Bottom layer composition and patterning method

Abstract

Disclosed is a primer composition comprising a polymer comprising repeating units of formula (1), wherein Ar is a monocyclic or polycyclic C 5‑60 An aromatic group, wherein the aromatic group contains one or more aromatic ring heteroatoms, substituents containing heteroatoms, or combinations thereof; X is C or O; R 1 , R 2 , R a and R b is as provided herein; optionally, R 1 and R 2 can form a 5- to 7-membered ring together; optionally, R 11 To R 13 One of the 1 Together they form a 5- to 7-membered ring; wherein R a and R b Optionally, they may be combined to form a 5- to 7-membered ring; wherein R a or R b One of the 2 together to form a 5- to 7-membered ring; and when X is O, R a and R b does not exist.

Description

Technical Field

[0001] The present invention relates generally to the field of manufacturing electronic devices, and more particularly to the field of materials used in semiconductor manufacturing. Background Art

[0002] Photoresist underlayer compositions are used in the semiconductor industry as etch masks for photolithography in advanced technology nodes of integrated circuit fabrication. These compositions are typically used in three-layer and four-layer photoresist integration schemes, where an organic or silicon-containing anti-reflective coating and a patternable photoresist film layer are disposed on an underlayer having a high carbon content.

[0003] An ideal photoresist base material should have certain specific characteristics: it should be able to be cast onto a substrate by a spin coating process, should be thermally cured when heated, have low outgassing and sublimation, should be soluble in common solvents to have good spin bowl compatibility, should have appropriate n and k values ​​to work with anti-reflective coatings to impart the low reflectivity required for photoresist imaging, and should have high thermal stability to avoid being damaged during subsequent processing steps. In addition to these requirements, an ideal photoresist base material must provide a flat film when spin coated and thermally cured on a substrate, with topography and sufficient dry etch selectivity to silicon-containing layers located above and below the photoresist base film to transfer the optical pattern into the final substrate in a precise manner.

[0004] Crosslinkable novolac resins have been used for bottom layer applications. Novolac is a polycondensation product of one or more activated aromatic compounds and another monomer, and the other monomer is selected from aliphatic or aromatic carbonyl compounds, benzyl ethers, benzyl alcohols or benzyl halides. The most widely studied novolac resin is a polycondensation product of activated aromatic derivatives and formaldehyde-type or aromatic aldehyde comonomers. These resins have been widely used in various photolithographic compositions. However, their rigid and highly aromatic skeletons usually cause the resin to have an increased glass transition temperature (which may inhibit the gap filling and planarization characteristics of the resin).

[0005] There remains a need for new underlayer materials, such as photoresist underlayer materials, which can provide properties such as improved solubility, lower glass transition temperature, reduced curing temperature, high thermal stability, solvent resistance after curing, improved gap fill, and improved planarization. Summary of the invention

[0006] A primer composition is provided, comprising a polymer comprising repeating units having formula (1):

[0007]

[0008] Ar is a monocyclic or polycyclic C 5-60 An aromatic group, wherein the aromatic group contains one or more aromatic ring heteroatoms, substituents containing heteroatoms, or combinations thereof; X is C or O; R 1 is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl; R 2 is substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl, or -NR 11 R 12 , where R 11 To R 12 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 heteroarylalkyl; optionally, R 1 and R 2 can form a 5- to 7-membered ring together; optionally, R 11 To R 12One of the 1 together to form a 5- to 7-membered ring; when X is C, R a and R b are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl; wherein R a and R b Optionally, they may be combined to form a 5- to 7-membered ring; wherein R a or R b One of the 2 together to form a 5- to 7-membered ring; and when X is O, R a and R b does not exist.

[0009] Also provided is a method of forming a pattern, the method comprising: (a) applying a layer of an underlying composition on a substrate; (b) curing the applied underlying composition to form an underlying layer; and (c) forming a photoresist layer on the underlying layer. DETAILED DESCRIPTION

[0010] Reference will now be made in detail to exemplary embodiments, examples of which are shown in this specification. In this regard, exemplary embodiments of the present invention may have different forms and should not be construed as being limited to the descriptions described herein. Therefore, exemplary embodiments are described below only by reference to the accompanying drawings to explain aspects of this specification. As used herein, the term "and / or" includes all combinations of one or more of the relevant listed items. When a statement such as "at least one of..." precedes a list of elements, it modifies the entire list of elements and does not modify a single element in the list.

[0011] As used herein, the terms "a / an" and "said" do not represent a limit to quantity, and unless otherwise indicated herein or clearly contradictory to the context, are interpreted as including both the singular and the plural. Unless otherwise clearly indicated, "or" means "and / or". The full range disclosed herein includes endpoints, and the endpoints are independently combinable with each other. The suffix "(s)" is intended to include both the singular and the plural of the terms it modifies, thereby including at least one of the terms. "Optional" or "optionally" means that the event or situation described subsequently may or may not occur, and the description includes examples of the occurrence of the event and examples of its non-occurrence. The terms "first", "second" and similar terms do not represent order, quantity, or importance in this article, but are used to distinguish one element from another. When an element is referred to as "on" another element, it may be in direct contact with the other element or an intervening element may exist therebetween. In contrast, when an element is referred to as "directly on" another element, there is no intervening element. It will be appreciated that components, elements, limitations and / or features of the described aspects may be combined in any suitable manner among the various aspects.

[0012] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. It will be further understood that terms (such as those defined in commonly used dictionaries) should be interpreted as having a meaning consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted as an idealized or overly formal meaning unless explicitly defined as such herein.

[0013] As used herein, the term "hydrocarbyl" refers to an organic compound having at least one carbon atom and at least one hydrogen atom, which is optionally substituted where indicated by one or more substituents; "alkyl" refers to a straight or branched saturated hydrocarbon having the specified number of carbon atoms and having a valence of 1; "alkylene" refers to an alkyl having a valence of 2; "hydroxyalkyl" refers to an alkyl substituted with at least one hydroxyl (-OH) group; "alkoxy" refers to "alkyl-O-"; "carboxylic acid" refers to a group having the formula "-C(=O)-OH"; "cycloalkyl" refers to a monovalent group having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl having a valence of 2; "alkenyl" refers to a straight or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenyloxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl having a valence of at least 2; "cycloalkenyl" refers to a cycloalkyl having at least one carbon-carbon double bond. cycloalkyl; "alkynyl" refers to a monovalent hydrocarbon radical having at least one carbon-carbon triple bond; the term "aromatic group" represents the conventional concept of aromaticity as defined in the literature, in particular in IUPAC 19, and refers to a monocyclic or polycyclic aromatic ring system, the system includes carbon atoms in one or more rings, and optionally may include one or more heteroatoms independently selected from N, O and S replacing one or more carbon atoms in the one or more rings; "aryl" refers to a monovalent, monocyclic or polycyclic aromatic group, which contains only carbon atoms in one or more aromatic rings, and may include groups having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "arylene" refers to an aryl group with a valence of at least 2; "alkylaryl" refers to an aryl group that has been substituted by an alkyl group; "arylalkyl" refers to an alkyl group that has been substituted by an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0014] The prefix "hetero" means that the compound or group includes at least one member (e.g., 1, 2, 3, or 4 or more heteroatoms) that is a heteroatom replacing a carbon atom, wherein the heteroatoms are each independently selected from N, O, S, Si, or P; "heteroatom-containing group" refers to a substituent that includes at least one heteroatom; "heteroalkyl" refers to an alkyl group having 1-4 heteroatoms replacing a carbon atom; "heterocycloalkyl" refers to a cycloalkyl group having one or more N, O or S atoms replacing a carbon atom; "heterocycloalkylene" refers to a heterocycloalkyl group having a valence of at least 2; "heteroaryl" refers to an aryl group having 1 to 3 separate or fused rings having one or more N, O or S atoms as ring members replacing a carbon atom; and "heteroarylene" refers to a heteroaryl group having a valence of at least 2.

[0015] The term "halogen" means a monovalent substituent of fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" means a group comprising one or more of the fluorine, chlorine, bromine, or iodine substituents replacing a hydrogen atom. A combination of halides (e.g., bromine and fluorine) or only fluorine groups may be present.

[0016] The symbol "*" indicates the bonding site (ie, point of attachment) of the repeating unit.

[0017] "Substituted" means that at least one hydrogen atom on the group is replaced by another group, provided that the normal valence of the designated atom is not exceeded. When the substituent is oxo (i.e., =O), then two hydrogens on the carbon atom are replaced. Combinations of substituents or variables are permissible. Exemplary groups that may be present in a "substituted" position include, but are not limited to, nitro (-NO 2 ), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH 2 ), single- or double-(C 1-6 ) alkylamino, alkanoyl (such as C 2-6 Alkanoyl such as acyl), formyl (-C(=O)H), carboxylic acid or its alkali metal or ammonium salt, C 2-6 Alkyl esters (-C(=O)O-alkyl or -OC(=O)-alkyl), C 7-13 Aryl esters (-C(=O)O-aryl or -OC(=O)-aryl), amides (-C(=O)NR 2 , where R is hydrogen or C 1-6 alkyl), carboxamide (-CH 2 C(=O)NR 2 , where R is hydrogen or C 1-6 alkyl), halogen, mercapto (-SH), C 1-6 Alkylthio (-S-alkyl), thiocyanato (-SCN), C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Haloalkyl, C 1-9 Alkoxy, C 1-6 Halogenated alkoxy, C 3-12 Cycloalkyl, C 5-18 Cycloalkenyl, C 6-12 Aryl (e.g., phenyl, biphenyl, naphthyl, etc., each ring is substituted or unsubstituted aromatic), C having 1 to 3 separate or condensed rings and 6 to 18 ring carbon atoms 7-19 Arylalkyl, arylalkoxy having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms, C 7-12 Alkyl aryl, C 4-12 Heterocycloalkyl, C3-12 Heteroaryl, C 1-6 Alkylsulfonyl (-S(=O) 2 -alkyl), C 6-12 Arylsulfonyl (-S(=O) 2 -aryl), or tosyl (CH 3 C 6 H 4 SO 2 -). When a group is substituted, the number of carbon atoms indicated is the total number of carbon atoms in the group, excluding those of any substituents. For example, the group -CH 2 CH 2 CN is C substituted by cyano 2 alkyl.

[0018] As mentioned above, one of the most widely studied novolac resins is the polycondensation product of activated aromatic derivatives and formaldehyde-type or aromatic aldehyde comonomers. These resins have been widely used in various photolithographic compositions. However, their rigid, highly aromatic skeletons increase the glass transition temperature and inhibit their gap filling and planarization characteristics. There is still a continuous need for new photoresist bottom materials that can provide the following characteristics: such as improved solubility, lower glass transition temperature, reduced curing temperature, high thermal stability, solvent resistance after curing, improved gap filling and improved planarization.

[0019] To overcome these limitations, the present invention introduces novolac resins based on conjugated aliphatic aldehyde comonomers. The polymers of the compositions of the present invention achieve improved solubility and lower glass transition temperatures compared to novolac resins that are polycondensation products of activated aromatic derivatives with formaldehyde-type or aromatic aldehyde comonomers.

[0020] According to an embodiment, the primer composition comprises a polymer comprising a repeating unit having formula (1):

[0021]

[0022] In formula (1), Ar is a monocyclic or polycyclic C 5-60 Aromatic groups, wherein the aromatic groups contain one or more aromatic ring heteroatoms, substituents containing heteroatoms, or combinations thereof. For convenience, monocyclic or polycyclic C 5-60 Aromatic groups may be referred to herein as "Ar groups". Typically, one or more heteroatoms may be independently selected from N, O or S. 5-60When the aromatic group is polycyclic, the ring or ring groups may be fused (such as naphthyl, etc.), directly connected (such as biaryl, biphenyl, etc.), and / or bridged by heteroatoms (such as triphenylamino or diphenylene ether). In embodiments, the polycyclic aromatic group may include a combination of fused and directly connected rings (such as binaphthyl, etc.). It should be understood that monocyclic or polycyclic C 5-60 The one or more heteroatoms of an aromatic group can be present as an aromatic ring member replacing a carbon atom (eg, a heteroarylene group), as one or more heteroatoms of a heteroatom-containing substituent (eg, a hydroxy substituent), or a combination thereof.

[0023] Monocyclic or polycyclic C 5-60 Aromatic groups may be substituted or unsubstituted. Exemplary substituents include, but are not limited to, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Haloalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl, halogen, -OR 21 、-SR 22 or -NR 23 R 24 , where R 21 To R 24 are each independently hydrogen, or substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0024] In an embodiment, the monocyclic or polycyclic C 5-60 The aromatic group can be monocyclic or polycyclic C 6-60 Arylene, or monocyclic or polycyclic C 5-60 Heteroarylene. 5-60 Aromatic groups are monocyclic or polycyclic C 6-60In the case of an arylene group, at least one hydrogen atom is replaced by a heteroatom-containing substituent as described above, such as -OR 21 、-SR 22 , or -NR 23 R 24 Substitution, where R 21 To R 24 are each independently hydrogen or substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Preferably, Ar is a polycyclic C 10-60 Arylene or polycyclic C 7-60 Heteroarylene. Exemplary Ar groups include, but are not limited to, substituted or unsubstituted carbazolediyl, substituted phenylene, substituted biphenylene, substituted naphthylene, and substituted pyrenylene.

[0025] In an embodiment, the monocyclic or polycyclic C 5-60 Aromatic groups can be -OR 21 、-SR 22 or -NR 23 R 24 Substituted monocyclic or polycyclic C 6-60 Arylene, where R 21 To R 24 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl. For example, monocyclic or polycyclic C 5-60 The aromatic group may be a monocyclic or polycyclic C 6-60 Arylene.

[0026] It should be understood that when "monocyclic or polycyclic C 6-60 When the "arylene" is polycyclic, the number of carbon atoms is sufficient to make the group chemically feasible. For example, "monocyclic or polycyclic C 6-60 "Arylene" may refer to "monocyclic C 6-60 Arylene or polycyclic C 10-60"Arylene"; or for example "monocyclic C 6-30 Arylene or polycyclic C 12-60 "Arylene".

[0027] It should be understood that when "monocyclic or polycyclic C 5-60 When the "heteroarylene" is polycyclic, the number of carbon atoms is sufficient to make the group chemically feasible. For example, a "monocyclic or polycyclic C 5-60 "Heteroarylene" may refer to "monocyclic C 5-60 Heteroarylene or polycyclic C 10-60 "heteroarylene"; or for example "monocyclic C 5-30 Heteroarylene or polycyclic C 12-60 "Heteroarylene".

[0028] In formula (1), X is C or O. When X is C, R a and R b can each independently be hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl; wherein R a and R b Optionally, they may be combined to form a 5- to 7-membered ring; wherein R a or R b One of the 2 When X is O, R a and R b In an embodiment, any one of the above 5- to 7-membered rings may optionally be fused to one or more additional rings to form a polycyclic structure. Preferably, X is C.

[0029] In formula (1), R 1 is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Preferably, R 1 is hydrogen, or substituted or unsubstituted C 1-10 Alkyl groups, of which hydrogen is typical.

[0030] In formula (1), R 2 is substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl, -NR 11 R 12 , where R 11 To R 12 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 In some embodiments, R 11 To R 12 One of the 1 Together they form a 5- to 7-membered ring.

[0031] Optionally, R 1 and R 2 They can form a 5- to 7-membered ring together.

[0032] In an embodiment, the Ar group may be a group having formula (2):

[0033]

[0034] A1, A2 and A3 may be present or absent, and each independently represents 1 to 3 condensed aromatic rings.

[0035] In formula (2), R 3 and R 4 are each independently substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl, halogen, -OR 31 、-SR 32 or -NR 33 R 34 , provided that R 3 or R 4 At least one of -OR 31 、-SR 32 or -NR 33 R 34 .

[0036] In formula (2), R 31 To R 34 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0037] In formula (2), m is an integer from 0 to 4, and n is an integer from 0 to 4, provided that the sum of m and n is an integer greater than 0. For example, the sum of m and n may be 1, 2, 3, or 4 or greater, typically 1 or 2.

[0038] In another embodiment, the Ar group can be a group having formula (3a), (3b) or (3c):

[0039]

[0040] wherein A4 represents 1 to 3 fused aromatic rings and A4 may be present or absent. Preferably, A4 represents 1 to 3 aromatic rings, more preferably 1 to 2 fused aromatic rings, and most preferably 1 fused aromatic ring.

[0041] In formulas (3a), (3b) and (3c), Z 1 and Z 2 are each independently C or N, provided that A4 contains at least one heteroaryl ring, Z 1 and Z 2 At least one of is N, or a combination thereof.

[0042] In formulas (3a), (3b) and (3c), each R 5 is independently substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 In formulae (3a), (3b) and (3c), p is an integer from 0 to 4, typically 0 or 1.

[0043] In another embodiment, the Ar group can be a group having formula (4):

[0044]

[0045] Provided that the Ar group contains one or more aromatic ring heteroatoms, heteroatom-containing substituents, or combinations thereof.

[0046] In formula (4), L 1 is a single bond, -O-, -S-, -S(O)-, -SO 2 -、-C(O)-、-CR 51 R 52 -、-NR 53 -or-PR54 -, where R 51 To R 54 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Preferably, L 1 Is -O- or -NR 53 -, more preferably -NR 53 -.

[0047] In formula (4), L 2 does not exist, is a single bond, -O-, -S-, -S(O)-, -SO 2 -, -C(O)-, substituted or unsubstituted C 1-2 Alkylene, substituted or unsubstituted C 6-30 Arylene, or substituted or unsubstituted C 5-30 Preferably, L 2 It is a single bond.

[0048] In formula (4), R 8 and R 9 are each independently substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl, halogen, -OR 55 、-SR 56 or -NR 57 R 58 .

[0049] In formula (4), R 55 To R 58are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0050] In formula (4), a is an integer from 0 to 4, typically from 0 to 2, more typically 0; and b is an integer from 0 to 4, typically from 0 to 2, more typically 0.

[0051] The polymers of the present invention can be prepared by combining one or more monocyclic or polycyclic C 5-60 The aromatic compound (aromatic monomer) is prepared by reacting a 1,2-diketone having the formula (5) or a conjugated aliphatic aldehyde (carbonyl monomer) in the presence of an acid catalyst and optionally in a suitable solvent.

[0052]

[0053] wherein X is C or O; and R 1 is hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0054] In formula (5), R 2 is substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl, or -NR 11 R 12 , where R 11 and R 12 are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl.

[0055] Optionally, R 1 and R 2 They can form a 5- to 7-membered ring together.

[0056] Optionally, R 11 or R 12 One of the 1 They can form a 5- to 7-membered ring together.

[0057] In formula (5), when X is C, R a and R b are each independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl; wherein R a and R b Optionally, they may be combined to form a 5- to 7-membered ring; wherein R a or R b One of the 2 Together they form a 5- to 7-membered ring.

[0058] In formula (5), when X is O, R a and R b does not exist.

[0059] Aromatic monomers are monocyclic or polycyclic C 5-60 An aromatic compound, wherein the aromatic compound comprises one or more aromatic ring heteroatoms, a substituent comprising a heteroatom, or a combination thereof. 5-60 Aromatic compounds include, but are not limited to, substituted benzenes, substituted biphenyls, substituted naphthalenes, substituted binaphthyls, substituted anthracenes, substituted benzo[a]anthracenes, substituted fluorenes, substituted fluoranthenes, substituted benzo[b]fluoranthenes, substituted dibenzo(a,h)anthracenes, substituted phenanthrenes, substituted phenacenes, substituted tetracenes, substituted Substituted triphenylene, substituted pyrene, substituted pentacene, substituted benzo[a]pyrene, substituted cardiocyclic olefins, substituted benzoperylene, substituted coronene, substituted ovalene, substituted benzo[c]fluorene, substituted or unsubstituted benzothiophene, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted carbazole, substituted or unsubstituted indole, substituted or unsubstituted quinoline, substituted or unsubstituted isoquinoline, substituted or unsubstituted purine, substituted or unsubstituted phenoxazine, substituted or unsubstituted phenothiazine, substituted or unsubstituted oxyphenothiazine, substituted or unsubstituted dioxyphenothiazine, and the like.

[0060] Monomer and optional solvent can be combined in any order. Typically, an acid catalyst is added to the reaction mixture after the monomer and any optional solvent. After adding the acid catalyst, the reaction mixture can be heated (such as under reflux) for a period of time (such as 1 to 48 hours). After heating, the reaction product is separated (such as by precipitation) from the reaction mixture, and can be dried, and optionally purified before use. The molar ratio of total aromatic monomers to total carbonyl monomers is 0.5:1 to 2:1, and typically 0.67:1 to 1.5:1.

[0061] In an embodiment, the polymer is prepared from a carbonyl monomer having formula (5) without using an additional aldehyde, ketone, or 1,2-dicarbonyl monomer different from formula (5). In an embodiment, the polymer is prepared without using an aldehyde or ketone compound different from the carbonyl monomer having formula (5). For example, the polymer does not contain repeating units derived from an aldehyde having the formula Ar′-CHO, wherein Ar′ is a substituted or unsubstituted C 6-30 Aromatic group.

[0062] Various solvents can be used to prepare the polymer of the present invention, such as but not limited to alcohol, glycol ether, lactone, ester, ether, ketone, water and aromatic hydrocarbon. Preferably, a relatively polar solvent is used, such as alcohol, glycol ether, lactone, ester, ether, ketone or water. A mixture of solvents can be used. Exemplary solvents include but are not limited to methanol, ethanol, propanol, propylene glycol, propylene glycol monomethyl ether (PGME), propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate (PGMEA), γ-butyrolactone (GBL), γ-valerolactone, δ-valerolactone, ethyl lactate, 1,4-dioxane, cyclohexanone, cyclopentanone, methyl ethyl ketone, water, mesitylene, xylene, anisole, 4-methylanisole, etc. Preferred solvents are methanol, ethanol, propanol, propylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ethyl lactate, 1,4-dioxane, cyclohexanone and water.

[0063] A variety of acids may be suitable as catalysts for preparing the polymers of the present invention. Exemplary acids include, but are not limited to, organic carboxylic acids and dicarboxylic acids (such as propionic acid and oxalic acid), inorganic acids, and sulfonic acids, and preferably the acid catalyst is an inorganic acid or a sulfonic acid. Suitable inorganic acids are HF, HCl, HBr, HNO 3 , H 2 SO 4 , H 3 PO 4 and HClO 4 Suitable sulfonic acids include alkanesulfonic acids and arylsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, benzenesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and cresolsulfonic acid. Preferred acid catalysts are HCl, HBr, HNO 3 , H 2 SO 4 , H 3 PO 4 , methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, phenolsulfonic acid and p-toluenesulfonic acid (pTSA).

[0064] In another embodiment, the polymer comprises repeating units having any one or more of formulae (6) to (12):

[0065]

[0066]

[0067] wherein Ar is as defined in formula (1). Preferably, the polymer comprises a repeating unit having formula (6).

[0068] The polymers of the present invention may have a weight average molecular weight (MW) of 500 to 20,000 Daltons (Da), preferably 500 to 15,000 Da, and more preferably 500 to 10,000 Da, as determined by gel permeation chromatography (GPC) using polystyrene standards. w ).

[0069] The primer composition may further comprise a solvent and optionally one or more additives selected from the group consisting of a curing agent, a cross-linking agent and a surfactant. It will be appreciated by those skilled in the art that other additives may be suitable for use in the composition of the present invention.

[0070] The solvent can be an organic solvent typically used in the electronics industry, such as PGME, PGMEA, methyl 3-methoxypropionate (MMP), ethyl lactate, n-butyl acetate, anisole, N-methylpyrrolidone, γ-butyrolactone (GBL), ethoxybenzene, benzyl propionate, benzyl benzoate, cyclohexanone, cyclopentanone, propylene carbonate, xylene, mesitylene, cumene, limonene, and mixtures thereof. Typically, the total solids of the bottom layer composition are 0.5 to 20 wt %, typically 0.5 to 10 wt %, of the total weight of the bottom layer composition, and the solvent accounts for the balance of the bottom layer composition.

[0071] Optionally, the bottom layer composition of the present invention may further include one or more curing agents to assist in the curing of the deposited polymer film. A curing agent is any component that cures the bottom layer composition on the substrate surface. A preferred curing agent is a thermal acid generator (TAG). TAG is any compound that releases acid when exposed to heat. Thermal acid generators are well known in the art and are typically commercially available from King Industries, Norwalk, Connecticut. Exemplary thermal acid generators include, but are not limited to, amine-terminated strong acids, such as amine-terminated sulfonic acids, such as amine-terminated dodecylbenzene sulfonic acid. It will also be understood by those skilled in the art that certain photoacid generators are capable of releasing acid when heated and can be used as thermal acid generators. The amount of such curing agents that can be used in the composition of the present invention can be, for example, greater than 0 to 10 wt % based on the total solids of the bottom layer composition, and typically greater than 0 to 3 wt %.

[0072] Any suitable crosslinking agent may be used in the primer composition of the present invention, provided that such crosslinking agent has at least 2, and preferably at least 3, moieties that can react with the polymer of the present invention under suitable conditions (e.g., under acidic conditions). Exemplary crosslinking agents include, but are not limited to, novolac resins, epoxy-containing compounds, melamine compounds, guanamine compounds, isocyanate-containing compounds, benzocyclobutene, benzoxazine, and the like, and typically are selected from the group consisting of hydroxymethyl, C 1-10Alkoxymethyl, and C 2-10 Any of the substituents of the acyloxymethyl group. Examples of suitable crosslinking agents are those shown by formulae (13) and (14).

[0073]

[0074] Such crosslinking agents are well known in the art and are commercially available from a variety of sources. The amount of such crosslinking agents useful in the compositions of the present invention may, for example, range from greater than 0 to 30 wt%, and preferably greater than 0 to 10 wt%, based on the total solids of the base layer composition.

[0075] The base composition of the present invention may optionally include one or more surface leveling agents (or surfactants) and antioxidants. Typical surfactants include those that exhibit amphiphilic properties, which means that they can be both hydrophilic and hydrophobic. Amphiphilic surfactants have one or more hydrophilic head groups (which have a strong affinity for water) and long hydrophobic tails that are organophilic and repel water. Suitable surfactants can be ionic (i.e., anionic, cationic) or nonionic. Additional examples of surfactants include silicone surfactants, poly (oxyalkylene) surfactants, and fluorochemical surfactants. Suitable nonionic surfactants include, but are not limited to, octyl and nonylphenol ethoxylates, such as X-114, X-100, X-45, X-15, and branched secondary alcohol ethoxylates, such as TERGITOL TM TMN-6 (Dow Chemical Company, Midland, Michigan, USA) and PF-656 (Omnova Solutions, Beachwood, Ohio, USA). Still other exemplary surfactants include, alcohol (primary and secondary) ethoxylates, amine ethoxylates, glucosides, glucosamines, polyethylene glycols, poly(ethylene glycol-co-propylene glycol), or other surfactants disclosed in the 2000 North American edition of McCutcheon's Emulsifiers and Detergents published by Manufacturers Confectioners Publishing Co. of Glen Rock, NJ. Nonionic surfactants that are derivatives of acetylenic diols may also be suitable. Such surfactants are commercially available from Air Products and Chemicals, Inc. of Allentown, Pennsylvania and are sold under the trade name and Other suitable surfactants include other polymer compounds, such as triblock EO-PO-EO copolymers 25R2, L121, L123, L31, L81, L101 and P123 (BASF Corporation). If used, such surfactants may be present in the composition in small amounts, for example, greater than 0 to 1 wt % based on the total solids of the primer composition.

[0076] Antioxidants can be added to the bottom layer composition to prevent or minimize the oxidation of organic materials in the composition. Suitable antioxidants include, for example, phenol-based antioxidants, antioxidants composed of organic acid derivatives, sulfur-containing antioxidants, phosphorus-based antioxidants, amine-based antioxidants, antioxidants composed of amine-aldehyde condensates, and antioxidants composed of amine-ketone condensates. Examples of phenol-based antioxidants include substituted phenols such as 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, butylated hydroxyanisole, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2-methyl-4,6-dinonylphenol, 2,6-di-tert-butyl-α-dimethylamino-p-cresol, 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-dioctyl-thio-1,3,5-triazine, n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl) propionate, octylated phenol, arylalkyl-substituted phenol, alkylated p-cresol and hindered phenol; bisphenols, triphenols and polyphenols, such as 4,4'-dihydroxydiphenyl, methylenebis(dimethyl-4,6-phenol), 2,2 '-Methylene-bis-(4-methyl-6-tert-butylphenol), 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(4-ethyl-6-tert-butylphenol), 4,4'-methylene-bis-(2,6-di-tert-butylphenol), 2,2'-methylene-bis-(6-α-methyl-benzyl-p-cresol), methylene-cross-linked polyvalent alkylphenols, 4,4'-butylene-bis-(3-methyl-6-tert-butylphenol), 1, 1-bis-(4-hydroxyphenyl)-cyclohexane, 2,2'-dihydroxy-3,3'-di-(α-methylcyclohexyl)-5,5'-dimethyldiphenylmethane, alkylated bisphenols, hindered bisphenols, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris-(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, and tetrakis-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane. Suitable antioxidants are commercially available, for example, Irganox TMAntioxidant (Ciba Specialty Chemicals Corp.) If used, the antioxidant may be present in the primer composition in an amount, for example, greater than 0 to 1 wt % based on the total solids of the primer composition.

[0077] Another aspect of the present invention provides a coated substrate, which includes a layer of a bottom layer composition disposed on the substrate; and a photoresist layer disposed on the layer of the bottom layer composition. The coated substrate may further include a silicon-containing layer and / or an organic anti-reflective coating disposed on the bottom layer composition and below the photoresist layer.

[0078] Yet another aspect of the present invention provides a method for forming a pattern. The method comprises: (a) applying a layer of a bottom layer composition on a substrate; (b) curing the applied bottom layer composition to form a bottom layer; and (c) forming a photoresist layer on the bottom layer. The method may further comprise forming a silicon-containing layer and / or an organic anti-reflective coating on the bottom layer before forming the photoresist layer. The method may further comprise patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the bottom layer and the layer below the bottom layer.

[0079] As used herein, the term "underlayer" refers to all removable processing layers between the substrate and the photoresist layer, such as an organic antireflective agent layer, a silicon-containing intermediate layer, a spin-on carbon layer, and a photoresist underlayer.

[0080] A variety of substrates can be used in the patterning method, of which electronic device substrates are typical. Suitable substrates include, for example, packaging substrates such as multi-chip modules; flat panel display substrates; integrated circuit substrates; substrates for light emitting diodes (LEDs) including organic light emitting diodes (OLEDs); semiconductor wafers; polycrystalline silicon substrates; etc. Suitable substrates can be in the form of wafers, such as those used to manufacture integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. As used herein, the term "semiconductor wafer" is intended to cover "electronic device substrates", "semiconductor substrates", "semiconductor devices" and various packages for various interconnect levels, including single-chip wafers, multi-chip wafers, packages for various levels, or other components requiring solder connections. Such substrates can be of any suitable size. Typical wafer substrate diameters are 200mm to 300mm, although wafers with smaller and larger diameters can be appropriately used according to the present invention. As used herein, the term "semiconductor substrate" includes any substrate having one or more semiconductor layers or structures, which may optionally include active or operable portions of semiconductor devices. A semiconductor device refers to a semiconductor substrate on which at least one microelectronic device has been or is being mass-produced.

[0081] The substrate is typically composed of one or more of silicon, polysilicon, silicon oxide, silicon nitride, silicon oxynitride, silicon germanium, gallium arsenide, aluminum, sapphire, tungsten, titanium, titanium-tungsten, nickel, copper and gold. The substrate may include one or more layers and patterned features. The layers may include, for example, one or more conductive layers, such as aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys of these metals, nitrides or silicides, layers of doped amorphous silicon or doped polycrystalline silicon; one or more dielectric layers, such as layers of silicon oxide, silicon nitride, silicon oxynitride or metal oxide; semiconductor layers, such as single crystal silicon; and combinations thereof. The layers may be formed by various techniques, such as chemical vapor deposition (CVD), such as plasma enhanced CVD (PECVD), low pressure CVD (LPCVD) or epitaxial growth, physical vapor deposition (PVD), such as sputtering or evaporation, or electroplating.

[0082] The bottom layer composition can be coated on the substrate by any suitable means such as spin coating, slot die coating, scraping, curtain coating, roller coating, spray coating, dip coating, etc. In the case of semiconductor wafer, spin coating is preferred. In a typical spin coating method, the bottom layer composition is applied to the substrate rotating at a speed of 500 to 4000 rpm for a period of 15 to 90 seconds to obtain the layer of the bottom layer composition of hope on the substrate. It will be appreciated by those skilled in the art that the thickness of the bottom layer composition applied can be regulated by changing the solid content of the rotation speed and the composition. The bottom layer formed by the bottom layer composition typically has a dry layer thickness of 5nm to 50 μm, typically 25nm to 3 μm and more typically 50 to 500nm. The bottom layer composition can be applied so as to fill substantially, preferably fill and more preferably fill a plurality of gaps on the substrate completely.

[0083] The applied bottom layer composition is optionally soft-baked at a relatively low temperature to remove any solvent and other relatively volatile components in the composition. Exemplary baking temperatures can be 60° C. to 170° C., although other suitable temperatures can be used. This baking to remove residual solvent can be performed for 10 seconds to 10 minutes, although longer or shorter times can be used appropriately. When the substrate is a wafer, this baking step can be performed by heating the wafer on a hot plate.

[0084] Then the applied bottom layer composition is cured to form a bottom layer, such as a photoresist bottom layer. The bottom layer composition should be fully cured so that the bottom layer is not mixed with the layer applied subsequently (such as a photoresist or other organic or inorganic layer directly arranged on the bottom layer), or is minimally mixed. The bottom layer composition can be cured in an oxygen-containing atmosphere (such as air) or in an inert atmosphere (such as nitrogen) and under conditions (such as heating) sufficient to provide a cured coating. This curing step is preferably carried out on a hot plate type device, although oven curing can be used to obtain equivalent results. The curing temperature should be sufficient to cure the entire layer, for example, sufficient to crosslink a curing agent such as a free acid, or to release an acid from a thermal acid generator and crosslink the released acid, wherein the curing agent is TAG. Typically, curing is carried out at a temperature of 150°C or higher, and preferably 150°C to 450°C. More preferably, the curing temperature is 180°C or higher, still more preferably 200°C or higher, and even more preferably 200°C to 400°C. The curing time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, more preferably 45 seconds to 5 minutes and also more preferably 45 to 90 seconds. Optionally, a ramp-up or multi-stage curing process can be used. The ramp-up baking typically starts at a relatively low (e.g., ambient) temperature, and the temperature is increased to a higher target temperature with a constant or variable ramp-up rate. The multi-stage curing process involves curing at two or more temperature platforms, typically carrying out the first stage at a lower baking temperature, and carrying out one or more additional stages at a higher temperature. The conditions of such ramp-up or multi-stage curing processes are known to those skilled in the art, and it is possible to allow the previous soft baking process to be omitted.

[0085] After the bottom layer composition is cured, one or more treatment layers such as a photoresist layer, a hard mask layer (such as a metal hard mask layer), an organic or inorganic BARC layer, etc. can be arranged on the cured bottom layer. The photoresist layer can be directly formed on the surface of the bottom layer, or alternatively, it can be formed on one or more intermediate layers on the bottom layer. In this case, one or more intermediate treatment layers (as described above) can be formed sequentially on the bottom layer, and then a photoresist layer is formed. The determination of suitable layers, thicknesses and coating methods is well known to those skilled in the art.

[0086] A wide variety of photoresists can be suitably used in the methods of the present invention and are typically positive-working materials. Suitable photoresists include, for example, EPIC available from DuPont Electronics & Imaging of Marlborough, Massachusetts. TM The photoresist may be applied to the substrate by known coating techniques (as described above with respect to the bottom layer composition, of which spin coating is typical). The typical thickness of the photoresist layer is 500 to Next, the photoresist layer is typically soft baked to minimize the solvent content in the layer, thereby forming a tack-free coating and improving the adhesion of the layer to the substrate. The soft bake can be performed on a hot plate or in an oven, with a hot plate being typical. A typical soft bake is performed at a temperature of 90°C to 150°C and for a time of 30 to 90 seconds.

[0087] Optionally, one or more barrier layers may be disposed on the photoresist layer. Suitable barrier layers include topcoats, top antireflective coatings (or TARC layers), and the like. Preferably, a topcoat is used when the photoresist is patterned using immersion lithography. Such topcoats are well known in the art and are generally commercially available, such as OCTL® available from DuPont Electronics & Imaging. TM 2000. Those skilled in the art will recognize that when an organic antireflective agent layer is used beneath the photoresist layer, a TARC layer is not required.

[0088] Next, the photoresist layer is exposed to activating radiation through a photomask to produce a solubility difference between the exposed area and the unexposed area. The photoresist composition mentioned herein is exposed to the radiation indicating radiation having an activating effect on the composition to form a latent image in the photoresist composition. The photomask has optically transparent and optically opaque regions, corresponding to the regions to be exposed and unexposed by the activating radiation in the resist layer, respectively. The exposure wavelength is typically lower than 400nm, lower than 300nm, such as 248nm (KrF), 193nm (ArF) or EUV wavelength (e.g. 13.5nm). In a preferred aspect, the exposure wavelength is 193nm. The exposure energy is typically 10 to 80mJ / cm 2 , depending on, for example, the exposure tool and the components of the photosensitive composition.

[0089] After exposing the photoresist layer, a post-exposure bake (PEB) is typically performed. PEB can be performed, for example, on a hot plate or in an oven. PEB is typically performed at a temperature of 80° C. to 150° C. and for 30 to 90 seconds. A latent image defined by the boundary between the polarity-converted and unconverted regions (corresponding to the exposed and unexposed regions, respectively) is thereby formed. The exposed photoresist layer is then developed using an appropriate developer to provide a patterned photoresist layer.

[0090] The pattern of the photoresist layer can then be transferred to one or more underlying layers including the bottom layer and to the substrate by an appropriate etching technique, such as by plasma etching or wet etching. Plasma etching can use appropriate gas species for each layer being etched. Suitable wet chemical etching chemicals include, for example, a mixture containing ammonium hydroxide, hydrogen peroxide and water (e.g., SC-1 cleaning solution); a mixture containing hydrochloric acid, hydrogen peroxide and water (e.g., SC-2 cleaning solution); a mixture containing sulfuric acid, hydrogen peroxide and water (e.g., SPM cleaning solution); a mixture containing phosphoric acid, hydrogen peroxide and water; a mixture containing hydrofluoric acid and water; a mixture containing hydrofluoric acid, phosphoric acid and water; a mixture containing hydrofluoric acid, nitric acid and water; a mixture containing tetramethylammonium hydroxide and water; etc.

[0091] Depending on the number of layers and materials involved, pattern transfer may involve multiple etching steps using different techniques. After pattern transfer to the substrate using conventional techniques, the patterned photoresist layer, the bottom layer, and other optional layers in the photolithography stack may be removed. Optionally, one or more of the layers of the stack may be removed or consumed after the pattern is transferred to the underlying layer and before the pattern is transferred to the substrate. The substrate is then further processed according to known methods to form an electronic device.

[0092] The bottom layer composition can also be used for self-aligned double patterning process. In this process, a layer of the above-mentioned bottom layer composition is coated on a substrate such as by spin coating. Any remaining organic solvent is removed and the coating is cured to form a photoresist bottom layer. A suitable intermediate layer such as a silicon-containing hard mask layer is optionally coated on the photoresist bottom layer. Then a suitable photoresist layer is coated on the intermediate layer such as by spin coating. The photoresist layer is then imaged (exposed), and then the exposed photoresist layer is developed using a suitable developer to provide a patterned photoresist layer. Next, the pattern is transferred from the photoresist layer to the intermediate layer and the bottom layer by a suitable etching technique to expose a part of the substrate. Typically, the photoresist is also removed during this etching step. Next, a conformal silicon-containing layer is arranged on the exposed portion of the patterned bottom layer and the substrate. Such silicon-containing layers are typically inorganic silicon layers conventionally deposited by CVD, such as SiON or SiO 2. Such conformal coating produces a silicon-containing layer on the exposed portion of the substrate surface and on top of the underlying pattern, i.e., such silicon-containing layer substantially covers the sides and top of the underlying pattern. Next, the silicon-containing layer is partially etched (trimmed) to expose the top surface of the patterned underlying layer and a portion of the substrate. After this partial etching step, the pattern on the substrate comprises a plurality of features, each feature comprising a line or column of the underlying layer, wherein the silicon-containing layer is directly adjacent to the side of each underlying feature. Next, the exposed area of ​​the underlying layer is removed, such as by etching, to expose the substrate surface below the underlying pattern, and to provide a patterned silicon-containing layer on the substrate surface, wherein such patterned silicon-containing layer is double (i.e., twice as many lines and / or columns) compared to the patterned underlying layer.

[0093] The bottom layer (such as a photoresist bottom layer) formed by the bottom layer composition of the present invention shows excellent planarization and good solvent resistance. Therefore, the preferred bottom layer composition of the present invention can be used in various semiconductor manufacturing processes.

[0094] The inventive concept is further illustrated by the following examples. All compounds and reagents used herein are commercially available, except for the procedures provided below.

[0095] Examples

[0096] Polymer synthesis

[0097] Synthesis Example 1

[0098] 8.0g of 1-naphthol (1 equivalent), 8.34g of (1R)-(-)-myrtle aldehyde (1 equivalent) and 20mL of PGME were added to a round-bottom flask. The reaction mixture was warmed to 60°C and stirred for 5 minutes, and then 5.33g of methanesulfonic acid was added at one time. The reaction was then heated to 120°C for 20h. After this reaction time, the reaction mixture was cooled to room temperature and poured into a 9 / 1 (v / v) methanol / water solution to obtain a solid polymer product. The product was filtered out and washed with methanol, then air-dried for 4h and vacuum-dried for 20h at 50°C to obtain Synthesis Example 1 (P-1). (61% yield, Mw=1010, PDI=1.2).

[0099] Synthesis Examples 2 to 6

[0100] Synthesis Examples 2 (P-2) to 6 (P-6) were prepared using the same procedure as above using the corresponding aromatic monomers to obtain the desired polymers (as shown by the following structures). Citral was used as the aldehyde monomer for Synthesis Examples 5 and 6.

[0101] Synthesis Example 7

[0102] 10.0 g of 4,4'-(9-fluorenyl)biphenol (1 equivalent), 5.21 g of acenaphthenequinone (1 equivalent) and 40 mL of PGME were added to a round-bottom flask. The reaction mixture was warmed to 60 ° C and stirred for 5 minutes, and then 2.00 g of methanesulfonic acid was added at one time. The reaction was then heated to 120 ° C for 24 h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to obtain a solid polymer product. The product was filtered out and washed in water and methanol, then air-dried for 4 h and vacuum-dried at 50 ° C for 20 h to obtain Synthesis Example 7 (P-7). (40% yield, Mw=1120, PDI=1.3).

[0103] Synthesis Examples 8 to 12

[0104] Synthesis Examples 8 (P-8) to 12 (P-12) were prepared using the same procedure as above using the corresponding aromatic monomers and diketone monomers to obtain the desired polymers (as shown by the following structures).

[0105]

[0106] Comparative polymer synthesis

[0107] Comparative Synthesis Example 1

[0108] 5.0g of 1-naphthol (1 equivalent), 1.04g of paraformaldehyde (1 equivalent) and 25mL of propylene glycol monomethyl ether acetate (PGMEA) were added to a round-bottom flask. The reaction mixture was warmed to 60°C and stirred for 5 minutes, and then 0.20g of methanesulfonic acid was added at one time. The reaction was then heated to 120°C for 16h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to obtain a solid polymer product. The product was filtered out and washed in water and methanol, then air-dried for 4h and vacuum-dried for 20h at 50°C to obtain comparative synthesis example 1 (CP-1). (52% yield, Mw=2240, PDI=2.0).

[0109] Comparative Synthesis Example 2

[0110] 5.0g carbazole (1.5 equivalents), 0.60g paraformaldehyde (1 equivalent) and 20mL propylene glycol monomethyl ether acetate (PGMEA) were added to a round-bottom flask. The reaction mixture was warmed to 60°C and stirred for 5 minutes, and then 1.45g methanesulfonic acid was added at one time. The reaction was then heated to 120°C for 16h. A solid precipitate was formed in the reaction mixture during the reaction. After this specified time, the reaction mixture was cooled to room temperature and the suspension was poured into 9 / 1 (v / v) methanol / water to obtain a solid polymer product. The product was filtered out and washed with methanol, then air-dried for 4h and vacuum-dried for 20h at 50°C to obtain comparative synthesis example 2 (CP-2). (80% yield, Mw=2730, PDI=2.5).

[0111] Comparative Synthesis Example 3

[0112] 5.0g of 1-pyrenol (1 equivalent), 0.69g of paraformaldehyde (1 equivalent) and 20mL propylene glycol monomethyl ether (PGME) are added to a round-bottomed flask. The reaction mixture is warmed to 60°C and stirred for 5 minutes, then 2.20g of methanesulfonic acid is added at once. The reaction is then heated to 120°C for 1h. After this reaction time, the reaction is mostly solidified. Solid is taken out from the flask and washed in water and methanol, then air-dried for 4h and vacuum dried for 20h at 50°C to obtain comparative synthesis example 3 (CP-3).

[0113] Comparative Synthesis Example 4

[0114] 10.0g of 1-naphthol (1 equivalent), 7.78g of cyclohexanecarboxaldehyde (1 equivalent) and 30mL propylene glycol monomethyl ether (PGME) are added to a round-bottom flask. The reaction mixture is warmed to 60°C and stirred for 5 minutes, then 6.70g of methanesulfonic acid is added at once. The reaction is then heated to 120°C for 20h. After this reaction time, the reaction mixture is cooled to room temperature and poured into 9 / 1 (v / v) methanol / water to obtain a solid product. The product is filtered out and washed in methanol, then air-dried for 4h and vacuum-dried for 20h at 50°C to obtain. Comparative synthesis example 4 (CP-4) is identified as a non-polymerized small molecule product by GPC analysis.

[0115] Comparative Synthesis Example 5

[0116] In a round-bottomed flask, 10.0g of 1-naphthol (1 equivalent), 7.92g of heptaldehyde (1 equivalent) and 35mL of propylene glycol monomethyl ether (PGME) were added. The reaction mixture was warmed to 60°C and stirred for 5 minutes, then 6.70g of methanesulfonic acid was added at once. The reaction was then heated to 120°C for 20h. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water. Precipitation was not observed, so the crude mixture was concentrated to obtain an oily substance. Comparative synthesis example 5 (CP-5) was identified as a non-polymerized small molecule product by GPC analysis.

[0117]

[0118] Physical Testing

[0119] The number average molecular weight and weight average molecular weight (M n and M w ) and polydispersity (PDI) value (M w / M n ) was measured by gel permeation chromatography (GPC) on an Agilent 1100 series LC system (Wyatt Technology Co.) equipped with an Agilent 1100 series refractive index and MiniDAWN light scattering detector. The sample was dissolved in HPLC grade THF at a concentration of approximately 10 mg / mL and filtered through a 0.45 μm syringe filter and then injected through four Shodex columns (KF805, KF804, KF803 and KF802). A flow rate of 1 mL / min and a temperature of 35° C. were maintained. The column was calibrated with a narrow molecular weight PS standard (EasiCal PS-2, Polymer Laboratories, Inc.).

[0120] The glass transition temperature of the bulk polymer was determined using differential scanning calorimetry (DSC). The sample (1-3 mg) was heated to and held at 150° C. for 10 minutes to remove residual solvent on the first cycle, then cooled to 0° C. and ramped back to 300° C. at a heating rate of 10° C. / min. The glass transition temperature was determined using the second heating curve and the reversible heating curve.

[0121] Table 1 shows the molecular weight, solubility and thermal characteristics of polymers P-1 to P-12 and comparative polymers CP-1 to CP-5.

[0122] Table 1

[0123]

[0124] aSolubility measured at 10 wt% in PGMEA. +++ indicates complete dissolution, + indicates partial dissolution with some particles observed, and X indicates minimal dissolution or no dissolution at this concentration.

[0125] b Measured by DSC with a heating rate of 10°C / min; N / A indicates "not observed".

[0126] c The reaction involved 4 equivalents of aldehyde compared to the aryl alcohol.

[0127] As shown in Table 1, the polymers of the present invention have better solubility and lower glass transition temperature than the comparative examples.

[0128] Preparations

[0129] The primer composition was prepared by combining the polymers described in Table 1 with the composition forming components summarized in Table 2. Prior to coating, the composition was filtered through a 0.2 μm PTFE syringe filter. The amounts of polymer, additive 1, additive 2, and solvent are listed in grams (g).

[0130] Table 2

[0131]

[0132] * Solvent resistance and planarization are described below.

[0133] The structures of Additive B-1, Additive C-1, Solvent D-1 and Solvent D-2 are as follows.

[0134]

[0135] Coating and Film Testing

[0136] The primer composition was coated at 100-200 nm and baked at 240° C. for 60 seconds. The film thickness was measured by ellipsometry.

[0137] Solvent resistance

[0138] Solvent resistance was measured as an indicator of film crosslinking. The bottom layer composition was coated on an 8-inch silicon wafer using an ACT-8 Clean Track (Tokyo Electron Co.) and baked. The thickness of the film was measured using an OptiProbeTM from Therma-wave Co. Propylene glycol monomethyl ether acetate (PGMEA) was applied to the film for 90 seconds and then post-peeled and baked (PSB) at 105°C for 60 seconds. Solvent resistance was calculated according to et al. 1:

[0139] [(FT before stripping) - (FT after PSB)] / (FT before stripping) * 100% Equation 1

[0140] Where FT is the film thickness. Solvent resistance is reported in Table 2, where A is defined as 95%-100% solvent resistance and B is defined as less than 95% solvent resistance.

[0141] Flatness test

[0142] The bottom layer compositions of the present invention were evaluated to determine their planarization properties. Templates were created at CNSE Nano-FAB (Albany, NY). The templates had 100 nm of SiO 2 Film thickness, and various spacings and patterns of mold size of 1cm×1cm. Each mold starts with a 100nm single step pattern, followed by a 2000μm non-patterned open area, followed by various line / space patterns covering 45nm / 90nm to 2μm / 5μm spacing grooves. The first step pattern is used to judge the flattening performance. Before coating the sample with the composition of the present invention, the template sample is baked at 150°C for 60 seconds as a dehydration bake. Use a spin coater and apply each bottom layer composition to the template sample at a spin coating rate of 1500rpm+ / -200rpm. The target film thickness after curing is 100nm, and the composition dilution is adjusted accordingly to approximately obtain the target film thickness after curing. The film is cured by placing the wafer on a hot plate at 240°C for 60 seconds. The flattening quality of the entire step film is evaluated by a KLATencor P-7 stylus profiler.

[0143] In Table 2, the planarization quality is defined as follows: A indicates a height variation of less than 30 nm, and B indicates a height variation of more than 30 nm. A smaller number indicates a better planarization performance, so A indicates the best planarization and B indicates the worst planarization performance.

[0144] As can be seen from Table 2, the primer composition of the present invention has excellent planarization performance compared to the comparative primer composition.

[0145] While the disclosure has been described in connection with what are presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

Claims

1. A primer composition comprising a polymer comprising repeating units having one or more of the formulae (6) to (9): in, Ar is a monocyclic or polycyclic C 5-60 Heteroarylene or monocyclic or polycyclic C 6-60 Arylene, which is optionally substituted by at least one of the following: substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Haloalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 1-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, substituted or unsubstituted C 4-30 Heteroarylalkyl, halogen, -OR 21 、-SR 22 or -NR 23 R 24 , where R 21 To R 24 are independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl, The premise is that the monocyclic or polycyclic C 6-60 The arylene group is substituted with at least one substituent containing a heteroatom.

2. The primer composition according to claim 1, wherein Ar comprises a group having formula (2): in, A1, A2 and A3 may be present or absent, and each independently represents 1 to 3 condensed aromatic rings; R 3 and R 4 are each independently substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl, halogen, -OR 31 、-SR 32 or -NR 33 R 34 ; The premise is R 3 or R 4 At least one of -OR 31 、-SR 32 or -NR 33 R 34 ; R 31 To R 34 are independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 heteroarylalkyl; m is an integer from 0 to 4; n is an integer from 0 to 4; and The premise is that the sum of m and n is an integer greater than 0.

3. The primer composition according to claim 1, wherein Ar comprises a group having formula (3a), (3b) or (3c): in, A4 may be present or absent and represents 1 to 3 fused aromatic rings; Z 1 and Z 2 each independently is C or N; Each R 5 is independently substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 heteroarylalkyl; and p is an integer from 0 to 4, Where A4 contains at least one heteroaryl ring, Z 1 and Z 2 At least one of is N, or a combination thereof.

4. The primer composition according to claim 1, wherein Ar comprises a group having formula (4): in, L 1 It is a single bond, -O-, -S-, -S(O)-, -SO2-, -C(O)-, -CR 51 R 52 -、-NR 53 -or-PR 54 -; L 2 is absent, a single bond, -O-, -S-, -S(O)-, -SO2-, -C(O)-, substituted or unsubstituted C 1-2 Alkylene, substituted or unsubstituted C 6-30 Arylene, or substituted or unsubstituted C 5-30 heteroarylene; R 8 and R 9 are each independently substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 2-30 Alkenyl, substituted or unsubstituted C 2-30 Alkynyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 7-30 Alkyl aryl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 Heteroarylalkyl, halogen, -OR 55 、-SR 56 or -NR 57 R 58 ; R 51 To R 58 are independently hydrogen, substituted or unsubstituted C 1-30 Alkyl, substituted or unsubstituted C 1-30 Heteroalkyl, substituted or unsubstituted C 3-30 Cycloalkyl, substituted or unsubstituted C 2-30 Heterocycloalkyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 7-30 Arylalkyl, substituted or unsubstituted C 3-30 Heteroaryl, or substituted or unsubstituted C 4-30 heteroarylalkyl; a is an integer from 0 to 4; and b is an integer from 0 to 4.

5. The primer composition according to claim 1, wherein The monocyclic or polycyclic C 5-60 Aromatic groups are monocyclic or polycyclic C 6-60 Arylene. The primer composition according to claim 1 , further comprising one or more of a curing agent, a cross-linking agent or a surfactant.

7. A method for forming a pattern, the method comprising: (a) applying a layer of the primer composition according to any one of claims 1 to 6 on a substrate; (b) curing the applied primer composition to form a primer layer; and (c) forming a photoresist layer on the primer layer.

8. The method of claim 7, further comprising forming a silicon-containing layer, an organic anti-reflective coating, or a combination thereof on the underlying layer before forming the photoresist layer.

9. The method of claim 7 or 8, further comprising: The photoresist layer is patterned, and a pattern is transferred from the patterned photoresist layer to the underlying layer and layers below the underlying layer.

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