration extract of the present invention is set on this diaphragm, also can form excellent resist pattern.

Therefore, when using maceration extract of the present invention, can effectively use the formation of the resist pattern of liquid for immersion exposure process.

Description of drawings

Fig. 1 is the curve chart of the film thickness value of expression resist film to the variation of dip time.

Fig. 2 is the curve chart of the film thickness value of expression resist film to the variation of dip time.

Embodiment

Maceration extract of the present invention, as mentioned above, by exposure optical transparency, its boiling point that uses in liquid for immersion exposure process constituted as 70-270 ℃ fluorinated liquid.

By the maceration extract that the fluorinated liquid of this specific character constitutes, can provide the effect of following excellence:

(i) be inertia for the resist film that forms by all habitual resist compositions, do not make resist film rotten; (ii) owing to can not make the composition stripping of resist film, therefore the composition of maceration extract self can be remained constantly before and after the exposure, will keep constantly to the refractive index of exposure light, stable excellent exposure light path can be provided; (iii) because boiling point is more than 70 ℃, therefore near the exposure process that carries out room temperature, the change of the maceration extract self component ratio that can prevent evaporates causes and the change of liquid level can be kept stable excellent exposure light path; (iv) because boiling point is below 270 ℃, the resist film that therefore can adopt methods such as easy method, for example drying at room temperature, Rotary drying, heat drying, nitrogen current to carry out easily and fully after finishing immersion exposure is removed maceration extract.In addition, therefore above-mentioned maceration extract can suppress lithographic printing is caused the generation of dysgenic micron bubble or nano bubble etc. effectively owing to the dissolubility height to gases such as oxygen, nitrogen.

The fluorinated liquid that is suitable for maceration extract of the present invention, as mentioned above, boiling point is 70-270 ℃, more preferably boiling point is 80-220 ℃.As such fluorinated liquid, specifically can enumerate all-fluoroalkyl compound, as this all-fluoroalkyl compound, can enumerate perfluoroalkyl ether compound and perfluoroalkyl amines.

Further specifically,, the perfluoroalkyl ring type ether of perfluor (2-butyl-oxolane) (102 ℃ of boiling points) and so on can be enumerated,, PFTPA N (C can be enumerated as above-mentioned perfluoroalkyl amines as above-mentioned perfluoroalkyl ether compound ₃F ₇) ₃(130 ℃ of boiling points), perfluor tri-butylamine N (C ₄F ₉) ₃(174 ℃ of boiling points), perfluor three amylamine N (C ₅F ₁₁) ₃(215 ℃ of boiling points), perfluor three hexyl amine N (C ₆F ₁₃) ₃(about 255 ℃ of boiling point) etc.Wherein, to below the 10ppm, the dissolving and the swelling of resist film are little with the hydrogen concentration high-purityization in the fluorinated liquid, and various in addition compositions are few from oozing out of resist film, so preferably.

In addition, in these materials, preferably to the exposure light absorption little, as liquid immersion liquid have the appropriateness volatile material.As such material, preferred PFTPA, perfluor tri-butylamine.

As mentioned above, in non-patent literature as the look-ahead technique document that relates to immersion exposure, as maceration extract the perfluoroalkyl polyethers has been proposed, but the inventor etc. finish when of the present invention, viewpoint from the above-mentioned exploitation has been discussed practicality as maceration extract for the various commercially available products of this perfluoroalkyl polyethers.Affirmation such as inventor's grade as a result: less than the boiling point that is judged as one of necessary factor as the maceration extract characteristic is below 270 ℃, for this reason, the removal of the maceration extract that carries out behind end exposure is used at least and is stated easy method and can not fully carry out, because the residue of this maceration extract, the formation of resist pattern becomes impossible.

In addition, these perfluoroalkyl polyethers, the decentralization of its molecular weight is big, and such characteristic becomes the principal element of the refractive index stabilisation of infringement exposure light, and then can become the reason of the optical stability of infringement conditions of exposure.

Maceration extract of the present invention thinks that the decentralization of molecular weight is smaller, considers to infer to be preferred liquid from the aspect of also not damaging this optical stability.

Spendable in the present invention resist film, all resist films that can use the always habitual resist composition of employing to obtain do not need the special ground that limits to use.This point also is a maximum feature of the present invention.

As mentioned above, as the resist composition that in liquid for immersion exposure process of the present invention, uses, can use habitual eurymeric resist, the resist composition that negative type photoresist is used.Below exemplify their concrete example.

At first, as the base polymer that uses in positive light anti-etching agent composition (resinous principle), can use acrylic resin, cyclic olefine resin, silsesquioxane (シ Le セ ス キ オ キ サ Application) is resin, fluoropolymer etc.

Acid is resin as aforesaid propylene, for example preferably has the formation unit (a1) of deriving by (methyl) acrylate that has the acid dissociation dissolving to suppress base, also comprise by this and constitute the formation unit that other following (methyl) acrylate of unit (a1) are derived, contain that the 80 moles of % in formation unit that derived by (methyl) acrylate are above, the resin of preferred 90 moles of % above (most preferably 100 moles of %).

In addition, above-mentioned resinous principle is in order to satisfy resolving power, anti-dry ecthing and meticulous pattern form, adopts a plurality of beyond above-mentioned (a1) unit to have the monomeric unit of difference in functionality, for example followingly constitute constituting of unit.

That is, the formation unit of deriving by (methyl) acrylate with lactone unit (below be called (a2) or (a2) unit.), the formation unit of deriving by (methyl) acrylate with the polycycle base that contains alcohol hydroxyl group (below be called (a3) or (a3) unit.), contain with the acid dissociation dissolving of above-mentioned (a1) unit suppress the lactone unit of base, above-mentioned (a2) unit and above-mentioned (a3) unit the polycycle base that contains alcohol hydroxyl group any all different polycycle base the formation unit (below be called (a4) or (a4) unit.) etc.

These (a2), (a3) and/or (a4) can be according to appropriate combination such as desired characteristics.Preferably contain (a1) and be selected from (a2), (a3) and at least one unit (a4), resolving power and resist pattern form become good thus.Moreover, (a1)-(a4) among the unit, about each unit, also can and with multiple different unit.

Constitute the unit and constitute the unit for what derive by what acrylate was derived by methacrylate, total amount with respect to the molal quantity that constitutes the unit that constitutes the unit and derive by acrylate of deriving by methacrylate, the preferred unit that constitutes of being derived by methacrylate that uses reaches 10-85 mole %, preferred 20-80 mole %, and the unit that constitutes of being derived by acrylate reaches 15-90 mole %, preferred 20-80 mole %.

Then, describe above-mentioned (a1)-(a4) unit in detail.

(a1) unit suppresses the formation unit that base (methyl) acrylate is derived by having the acid dissociation dissolving.The acid dissociation dissolving of being somebody's turn to do in (a1) suppresses base, make resinous principle all be the insoluble alkali dissolving inhibition of alkali as long as have before exposing, simultaneously, dissociate because of the effect of the acid of generation in the exposure back, this resinous principle is all changed to alkali-soluble, then can be not particularly limited to use.General extensive base, uncle's alkoxy carbonyl or the chain alkoxyalkyl etc. of knowing (methyl) acrylic acid carboxyl and forming ring-type or chain tertiary alkyl ester.

Suppress base as the acid dissociation dissolving in above-mentioned (a1), for example can preferably use the acid dissociation dissolving that contains aliphat polycycle base to suppress base.

As above-mentioned polycycle base, can enumerate from replacing, also can remove the base etc. of 1 hydrogen atom with fluorine atom or fluoro-alkyl without the bicyclic alkane of its replacement, three cycloalkane, Fourth Ring alkane etc.Specifically can enumerate the base etc. of removing 1 hydrogen atom from polycyoalkanes such as adamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecanes.Such polycycle base is suitably selected among a plurality of bases that can propose from the ArF resist to use.In these bases, industrial preferred adamantyl, norborneol alkyl, Fourth Ring dodecyl.

The preferred monomeric unit as above-mentioned (a1) is expressed in following general formula (1)-(7).In these general formulas (1)-(7), R is hydrogen atom or methyl, R ₁Be low alkyl group, R ₂And R ₃Be respectively low alkyl group independently, R ₄Be tertiary alkyl, R ₅Be methyl, R ₆It is low alkyl group.

Above-mentioned R ₁-R ₃And R ₆The rudimentary straight or branched alkyl of preferred carbon number 1-5 can be enumerated methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, amyl group, isopentyl, neopentyl etc. respectively.Industrial preferable methyl or ethyl.

In addition, R ₄Be the tertiary alkyl of the tert-butyl group or tertiary pentyl and so on, the situation of the industrial preferably tert-butyl group.

As (a1) unit, above-mentioned enumerate among, the formation unit of general formula (1), (2), (3) expression particularly is owing to can form transparency height, high resolution, anti-dry ecthing excellent pattern, so more preferably.

Above-mentioned (a2) unit is owing to have lactone unit, and therefore the hydrophily to raising and imaging liquid is effective.

(a2) like this is as long as the unit has lactone unit, can constitute unit copolymerization with other of resinous principle.

For example, as the lactone unit of monocyclic, can list the base etc. of removing 1 hydrogen atom from gamma-butyrolacton.In addition, as the lactone unit of polycycle, can list the base etc. of removing 1 hydrogen atom from the polycyoalkane that contains lactone.

The preferred monomeric unit as above-mentioned (a2) is expressed in following general formula (8)-(10).In these general formulas, R is hydrogen atom or methyl.

(methyl) that have ester bond on the α carbon acrylic acid gamma-butyrolacton ester shown in the above-mentioned general formula (10) and the norbornane lactone of general formula (8) and (9) are easy to get industrial, thereby preferred especially.

Above-mentioned (a3) unit is the formation unit of being derived by (methyl) acrylate with the polycycle base that contains alcohol hydroxyl group.

Because the hydroxyl in the above-mentioned polycycle base that contains alcohol hydroxyl group is a polar group, therefore by using it, all hydrophilies with imaging liquid of resinous principle improve, the alkali dissolubility raising of exposure portion.Therefore, when resinous principle had (a3), resolving power improved, so preferred.

As the polycycle base in (a3), can from the explanation of above-mentioned (a1) the basic same aliphat polycycle base that exemplifies suitably select to use.

The polycycle base that contains alcohol hydroxyl group in above-mentioned (a3) is not particularly limited, and for example preferably uses the adamantyl of hydroxyl etc.

And, when the adamantyl of this hydroxyl be following general formula (11) expression the time, have the effect that improves anti-dry ecthing, improves the up rightness of pattern cross sectional shape, so preferably.Moreover 1 is the integer of 1-3 in the general formula.

Above-mentioned (a3) is as long as the unit has the above-mentioned polycycle base that contains alcohol hydroxyl group and can constitute unit copolymerization with other of resinous principle.

Specifically, the formation unit of preferred following general formula (12) expression.In the general formula (12), R is hydrogen atom or methyl.

In above-mentioned (a4) unit, so-called " suppress base with above-mentioned acid dissociation dissolving; above-mentioned lactone unit; and any of the above-mentioned polycycle base that contains alcohol hydroxyl group is all different " the polycycle base, be meant in resinous principle, (a4) the polycycle base of unit is basic with the acid dissociation dissolving inhibition of (a1) unit, (a2) lactone unit of unit, and (a3) meaning of any all unduplicated polycycle base of the polycycle base that contains alcohol hydroxyl group of unit, mean: the acid dissociation dissolving that (a4) does not keep constituting (a1) unit of resinous principle suppresses base, (a2) lactone unit of unit, and (a3) any one in the polycycle base that contains alcohol hydroxyl group of unit.

Polycycle base in above-mentioned (a4) unit can be selected to make in a resinous principle, does not repeat to get final product with the formation unit that uses as above-mentioned (a1)-(a3) unit, is not particularly limited.For example,, can use and the basic same aliphat polycycle base that exemplifies as above-mentioned (a1) unit, can use known in the past multiple material as ArF eurymeric anticorrosive additive material as the polycycle base in (a4) unit.

Particularly be selected from tristane base, adamantyl, Fourth Ring dodecyl more than at least a kind the time, preferred at industrial aspect such as be easy to get.

As (a4) unit, as long as have above-mentioned polycycle base and can constitute unit copolymerization with other of resinous principle.

The preferred example of above-mentioned (a4) is expressed in following general formula (13)-(15).In these general formulas, R is hydrogen atom or methyl.

Aforesaid propylene acid is the composition of resinous principle, with respect to the total amount of the formation unit that constitutes this resinous principle, (a1) unit be 20-60 mole %, when being preferably 30-50 mole %, the resolving power excellence, preferred.

In addition, with respect to the total amount of the formation unit that constitutes resinous principle, (a2) unit be 20-60 mole %, when being preferably 30-50 mole %, the resolving power excellence, preferred.

In addition, use the occasion of (a3) unit, with respect to the total amount of the formation unit that constitutes resinous principle, for 5-50 mole %, when being preferably 10-40 mole %, resist pattern form excellence, preferred.

Use the occasion of (a4) unit, with respect to the total amount of the formation unit that constitutes resinous principle, for 1-30 mole %, when being preferably 5-20 mole %, the resolving power excellence from isolated patterns to dense (セ ミ デ Application) pattern, preferred.

(a1) unit and be selected from (a2), (a3) and (a4) at least one unit of unit, can be according to the suitable combination of purpose, but (a1) unit and (a 2) and (a3) 3 yuan of polymer of unit are excellent, preferred on resist pattern form, exposure abundant intensity, thermal endurance, resolving power.As respectively constituting unit (a1)-(a3) content separately this moment, preferred (a1) be 20-60 mole %, (a2) for 20-60 mole %, and (a3) is 5-50 mole %.

In addition, the quality mean molecule quantity of resinous principle resin of the present invention (polystyrene conversion, below same) is not particularly limited, and is 5000-30000, more preferably 8000-20000.When greater than this scope, the dissolubility in the resist solvent degenerates, and when less than this scope, anti-dry ecthing and resist pattern cross sectional shape might degenerate.

In addition, as above-mentioned cyclic olefine resin, preferably make the formation unit (a5) shown in the following general formula (16) and resin that the formation unit copolymerization that obtained by above-mentioned (a1) as required forms.

(in the formula, R ₈Be to suppress the substituting group that base exemplifies as the acid dissociation dissolving in above-mentioned (a1) unit, m is the integer of 0-3)

Moreover in above-mentioned (a5) unit, m is 0 occasion, preferably uses as the copolymer with (a1) unit.

And, be resin as above-mentioned silsesquioxane, can list the resin of the formation unit (a7) of formation unit (a6) with following general formula (17) expression and following general formula (18) expression.

(in the formula, R ₉Be to suppress base, R by the acid dissociation dissolving that the alkyl that contains aliphat monocycle or polycycle base constitutes ₁₀Be the representative examples of saturated aliphatic alkyl of straight chain shape, a chain or ring-type, X is that the carbon number that at least 1 hydrogen atom is replaced by fluorine atom is the alkyl of 1-8, and m is the integer of 1-3)

(in the formula, R ₁₁Be the alkyl of hydrogen atom or straight chain shape, a chain or ring-type, R ₁₂Be the representative examples of saturated aliphatic alkyl of straight chain shape, a chain or ring-type, X is that the carbon number that at least 1 hydrogen atom is replaced by fluorine atom is the alkyl of 1-8)

At above-mentioned (a6) with (a7), R ₉The acid dissociation dissolving suppress base, be to have the preceding silsesquioxane resin of the exposure of making all to be the insoluble alkali dissolving inhibition of alkali, simultaneously, dissociating because of the effect of the acid that acid-producing agent produces in the exposure back, makes this silsesquioxane resin all become the base of alkali-soluble.

As such base, for example can list by containing the acid dissociation dissolving that following general formula (19)-(23) alkyl such, bulky aliphat monocycle or polycycle base constitutes and suppress base.By using such acid dissociation dissolving to suppress base, the dissolving after dissociating suppresses the difficult gasification of base, and degassing phenomenon is prevented from.

Above-mentioned R ₉Carbon number, difficult gasification when dissociating, the dissolubility of appropriateness and the dissolubility of imaging liquid considered in the resist solvent is preferably 7-15, more preferably 9-13 simultaneously.

Suppress base as above-mentioned acid dissociation dissolving, so long as contain the acid dissociation dissolving inhibition base that the alkyl of aliphat monocycle or polycycle base constitutes, just can from the multiple base that the resin of for example the resist composition of ArF excimer laser being used proposes, suitably select to use according to the light source that uses.Usually extensively know the base of (methyl) acrylic acid carboxyl and formation ring-type tertiary alkyl ester.

The special acid dissociation dissolving that preferably contains aliphat polycycle base suppresses base.As aliphat polycycle base, can from the multiple base that the ArF resist is proposed, suitably select to use.For example, as aliphat polycycle base, can enumerate the base of removing 1 hydrogen atom by bicyclic alkane, three cycloalkane, Fourth Ring alkane etc., more specifically can enumerate the base etc. of removing 1 hydrogen atom from polycyoalkanes such as adamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecanes.

Among above-mentioned general formula, have the silsesquioxane resin of the 2-methyl adamantane base and/or the 2-ethyl adamantyl that general formula (22) is represented of general formula (21) expression, so the difficult degassing, and resist excellents such as resolving power and thermal endurance are preferred.

In addition, above-mentioned R ₁₀And R ₁₂Carbon number, consider that from aspect preferably 1-20 is more preferably 5-12 to the control of the dissolubility of resist solvent and molecular dimension.The representative examples of saturated aliphatic alkyl of ring-type particularly, so owing to have following advantage preferred: resulting silsesquioxane resin is high to the transparency of high-energy light; Glass transition point (Tg) uprises, and produces acid etc. by acid-producing agent during PEB easy to control (heating of exposure back).

As the representative examples of saturated aliphatic alkyl of above-mentioned ring-type, can be the monocyclic base, also can be the polycycle base.As the polycycle base, can enumerate the base of removing 2 hydrogen atoms from bicyclic alkane, three cycloalkane, Fourth Ring alkane etc., more specifically can enumerate the base etc. of removing 2 hydrogen atoms from polycyoalkanes such as adamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecanes.

As these R ₁₀And R ₁₂, more specifically can enumerate the base of removing 2 hydrogen atoms from the ester ring type compound or their derivative of following general formula (24)-(29) expression.

Above-mentioned so-called derivative means: in the ester ring type compound of above-mentioned chemical formula (24)-(29), at least 1 hydrogen atom is replaced by bases such as halogen atoms such as low alkyl groups such as methyl, ethyl, oxygen atom, fluorine, chlorine, bromine.Wherein, remove the base of 2 hydrogen atoms preferred aspect transparency height and industrial being easy to get from the ester ring type compound that is selected from chemical formula (24)-(29).

And, above-mentioned R ₁₁, from the dissolubility of resist solvent is considered, 1-10 preferably is more preferably the low alkyl group of 1-4.As this alkyl, more specifically can enumerate methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, cyclopenta, cyclohexyl, 2-ethylhexyl, n-octyl etc.

R ₁₁Select according to the desired alkali dissolubility of silsesquioxane resin is suitable from above-mentioned candidate.At R ₁₁Be the occasion of hydrogen atom, the alkali dissolubility is the highest.When the alkali dissolubility uprises, but the advantage of high sensitivityization is arranged.

On the other hand, the carbon number of abovementioned alkyl is big more, and in addition, volume is big more, and the alkali dissolubility of silsesquioxane resin is low more.When alkali dissolubility step-down, to the patience raising of alkali imaging liquid, therefore, the exposure border when using this silsesquioxane resin to form resist pattern is good, follows the dimensional variations of exposure to diminish.In addition, owing to there is not video picture irregular, therefore the roughness of the marginal portion of the resist pattern that forms also is enhanced.

For the X in above-mentioned general formula (17), (18), the alkyl of preferred especially straight chain shape.The carbon number of alkyl is considered from the glass transition point (Tg) of silsesquioxane resin with to the dissolubility of resist solvent, is 1-8, the low alkyl group of preferred 1-4.In addition, the number of the hydrogen atom that is replaced by fluorine atom is many more, the transparency of high-energy light below the 200nm or electron ray is improved more, so preferably, most preferably be the perfluoroalkyl that whole hydrogen atoms are replaced by fluorine atom.Each X can be identical respectively, also can be different.Moreover the m in the general formula (17) suppresses the reason of base for legibility from the acid dissociation dissolving, is the integer of 1-3, preferably 1.

As silsesquioxane resin, more specifically can list the resin of following general formula (30), (31) expression.

(in the formula, R ₆, R ₁₀, R ₁₂, and n and aforementioned same.)

In whole formations unit of formation silsesquioxane resin of the present invention, (a6) and (a7) ratio of the formation unit of expression is 30-100 mole %, and preferably 70-100 mole % is more preferably 100 moles of %.

In addition, with respect to (a6) and (a7) the total amount of formation unit of expression, (a6) ratio of Biao Shi formation unit 5-70 mole % preferably is more preferably 10-40 mole %.(a7) ratio of Biao Shi formation unit 30-95 mole % preferably is more preferably 60-90 mole %.

The ratio of formation unit by making (a6) expression is in above-mentioned scope, the ratio of acid dissociation dissolving inhibition base determines that naturally the deliquescent variation of alkali becomes as the suitable variation of the base resin of eurymeric resist composition before and after the silsesquioxane resin exposure.

Silsesquioxane is a resin, in the formation unit in addition, formation unit that the scope of not damaging effect of the present invention also can have (a6) and (a7) represent.For example can enumerate the unit that uses in the silsesquioxane resin that the resist composition of ArF excimer laser uses, as have alkyl silsesquioxane unit of alkyl such as methyl, ethyl, propyl group, butyl etc.

Silsesquioxane is that the quality mean molecule quantity (Mw) (polystyrene conversion of being undertaken by gel permeation chromatography) of resin is not particularly limited, but is preferably 2000-15000, more preferably 3000-8000.When greater than this scope, the dissolubility of resist solvent is degenerated, when less than this scope, resist pattern cross sectional shape might degenerate.

In addition, quality mean molecule quantity (Mw)/number-average molecular weight (Mn) is not particularly limited, but is preferably 1.0-6.0, more preferably 1.5-2.5.When greater than this scope, resolution, the possible deterioration of pattern form.

In addition, silsesquioxane of the present invention is a resin, is to have in basic framework by (a6) and (a7) polymer of the silsesquioxane that constitutes of the formation unit of expression, and therefore the transparency for high-energy light below the 200nm or electron ray is high.Therefore, the eurymeric resist composition that contains silsesquioxane resin of the present invention, for example useful in the lithographic printing of the light source that uses the wavelength shorter than ArF excimer laser, particularly in individual layer technology, also can form the meticulous resist pattern that live width 150nm is following and then 120nm is following.In addition, also useful in the technology that forms the meticulous resist pattern below the 120nm and then below the 100nm by the upper strata that is used as 2 layers of resist laminated body.

And, as the resinous principle that in above-mentioned negative resist composition, uses, so long as habitual just unqualified, specifically preferably following resinous principle.

As such resinous principle, be to become the insoluble resinous principle of alkali because of acid, the preferred following resin (a8) that uses: having in molecule reacts to each other can form 2 kinds of functional groups of ester, it is by being dewatered by the effect of the acid of adding the acid-producing agent generation in the anticorrosive additive material simultaneously to, form ester, it is insoluble to become alkali thus.Said herein, reacting to each other to form 2 kinds of functional groups of ester, means the hydroxyl that for example is used to form carboxylate and the functional group of carboxyl or carboxylate and so on.In other words, be 2 kinds of functional groups that are used to form ester.As such resin, for example preferably has at least one resin of hydroxy alkyl and carboxyl and carboxylic acid ester groups at the side chain of resin main framing.

And, as above-mentioned resinous principle, also preferably have the resinous principle (a9) of the polymer formation of dicarboxylic acid monoesters unit.

Above-mentioned (a8) in other words is the resinous principle that has the formation unit of following general formula (32) expression at least.

(in the formula, R ₁₃It is the alkyl that the alkyl of hydrogen atom, C1-C6 or bornyl, adamantyl, Fourth Ring dodecyl, three ring decyls etc. have polycycle ring skeleton.)

Example as such resin preferably lists: at least a kind of polymer of monomers (homopolymers or copolymer) of selecting among α-(hydroxy alkyl) acrylic acid and α-(hydroxy alkyl) alkyl acrylate (a8-1) and at least a kind of monomer selecting among α-(hydroxy alkyl) acrylic acid and α-(hydroxy alkyl) alkyl acrylate, with the copolymer (a8-2) of at least a kind of monomer among other ethene unsaturated carboxylic acids and ethene esters of unsaturated carboxylic acids, selecting etc.

As above-mentioned polymer (a8-1), the copolymer of preferred α-(hydroxy alkyl) acrylic acid and α-(hydroxy alkyl) alkyl acrylate, in addition, as copolymer (a8-2), preferably use at least a kind the copolymer of selecting among acrylic acid, methacrylic acid, alkyl acrylate and the alkyl methacrylate as above-mentioned other ethene unsaturated carboxylic acid or ethene esters of unsaturated carboxylic acids.

Example as the hydroxy alkyl in above-mentioned α-(hydroxy alkyl) acrylic acid or α-(hydroxy alkyl) alkyl acrylate can list rudimentary hydroxy alkyls such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl.Among these bases, consider preferred hydroxyethyl or hydroxymethyl from the easy formation degree of ester.

In addition, example as the alkyl of the Arrcostab of α-(hydroxy alkyl) alkyl acrylate part can list low alkyl group, dicyclo [2.2.1] heptyl, bornyl, adamantyl, Fourth Ring [4.4.0.1 such as methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, amyl group ^2.5.1 ^7.10] dodecyl, three the ring [5.2.1.0 ^2.6] bridging type polycycle cyclic hydrocarbon group such as decyl etc.The alkyl of ester moiety is the polycycle cyclic hydrocarbon group, and is effective to improving anti-dry ecthing.Among these alkyl, particularly the occasion of low alkyl groups such as methyl, ethyl, propyl group, butyl as the pure composition that forms ester, is used material cheap, that can obtain easily, so preferred.

The occasion of lower alkyl esters, same with carboxyl, the esterification of generation and hydroxy alkyl, but the occasion of the ester that bridging type polycycle cyclic hydrocarbon forms is difficult to take place such esterification.Therefore, introduce the occasion of the ester that forms with bridging type polycycle cyclic hydrocarbon in resin, preferred have carboxyl at the resin side chain simultaneously.

On the other hand, as other ethene unsaturated carboxylic acids in above-mentioned (a8-2) or the example of ethene esters of unsaturated carboxylic acids, list Arrcostabs such as the methyl esters, ethyl ester, propyl ester, isopropyl ester of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, these unsaturated carboxylic acids, positive butyl ester, isobutyl ester, just own ester, monooctyl ester etc.In addition, also can use alkyl to have dicyclo [2.2.1] heptyl, bornyl, adamantyl, Fourth Ring [4.4.0.1 as ester moiety _2.5.1 _7.10] dodecyl, three the ring [5.2.1.0 _2.6] ester of acrylic or methacrylic acid of bridging type polycycle cyclic hydrocarbon group such as decyl.Wherein, consider lower alkyl esters such as preferred acrylic acid and methacrylic acid or their methyl esters, ethyl ester, propyl ester, positive butyl ester from aspect cheap and that obtain easily.

In the resin of above-mentioned resinous principle (a8-2), be selected from least a kind of monomeric unit in α-(hydroxy alkyl) acrylic acid and α-(hydroxy alkyl) alkyl acrylate, with the ratio that is selected from least a kind of monomeric unit in other ethene unsaturated carboxylic acids and the ethene esters of unsaturated carboxylic acids, count in molar ratio, preferred 20: 80 to 95: 5 scope, preferred 50: 50 to 90: 10 especially scope.If the ratio of Unit two in above-mentioned scope, then in molecule or intermolecular easy formation ester, obtains good resist pattern.

In addition, above-mentioned resinous principle (a9) is the resinous principle that has the formation unit of following general formula (33) or (34) expression at least.

(in the formula, R ₁₄Or R ₁₅The alkyl chain of expression carbon number 0-8, R ₁₆The substituting group that expression has at least 2 above ester ring type structures, R ₁₇And R ₁₈The alkyl of expression hydrogen atom or carbon number 1-8.)

Use this negative resist composition with resinous principle of dicarboxylic acid monoesters monomeric unit, the resolution height, preferred aspect the reduction line edge roughness.In addition, swelling patience height, in liquid for immersion exposure process more preferably.

As this dicarboxylic acid monoesters compound, can list the monoester compound of fumaric acid, itaconic acid, mesaconic acid, glutaconate, traumatic acid etc.

And, resin as having above-mentioned dicarboxylic acid monoesters unit preferably lists: dicarboxylic acid monoesters polymer of monomers or copolymer (a9-1) and dicarboxylic acid monoesters monomer and the copolymer (a9-2) etc. that is selected from least a kind of monomer in above-mentioned α-(hydroxy alkyl) acrylic acid, α-(hydroxy alkyl) alkyl acrylate, other ethene unsaturated carboxylic acids and the ethene esters of unsaturated carboxylic acids.

The resinous principle that uses in the above-mentioned negative resist can use separately, also can make up more than 2 kinds and use.In addition, the weight average molecular weight of resinous principle is 1000-50000, preferably 2000-30000.

For above-mentioned fluoropolymer, so far as F ₂The resinous principle of eurymeric resist has proposed various materials, can be not particularly limited any use among them.Wherein, preferably (a10) contains the fluoropolymer that the effect alkali-soluble formation unit (a10-1) of alkali-soluble, by acid changes, and the formation unit (a10-1) of described alkali-soluble contains simultaneously and has (i) fluorine atom or fluoro-alkyl and the (ii) aliphat cyclic group of alcohol hydroxyl group.

" the effect alkali-soluble by acid changes " in the polymer (a10), it is the variation of this polymer of exposure portion, if increase at exposure portion alkali-soluble, then exposure portion becomes alkali-soluble, therefore use as the eurymeric resist, on the other hand, if reduce at exposure portion alkali-soluble, then exposure portion to become alkali insoluble, therefore can be used as negative resist and use.

Above-mentioned containing simultaneously has (i) fluorine atom or fluoro-alkyl and the (ii) formation unit (a10-1) of the alkali-soluble of the aliphat cyclic group of alcohol hydroxyl group, as long as have above-mentioned (i) simultaneously and organic group (ii) combines with the aliphat cyclic group, in the formation unit of polymer, have this cyclic group and get final product.

So-called this aliphat cyclic group can be enumerated the base etc. of removing one or more hydrogen atoms from monocycle such as pentamethylene, cyclohexane, dicyclo alkane, three cycloalkane, Fourth Ring alkane or polycycle hydrocarbon.

The polycycle hydrocarbon more specifically can list base of removing one or more hydrogen atoms from polycyoalkanes such as adamantane, norbornane, isoborneol alkane, tristane, Fourth Ring dodecanes etc.

Among them, industrial base of preferably deriving from pentamethylene, cyclohexane, norbornane removal hydrogen atom.

As above-mentioned (i) fluorine atom or fluoro-alkyl, can list fluorine atom or replace part or all base that obtains of the hydrogen atom of low alkyl group with fluorine atom.Specifically can list trifluoromethyl, pentafluoroethyl group, seven fluoropropyls, nine fluorine butyl etc., industrial preferred fluorine atom or trifluoromethyl.

So-called above-mentioned (ii) alcohol hydroxyl group can only be a hydroxyl, also can list alkyl oxy, alkyl oxy alkyl or alkyl with hydroxyl and so on the alkyl oxy that contains alcohol hydroxyl group, contain the alkyl oxy alkyl of alcohol hydroxyl group or contain the alkyl etc. of alcohol hydroxyl group.As this alkyl oxy, this alkyl oxy alkyl or this alkyl, can list low alkyl group oxygen base, low alkyl group oxygen base low alkyl group, low alkyl group.

As above-mentioned low alkyl group oxygen base, specifically can list methyl oxygen base, ethyl oxygen base, propyl group oxygen base, butyl oxygen base etc., as low alkyl group oxygen base low alkyl group, specifically can list methyl oxygen ylmethyl, ethyl oxygen ylmethyl, propyl group oxygen ylmethyl, butyl oxygen ylmethyl etc., as low alkyl group, specifically can list methyl, ethyl, propyl group, butyl etc.

In addition, the above-mentioned alkyl oxy that contains alcohol hydroxyl group, part or all of hydrogen atom that contains the alkyl oxy alkyl of alcohol hydroxyl group or contain this alkyl oxy, this alkyl oxy alkyl or this alkyl in the alkyl of alcohol hydroxyl group (ii) also can be replaced by fluorine atom.

Preferably can list: above-mentionedly contain the alkyl oxy of alcohol hydroxyl group or contain the base that the part of the hydrogen atom of this alkyl in base that the part of the hydrogen atom of those alkyl oxies parts in the alkyl oxy alkyl of alcohol hydroxyl group replaced by fluorine atom, the above-mentioned alkyl that contains alcohol hydroxyl group is replaced by fluorine atom, promptly contain alcohol hydroxyl group fluoro-alkyl oxygen base, contain the fluoro-alkyl oxygen base alkyl of alcohol hydroxyl group or contain the fluoro-alkyl of alcohol hydroxyl group.

As the above-mentioned fluoro-alkyl oxygen base that contains alcohol hydroxyl group, can list (HO) C (CF ₃) ₂CH ₂O-base (two (hexafluoro the methyl)-2-hydroxyls of 2--ethyl oxygen base, (HO) C (CF ₃) ₂CH ₂CH ₂(two (hexafluoro the methyl)-3-hydroxyls of 3--propyl group oxygen base etc. as the fluoro-alkyl oxygen base alkyl that contains alcohol hydroxyl group, can list (HO) C (CF to the O-base ₃) ₂CH ₂O-CH ₂-Ji, (HO) C (CF ₃) ₂CH ₂CH ₂O-CH ₂-Ji etc. as the fluoro-alkyl that contains alcohol hydroxyl group, can list (HO) C (CF ₃) ₂CH ₂-Ji (two (hexafluoro the methyl)-2-hydroxyl-ethyls of 2-, (HO) C (CF ₃) ₂CH ₂CH ₂-Ji (two (hexafluoro the methyl)-3-hydroxyl-propyl group of 3-etc.

These (i) or base (ii) directly combine with above-mentioned aliphat cyclic group and get final product.Particularly constitute the unit for (a10-1), contain the fluoro-alkyl oxygen base of alcohol hydroxyl group, fluoro-alkyl and the norborene loops that contains the fluoro-alkyl oxygen base alkyl of alcohol hydroxyl group or contain alcohol hydroxyl group closes, the two keys cracking of this norborene ring and the unit of following general formula (35) expression that forms, the transparency and alkali-soluble and anti-dry ecthing excellence, so industrial in addition being easy to get is preferred.

(in the formula, Z is an oxygen atom, oxygen methylene (O (CH ₂)-) or singly-bound, n ' and m ' are respectively the integer of 1-5 independently).

With the polymer unit of (a10-1) unit combination use, so long as known so far just unqualified.The occasion that the polymer that increases as the effect alkali-soluble that passes through acid of eurymeric uses, by having that above-mentioned acid dissociation dissolving suppresses formation unit (a1) that (methyl) acrylate of base derives because the resolving power excellence, so preferably.

As such formation unit (a1), can list the formation unit of deriving as preferred cell by (methyl) acrylic acid tertiary alkyl esters such as (methyl) tert-butyl acrylate, (methyl) acrylic acid tert-pentyl esters.

Polymer (a10) also can be that the fluoro alkylidene that contains the transparency of further raising polymer constitutes the polymer (a11) that effect alkali-soluble unit (a10-2), that pass through acid increases.By containing such formation unit (a10-2), the transparency further improves.Constitute unit (a10-2), the preferably unit of deriving as this by tetrafluoroethene.

General formula (36), (37) of expression polymer (a10) and polymer (a11) are as follows.

(in the formula, Z, n ', m ' are identical with the occasion of above-mentioned general formula (35), and R is hydrogen atom or methyl, R ¹⁹Be that the acid dissociation dissolving suppresses base.)

(in the formula, Z, n ', m ' and R ¹⁹Identical with the occasion of above-mentioned general formula (36).)

In addition, the polymer as effect alkali-soluble different with polymer (a11) with above-mentioned polymer (a10), that contain other above-mentioned formation unit (a10-1), that pass through acid changes can have following formation unit.

That is, in constituting unit (a10-1), (i) fluorine atom or fluoro-alkyl and (ii) alcohol hydroxyl group be combined in respectively on the aliphat ring type, this cyclic group constitutes main chain.

As this (i) fluorine atom or fluoro-alkyl, can list and above-mentioned same base.In addition, what is called (ii) alcohol hydroxyl group only be hydroxyl.

The cyclopolymerization of the diolefin compound of the polymer (a12) with such unit by having hydroxyl and fluorine atom forms.As this diolefin compound, the heptadiene that forms polymer preferably clear, anti-dry ecthing excellence, easy with 5 yuan of rings or 6 yuan of rings, industrial most preferably by 1,1,2,3 further, 3-five fluoro-4-trifluoromethyl-4-hydroxies-1,6-heptadiene (CF ₂=CFCF ₂C (CF ₃) (OH) CH ₂CH=CH ₂) the polymer that forms of cyclopolymerization.

The occasion that the polymer (a13) that increases as the effect alkali-soluble that passes through acid of eurymeric uses, the hydrogen atom that preferably contains its alcohol hydroxyl group is suppressed the polymer that formation unit (a10-3) that base replaces forms by the acid dissociation dissolving.Suppress base as its acid dissociation dissolving, from the dissociating property of acid, the lower alkoxy methyl resolving power and the pattern form excellence of the alkyl oxy methyl, particularly methoxy and so on of the carbon number 1-15 of preferred chain, a chain or ring-type, preferred.When this acid dissociation dissolving inhibition base was the scope of 10-40%, preferred 15-30% with respect to all hydroxyls, pattern forms the ability excellence, and was preferred.

The general formula (38) of expression polymer (a13) is as follows.

(in the formula, R ²⁰Be the alkyl oxy methyl of hydrogen atom, C1-C15, x, y are respectively 10-50 mole %.)

These polymer (a10), (a11), (a12) and (a13) can adopt for example S.Kodama et al. of known, non-patent literature, " Synthesis of NovelFluoropolymer for 157nm Photoresists by Cyclo-polymerization " Proceedings of SPIE, Vol.4690, (2002) pp76-83 or patent documentation be for example international disclose No. 00/67072 brochure of WO, internationally disclose No. 02/65212 brochure of WO, the world discloses the method for putting down in writing in No. 02/64648 brochure of WO and synthesizes.

In addition, should (a10), (a11), (a12) and (a13) the polystyrene conversion quality mean molecule quantity that obtains by GPC of the resin of composition be not particularly limited, be 5000-80000, more preferably 8000-50000.

In addition, polymer (a10) can be made of the resin more than a kind or 2 kinds, for example can will reach several mixing of (a13) selecting and use more than 2 kinds from above-mentioned (a10), (a11), (a12), and then, also can mix known in the past photo-corrosion-resisting agent composition in addition and use with resin.

Among above-mentioned resin, for the eurymeric resist that uses acrylic resin ((a1)-(a4)), though be to contain the eurymeric resist that relatively has water liquid to soak the resin of patience, maceration extract of the present invention also can obtained effect equal or more than it as the occasion that liquid soaks the medium use.Particularly can infer near the effect that occurs maceration extract of the present invention the limit of resolution below about 50nm.

In addition, about using silsesquioxane is the eurymeric resist of resin ((a6) and (a7)), is that the eurymeric resist of resin is compared with using aforesaid propylene acid, and it is low that water liquid soaks patience, but the application of the invention maceration extract can improve the appropriateness in the immersion exposure.

In addition, about using specific resin (a8) and/or negative resist (a9), with using above-mentioned silsesquioxane is that the eurymeric resist of resin is same, compare with the eurymeric resist that uses acrylic resin, it is low that water liquid soaks patience, but the application of the invention maceration extract, the influence of the swelling that takes place in the time of can reducing water liquid and soak etc.And know, in such negative resist, also can obtain the effect of improving of line edge roughness.

And, the occasion of use cyclic olefine resin, as in the application's comparative example, the inventor recognizes that water immersion exposure patience is very low, pattern forms and itself becomes impossible.Even use the occasion of such resin, the application of the invention maceration extract can be suitable for immersion exposure.

That is, maceration extract of the present invention with respect to making water liquid soak the resist of the low resin of patience, is useful as expansion to the measure of the versatility of liquid for immersion exposure process.

In addition, use the occasion of the resist of fluoropolymer, mainly as F ₂The excimer laser exposure is used with resist, but maceration extract of the present invention also is suitable for the liquid for immersion exposure process of the excimer laser of 157nm wavelength, and is preferred.

In addition, the acid-producing agent that is used in combination as the resinous principle of using with above-mentioned eurymeric or negative resist can select arbitrarily that acid-producing agent uses from suitable among known as the acid-producing agent the chemical amplification type anti-corrosion agent in the past.

As the concrete example of above-mentioned acid-producing agent, can list diphenyl iodine trifluoro-methanyl sulfonate, (4-methoxyphenyl) phenyl-iodide trifluoro-methanyl sulfonate, two (to tert-butyl-phenyl) iodine trifluoro-methanyl sulfonate, the triphenylsulfonium trifluoro-methanyl sulfonate, (4-methoxyphenyl) diphenyl sulfonium trifluoro-methanyl sulfonate, (4-aminomethyl phenyl) diphenyl sulfonium nine fluorine butane sulfonate, (to tert-butyl-phenyl) diphenyl sulfonium trifluoro-methanyl sulfonate, diphenyl iodine nine fluorine butane sulfonate, two (to tert-butyl-phenyl) iodine nine fluorine butane sulfonate, triphenylsulfonium nine fluorine butane sulfonate, (4-trifluoromethyl) diphenyl sulfonium trifluoro-methanyl sulfonate, (4-trifluoromethyl) diphenyl sulfonium nine fluorine butane sulfonate, salt such as three (to tert-butyl-phenyl) sulfonium trifluoro-methanyl sulfonate etc.

Among salt, the triphenyl sulfonium salt is because difficulty is decomposed, and difficult generation organic gas is so preferably use.The use level of triphenyl sulfonium salt is preferably 50-100 mole % with respect to the total amount of acid-producing agent, and more preferably 70-100 mole % most preferably is 100 moles of %.

In addition, among the triphenyl sulfonium salt, the perfluoro alkyl sulfonic acid ion of particularly following general formula (39) expression is that anionic triphenyl sulfonium salt is owing to the energy high sensitivityization, so preferably use.

(in the formula, R ₂₁, R ₂₂, R ₂₃Be respectively halogen atoms such as the low alkyl group of hydrogen atom, carbon number 1-8, preferred 1-4 or chlorine, fluorine, bromine independently; P is 1-12, preferred 1-8, the more preferably integer of 1-4.)

Above-mentioned acid-producing agent can use separately, can also make up more than 2 kinds and use.Its use level is 0.5 mass parts with respect to above-mentioned resinous principle 100 mass parts, preferred 1-10 mass parts.When less than 0.5 mass parts, can not fully carry out pattern and form, when surpassing 30 mass parts, seldom arrive uniform solution, might become the reason that storage stability reduces.

In addition, eurymeric of the present invention or negative resist composition preferably make above-mentioned resinous principle and acid-producing agent and any composition described later be dissolved in the organic solvent and make.

As organic solvent, as long as above-mentioned resinous principle of solubilized and acid-producing agent, make uniform solution and get final product, can from the past as the solvent of chemical amplification type anti-corrosion agent and among known any organic solvent of suitable selection more than a kind or 2 kinds use.

For example can enumerate ketones such as acetone, methylethylketone, cyclohexanone, methyl isoamyl ketone, 2-heptane; Polyalcohols and derivatives thereof such as the monomethyl ether of ethylene glycol, ethylene glycol monoacetate, diethylene glycol (DEG), diglycol monotertiary acetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol or dipropylene glycol monoacetate, single ethylether, single propyl ether, single-butyl ether or single phenyl ether; Ring type ethers such as dioxane; And ester class such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate etc.These organic solvents can use separately, also can use as mixed solvent more than 2 kinds.

In addition, in such eurymeric or negative resist, in order to improve resist pattern form, time dependent stability etc., can also contain as quencher and the organic acids such as oxyacid of known amine, preferred secondary lower aliphatic amine and uncle's lower aliphatic amine etc. and organic carboxyl acid and phosphorus.

So-called above-mentioned lower aliphatic amine, be meant the alkyl of carbon number below 5 or the amine of alkylol, example as this secondary amine and tertiary amine, can list Trimethylamine, diethylamide, triethylamine, di-n-propyl amine, three n-pro-pyl amine, three amylamines, diethanol amine, triethanolamine etc., the alkanolamine of preferred especially triethanolamine and so on.These amine can use separately, also can make up more than 2 kinds and use.

These amine use in the scope of 0.01-2.0 quality % usually with respect to above-mentioned resinous principle.

As above-mentioned organic carboxyl acid, for example preferred malonic acid, citric acid, malic acid, butanedioic acid, benzoic acid, salicylic acid etc.

As the oxyacid or derivatives thereof of above-mentioned phosphorus, can list the derivative of phosphoric acid such as phosphoric acid, phosphoric acid di-n-butyl, di(2-ethylhexyl)phosphate phenylester or their ester and so on; The derivative of phosphonic acids such as phosphonic acids, dimethyl phosphonate, phosphonic acids di-n-butyl, phosphonic acids phenylester, phosphonic acids diphenyl, phosphonic acids dibenzyl ester and their ester and so on; The derivative of phosphinic acids such as phosphinic acids, phosphinic acids phenylester and their ester and so on, preferred especially phosphonic acids in these materials.

Above-mentioned organic acid uses with the ratio of 0.01-5.0 mass parts with respect to resinous principle 100 mass parts.These materials can use separately, also can make up more than 2 kinds and use.

These organic acids preferably with the following scope use of mole such as above-mentioned amine.

In the eurymeric resist composition of the present invention, can further add as required to contain has blended additive, for example is used to improve the additional resin of the performance of resist film, the surfactant that is used to improve coating, dissolution inhibitor, plasticizer, stabilizer, colouring agent, anti hazing agent etc.

And, in negative resist composition of the present invention,, also can cooperate crosslinking agent as required for improving crosslink density, the shape that improves the resist pattern and the purpose of resolving power and anti-dry ecthing more.

As this crosslinking agent, be not particularly limited, suitablely among the known crosslinking agent that can from the negative resist of chemical amplification type in the past, use select arbitrarily that crosslinking agent uses.Example as this crosslinking agent, can list 2,3-dihydroxy-5-hydroxymethyl norbornane, 2-hydroxyl-5, two (hydroxymethyl) norbornanes of 6-, cyclohexanedimethanol, 3,4,8 (or 9)-trihydroxy tristanes, 2-methyl-2-adamantanol, 1,4-diox-2, the 3-glycol, 1,3,5-trihydroxy cyclohexane etc. has hydroxyl or hydroxy alkyl or its both aliphat cyclic hydrocarbons or its containing oxygen derivative, and make melamine, acetylguanamine, benzoguanamine, urea, ethylene urea, glycolurils etc. contain amino-compound and formaldehyde or formaldehyde and lower alcohol reaction, with hydroxymethyl or lower alkoxy methyl substituted should amino the compound that obtains of hydrogen atom, hexamethoxy methyl cyanuramide is specifically arranged, dimethoxy-methyl urea, dimethoxy-methyl dimethoxy ethylene urea, tetramethoxymethylglycoluril, four butoxymethyl glycolurils etc. particularly preferably are four butoxymethyl glycolurils.

These crosslinking agents can use separately, also can make up more than 2 kinds and use.

Below, the resist pattern formation method of the immersion exposure method of using maceration extract of the present invention is described.

The 1st kind of resist pattern formation method of the present invention is to use the resist pattern formation method of liquid for immersion exposure process, it is characterized in that, comprises following operation: the operation that forms photoresist film on substrate at least; To directly be configured in the operation on the above-mentioned resist film to the exposure optical transparency that uses in the above-mentioned exposure technology, its boiling point as the maceration extract that 70-270 ℃ fluorine-containing liquid constitutes; By above-mentioned maceration extract optionally with the operation of above-mentioned resist film exposure; The operation of the above-mentioned resist film of heat treated as required; Then, with above-mentioned resist film video picture, form the operation of resist pattern.

In addition, the 2nd kind of resist pattern formation method of the present invention is to use the resist pattern formation method of liquid for immersion exposure process, it is characterized in that, comprises following operation: the operation that forms photoresist film on substrate at least; On above-mentioned resist film, form the operation of diaphragm; To directly be configured in the operation on the said protection film to the exposure optical transparency that uses in the above-mentioned exposure technology, its boiling point as the maceration extract that 70-270 ℃ fluorine-containing liquid constitutes; By above-mentioned maceration extract and diaphragm optionally with the operation of above-mentioned resist film exposure; The operation of the above-mentioned resist film of heat treated as required; Then, with above-mentioned resist film video picture, form the operation of resist pattern.

The 1st kind of resist pattern formation method at first behind the resist composition that coatings such as adopting spinner on the substrates such as silicon wafer is habitually practised, carried out prebake (PAB processing).

In addition, also can be formed in the 2 layer laminate bodies that are provided with the antireflection film of organic system or inorganic system between the coating layer of substrate and resist composition.

Operation so far can use well-known method to carry out.Operating conditions etc. are preferably suitably set according to the composition and the characteristic of the resist composition that uses.

Then, the resist film on the substrate is contacted with the maceration extract of " exposure optical transparency, its boiling point that uses in the liquid for immersion exposure process constituted as 70-270 ℃ fluorine-containing liquid ".There is no particular limitation in so-called contact, is meant substrate is immersed in the above-mentioned maceration extract, or directly disposes above-mentioned maceration extract on resist film.

Resist film for the substrate of this impregnation state optionally exposes by desired mask pattern.Therefore, at this moment, exposure light arrives on the resist film by maceration extract.

At this moment, resist film directly contacts maceration extract, but maceration extract is an inertia to resist film as mentioned above, and resist film does not go bad, and self can be because of resist film go bad yet, and also can not make optical characteristics such as its refractive index rotten.In addition, boiling point is 70 ℃ at least, and the temperature in the exposure process roughly is near the room temperature, therefore also can not reduce or change in concentration because of volatilization causes liquid level, and the light path of having kept stable constant refractive index, the transparency can be provided.

There is no particular limitation for the wavelength that the exposure of this occasion is used, and can use ArF excimer laser, KrF excimer laser, F2 laser, EUV (extreme ultraviolet light), VUV (vacuum ultraviolet), electron ray, X ray, grenz ray isoradial.Maceration extract of the present invention is transparent to these wavelength light, uses the light of which wavelength mainly to determine according to the characteristic of resist film.

After using the liquid of above-mentioned maceration extract to soak exposure process under the state to finish, for example from maceration extract, take out substrate, for example adopt methods such as drying at room temperature, Rotary drying, heat drying, nitrogen flushing to remove maceration extract from substrate.The boiling point of maceration extract is the highest to be 270 ℃, therefore can remove from resist film fully by above-mentioned processing.

Then, the resist film of exposure is carried out PEB (exposure back heating), then use the alkaline imaging liquid that constitutes by alkaline aqueous solution to carry out video picture and handle.In addition, after video picture is handled, cure after also can carrying out.And, preferably use pure water to carry out rinsing.This water rinse, for example rotary plate drips water or spraying at substrate surface on one side on one side, and the imaging liquid on the flushing substrate reaches the resist composition by this imaging liquid dissolving.Then, by carrying out drying, resist film is patterned into the shape corresponding to mask pattern, obtains the resist pattern.

The 2nd kind of resist pattern formation method except in the 1st kind of resist pattern formation method, is being provided with between resist film and the maceration extract beyond the diaphragm, and other are same.

Maceration extract of the present invention for having used water liquid to soak the resist of the low resin of patience, is useful as expansion to the measure of the versatility of liquid for immersion exposure process as mentioned above, is provided with on such resist film in the technology of diaphragm, also can preferably use.Form coating fluid as the diaphragm that this diaphragm is set, preferably contain the aqueous solution water-soluble or that alkali-soluble film formation composition forms.

Form composition about this water-solubility membrane, as long as have water-soluble or alkali-soluble, and there is permeability to get final product to irradiates light, can use any composition, be not particularly limited for example preferred material that uses: i) adopt habitual coating process such as spin-coating method can form uniform coating with following or the like characteristic; Even ii) on photoresist film, film, and photoresist film between can not form metamorphic layer yet; Iii) abundant transmission active ray; Iv) can form the little transparent high tunicle of absorption coefficient.

Form composition as such water-solubility membrane, for example can list cellulosic polymers such as HPMCP, hydroxypropyl methyl cellulose acetate phthalic acid ester, hydroxypropyl methyl cellulose acetate succinate, hydroxypropyl methylcellulose hexahydrophthalic acid ester, hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethylcellulose, cellulose ethanoate hexahydrophthalic acid ester, carboxymethyl cellulose, ethyl cellulose, methylcellulose; With N, N-DMAA, N, N-dimethylamino-propyl Methacrylamide, N, N-dimethylamino propyl acrylamide, N methacrylamide, DAAM, N, N-dimethylaminoethyl methacrylate, N, N-diethyllaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, acryloyl morpholine, acrylic acid etc. are the acrylic polymer of monomer; Vinyl class in polymer such as polyvinyl alcohol, polyvinylpyrrolidone; Or the like.Wherein, do not have the water-soluble polymer of hydroxyl in the preferred molecule, acrylic polymer and polyvinylpyrrolidone etc.These water-solubility membranes form composition, may be used alone, two or more kinds can also be used in combination.

In addition, form composition as the alkali-soluble film, for example list phenols (phenol, metacresol, xylenols, front three phenol etc.) and aldehydes (formaldehyde, formaldehyde precursor, propionic aldehyde, 2-hydroxy benzaldehyde, 3-hydroxy benzaldehyde, 4-hydroxy benzaldehyde etc.) and/or ketone (methylethylketone, acetone etc.) condensation and the novolac resin that obtains in the presence of acidic catalyst; The hydroxy styrenes resinoids such as copolymer of the copolymer of the homopolymers of hydroxy styrenes, hydroxy styrenes and other styrene monomers, hydroxy styrenes and acrylic or methacrylic acid or its derivative.These alkali-soluble films form composition and may be used alone, two or more kinds can also be used in combination.

Water-solubility membrane forms composition and the alkali-soluble film is formed among the branch, and the preferred water soluble film forms composition.

Diaphragm forms coating fluid also can further contain at least a kind that selects among acid-producing agent and the acid compound.Acid-producing agent can use the known compound that uses in the chemical amplification type anti-corrosion agent.As its concrete example, can list diphenyl iodine trifluoro-methanyl sulfonate, (4-methoxyphenyl) phenyl-iodide trifluoro-methanyl sulfonate, two (to tert-butyl-phenyl) iodine trifluoro-methanyl sulfonate, the triphenylsulfonium trifluoro-methanyl sulfonate, (4-methoxyphenyl) diphenyl sulfonium trifluoro-methanyl sulfonate, (4-aminomethyl phenyl) diphenyl sulfonium trifluoro-methanyl sulfonate, (4-aminomethyl phenyl) diphenyl sulfonium nine fluorine butane sulfonate, (to tert-butyl-phenyl) diphenyl sulfonium trifluoro-methanyl sulfonate, diphenyl iodine nine fluorine butane sulfonate, two (to tert-butyl-phenyl) iodine nine fluorine butane sulfonate, triphenylsulfonium nine fluorine butane sulfonate, (4-trifluoromethyl) diphenyl sulfonium trifluoro-methanyl sulfonate, (4-trifluoromethyl) diphenyl sulfonium nine fluorine butane sulfonate, salt such as three (to tert-butyl-phenyl) sulfonium trifluoro-methanyl sulfonate etc.

As acid compound, for example can enumerate inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, organic acids such as formic acid, acetate, propionic acid, benzene sulfonic acid, toluenesulfonic acid.These organic acids can use separately, also can make up more than 2 kinds and use.

Among above-mentioned acid compound; as preferred acid, can list part or all aliphatic carboxylic acid that obtains or the aliphatic sulfonic and the fluorine substituted sulphonyl compound etc. of hydrogen atom of counting the saturated or unsaturated alkyl of 1-20 with the fluorine atom alternate c atoms.

At this, as above-mentioned fluorine substituted carboxylic acid, can list perfluoro-heptanoic acid, perfluoro caprylic acid etc., in addition,, can list perfluoro propyl sulfonic acid, perfluoro octyl sulfonic acid, perfluor decyl sulfonic acid etc. as above-mentioned fluorine substituted sulfonic acid.Specifically, for example perfluoro-heptanoic acid is commercially available as EF-201 etc., and perfluoro octyl sulfonic acid can preferably use these materials as commercially available (being ト-ケ system プ ロ ダ Network Star (strain) system) such as EF-101.

As above-mentioned fluorine substituted sulphonyl compound, can list three (trifluoromethyl sulfonyl) methane (CF ₃SO ₂) ₃CH, two (trifluoromethyl sulfonyl) amine (CF ₃SO ₂) ₂NH, two (pentafluoroethyl group sulfonyl) amine (C ₂F ₅SO ₂) ₂NH etc.

By adding such acid compound and/or acid-producing agent, can obtain the effect that the resist pattern form improves, and then the film that is protected forms the time dependent stabilization effect with material.

Diaphragm forms coating fluid and uses with the form of the aqueous solution usually, and the content that water-soluble and alkali-soluble film forms composition is 0.5-10.0 weight % preferably, and in addition, the content of above-mentioned acid compound and/or acid-producing agent is 1.0-15.0 weight % preferably.The pH that diaphragm forms coating fluid is not particularly limited, and is preferably acid.

Diaphragm forms coating fluid also can further contain nitrogen-containing compound.As preferred nitrogen-containing compound, for example can list quaternary ammonium hydroxide, chain triacontanol amine compound, amino acid derivativges etc.

By adding nitrogen-containing compound, can adjust the pH of protection film formation material, and then the shape that can obtain the resist pattern is improved effect.

By such formation resist pattern, can adopt good resolution to make the resist pattern of fine live width, particularly closely spaced lines and interval (line and space) pattern.Wherein, the spacing in so-called lines and the intermittent pattern is meant the total distance wide and wide at interval at the live width direction resist pattern of pattern.

Embodiment

Embodiments of the invention below are described, these embodiment are preferred descriptions illustration of the present invention only, and the present invention is not done any qualification.In addition, in the following description, also put down in writing comparative example with embodiment.

(embodiment 1)

The following resinous principle of uniform dissolution, acid-producing agent, and organic compounds containing nitrogen in organic solvent, preparation eurymeric resist composition 1.

As resinous principle, use copolymer 1 00 mass parts that constitutes the methacrylate acrylate of unit formation by 3 kinds shown in following chemical formula (40a), (40b), (40c).The ratio that respectively constitutes unit p, q, r that uses in the preparation of resinous principle is p=50 mole %, q=30 mole %, r=20 mole %.The quality mean molecule quantity of the resinous principle of preparation is 10000.

As above-mentioned acid-producing agent, use triphenylsulfonium nine fluorine fourth sulfonate 3.5 mass parts and (4-aminomethyl phenyl) diphenyl sulfonium fluoroform sulphonate 1.0 mass parts.

In addition, as above-mentioned organic solvent, use the mixed solvent (mass ratio 6: 4) of mixed solvent 1900 mass parts of propylene glycol methyl ether acetate and ethyl lactate.

And, as above-mentioned organic compounds containing nitrogen, use triethanolamine 0.3 mass parts.

Use the eurymeric resist composition of making as described above 1 to carry out the formation of resist pattern.

At first, use spinner on silicon wafer, to be coated with organic system antireflection film composition " AR-19 " (trade name, Shipley corporate system), on electric hot plate, fired for 60 seconds, make it dry, form the organic system antireflection film of thickness 82nm at 215 ℃.Then, on this antireflection film, use spinner to be coated with above-mentioned eurymeric resist composition 1, on electric hot plate with 115 ℃, 90 second prebake, make it dry, on antireflection film, form the resist film of thickness 150nm.

As maceration extract, the use boiling point is 102 ℃ a perfluor (2-butyl tetrahydrofuran), as liquid immersion exposure apparatus, use " the immersion exposure experimental provision of Nikon Corp.'s system of realization " two-beam interference exposure method "; it constitutes the pattern light that the interference light that produces with prism replaces exposure; place liquid to soak state on sample, makes it exposure ", adopt the exposure light (ArF excimer laser) of wavelength 193nm that above-mentioned resist film is carried out impregnated exposure.At this moment, the prism that is positioned at the device foot contacts with resist film below by maceration extract perfluor (2-butyl tetrahydrofuran).

After exposure is finished, make the substrate Rotary drying, remove maceration extract perfluor (2-butyl tetrahydrofuran) fully from resist film.

Then, under 115 ℃, the condition in 90 seconds, carry out PEB and handle, again at 23 ℃ with 60 seconds of alkaline imaging liquid video picture.Use the 2.38 quality % tetramethyl ammonium hydroxide aqueous solution as alkaline imaging liquid.

Observe the lines of the 65nm that obtains like this and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), this pattern contour is good as a result, does not observe bad phenomenon such as fluctuating (the part stricturizations of lines) phenomenon fully.And then the pattern to obtaining, observe cross sectional shape with focused ion beam SEM (the system Altura835 of FEI Co.), know that cross sectional shape is the excellent in shape of rectangle.

(embodiment 2)

Except that using following formation, adopt operation similarly to Example 1 to form the resist pattern as the photo-corrosion-resisting agent composition 2.

As resinous principle, use formation unit 100 mass parts shown in the following chemical formula (41).The quality mean molecule quantity of the resinous principle of preparation is 10000.

As acid-producing agent, use triphenylsulfonium nine fluorine fourth sulfonate 3.5 mass parts and (4-aminomethyl phenyl) diphenyl sulfonium fluoroform sulphonate 1.0 mass parts.

In addition, as organic solvent, use the mixed solvent (mass ratio 6: 4) of mixed solvent 1900 mass parts of propylene glycol methyl ether acetate and ethyl lactate.

And, as organic compounds containing nitrogen, use triethanolamine 0.3 mass parts.

In addition, the resist thickness of formation is 140nm, and the resist pattern is the 90nm lines and is spaced apart 1: 1.

Observe resulting resist pattern with scanning electron microscope (SEM), pattern contour is good as a result, does not observe fluctuating (the part stricturizations of lines) phenomenon etc. fully.

(embodiment 3)

Except that using the following negative resist composition that constitutes as the photo-corrosion-resisting agent composition 3, adopt and the foregoing description 2 complete same operations, form the lines of 90nm and be spaced apart 1: 1 resist pattern.

As resinous principle, use by 2 kinds shown in the following chemical formula (42) to constitute copolymer 1 00 mass parts that the unit constitutes.The ratio that respectively constitutes unit m and n that uses in the preparation of this resinous principle is m=84 mole %, n=16 mole %.The quality mean molecule quantity of the resinous principle of preparation is 8700.

With respect to above-mentioned resinous principle, make four butoxymethyl glycolurils as 10 quality % of crosslinking agent, and be dissolved in the mixed solvent of propylene glycol methyl ether acetate and ethyl lactate as the triphenylsulfonium nine fluorine fourth sulfonate of 1 quality % of acid-producing agent and the 4-phenylpyridine of 0.6 quality %, making solid constituent weight is 8.1 quality %.The resist thickness that obtains is 220nm.

Adopt the observable resist pattern of scanning electron microscope (SEM), pattern contour is good as a result, does not observe fluctuating (the part stricturizations of lines) phenomenon etc. fully.

(comparative example 1)

Except that using pure water as the maceration extract, the resist film to same with the foregoing description 1 with same operation, similarly forms the resist pattern.

Its result observes some fluctuations in pattern contour.

(comparative example 2)

As maceration extract, using 200 ℃ vapour pressure is 10 ^-1Below the torr, the perfluoroalkyl polyether compound that promptly volatility is extremely low, Daikin Ind Ltd's system, trade name: DEMNUM S-20, in addition, the resist film to same with the foregoing description 1 with same operation, similarly forms the resist pattern.

Its result, remove maceration extract by the Rotary drying operation of behind exposure process, carrying out, even spended time can not be removed, the measure of taking other is that heating process, nitrogen flushing operation can not be removed, residual maceration extract per-fluoro polyether compound on the resist film, the result can not form the resist pattern.

(comparative example 3)

Making the medium below prism and between the substrate is water, in addition, and according to obtaining the 90nm lines and be spaced apart 1: 1 resist pattern with the foregoing description 2 identical steps.

Adopt scanning electron microscope (SEM) to observe this resist pattern, the resist pattern is seriously rotten as a result.

(comparative example 4)

Making the medium below prism and between the substrate is water, in addition, and according to obtaining the 90nm lines and be spaced apart 1: 1 resist pattern with the foregoing description 3 identical steps.

Adopt scanning electron microscope (SEM) to observe this resist pattern, the result observes some fluctuations in pattern contour.

(embodiment 4)

Make as the resinous principle of the repetitive shown in the following chemical formula of having of resinous principle (43) and with respect to this resinous principle, the crosslinking agent that the four butoxymethyl glycolurils of 10 quality % constitute, the acid-producing agent that the triphenylsulfonium perfluor fourth sulfonate of 1.5 quality % constitutes, the amine component that the triethanolamine of 0.2 quality % constitutes are dissolved in the propylene glycol monomethyl ether, and preparation solid constituent weight is the negative resist of 7.0 quality %.

(in the formula, l: m: n=20: 40: 40 (mole %))

On the other hand, use spinner on silicon wafer substrate, to be coated with organic system antireflection film " AR-19 " (trade name, Shipley corporate system), on electric hot plate, fired for 60 seconds, make it dry, form the organic system antireflection film of thickness 82nm at 215 ℃.On this antireflection film, use spinner to be coated with above-mentioned negative resist, 140 ℃ of 60 seconds of prebake, make it dry, on antireflection film, form the resist film of thickness 150nm.

Use " shining two beam interference light by prism; the two beam interference exposure devices (experimental provision of Nikon Corp.'s system) of simulation pattern exposure light ", maceration extract uses perfluor (2-butyl tetrahydrofuran), light source uses the ArF excimer laser of wavelength 193nm, and aforesaid substrate is carried out impregnated exposure.In addition, the prism of the device of use contacts with resist film below by perfluor (2-butyl tetrahydrofuran).

After the above-mentioned exposure, under 130 ℃, the condition in 60 seconds, carry out PEB and handle, again at 23 ℃ with 60 seconds of alkaline imaging liquid video picture.Use the 2.38wt% tetramethylammonium hydroxide aqueous solution as alkaline imaging liquid.

Observe the lines of the 90nm obtain like this and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), the profile of this pattern is good, does not see that pattern such as swelling is bad.

In addition, observe the line edge roughness (LER) of this resist pattern equally with SEM, be 2.9nm.

(embodiment 5)

Observe the lines by the 65nm that obtains with the same fully operation of the foregoing description 4 and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), the profile of this pattern is good, does not see that pattern such as swelling is bad.

(embodiment 6)

The eurymeric resist of mixed solvent 1900 weight portions (mass ratio 6: the 4) formation of acid-producing agent, triethanolamine 0.3 weight portion, propylene glycol methyl ether acetate and the ethyl lactate of preparing resinous principle 100 mass parts of the quality mean molecule quantity 10000 of following general formula (44) expression, constituting by triphenylsulfonium nine fluorine fourth sulfonate 2.5 weight portions and (4-aminomethyl phenyl) diphenyl sulfonium fluoroform sulphonate 1.0 weight portions.

(in the formula, j: k: l=50: 30: 20 (mole %))

On the other hand, use spinner on silicon wafer substrate, to be coated with organic system antireflection film " AR-19 " (trade name, Shipley corporate system), on electric hot plate, fired for 60 seconds, make it dry, form the organic system antireflection film of thickness 82nm at 215 ℃.On this antireflection film, use spinner to be coated with above-mentioned eurymeric resist, 115 ℃ of 90 seconds of prebake, make it dry, on above-mentioned antireflection film, form the resist film of thickness 140nm.

Use " shining two beam interference light by prism; the two beam interference exposure devices (experimental provision of Nikon Corp.'s system) of simulation pattern exposure light ", maceration extract uses perfluor (2-butyl tetrahydrofuran), light source uses the ArF excimer laser of wavelength 193nm, and aforesaid substrate is carried out impregnated exposure.In addition, the prism of the device of use contacts with resist film below by perfluor (2-butyl tetrahydrofuran).

After the above-mentioned exposure, under 115 ℃, the condition in 90 seconds, carry out PEB and handle, again at 23 ℃ with 60 seconds of alkaline imaging liquid video picture.As alkaline imaging liquid, use the 2.38wt% tetramethylammonium hydroxide aqueous solution.

Observe the lines of the 50nm obtain like this and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), the profile of this pattern is good, does not see that pattern such as swelling is bad.

(embodiment 7)

Making the resist thickness in the foregoing description 6 is 110nm, and to make the condition of curing before the exposure be 125 ℃, 90 seconds, forms the lines of 45nm and is spaced apart 1: 1 resist pattern with fully same step in addition.Same observe with scanning electron microscope (SEM), the profile of this pattern is good, does not see that pattern such as swelling is bad.

(embodiment 8)

Making the acid-producing agent in the foregoing description 6 is perfluorooctane sulfonate 5.0 weight portions, forms the lines of 50nm and is spaced apart 1: 1 resist pattern with same fully step in addition.Same observe with scanning electron microscope (SEM), the profile of this pattern is good, does not see that pattern such as swelling is bad.

(embodiment 9: use the evaluation test 1 of the resist of fluoropolymer)

The following resinous principle of uniform dissolution, acid-producing agent, and organic compounds containing nitrogen in organic solvent, preparation eurymeric resist composition F 1.As resinous principle, use 2 kinds shown in the following chemical formula to constitute copolymer 1 00 mass parts that the unit constitutes.The ratio that respectively constitutes unit m, n that uses in the preparation of resinous principle is m=50 mole %, n=50 mole %.The quality mean molecule quantity of the resinous principle of preparation is 10000.

In general formula (45) and (46), R is CH ₂OCH ₃, or H.

As above-mentioned acid-producing agent, use triphenylsulfonium perfluor fourth sulfonate 5.0 mass parts.

In addition, as above-mentioned organic solvent, use propylene glycol methyl ether acetate (PGMEA).

And, as above-mentioned organic compounds containing nitrogen, use triisopropanolamine 0.4 mass parts, reach salicylic acid 0.1 mass parts.

In addition, as dissolution inhibitor, use fluorine compounds 5 mass parts of following chemical formula (47) expression.

Use the eurymeric resist composition F of making as described above 1, form the resist pattern.At first, use spinner on silicon wafer, to be coated with organic system antireflection film composition " AR-19 " (trade name, Shipley corporate system), on electric hot plate, fired for 60 seconds, make it dry, form the organic system antireflection film of thickness 82nm at 215 ℃.Then, on this antireflection film, use spinner to be coated with above-mentioned eurymeric resist composition F 1, on electric hot plate, carry out prebake, make it dry, on antireflection film, form the resist film of thickness 250nm with 90 ℃, 90 seconds.

On the other hand, will be as perfluorooctane sulfonate (C ₈F ₁₇SO ₃H) the 20 weight % aqueous solution 500g of EF-101 (ト-ケ system プ ロ ダ Network Star (strain) system) and 20 weight % aqueous solution 80g of monoethanolamine mix.This mixed solution 25g is added among the 10 weight % polyvinylpyrrolidone aqueous solution 20g, in the aqueous solution that obtains, add pure water, make the overall 200g that is, be mixed with diaphragm formation coating fluid.In addition, the pH of this coating fluid is 2.7.

The coating said protection film forms and uses coating fluid on above-mentioned resist film, Rotary drying (spindry), the diaphragm of formation thickness 44nm.

Then,, adopt exposure device NSR-S302B (NIKON's system, NA (opening number)=0.60,2/3 annular diaphragm (wheel band)), use ArF excimer laser (wavelength 193nm) irradiation pattern light (exposure) by mask pattern.Then, under 120 ℃, carry out PEB and handled for 90 seconds, again 23 ℃ of 60 seconds of alkaline imaging liquid video picture that constitute with the 2.38 quality % tetramethylammonium aqueous solution.

Observe the lines of the 130nm that obtains like this and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), this pattern contour is good, does not observe fluctuating etc. fully.In addition, exposure sensitivity is 18.55mJ/cm ²(sensitivity under the common dry process).

On the other hand, in above-mentioned pattern forms, handle as immersion exposure, the silicon wafer that is provided with the resist film after this exposure is rotated, on this resist film, continue to drip 1 minute fluorine-containing liquid at 23 ℃ on one side, this fluorine-containing liquid is made of perfluor (2-butyl tetrahydrofuran), in addition, similarly forms the resist pattern.

In addition, the operation of this part is in the manufacturing process of reality, be to soak the operation of exposing under the state at complete liquid, but based on previous analysis to the immersion exposure method, guaranteed also that in theory the exposure in the optical system self carries out fully, therefore adopt following simple formation: with the resist film exposure,, make it possible to the influence of an evaluating liquid immersion liquid earlier to resist film making the fluorine-containing liquid load of refractive index liquid (liquid immersion liquid) after the exposure on resist film.

Observe the lines of the 130nm that obtains like this and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), this pattern contour is good, does not observe fluctuating etc. fully.In addition, exposure sensitivity is 18.54mJ/cm ²(sensitivity under the immersion exposure processing) is 0.05% with respect to the variable quantity of the sensitivity under the common dry process, does not have difference substantially with the occasion that does not drip fluorine-containing liquid.It can be said that, contain fluorous solvent in the liquid soaking technology, can not produce any harmful effect resist film by what perfluor (2-butyl tetrahydrofuran) constituted.

(embodiment 10)

In embodiment 9, handle as immersion exposure, fluorine-containing liquid perfluor (2-butyl tetrahydrofuran) is become PFTPA, form the resist pattern in addition equally.

Observe the lines of the 130nm that obtains like this and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), this pattern contour is good, does not observe fluctuating etc. fully.In addition, exposure sensitivity is 19.03mJ/cm ²(sensitivity under the immersion exposure processing) is 2.58% with respect to the variable quantity of the sensitivity under the common dry process, does not have difference substantially with the occasion that does not drip fluorine-containing liquid.It can be said that, contain fluorous solvent in the liquid soaking technology, can not produce harmful effect resist film by what PFTPA constituted.

(embodiment 11)

Eurymeric resist composition F 2 among the aftermentioned embodiment 13 is spin-coated on the silicon wafer, heated for 90 seconds at 90 ℃, the resist that thickness 150nm is set is filmed.Be referred to as unexposed filming.On the other hand, film, adopt adherence exposure device VUVES-4500 (Japanese リ ソ テ Star Network corporate system), use F2 excimer laser (157nm) visual certifiable large tracts of land (about 10mm for above-mentioned resist ²) regional exposure.In addition, exposure is 40mJ/cm ²Then, carrying out PEB under 120 ℃, the condition in 90 seconds handles.Being referred to as exposure films.

Then, with above-mentioned unexposed film and expose film that to be immersed in boiling point be in 130 ℃ the PFTPA, under the state of dipping, pass through to use quartzy balance (Quarts CrystalMicrobalance, below be called QCM) the determining film thickness device, " RDA-QZ3 " of Japan リ ソ テ Star Network corporate system, making maximum minute was 300 seconds, measured the variation of two thickness of filming.

In addition, measure the frequency variation of quartz base plate, the data that obtain are handled with attached parsing software, make the curve of film thickness value to dip time.This curve chart of present embodiment as shown in Figure 1.

In addition, for understand fully sample exposure and the thickness when unexposed change different, each curve chart as benchmark, is used the difference mark from that time film thickness value with dip time 0 second, is depicted as curve once again.That is to say,,, then show positive value if thicker than it if than initial film thickness then show negative value.Each sample is obtained the maximum that shows on the maximum that shows on the positive direction of thickness change value and the negative direction respectively., its value is not designated as 0nm towards just or the occasion of negative behavior.

Mensuration began for 10 seconds with interior maximum film thickness recruitment, and unexposed filming is 1.26nm, and it is 1.92nm that exposure is filmed.10 seconds, unexposed filming was 0nm with interior maximum film thickness reduction, and it is 0.49nm that exposure is filmed.

(embodiment 12)

In embodiment 11, PFTPA is become perfluor (2-butyl tetrahydrofuran), measure two Thickness Variation of filming with QCM equally in addition.

In addition, Fig. 2 represents this curve chart of present embodiment.

Mensuration began for 10 seconds with interior maximum film thickness recruitment, and unexposed filming is 1.62nm, and it is 2.76nm that exposure is filmed.10 seconds, unexposed filming was 0nm with interior maximum film thickness reduction, and it is 0nm that exposure is filmed.

(embodiment 13)

With resinous principle 100 weight portions of the general formula (45) that uses in the eurymeric resist composition F 1 of embodiment 9 and (46) expression, as triphenylsulfonium nine fluorine fourth sulfonate 2.0 weight portions of acid-producing agent, be dissolved into the propylene glycol methyl ether acetate solution that solid component concentration is 8.5 weight % as tridodecylamine 0.6 weight portion of amine, make uniform solution, obtain eurymeric resist composition F 2.

Use the eurymeric resist composition F of making as described above 2, form the resist pattern.At first, use spinner on silicon wafer, to be coated with organic system antireflection film composition " AR-19 " (trade name, Shipley corporate system), on electric hot plate, fired for 60 seconds, make it dry, form the organic system antireflection film of thickness 82nm at 215 ℃.Then, on antireflection film, use the above-mentioned eurymeric resist composition F 2 that obtains of spinner coating, on electric hot plate with 95 ℃, 90 second prebake, make it dry, on antireflection film, form the resist layer of thickness 102nm.

And as evaluation test 2, the experimental provision that impregnated exposure uses NIKON to make is by prism, 2 beam interferences that contain fluorous solvent and 193nm of being made of PFTPA experimentize (experiment of two beam interferences).Same method also is disclosed in the above-mentioned non-patent literature 2 (J.Vac.Sci.Technol.B (2001) 19 (6) p2353-2356), is known as the method that obtains lines and intermittent pattern under laboratory level simply.

In the impregnated exposure of present embodiment, on diaphragm and between below the prism,, form above-mentioned fluorine-containing solvent layer as immersion solvent.

In addition, exposure is selected to stablize the exposure that obtains lines and intermittent pattern, behind mask exposure, wipes away above-mentioned fluorine-containing liquid, carries out PEB then under 115 ℃, the condition in 90 seconds and handles.

Then, carry out video picture at 23 ℃ with 2.38 quality % tetramethylammonium hydroxide aqueous solutions again and handled for 60 seconds.

Its result has obtained the lines of 65nm and at interval (1: 1) as can be known.In addition, sensitivity at that time is 11.3mJ/cm ², its pattern form is the T-top shape a little, but good.

(embodiment 14)

In embodiment 13, at resist film with contain between the fluorous solvent diaphragm that uses among the coating embodiment 9 and form and use coating fluid, at 95 ℃ of 60 seconds of heat drying, the diaphragm of formation thickness 35nm.In addition, similarly to Example 13, form pattern by the experiment of two beam interferences.

Its result has obtained the lines of 90nm and at interval (1: 1) as can be known.In addition, sensitivity at that time is 10.4mJ/cm ², its pattern form is rectangular-shaped excellent in shape.

(embodiment 15)

In embodiment 13, the resist thickness is changed over 125nm from 102nm, and, at this resist film with contain between the fluorous solvent diaphragm that uses among the coating embodiment 9 and form and use coating fluid, at 95 ℃ of 60 seconds of heat drying, the diaphragm of formation thickness 35nm.In addition, similarly to Example 13, form pattern by the experiment of two beam interferences.

Its result has obtained the lines of 65nm and at interval (1: 1) as can be known.In addition, sensitivity at that time is 7.3mJ/cm ², its pattern form is rectangular-shaped very excellent in shape.

(embodiment 16)

In embodiment 13; the eurymeric resist composition F of using 2 is changed over the eurymeric resist composition 1 that uses among the embodiment 1; making the prebake temperature is 125 ℃; make the resist thickness change over 95nm; and; the diaphragm that uses among the coating embodiment 9 between this resist film and fluorine-containing liquid forms use coating fluid, at 95 ℃ of 60 seconds of heat drying, the diaphragm of formation thickness 35nm.In addition, similarly to Example 13, form pattern by the experiment of two beam interferences.

Its result has obtained the lines of 90nm and at interval (1: 1) as can be known.In addition, sensitivity at that time is 14.8mJ/cm ², its pattern form is rectangular-shaped excellent in shape.

(embodiment 17)

It is 174 ℃ perfluor tri-butylamine that the maceration extract perfluor (2-butyl tetrahydrofuran) that uses among the embodiment 1 is changed over boiling point.In addition, form pattern by the experiment of two beam interferences similarly to Example 1.

Observe the 65nm lines obtain thus and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), this pattern contour is good, does not observe the badization phenomenon of fluctuating (the part stricturizations of lines) phenomenon etc. fully.And then the pattern to obtaining, observe cross sectional shape with focused ion beam SEM (the system Altra835 of FEI Co.), know that cross sectional shape is the excellent in shape of rectangle.

(embodiment 18)

It is 215 ℃ perfluor three amylamines that the maceration extract perfluor (2-butyl tetrahydrofuran) that uses among the embodiment 1 is changed over boiling point.In addition, similarly to Example 1, form by two beam interferences experiment carrying out pattern.

Observe the 65nm lines obtain thus and be spaced apart 1: 1 resist pattern with scanning electron microscope (SEM), this pattern contour is good, does not observe the badization phenomenon of fluctuating (the part stricturizations of lines) phenomenon etc. fully.And then the pattern to obtaining, observe cross sectional shape with focused ion beam SEM (the system Altra835 of FEI Co.), know that cross sectional shape is the excellent in shape of rectangle.

Industrial applicibility

As described above, immersion liquid for immersion exposure process of the present invention is by at immersion exposure Use in the operation, can make highly sensitive, resist pattern contour shape excellence, precision height The resist pattern, in this useful, be particularly suitable for the manufacturing of following resist pattern: Even use habitual any anti-corrosion agent composition to consist of resist film, in immersion exposure process Can not occur rough surface that the resist pattern becomes the resist patterns such as T-top shape, The badization phenomenons such as the fluctuating of pattern, wire drawing phenomenon.

In addition, use the resist pattern side of formation of immersion liquid for immersion exposure process of the present invention Method, useful aspect following: as no matter to be the direct field of the above-mentioned maceration extract of configuration on resist film Close, or form diaphragm at resist film, at this diaphragm dipping of the present invention is set The occasion of liquid can both be made excellent resist pattern.

List of references (References):

1.Journal of Vacuum Science﹠amp; Technology B (J.Vac.Sci.Technol.B) ((distribution state) U.S.), 1999, the 17th volume, No. 6,3306-3309 page or leaf.

2.Journal of Vacuum Science﹠amp; Technology B (J.Vac.Sci.Technol.B) ((distribution state) U.S.), calendar year 2001, the 19th volume, No. 6,2353-2356 page or leaf.

3.Proceedings of SPIE Vol.4691 ((distribution state) U.S.) 2002, the 4691st volume, 459-465 page or leaf.

Claims (15)

1. immersion liquid for immersion exposure process, this maceration extract is by the immersion liquid for immersion exposure process of liquid with the resist film exposure, it is characterized in that: by exposure optical transparency, its boiling point that uses in the above-mentioned exposure technology constituted as 70-270 ℃ perfluoroalkyl ether compound.

2. immersion liquid for immersion exposure process according to claim 1 is characterized in that, the boiling point of above-mentioned perfluoroalkyl ether compound is 80-220 ℃.

3. immersion liquid for immersion exposure process according to claim 1 is characterized in that, the base polymer that forms the resist composition of above-mentioned resist film is the polymer that (methyl) acrylic ester unit constitutes.

4. immersion liquid for immersion exposure process according to claim 1 is characterized in that, the base polymer that forms the resist composition of above-mentioned resist film is the polymer with formation unit of the acid anhydrides that contains dicarboxylic acids.

5. immersion liquid for immersion exposure process according to claim 1 is characterized in that, the base polymer that forms the resist composition of above-mentioned resist film is the polymer with the formation unit that contains the phenol hydroxyl.

6. immersion liquid for immersion exposure process according to claim 1 is characterized in that, the base polymer that forms the resist composition of above-mentioned resist film is a silsesquioxane resin.

7. immersion liquid for immersion exposure process according to claim 1 is characterized in that, the base polymer that forms the resist composition of above-mentioned resist film is the polymer with α-(hydroxy alkyl) acrylic acid units.

8. immersion liquid for immersion exposure process according to claim 1 is characterized in that, the base polymer that forms the resist composition of above-mentioned resist film is the polymer with dicarboxylic acid monoesters unit.

9. immersion liquid for immersion exposure process according to claim 1 is characterized in that, the base polymer that forms the resist composition of above-mentioned resist film is a fluoropolymer.

10. immersion liquid for immersion exposure process according to claim 9, it is characterized in that, the base polymer that forms the resist composition of above-mentioned resist film is that the alkali-soluble that contains fatty family cyclic group constitutes the fluoropolymer that the effect alkali-soluble unit, by acid changes, and described aliphat cyclic group has (i) fluorine atom or fluoro-alkyl and (ii) alcohol hydroxyl group simultaneously.

11. a resist pattern formation method, this method are to use the resist pattern formation method of liquid for immersion exposure process, it is characterized in that comprising following operation:

On substrate, form the operation of photoresist film at least;

To directly be configured in operation on the above-mentioned resist film by the maceration extract that the exposure optical transparency that uses in the above-mentioned exposure technology, its boiling point are constituted as 70-270 ℃ perfluoroalkyl ether compound;

By above-mentioned maceration extract, optionally with the operation of above-mentioned resist film exposure;

The operation of the above-mentioned resist film of heat treated as required;

Then, with above-mentioned resist film video picture, form the operation of resist pattern.

12. a resist pattern formation method is to use the resist pattern formation method of liquid for immersion exposure process, it is characterized in that comprising following operation:

On substrate, form the operation of photoresist film at least;

On above-mentioned resist film, form the operation of diaphragm;

To directly be configured in operation on the said protection film by the maceration extract that the exposure optical transparency that uses in the above-mentioned exposure technology, its boiling point are constituted as 70-270 ℃ perfluoroalkyl ether compound;

By above-mentioned maceration extract and diaphragm, optionally with the operation of above-mentioned resist film exposure;

The operation of the above-mentioned resist film of heat treated as required;

Then, with above-mentioned resist film video picture, form the operation of resist pattern.

13., it is characterized in that the boiling point of above-mentioned perfluoroalkyl ether compound is 80-220 ℃ according to claim 11 or 12 described resist pattern formation methods.

14., it is characterized in that the base polymer that forms the resist composition of above-mentioned resist film is a fluoropolymer according to claim 11 or 12 described resist pattern formation methods.

15. immersion exposure resist pattern formation method according to claim 14, it is characterized in that, form the base polymer of the resist composition of above-mentioned resist film, be that the alkali-soluble that contains fatty family cyclic group constitutes the fluoropolymer that the effect alkali-soluble unit, by acid changes, described aliphat cyclic group has (i) fluorine atom or fluoro-alkyl and (ii) alcohol hydroxyl group simultaneously.

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