CN100520578C

CN100520578C - Positive type corrosion-resisting composition and corrosion-resisting pattern formation method using same

Info

Publication number: CN100520578C
Application number: CNB2006100071638A
Authority: CN
Inventors: 岩井武; 久保田尚孝; 藤村悟史; 宫入美和; 羽田英夫
Original assignee: Tokyo Ohka Kogyo Co Ltd
Current assignee: Tokyo Ohka Kogyo Co Ltd
Priority date: 2001-12-03
Filing date: 2002-11-29
Publication date: 2009-07-29
Anticipated expiration: 2022-11-29
Also published as: CN1818785A; CN1841198A; CN1818785B; CN1841199A; CN100520579C

Abstract

There is provided a positive type resin composition comprising (A) a resin component comprising within the principal chain a structural unit derived from a (meth)acrylate ester and incorporating an acid dissociable, dissolution inhibiting group containing a polycyclic group on an ester side chain section, for which the solubility in alkali increases under the action of acid, (B) an acid generator component which generates acid on exposure, and (C) an organic solvent, wherein the component (A) comprises both a structural unit derived from a methacrylate ester and a structural unit derived from an acrylate ester. According to such a resist composition, a resist pattern can be formed which displays little surface roughness and line edge roughness on etching, and also offers excellent resolution and a wide depth of focus range.

Description

Eurymeric resist composition and use it to form the method for resist pattern

The application is patented claim a 02823454.5 (exercise question: eurymeric resist composition and use its method that forms resist pattern, the applying date: on November 29th, 2002, international application: dividing an application PCT/JP2002/012524).

Technical field

The present invention relates to eurymeric resist composition, reach the chemistry enhancing eurymeric resist composition that the wavelength that more clearly relates to use is not more than 200nm, particularly ArF excimer laser.

Background technology

Up to now, to the polycarboxylated styrene or derivatives thereof of KrF excimer laser (248nm) the demonstration high grade of transparency, be used as the basic resin component of chemical reinforced slushing compound, wherein hydroxyl group that dissociated by theobromine, that suppress dissolving is protected always.

Yet at present the miniaturization of semiconductor element also will further develop, and therefore pursuing development uses the method for ArF excimer laser (193nm) intensely.

When using the ArF excimer laser to make the method for light source, contain the resin such as the above-mentioned polycarboxylated styrene of phenyl ring, (193nm) do not have enough transparencies for the ArF excimer laser.

Therefore, a kind of resin that can address the above problem has caused suitable interest, this resin does not contain phenyl ring, and contain the structural unit that (methyl) acrylate is derived, main chain is combined with the hydrocarbon ring such as the diamantane ring of many rings, and has proposed a variety of materials (Jap.P. (authorizing) communique 2881969, Japanese unexamined patent discloses Hei 5-346668 for the first time, Japanese unexamined patent discloses Hei 7-234511 for the first time, Japanese unexamined patent discloses Hei 9-73173 for the first time, the patented claim of Japanese unexamined discloses Hei 9-90637 for the first time, Japanese unexamined patent discloses Hei10-161313 for the first time, openly Hei 10-319595 and Japanese unexamined patent disclose Hei 11-12326 for the first time for the first time in the patented claim of Japanese unexamined).

Yet along with the development of different etching-films, can use various etching gass now in recent years, the shaggy new problem of resist film that shows after the etching has appearred in the result.

The situation that this rough surface is run into during with traditional dry type resistance erosion is different, is using resist pattern as mask on the etched film, is shown as the distortion around the hole pattern in contact hole graph, and is online and be shown as the coarse of line edge in the figure at interval.The line edge roughness refers to incomparable inconsistent scrambling on the line sidewall.

In addition, except above-mentioned rough surface, after resist pattern develops the line edge roughness appears also.

This line edge roughness is shown as the distortion around the hole pattern in contact hole graph, or is shown as the incomparable inconsistent scrambling of line sidewall in online and the interval figure.

Essential design rule continues to become strict in the production of modern semiconductors element in addition, requires resolution characteristic to be not more than 150nm now, and near 100nm.The result must further improve resolution characteristic.

In addition, except improving resolution characteristic, also require the degree of depth of expansion focus characteristics scope.

Yet use traditional resist composition to address the above problem unsatisfactorily, and require consumingly further to improve.

Summary of the invention

Target of the present invention provides a kind of eurymeric resist composition of chemistry enhancing and uses this composition to form the method for resist pattern, rough surface appears during this composition etching hardly, and after resist pattern develops, the coarse of line edge seldom occur, and can also provide the outstanding resolution characteristic and the wide focusing range degree of depth.

Consider the result of above-mentioned situation and conduct further investigation, inventor of the present invention finds to use to be contained the two resin of structural unit that structural unit that methacrylate derives and acrylate derive and makes the base resin component, can address the above problem and therefore can finish the present invention.

In other words, plus tree oil/fat composition of the present invention is the plus tree oil/fat composition that contains following component: (A) a kind of resin Composition, it contains the structural unit that (methyl) acrylate is derived at main chain, and partly combine the group that can be dissociated by acid, that suppress dissolving that comprises many cyclic groups at lateral chain of ester group, under the effect of acid, increased its solubleness in alkali thus; (B) a kind of can be in acidic acid generator component of when exposure; Reach (C) organic solvent (C).

Wherein component (A) contain structural unit (hereinafter this element may be called " acrylate structural unit " for short) that structural unit (hereinafter this element may be called " metacrylic acid ester structure unit " for short) that methacrylate derives and acrylate derive the two.

Term " (methyl) acrylate " refer in acrylate and the methacrylate any one or they the two.Term " structural unit " refers to the monomeric unit that forms polymkeric substance in addition.

The step that method comprised of resist pattern formed according to the present invention is: eurymeric resist composition of the present invention is applied on the substrate, carry out prebake conditions, PEB (post exposure bake) is carried out in the exposure of enforcement selectivity then, and the enforcement alkaline development forms resist pattern.

Implement best mode of the present invention

Hereinafter will be described in more detail the present invention.

Because the effect of the acid that component (B) produces during exposure, cause the disassociation of the group that can be dissociated by acid and suppress the to dissolve anti-anti-etching ability of above-mentioned height, that comprise many cyclic groups in the component (A), it is the solvable state of alkali that whole components (A) are not dissolved state variation by alkali.

Therefore when exposing by mask pattern in forming the resist pattern process, the composition expose portion has increased significantly with respect to the solubleness of alkali, can use alkali to develop.

In the component (A), term " contain metacrylic acid ester structure unit and acrylate structural unit the two " is illustrated in component and has no particular limits in constituting, if component (A) combine metacrylic acid ester structure unit and acrylate structural unit the two.For example component (A) can be the material (A1) that contains multipolymer: the multipolymer that contains metacrylic acid ester structure unit and acrylate structural unit; Maybe can be the material (A2) that contains hybrid resin: the polymkeric substance and the hybrid resin that contains the polymkeric substance of at least a acrylate structural unit that contain at least a metacrylic acid ester structure unit.Form in the polymkeric substance of this hybrid resin (A2) any one or the two can be and the consistent multipolymer of multipolymer (A1).

Although preferably form component (A) among the present invention in addition, in component (A), also can add other resin Composition, as long as this interpolation does not weaken effect of the present invention by any one or the two in above-mentioned multipolymer (A1) and the above-mentioned hybrid resin (A2).

In addition, multipolymer (A1) and hybrid resin (A2) the two also can use the combination of two or more different materials.

The relative populations of metacrylic acid ester structure unit and acrylate structural unit is in the component (A): with respect to the molal quantity of metacrylic acid ester structure unit and the merging of acrylate structural unit, the metacrylic acid ester structure unit accounts for 10～85 moles of %, preferred 20～80 moles of %; And the acrylate structural unit accounts for 15～90 moles of %, preferred 20～80 moles of %.

If the quantity of metacrylic acid ester structure unit is excessive, then the effect of surfaceness improvement reduces; If instead the acrylate structural element number is excessive, the danger that reduces resolution characteristic is arranged.

In addition, component (A) can also be formed by the monomeric unit combination of multiple difference in functionality, as long as a kind of above-mentioned metacrylic acid ester structure unit and acrylate structural unit of combining in these monomeric units.

For example, component (A) can be formed by following structural unit ideally:

(i) (methyl) acrylate structural unit (hereinafter being also referred to as first structural unit) that derive and that comprise the many cyclic groups that contain the group that can be dissociated by acid, suppress dissolving;

(ii) (methyl) acrylate derive and comprise the monocyclic groups that contains lactone or the structural unit (wherein in the expression of " monocyclic groups or many cyclic groups ", term " cyclic group " comprises lactone groups) (hereinafter being also referred to as second structural unit) of many cyclic groups; And

(iii) (methyl) acrylate derive and comprise the structural unit (hereinafter being also referred to as the 3rd structural unit) of the many cyclic groups that contain hydroxyl.

In this instructions and subsidiary claim, term " monocyclic groups or the many cyclic groups that comprise lactone " refers to the monocyclic groups that is formed by lactonic ring or comprises many cyclic groups of lactonic ring.Here, lactonic ring refers to and contains-monocycle of CO-0-structure, and this ring is considered to first ring.Thereby, can use the title of " monocyclic groups that comprises lactone " in the situation of having only the lactonic ring group, otherwise in group, also comprise the situation of other ring structure, no matter the structure of other ring, the title of use " the many cyclic groups that comprise lactone ".

In this situation, first structural unit is basic, although can adopt combining of first structural unit second structural unit or the 3rd structural unit with no matter, according to resistance to corrosion, resolution characteristic, and resist film and substrate between adhesiveness, preferably contain the whole three kinds component of first to the 3rd structural unit.The more preferably resin of forming by first to the 3rd structural unit.

In addition, component (A) also contains following structural unit (hereinafter being also referred to as the 4th structural unit or structural unit (a4)):

(iv) (methyl) acrylate derive and contain the structural unit of many cyclic groups, these many cyclic groups are different from and contain many cyclic groups that can be dissociated by acid, suppress the group of dissolving in first structural unit, be different from the monocyclic groups or the many cyclic groups that comprise lactone in second structural unit, or be different from the many cyclic groups that comprise hydroxyl in the 3rd structural unit

The component (A) that contains this structural unit has the resolution characteristic of outstanding isolation pattern to the close figure of hemicompact (line and figure at interval, wherein line width is 1, interval width is in 1.2～2 scope), is preferred therefore..

Thereby the combination of first structural unit to the, four structural unit reality can wait suitably according to needed characteristic and adjust.

Preferred ingredient (A) contains following any one or the two:

That acrylate is derived and comprise the structural unit (a1) of the many cyclic groups that contain the group that can be dissociated by acid, suppress dissolving, and

That methacrylate is derived and comprise the structural unit (a1 ') of the many cyclic groups that contain the group that can be dissociated by acid, suppress dissolving.

If structural unit that (methyl) acrylate is derived, that comprise the many cyclic groups that contain the group that can be dissociated by acid, suppress dissolving is the two combination of said structure unit (a1) and said structure unit (a1 '), then improved resolution characteristic, this is preferred.

Therein under the situation that two kinds of structural units all exist, structural unit (a1): the mol ratio of structural unit (a1 ') is typically in 0.4～2.5 scope, and preferred 0.6～1.5, so that guarantee outstanding cosolubility between the polymkeric substance of the polymkeric substance of structural unit (a1) and structural unit (a1 ').

In addition, go back preferred ingredient (A) and contain following any one or the two:

That acrylate is derived and contain the monocyclic groups of lactone or the structural unit of many cyclic groups (a2), and

That methacrylate is derived and contain the monocyclic groups of lactone or the structural unit of many cyclic groups (a2 ').

(methyl) acrylate is derived and structural unit that comprise the monocyclic groups that contains lactone or many cyclic groups is that the example by said structure unit (a2) and the two combination of said structure unit (a2 ') is preferred.

In these situations, if wherein the said structure unit the two all exist, structural unit (a2): the mol ratio of structural unit (a2 ') is typically in 0.2～5.0 scope, and preferred 0.6～1.5, so that guarantee outstanding cosolubility between the polymkeric substance of the polymkeric substance of structural unit (a2) and structural unit (a2 ').

Go back preferred ingredient (A) in addition and contain following any one or the two:

Acrylate is derived, and comprises the structural unit (a3) of the many cyclic groups that contain hydroxyl, and

Methacrylate is derived, and comprises the structural unit (a3 ') of the many cyclic groups that contain hydroxyl.

(methyl) acrylate structural unit that derive and that comprise the many cyclic groups that contain hydroxyl is that the example by said structure unit (a3) and the two combination of said structure unit (a3 ') is preferred.

In these situations, if wherein the said structure unit the two all exist, structural unit (a3): the mol ratio of structural unit (a3 ') is typically in 0.2～5.0 scope, and preferred 0.6～1.5, so that guarantee outstanding cosolubility between the polymkeric substance of the polymkeric substance of structural unit (a3) and structural unit (a3 ').

In addition, among these three pairs of combinations, be among a pair of, the structural unit (a3) of a pair of, the structural unit (a2) of structural unit (a1) and (a1 ') and (a2 ') and (a3 ') a pair of, preferably to contain wherein 2 pairs component at least, it is preferably containing whole 3 pairs components.

In structural unit (a1) and (a1 '), the example of many cyclic groups comprises the group of removing a hydrogen atom from dicyclo alkane, three naphthenic hydrocarbon or Fourth Ring alkane.

Special example comprises the group of removing a hydrogen atom from polycyoalkane such as diamantane, norbornane, isoborneol alkane, tristane or Fourth Ring dodecane.

Can suitably select many cyclic groups of these types from the most types of radicals that propose to be used for the ArF resist.

From industrial viewpoint, in these groups, preferred adamantyl, norborneol alkyl and Fourth Ring dodecyl.

In addition above-mentioned group that can be dissociated by acid, that suppress dissolving there is not special restriction, as long as it produces and is suppressed at the effect of dissolving in the alkali before the exposure, make whole components (A) in alkali, not dissolve, it dissociates by the effect of the acid of component (B) generation after the exposure, and whole components (A) are changed into can be by the state of alkali dissolution.

Typical example comprises and the ring-type of (methyl) acrylic acid carboxyl formation or the tertiary alkyl ester of chain.

Although following examples is preferred, but structural unit (a1) and (a1 ') there is not special restriction, as long as these structural units have above-mentioned functions, preferred examples is to comprise many cyclic groups that can be dissociated, suppress the dissolving group by acid among structural unit (a1) and (a1 ') one or both of (preferably the two) to be selected from following chemical general formula (I), (II) and (III), because these structural units have shown outstanding resolution characteristic and dry type resistance to corrosion.

(wherein, R ¹The expression low alkyl group)

(wherein, R ²And R ³Each represents low alkyl group independently)

(R wherein ⁴The expression tertiary alkyl)

Clearly, preferred structure unit (a1) and (a1 ') one or both of (preferably the two) are the structural units that is selected from least a type among following chemical general formula (I '), (II ') and (III '):

(wherein R represents hydrogen atom or methyl, R ¹The expression low alkyl group, therefore above-mentioned group is represented structural unit (a1) when R is hydrogen atom, represents structural unit (a1 ') when R is methyl)

(wherein R represents hydrogen atom or methyl, R ²And R ³Each represents low alkyl group independently, and therefore above-mentioned group is represented structural unit (a1) when R is hydrogen atom, represents structural unit (a1 ') when R is methyl)

(wherein R represents hydrogen atom or methyl, R ⁴The expression tertiary alkyl, therefore above-mentioned group is represented structural unit (a1) when R is hydrogen atom, represents structural unit (a1 ') when R is methyl).

In the represented example of the structural unit of above-mentioned chemical general formula (I ') expression, (O-) adjacent carbon atom is the tertiary alkyl on cyclic skeleton such as the adamantyl with the oxygen atom of (methyl) acrylate base section.

Among this external chemical general formula (I) and (I '), R is hydrogen atom or methyl.

In addition, radicals R ¹Be preferably the lower straight or the branched alkyl of 1～5 carbon atom, its suitable example comprises methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group, amyl group, isopentyl and neopentyl.Wherein the alkyl of at least 2 carbon atoms, preferred 2～5 carbon atoms is preferred, in these examples, with R ¹The situation that is methyl compares, and the tendency of increase can be arranged by the performance of acid disassociation.Yet opposite, from industrial viewpoint, methyl is optimum.

In the example that the structural unit of chemical general formula (II ') expression is represented, (O-) adjacent carbon atom is a tertiary alkyl, has a cyclic skeleton such as adamantyl in this tertiary alkyl with the oxygen atom of (methyl) acrylate base section.

Among chemical general formula (II) and (II '), identical among the implication that R represents and chemical general formula (I) and (I ').

In addition, preferred R ²And R ³Each represents the low alkyl group of 1～5 carbon atom independently.Compare with 2-methyl-2-adamantyl, this class group often demonstrates higher energy by the performance of acid disassociation.

Clearly, radicals R ²And R ³Expression and above-mentioned R independently ¹Identical straight or branched alkyl type.In these groups, industrial preferred examples is R wherein ²And R ³The two all is a methyl.

In the example that the structural unit of chemical general formula (III ') expression is represented, (O-) adjacent carbon atom is a tertiary alkyl to the oxygen atom of the ester group part that partly separates with (methyl) acrylate, and this ester group that separates part and (methyl) acrylate partly are connected by cyclic skeleton such as Fourth Ring dodecyl group.

In chemical general formula (III) and (III '), the implication that R represents is identical with chemical general formula (I) and (I's ').

In addition, R ⁴Be the tertiary alkyl such as the tert-butyl group or tertiary pentyl, although industrial preferably R wherein ⁴It is the structural unit of the tert-butyl group.

Particularly, preferably use chemical general formula (I ') and (any one or the two in the structural unit of I ") expression (and preferred the two), and R wherein ¹Be methyl, R ²And R ³The two all is that the example of methyl provides good especially resolution characteristic, is preferred therefore.

In structural unit (a2) and (a2 '), lactone functional group is being effective aspect the affinity that increases adhesiveness between resist film and the substrate and improvement and developer solution.

Structural unit (a2) and (a2 ') there is not special restriction, as long as exist this class to comprise monocyclic groups or many cyclic groups of lactone groups in this structural unit.

A concrete example that comprises the monocyclic groups of lactone is a group of removing a hydrogen atom in the gamma-butyrolacton.

In addition, the concrete example that comprises many cyclic groups of lactone comprises the group of removing a hydrogen atom in the dicyclo alkane that contains lactone by one of the following chemical structure formula.

No matter a kind of in structural unit (a2) and structural unit (a2 ') or the two (preferably the two), the lactone that preferably comprises monocyclic groups or many cyclic groups is to be selected from following chemical general formula (IV) or a kind of structure (V) at least in addition:

The instantiation of structural unit (a2) and (a2 ') comprises the structural unit that (methyl) acrylate is derived, and these (methyl) acrylate or contain lactone groups perhaps contain the bicyclic alkyl that comprises lactone, shown in following chemical structural formula:

(wherein R is with above-mentioned)

(wherein R is with above-mentioned)

Certainly, according to industrial applicibility, particularly preferably in the ester of (methyl) acrylic acid that connects with ester bond on the alpha-carbon atom and gamma-butyrolacton or with the ester of norbornane lactone.

Because the hydroxyl among structural unit (a3) and (a3 ') is a polar group, by using these structural units, major tuneup the affinity of resin Composition (A) with developer solution, and improved the solubleness of expose portion in alkali.Thereby structural unit (a3) and (a3 ') help to improve resolution characteristic.

In structural unit (a3) and (a3 '), many cyclic groups can suitably be selected from described identical multiple many cyclic groups with said structure unit (a1) and (a1 ').

Structural unit (a3) and (a3 ') are not had special restriction, as long as they are the many cyclic groups that contain hydroxyl, the instantiation of preferred structure comprises the adamantyl that contains hydroxyl.

In addition, if contain the structure that the adamantyl of hydroxyl is following chemical general formula (VI) expression, then can improve its dry type resistance to corrosion, and the perpendicularity that can improve the figure xsect, they the two all be desirable.

Clearly, preferred examples is that wherein any one or the two among structural unit (a3) and (a3 ') (preferably the two) are the structural units of following chemical general formula (VI ') expression.

(wherein R is with above-mentioned)

In the component (A), with respect to the total total amount of forming component (A) entire infrastructure unit, structural unit (a1) and structural unit (a1 ') occupy 30～60 moles of %, preferred 30～50 moles of % altogether, and this component (A) provide outstanding resolution characteristic, are preferred therefore.

In addition, in the component (A), with respect to the total total amount of the entire infrastructure unit of forming component (A), structural unit (a2) and structural unit (a2 ') occupy 20～60 moles of %, preferred 20～50 moles of % altogether, this component (A) provide outstanding resolution characteristic, is preferred therefore.

In addition, in the component (A), with respect to the total total amount of the entire infrastructure unit of forming component (A), structural unit (a3) and structural unit (a3 ') occupy 1～50 mole of %, preferred 20～40 moles of % altogether, this component (A) provides the formation of outstanding resist pattern, is preferred therefore.

In addition, for above-mentioned multipolymer (A1), preferred following multipolymer (a), it provides outstanding resolution characteristic.

Multipolymer (a): the multipolymer that forms by said structure unit (a1 '), said structure unit (a2 ') and said structure unit (a3).

In this multipolymer (a), viewpoint from resolution characteristic and formation resist pattern, in the preferred multipolymer, with respect to structural unit (a1 '), (a2 ') and total total amount (a3), wherein structural unit (a1 ') occupies 30～60 moles of %, preferred 30～50 moles of %, structural unit (a2 ') occupies 20～60 moles of %, preferred 20～50 moles of %, and structural unit (a3) occupies 1～50 mole of %, preferred 20～40 moles of %.

In addition, for above-mentioned hybrid resin (A2), the hybrid resin of preferred following multipolymer (b) and following multipolymer (c), it can reach good balance improving between resistance to corrosion (rough surface) and the resolution characteristic.

Multipolymer (b): by the said structure unit (a1) of 30～60 moles of %, the said structure unit (a2) of 20～60 moles of %, and the multipolymer of the structural unit (a3) of 1～50 mole of %, preferred 5～40 moles of % formation.

Multipolymer (c): by the structural unit (a1 ') of 30～60 moles of %, the structural unit of 20～60 moles of % (a2 '), and the multipolymer of the said structure unit (a3 ') of 1～50 mole of %, preferred 5～40 moles of % formation.

In addition, in this hybrid resin, the mass ratio between preferred copolymer (b) and the multipolymer (c) was 80: 20～20: 80 scope.

At multipolymer (b) with (c), also can choose wantonly and add structural unit (a3) and structural unit (a3 ') respectively.

In any case, by comprising in structural unit (a3) and the structural unit (a3 ') any one or the two (preferably the two), because hydroxyl is a polar group, as the above-mentioned comprehensive affinity of resin Composition (A) of having improved with developer solution, improved the solubleness of expose portion in alkali, this structural unit also helps to improve resolution characteristic, and all these all are desirable.

In addition, for hybrid resin (A2), the hybrid resin of above-mentioned multipolymer (a) and above-mentioned multipolymer (b) also can reach good balance improving between resistance to corrosion (rough surface) and the resolution characteristic, is preferred therefore.

In this hybrid resin, the mass ratio between preferred copolymer (a) and the multipolymer (b) 80: 20～20: 80 scopes.

Also can choose adding structural unit (a3) wantonly in multipolymer (b), comprise structural unit (a3) and help to improve resolution characteristic, be preferred therefore.

In addition, for above-mentioned multipolymer (A1), following multipolymer (d) also provide outstanding resolution characteristic, and in etching process rough surface is arranged seldom, is preferred therefore.

Multipolymer (d): by the structural unit (a1 ') of 30～60 moles of %, preferred 30～50 moles of %, the said structure unit (a2) of 20～60 moles of %, preferred 20～50 moles of %, and the multipolymer of the structural unit (a3) of 1～50 mole of %, preferred 20～40 moles of % formation.

In addition as above-mentioned, also preferred ingredient (A) contains a kind of structural unit [structural unit (a4)] of conduct the 4th structural unit that (methyl) acrylate derives, many cyclic groups that structural unit (a4) contains " are different from the above-mentioned many cyclic groups that can be dissociated by acid, suppress the group of dissolving that contain; be different from above-mentioned monocyclic groups or the many cyclic groups that contains lactone, or be different from the above-mentioned many cyclic groups that contain hydroxyl ".

Wording " be different from the above-mentioned many cyclic groups that can be dissociated by acid, suppress the group of dissolving that contain; be different from above-mentioned monocyclic groups or the many cyclic groups that contains lactone; or be different from the above-mentioned many cyclic groups that contain hydroxyl " many cyclic groups of expression structural unit (a4), many cyclic groups that neither can be dissociated by acid, suppress dissolving with comprising of any first structural unit, and the monocyclic groups that comprises lactone of second structural unit or the repetition of many cyclic groups, also the many cyclic groups that comprise hydroxyl with the 3rd structural unit are not identical.In other words, that structural unit (a4) does not keep is that can be dissociated comprising of any first structural unit by acid, suppress many cyclic groups of the group of dissolving, the monocyclic groups that comprises lactone of any second structural unit or many cyclic groups do not keep the many cyclic groups that comprise hydroxyl of any the 3rd structural unit yet.

Such many cyclic groups are not had special restriction,, make and do not repeat first to the 3rd structural unit in component (A) unit as long as select these many cyclic groups.For example many cyclic groups can utilize relevant said structure unit (a1) with (a1 ') in identical many cyclic groups, and can use most tradition to be used for any material of ArF eurymeric anticorrosive additive material.

Preferred especially at least one many cyclic group are selected from three ring decyl, adamantyl and Fourth Ring dodecane groups, because these groups are commercially available.

Component (A) unit also can comprise in the unit that unit that acrylate derives and methacrylate derive any one or they the two, as structural unit (a4).

Clearly, structural unit (a4) can be a kind of structural unit that is used for above-mentioned multipolymer (A1), or is the structural unit of one or more resins of a kind of composition hybrid resin (A2) at least.From the viewpoint of obtaining effect, preferably add the unit of structural unit (a4) as multipolymer with first to the 3rd structural unit.

The instantiation that hereinafter shows structural unit (a4).

(wherein R is hydrogen atom or methyl)

(wherein R is hydrogen atom or methyl)

(wherein R is hydrogen atom or methyl)

If add up to total amount with respect to component (A) entire infrastructure unit, the ratio of structural unit (a4) is at the scope of 1～25 mole of %, preferred 10～20 moles of %, and isolation pattern is outstanding to the resolution characteristic of the close figure of hemicompact, and Here it is preferably.

In this external above-mentioned example that comprises structural unit (a4), if multipolymer (A1) is following multipolymer (e), except effect with said units (a4), also improved surfaceness and the line edge roughness in the etching process, these all are desirable.

Multipolymer (e): the multipolymer that forms by structural unit (a1 '), structural unit (a2), structural unit (a3) and structural unit (a4).

In this multipolymer (e), viewpoint from resolution characteristic and formation resist pattern, with respect to structural unit (a1 '), (a2), (a3) and total total amount (a4), structural unit in the preferred copolymer (a1 ') occupies 30～60 moles of %, preferred 30～50 moles of %, structural unit (a2) occupies 20～60 moles of %, preferred 20～50 moles of %, structural unit (a3) occupies 1～30 mole of %, preferred 10～20 moles of %, and structural unit (a4) occupies 1～25 mole of %, preferred 10～20 moles of %.

In addition, if hybrid resin (A2) is the hybrid resin of above-mentioned multipolymer (d) and multipolymer (e), then the resolution characteristic of the interval figure (groove) of Ge Liing can be good, and this is desirable.

In addition in this hybrid resin, the mass ratio between preferred copolymer (d) and the multipolymer (e) was 80: 20～20: 80 scope.

Multipolymer (d) and (e) in, also can choose wantonly and add structural unit (a3) and structural unit (a3 ').

In any case, by comprising in structural unit (a3) and the structural unit (a3 ') any one or they the two (preferably the two), because hydroxyl is a polar group, as the above-mentioned comprehensive affinity of resin Composition (A) of having improved with developer solution, and improved the solubleness of expose portion in alkali, these structural units also help to improve resolution characteristic, and all these all are desirable.

In addition, in the component (A) no matter multipolymer (A1) or the quality mean molecular weight of forming the polymkeric substance of resin compound (A2) do not have special restriction, although should value typically 5000～30,000 scope, preferred 8000～20,000.If the quality mean molecular weight is greater than this scope, the solubleness variation in the resist solvent, if instead molecular weight is too little, the shape of resist pattern xsect has the danger of deterioration.

Use radical polymerization initiator such as azo two isobutyl hydrazines (AIBN),, can easily produce the polymkeric substance of multipolymer (A1) or hybrid resin (A2) by the methods such as free radical polymerization of known corresponding (methyl) acrylate monomer.

Acid generator component (B) can suitably strengthen in the known materials that is used as acid agent in the resist at traditional chemical to be selected.

The example of acid agent comprises salt such as trifluoromethanesulfonic acid diphenyl iodnium, trifluoromethanesulfonic acid (4-methoxyphenyl) phenyl salt compounded of iodine, two (to the tert-butyl-phenyl) salt compounded of iodine of trifluoromethanesulfonic acid, trifluoromethanesulfonic acid triphenyl sulfonium salt, trifluoromethanesulfonic acid (4-methoxyphenyl) diphenyl sulfonium salt, nine fluorine fourth sulfonic acid (4-tolyl) diphenyl sulfonium salts, trifluoromethanesulfonic acid (right-tert-butyl-phenyl) diphenyl sulfonium salt, nine fluorine fourth sulfonic acid diphenyl iodnium, two (right-tert-butyl-phenyl) salt compounded of iodine of nine fluorine fourth sulfonic acid and nine fluorine fourth sulfonic acid triphenyl sulfonium salts.In these salt, preferably with the fluoro-alkyl sulfonate ion as anionic salt.

This component (B) can be used the simplification compound, or the combination of two or more compounds.

With respect to per 100 mass parts resin Compositions (A), the quantity of component (B) is preferably in 0.5～30 mass parts, more preferably select in the scope of 1～10 mass parts.If quantity, has the danger that can not form figure satisfactorily less than 0.5 mass parts, if instead quantity surpasses 30 mass parts, then be not easy to obtain uniform solution, the danger of storage stability variation is arranged.

In addition, preferably dissolved constituent (A), component (B) and following optional component (D) in organic solvent (C) are produced eurymeric resist composition of the present invention.

Organic solvent (C) can be can dissolved constituent (A) and component (B) produce any solvent of homogeneous solution, can use a kind of, two or more solvents, these solvents can be selected among the solvent that traditional chemical strengthens resist in known being used for.

The example of solvent comprises ketone such as acetone, MEK, cyclohexanone, methyl isoamyl ketone and 2-heptanone; Polyhydroxy alcohols and derivant thereof such as ethylene glycol, ethylene glycol monoacetate, diglycol, diglycol monotertiary acetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol; Or the monomethyl ether of dipropylene glycol monoacetate, single ether, single propyl ether, monobutyl ether or monophenyl ether; Ring-type ethers such as diox; And ester class such as methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid methyl esters and ethoxyl ethyl propionate.These organic solvents can use separately, or use as the mixed solvent of two or more solvents.

Particularly, the mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and a kind of polar solvent has improved the storage stability of plus tree oil/fat composition well, this polar solvent comprises hydroxyl or lactone such as propylene glycol monomethyl ether (PGME), ethyl lactate (EL) or gamma-butyrolacton, so these mixed solvents are preferred.

In the example that uses EL, the mass ratio of preferred PGMEA:EL is in the scope of 6:4～4:6.

In the example that uses PGME, the mass ratio of PGMEA:PGME is typically in the scope of 8:2～2:8, preferred 8:2～5:5.

Contain in the example of whole first to the 4th structural units in those components (A), the mixed solvent of PGMEA and PGME has improved storage stability, is preferred therefore.

The mixed solvent that also preferably comprises a kind of and gamma-butyrolacton in PGMEA and the ethyl lactate at least is as organic solvent (C).In this example, the mass ratio of component is preferably in the scope of 70:30～95:5 before and after in the mixed solvent.

In addition, in order to improve the exposure rear stability of the sub-image that resist pattern shape and resist layer graph exposure form, can add lower aliphatic secondary amine or tertiary lower aliphatic amine (D) in the eurymeric resist composition of the present invention as optional components (D).

Here, lower aliphatic amine refers to alkyl amine or the alkanolamine that is not more than 5 carbon atoms, the example of these secondary amine classes and tertiary amines comprises trimethylamine, diethylamine, triethylamine, di-n-propylamine, Tri-n-Propylamine, triamylamine, diethanolamine and triethanolamine, and preferred alkanol amine such as triethanolamine.

They can use separately, or two or more compounds are used in combination.

With respect to the quantity of component (A), the quantity that this amine adds is typically in the scope of 0.01～0.2 quality %.

Can add miscible adjuvant as required in the eurymeric resist composition of the present invention, comprise and add the resin that improves the resist film performance, surfactant, dissolution inhibitor, plastifier, stabilizing agent, colorant and the halation prophylactic that improves easy coating.

The present invention forms graphical method and can be undertaken by for example following manner.

That is, at first use a kind of spinner or similar device, eurymeric resist composition of the present invention is applied on substrate such as the silicon wafer surface; At temperature conditions is the prebake conditions of carrying out 40～120 seconds, preferred 60～90 seconds under 80～150 ℃; For example use the ArF exposure device to carry out the selectivity exposure by the ArF excimer laser by the mask pattern that requires then, selectivity exposure back is the PEB (postexposure bake) that carries out 40～120 seconds, preferred 60～90 seconds under 80～150 ℃ at temperature conditions.Use alkaline development liquid to develop subsequently as the tetramethylammonium hydroxide aqueous solution of 0.1～10 quality %.Can obtain the resist pattern consistent in this way with mask pattern.

The anti-reflective film of organic or inorganic also can be provided between substrate and resist composition coating layer.

In addition, although the present composition is used in particular for the ArF excimer laser, radiation such as the F short to other type wavelength ₂The radiation of laser, EUV (EUV (Extreme Ultraviolet Radiation)), VUV (vacuum ultraviolet), electron beam, X-ray and soft X-ray also is effective.

Among the present invention, by using this structure type, available chemistry strengthens eurymeric resist composition and occurs the coarse of the coarse of etched surfaces or line edge hardly, and outstanding resolution characteristic and wide depth of focus scope also are provided.

The reason of these effects is not also thoroughly understood, but can be believed that the following reason is arranged.

That is, think that the structural unit that methacrylate is derived can show outstanding lithography characteristic such as the resolution characteristic and the depth of focus, but present the tendency that surfaceness increases.

On the contrary, think that the structural unit that acrylate is derived shows the big effect of improving surfaceness, but their lithography characteristic such as resolution characteristic are often dissatisfied.

Past does not know that always the structural unit that acrylate is derived has the fact that helps improve surfaceness, and this is found first by inventor of the present invention.

Thereby, contain the base resin (component (A)) of the structural unit combination that structural unit that methacrylate derives and acrylate derive by use, can infer that the shortcoming of the two can be cancelled, can produce the resin that shows the two advantage.

In addition, in the eurymeric resist composition of the present invention, except having the effect of being expected based on this two kinds of structures element characteristics, also reached the additional effect that reduces defective.Here, term " defective " refers to the surface defect inspection apparatus (brand name: KLA), direct to the scum silica frost of above-mentioned resist pattern inspection discovery and the generally distortion of resist pattern in resist pattern development back of using KLA Tencor company.

Embodiment

Hereinafter will use a series of embodiment that the present invention is described in more detail.

Embodiment 1

By in component (C) equably dissolved constituent (A), component (B) and component (D) come production eurymeric resist composition, all components are as mentioned below.

-component (A): the hybrid resin that contains 50 mass parts acrylate base co-polymers and the methacrylate based multipolymer of 50 mass parts, acrylate base co-polymer (quality mean molecular weight: 14,000) forms by following structural unit x, y and z (x=40 mole %, y=30 mole %, z=30 mole %)

(the quality mean molecular weight: be by following structural unit p 10,000), q and l (p=40 mole %, q=40 mole %, 1=20 mole %) form methacrylate based multipolymer;

-component (B): 3 mass parts, nine fluorine fourth sulfonic acid triphenyl sulfonium salts;

-component (C): the mixed solvent of 450 mass parts propylene glycol monomethyl ether acetate and 300 mass parts ethyl lactates;

-component (D): 0.2 mass parts triethanolamine.

Then, use spinner that this eurymeric resist composition is applied to silicon wafer surface, 120 ℃ of 90 seconds of prebake conditions, dry then to form film thickness be the resist layer of 400nm on electric furnace.

Use ArF exposure device (Micro Step, ISI company makes, NA (numerical aperture)=0.60, σ=0.75), (193nm) optionally shines above-mentioned film by mask pattern with the ArF excimer laser.

This film carries out PEB at 110 ℃ and handled for 90 seconds then, stirs 60 seconds of developing in 23 ℃ subsequently in 2.38 quality % tetramethylammonium hydroxide aqueous solutions, and water cleans 20 seconds and dry then.

The result has formed the good 130nm resist line graph (1:1) of shape, and the degree of depth of focusing range is 700nm.

Measured 3 σ values in addition, this value is the standard of measurement of the line edge roughness of line and interval figure, and the result is 6.3nm.

The mensuration of 3 σ values is to use metering SEM (brand name S-9220, Hitachi company limited makes) resist pattern width of measuring samples on 32 sites, calculates 3 times of standard deviations (3 σ) value by these measurement results.This 3 σ value is more little, and roughness levels is low more, and the expression resist pattern has the width of homogeneous.

Use the surface defect inspection apparatus KLA2132 of KLA Tencor company, check that the aperture is the defective of the resist cellular type figure of 250nm, the display defect number is 0.

In addition, in order to estimate the roughness of etching rear surface, preparation does not form the resist film (by eurymeric resist composition is applied on the substrate, and not using mask pattern to expose) of figure, etching under following condition subsequently.

-etching condition:

The mixed gas of gas: contain tetrafluoromethane: 30sccm, fluoroform: 30sccm and helium: 100sccm.

Pressure: 0.3 holder.

RF (radio frequency): frequency: 400 kilo hertzs; Output: 600 watts

Temperature: 20 ℃; Time: 2 minutes

Etaching device: TCE-7612X (brand name, Tokyo Ohka Kogyo company limited makes)

The reason of using the resist film do not form figure to estimate is that it can make the measurement of surfaceness easier.

Surface after the etching quantizes with AFM (atomic force microscope), measures Rms value (root mean square surfaceness), and it is the value of presentation surface roughness, and the result is 2.5nm.

Embodiment 2

Except changing component (A) in the following manner, use the mode identical to prepare eurymeric resist composition and finish the formation of figure with embodiment 1.

-component (A): a kind of hybrid resin, a kind of polymkeric substance (quality mean molecular weight: 15 that it contains, 000) in, structural unit y and z with the acrylate base co-polymer of use among the embodiment 1, change to 50 moles of % and 20 moles of % respectively, structural unit x is replaced by 30 moles of following structural unit m of %, and

(the quality mean molecular weight: 10,000), the structural unit q of employed methacrylate based multipolymer is replaced by following structural unit n the another kind of polymkeric substance that hybrid resin contains among the embodiment 1.The ratio with embodiment 1 employed structural unit p, q and 1 is identical respectively with 1 ratio for structural unit p, n.

The result forms 130nm line and the interval figure (1:1) with excellent in shape, and the degree of depth of focusing range is 700nm.In addition, measuring 3 σ value result displayed is 5.8nm.

Defect inspection also uses the mode identical with embodiment 1 to carry out, and the display defect number is 0.

In addition, use the mode evaluation table surface roughness identical with embodiment 1, demonstration Rms value is 2.2nm.

Embodiment 3

Except changing component (A) in the following manner, use the mode identical to prepare eurymeric resist composition with embodiment 1, and the formation of finishing figure.

-component (A): a kind of hybrid resin, it contain the acrylate base co-polymer that 50 mass parts are used for embodiment 1 (the quality mean molecular weight: 14,000) and

50 mass parts acrylate/methacrylate multipolymers (wherein the structural unit 1 of the methacrylate based multipolymer of embodiment 1 is replaced by the corresponding acrylate derivative of identical mole %) (quality mean molecular weight: 10,000).

The result forms 130nm line and the interval figure (1:1) with excellent in shape, and the focusing range degree of depth is 600nm.In addition, measuring 3 σ value display result is 5.9nm.

In addition, use the mode evaluation table surface roughness identical with embodiment 1, demonstration Rms value is 2.0nm.

Embodiment 4

-component (A): 100 mass parts acrylate/methacrylate multipolymers (wherein do not use the acrylate copolymer of embodiment 1, the structural unit 1 of the methacrylate based multipolymer of embodiment 1 is replaced by the corresponding acrylate of identical mole %) (quality mean molecular weight: 10,000).

The result forms 130nm line and the interval figure (1:1) with excellent in shape, and the focusing range degree of depth is 800nm.In addition, measuring 3 σ value display result is 6.8nm.

In addition, use the mode evaluation table surface roughness identical with embodiment 1, demonstration Rms value is 2.5nm.

Comparative example 1

Except changing component (A) in the following manner, prepare eurymeric resist composition with embodiment 1 identical mode, and the formation of finishing figure.

-component (A): only 100 mass parts are used for the methacrylate copolymer of embodiment 1.

The result forms 130nm line and the interval figure (1:1) with excellent in shape, although the focusing range degree of depth is 500mm.In addition, measuring 3 σ value display result is 14.0nm.

In addition, use the mode evaluation table surface roughness identical with embodiment 1, demonstration Rms value is 12.8nm.

Comparative example 2

-component (A): only 100 mass parts are used for the acrylate copolymer of embodiment 1.

The result forms 130nm line and the interval figure (1:1) with excellent in shape, although the focusing range degree of depth is 200mm.In addition, measuring 3 σ value display result is 3.7nm.

Defect inspection also uses the mode identical with embodiment 1 to carry out, and the display defect number is 500.

In addition, use the mode evaluation table surface roughness identical with embodiment 1, demonstration Rms value is 1.1nm.

The above results shows in the various embodiments of the present invention that the shape of line and interval figure is good, and the degree of depth of focusing range is big, and line edge roughness is minimum, and does not observe defective fully.

On the contrary, comparative example 1 uses the base resin that is only formed by the metacrylic acid ester structure unit, and line edge roughness and surface roughness are big.Otherwise comparative example 2 uses the base resin that is only formed by the acrylate structural unit, and the degree of depth of focusing range is little, and observes a lot of defectives.

Embodiment 5

Dissolved constituent (A), component (B), component (D) and adjuvant equably in component (C) come production eurymeric resist composition, and all components are as mentioned below.

-component (A): 100 mass parts acrylate/methacrylate multipolymers (the quality mean molecular weight: 10,000, polydispersity: 1.80), this multipolymer is by following structural unit x, y, z and p (x=35 mole %, y=40 mole %, z=15 mole %, p=10 mole %) form;

-component (B): 3.5 mass parts, nine fluorine fourth sulfonic acid triphenyl sulfonium salts;

-component (D): 0.3 mass parts triethanolamine;

-adjuvant: 0.1 mass parts fluorine/silica-based surfactant R08 (big Japanese ink and chemical company make);

-component (C): the mixed solvent of 450 mass parts PGMEA, 300 mass parts PGME and 25 mass parts gamma-butyrolactons.

Organic antireflecting film AR-19 (manufacturing of Shipley company limited) is provided at the silicon wafer top (film thickness: 82nm), use spinner that above-mentioned eurymeric resist composition is applied on the anti-reflective film of silicon wafer then.

Subsequently, eurymeric resist composition is dry 90 seconds (prebake conditions) on 95 ℃ of electric furnaces, and forming film thickness is the resist layer of 330nm.

(Nikon company makes to use ArF exposure device S302, NA=0.60) by ArF excimer laser (193nm) this film is carried out elective irradiation by mask, carry out PEB at 95 ℃ and handled for 90 seconds, stand to stir 30 seconds of developing in 23 ℃ subsequently in 2.38 quality % tetramethylammonium hydroxide aqueous solutions, water cleans 20 seconds and dry.

Formed the isolated line graph of 100nm with excellent in shape with aforesaid operations, sensitivity is 23mJ/cm ², and the focusing range degree of depth is 450nm.In addition, the limit resolution characteristic of isolated line figure is 60nm.

In addition, the use identical operations forms 130nm line and the interval figure (the close figure of hemicompact, wherein resist pattern width and interval graphic width amount to 340nm) with excellent in shape, and the focusing range degree of depth is 1000nm.

In addition, measuring 3 σ value result displayed is 5.0nm.

In addition, in order to estimate etching rear surface roughness, measured Rms value (root mean square surfaceness) with mode similar to Example 1, display result is 2.5nm.

In addition, even with the eurymeric resist composition room temperature storage of present embodiment 60 days, as resist solution, its storage stability is good.

Embodiment 6

Except the component (C) of embodiment 5 is changed into the mixed solvent of 750 mass parts PGMEA and 25 mass parts gamma-butyrolactons, prepare eurymeric resist composition in the mode identical with embodiment 5.

In addition, if under the lithography condition identical, finish the formation of figure, except sensitivity is 22mJ/cm with embodiment 5 ²The fact outside, can obtain the lithography characteristic identical with embodiment 5.

In addition, though with the eurymeric resist composition of present embodiment room temperature storage 30 days, as resist solution, its storage stability is good.

Result by embodiment 5 and 6 shows, uses the resin comprising the 4th structural unit, and the eurymeric resist composition that obtains except effects such as above-mentioned described surfaceness, also goes out outstanding resolution characteristic to isolation pattern and the close graphic presentation of hemicompact.

Embodiment 7

-component (A): 100 mass parts acrylate/methacrylate multipolymers (the quality mean molecular weight: 11,000, polydispersity: 1.9), this multipolymer is formed by following structural unit (x=30 mole %, y=50 mole %, z=20 mole %);

-component (B): 3.5 mass parts, nine fluorine fourth sulfonic acid (right-tolyl) diphenyl sulfonium salts;

-component (C): the mixed solvent of 450 mass parts propylene glycol monomethyl ether acetate (PGMEA), 300 mass parts propylene glycol monomethyl ethers (PGME) and 25 mass parts gamma-butyrolactons;

-component (D): 0.3 mass parts triethanolamine;

It is the organic antireflecting film AR-19 (manufacturing of Shipley company limited) of 82nm that film thickness is provided at the silicon wafer top, use spinner that above-mentioned resist composition is applied on the anti-reflective film of this silicon wafer, then dry (prebake conditions) 90 seconds on 105 ℃ of electric furnaces, forming film thickness is the resist layer of 340nm.

(Nikon company makes to use ArF exposure device NSR-S302, NA=0.60), by ArF excimer laser (193nm) this film is carried out elective irradiation by mask, carry out PEB at 100 ℃ and handled for 90 seconds, stand to stir 30 seconds of developing in 23 ℃ subsequently in 2.38 quality % tetramethylammonium hydroxide aqueous solutions, water cleans 20 seconds and dry.

The result has formed good 130nm line and the interval figure (1:1) of shape, and the focusing range degree of depth is 800nm.

In addition, measure 3 σ values, it is the standard of measurement of line and interval figure LER, and display result is 6.0nm.

In addition, in order to estimate the surfaceness after the etching, measured Rms value (root mean square surfaceness) with mode similar to Example 1, display result is 2.5nm.

Even above-mentioned in addition resist solution room temperature storage 30 days, as resist solution, its storage stability is good.

Embodiment 8

Except the quaternary acrylate/methacrylate multipolymer that is used for embodiment 5 with 50 mass parts replaces embodiment 7 employed 50 mass parts acrylate/methacrylate multipolymers, and make two kinds of multipolymers in conjunction with forming outside the component (A), use the mode production eurymeric resist composition identical, and use the mode identical to finish the formation of figure with embodiment 7 with embodiment 7.

The result has formed the good 100nm isolated line figure that passes through aforesaid operations formation of shape, and sensitivity is 23mJ/cm ², the focusing range degree of depth is 450nm.In addition, the limit resolution characteristic of isolated line figure is 75nm.

In addition, formed good 130nm line and the interval figure (the close figure of hemicompact, wherein resist pattern width and interval graphic width amount to 340nm) by same operation production of shape with identical operations, the focusing range degree of depth is 1000nm.

In addition, measure 3 σ values, it is the standard of measurement of line and interval figure LER, and display result is 5.3nm.

In addition, in order to estimate the surfaceness after the etching, measured Rms value (root mean square surfaceness) with mode similarly to Example 1, display result is 2.5nm.

Embodiment 7 and 8 result represent that significantly embodiment 7 uses the resin of 3 structural units, have reached the effect that reduces surfaceness; The resin that embodiment 8 uses also comprises the 4th structural unit, and the eurymeric resist composition that obtains has also shown isolation pattern and the outstanding resolution characteristic of the close figure of hemicompact except the effect of above-mentioned reduction surface roughness.This external embodiment 7 and embodiment 8 have used the mixed solvent of PGMEA and polar solvent in the two, and therefore excellent storage stability arranged.

Industrial usability

As mentioned above, the method for eurymeric anti-corrosion agent composition of the present invention and formation resist pattern can provide one Plant chemistry and strengthen the eurymeric anti-corrosion agent composition, and the method for using this composition formation resist pattern, Rough surface and line edge roughness seldom appear in wherein said composition in etching, and provide outstanding Resolution capability and the wide focusing range degree of depth can also reduce defects count.

Claims

1. eurymeric resist composition, it contains: (A) a kind of resin Composition, the resin Composition main chain contains the structural unit that (methyl) acrylate is derived, partly combine the many cyclic groups that comprise group that can be dissociated by acid, the inhibition dissolving at ester side chain, its solubleness in alkali has increased under the acid effect thus; (B) acidic acid generator component during a kind of exposure; Reach (C) a kind of organic solvent; Wherein:

Described component (A) contain structural unit that structural unit that methacrylate derives and acrylate derive the two,

Condition is that described component (A) comprises in the following structural unit any one or the two:

The structural unit that acrylate is derived (a1), it comprises and contains many cyclic groups that can be dissociated by acid, suppress the group of dissolving; And

The structural unit that methacrylate is derived (a1 '), it comprises and contains many cyclic groups that can be dissociated by acid, suppress the group of dissolving, and,

Condition is the structural unit that any one or two kinds of among described structural unit (a1) and (a1 ') comprise following general formula (I ') and (II ') expression

Wherein, R represents hydrogen atom or methyl, R ¹The straight or branched alkyl of 1～5 carbon atom of expression,

Wherein, R represents hydrogen atom or methyl, R ²And R ³The straight or branched alkyl of representing 1～5 carbon atom independently of one another.

2. according to the eurymeric resist composition of claim 1, R wherein ¹Be methyl, R ²And R ³The two all is a methyl.

3. according to the eurymeric resist composition of claim 1, wherein said component (A) contains a kind of multipolymer (A1), and this multipolymer (A1) has the structural unit that structural unit that methacrylate derives and acrylate are derived.

4. according to the eurymeric resist composition of claim 1, wherein said component (A) contains a kind of hybrid resin (A2), and it is the hybrid resin that contains the polymkeric substance of the structural unit that methacrylate derives at least and contain the polymkeric substance of the structural unit that acrylate derives at least.

5. according to the eurymeric resist composition of claim 1, wherein said component (A) also contains:

The structural unit that (methyl) acrylate is derived, it comprises monocyclic groups or the many cyclic groups that contains lactone.

6. according to the eurymeric resist composition of claim 5, wherein said component (A) also contains:

The structural unit that (methyl) acrylate is derived, it comprises the many cyclic groups that contain hydroxyl.

7. according to the eurymeric resist composition of claim 5, wherein said component (A) contains in the following structural unit any one or the two:

The structural unit that acrylate is derived (a2), it comprises monocyclic groups or the many cyclic groups that contains lactone, and

The structural unit that methacrylate is derived (a2 '), it comprises monocyclic groups or the many cyclic groups that contains lactone.

8. according to the eurymeric resist composition of claim 5, wherein said component (A) contains in the following structural unit at least a:

The structural unit that acrylate is derived (a3), it comprises the many cyclic groups that contain hydroxyl, and

The structural unit that methacrylate is derived (a3 '), it comprises the many cyclic groups that contain hydroxyl.

9. according to the eurymeric resist composition of claim 7, wherein in any one or the two of described structural unit (a2) and described structural unit (a2 '):

The described monocyclic groups that comprises lactone or many cyclic groups be selected from following chemical general formula (IV) and (V) at least a group:

10. eurymeric resist composition according to Claim 8, wherein at least a at described structural unit (a3) and described structural unit (a3 '):

The described many cyclic groups that contain hydroxyl are the adamantyls that contain hydroxyl.

11. according to the eurymeric resist composition of claim 10, the wherein said adamantyl that contains hydroxyl is the group by following chemical general formula (VI) expression:

12. according to the eurymeric resist composition of claim 1, wherein:

With respect to the total total amount of the entire infrastructure unit of forming described component (A), described structural unit (a1) and described structural unit (a1 ') occupy 30～60 moles of % altogether.

13. according to the eurymeric resist composition of claim 7, wherein:

With respect to the total total amount of the entire infrastructure unit of forming described component (A), described structural unit (a2) and described structural unit (a2 ') occupy 20～60 moles of % altogether.

14. eurymeric resist composition according to Claim 8, wherein:

With respect to the total total amount of the entire infrastructure unit of forming described component (A), described structural unit (a3) and described structural unit (a3 ') occupy 1～50 mole of % altogether.

15. according to the eurymeric resist composition of claim 3, wherein said multipolymer (A1) is following multipolymer (a):

Multipolymer (a): the multipolymer that the structural unit (a2 ') of a kind of structural unit by 30～60 moles of % (a1 '), 20～60 moles of % and the structural unit (a3) of 1～50 mole of % form, structural unit (a1 ') is derived by methacrylate and is comprised and contains many cyclic groups that can be dissociated by acid, suppress the group of dissolving, structural unit (a2 ') is derived by methacrylate and is comprised monocyclic groups or the many cyclic groups that contains lactone, and structural unit (a3) is derived by acrylate and comprised the many cyclic groups that contain hydroxyl.

16. according to the eurymeric resist composition of claim 4, wherein:

Described hybrid resin (A2) is the hybrid resin of following multipolymer (b) and multipolymer (c):

Multipolymer (b): the formed multipolymer of structural unit (a3) of the structural unit (a2) of a kind of structural unit (a1), 20～60 moles of % and 1～50 mole of % by 30～60 moles of %, structural unit (a1) is derived by acrylate and is comprised and contains many cyclic groups that can be dissociated by acid, suppress the group of dissolving, structural unit (a2) is derived by acrylate and is comprised monocyclic groups or the many cyclic groups that contains lactone, and structural unit (a3) is derived by acrylate and comprised the many cyclic groups that contain hydroxyl;

Multipolymer (c): the formed multipolymer of structural unit (a3 ') of the structural unit (a2 ') of a kind of structural unit (a1 '), 20～60 moles of % and 1～50 mole of % by 30～60 moles of %, structural unit (a1 ') is derived by methacrylate and is comprised and contains many cyclic groups that can be dissociated by acid, suppress the group of dissolving, structural unit (a2 ') is derived by methacrylate and is comprised monocyclic groups or the many cyclic groups that contains lactone, and structural unit (a3 ') is derived by methacrylate and comprised the many cyclic groups that contain hydroxyl.

17. according to the eurymeric resist composition of claim 4, wherein:

Described hybrid resin (A2) is the hybrid resin of following multipolymer (a) and multipolymer (b):

Multipolymer (a): the multipolymer that the structural unit (a2 ') of a kind of structural unit by 30～60 moles of % (a1 '), 20～60 moles of % and the structural unit (a3) of 1～50 mole of % form, structural unit (a1 ') is derived by methacrylate and is comprised and contains many cyclic groups that can be dissociated by acid, suppress the group of dissolving, structural unit (a2 ') is derived by methacrylate and is comprised monocyclic groups or the many cyclic groups that contains lactone, and structural unit (a3) is derived by acrylate and comprised the many cyclic groups that contain hydroxyl;

Multipolymer (b): the multipolymer that the structural unit (a2) of a kind of structural unit by 30～60 moles of % (a1), 20～60 moles of % and the structural unit (a3) of 1～50 mole of % form, structural unit (a1) is derived by acrylate and is comprised and contains many cyclic groups that can be dissociated by acid, suppress the group of dissolving, structural unit (a2) is derived by acrylate and is comprised monocyclic groups or the many cyclic groups that contains lactone, and structural unit (a3) is derived by acrylate and comprised the many cyclic groups that contain hydroxyl.

18. according to the eurymeric resist composition of claim 3, wherein said multipolymer (A1) is following multipolymer (d):

Multipolymer (d): the multipolymer that the structural unit (a2) of a kind of structural unit by 30～60 moles of % (a1 '), 20～60 moles of % and the structural unit (a3) of 1～50 mole of % form, structural unit (a1 ') is derived by methacrylate and is comprised and contains many cyclic groups that can be dissociated by acid, suppress the group of dissolving, structural unit (a2) is derived by acrylate and is comprised monocyclic groups or the many cyclic groups that contains lactone, and structural unit (a3) is derived by acrylate and comprised the many cyclic groups that contain hydroxyl.

19. according to the eurymeric resist composition of claim 5, wherein said component (A) also contains:

Structural unit (a4), it is derived by (methyl) acrylate and contains many cyclic groups, and these many cyclic groups are different from described many cyclic groups, described monocyclic groups or the many cyclic groups or the described many cyclic groups that contain hydroxyl that contain lactone that can be dissociated by acid, suppress the group of dissolving that contain.

20. according to the eurymeric resist composition of claim 19, many cyclic groups of wherein said structural unit (a4) are at least a groups that is selected from three ring decyl, adamantyl and Fourth Ring dodecyls.

21. according to the eurymeric resist composition of claim 3, wherein said multipolymer (A1) is following multipolymer (e):

Multipolymer (e): by the structural unit (a1 ') of 30～60 moles of %, the structural unit of 20～60 moles of % (a2), the structural unit of 1～30 mole of % (a3), and the multipolymer of the structural unit of 1～25 mole of % (a4) formation, structural unit (a1 ') is derived by methacrylate and is comprised and contains and can be dissociated by acid, the many cyclic groups that suppress the group of dissolving, structural unit (a2) is derived by acrylate and is comprised monocyclic groups or the many cyclic groups that contains lactone, structural unit (a3) is derived by acrylate and is comprised the many cyclic groups that contain hydroxyl, structural unit (a4) is derived by (methyl) acrylate and is contained many cyclic groups, this many cyclic groups are different from described containing and can be dissociated by acid, the many cyclic groups that suppress the group of dissolving, described monocyclic groups or the many cyclic groups that contains lactone, or the described many cyclic groups that contain hydroxyl.

22. according to the eurymeric resist composition of claim 4, wherein:

Described hybrid resin (A2) is the hybrid resin of following multipolymer (d) and multipolymer (e):

Multipolymer (d): the multipolymer that forms by the structural unit (a3) of the structural unit (a2) of the structural unit (a1 ') of 30～60 moles of %, 20～60 moles of % and 1～50 mole of %, structural unit (a1 ') is derived by methacrylate and is comprised and contains many cyclic groups that can be dissociated by acid, suppress the group of dissolving, structural unit (a2) is derived by acrylate and is comprised monocyclic groups or the many cyclic groups that contains lactone, and structural unit (a3) is derived by acrylate and comprised the many cyclic groups that contain hydroxyl;

Multipolymer (e): by the structural unit (a1 ') of 30～60 moles of %, the structural unit of 20～60 moles of % (a2), the structural unit of 1～30 mole of % (a3), and the multipolymer of the structural unit of 1～25 mole of % (a4) formation, structural unit (a1 ') is derived by methacrylate and is comprised and contains and can be dissociated by acid, the many cyclic groups that suppress the group of dissolving, structural unit (a2) is derived by acrylate and is comprised monocyclic groups or the many cyclic groups that contains lactone, structural unit (a3) is derived by acrylate and is comprised the many cyclic groups that contain hydroxyl, structural unit (a4) derived by (methyl) acrylate and contains many cyclic groups, and these many cyclic groups are different from described containing and can be dissociated by acid, the many cyclic groups that suppress the group of dissolving, described monocyclic groups or the many cyclic groups that contains lactone, or the described many cyclic groups that contain hydroxyl.

23. according to the eurymeric resist composition of claim 19, wherein with respect to the total total amount of the entire infrastructure unit of forming described component (A), the ratio of described structural unit (a4) is in the scope of 1～25 mole of %.

24. according to the eurymeric resist composition of claim 1, wherein said component (B) is that the fluorinated alkyl sulfonate ion is made anionic salt.

25. according to the eurymeric resist composition of claim 1, wherein said organic solvent (C) is the mixed solvent of propylene glycol monomethyl ether acetate and polar solvent.

26. according to the eurymeric resist composition of claim 25, wherein said polar solvent be a kind of, two or more are selected from the solvent of propylene glycol monomethyl ether, ethyl lactate and gamma-butyrolacton.

27. the eurymeric resist composition according to claim 1 also contains: (D) a kind of lower aliphatic secondary amine or tertiary amine, with respect to the quantity of described component (A), the quantity of amine is in the scope of 0.01～0.2 quality %.

28. method that forms resist pattern, it comprises the steps: the eurymeric resist composition according to claim 1 is applied on the substrate, carries out prebake conditions, implements the selectivity exposure, carry out postexposure bake, and carry out alkaline development to form resist pattern.

29. eurymeric resist composition, it contains: (A) a kind of resin Composition, the resin Composition main chain contains the structural unit that (methyl) acrylate is derived, partly combine the many cyclic groups that comprise group that can be dissociated by acid, the inhibition dissolving at ester side chain, its solubleness in alkali has increased under the acid effect thus; (B) acidic acid generator component during a kind of exposure; Reach (C) a kind of organic solvent; Wherein:

Condition is that any one or two kinds of among described structural unit (a1) and (a1 ') had both comprised by R wherein ¹Represent and comprise many cyclic groups that can be dissociated by acid, suppress the group of dissolving for the general formula (I) of methyl, comprise again by R wherein ¹For many cyclic groups that can be dissociated by acid, suppress the group of dissolving are represented and comprised to the general formula (I) of ethyl

30. according to the eurymeric resist composition of claim 29, wherein said component (A) contains a kind of multipolymer (A1), this multipolymer (A1) has the structural unit that structural unit that methacrylate derives and acrylate are derived.

31. eurymeric resist composition according to claim 29, wherein said component (A) contains a kind of hybrid resin (A2), and it is the hybrid resin that contains the polymkeric substance of the structural unit that methacrylate derives at least and contain the polymkeric substance of the structural unit that acrylate derives at least.

32. according to the eurymeric resist composition of claim 29, wherein said component (A) also contains:

33. according to the eurymeric resist composition of claim 32, wherein said component (A) also contains:

34. according to the eurymeric resist composition of claim 32, wherein said component (A) contains in the following structural unit any one or the two:

35. according to the eurymeric resist composition of claim 32, wherein said component (A) contains in the following structural unit one or both:

36. according to the eurymeric resist composition of claim 34, wherein in any one or the two of described structural unit (a2) and described structural unit (a2 '):

37. according to the eurymeric resist composition of claim 35, wherein in one or both of described structural unit (a3) and described structural unit (a3 '):

38. according to the eurymeric resist composition of claim 37, the wherein said adamantyl that contains hydroxyl is the group by following chemical general formula (VI) expression:

39. according to the eurymeric resist composition of claim 29, wherein:

40. according to the eurymeric resist composition of claim 34, wherein:

41. according to the eurymeric resist composition of claim 35, wherein:

42. according to the eurymeric resist composition of claim 30, wherein said multipolymer (A1) is following multipolymer (a):

43. according to the eurymeric resist composition of claim 31, wherein:

44. according to the eurymeric resist composition of claim 31, wherein:

45. according to the eurymeric resist composition of claim 30, wherein said multipolymer (A1) is following multipolymer (d):

46. according to the eurymeric resist composition of claim 32, wherein said component (A) also contains:

47. according to the eurymeric resist composition of claim 46, many cyclic groups of wherein said structural unit (a4) are at least a groups that is selected from three ring decyl, adamantyl and Fourth Ring dodecyls.

48. according to the eurymeric resist composition of claim 30, wherein said multipolymer (A1) is following multipolymer (e):

49. according to the eurymeric resist composition of claim 31, wherein:

50. according to the eurymeric resist composition of claim 46, wherein with respect to the total total amount of the entire infrastructure unit of forming described component (A), the ratio of described structural unit (a4) is in the scope of 1～25 mole of %.

51. according to the eurymeric resist composition of claim 29, wherein said component (B) is that the fluorinated alkyl sulfonate ion is made anionic salt.

52. according to the eurymeric resist composition of claim 29, wherein said organic solvent (C) is the mixed solvent of propylene glycol monomethyl ether acetate and polar solvent.

53. according to the eurymeric resist composition of claim 52, wherein said polar solvent is the solvent that one or more kinds are selected from propylene glycol monomethyl ether, ethyl lactate and gamma-butyrolacton.

54. the eurymeric resist composition according to claim 29 also contains: (D) a kind of lower aliphatic secondary amine or tertiary amine, with respect to the quantity of described component (A), the quantity of amine is in the scope of 0.01～0.2 quality %.

55. method that forms resist pattern, it comprises the steps: the eurymeric resist composition according to claim 29 is applied on the substrate, carries out prebake conditions, implements the selectivity exposure, carry out postexposure bake, and carry out alkaline development to form resist pattern.