KR20120049640A - Composition for forming a photoresist top coat layer in extreme ultraviolet lithography and patterning method using the same - Google Patents

Abstract

PURPOSE: A composition for forming photoresist topcoat and a pattern forming method using the same are provided to improve line width roughness and to form uniform micro patterns by overcoming pattern defects due to exposure to ultraviolet ray out of the light in a band between 100 and 300nm. CONSTITUTION: A composition for forming photoresist topcoat includes 100 parts by weight of aqueous binder resins, 0.01 to 30 parts by weight of agents for blocking light out of an extreme ultraviolet ray band, and 1,000 to 10,000 parts by weight of protonic solvents. The main absorption wavelength of the agents is between 100 and 300nm. The agents are selected from a group including aqueous sulfonic acid ester, the salt of sulfonic acid ester, sulfonium compound, iodonium compound, and oxime compound. The agents are represented by chemical formula 24. In chemical formula 24, Bs are capable of being identical or different and are C1 to C10 alkyl groups or alicyclic substituted groups; m is the integer of 0 to 8; n is the natural number of 1 to 8; the sum of m and n is more than or equal to 8; As are capable of being identical or different and are hydroxyl groups, carboxylic groups, ether groups, or ester groups.

Description

Composition for forming a photoresist top coat layer in extreme ultraviolet lithography and patterning method using the same}

The present invention relates to a method of manufacturing a semiconductor circuit. More specifically, the present invention relates to a circuit pattern forming method using extreme ultraviolet lithography and a photoresist topcoat composition therefor.

A circuit structure designed to process a semiconductor wafer or a display glass into a desired semiconductor chip or display element should be implemented through an optical lithography process. In this photolithography process, technology development has been developed to enable high resolution patterning as the integration of circuits increases. The exposure source wavelength (λ), which is a key variable for determining resolution, is used by using short wavelength light, or between the photoresist and the lens. in the three developing technologies in the direction in which a refractive index is applied to a large liquid a technique for reducing the large, or k ₁ values of the process parameters introduce additional step the lens aberrations (NA) greater than 1 to less than 0.3 by filling consists than air come. In particular, in the semiconductor wafer processing process that requires high resolution, KrF laser light with a wavelength of 248 nanometer is used to manufacture 200-90 nanometer-class devices, and 60 nanometer-class below 90 nanometer class. In order to obtain a pattern resolution of, an ArF laser having an exposure source wavelength of 193 nanometers has been developed and applied to manufacture a semiconductor chip. In the less than 60 nanometer and 40 nanometer ultrafine pattern processes, the lens aberration is increased to greater than 1 by filling the wafer with a photoresist film and deionized water having a refractive index of 1.34 instead of air having a refractive index of 1 between the projection lens. Device production is underway by applying immersion lithography to obtain the desired resolution.

A technique being developed for processing a device of 30 nanometers or less is an extreme ultraviolet lithography (EUVL) technique having a wavelength of 13.4 nanometers of a used exposure source. Since the exposure source wavelength used in the previous technology is 194 nanometers, the exposure wavelength is reduced to less than 1/10, so it is possible to simultaneously process not only 32 nanometer devices but also multiple generation devices of 22 nanometers and below. It is a technology with merit.

Various types of technologies have been developed to solve the technical challenges emerging from the extreme ultraviolet lithography, and one of them is the out of band in addition to the 13.4 nanometer in-band (IB) wavelength band generated by the light source. (out of band, OOB) There is a development of countermeasures for resolution degradation caused by light in the wavelength band, pattern profile distortion, and deep surface roughness. In other words, in the current light source technology, a circuit structure designed to process a semiconductor wafer or display glass into a desired semiconductor chip or display element at the same time, in addition to the 13.4 nanometers intended for EUVL technology, has a wavelength band in the range of 100 nanometers to 300 nanometers. Should be implemented through photolithography process. In the photolithography process, technology development has been developed to enable high-resolution pattern formation as the degree of integration of circuits increases, and the exposure source wavelength (λ), which is a key parameter for determining resolution, uses short wavelength light, or a photoresist and a lens Fill the liquid with a higher refractive index to make the lens aberration (NA) greater than 1, or introduce an additional process so that the process variable k ₁ Three directions of technology development have been made to apply the technology of reducing the value to 0.3 or less. In particular, in the semiconductor wafer processing process requiring high resolution, KrF laser light with a wavelength of 248 nanometer is used for the manufacture of 200 nanometer to 90 nanometer class devices, and 60 nanometer class below 90 nanometer class. In order to obtain pattern resolution, a technology using an ArF laser having an exposure source wavelength of 193 nanometers has been developed and applied to produce a semiconductor chip. In the less than 60 nanometer and 40 nanometer ultrafine pattern processes, the lens aberration is improved by filling the wafer with a refractive index of 1.34 and DI water instead of a refractive index of 1 between the photosensitive film and the projection lens. Device production is being carried out by applying immersion lithography to obtain the desired resolution by making it larger than 1.

A technique being developed for processing a device of 30 nanometers or less is an extreme ultraviolet lithography (EUVL) technique having a wavelength of 13.4 nanometers of a used exposure source. Since the exposure source wavelength used in the previous technology is 194 nanometers, the exposure wavelength is reduced to less than 1/10, so it is possible to simultaneously process not only 32 nanometer devices but also several generations of microdevices corresponding to 22 nanometers and below. It is a technology with merit.

Various types of technologies are being developed to solve the technical difficulties emerging from the extreme ultraviolet lithography technology, and one of them is the problem of the light source. In other words, in the current light source technology, light having a wavelength range of 100 nanometers to 300 nanometers in addition to the 13.4 nanometer in-band (IB) wavelength band that is intended for use in EUVL technology is stochastic signal noise. It is formed simultaneously as stochastic noise. The ultraviolet rays in the 100 nm to 300 nm region are called out-of-band (OOB) ultraviolet rays. Since the mask material for photoresist and lithography reacts to ultraviolet light in this out-of-band wavelength region, the quality reduction of the pattern formation cannot be avoided unless the adverse effects of light in this wavelength band must be removed. Problems with the pattern forming process due to out-of-band ultraviolet rays include lower resolution, pattern profile distortion, and deeper surface roughness.

One important problem to be solved in EUVL technology is Line Width Roughness (LWR). This corresponds to the surface roughness of the pattern, which is an important variable that determines the performance of the final circuit. LWR, resolution, and sensitivity are inversely related to each other through acid diffusion and shot noise. Therefore, the performance of resist should be improved in order to overcome and minimize this to obtain satisfactory LWR for processing semiconductor chips. At the same time, technologies are being developed to introduce new additional processes fairly. One of them is the introduction of an underlayer, which has been shown to have a significant improvement but is not yet satisfactory.

An object of the present invention is to provide a means for increasing the line width roughness, the resolution reduction, and the pattern formation defect, which are caused when the mask is exposed to ultraviolet rays having a wavelength in an out-of-band region in a pattern forming process using extreme ultraviolet lithography.

In order to solve the above technical problem, in the present invention, a top coat is formed between the photoresist layer and the exposure source to block deep ultraviolet (UV) and vacuum ultraviolet rays that impair resolution and pattern uniformity. The composition for forming a photoresist topcoat includes a) 100 parts by weight of water-soluble binder resin, b) 0.01 to 10 parts by weight of the out-of-band sunscreen and c) 1,000 to 10,000 parts by weight of the protic solvent.

In the composition of the present invention, the water-soluble binder resin is a homopolymer of a vinyl monomer having a side chain selected from a carboxyl group, a carboxamide group, a hydroxy group, an N-substituted lactam group, an N-substituted imidazole group, and a 2-hexafluoroisopropanolylalkyl group. Or a copolymer of such a vinyl monomer with a vinyl monomer having no selected side chain. In one specific embodiment of the present invention, the weight average molecular weight of the water-soluble binder resin is 1,000 to 100,000. In another specific embodiment of the present invention, as the water-soluble binder resin, those having a dispersity of 1.02 to 3.5 are suitable.

In the composition of the present invention, the out-of-band sunscreen may be selected from the group consisting of water-soluble sulfonic acid esters, salts of sulfonic acid esters, sulfonium compounds, iodonium compounds, and oxime compounds having a main absorption wavelength of 100 to 300 nm. Can be.

The present invention also discloses an extreme ultraviolet lithography pattern forming process using the photoresist topcoat described above. This process

(1) sequentially depositing a photoresist underlayer, a photoresist layer having a desired circuit pattern, and a photoresist topcoat formed from the above-described composition for forming a photoresist on a substrate to obtain a photolithography mask;

(2) an exposure step of dissolving a mask according to the pattern by irradiating extreme ultraviolet rays to the laminate;

(3) a developing step of selectively removing the dissolved part of the exposed mask;

(4) etching the substrate on which the developed mask is laminated to form a pattern on the substrate.

In one embodiment of the pattern forming process of the present invention, the step of laminating the photoresist layer comprises (a) 0.5 to 10 parts by weight of a photoacid generator, (c) 0.01 to 100 parts by weight of an acid sensitive base resin; Laminating a composition comprising from about 5 parts by weight of a basic acid diffusion quencher and (d) 1,000 to 10,000 parts by weight of an organic solvent to the photoresist underlayer and soft baking the laminated composition. .

Here, the acid sensitive base resin is a polymer which is insoluble in the alkaline developer but becomes soluble in the alkaline developer after reacting with the proton. In one specific embodiment of the present invention, the acid sensitive base resin is a polymer having a weight average molecular weight of 2,000 to 20,000 and a dispersion degree of 1.0 to 2.0.

When the photoresist topcoat of the present invention is used for extreme ultraviolet lithography, defects in the pattern process due to out-of-band ultraviolet exposure in the region of 100 to 300 nm, which are problematic in the extreme ultraviolet lithography process, can be solved. Thanks to this, breakage of pattern uniformity can be prevented and a uniform fine pattern can be formed. Furthermore, there is a great effect in improving the linewidth roughness (LWR), which is the biggest problem in circuit pattern formation using extreme ultraviolet lithography. By using the composition for forming a photoresist topcoat of the present invention and the extreme ultraviolet lithography method using the same, the LWR can be improved to an excellent level of 3.3 nm or less, beyond the current technology level of 5 nm 3 sigma (σ). 1 nm in case It can also be implemented at levels below.

1 shows a mask for extreme ultraviolet lithography according to an embodiment of the present invention. The stacking order of the mask from the direction close to the light source toward the substrate SUB is a photoresist topcoat (OCB) -photoresist (PR) -lower layer (UL) -substrate (SUB).
Figure 2 is a schematic diagram of an extreme ultraviolet lithography process showing the principle of operation of the photoresist topcoat in one embodiment of the present invention. IB is ultraviolet (solid line) in the in-band wavelength region of extreme ultraviolet lithography and OOB refers to ultraviolet (dotted line) in the out-of-band wavelength region of extreme ultraviolet lithography.
3 is a flowchart illustrating a pattern forming process of a mask for extreme ultraviolet lithography having only a lower layer according to the prior art.
4 is a flowchart illustrating a pattern forming process of a mask for an extreme ultraviolet lithography having a photoresist topcoat and a lower layer together according to an embodiment of the present invention.
5 is a CD-SEM photograph of a line in which a pattern is formed according to one embodiment of the present invention.
6 is a graph showing the ultraviolet absorption spectrum of the photoresist topcoat prepared according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention relates to a photoresist topcoat composition and a pattern forming method using the same, which can solve problems such as lowering of resolution due to extra-area ultraviolet rays generated in extreme ultraviolet lithography, pattern profile distortion, and surface roughening.

In one aspect of the invention there is provided a photoresist topcoat composition for extreme ultraviolet lithography.

The photoresist topcoat for extreme ultraviolet lithography of the present invention sits between an exposure source and a photoresist and absorbs out-of-band ultraviolet light. The schematic diagram of the mask for extreme ultraviolet lithography which employ | adopted the top coat of this invention is shown in FIG. In FIG. 1, a photoresist underlayer (UL), a photoresist (PR), and a photoresist topcoat (OCB) may be stacked on a substrate (SUB) layer, and then the mask may be exposed to extreme ultraviolet rays to form a pattern. A top view of a photoresist agent topcoat (OCB) in the first is exposed to extreme ultraviolet radiation during exposure.

The principle of operation of the photoresist topcoat of the present invention is briefly summarized in FIG. In-band ultraviolet (IB, thick solid arrow in FIG. 2) penetrates the top coat and reaches the photoresist or lower layer by the out-of-band sunscreen of the photoresist topcoat to produce an exposure effect for forming a pattern in subsequent processes. . On the other hand, out-of-band ultraviolet light (OOB) indicated by a dotted arrow in FIG. 2 is absorbed in the top coat and thus does not reach the photoresist. Thereafter, the exposed mask may be developed and processed into a desired pattern.

The composition for forming a photoresist topcoat of the present invention includes a water-soluble binder resin, an out-of-band sunscreen and a protic solvent, and may further include an additive such as a surfactant.

Hereinafter, the copolymer in the present invention refers to a polymer having two or more kinds of repeating units, and encompasses more than two kinds of repeating unit copolymers such as ternary copolymers and quaternary copolymers. In addition, all types of copolymers, including random copolymers, block copolymers, alternating copolymers, and graft copolymers, also encompass the concept.

In one aspect of the present invention, the water-soluble binder resin of the composition for forming a photoresist topcoat is a homopolymer or copolymer of repeating units having a fluorine substituted ester side chain shown in Formula 1 below.

In Formula 1, R ₁ is a hydrogen atom (H), a fluorine atom (F), a methyl group (-CH ₃ ), a fluorinated alkyl group of 1 to 20 carbon atoms or a hydroxyalkyl group of 1 to 5 carbon atoms, X is hexafluoro An alkyl group substituted with tert- butyl hexafluoroisopropyl carbonate, wherein the alkyl group is substituted via carbon 2 of hexafluoroisopropyl to the opposite carbon on the side bonded to R ₂ . Specifically, the repeating unit of Formula 1 containing X is

와 같다(여기서 n은 0 내지 5의 정수, *는 화학식 1의 반복 단위에서 X에 연결되는 나머지 부분, 즉 나머지 부분, 즉 -CH₂CH(R₁)(COOR₂-)- 부위를 나타냄)이며, m은 X의 개수로서, 1 또는 2이다. m이 1일 때 화학식 1에서 R₂는 탄소수 1 내지 10의 사슬형 또는 분지형 알킬렌기 또는 알킬리덴(alkylidene)기, 또는 탄소수 5 내지 10의 고리형 알킬렌기 또는 알킬리덴(alkylidene)기이고, m이 2일 때 화학식 1에서 R₂는 탄소수 1 내지 10의 탄화수소로서 결합수가 세 개인 3가 작용기인 직쇄형, 분지형 또는 고리형 하이드로카빈(hydrocarbine) 탄화수소이다. 여기서 하이드로카빈이란 탄소와 수소로 이루어져 있으며, 2중 결합이 결합수가 세 개인 탄화수소 부위(moiety)를 일컫는 용어로서, 메틸(-CH₃), 메틸렌((-CH₂-), 메틴(-C(-)H-)의 계열과 유사하게 하이드로카빌(hydrocarbyl), 하이드로카빌렌(hydrocarbylene), 하이드로카빈의 관계에 있다. m이 2일 때 화학식 1의 하이드로카빈 R₂ 결합수 중 하나는 -COO에 연결되며, 나머지 2개는 X에 연결된다.

(Where n is an integer from 0 to 5, * denotes the remainder of the moiety linked to X in the repeating unit of Formula 1, ie, the remainder, ie -CH ₂ CH (R ₁ ) (COOR ₂ -)-moiety) M is the number of X, 1 or 2. When m is 1, R ₂ in the general formula (1) is a chain or branched alkylene group or alkylidene group having 1 to 10 carbon atoms, or a cyclic alkylene group or alkylidene group having 5 to 10 carbon atoms, When m is 2, R ₂ in the general formula (1) is a straight chain, branched or cyclic hydrocarbine hydrocarbon having a trivalent functional group having three bonds as a hydrocarbon having 1 to 10 carbon atoms. Herein, hydrocarbine is a term used to refer to a hydrocarbon moiety having three bonds formed of carbon and hydrogen, and methyl (-CH ₃ ), methylene ((-CH _2- ), and methine (-C ( Similar to the class of-) H-), hydrocarbyl, hydrocarbylene, and hydrocarbine are related.When m is 2, one of the hydrocarbine R ₂ bonds of Formula 1 is represented by -COO. The other two are connected to X.

The water-soluble binder resin according to the present invention may be composed of only one repeating unit according to Chemical Formula 1 or a copolymer therebetween, and may be a composite copolymer including other repeating units in addition to the repeating unit of Chemical Formula 1. In the composite copolymer, the proportion of the repeating unit of Formula 1 is 1 to 99% by weight, preferably 1 to 90% by weight, more preferably 5 to 90% by weight of the total weight of the total repeating unit in the case of the binary copolymer. And most preferably 5 to 50% by weight. In the case of the terpolymer, the repeating unit of formula 1 is 1 to 98% by weight, preferably 1 to 90% by weight, more preferably 5 to 90% by weight, most preferably 5 to 50% of the total weight of the total repeating units. Weight percent. In the composite copolymer, the remaining repeating units other than the repeating unit of Formula 1 may include repeating units used in a conventional resist protective film-forming polymer.

Representative examples of the repeating unit represented by Formula 1 may include a repeating unit represented by the following Formulas 1a to 1o.

[Formula 1a]

[Chemical Formula 1b]

[Formula 1c]

≪ RTI ID = 0.0 &

[Formula 1e]

(1f)

[Formula 1g]

[Formula 1h]

Formula 1i]

[Formula 1j]

[Formula 1k]

[Formula 1l]

[Formula 1m]

[Formula 1n]

[Formula 1o]

The repeating unit represented by the formula (1) used in the present invention is a monomer molecule

Wherein R ₁ , R ₂ , X and m are as defined in Formula 1 above. This monomer molecule can be obtained by reacting the hydroxy group (-OH) of the hexafluoroalcohol group with di-tert-butyl dicarbonate in a compound containing a hexafluoroalcohol group or the like. For example, as in Scheme 1, 4-dimethylaminopyridine (DMAP) is used as a catalyst, and tetrahydrofuran (THF) is used as a solvent, di-tert-butyldicarbonate and hexa A monomer corresponding to the repeating unit represented by Chemical Formula 1a may be obtained by reacting a compound (MA-3,5-Bis (hexafluoro-2-hydroxy-2-propyl) cyclohexyl methacrylate) including a fluoroalcohol group.

[Reaction Scheme 1]

To give an example of the water-soluble binder resin according to the present invention, a homopolymer consisting of only the repeating unit represented by the formula (1), a copolymer having the repeating unit represented by the following formula (2), the air having a repeating unit represented by the formula (3) A copolymer having a copolymer or repeating units represented by the following Chemical Formula 4 may be exemplified. That is, the water-soluble binder resin according to the present invention includes a repeating unit containing R ₃ , as shown in the following Formula 2, or as shown in the following Formula 3, comprising a repeating unit and a R ₄ including R ₃ It may include a repeating unit, and as shown in the following formula 4, it may include a repeating unit including a R ₄ and a sulfonyl group (sulfonyl group).

In Formula 2, R ₁ , R ₂ , X and m are the same as defined in Formula 1, R ₃ is a hydrogen atom, or a carbon number containing one or more hydroxy group (-OH) or carboxyl group (-COOH) 1 to 25 alkyl groups, for example, a chain, branched alkyl group of 2 to 18, a cyclic alkyl group of 5 to 25 carbon atoms, for example, 6 to 18, and p is an integer of 0 to 3. The proportion of a in formula (2) is such that the repeating unit is 1 to 99% by weight, preferably 1 to 90% by weight, more preferably 5 to 90% by weight, particularly preferably 10 to 90% by weight of the total repeating unit weight. , Most preferably 5 to 50% by weight, and the proportion of b is 1 to 99% by weight, preferably 1 to 90% by weight, more preferably 5 to 90% by weight, of the total repeating unit. Particular preference is given to occupying 10 to 90% by weight, most preferably 5 to 50% by weight. In Chemical Formula 2, the above two repeating units are not necessarily connected in the form of block copolymers or alternating copolymers connected in the order shown in the figure, and of course, they cover all copolymers of the two repeating units.

In Chemical Formula 3, R ₁ , R ₂ , R ₃ , X, p, and m are as defined in Chemical Formulas 1 and 2, and R ₄ is an alkyl group having 1 to 25 carbon atoms unsubstituted or substituted with one or more fluorine atoms, eg For example, it is a 2-18 chain, branched alkyl group, or a C5-C25 cyclic alkyl group, for example, a 6-18 cyclic alkyl group. The ratio of a in formula (3) is such that the repeating unit is 1 to 98% by weight, preferably 1 to 90% by weight, more preferably 5 to 90% by weight, particularly preferably 10 to 90% by weight of the total repeating unit weight. , Most preferably 5 to 50% by weight, and the proportion of b is 1 to 98% by weight, preferably 1 to 90% by weight, more preferably 5 to 90% by weight of the total repeating unit, Especially preferably, it is 10 to 90 weight%, most preferably 5 to 50 weight%, and the ratio of c is 1 to 98 weight%, preferably 1 to 90 weight%, of the said repeating unit weight of the whole repeating unit It is appropriate to determine that it preferably accounts for 5 to 90% by weight, particularly preferably 10 to 90% by weight, most preferably 5 to 50% by weight. In Formula 3, the above three repeating units are not necessarily connected in the form of block copolymers or alternating copolymers connected in the order depicted in the figure, and of course, they encompass all copolymers of the three repeating units.

In Formula 4, R ₁ , R ₂ , R ₄ , X and m are as defined in Formulas 1 and 3, q is an integer of 0 to 3. The proportion of a in formula (4) is such that the repeating unit is 1 to 98% by weight, preferably 1 to 90% by weight, more preferably 5 to 90% by weight, particularly preferably 10 to 90% by weight of the total repeating unit weight. , Most preferably 5 to 50% by weight, and the proportion of c is 1 to 98% by weight, preferably 1 to 90% by weight, more preferably 5 to 90% by weight, of the total repeating unit. Especially preferably, it is 10 to 90 weight%, most preferably 5 to 50 weight%, and the ratio of d is 1 to 98 weight%, preferably 1 to 90 weight%, more preferably the weight of the said repeating unit is total. It is appropriate to determine that it preferably accounts for 5 to 90% by weight, particularly preferably 10 to 90% by weight, most preferably 5 to 50% by weight. In Chemical Formula 4, the above three repeating units are not necessarily connected in the form of block copolymers or alternating copolymers connected in the order depicted in the figure, and of course, they cover all copolymers of the three repeating units.

(화학식 2a),

(화학식 2b),

(화학식 2c),

(화학식 2d),

(화학식 2e),

(화학식 2f),

(화학식 2g),

(화학식 2h),

(화학식 2i),

(화학식 2j),

(화학식 2k),

(화학식 2l),

(화학식 2m) 등을 예시할 수 있고, 상기 R₄를 포함하는 반복단위는,

(화학식 3a),

(화학식 3b),

(화학식 3c),

(화학식 3d),

(화학식 3e),

(화학식 3f),

(화학식 3g),

(화학식 3h),

(화학식 3i),

(화학식 3j),

(화학식 3k),

(화학식 3l),

(화학식 3m),

(화학식 3n),

(화학식 3o),

(화학식 3p),

(화학식 3q),

(화학식 3r) 등을 예시할 수 있다.The repeating unit including R ₃ , the repeating unit including R ₄ , and the repeating unit including a sulfonyl group may form a polymer for forming a conventional resist protective film, and include the repeating R ₃ . The unit is

(Formula 2a),

(Formula 2b),

(Formula 2c),

(Formula 2d),

(Formula 2e),

(Formula 2f),

(Formula 2g),

(Formula 2h),

(Formula 2i),

(Formula 2j),

(Formula 2k),

(Formula 2l),

(Formula 2m) etc. can be illustrated, The repeating unit containing said R <_4> ,

(Formula 3a),

(Formula 3b),

(Formula 3c),

(Formula 3d),

(Formula 3e),

(Formula 3f),

(Formula 3g),

(Formula 3h),

(Formula 3i),

(Formula 3j),

(Formula 3k),

(Formula 3l),

(Formula 3m),

(Formula 3n),

(Formula 3o),

(Formula 3p),

(Formula 3q),

(Formula 3r) and the like can be exemplified.

The water-soluble binder polymer used in the present invention is a monomer of a repeating unit represented by Formula 1

Wherein R ₁ , R ₂ , X and m are as defined in Formula 1 above, and a monomer of a repeating unit comprising R ₃

Wherein R ₁ , R ₃ and p are as defined in Formula 2 above, and a monomer of a repeating unit comprising R ₄ .

Where R ₁ And R ₄ is as defined in Chemical Formula 3), a monomer of a repeating unit including the sulfonyl group,

Where R ₁ And q may be prepared by polymerization in a conventional manner, for example, and the like, and for example, polymerization initiators such as azobis (isobutyronitrile) (AIBN) and tetramer are commonly known in the art. It can also superpose | polymerize using solvents, such as hydrofuran (THF).

In addition, the water-soluble binder polymer used in the present invention, the homopolymer, the compound represented by the general formula (2), 3 or 4, the conventional polymer for forming a resist protective film, for example, the compound represented by the following formula (5) It may be).

In Formula 5, R ₁ , R ₃ , and p are as defined in Formulas 1 to 3, the ratio of e in Formula 5 is 1 to 99% by weight of the total repeat unit weight, preferably 5 The ratio of to 90% by weight, f is appropriately determined such that the repeating unit accounts for 1 to 99% by weight, preferably 5 to 90% by weight of the total repeating unit weight. In Formula 5, the above two repeating units are not necessarily connected in the form of block copolymers or alternating copolymers connected in the order depicted in the figure, and of course, they cover all copolymers of the two repeating units.

In the blend of the homopolymer, the compound represented by the formula (2), 3 or 4 and the compound represented by the formula (5), the content of the homopolymer, the compound represented by the formula (2), 3 or 4 is 1 to 99% by weight, preferably Preferably it is 5 to 90% by weight, the content of the compound represented by the formula (5) is 1 to 99% by weight, preferably 5 to 90% by weight.

The weight average molecular weight of the water-soluble binder resin is 1,000 to 100,000, preferably 3,000 to 30,000. If the weight average molecular weight is less than 1,000, the protective film may not be formed. If the weight average molecular weight is more than 100,000, the solvent may not be dissolved in the solvent.

In another aspect of the present invention, the water-soluble binder resin in the composition for forming a top coat is a carboxyl group, a carboxamide group, a hydroxy group, an N-substituted lactam group, an N-substituted imidazole group, a 2-hexafluoroisopropanolyl group, and 2-hexafluoro Homopolymers of vinyl monomers having a particular side chain selected from the leusopropanolylalkyl group or copolymers of such vinyl monomers with other vinyl monomers not having the specific side chains selected above may be used.

In another aspect of the present invention, the water-soluble binder polymer includes at least one or more repeating units represented by Formula 6 below.

In Formula 6, R is a hydrocarbon having less than 10 carbon atoms that may contain up to 5 hydrogen or heteroatoms. In the repeating unit having a lactam side chain in Formula 6, m and n are independent of each other, and any one of 1 to 6 is a natural number. R 'is hydrogen or an alkyl group of 1 to 10 carbon atoms and m represents that this R' substituent may be substituted m times in the lactam ring. n indicates that the constituent carbon number of the lactam ring is included from 4 to 9 membered ring. For example, when n = 2, the lactam ring of the repeating unit is a 5-membered ring. In the repeating unit having a 2-hexafluoroisopropanolyl side chain in Chemical Formula 6, X is a single bond or an alkylene group having 1 to 10 carbon atoms.

In a more specific embodiment of the present invention, the water-soluble binder resin exemplified in Chemical Formula 6 may be a repeating unit derived from a monomer group of vinyl alcohol, acrylamide, methacrylamide, N-vinyl caprolactam and N-vinylpyrrolidone. Homopolymer or copolymer comprising at least one.

In one specific embodiment of the present invention, as a copolymer between the repeating units represented by Chemical Formula 6, a combination represented by Chemical Formula 7 may be used.

In another embodiment of the present invention, a copolymer of a repeating unit having a specific side chain described above, for example, the repeating unit shown in Formula 6, and a vinyl monomer having no specific side chain can be used as the water-soluble binder resin. In one specific embodiment of the present invention, the vinyl monomer having no specific functional group side chain is methyl acrylate, methyl methacrylate, ethyl acrylate or ethyl methacrylate.

In one specific embodiment of this invention, the said water-soluble binder resin is a polymer of the specific side chain structure mentioned above, the weight average molecular weights are 1,000-100,000, and dispersion degree is 1.02-3.5.

In the composition for forming a photoresist topcoat of the present invention, the content of the water-soluble binder resin in the total composition is preferably 1 to 30% by weight. More preferably, it may be 1 to 20% by weight. If the content of the water-soluble binder resin is less than 1% of the total composition, there is a risk that the formation of the photoresist protective film is difficult, if it exceeds 30% by weight, the formation of the photoresist protective film is too thick to develop during the photoresist pattern development There is concern about quality.

The out-of-band sunscreen in the composition for forming a photoresist topcoat of the present invention refers to a material capable of absorbing out-of-band ultraviolet rays other than 13.4 nm, which is the wavelength of the light source for extreme ultraviolet photolithography. The out-of-band sunscreen does not absorb ultraviolet light in the region around 13.4 nm, or the absorbance value is close to zero, and the main absorption wavelength band is in the deep ultraviolet and vacuum ultraviolet regions of 100 nm to 300 nm, or at least It means the substance which has the maximum extinction value in the ultraviolet range of this wavelength range.

In one embodiment of the present invention, the out-of-band sunscreen may be selected from sulfonic acid esters, salts of sulfonic acid esters, sulfonium compounds, iodonium compounds, and oxime compounds. In the present invention, the "compound" of the sulfonium compound, the iodonium compound, and the oxime compound includes an ionic salt.

In one specific embodiment of the present invention, the out-of-band sunscreen is phthalimidotrifluoromethane sulfonate, phthalimidotosylate, phthalimidotosylate, dinitrobenzyl tosylate, and naphthylimidotrifluoro. One or more of naphthylimidotrifluoromethane sulfonate and triphenylsulfonium methanesulfonate (group 1) are selected.

In another specific embodiment of the present invention, diphenyl iodonium triflate, diphenyl iodonium nonaplate, hexafluorophosphate diphenyl iodonium, hexafluorobisoric acid diphenyl iodonium, hexafluoro Roantimonic acid diphenyl iodonium, diphenyl paramethoxy phenylsulfonium triflate, diphenyl paratoluenyl sulfonium triflate, diphenyl para tert-butyl phenyl sulfonium triflate, diphenyl paraisobutyl phenyl sulfonium tri Plate, triphenylsulfonium triflate, trispara tert-butyl phenylsulfonium triflate, diphenyl paramethoxy phenylsulfonium nona plate, diphenyl para toluenyl sulfonium nona plate, diphenyl para tert-butyl phenyl sulfonium nona Plate, diphenylparaisobutylphenylsulfonium nona plate, triphenylsulfonium nona plate, trispar tertiary butylphenylsulfonium nona plate, hexa Topcoat formation with a first group of out-of-band sunscreens selected from the group consisting of fluorosorbic acid triphenylsulfonium, triphenylsulfonium triflate, and dibutylnaphthylsulfonium triflate (group 2) By incorporating in the composition for an out-of-band ultraviolet blocking effect, it can be made more effective. Of course, the second group of out-of-band sunscreens may be used alone without the first group of blockers.

In another embodiment of the present invention, the out-of-band sunscreen is a substance having a naphthalene skeleton represented by the formula (8).

In Formula 8B is It is a C1-C10 alkyl group or alicyclic substituent. m is an integer of 0 to 8 and when there are several B in the naphthalene ring, each B may be the same or different.

A is a hydroxyl group or monovalent organic group, n is independently substituted with each other in the naphthalene skeleton of the formula (8). In formula (8), n is an integer of 1 to 8 and m + n ≦ 8 as is apparent from the skeleton of naphthalene. When there are multiple A's, each A can be the same or different.

The monovalent organic group constituting A is preferably at least one selected from a carboxyl group, an ether group and an ester group. When A is an ester group here, it is preferable that the carbonyl group side which comprises this ester group couple | bonds with naphthalene. Moreover, it is preferable that the position which couple | bonds in a naphthalene skeleton is a 1st position or a 2nd position.

When A is an ether group, it is preferable that A is a radical represented by [OZ] (However, Z represents a hydrogen atom or a C1-C10 linear or alicyclic substituent.). Examples of the substituent having 1 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclofuthyl group, a cycloheptyl group, and a cyclooctyl group. When A is an ester group, A is preferably a methyl ester group, an ethyl ester group, an n -propyl ester group, an i -propyl ester group, an n -butyl ester group, a tertiary butyl ester group or the like. However, it is preferable that the carbon atom of the carbonyl group which comprises an ester group couple | bonds with naphthalene.

In the out-of-band sunscreen of Formula 8, A may be a material having a skeleton of Formula 9 represented by the following structure.

In the formula (9), J represents a single bond, a methylene group or a linear or branched alkyl group having 2 to 10 carbon atoms, and Q represents an acid dissociable group which can be released by the action of an acid. Suitable for Q are tertiary butyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl, ethyl adamantyl, isopropyladamantyl, gamma butyrolactone, Norbornenebutyrolactone, oxonorbornenebutyrolactone, and the like, but are not limited thereto.

Preferred examples of the compound represented by the out-of-band sunscreen include 1-naphthol, 2-naphthol, 1,8-naphthalenediol, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1-methoxynaphthalene, 2-methoxynaphthalene, 1-ethoxynaphthalene, 2-ethoxynaphthalene, 1- n -propoxynaphthalene, 2- n -propoxynaphthalene, 1-i-propoxynaphthalene, 2- i -propoxy naphthalene, 1- n -butoxynaphthalene, 2- n -butoxynaphthalene, 1-methoxycarbonyl naphthalene, 1-3-butoxycarbonyl naphthalene, 1- (methoxycarbonyl methoxynaphthalene), 1- (tertiary part Methoxycarbonyl methoxynaphthalene). Particularly preferred examples of the compound represented by the formula (8) include those represented by the following formula (10), but are not limited thereto.

In the photoresist topcoat composition for extreme ultraviolet lithography of the present invention, the out-of-band sunscreen may be included in a ratio of 0.01 to 30 parts by weight with respect to 100 parts by weight of the aforementioned water-soluble binder resin. Including an out-of-band sunscreen in this content range can provide economical effects while improving pattern resolution, reducing line width roughness (LWR), and improving pattern profile. On the other hand, if the content of the out-of-band sunscreen is less than 0.01 parts by weight, the out-of-band sunscreen effect is not seen, and even if it exceeds 30 parts by weight, the sunscreen effect is hardly further enhanced, absorbs excessive ultraviolet rays in excess and generates acid by ultraviolet rays. Because of this excess, the cross section of the pattern worsens and economic efficiency is reduced.

The photoresist topcoat composition for extreme ultraviolet lithography of the present invention comprises a solvent. It is preferable to use a solvent that can prevent mixing (intermixing) with the photoresist layer, which is the lower layer of the top coat. As the solvent that can be used in the topcoat composition of the present invention, a solvent used for a composition for forming a general photoresist protective film can be used. Among them, it is preferable to use a protic solvent. In general, other solvents which do not mix with the topcoat composition solvent may be selected as the solvent for the photoresist layer composition. Of course, two or more kinds of mixed protic solvents may be used.

Some examples of suitable protic solvents include methanol, isopropanol, ethanol, butanol, 1-propanol, 2-propanol, 2-butanol, 1,2-butanediol, 1,2-propanediol, 2-hexanol, 3-hexane Ol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 5-methyl-2-hexanol, water, isobutanol, 4-methyl-2-pentanol, cyclopentanol, normalpentanol , Glycerol and propanol. If necessary, a small amount of aprotic solvent may be mixed with the protic solvent within a range that does not affect the intermixing. When the solvent for forming photoresist is a protic solvent, the solvent for forming a top coat may be used as an aprotic solvent. As an aprotic solvent, alkyl ethers of polyhydric alcohols such as cyclic ethers such as dioxane, diisoheptyl ether, diisoamyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether and diethylene glycol diethyl ether There is Liu.

In the topcoat composition of the present invention, the amount of the solvent is required in terms of the viscosity required for applying the composition such as spin coating on the photoresist layer, and the time, temperature, and cost of the drying or curing process for removing the solvent of the topcoat, such as a soft baking process. Considering this, the average technician in this field can adjust accordingly. Therefore, it is not necessary to specifically present the content of the solvent in this specification, but in a typical case 1,000 to 10,000 with respect to 100 parts by weight of the above-mentioned water-soluble binder resin It is appropriate to include the solvent in the range by weight.

The topcoat composition of the present invention may further comprise a surfactant as well. Surfactants smooth the topcoat surface and improve the linewidth roughness (LWR) of the lithographic pattern by helping the topcoat composition to coat the photoresist layer with an even thickness.

There is no particular limitation on the surfactant of the present invention, and cationic surfactants, anionic surfactants, and nonionic surfactants may be used widely.

In one specific embodiment of the present invention, an alkylamine oxide or an alkyl ether sulfate ester may be used as the surfactant. Examples are n-octylamine oxide and n-dodecyl phenol ether.

In the topcoat composition of the present invention, the surfactant may be included in a ratio of 0.00001 to 0.1 parts by weight (that is, 10 ppm to 100,000 parts by weight of the composition) based on 100 parts by weight of the total weight of the composition excluding the surfactant.

In addition, the topcoat composition of the present invention may further include additives commonly used in the art.

In another aspect of the present invention, there is provided an extreme ultraviolet lithography microprocess, that is, a method of forming a pattern of a substrate using the above-described topcoat composition. In the pattern formation method of the present invention, an extreme ultraviolet lithography mask including a top coat formed of the photoresist topcoat composition is formed.

In one embodiment of the method of forming a pattern of the present invention, the mask comprises a triple structure of a photoresist topcoat-photoresist-undelayer.

The role of the lower layer is to enhance the adhesion of the lower layer of the photoresist and to improve the pattern profile line edge roughness by promoting the generation of secondary electrons known to occur in the exposure process to promote acid generation. The lower layer film composition used in the present invention is composed of a base resin, a crosslinking agent, a thermal acid generator, and a surfactant. The base resin may include at least one repeating unit represented by Formula 11 below

R is a hydrocarbon having less than 10 carbon atoms which may contain up to 5 hydrogen or heteroatoms. B ¹ , B ² , B ³ and Q are each independently a hydrocarbon of less than 15 carbon atoms which may optionally contain up to 5 heteroatoms

In the extreme ultraviolet lithography using the composition for forming a top coat of the present invention, the weight average molecular weight range of the lower layer base resin is 2,000 to 45,000, and the dispersion degree range is appropriately 1 to 3.5.

The crosslinking agent can apply the compound which has the amide which substituted the alkoxy methyl group as a basic structure. Representative examples include compounds of the formula (12) below.

The thermal acid generator plays a role of generating an acid by thermal decomposition in the range of 120 to 250 ° C., and an amine salt that reacts sensitively to heat, for example, a salt of Chemical Formula 13 below is applied.

In Formula 13, D ¹ to D ⁵ are each independently a hydrocarbon having less than 15 carbon atoms which may contain 5 or less heteroatoms.

In one embodiment of the pattern formation method of the present invention, a pattern formation method of a substrate including the following steps is disclosed. A flowchart of a typical process according to this method is shown in FIG. 4. The main part of the prior art pattern formation process consisting only of the photoresist-underlayer without topcoat according to the invention is shown in FIG. 3. 4 and 3, most of the processes except for the top coat are very similar.

(1) sequentially depositing a photoresist underlayer, a photoresist layer having a desired circuit pattern, and a photoresist topcoat formed from the above-described topcoat composition on a substrate to obtain a photolithography mask;

(2) an exposure step of dissolving a mask according to the pattern by irradiating extreme ultraviolet rays to the laminate;

(3) a developing step of selectively removing the dissolved portion in the exposed mask,

(4) forming a pattern on the substrate by etching the substrate on which the developed mask is laminated.

The substrate to which the method of the present invention can be applied is not particularly limited, and for example, silicon, aluminum, polymer resin, silicon dioxide, doped silicon dioxide, silicon nitride, tantalum, copper, polysilicon, ceramic, aluminum / copper mixture Gallium arsenide and other Group III / V mixtures.

The method of laminating the photoresist underlayer, photoresist layer and photoresist topcoat on the substrate in step (1) is well known in the art and will not be described here. The method of laminating the lower layer, the photoresist layer, and the top coat is not particularly limited, and a method commonly used in the photolithography field is sufficient. For example, these layers can be formed by applying the above-mentioned photoresist topcoat or the composition for forming a photoresist layer on an appropriate substrate or a layer set in the lower portion and processing the same through a drying or curing treatment such as soft baking. The thickness of the photoresist, lower layer and topcoat may be appropriately selected by the average person skilled in the art depending on the aspect of the overall extreme ultraviolet lithography process, i.e., the type of developing solution, the thickness of the desired pattern and the degree of LWR.

Composition application methods that may be used in the present invention include, for example, dipping, spraying, whirling and spin coating. When applying the film-forming composition by spin coating, the solid content of the photoresist-forming composition or other composition can be appropriately adjusted to form a layer having a desired thickness according to the type and rotation time of the spin coating apparatus.

Thus, after apply | coating the composition for layer formation, soft baking and a hardening process can be performed. In the case of an underlayer, a curing bake may be performed, and a soft bake may be applied to the photoresist and the top coat. Conditions for proper drying, curing temperature and time, apparatus, etc. may vary depending on the composition of the composition and the desired final physical properties. For example, in a typical case the curing treatment may use temperatures of around 200 ° C. The treatment is around 100 ° C. and hotplates or convection ovens can be used. However, these specific conditions are for illustrative purposes only, and can be appropriately modified by an average person skilled in the art without departing from the technical spirit of the present invention.

The step of stacking the photoresist layer in the step (1) may be made by laminating and soft baking the following composition.

The composition for the photoresist layer comprises 0.5 to 10 parts by weight of a photoacid generator, 0.01 to 5 parts by weight of a basic acid diffusion quencher and 100 to 1500 parts by weight of an organic solvent based on 100 parts by weight of an acid sensitive base resin. . The photoresist layer lamination method includes laminating such a photoresist layer composition on the photoresist underlayer and soft baking the laminated composition.

In the photoresist layer composition, the acid sensitive base resin is a polymer which is insoluble in the alkaline developer but becomes soluble in the alkaline developer after reacting with a proton. Such acid-sensitive base resins may be any one widely used in the art and are not particularly limited. The average person skilled in the art can properly select an acid sensitive base with reference to the technical common sense and the technical spirit of the present invention, and thus will not be described in detail herein. For example, as the acid sensitive base resin, one having a structure represented by Chemical Formula 14 may be used.

In this case, R is hydrogen, C ₁ ~ C ₉ unsubstituted hydrocarbon or C ₁ ~ C ₉ substituted hydrocarbon containing up to 5 heteroatoms, wherein a, b, c is a + b + c = 1, 0.10 ≦ a ≦ 0.55, 0.15 ≦ b ≦ 0.80, and 0.10 ≦ c ≦ 0.35,

P, L, and H are independent of each other.

P is a non-aromatic aliphatic ring hydrocarbon or a branched aliphatic hydrocarbon which is unsubstituted or substituted with an ether (-OR), an ester, a hydroxyl group or the like and may be further substituted with fluorine. In one specific embodiment of the present invention, P is preferably a cyclic hydrocarbon such as adamantyl having a high steric volume.

L is a branched aliphatic hydrocarbon containing an ester group. In one specific embodiment of the present invention, L is lactone, and a ring having a steric volume may be used. H is an aliphatic cyclic hydrocarbon having a hydroxy group, wherein the aliphatic ring may have a fluorine-substituted alkyl substituent in addition to the hydroxy group.

In one specific embodiment of the present invention, the above-mentioned substance may be used as the acid sensitive base resin, and the weight average molecular weight is 2,000 to 20,000, and the dispersity is 1.0 to 2.0.

In the present invention, the photoacid generator may be a material widely used in this field as a material capable of generating an acid by light. For example, a sulfonium salt-based or iodonium-based compound may be used.

In one specific embodiment of the present invention, as the photoacid generator, phthalimidotrifluoromethane sulfonate, phthalimidotrifluoromethane sulfonate, dinitrobenzyl tosylate, n-decyl disulfone, and naphthylimidotrifluoro Any one or more of naphthylimidotrifluoromethane sulfonate may be used.

In a more specific embodiment of the present invention, in addition to the above-described photoacid generator, diphenyl iodonium triflate, diphenyl iodonium nona plate, hexafluorophosphate diphenyl iodonium, hexafluorobisoric acid di Phenyl iodonium, hexafluoroantimonate diphenyl iodonium, diphenyl paramethoxy phenylsulfonium triflate, diphenyl paratoluenyl sulfonium triflate, diphenyl para tert-butyl phenyl sulfonium triflate, diphenyl Paraisobutylphenylsulfonium triflate, triphenylsulfonium triflate, trispara tert-butylphenylsulfonium triflate, diphenyl paramethoxyphenylsulfonium nona plate, diphenyl paratoluenylsulfonium nona plate, diphenyl para Tertiary butylphenylsulfonium nona plate, diphenyl paraisobutylphenylsulfonium nona plate, triphenylsulfonium nona plate, trispar tertiary butyl pen Nylsulfonium nonaplate, hexafluorobisoric acid triphenylsulfonium, triphenylsulfonium triflate and dibutylnaphthylsulfonium triflate can be used together.

The photoacid generator of the present invention is included in a ratio of 0.5 to 10 parts by weight based on 100 parts by weight of the acid sensitive base resin. Including the photoacid generator in this content range can improve the pattern resolution, reduce the line width roughness, and improve the pattern profile while economical. On the other hand, if the content of the photoacid generator is less than 0.05 parts by weight, the sensitivity to extreme ultraviolet rays becomes weak, and even if it exceeds 10 parts by weight, the pattern formation does not become better, but it absorbs excessive ultraviolet rays excessively and generates excessive acid by ultraviolet rays. As a result, acid diffusion occurs, the cross section of the pattern worsens, and the resolution deteriorates.

The composition for forming a photoresist layer of the present invention includes a basic acid diffusion regulator. In one embodiment of the present invention, as the basic acid diffusion regulator, an organic base such as triethylamine, trioctylamine, triisobutylamine, triisooctylamine, diethanolamine and triethanolamine can be used.

In another embodiment of the present invention, the basic acid diffusion regulator is a polymer having the composition represented by the following formula (15) or a mixture of the aforementioned organic base and the polymer.

In this case, L ¹ , L ² , L ³ , L ⁴ and L ⁵ are each independently hydrogen, C ₁ ~ C ₉ unsubstituted hydrocarbon or C ₁ ~ C ₉ containing up to 5 heteroatoms Substituted hydrocarbons,

E may use any of P, L, or H seen above,

Α and β are α + β = 1, and are 0.75 ≦ β ≦ 0.99 while 0.01 ≦ α ≦ 0.25. The basic acid diffusion regulator of the present invention is included in a ratio of 0.01 to 5 parts by weight based on 100 parts by weight of the acid sensitive base resin. Including the basic acid diffusion regulator in this content range can improve the pattern resolution, reduce the line width roughness, and improve the pattern profile while achieving economical efficiency. On the other hand, if the content of the regulator is less than 0.01 parts by weight of the acid diffusion can not be prevented, the resolution is worse, even if it exceeds 5 parts by weight, the sensitivity of the photoresist is deteriorated and it is not preferable because it produces a steep slope (slope) in the profile of the pattern.

The composition for forming a photoresist of the present invention contains 1,000 to 10,000 parts by weight of a solvent based on 100 parts by weight of the acid sensitive base resin. The solvent of the composition for forming a photoresist is not particularly limited. Some examples of suitable solvents include ethylene glycol monomethylethyl, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol , Propylene glycol monoacetate, toluene, xylene, methyl ethyl ketone, methyl isoamyl ketone, cyclohexanone, dioxane, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methyl methoxy propionate , Ethyl ethoxy propionate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl 2-pyrrolidone, 3-ethoxyethyl propionate, 2-heptanone, gamma-part Tyrollactone, 2-hydroxypropionethyl, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxyacetate, 2-hydroxy 3-methylbutanoic acid Methyl, 3-methoxy 2-methylpropionate, ethyl 3-ethoxypropionate, 3-methoxy ethyl 2-methylpropionate, 4-methyl-2-pentanol, 4-methyl-2-pentyl acetate, isopropanol, methyl Alcohol, ethyl alcohol, normal butyl alcohol, cyclopentanol, cyclopentanone, ethyl acetate, butyl acetate and the like may be used alone or in a mixture thereof.

The composition for forming a photoresist of the present invention may further include an additive such as a surfactant. As the surfactant, surfactants used in the art, such as fluorine-based surfactants, anionic, cationic, and nonionic, can be used without particular limitation.

Steps (2) to (4) in the pattern forming method of the substrate of the present invention may be made using a method well known in the art, and thus will not be described in detail here.

For example, an exposure step of dissolving a mask according to the pattern by irradiating extreme ultraviolet rays to the laminate may be performed by irradiating a 13.4 nm light source.

The developing step of (3) and the etching step of (4) may also use methods well known in the art and are not particularly limited.

EXAMPLES

Hereinafter, the present invention will be described in more detail with reference to Preparation Examples and Experimental Examples. The following examples are intended to illustrate the invention in detail and are not intended to limit the scope of the invention in any case.

[Preparation Example 1]

Synthesis of monomer molecules corresponding to repeating units represented by Formula 1a

As shown in the following formula (16), a magnetic stirring bar was placed in a 500 mL two-necked flask, and the monomer (MA-3,5-Bis (hexa fluoro-2-hydroxy-2) containing the following hexafluoroalcohol group, etc. -propyl) cyclohexyl methacrylate) 100 g (0.2 mol), 94.06 g (0.422 mol) of di-tert-butyl dicarbonate, 4.79 g (0.038 mol) of 4-dimethylaminopyridine and 600 mL of tetrahydrofuran were added, followed by room temperature. The reaction was carried out for 20 hours. After the reaction was completed, tetrahydrofuran was removed under reduced pressure to obtain 134.6 g of the monomer of the repeating unit represented by Chemical Formula 1a (yield 96%, NMR: CH ₃ (1.93, 1.4), CH ₂ (1.64, 1.36) , CH (3.91, 2.01), H (6.15, 5.58)}.

[Preparation Example 2]

Preparation of out-of-band sunscreen 1-butoxynaphthalene

To a 1 L round-bottomed flask equipped with a stirrer and a reflux condenser, 17 g of 1-hydroxynaphthalene, 15 g of 1-bromobutane, 16 g of potassium carbonate, and 500 g of acetone were added, and the mixture was heated to 70 ° C. under nitrogen substitution. Heat and react for hours. After completion of the reaction, distillation under reduced pressure was carried out to remove acetone, which was dissolved in 500 g of ethyl acetate, and washed three times with 500 g of water using a separatory funnel. The obtained solution was concentrated under reduced pressure and dried in vacuo to obtain 21 g of 1-butoxynaphthalene represented by the formula (10).

Preparation of out-of-band sunscreen 2- (naphthalen-5yloxy) tert.butyl

To a 1 L branched round bottom flask equipped with a stirrer and a reflux condenser, 15 g of 1-hydroxynaphthalene, 15 g of 2-chloroacetic acid tert-butyl 15 g of potassium carbonate, and 500 g of acetone were added, and the mixture was heated to 70 ° C. under nitrogen substitution. It heated and reacted for 12 hours. After the reaction was distilled under reduced pressure, the acetone was removed, and then dissolved in 500 g of ethyl acetate, and washed three times with 500 g of water using a separatory funnel. The resulting solution was concentrated under reduced pressure and dried in vacuo to give 25 g of 2- (naphthalene-5yloxy) acetic acid tert-butyl as shown in the formula (10).

Preparation of out-of-band sunscreen 1-acetoxynaphthalene

 15 g of 1-hydroxynaphthalene, 11 g of triethylamine, and 100 g of methylene chloride were added to a 1 L branched round bottom flask, and the mixture was dissolved under nitrogen substitution using a round magnet rod. The reaction was time. After the reaction was washed three times with 500 g of water using a separatory funnel. The obtained solution was concentrated under reduced pressure and dried in vacuo to obtain 18 g of 1-acetoxynaphthalene represented by the formula (10).

Manufacture of water-soluble binder resin for photoresist topcoat

1-1. Synthesis of Polyacrylamide-co-poly-N-vinylcaprolactam

49.7 g (0.7 mol) of acrylamide, 41.8 g (0.3 mol) of N-vinylcaprolactam, and 11.2 g of 4,4'-azobis (4-cyanovaleric acid) were degassed with nitrogen in isopropyl alcohol ( IPA) was dissolved in 500 g and the reaction was then polymerized at 70 ° C. for 16 hours. After the polymerization was completed, the formed precipitate was filtered to obtain a copolymer (yield 90%). The obtained polymer was dissolved in 300 g of methanol, and then 300 g of IPA was added dropwise for 2 hours, followed by mixing for 3 hours to obtain 59.5 g of a purified copolymer (yield 65%). The weight average molecular weight and polydispersity of the obtained copolymer were 6,500 and 1.80, respectively.

1-2. Synthesis of Poly-N-vinylpyrrolidone-co-poly-N-vinylcaprolactam

77.8 g (0.7 mol) of N-vinylpyrrolidone, 41.8 g (0.3 mol) of N-vinylcaprolactam, and 11.2 g of 4,4'-azobis (4-cyanovaleric acid) were degassed with nitrogen. After dissolving in 500 g of coarse isopropyl alcohol (IPA), the reaction was then polymerized at 70 ° C. for 16 hours. After the polymerization was completed, the formed precipitate was filtered to obtain a copolymer (yield 82%). The obtained polymer was dissolved in 300 g of methanol, and then 300 g of IPA was added dropwise thereto for 2 hours, followed by further mixing for 3 hours to obtain 72 g of a purified copolymer (yield 60%). The weight average molecular weight and the multiple dispersion degree of the obtained copolymer were 6,200 and 1.70, respectively.

1-3. Polymerization of 5- (hexafluoro-2-hydroxyisopropylmethyl) norbonane-2-acrylate

Isopropyl alcohol (IPA) by degassing 346 g (1 mol) of 5- (hexafluoro-2-hydroxyisopropylmethyl) norbonane-2-acrylate and 11.2 g of 4,4'-azobis (4-cyanovaleric acid) ) Was dissolved in 500 g and the reaction was then polymerized at 70 ° C. for 16 hours. After the polymerization was completed, the formed precipitate was filtered to obtain a copolymer (yield 80% or more). The obtained polymer was dissolved in 300 g of methanol, and then 300 g of IPA was added dropwise for 2 hours, followed by mixing for 3 hours to filter the obtained polymer precipitate to obtain 190 g of a purified copolymer (yield 55%). The weight average molecular weight and the polydispersity of the obtained polymer were 7,500 and 1.80, respectively.

1-4. Polymerization of 1- (hexafluoro-2-hydroxy-iso-propyl) propan-2-methacrylate

294 g (1 mol) of 1- (hexafluoro-2-hydroxy-iso-propyl) propan-2-methacrylate and 11.2 g of 4,4'-azobis (4-cyanovaleric acid) were degassed with nitrogen. After dissolving in 500 g of propyl alcohol (IPA), the reaction was polymerized at 70 ° C. for 16 hours. After the polymerization was completed, the formed precipitate was filtered to obtain a copolymer (yield 80% or more). The obtained polymer was dissolved in 300 g of methanol, 300 g of isopropanol was added dropwise for 2 hours, and the obtained polymer precipitate was filtered for 3 hours to obtain 147 g of a purified copolymer (yield 50%). The weight average molecular weight and the polydispersity of the obtained polymer were 7,300 and 1.85, respectively.

1-5. Preparation of Ternary Copolymer Binder Resin

35.03 g (0.05 mol) of monomers corresponding to the repeating unit represented by Chemical Formula 1a synthesized in the preparation example and 15.22 g (0.2 mol) of the monomers corresponding to the repeating unit represented by Chemical Formula 2a, represented by Chemical Formula 3a 62.54 g (0.25 mol) of repeating monomers and 17 g of azobis (isobutyronitrile) (AIBN) initiator were dissolved in 500 g of isopropyl alcohol (IPA) degassed with nitrogen, and the reaction was then carried out at 70 ° C. for 16 hours. During the polymerization. After the polymerization was completed, the formed precipitate was filtered to obtain a crude polymer. The crude polymer was dissolved in 300 g of methanol, 300 g of isopropanol was added dropwise for 2 hours, and the polymer precipitate obtained by mixing for 3 hours was filtered to filter the ternary copolymer represented by Formula 1 7 (repeating unit in the above formula). The content indication of was obtained 53 g (yield: 47%, weight average molecular weight (Mw): 7600, PDI: 2.42) polymer for forming a resist protective film represented by mol%.

1-6. Preparation of Binary Copolymer Binder Resin

89.57 g (0.125 mol) of monomers corresponding to the repeating unit represented by Formula 1a, 32.28 g (0.375 mol) of monomers corresponding to the repeating unit represented by Formula 2a, and azobis (isobutyronitrile) (AIBN) initiator 18 g was dissolved in 500 g of degassed isopropyl alcohol (IPA), and the reaction was then polymerized at 70 ° C. for 16 hours. After the polymerization was completed, the formed precipitate was filtered to obtain a crude polymer. The crude polymer was dissolved in 300 g of methanol, 300 g of isopropanol was added dropwise for 2 hours, and the polymer precipitate obtained by mixing for 3 hours was filtered to filter the ternary copolymer represented by the formula (18). 92 g (yield: 75%, weight average molecular weight (Mw): 7514, PDI: 2.45) of the polymer for forming a resist protective film represented by the content indication were obtained in mol%.

Top coat  Preparation of the composition

After mixing the components of the following top cord composition was stirred for 6 hours to completely dissolve, the top cord composition was prepared by passing a filter made of nylon and a PTE material having a pore size of 0.01 micrometer. The composition is summarized in Table 1 below.

Water soluble binder resin
(Example number and amount of the material) Out of band sunscreen Surfactants menstruum Example 2-1 1-1, 2.5 g 0.030 g of triphenylsulfonium triflate n-octylamine
Oxide
600 ppm 4-methyl-2-pentanol, 100 g Example 2-2 1-2, 2.5 g Example 2-3 1-1, 2.5 g 0.026 g of methanesulfonic acid triphenylsulfonium Examples 2-4 1-2, 2.5 g Example 2-5 1-1, 2.5 g 0.030 g of triphenylsulfonium triflate  N-dodecylphenol ether sulfate 600 ppm Example 2-6 1-2, 2.5 g Example 2-7 1-1, 2.5 g Methanesulfonic acid triphenylsulfonium 0.026 g Example 2-8 1-2, 2.5 g Example 2-9 1-3, 2.5 g Diphenyl iodonium triflate 0.039 g n-octylamine
Oxide
600 ppm Example 2-10 1-4, 2.5 g Triphenylsulfonium Triflate 0.030g Example 2-11 1-3, 2.5 g Diphenyl iodonium triflate 0.039 g N-dodecylphenol ether sulfate 600 ppm Example 2-12 1-4, 2.5 g Triphenylsulfonium Triflate 0.030g Example 2-13 1-3, 2.5 g Phthalimidotosylate 0.023 g

For photoresist (PR)  Acid Sensitive Base Resin Synthesis

117.2 g (0.5 mol) of 2-methyl-2-adamantyl methacrylate, 23.6 g (0.1 mol) of 3-hydroxyadamantyl methacrylate, 88.9 g (0.4 mol) of norbornyllactone methacrylate and azo 6.6 g of bis (isobutyronitrile) (AIBN) was dissolved in 125 g of anhydrous tetrahydrofuran (THF), and the gas was removed using an ampoule as a freezing method. The reaction was then polymerized at 68 ° C. for 24 hours. After the polymerization was completed, the reactant was slowly dropped into excess diethyl ether, precipitated, dissolved in THF, and reprecipitated in diethyl ether to obtain a terpolymer (yield 53%). The weight average molecular weight and the multidispersity of the obtained terpolymer were 8,500 and 1.8, respectively.

Photoresist  Preparation of the composition for preparation

The photoresist was prepared by mixing the components of the photoresist composition shown in Table 2 below, stirring for 6 hours to completely dissolve, and passing a filter made of nylon having a pore size of 0.01 micron and a filter made of PTE. Surfactant FC4430 was obtained from 3M company.

ingredient Acid Sensitive Base Resin Mine generator Basic acid diffusion regulators Surfactants menstruum content 6 g of resin of Example 3 0.3 g of diphenyl paratoluenyl sulfonium nona plates 0.08 g of triethanolamine FC4430 600 ppm PGMEA 100g

For lower layer (UL)  Base Resin Synthesis

97.2 g (0.6 mol) of 4-acetoxystyrene, 52.0 g (0.4 mol) of 2-hydroxyethyl methacrylate and 6.6 g of azobis (isobutyronitrile) (AIBN) were dissolved in 125 g of anhydrous tetrahydrofuran And degassed using ampoule as a freezing method. The reaction was then polymerized at 68 ° C. for 24 hours. After the polymerization was completed, 3 L of excess water was slowly dropped and precipitated, and the filtrate was dried to obtain a pure polymer compound. The ammonia and methanol were added to the obtained compound to undergo a hydrolysis reaction at 60 degrees Celsius for 12 hours. After the reaction was completed, 3L of water was added again to obtain the desired (4-hydroxy styrene)-(2-hydroxyethyl methacrylate) copolymer. (128 g, 85% yield). The weight average molecular weight and the multiple dispersion degree of the obtained copolymer were 8,200 and 2.1, respectively.

Lower layer  Preparation of the composition for preparation

The components of the lower layer composition were mixed and stirred for 6 hours to completely dissolve, and the lower layer composition was prepared by passing a filter made of nylon having a pore size of 0.01 micrometer and a filter made of PTE. The composition is summarized in Table 3 below.

Ingredient Name Base resin Crosslinking agent Thermal acid generator Surfactants menstruum Quantity Lower layer polymer, 0.13 g 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 0.65 g Benzyl trimethylammonium tosyl acid, 0.01 g FC4430,
500 ppm PGEMA, 13.6 g

In order to compare the performance of the prepared example, the results were compared by performing an extreme ultraviolet lithography (EUVL) process. The results are summarized in Table 3 below.

EUVL exposure was performed using an ASML ADT exposure machine (0.25 NA, 0.5 sigma). Commonly, the photoresist underlayer was 33 nm thick using the one prepared in Example 5, and the photoresist layer was used in Example 4. Using the manufactured material, a mask was formed such that the thickness was 60 nm and the top coat layer was 33 nm. Curing bake temperature of the lower layer (220 ℃), after the photoresist coating the soft bake process 110 seconds to 110 ℃, after the top coat coating the soft bake process was performed to 105 ℃ 60 seconds. After the photoresist exposure, the baking process was performed at 125 ° C. for 60 seconds and the developing process was performed for 30 seconds using a 2.38% TMAH aqueous solution. During the process, the film thickness was measured using the KLA's Opti-2600 measurement equipment, and the CD-SEM was measured using the S9220 instrument from Hitachi, Japan, to measure the resolution, LWR, scum, profile, and CD uniformity. .

Scum determined the presence by measuring the top-down profile in the S9220 device by measuring the degree of photoresist removal of the exposed part, and the profile was also determined by measuring the top-down picture of the CD SEM device. CD uniformity was judged to be good if the 3 sigma standard deviation of CD measurements was 3.3 nanometers or less, and was determined to be "bad" if the standard deviation was 3.3 nanometers or more.

In order to verify the effect of the present invention, the experiment was performed by applying the lower layer and the photoresist layer without applying the top coating layer as a comparative example experiment.

Test results patterned with extreme ultraviolet lithography (EUVL) Photoresist layer Top coat resolution LWR Scum control profile CD uniformity Comparative Example 1 Do not use > 32 nm 5.5 nm Partial remnant Slop Bad Example 6-1 Example 2-1 <32 nm 1.5 nm No scum Rectangle Good Example 6-2 Example 2-2 <32 nm 1.6 nm No scum Rectangle Good Example 6-3 Example 2-3 <32 nm 1.2 nm No scum Rectangle Good Example 6-4 Examples 2-4 <32 nm 1.8 nm No scum Rectangle Good Example 6-5 Example 2-5 <32 nm 1.4 nm No scum Rectangle Good Example 6-6 Examples 2-6 <32 nm 1.5 nm No scum Rectangle Good Example 6-7 Examples 2-7 <32 nm 1.3 nm No scum Rectangle Good Example 6-8 Examples 2-8 <32 nm 1.1 nm No scum Rectangle Good Example 6-9 Examples 2-9 <32 nm 1.2 nm No scum Rectangle Good Example 6-10 Example 2-10 <32 nm 1.3 nm No scum Rectangle Good Example 6-11 Examples 2-11 <32 nm 1.0 nm No scum Rectangle Good Example 6-12 Example 2-12 <32 nm 1.2 nm No scum Rectangle Good Example 6-13 Example 2-13 <32 nm 0.9 nm No scum Rectangle Good

5 is a CD-SEM photograph of the pattern obtained by the lithography process of Example 6-8. It can be seen that the thickness of the line width is even and the outline of the line width is close to the straight line with almost no bend. The pattern of Example 6-8 was very good with LWR of 1.1 nm.

Through the above data, it was confirmed that the topcoat composition of the present invention and the pattern forming method using the same could satisfactorily satisfy the incompatible conditions of high resolution of 30 nm or less, even LWR, and distinct pattern profile.

In order to examine the performance of the topcoat without using a surfactant, the terpolymer copolymer resin synthesized in Example 1-5 or the binary copolymer binder resin synthesized in 1-6 and the naphthalene-based out-of-band ultraviolet ray of the formula (10) Photoresist topcoats containing the blocking agents and photoresists of Table 2 were prepared and subjected to extreme ultraviolet lithography (EUVL) processes to test their performance. Topcoat compositions (Comparative Examples 2 and 3), which were not equipped with an out-of-band sunscreen as a comparative topcoat, were also prepared and subjected to an extreme ultraviolet lithography process and tested for performance.

The composition of the photoresist topcoat composition is summarized in Table 5 below.

Composition Water soluble binder resin Out of band sunscreen
(Parts by weight of binder resin) menstruum Comparative Example 2 Examples 1-5 0 4-methyl-2pentanol Example 7-1 Examples 1-5 1-butoxynaphthalene (5) Example 7-2 Examples 1-5 1-butoxynaphthalene (10) Example 7-3 Examples 1-5 2- (naphthalen-5yloxy) acetic acid tert-butyl (10) Example 7-4 Examples 1-5 1-acetoxynaphthalene (10) Comparative Example 3 Examples 1-6 0 Example 7-5 Examples 1-6 1-butoxynaphthalene (5) Example 7-6 Examples 1-6 1-butoxynaphthalene (10) Example 7-7 Examples 1-6 2- (naphthalen-5yloxy) acetic acid tert-butyl (10) Example 7-8 Examples 1-6 1-acetoxynaphthalene (10)

EUVL exposure was performed using an ASML ADT exposure machine (0.25 NA, 0.5 sigma). Commonly, the lower layer film was formed to have a thickness of 33 nm using Example 5, the photoresist layer to have a thickness of 60 nm using Example 3, and the top coat shown in Table 6 below to have a thickness of 30 nm. The lower layer film curing temperature was 220 ℃, after the photoresist coating bake process 110 ℃ / 60 seconds, the top coat coating baking process proceeded to 90 ℃ / 60 seconds respectively. After the photoresist exposure, the baking process was performed at 125 ° C./60 seconds, and the developing process was performed for 30 seconds using a 2.38% TMAH aqueous solution. During the process, the film thickness was measured using the KLA company's measuring equipment, Opti-2600, and CD-SEM was measured using the Hitachi S9220 instrument to measure the resolution, LWR, scum, profile, and CD uniformity. The light absorption spectrum of each wavelength was investigated.

The performance test results are summarized in Table 6 below. The performance evaluation method is the same as that of Example 6 mentioned above.

Top coat definition LWR Scum control profile CD uniformity Comparative Example 2 <32 nm 5.4 nm No scum Right angle Good Example 7-1 <32 nm 3.2 nm No scum Right angle Good Example 7-2 <32 nm 2.9 nm No scum Right angle Good Example 7-3 <32 nm 3.2 nm No scum Right angle Good Example 7-4 <32 nm 3.1 nm No scum Right angle Good Comparative Example 3 <32 nm 5.3 nm No scum Right angle Good Example 7-5 <32 nm 2.8 nm No scum Right angle Good Example 7-6 <32 nm 2.7 nm No scum Right angle Good Example 7-7 <32 nm 2.7 nm No scum Right angle Good Example 7-8 <32 nm 3.0 nm No scum Right angle Good

In the data of Table 6, the mask using the top coat without the out-of-band sunscreen was excellent in terms of resolution, scum generation, profile, and CD uniformity, but the mask using the topcoat of the present invention using the out-of-band sunscreen was used. Compared to this, the line width roughness LWR was very poor.

Therefore, it was confirmed that the line width roughness is greatly improved when the extreme ultraviolet lithography is performed using the composition for forming the photoresist topcoat of the present invention.

6 is an ultraviolet absorption spectrum of a mask using the photoresist topcoat of Examples 7-1 to 7-4. As shown in the graph of Figure 6 it can be seen that the mask formed using the top-coat composition for extreme ultraviolet lithography of the present invention has a high ultraviolet absorbance in the deep ultraviolet region of 100 ~ 300 nm.

Optimal embodiments of the present invention described above have been disclosed. Although specific terms have been used herein, they are used only for the purpose of describing the present invention in detail to those skilled in the art, and are not used to limit the scope of the present invention as defined in the meaning or claims.

Claims (13)

100 parts by weight of water-soluble binder resin;
0.01 to 30 parts by weight of an extreme ultraviolet out-of-band sunscreen; And
A composition for forming a photoresist topcoat comprising 1,000 to 10,000 parts by weight of a protic solvent. The method of claim 1, wherein the water-soluble binder resin is a carboxyl group, carboxamide group, hydroxy group, N-substituted lactam group, N-substituted imidazole group, 2-hexafluoroisopropanolyl group and 2-hexafluoroisopropanolylalkyl group A photoresist topcoat composition, characterized in that it is a homopolymer of a vinyl monomer having a selected side chain or a copolymer of such a vinyl monomer with a vinyl monomer not having said selected side chain. The method of claim 2,
The vinyl monomer having no selected side chain is any one or more selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate. The composition of claim 1, wherein the water-soluble binder resin is a homopolymer of any one of the repeating units represented by Formula 19 or a copolymer of these repeating units:
[Chemical Formula 19]

In this case, in Formula 19, R ₁ is a hydrogen atom (H), a fluorine atom (F), a methyl group (-CH ₃ ), a fluorinated alkyl group of 1 to 20 carbon atoms or a hydroxyalkyl group of 1 to 5 carbon atoms,
X is a substituent represented by the formula (20),
[Chemical Formula 20]

m is the number of X, 1 or 2,
when m is 1, R ₂ in the formula (19) is a linear or branched alkylene group or alkylidene group having 1 to 10 carbon atoms, or a cyclic alkylene group or alkylidene group having 5 to 10 carbon atoms,
When m is 2, R ₂ in the formula (19) is a straight chain, branched or cyclic hydrocarbine hydrocarbon having three bonds as a hydrocarbon having 1 to 10 carbon atoms. The composition of claim 1, wherein the water-soluble binder resin is selected from any one of copolymers represented by the following Chemical Formulas 21 to 23.
[Chemical Formula 21]

[Chemical Formula 22]

(23)

In this Formula 21 to 23, R ₁ , R ₂ , X and m are as defined in claim 4,
In Formulas 21 and 22, p is an integer of 0 to 3, R ₃ is a hydrogen atom, or an alkyl group having 1 to 25 carbon atoms containing at least one hydroxy group (-OH) or carboxyl group (-COOH),
In Formulas 22 and 23, R ₄ is an alkyl group having 1 to 25 carbon atoms unsubstituted or substituted with one or more fluorine atoms,
In Formula 23, q is an integer of 0 to 3,
In Formula 21, the value of a is 1 to 99% by weight, and the value of b is 1 to 99% by weight and a + b = 100% by weight.
In Formula 22, the value of a is 1 to 98% by weight, the value of b is 1 to 98% by weight, and the value of c is 1 to 98% by weight and a + b + c = 100. Weight percent
In Formula 23, the value of a is 1 to 98% by weight, the value of c is 1 to 98% by weight, the value of d is 1 to 98% by weight and a + c + d = 100. Weight percent. The composition of claim 1, wherein the extreme ultraviolet light-blocking UV blocker has a main absorption wavelength of 100 nm to 300 nm. 7. The photoresist topcoat formation according to claim 6, wherein the extreme ultraviolet out-of-band sunscreen is selected from the group consisting of water-soluble sulfonic acid esters, salts of sulfonic acid esters, sulfonium compounds, iodonium compounds, and oxime compounds. Composition. According to claim 7, wherein the extreme ultraviolet out-of-band sunscreen agent is phthalimidotrifluoromethane sulfonate (phthalimidotrifluoromethane sulfonate), phthalimidotosylate (phthalimidotosylate), dinitrobenzyl tosylate, naphthylimidotrifluoromethane Naphthylimidotrifluoromethane sulfonate, triphenylsulfonium methanesulfonate, diphenyliodonium triflate, diphenyliodonium nonaplate, hexafluorophosphate diphenyliodonium, hexafluorobisoric acid ) Diphenyl iodonium, hexafluoro antimonic acid diphenyl iodonium, diphenyl paramethoxy phenylsulfonium triflate, diphenyl paratoluenyl sulfonium triflate, diphenyl para tert-butyl phenyl sulfonium triflate, Diphenylparaisobutylphenylsulfonium triflate, triphenylsulfonium triflate, trispar tertiary butyl pen Sulfonium triflate, diphenylparamethoxyphenylsulfonium nonaplate, diphenylparatoluenylsulfonium nonaplate, diphenylpara tert-butylphenylsulfonium nonaplate, diphenylparaisobutylphenylsulfonium nonaplate, triphenyl Feature selected from the group consisting of sulfonium nona plate, trispara tert-butyl phenylsulfonium nona plate, hexafluoroarsenic acid triphenylsulfonium, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate and mixtures thereof A composition for forming a photoresist topcoat. 7. The composition of claim 6, wherein the extreme ultraviolet light-blocking sunscreen agent is a material represented by the following Chemical Formula 24.
[Formula 24]

In Formula 24, B is an alkyl group or alicyclic substituent having 1 to 10 carbon atoms,
m is an integer of 0 to 8, n is a natural number of 1 to 8, m + n ≤ 8,
When there are several B in the naphthalene ring, each B may be the same or different from each other,
A is a hydroxyl group, a carboxyl group (-COOH), an ether group or an ester group (-COOR),
When there are a plurality of A in the naphthalene ring, each A may be the same or different composition for forming a photoresist topcoat. The method according to claim 1, wherein the protic solvent comprises methanol, isopropanol, ethanol, butanol, water, isobutanol, 4-methyl-2-pentanol, cyclopentanol, normalpentanol, glycerol, propanol and isoamyl ether A composition for forming a photoresist topcoat, characterized in that at least one selected from the group. The method of claim 1, wherein the composition for forming a photoresist topcoat further comprises a surfactant, and the amount of the surfactant is 0.00001 to 100 parts by weight of the total weight of the composition excluding the surfactant. The composition for forming a photoresist topcoat, characterized in that 0.1 parts by weight. Sequentially depositing a photoresist underlayer, a photoresist layer of a desired circuit pattern, and a photoresist topcoat formed from the composition of claim 1 on a substrate to obtain a photolithography mask;
An exposure step of dissolving a mask according to the pattern by irradiating extreme ultraviolet rays to the laminate;
A developing step of selectively removing the dissolved part of the exposed mask; And
Forming a pattern on the substrate by etching the substrate on which the developed mask is laminated. The method of claim 12, wherein the stacking of the photoresist layer is performed.
100 parts by weight of acid sensitive base resin;
0.5 to 10 parts by weight of photoacid generator;
0.01 to 5 parts by weight of a basic acid diffusion regulator;
Stacking a composition comprising 1,000 to 10,000 parts by weight of an organic solvent on the photoresist underlayer; and
Soft baking the laminated composition,
Wherein the acid sensitive base resin is a polymer which is insoluble in the alkaline developer but becomes soluble in the alkaline developer after reacting with the proton.

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