WO2024224654A1 - Poly-arm-type resin having polyamide structure or heterocyclic structure, lithography film-forming composition containing same, and production method - Google Patents

Abstract

Provided is a resin excellent in film-forming property.　This poly-arm-type resin having a polyamide structure is produced by a method comprising: (I) a step for preparing a diamino compound represented by formula (A) and a tricarboxylic acid-based compound represented by formula (B) (in the formulae, Y represents an alkylene group optionally having a fluorine atom, Z independently represents -OH, -SH, or -NH₂, each R independently represents a hydrogen atom, an alkyl group having 1-30 carbon atoms and optionally having a substituent, or the like, m is an integer of 1-3 and is the number of the groups represented by R in the case where R is a group other than hydrogen atom, Ar is a group having an aromatic group, E is -COOH, -COHal, -O-R^b-COOH, or -O-R^b-COHal, Hal is a halogen atom, and R^b is an alkylene group having 1-6 carbon atoms); and (II) a step for causing condensation reaction of these compounds to form a polyamide structure.

Description

Polyamide or heterocyclic structure-containing hyperbranched resin, lithographic film-forming composition containing same, and method for producing same

The present invention relates to a polybranched resin having a polyamide structure or a heterocyclic structure, a lithography film-forming composition containing the same, and a manufacturing method.

Polybenzoxazole (PBO) resin has excellent heat resistance, chemical resistance, and mechanical properties, and is therefore expected to be used in a variety of applications. However, because this resin has a rigid structure, it has poor solubility and film-forming properties. Therefore, PBO with branched chains has been proposed (for example, Non-Patent Document 1).

Hiroto Kudo et. al., Journal of Polymer Science Part A Polymer Chemistry 44(11):3640 - 3649 (2006).

The resin described in Non-Patent Document 1 is amorphous and soluble in solvents. However, there is room for improvement in terms of film-forming properties. In view of these circumstances, the objective of the present invention is to provide a resin with excellent film-forming properties.

The inventors have found that a resin having a group with a specific structure introduced therein can solve the above problems.
Aspect 1
(I) preparing a diamino compound represented by formula (A) and a tricarboxylic acid compound represented by formula (B)
(II) a step of subjecting these compounds to a condensation reaction to form a polyamide structure;
Manufactured by a method comprising:
A hyperbranched resin with a polyamide structure.
Aspect 2
2. The resin according to claim 1, wherein Y in the formula is a branched alkylene group.
Aspect 3
3. The resin of claim 1 or 2, wherein Y in the formula is a fluorinated alkylene group.
Aspect 4
(i) preparing a hyperbranched resin having a polyamide structure according to any one of aspects 1 to 3; and (ii) intramolecularly condensing the resin to form a heterocyclic structure.
Manufactured by a method comprising:
A hyperbranched resin with a heterocyclic structure.
Aspect 5
There are units in which Y is an alkylene group and units in which Y is a fluorinated alkylene group,
5. The resin of claim 4, wherein the molar ratio of alkylene groups to fluorinated alkylene groups is 1:(1.5 to 10).
Aspect 6
A lithographic film-forming composition comprising the resin according to any one of aspects 1 to 5.
Aspect 7
A lithography underlayer film-forming composition comprising the resin according to embodiment 3.
Aspect 8
8. The composition of claim 6 or 7, comprising a solvent.
Aspect 9
Aspect 9. The composition of any of aspects 6 to 8, comprising a component selected from the group consisting of a solvent, an acid generator, an acid crosslinker, and combinations thereof.
Aspect 10
A lithographic underlayer film formed using the composition of embodiment 7.
Aspect 11
A lithographic underlayer film comprising the resin of embodiment 4 or 5.
Aspect 12
forming an underlayer film on a substrate using the composition according to embodiment 7, and heating the precursor to 300° C. or higher to form an underlayer film containing a hyperbranched resin having a heterocyclic structure;
forming at least one photoresist layer on the underlayer film; and irradiating a predetermined area of the photoresist layer with radiation and developing the photoresist layer.
A method for forming a resist pattern comprising the steps of:
Aspect 13
A hyperbranched resin having a polyamide structure represented by the formula (1) described below.
Aspect 14
A hyperbranched resin having a heterocyclic structure represented by formula (2) described below.
Aspect 15
The resin according to aspect 13 or 14, wherein X in the formula is represented by any one of formulas (X1) to (X4) described below.

We can provide resins with excellent film-forming properties.

¹ H-NMR and ¹³ C-NMR spectra of the tricarboxylic acid intermediate FT-IR spectrum of tricarboxylic acid intermediate ^1H -NMR spectrum of tricarboxylic acid compounds ^1H -NMR spectrum of hyperbranched PA resin GPC chart of hyperbranched PA resin ¹ H-NMR and ¹³ C-NMR spectra of tricarboxylic acid compounds ^1H -NMR spectrum of hyperbranched PA resin GPC chart of hyperbranched PA resin TGA (thermogravimetric analysis) chart of hyperbranched PA resin GPC chart of hyperbranched PA resin GPC chart of hyperbranched PA resin FT-IR spectrum of hyperbranched PA resin FT-IR spectrum of hyperbranched PBO resin TGA (thermogravimetric) chart of hyperbranched PBO resin

1. Hyperbranched resin having a polyamide structure In one embodiment, a hyperbranched resin having a polyamide structure is obtained by reacting a diamino compound represented by formula (A) with a tricarboxylic acid compound represented by formula (B). The hyperbranched resin is a resin having a branched chain bonded to the main chain, and the branched chain is not so long as to form a gel. In the present disclosure, "X to Y" include the end values.

(1) (A) Diamino Compound The diamino compound represented by formula (A) (hereinafter also referred to as "compound A") is a compound essentially containing two amino groups. The amino groups are preferably primary amino groups. In addition to the two amino groups, compound A has a group Z. The group Z is selected from the group consisting of -OH, -SH, -NH ₂ , and combinations thereof.

 

 

Y is an alkylene group which may contain fluorine. Examples of Y include an alkylene group having 1 to 6 carbon atoms and a fluorinated alkylene group having 1 to 6 carbon atoms. The number of carbon atoms in these groups is more preferably 1 to 3. Y is preferably a branched alkylene group or a branched fluorinated alkylene group. From the viewpoint of availability, etc., Y is preferably -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -CH(CF ₃ )-, -C(CF ₃ ) ₂ -, etc.

Z is independently -OH, -SH, or _-NH2 . Among them, from the viewpoint of solubility in a solvent or ease of availability of a polyamide structure-containing multi-branched resin, Z is preferably -OH.

R is each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an aralkyl group having 7 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an arylalkenyl group having 7 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a cyano group, a carboxylic acid group, a thiol group, or a hydroxyl group. The aryl group, aralkyl group, alkenyl group, alkynyl group, and arylalkenyl group may contain an ether bond, a ketone bond, an ester bond, or a urethane bond. However, in consideration of heat resistance, etc., R is preferably a hydrogen atom.

m is the number of groups other than hydrogen when R is a group other than hydrogen, and is an integer from 1 to 3. When R is a group other than hydrogen, m is preferably 1 in consideration of heat resistance, etc. Examples of preferred embodiments of compound A are shown below.

 

 

(2) (B) Tricarboxylic Acid Compound The tricarboxylic acid compound represented by formula (B) (hereinafter also referred to as "compound B") is a compound having three carboxyl groups or groups derived therefrom.

 

 

Ar is a group having an aromatic group. Ar is not limited to, but may be, for example, an aryltriyl group obtained by removing three hydrogen atoms from an aromatic compound, or a group obtained by removing three hydrogen atoms from the aromatic ring of a triarylalkane.

E is -COOH, -COHal, -O-R ^b -COOH or -O-R ^b -COHal. Hal is a halogen atom, preferably a chlorine atom. R ^b is an alkylene group having 1 to 6 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms. More preferably, R ^b is a methylene group or an ethylene group. Preferred embodiments of compound B are exemplified below.

 

 

(3) Structure The resin (hereinafter, for convenience, also referred to as "hyperbranched PA resin") is obtained by a condensation reaction of compound A and compound B. This reaction produces an amide bond, resulting in a polymer having a polyamide structure. The structure of the hyperbranched PA resin is represented as follows.

In the formula, Y, Z, R, and m are defined as above. n is the number of repetitions in the main chain, and r is the number of repetitions in the branched chain, where n>r. n is not limited, but is preferably 1 to 100, and more preferably 2 to 30. If r is too large, gelation will occur, and if r is too small, solubility in the solvent will decrease. r is selected so that the hyperbranched PA resin does not gel and exhibits solubility. In one embodiment, r can be approximately 10 to 60% of n.

(4) Characteristics The hyperbranched PA resin has flexibility due to the presence of Y, and has a moderately low density due to the branched chain. Therefore, it has good solubility in a solvent and good film-forming properties. Furthermore, when Y is a part or all of a fluorinated alkylene group, the density of the resin is appropriately reduced and the solubility is further increased, which is preferable. Furthermore, when Y is a part or all of a fluorinated alkylene group, deterioration of the resin can be avoided when the hyperbranched PA resin is subjected to intramolecular condensation. When a unit in which Y is an alkylene group and a unit in which Y is a fluorinated alkylene group are present, the molar ratio of the alkylene group to the fluorinated alkylene group is preferably 1:(1.5 to 10), more preferably 1:(2 to 6).

The resin is useful as a lithography material. In addition, since the resin has a high refractive index, it is also useful as an optical component. Furthermore, since the amino group reacts with Z to form a ring, the multi-branched PA resin can be converted into a resin having a heterocyclic structure. Resins having a heterocyclic structure have extremely high heat resistance and are useful as lithography films, particularly as lithography underlayer films.

2. Method for Producing Hyperbranched PA Resin Hyperbranched PA resin is obtained by condensing compound A and compound B. The charge ratio is selected so as to produce a desired molecular weight and branched chain. The charge ratio of the two can be determined as the ratio of functional group equivalents forming an amide bond. The functional group equivalent ratio (functional group equivalent of compound A: functional group equivalent of compound B) is preferably (1-2):1, more preferably (1.1-1.6):1. The reaction temperature is selected so as not to produce a gel, and is 20-40°C in one embodiment. The reaction time is not limited, and can be, for example, about 20-72 hours.

If the amount of solvent is small, gelation is likely to occur, and if it is large, production efficiency decreases. In one embodiment, the amount of solvent is 8 to 10 parts by weight per 1 part by weight of the total amount of compounds A and B. The solvent is preferably an aprotic solvent such as NMP (N-methylpyrrolidone) or DMF (dimethylformamide). The reaction is preferably carried out under an inert atmosphere. Also, a known condensing agent can be used for the condensation reaction.

3. Multibranched resin having a heterocyclic structure The resin (hereinafter, for convenience, also referred to as "multibranched heterocyclic resin") is obtained by subjecting a multibranched PA resin to an intramolecular condensation reaction. Through this reaction, the amino group and Z form a heterocyclic structure. As described above, it is preferable that a part or all of Y is a fluorinated alkylene group. When there are units in which Y is an alkylene group and units in which Y is a fluorinated alkylene group, the molar ratio of the alkylene group:fluorinated alkylene group is preferably 1:(1.5 to 10), and more preferably 1:(2 to 6). The structure of the resin is preferably represented as follows:

 

 

^Y1 and ^Y2 are derived from Y of the hyperbranched PA resin. ^Y1 is a fluorinated alkylene group, and ^Y2 is an alkylene group. The alkylene group is as described for the hyperbranched PA resin.

Z' is derived from Z in hyperbranched PA resin. Z' is independently -O-, -S-, or -NH-. From the standpoint of ease of synthesis, etc., Z' is preferably -O-. In this case, the heterocycle is a benzoxazole ring, so the resin in this case is also called a "hyperbranched PBO resin."

X is a group having an aromatic group derived from Ar of the hyperbranched PA resin. X is preferably a group represented by the following formula:

Ar is an aromatic group, as described above for the hyperbranched PA resin. ^Rb is an alkylene group having 1 to 6 carbon atoms, and preferred embodiments thereof are as described above for the hyperbranched PA resin.

R and m are as explained for hyperbranched PA resin.

ⁿ¹ and ⁿ² are the repeat numbers in the main chain. ^r1 and ^r2 are the repeat numbers in the branched chain. ⁿ¹ > ^r1 and ⁿ² > ^r2 . The sum of ⁿ¹ and ⁿ² corresponds to n of the hyperbranched PA resin, and the sum of ^r1 and ^r2 corresponds to r of the hyperbranched PA resin. The ratio of ⁿ¹ : ⁿ² and ^r1 : ^r2 depends on the ratio of Y1: ^Y2 . For example, when the hyperbranched PA resin does not contain a fluorinated alkylene as Y, ⁿ¹ and ^r1 in formula (2 ⁾ are 0. In one embodiment, the sum of ^r1 and ^r2 can be about 10 to 60% of the sum of ⁿ¹ and ⁿ² .

4. Method for Producing Hyperbranched Heterocyclic Resin The resin is produced by a method comprising the steps of (i) preparing a hyperbranched PA resin, and (ii) intramolecularly condensing the resin to form a heterocyclic structure. Step (i) is as described above. Step (ii) can be carried out by heating the hyperbranched PA resin to 250° C. or higher. The temperature is preferably 300 to 320° C. This step is preferably carried out under an inert atmosphere.

　Multi-branched heterocyclic resins have extremely high chemical resistance. For this reason, it is preferable to cast the precursor multi-branched PA resin into the desired shape (such as a membrane) and then carry out this process in that state.

5. Composition [Composition]
The hyperbranched resin is suitable for lithography or optical article applications, and is therefore useful in compositions for such applications.

Lithographic Film-Forming Composition
The lithography film-forming composition is a composition containing the hyperbranched resin as an essential component, and preferably contains a solvent. The composition can reduce defects in the film (thin film formation), has good storage stability, has high sensitivity, a high refractive index in a specific wavelength region, heat resistance, and chemical resistance, and can provide a good resist pattern shape. From the viewpoint of solubility in the solvent, the hyperbranched resin is preferably a hyperbranched PA resin.

(Physical properties of lithography film-forming composition, etc.)
The composition can be used to form an amorphous film by a known method such as spin coating. Depending on the type of developer used, either a positive resist pattern or a negative resist pattern can be produced. The following describes the use of the composition as a resist composition.

When the lithography film-forming composition is a positive resist pattern, the dissolution rate of the amorphous film formed by spin coating in a developer at 23°C is preferably 5 Å/sec or less, more preferably 0.0005 to 5 Å/sec, and even more preferably 0.05 to 5 Å/sec. If the dissolution rate is 5 Å/sec or less, the resist can be insoluble in the developer. If the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. This is presumably because the change in solubility of the resin before and after exposure increases the contrast at the interface between the exposed portion that dissolves in the developer and the unexposed portion that does not dissolve in the developer. It also has the effect of reducing line edge roughness and defects.

When the lithography film-forming composition is a negative resist pattern, the dissolution rate of the amorphous film formed by spin coating in a developer at 23°C is preferably 10 Å/sec or more. When the dissolution rate is 10 Å/sec or more, the film is easily soluble in the developer, making it more suitable for use as a resist. In addition, a dissolution rate of 10 Å/sec or more may improve resolution. This is presumably because the microscopic surface portion of the resin dissolves, reducing line edge roughness. There is also an effect of reducing defects. The dissolution rate can be determined by immersing the amorphous film in a developer at 23°C for a predetermined time and measuring the film thickness before and after the immersion by a known method such as visual observation, an ellipsometer, or a QCM method.

In the case of a positive resist pattern, the dissolution rate in a developer at 23°C of the portion of the amorphous film formed by spin coating that has been exposed to radiation such as a KrF excimer laser, extreme ultraviolet light, electron beam or X-ray is preferably 10 Å/sec or more. A dissolution rate of 10 Å/sec or more means that the film is easily soluble in a developer, making it more suitable for use as a resist. A dissolution rate of 10 Å/sec or more may also improve resolution. This is presumably because the micro surface portions of the resin dissolve, reducing line edge roughness. There is also an effect of reducing defects.

In the case of a negative resist pattern, the dissolution rate in a developer at 23°C of the portion of the amorphous film formed by spin coating that has been exposed to radiation such as a KrF excimer laser, extreme ultraviolet light, electron beam or X-ray is preferably 5 Å/sec or less, more preferably 0.0005 to 5 Å/sec, and even more preferably 0.05 to 5 Å/sec. If the dissolution rate is 5 Å/sec or less, the resist can be insoluble in the developer. Furthermore, if the dissolution rate is 0.0005 Å/sec or more, the resolution may be improved. This is presumably because the change in solubility of the resin before and after exposure increases the contrast at the interface between the unexposed portion that dissolves in the developer and the exposed portion that does not dissolve in the developer. It also has the effect of reducing line edge roughness and defects.

(Other ingredients)
The solvent used in the lithography film-forming composition is not particularly limited, and those disclosed in WO 2020/226150 can be used. The solvent is preferably a safe solvent, more preferably at least one selected from PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), CHN (cyclohexanone), CPN (cyclopentanone), 2-heptanone, anisole, butyl acetate, ethyl propionate, and ethyl lactate, and more preferably at least one selected from PGMEA, PGME, and CHN. In addition, it may be a mixed solvent by combining these solvents.

In the composition, the relationship between the amount of the solid component and the amount of the solvent is not particularly limited, but may be the following, with the total weight of the solid component and the solvent being 100% by weight:
Solid content: 1-80% by weight; Solvent: 20-99% by weight
Solid content 1-50% by weight: Solvent 50-99% by weight
Solid content: 2-40% by weight; Solvent: 60-98% by weight
Solid content: 2-10% by weight; Solvent: 90-98% by weight

The composition may contain at least one solid component selected from the group consisting of an acid generator (C), an acid crosslinker (G), an acid diffusion controller (E), and other components (F).

In the composition, the content of the hyperbranched resin is not particularly limited, but is preferably 50 to 99.4% by weight of the total weight of solid components (the sum of optional solid components such as the resin, acid generator (C), crosslinking agent (G), acid diffusion controller (E) and other components (F), the same applies below), more preferably 55 to 90% by weight, even more preferably 60 to 80% by weight, and particularly preferably 60 to 70% by weight. With this content, the resolution is further improved and the line edge roughness (LER) is further reduced.

(Acid Generator (C))
The composition preferably contains one or more acid generators (C) that generate an acid directly or indirectly when irradiated with any radiation selected from visible light, ultraviolet light, an excimer laser, an electron beam, extreme ultraviolet light (EUV), X-rays, and an ion beam.

In this case, the content of the acid generator (C) in the composition is preferably 0.001 to 49 wt %, more preferably 1 to 40 wt %, even more preferably 3 to 30 wt %, and particularly preferably 10 to 25 wt % of the total weight of the solid components. By using the acid generator (C) within the above content range, a pattern profile with higher sensitivity and lower edge roughness can be obtained.

As long as the composition generates an acid within the system, there are no limitations on the method of generating the acid. If an excimer laser is used instead of ultraviolet rays such as g-rays or i-rays, finer processing is possible, and if high-energy rays such as electron beams, extreme ultraviolet rays, X-rays, or ion beams are used, even finer processing is possible.

The acid generator (C) is not particularly limited, and examples thereof include the compounds disclosed in International Publication No. 2017/033943. As the acid generator (C), an acid generator having an aromatic ring is preferable, an acid generator having a sulfonate ion with an aryl group is more preferable, and diphenyltrimethylphenylsulfonium p-toluenesulfonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluorobutanesulfonate are particularly preferable. By using such an acid generator, line edge roughness can be reduced.

The composition preferably further contains a diazonaphthoquinone photoactive compound described in WO 2020/226150 as an acid generator. Among these, from the viewpoint of low roughness and solubility, a non-polymeric diazonaphthoquinone photoactive compound is preferable, more preferably a low molecular weight compound having a molecular weight of 1500 or less, even more preferably a molecular weight of 1200 or less, and particularly preferably a molecular weight of 1000 or less. A preferred example of such a non-polymeric diazonaphthoquinone photoactive compound is the non-polymeric diazonaphthoquinone photoactive compound disclosed in WO 2016/158881. The acid generator (C) can be used alone or in combination with two or more kinds.

(Crosslinking Agent (G))
When the resist is used as a negative resist material or as an additive for increasing the strength of the pattern in a positive resist material, it is preferable to include one or more crosslinking agents (G). The crosslinking agent is preferably an acid crosslinking agent. The acid crosslinking agent (G) is a compound capable of intramolecular or intermolecular crosslinking of the resin in the presence of an acid generated from the acid generator (C). Such an acid crosslinking agent (G) is not particularly limited, but may be, for example, a compound having one or more groups capable of crosslinking the resin (hereinafter referred to as "crosslinkable group").

Specific examples of such crosslinkable groups include, but are not limited to, those described in WO 2020/226150. As the crosslinkable group of the acid crosslinker (G), hydroxyalkyl groups and alkoxyalkyl groups are preferred, and alkoxymethyl groups are particularly preferred.

The acid crosslinking agent (G) having a crosslinkable group is not particularly limited, but examples thereof include those described in WO 2020/226150.

Further examples of the acid crosslinking agent (G) that can be used include compounds having a phenolic hydroxyl group as described in WO 2020/226150, as well as compounds and resins that have been given crosslinkability by introducing the crosslinkable group into the acidic functional group in an alkali-soluble resin.

In the composition, the acid crosslinker (G) is preferably an alkoxyalkylated urea compound or a resin thereof, or an alkoxyalkylated glycoluril compound or a resin thereof (acid crosslinker (G1)), a phenol derivative having 1 to 6 benzene rings in the molecule and having two or more hydroxyalkyl groups or alkoxyalkyl groups throughout the molecule, with the hydroxyalkyl groups or alkoxyalkyl groups bonded to any of the benzene rings (acid crosslinker (G2)), or a compound having at least one α-hydroxyisopropyl group (acid crosslinker (G3)). Examples include the compounds disclosed in WO 2017/033943.

In the composition, the content of the acid crosslinking agent (G) is preferably 0.5 to 49% by weight, more preferably 0.5 to 40% by weight, even more preferably 1 to 30% by weight, and particularly preferably 2 to 20% by weight, of the total weight of the solid components. A content of the acid crosslinking agent (G) of 0.5% by weight or more is preferable because it improves the effect of suppressing the solubility of the resist film in an alkaline developer and can suppress a decrease in the remaining film rate and the occurrence of swelling and meandering of the pattern, while a content of 49% by weight or less is preferable because it can suppress a decrease in the heat resistance of the resist.

The content of at least one compound selected from the acid crosslinker (G1), the acid crosslinker (G2), and the acid crosslinker (G3) in the acid crosslinker (G) is not particularly limited, and can be in various ranges depending on the type of substrate used when forming the resist pattern, etc.

(Acid Diffusion Controller (E))
The composition may contain an acid diffusion controller (E) that has the effect of controlling the diffusion of the acid generated from the acid generator by radiation exposure in the resist film, thereby preventing undesirable chemical reactions in unexposed regions. By using such an acid diffusion controller (E), the storage stability of the composition is improved. In addition, the resolution is further improved, and the line width change of the resist pattern caused by the variation of the exposure time before and after radiation exposure can be suppressed, resulting in extremely excellent process stability.

Such an acid diffusion controller (E) is not particularly limited, and examples thereof include radiolytic basic compounds such as nitrogen atom-containing basic compounds, basic sulfonium compounds, and basic iodonium compounds. Examples of the acid diffusion controller (E) include the compounds disclosed in WO 2017/033943. The acid diffusion controller (E) may be used alone or in combination of two or more kinds.

The content of the acid diffusion control agent (E) is preferably 0.001 to 49% by weight, more preferably 0.01 to 10% by weight, even more preferably 0.01 to 5% by weight, and particularly preferably 0.01 to 3% by weight, based on the total weight of the solid components. When the content of the acid diffusion control agent (E) is within the above range, the deterioration of the resolution, pattern shape, dimensional fidelity, etc. can be further suppressed. Furthermore, even if the waiting time from electron beam irradiation to heating after radiation irradiation is long, the shape of the upper layer of the pattern does not deteriorate. Furthermore, when the content of the acid diffusion control agent (E) is 10% by weight or less, the deterioration of the sensitivity, developability of the unexposed part, etc. can be prevented. Furthermore, by using such an acid diffusion control agent, the storage stability of the composition is improved, the resolution is improved, and changes in the line width of the resist pattern due to fluctuations in the waiting time before radiation irradiation and the waiting time after radiation irradiation can be suppressed, resulting in extremely excellent process stability.

(Other Components (F))
To the composition, one or more of various additives such as a dissolution promoter, a dissolution control agent, a sensitizer, a surfactant, and an organic carboxylic acid or a phosphorus oxo acid or a derivative thereof can be added as other components (F) as necessary, within the scope of not impairing the object of this embodiment. Examples of other components (F) include the compounds disclosed in WO 2017/033943.

The total content of other components (F) is preferably 0 to 49% by weight, more preferably 0 to 5% by weight, even more preferably 0 to 1% by weight, and particularly preferably 0% by weight, of the total weight of the solid components.

In the composition, the content of the resin, the acid generator (C), the acid diffusion controller (E), and the other components (F) (the resin/the acid generator (C)/the acid diffusion controller (E)/the other components (F)) is, in weight % on a solid basis, preferably 50 to 99.4/0.001 to 49/0.001 to 49/0 to 49, more preferably 55 to 90/1 to 40/0.01 to 10/0 to 5, still more preferably 60 to 80/3 to 30/0.01 to 5/0 to 1, and particularly preferably 60 to 70/10 to 25/0.01 to 3/0.
The content of each component is selected from the respective ranges so that the sum of the components is 100% by weight. When the content is within the above range, the performance such as sensitivity, resolution, developability, etc. is further improved.

The method for preparing the composition is not particularly limited, and examples include a method in which each component is dissolved in a solvent at the time of use to prepare a homogeneous solution, and then, if necessary, filtered using a filter with a pore size of about 0.2 μm.

The composition may contain other resins to the extent that the effect is not impaired. The other resins are not particularly limited, and examples thereof include novolac resins, polyvinylphenols, polyacrylic acid, polyvinyl alcohol, styrene-maleic anhydride resins, and polymers containing acrylic acid, vinyl alcohol, or vinylphenol as monomer units, or derivatives thereof. The content of the other resins is not particularly limited, and is adjusted appropriately depending on the type. The content of the other resins is preferably 30 parts by weight or less, more preferably 10 parts by weight or less, even more preferably 5 parts by weight or less, and particularly preferably 0 parts by weight, per 100 parts by weight of the multi-branched resin.

[Pattern formation method]
The pattern forming method includes a film forming step of applying the lithography film forming composition onto a substrate to form a film (resist film), an exposure step of exposing the formed film (resist film), and a development step of developing the film (resist film) exposed in the exposure step to form a pattern (resist pattern). The resist pattern can also be used as an upper layer resist in a multilayer process.

(Film formation process)
For example, this process can be carried out as follows. First, the resist composition is applied onto a conventionally known substrate by a coating means such as spin coating, casting coating, or roll coating to form a resist film. The conventionally known substrate is not particularly limited, and examples thereof include substrates for electronic components and those on which a predetermined wiring pattern is formed. More specifically, examples thereof include, but are not particularly limited to, silicon wafers, metal substrates such as copper, chromium, iron, and aluminum, and glass substrates. Examples of materials for the wiring pattern include, but are not particularly limited to, copper, aluminum, nickel, and gold. If necessary, an inorganic film or an organic film may be provided on the substrate. Examples of inorganic films include, but are not particularly limited to, inorganic anti-reflective films (inorganic BARC). Examples of organic films include, but are not particularly limited to, organic anti-reflective films (organic BARC). Surface treatment with hexamethylenedisilazane or the like may be performed. Next, if necessary, the coated substrate is heated. The heating conditions vary depending on the composition of the composition, etc., but are preferably 20 to 250° C., more preferably 20 to 150° C. Heating is preferable because it may improve the adhesion of the resist to the substrate.

(Exposure process)
For example, this step can be carried out as follows. The resist film is exposed to any radiation selected from the group consisting of visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-rays, and ion beams in a desired pattern. The exposure conditions and the like are appropriately selected depending on the composition and the like of the composition. In the method for forming a resist pattern, it is preferable to heat the resist film after irradiation with radiation in order to stably form a highly accurate fine pattern in the exposure. The heating conditions vary depending on the composition and the like of the composition, but are preferably 20 to 250°C, more preferably 20 to 150°C.

(Developing process)
For example, this process can be carried out as follows. The exposed resist film is developed with a developer to form a predetermined resist pattern. As the developer, it is preferable to select a solvent having a solubility parameter (SP value) close to that of the resin. Suitable solvents include those disclosed in International Publication No. 2020/226150.

If necessary, an appropriate amount of a surfactant can be added to the developer. The surfactant is not particularly limited, but for example, an ionic or nonionic fluorine-based or silicon-based surfactant can be used. Examples of these surfactants include those disclosed in International Publication No. 2020/226150. It is more preferable to use a fluorine-based surfactant or a silicon-based surfactant as the nonionic surfactant.

The amount of surfactant used is usually 0.001 to 5% by weight, preferably 0.005 to 2% by weight, and more preferably 0.01 to 0.5% by weight, based on the total amount of the developer.

Development methods that can be applied include, for example, a method in which the substrate is immersed in a tank filled with developer for a certain period of time (dip method), a method in which developer is piled up on the substrate surface by surface tension and left to stand for a certain period of time (paddle method), a method in which developer is sprayed onto the substrate surface (spray method), and a method in which developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispensing nozzle is scanned at a constant speed (dynamic dispensing method). There is no particular limit to the time for developing the pattern, but it is preferably 10 to 90 seconds. After the development step, a step of stopping development by replacing the solvent with another solvent may be carried out.

(Other processes)
After the development, it is preferable to include a step of washing with a rinse solution containing an organic solvent. Examples of the rinse solution and rinse method used in the rinse step after development include those disclosed in WO 2020/226150.

After forming the resist pattern, a patterned wiring board is obtained by etching. Etching can be performed by known methods such as dry etching using plasma gas and wet etching using an alkaline solution, cupric chloride solution, ferric chloride solution, etc.

After forming the resist pattern, plating can also be performed. The plating method is not particularly limited, but examples include copper plating, solder plating, nickel plating, and gold plating.

The remaining resist pattern after etching can be stripped off with an organic solvent. Examples of the organic solvent and stripping method include those disclosed in WO 2020/226150.

The wiring board can also be formed by forming a resist pattern, evaporating metal in a vacuum, and then dissolving the resist pattern in a solution, i.e., by the lift-off method.

[Lithography underlayer film forming composition, lithography underlayer film, and pattern formation method]
First Embodiment
<Lithography underlayer film forming composition>
The lithography underlayer film forming composition according to this embodiment (hereinafter also referred to as "underlayer film forming composition") contains the above-mentioned multi-branched resin and a silicon-containing compound (for example, hydrolyzable organosilane, its hydrolyzate or its hydrolyzed condensate). The underlayer film forming composition has a relatively high carbon concentration, a relatively low oxygen concentration, high heat resistance, and high solvent solubility. Therefore, the pattern has excellent rectangularity. In addition, it is possible to reduce film defects (thin film formation), has good storage stability, has high sensitivity, a high refractive index and transparency in a specific wavelength region, and can impart a good resist pattern shape.

The underlayer film forming composition can be suitably used, for example, in a multilayer resist method in which a resist underlayer film is provided between an upper layer resist (photoresist, etc.) and a hard mask or organic underlayer film. In such a multilayer resist method, for example, a resist underlayer film is formed on an organic underlayer film or hard mask on a substrate by a coating method or the like, and an upper layer resist (for example, photoresist, electron beam resist, EUV resist) is formed on the resist underlayer film. A resist pattern is then formed by exposure and development, and the resist underlayer film is dry etched using the resist pattern to transfer the pattern, and the organic underlayer film is etched to transfer the pattern, and the substrate is processed using the organic underlayer film.

That is, the lithography underlayer film (resist underlayer film) formed using the underlayer film forming composition is less likely to cause intermixing with the upper layer resist and has heat resistance. For example, the etching rate of the underlayer film against a halogen-based (fluorine-based) etching gas is higher than that of the patterned upper layer resist used as a mask, so that a good rectangular pattern can be obtained. Furthermore, since the resist underlayer film has high resistance to oxygen-based etching gas, it can function as a good mask when patterning a layer provided on a substrate, such as a hard mask. The underlayer film forming composition can also be used in an embodiment in which multiple resist underlayer films are laminated. In this case, the position of the resist underlayer film (which layer it is laminated in) is not particularly limited, and it may be directly under the upper layer resist, may be the layer located closest to the substrate, or may be sandwiched between the resist underlayer films. In this disclosure, the terms lithography underlayer film and resist underlayer film are used interchangeably.

In forming fine patterns, the resist film tends to be thin to prevent pattern collapse. When the resist is thinned, the dry etching for transferring the pattern to the film existing in the lower layer cannot transfer the pattern unless the etching rate is higher than that of the upper layer film. In this embodiment, an organic underlayer film is placed on a substrate, and the resist underlayer film (containing a silicon-based compound) of this embodiment is coated on top of the organic underlayer film, which is then coated with a resist film (organic resist film). The dry etching rate of organic component films and inorganic component films differs greatly depending on the etching gas selected, and the dry etching rate of organic component films is high with oxygen-based gases, and the dry etching rate of inorganic component films is high with halogen-containing gases. For example, the resist underlayer film with the pattern transferred thereto can be used to dry etch the organic underlayer film below it with oxygen-based gases to transfer the pattern to the organic underlayer film, and the substrate can be processed using the organic underlayer film with the pattern transferred thereto using halogen-containing gases.

Furthermore, when the resist underlayer film contains the hyperbranched resin and a silicon-containing compound (e.g., hydrolyzable organosilane, its hydrolysate, or its hydrolyzed condensate), the sensitivity of the upper resist layer is improved, no intermixing with the upper resist layer occurs, and the pattern of the resist underlayer film formed after exposure and development becomes rectangular. This makes it possible to process substrates with fine patterns.

In particular, it is preferable for the resist underlayer film to be composed of a hyperbranched heterocyclic resin (e.g., hyperbranched PBO resin), since this has extremely high heat resistance and is extremely unlikely to cause intermixing with the upper resist layer.

The resist underlayer film also has high heat resistance, so it can be used under high temperature baking conditions. Furthermore, because it has a relatively low molecular weight and low viscosity, it is easy to fill even the corners of a substrate with steps (especially fine spaces or hole patterns, etc.), and as a result, there is a tendency for the planarization and filling characteristics to be relatively advantageously improved.

The underlayer film-forming composition may further contain, in addition to the hyperbranched resin and silicon-containing compound, a solvent, an acid, an acid crosslinking agent, and the like. In addition, as optional components, it may contain an organic polymer compound, an acid generator, a surfactant, and other components such as water, alcohol, and a curing catalyst. From the standpoint of coatability and quality stability, the content of the hyperbranched resin in the lithography underlayer film is preferably 0.1 to 70% by weight, more preferably 0.5 to 50% by weight, and particularly preferably 3.0 to 40% by weight.

Any known solvent can be used as long as it dissolves the hyperbranched resin. The type and amount of the solvent can be as disclosed in WO 2020/226150.

The underlayer film-forming composition may contain an acid from the viewpoint of promoting curing. The type and amount of the acid may be as disclosed in WO 2020/226150.

The underlayer film-forming composition may contain one or more acid crosslinkers when used as a negative resist material or as an additive to increase the strength of a pattern in a positive resist material. An acid crosslinker is a compound that can intramolecularly or intermolecularly crosslink the resin in the presence of the above-mentioned acid. The type and amount of the acid crosslinker may be as disclosed in WO 2020/226150.

The underlayer film-forming composition includes a silicon-containing compound. The silicon-containing compound may be either an organic silicon-containing compound or an inorganic silicon-containing compound, but is preferably an organic silicon-containing compound. The type and amount of the silicon-containing compound may be as disclosed in WO 2020/226150.

The underlayer film-forming composition may contain, in addition to the above-mentioned components, an organic polymer compound, a crosslinking agent, a photoacid generator, a surfactant, etc., as necessary. The types and amounts of these components may be as disclosed in WO 2020/226150.

Lithography Underlayer Film and Pattern Formation Method
The lithography underlayer film of this embodiment can be suitably used as an underlayer (resist underlayer film) of a photoresist (upper layer) used in a multi-layer resist method.

In this embodiment, for example, a resist underlayer film is formed using the underlayer film forming composition, at least one photoresist layer is formed on the resist underlayer film, and then a predetermined region of the photoresist layer is irradiated with radiation and developed to form a pattern. The resist underlayer film is preferably formed by forming an underlayer film precursor from a multi-branched PA resin, heating the precursor at 300°C or higher, and converting the multi-branched PA resin into a multi-branched PBO resin.

Also, as one aspect of the pattern forming method according to the first embodiment, there can be mentioned a method including the following steps: forming an organic underlayer film on a substrate using a coating-type organic underlayer film material; forming a resist underlayer film on the organic underlayer film using the underlayer film forming composition of the first embodiment; forming an upper-layer resist film on the resist underlayer film using an upper-layer resist film composition; forming an upper-layer resist pattern on the upper-layer resist film and transferring the pattern to the resist underlayer film by etching using the upper-layer resist pattern as a mask; transferring the pattern to the organic underlayer film by etching using the resist underlayer film to which the pattern has been transferred as a mask; transferring the pattern to the substrate (workpiece) by etching using the organic underlayer film to which the pattern has been transferred as a mask.

Another aspect of the present invention is a method including the following steps: forming an organic hard mask mainly composed of carbon on a substrate by a CVD method; forming a resist underlayer film on the organic hard mask using the underlayer film forming composition of the first embodiment; forming an upper layer resist film on the resist underlayer film using an upper layer resist film composition; forming an upper layer resist pattern on the upper layer resist film and transferring the pattern to the resist underlayer film by etching using the upper layer resist pattern as a mask; transferring the pattern to the organic hard mask by etching using the resist underlayer film to which the pattern has been transferred as a mask; transferring the pattern to the substrate (workpiece) by etching using the organic hard mask to which the pattern has been transferred as a mask.

As the substrate, for example, a semiconductor substrate can be used. As the semiconductor substrate, a silicon substrate can generally be used, but is not particularly limited, and a material different from the workpiece layer, such as Si, amorphous silicon (α-Si), p-Si, SiO ₂ , SiN, SiON, W, TiN, or Al, can be used. In addition, as the metal constituting the substrate (workpiece; including the semiconductor substrate), those disclosed in International Publication No. 2020/226150 can be used.

In the pattern formation method of this embodiment, an organic underlayer film or an organic hard mask can be formed on a substrate. Of these, the organic underlayer film can be formed from a coating-type organic underlayer film material using a spin-coating method or the like, and the organic hard mask can be formed from a carbon-based organic hard mask material using a CVD method. The types of such organic underlayer film and organic hard mask are not particularly limited, but when the upper resist film is patterned by exposure, it is preferable that the organic underlayer film and organic hard mask exhibit sufficient anti-reflective film function. By forming such an organic underlayer film or organic hard mask, the pattern formed in the upper resist film can be transferred onto the substrate (workpiece) without causing a size conversion difference. A "carbon-based" hard mask means a hard mask in which 50% or more by weight of the solid content is composed of a carbon-based material such as amorphous hydrogenated carbon, also called amorphous carbon and denoted as a-C:H. The a-C:H film can be deposited by various techniques, but plasma enhanced chemical vapor deposition (PECVD) is widely used due to its cost-effectiveness and film quality adjustability. Examples of the hard mask can be found in, for example, JP2013-526783A.

The resist underlayer film used in the pattern formation method of this embodiment can be formed by spin coating or the like on a workpiece provided with an organic underlayer film or the like. When forming the resist underlayer film by spin coating, it is desirable to evaporate the solvent after spin coating and bake to promote a crosslinking reaction in order to prevent mixing with the upper resist film. The bake temperature is preferably within the range of 50 to 500°C. At this time, although it depends on the structure of the device to be manufactured, a bake temperature of 400°C or less is particularly preferable in order to reduce thermal damage to the device. A bake time within the range of 10 to 300 seconds is preferably used.

In addition, in the pattern formation method of this embodiment, any of the following methods can be suitably used to form a pattern on the upper resist film: lithography using light with a wavelength of 300 nm or less or EUV light, direct electron beam writing, and induced self-organization. By using such methods, a fine pattern can be formed on the upper resist film.

The upper layer resist film composition can be appropriately selected depending on the method for forming a pattern in the above-mentioned upper layer resist film. For example, when lithography is performed using light of 300 nm or less or EUV light, a chemically amplified photoresist film material can be used as the upper layer resist film composition. Examples of such photoresist film materials include those that form a positive pattern by dissolving the exposed parts using an alkaline developer after forming a photoresist film and exposing it, and those that form a negative pattern by dissolving the unexposed parts using a developer made of an organic solvent.

The resist underlayer film formed in this embodiment may absorb light depending on the wavelength of the light used in the lithography process. In such a case, it can function as an anti-reflective film that has the effect of preventing light from being reflected from the substrate.

The resist underlayer film formed in this embodiment can be used as an underlayer anti-reflective film for EUV resist in addition to its function as a hard mask. Furthermore, since the film formed from the underlayer film-forming composition has excellent EUV absorption ability, it is possible to exert a sensitizing effect on the upper layer resist composition, which contributes to improving sensitivity. When the resist underlayer film formed in this embodiment is used as an EUV resist underlayer film, the process can be carried out in the same manner as for the underlayer film for photoresist.

Second Embodiment
<Resist Underlayer Film Forming Composition>
The composition for forming a resist underlayer film according to the second embodiment (hereinafter also referred to as "underlayer film forming composition") contains the multi-branched resin, but may not contain a silicon-containing compound.

The underlayer film forming composition of this embodiment is applicable to a wet process and is useful for forming a photoresist underlayer film having excellent heat resistance, step filling properties, and flatness. The underlayer film forming composition uses a compound having a specific structure with a relatively high carbon concentration, a relatively low oxygen concentration, and high solvent solubility, and therefore can form an underlayer film that is suppressed from deteriorating during baking and has excellent etching resistance against fluorine gas plasma etching and the like. Furthermore, it has excellent adhesion to the resist layer, so that an excellent resist pattern can be formed. The underlayer film forming composition of this embodiment is particularly excellent in heat resistance, step filling properties, and flatness, and can therefore be used, for example, to form a resist underlayer film that is provided as the lowest layer among a plurality of resist layers. However, the resist underlayer film formed in this embodiment may further include another resist underlayer between the substrate.

The underlayer film-forming composition according to this embodiment may further contain a solvent, an acid generator, an acid crosslinking agent, and the like. In addition, as optional components, it may contain a basic compound, as well as water, alcohol, a curing catalyst, and the like. From the viewpoint of coatability and quality stability, the content of the resin in the underlayer film-forming composition is preferably 0.1 to 70% by weight, more preferably 0.5 to 50% by weight, and particularly preferably 3.0 to 40% by weight.

In this embodiment, any known solvent can be used as long as it at least dissolves the resin. The type and amount of the solvent can be as disclosed in WO 2020/226150.

The underlayer film-forming composition of this embodiment may contain an acid crosslinker as necessary from the viewpoint of suppressing intermixing, etc. The type and amount of the acid crosslinker may be as disclosed in WO 2020/226150.

The underlayer film-forming composition of this embodiment may contain an acid generator as necessary, from the viewpoint of further promoting the crosslinking reaction by heat. The type and amount of the acid generator may be as disclosed in WO 2020/226150.

Furthermore, the underlayer film-forming composition of this embodiment may contain a basic compound from the viewpoint of improving storage stability, etc. The type and amount of the basic compound may be as disclosed in WO 2020/226150.

The underlayer film-forming composition of this embodiment may also contain other resins or compounds for the purpose of imparting thermosetting properties or controlling absorbance. As such other resins or compounds, those disclosed in WO 2020/226150 can be used.

<Lithography Resist Underlayer Film and Pattern Forming Method>
The pattern formed in this embodiment can be used as, for example, a resist pattern or a circuit pattern. The method for producing the resist underlayer film in this embodiment is the same as that described in the first embodiment.

The pattern forming method according to the second embodiment includes a step (A-1 step) of forming a resist underlayer film on a substrate using the underlayer film forming composition of the second embodiment, a step (A-2 step) of forming at least one photoresist layer on the resist underlayer film, and a step (A-3 step) of irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer after forming at least one photoresist layer in the A-2 step. The photoresist layer refers to the outermost layer of the resist layer, i.e., the layer provided on the outermost side of the resist layer (the side opposite the substrate).

Furthermore, another pattern forming method of the second embodiment includes a step (B-1 step) of forming a resist underlayer film on a substrate using the underlayer film forming composition of the second embodiment, a step (B-2 step) of forming a resist intermediate layer film on the underlayer film using a resist intermediate layer film material (e.g., a silicon-containing resist layer), a step (B-3 step) of forming at least one photoresist layer on the resist intermediate layer film, a step (B-4 step) of irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer to form a resist pattern after the at least one photoresist layer is formed in the B-3 step, and a step (B-5 step) of etching the resist intermediate layer film using the resist pattern as a mask, etching the underlayer film using the obtained intermediate layer film pattern as an etching mask, and etching the substrate using the obtained underlayer film pattern as an etching mask to form a pattern on the substrate.

When forming the resist underlayer film, it is preferable to perform a bake treatment to suppress the occurrence of a mixing phenomenon with the upper resist layer (e.g., a photoresist layer or a resist intermediate layer film) and to promote a crosslinking reaction. The conditions can be as disclosed in WO 2020/226150.

After preparing the resist underlayer film on the substrate, a resist intermediate layer film can be provided between the photoresist layer and the resist underlayer film. For example, in the case of a two-layer process, a silicon-containing resist layer or a monolayer resist made of a normal hydrocarbon can be provided as a resist intermediate layer film on the resist underlayer film. Also, for example, in the case of a three-layer process, it is preferable to prepare a silicon-containing intermediate layer between the resist intermediate layer film and the photoresist layer, and a silicon-free monolayer resist layer on top of that. These photoresist layers, resist intermediate layer films, and photoresist layers provided between these layers can be formed using known photoresist materials. As the silicon-containing resist material, those disclosed in International Publication No. 2020/226150 can be used. In addition, a resist intermediate layer formed by a Chemical Vapor Deposition (CVD) method can also be used.

Furthermore, the resist underlayer film of this embodiment can be used as an anti-reflective film for a normal single-layer resist or as an underlayer material for suppressing pattern collapse. The resist underlayer film of this embodiment has excellent etching resistance for underlayer processing, so it can also be expected to function as a hard mask for underlayer processing.

When forming a resist layer using the above-mentioned known photoresist materials, wet processes such as spin coating and screen printing are preferably used, as in the case of forming the resist underlayer film. After applying the resist material by spin coating or the like, pre-baking is usually performed, and this pre-baking is preferably performed at a baking temperature of 80 to 180°C and for a baking time of 10 to 300 seconds. Thereafter, exposure is performed according to the usual method, followed by post-exposure baking (PEB) and development to obtain a resist pattern. The thickness of each resist film is not particularly limited, but generally, it is preferably 30 nm to 500 nm, and more preferably 50 nm to 400 nm.

The exposure light can be appropriately selected depending on the photoresist material used. Generally, high-energy rays with a wavelength of 300 nm or less, specifically excimer lasers with wavelengths of 248 nm, 193 nm, and 157 nm, soft X-rays with wavelengths of 3 to 20 nm, electron beams, X-rays, etc., are used.

The resist pattern formed by the above-described method is one in which pattern collapse is suppressed by the resist underlayer film of this embodiment. Therefore, by using the resist underlayer film of this embodiment, a finer pattern can be obtained, and the exposure dose required to obtain the resist pattern can be reduced.

Next, etching is performed using the obtained resist pattern as a mask. Gas etching is preferably used as etching of the resist underlayer film in the two-layer process. As the gas etching, etching using oxygen gas is suitable. In addition to oxygen gas, it is also possible to add inert gases such as He and Ar, and CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO ₂ , and H ₂ gases. Gas etching can also be performed using only CO, CO ₂ , NH ₃ , SO ₂ , N ₂ , NO ₂ , and H ₂ gases without using oxygen gas. In particular, the latter gas is preferably used for sidewall protection to prevent undercut of the pattern sidewall.

On the other hand, gas etching is also preferably used for etching the middle layer (the layer located between the photoresist layer and the resist underlayer film) in the three-layer process. Gas etching similar to that described in the two-layer process above can be applied. In particular, processing of the middle layer in the three-layer process is preferably performed using a fluorocarbon-based gas with the resist pattern as a mask. After that, the resist underlayer film can be processed by, for example, performing oxygen gas etching with the middle layer pattern as a mask as described above.

When forming an inorganic hard mask intermediate layer film as the intermediate layer, a silicon oxide film, a silicon nitride film, or a silicon oxide nitride film (SiON film) is formed by a CVD method, an ALD method, or the like. The method for forming the nitride film is not limited to the following, but for example, the methods described in JP-A-2002-334869 and WO 2004/066377 can be used. A photoresist film can be formed directly on such an intermediate layer film, but an organic anti-reflective coating (BARC) can also be formed on the intermediate layer film by spin coating, and a photoresist film can be formed on top of that.

As the intermediate layer, a polysilsesquioxane-based intermediate layer is also preferably used. By making the resist intermediate film effective as an anti-reflective film, reflection tends to be effectively suppressed. Specific materials for the polysilsesquioxane-based intermediate layer are not limited to the following, but for example, those described in JP-A-2007-226170 and JP-A-2007-226204 can be used.

The etching of the substrate can also be performed by a conventional method, for example, if the substrate is SiO ₂ or SiN, etching can be performed mainly with a fluorocarbon-based gas, and if the substrate is p-Si, Al, or W, etching can be performed mainly with a chlorine-based or bromine-based gas. When etching the substrate with a fluorocarbon-based gas, the silicon-containing resist of the two-layer resist process and the silicon-containing intermediate layer of the three-layer process are stripped at the same time as the substrate is processed. On the other hand, when the substrate is etched with a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is stripped separately, and generally, dry etching stripping with a fluorocarbon-based gas is performed after the substrate is processed.

The resist underlayer film of the present embodiment has excellent etching resistance for these substrates. As the substrate, a known one can be appropriately selected and used, and is not particularly limited, and examples thereof include Si, α-Si, p-Si, SiO ₂ , SiN, SiON, W, TiN, Al, and the like. The substrate may also be a laminate having a processed film (substrate to be processed) on a base material (support). Examples of such processed films include various low-k films such as Si, SiO ₂ , SiON, SiN, p-Si, α-Si, W, W-Si, Al, Cu, and Al-Si, and stopper films thereof, and films made of a material different from that of the base material (support) are usually used. The thickness of the substrate or processed film to be processed is not particularly limited, but is usually preferably about 50 nm to 10,000 nm, and more preferably 75 nm to 5,000 nm.

The resist underlayer film of this embodiment has excellent flatness and embedding properties for substrates having steps. As an evaluation method for embedding flatness, any known method can be appropriately selected and used, and is not particularly limited. For example, a solution of each compound adjusted to a predetermined concentration is applied by spin coating onto a silicon substrate having steps, and the substrate is dried at 110°C for 90 seconds to remove the solvent, forming an underlayer film to a predetermined thickness. After baking for a predetermined time at a temperature of about 240 to 300°C, the difference in underlayer film thickness (ΔT) between the line and space region and the open region without a pattern is measured by an ellipsometer, and the embedding flatness for substrates having steps can be evaluated.

[Optical article-forming composition and cured product thereof]
The multi-branched resin is useful for optical materials. The optical component forming composition containing the resin can provide optical components with a high refractive index, and is expected to have excellent storage stability, structure forming ability (film forming ability), and heat resistance. The refractive index of the optical article is preferably 1.60 or more, more preferably 1.65 or more, even more preferably 1.70 or more, and even more preferably 1.75 or more, from the viewpoint of miniaturization of optical components and improvement of light collection rate. The transparency of the optical article is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of improvement of light collection rate. The method of measuring the refractive index is not particularly limited, and a known method is used. For example, a spectroscopic ellipsometry method, a minimum deviation method, a critical angle method (Abbe method, Pulfrich method), a V-block method, a prism coupler method, and a liquid immersion method (Becke line method) can be mentioned. The method of measuring the transparency is not particularly limited, and a known method is used. For example, a spectrophotometer and a spectroscopic ellipsometry method can be mentioned.

In addition, the cured product obtained by curing the optical component-forming composition can be a three-dimensional crosslinked product, and coloring can be suppressed by a wide range of heat treatments from low to high temperatures, and a high refractive index and high transparency can be expected.

The optical component forming composition of this embodiment may further contain a solvent in addition to the resin. The solvent may be the same as the solvent used in the lithography film forming composition described above.

In the optical component forming composition of this embodiment, the relationship between the amount of solid components and the amount of solvent is not particularly limited, but is preferably 1-80% by weight of solid components and 20-99% by weight of solvent, more preferably 1-50% by weight of solid components and 50-99% by weight of solvent, even more preferably 2-40% by weight of solid components and 60-98% by weight of solvent, and particularly preferably 2-10% by weight of solid components and 90-98% by weight of solvent. The optical component forming composition of this embodiment may not contain a solvent.

The optical component forming composition of this embodiment may contain at least one other solid component selected from the group consisting of an acid generator (C), an acid crosslinker (G), an acid diffusion controller (E), and other components (F).

In the optical component forming composition of this embodiment, the content of the hyperbranched resin is not particularly limited, but is preferably 50 to 99.4% by weight of the total weight of the solid components, more preferably 55 to 90% by weight, even more preferably 60 to 80% by weight, and particularly preferably 60 to 70% by weight.

The acid generator (C), acid crosslinker (G), acid diffusion controller (E) and other components (F) contained in the optical component forming composition of this embodiment can be the same as those that can be contained in the lithography film forming composition described above.

In the optical component forming composition of this embodiment, the content of the resin, acid generator (C), acid diffusion controller (E), and other components (F) (resin/acid generator (C)/acid diffusion controller (E)/other components (F)) is preferably 50-99.4/0.001-49/0.001-49/0-49, more preferably 55-90/1-40/0.01-10/0-5, even more preferably 60-80/3-30/0.01-5/0-1, and particularly preferably 60-70/10-25/0.01-3/0, in terms of weight percent based on solids. The content ratio of each component is selected from each range so that the sum of the components is 100% by weight. The above content ratios provide even better performance in terms of sensitivity, resolution, developability, and the like.

The method for preparing the optical component forming composition of this embodiment is not particularly limited, and examples include a method in which each component is dissolved in a solvent at the time of use to form a homogeneous solution, and then, if necessary, filtered using a filter with a pore size of about 0.2 μm.

The optical component forming composition of this embodiment may contain other resins to the extent that the intended purpose is not impeded. The type and amount of the other resins may be as disclosed in WO 2020/226150.

The cured product of this embodiment is obtained by curing the optical component-forming composition and can be used as various resins. These cured products can be used for various applications as highly versatile materials that impart various properties such as a high melting point, high refractive index, and high transparency. The cured products can be obtained by subjecting the composition to light irradiation, heating, or other known methods corresponding to each composition.

These cured products can be used as various synthetic resins such as epoxy resin, polycarbonate resin, and acrylic resin, and can also be used to make optical components such as lenses and optical sheets by taking advantage of their functionality.

6. Purification method The multi-branched resin is preferably purified. The purification method is not particularly limited, but the method described in International Publication No. 2015/080240 or the method described in International Publication No. 2018/159707 can be used. Specifically, the purification method includes a step of dissolving the resin in an organic solvent that is not miscible with water to obtain an organic phase, contacting the organic phase with an acidic aqueous solution to perform an extraction process, thereby transferring the metal content contained in the organic phase containing the resin and the organic solvent to the aqueous phase, and then separating the organic phase from the aqueous phase. The organic solvent that is not miscible with water is usually an organic solvent classified as a non-water-soluble solvent. The organic solvent is not particularly limited, but an organic solvent that can be safely applied to a semiconductor manufacturing process is preferable. The amount of the organic solvent used is usually about 1 to 100 times by weight relative to the compound used.

Specific examples of organic solvents that can be used include those described in International Publication WO 2015/080240. Among these, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate, etc. are preferred, with cyclohexanone and propylene glycol monomethyl ether acetate being particularly preferred.

The acidic aqueous solution is appropriately selected from among aqueous solutions in which a commonly known organic or inorganic compound is dissolved in water. For example, the aqueous solution described in International Publication WO 2015/080240 can be mentioned. These acidic aqueous solutions can be used alone or in combination of two or more. Examples of the acidic aqueous solution include mineral acid aqueous solutions and organic acid aqueous solutions. Examples of the mineral acid aqueous solution include an aqueous solution containing one or more acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of the organic acid aqueous solution include an aqueous solution containing one or more acids selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. The pH range of the acidic aqueous solution is about 0 to 5, and more preferably about pH 0 to 3.

[Example 1] Hyperbranched resin 1 having a polyamide structure
(1) Synthesis of tricarboxylic acid compound intermediate The reaction shown in the following scheme was carried out.

The following was placed in a 100 mL recovery flask:
4,4',4"-trihydroxytriphenylmethane (MTP) 10.0 mmol, 2.92 g
K ₂ CO ₃ 35.0 mmol, 4.83 g
Dimethylformamide (DMF) 20 mL
The contents were stirred for 60 minutes at 80° C. Then, 35 mmol and 3.87 mL of ethyl bromoacetate (EBA) were added to the flask, and the mixture was further stirred at 80° C. for 24 hours to carry out the reaction.

The reaction mixture was poured into a 0.01N aqueous hydrochloric acid solution to cause reprecipitation. The precipitate was collected and subjected to an extraction operation using chloroform. This extraction operation was carried out a total of two times. Next, a saturated sodium bicarbonate solution was added to the organic phase for separation and washing. Furthermore, a saturated saline solution was added to the organic phase for separation and washing.

Anhydrous magnesium sulfate was added to the organic phase obtained after the washing process to dry it. The dried organic phase was concentrated using an evaporator to obtain a dark yellow liquid. The dark yellow liquid was subjected to column separation using ethyl acetate/hexane = 1:1 as the mobile phase to separate the residue. The liquid obtained from the column separation was further concentrated using an evaporator to obtain a light yellow viscous liquid. The light yellow viscous liquid was analyzed and it was confirmed that the desired intermediate was produced (Figures 1A and 1B). The yield was 99%.

(2) Synthesis of tricarboxylic acid compound The following reaction was carried out.

 

 

A 300 mL flask was charged with the following:
Intermediate obtained in the previous step 10 mmol, 5.5 g
KOH 90mmol 5.05g
Tetrahydrofuran (THF):water = 1:1 mixed solvent 150mL
The contents were stirred at 50° C. for 72 hours and the aqueous phase was collected.

The aqueous phase was made weakly acidic and subjected to extraction with ethyl acetate. The ethyl acetate phase was washed with saturated saline and anhydrous magnesium sulfate. After washing, the ethyl acetate phase was concentrated in an evaporator and washed with hexane. The ethyl acetate phase was filtered using a Kiriyama funnel and dried under reduced pressure at room temperature. In this way, the target product, a tricarboxylic acid compound (orange solid, molecular weight: 466.43), was obtained. The analysis results are shown in Figure 2.

(3) Synthesis of hyperbranched resin having polyamide structure The following reaction was carried out.

 

The following was placed in a test tube:
Tricarboxylic acid compound synthesized in (2) above: 0.23 g
N-methylpyrrolidone (NMP) 3.0 mL
2,2-bis(3-amino-4-hydroxyphenyl)propane (BAHP) 0.085g
Diisopropylcarbodiimide (DIC) 0.25 mL
The contents were stirred at 25° C. for 24 hours to carry out the reaction. The reaction mixture was reprecipitated using dichloromethane, and the precipitate was filtered using a Kiriyama funnel to obtain the target resin. The analysis results by ¹ H-NMR and GPC are shown in Figures 3A and 3B.
Yield: 97%
Mn=7400, Mn/Mn=2.40

　Apart from changing the amount of solvent as shown in the table below, the synthesis reaction of this resin was carried out using the method described above. However, when the amount of solvent was too small, gelation occurred and the desired resin could not be obtained.

Example 2 Hyperbranched Resin Having Polyamide Structure (1) Synthesis of Tricarboxylic Acid Chloride The reaction shown in the following scheme was carried out.

 

The following was placed in a 200 mL recovery flask:
Tricarboxylic acid obtained in Example 1: 2.33 g, 7.76 mmol
Chloroform: 30 mL
Thionyl chloride: 60 mmol, 7.14 g, 4.36 mL
Dimethylformamide (DMF): 1 drop

The contents were stirred at 70°C for 18 hours. The reaction mixture was concentrated using an evaporator and washed with hexane. The desired product was an orange viscous solid. The yield was 98%. The analytical results are shown in Figure 4.

(2) Synthesis of hyperbranched resin having polyamide structure The following reaction was carried out.

 

The following was placed in a test tube:
Compound obtained in (1) above (tricarboxylic acid chloride (MBOAC)) 0.26 g 0.5 mmol
2,2-bis(3-amino-4-hydroxyphenyl)propane (BAHP) 0.19 g 0.75 mmol
Dimethylformamide (DMF) 0.3 mL
4-Dimethylaminopyridine (DMAP) 0.19g

The contents were stirred at 25° C. for 20 hours to carry out the reaction. The reaction mixture was reprecipitated using diethyl ether. The precipitate was collected and washed with a 1N aqueous hydrochloric acid solution. The product was dried under reduced pressure to obtain the target hyperbranched resin having a polyamide structure. The results of the ¹ H-NMR and GPC analyses are shown in FIG. 5A and FIG. 5B.

The resin was produced in the same manner by changing the ratio of 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAHP) (Table 2 (B)) and tricarboxylic acid chloride (Table 2 (A)). The ratio was set to a value that would achieve the functional group equivalent ratio shown in the table below. The results are shown in the table.

(3) Physical Properties 1) Heat Resistance The thermal decomposition temperature of the obtained hyperbranched resin was measured by TGA (thermogravimetric analysis). The results are shown in FIG. 5C. The resin had excellent heat resistance.

2) Solubility The solubility of the hyperbranched resin in various solvents was evaluated. When 2 mg of the resin dissolved in 2 g of solvent at 20°C, it was evaluated as "completely soluble (+)" and when it did not dissolve, it was evaluated as "insoluble (-)". The results are shown in the table below. It is clear that the resin has good solubility in major solvents.

THF: tetrahydrofuran, DMF: dimethylformamide, DMSO: dimethylsulfoxide, PGMEA: propylene glycol monomethyl ether acetate)
NMP: N-methylpyrrolidone DMAc: N,N-dimethylacetamide MEK: methyl ethyl ketone PGME: propylene glycol monomethyl ether

3) Film-forming property The hyperbranched resin was dissolved in dimethylformamide (DMF) to obtain a composition having a concentration of 3% by weight. The solution was spin-coated on a silicon wafer under the following conditions, and post-baked to obtain a film. The film-forming property was good.
Rotational speed: 2500 rpm
Drying: 10 minutes at 200°C Film thickness: 32.4 nm
However, when dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAc), or N-methylpyrrolidone (NMP) was used as the solvent, it was not possible to form a film.

[Example 3]
The following reaction was carried out to synthesize a hyperbranched resin having a polyamide structure.

 

The following was placed in a test tube:
2,2-bis(3-amino-4-hydroxyphenyl)hexafluoromethylpropane (BAHFP) 0.75 mmol, 0.275 g
1,3,5-benzenetricarbonyl trichloride (BCC) 0.5 mmol, 0.132 g
Dimethylformamide (DMF) 1.5 mL
4-Dimethylaminopyridine (DMAP) 1.5 mmol 0.183 g

The contents were stirred at 25°C for 20 hours to carry out the reaction. The reaction mixture was reprecipitated using water. The precipitate was collected and washed with diethyl ether. The precipitate was then filtered using a Kiriyama funnel and dried under reduced pressure at room temperature to obtain the desired resin. The results of the GPC analysis are shown in Figure 6.

The resin was produced in the same manner, but the charge ratio of tricarboxylic acid chloride (BCC) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoromethylpropane (BAHFP) and the amount of solvent used were changed as shown in Table 4. The charge ratio was as shown in the table below. The results are shown in the table. The results of the GPC analysis are shown in Figure 6.

 

 

[Example 4]
Except for changing the reaction temperature, the resin was produced in the same manner as in Example 3. The results are shown in Table 5. The analysis results by GPC and FT-IR are shown in Figures 7A and 7B.

 

 

The solubility and film-forming properties of the resin in Run 3 in Table 4 were evaluated using the methods described above. The results are shown in Tables 6 and 7, respectively.

 

 

 

 

The refractive index was measured by the following procedure.
The resin was dissolved in DMF, and the solution was spin-coated onto a silicon wafer to prepare a thin film.
The refractive index of the thin film at 620 nm was measured using a film thickness/refractive index distribution measuring device SE-101 manufactured by Photonic Lattice Corporation.

[Example 5] Synthesis of hyperbranched polybenzoxazole A film having a thickness of 70 nm (corresponding to the film thickness of 70 nm in Table 7) produced from the hyperbranched PA resin obtained in Run 3 in Table 4 was heated at 300°C for 60 minutes in an inert atmosphere. As a result, intramolecular cyclization occurred to produce a film of hyperbranched polybenzoxazole (PBO). The analysis results are shown in Figures 8A and 8B.

Furthermore, a film of BCA[4]-DBH was formed on the hyperbranched polybenzoxazole film according to a standard method. BCA[4]-DBH is a main chain decomposition type cyclic molecular resist material synthesized from calixarene (see International Publication No. 2021/230185 or Journal of Photopolymer Science and Technology Volume 33, Number 1 (2020) 45 - 51). The material has the following structure, and is a highly sensitive resist material for extreme ultraviolet rays with excellent solubility and film-forming properties.

 

 

 

 

[Example 6] Study on fluorine introduction rate A hyperbranched PA resin was synthesized in the same manner as in Example 3. However, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoromethylpropane (BAHFP) and 2,2-bis(3-amino-4-hydroxyphenyl)propane (BAHP) were used as diamino compounds, 1,3,5-benzenetricarboxylic acid chloride (BCC) was used as tricarboxylic acid compound, and the amounts charged were changed as shown in Table 9. Furthermore, the reaction conditions were set to 25°C and 24 hours. Next, the hyperbranched PA resin was heated in the same manner as in Example 5 to attempt the production of a hyperbranched polybenzoxazole (PBO) resin film. The results are shown in Table 9.

 

 

In Run 1, BAHP was used as a diamino compound not containing fluorine. On the other hand, from Run 2 onwards, BAHP was replaced with BAHFP containing fluorine to increase the fluorine introduction rate. It was revealed that as the fluorine introduction rate increases, intramolecular cyclization occurs more easily, making it possible to form a hyperbranched PBO resin film. When fluorine atoms are introduced, the fluorine atoms repel each other, decreasing the polymer density, which is thought to improve solubility and film formability.

Claims (15)

(I) preparing a diamino compound represented by formula (A) and a tricarboxylic acid compound represented by formula (B);

(In the formula, Y is an alkylene group which may contain fluorine,
Z is independently -OH, -SH, or _-NH2 ;
R's each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an aralkyl group having 7 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an arylalkenyl group having 7 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a cyano group, a carboxylic acid group, a thiol group or a hydroxyl group, and the aryl group, aralkyl group, alkenyl group, alkynyl group and arylalkenyl group may contain an ether bond, a ketone bond, an ester bond or a urethane bond,
m is an integer from 1 to 3 and represents the number of groups other than hydrogen when R is a group other than hydrogen;
Ar is a group having an aromatic group;
E is -COOH, -COHal, -O-R ^b -COOH or -O-R ^b -COHal, Hal is a halogen atom, and R ^b is an alkylene group having 1 to 6 carbon atoms.
(II) a step of subjecting these compounds to a condensation reaction to form a polyamide structure;
Manufactured by a method comprising:
A hyperbranched resin with a polyamide structure. The resin according to claim 1, wherein Y is a branched alkylene group. The resin according to claim 1 or 2, wherein Y is a fluorinated alkylene group. (i) preparing a hyperbranched resin having a polyamide structure according to any one of claims 1 to 3; and (ii) intramolecularly condensing the resin to form a heterocyclic structure.
Manufactured by a method comprising:
A hyperbranched resin with a heterocyclic structure. There are units in which Y is an alkylene group and units in which Y is a fluorinated alkylene group,
5. The resin of claim 4, wherein the molar ratio of said alkylene groups to fluorinated alkylene groups is 1:(1.5 to 10). A lithography film-forming composition containing the resin described in any one of claims 1 to 5. A lithography underlayer film forming composition containing the resin described in claim 3. The composition according to claim 6 or 7, which contains a solvent. The composition according to any one of claims 6 to 8, comprising a component selected from the group consisting of a solvent, an acid generator, an acid crosslinker, and combinations thereof. A lithography underlayer film formed using the composition described in claim 7. A lithography underlayer film comprising the resin described in claim 4 or 5. A step of forming an underlayer film on a substrate using the composition according to claim 7, and heating the precursor to 300°C or higher to form an underlayer film containing a hyperbranched resin having a heterocyclic structure;
forming at least one photoresist layer on the underlayer film; and irradiating a predetermined area of the photoresist layer with radiation and developing the photoresist layer.
A method for forming a resist pattern comprising the steps of: Represented by the following formula (1):

(In the formula, Y is an alkylene group which may contain fluorine,
X is a group having an aromatic group;
Z is -OH, -SH, or _-NH2 ;
R's each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an aralkyl group having 7 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an arylalkenyl group having 7 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a cyano group, a carboxylic acid group, a thiol group or a hydroxyl group, and the aryl group, aralkyl group, alkenyl group, alkynyl group and arylalkenyl group may contain an ether bond, a ketone bond, an ester bond or a urethane bond,
m is an integer from 1 to 3 and represents the number of groups other than hydrogen when R is a group other than hydrogen;
n is the number of repeats in the main chain,
r is the number of repeats in the branched chain, and n>r.
A hyperbranched resin with a polyamide structure. Represented by the following formula (2):

(In the formula, Y ¹ is a fluorinated alkylene group, Y ² is an alkylene group,
Z' is independently -O-, -S-, or -NH-;
X is a group having an aromatic group;
R's each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 40 carbon atoms which may have a substituent, an aralkyl group having 7 to 40 carbon atoms which may have a substituent, an alkenyl group having 2 to 30 carbon atoms which may have a substituent, an alkynyl group having 2 to 30 carbon atoms which may have a substituent, an arylalkenyl group having 7 to 40 carbon atoms which may have a substituent, an alkoxy group having 1 to 30 carbon atoms which may have a substituent, a halogen atom, a nitro group, an amino group, a cyano group, a carboxylic acid group, a thiol group or a hydroxyl group, and the aryl group, aralkyl group, alkenyl group, alkynyl group and arylalkenyl group may contain an ether bond, a ketone bond, an ester bond or a urethane bond,
m is an integer from 1 to 3 and represents the number of groups other than hydrogen when R is a group other than hydrogen;
ⁿ¹ and ⁿ² are the repeat numbers in the main chain;
^r1 and ^r2 are the repeat numbers in the branched chain, and ⁿ¹ > ^r1 and ⁿ² > ^r2 .
A hyperbranched resin with a heterocyclic structure. The X is represented by any one of the following formulas:

(Ar is an aromatic group, and ^Rb is an alkylene group having 1 to 6 carbon atoms).
15. The resin according to claim 13 or 14.