Lower layer composition and patterning method

Abstract

To provide underlayer compositions and patterning methods.SOLUTION: There is provided an underlayer composition, comprising a polymer comprising a repeating unit of formula (1):wherein Ar is a monocyclic or polycyclic C5-60 aromatic group, wherein the aromatic group comprises one or more aromatic ring heteroatoms, a substituent group comprising a heteroatom, or a combination thereof; X is C or O; R1, R2, Ra and Rb are as provided herein; optionally, R1 and R2 can be taken together to form a 5- to 7-membered ring; optionally, one of R11 to R13 can be taken together with R1 to form a 5- to 7-membered ring; wherein Ra and Rb optionally may be taken together to form a 5- to 7-membered ring; wherein one of Ra or Rb optionally may be taken together with R2 to form a 5- to 7-membered ring; and the like.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention generally relates to the field of manufacturing electronic devices, and more specifically to the field of materials for use in semiconductor manufacturing. [Background technology]

[0002] Photoresist underlayer compositions are used in the semiconductor industry as etching masks for lithography in the latest technology nodes for integrated circuit manufacturing. These compositions are commonly used in 3- and 4-layer photoresist integration schemes in which layers of an anti-reflective film containing organic or silicon and a patternable photoresist film are placed on top of a high-carbon-content bottom layer.

[0003] An ideal photoresist underlayer material must possess specific characteristics. Specifically, it must be cast onto the substrate by a spin-coating process, thermally cure with minimal gas release and sublimation upon heating, be soluble in common solvents for excellent compatibility with spin bowls, have an appropriate n&k value to function with an anti-reflective coating layer to impart the low reflectivity required for photoresist imaging, and possess high thermal stability to avoid damage during subsequent processing steps. In addition to these requirements, an ideal photoresist underlayer material must, after spin-coating and thermal curing on the substrate, impart topography and sufficient dry etching selectivity to the silicon-containing layers above and below the photoresist underlayer film, resulting in a flat film for accurately transferring the photopattern to the final substrate.

[0004] For lower layer applications, crosslinkable novolac resins have been used. Novolacs are condensation polymerization products of one or more activated aromatic compounds with another monomer selected from aliphatic or aromatic carbonyl compounds, benzyl ethers, benzyl alcohols, or benzyl halides. The most widely studied novolac resins are polycondensation products of activated aromatic derivatives with formaldehyde-type or aromatic aldehyde comonomers. These resins have been widely used in various lithography compositions. However, their rigid, highly aromatic skeletons often result in resins with increased glass transition temperatures, which can impair the gap-fill and planarization properties of the resin.

[0005] Novel underlayer materials, such as photoresist underlayer materials, are still needed that can impart 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. [Overview of the project] [Means for solving the problem]

[0006] Formula (1): [ka] A lower layer composition is provided which includes a polymer containing repeating units of the formula (wherein Ar is a monocyclic or polycyclic C 5~60 It is an aromatic group, and the aromatic group comprises one or more aromatic ring heteroatoms, heteroatom-containing substituents, or combinations thereof; X is C or O; R 1 C is hydrogen, substituted or unsubstituted. 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 2~30alkynyl, substituted or unsubstituted C 6~30 aryl, substituted or unsubstituted C 7~30 arylalkyl, substituted or unsubstituted C 7~30 alkylaryl, 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 alkylaryl, substituted or unsubstituted C 3~30 heteroaryl, substituted or unsubstituted C4 ~30 heteroarylalkyl, or -NR 11 R 12 is, and R 11 ~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 may together form a 5- to 7-membered ring; optionally, R 11 ~R 12 at least one of may together with R 1 form a 5- to 7-membered ring; ; when X is C, R a and Rb These 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 2~30 Alkenyl, substituted, or unsubstituted C 2~30 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, or substituted or unsubstituted C 4~30 It is a heteroarylalkyl; R a and R b These may optionally come together to form a 5-7 member ring; R a or R b One of them is R, which is chosen at will. 2 They may also form a 5-7 member ring together; if X is O, R a and R b (It does not exist).

[0007] A method for forming a pattern is also provided, which includes (a) coating a layer of a base composition onto a substrate; (b) curing the coated base composition to form a base layer; and (c) forming a photoresist layer on top of the base layer. [Modes for carrying out the invention]

[0008] Hereafter, examples of exemplary embodiments shown herein will be referenced in detail. In this regard, these exemplary embodiments may take different forms and should not be construed as being limited to the descriptions expressed herein. Accordingly, exemplary embodiments are described below only by reference to the figures in order to illustrate the aspects described herein. As used herein, the terms “and / or” encompass any combination of one or more of the enumerated items relating thereto. Expressions such as “at least one” qualify the entire list of elements when preceding a list of elements, and do not qualify the individual elements of the list.

[0009] As used herein, the terms “a,” “an,” and “it” do not imply a limitation of quantity and should be interpreted as encompassing both singular and plural forms unless otherwise specifically indicated herein or the context clearly contradicts this interpretation. “Or” means “and / or” unless otherwise specified. All scopes disclosed herein include endpoints, which can be independently combined with one another. The suffix “(s)” is intended to include both singular and plural forms of the term it modifies, thereby including at least one of those terms. “Optional” or “optionally” means that the description includes whether the event or situation described thereafter may or may not occur, and whether the event occurs or does not occur. Terms such as “first,” “second,” etc., do not imply order, quantity, or importance and are used herein to distinguish one element from another. When an element is said to be "on" another element, it can either be in direct contact with the other element or an intervening element may exist between them. In contrast, when an element is said to be "directly on" another element, no intervening element is present. It should be understood that the components, elements, limitations and / or features described in the embodiments can be combined in any preferred manner in various embodiments.

[0010] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as those generally understood by those skilled in the art in which the present invention pertains. Terms such as those defined in commonly used dictionaries should be interpreted as having the same meaning as those in the context of the relevant art and this disclosure, and it will be further understood that unless explicitly defined herein, they should not be interpreted in an ideal or overly formal sense.

[0011] As used herein, the term "hydrocarbon group" means an organic compound having at least one carbon atom and at least one hydrogen atom, optionally substituted with one or more substituents, as indicated; "alkyl group" means a linear or branched saturated hydrocarbon having the specified number of carbon atoms and a valency of 1; "alkylene group" means an alkyl group having a valency of 2; "hydroxyalkyl group" means an alkyl group substituted with at least one hydroxyl group (-OH); and "alkoxy group" means an alkyl group having a valency of 2. "-O-" means; "carboxylic acid group" means a group having the formula "-C(=O)-OH"; "cycloalkyl group" means a monovalent group having one or more saturated rings in which all ring constituent atoms are carbon; "cycloalkylene group" means a cycloalkyl group with a valency of 2; "alkenyl group" means a monovalent hydrocarbon group that is straight-chain or branched-chain and has at least one carbon-carbon double bond; "alkenoxy group" means "alkenyl-O-"; "alkenylene group" means an alkenyl group that has a valency of at least 2; "cyclo "Alkenyl group" means a cycloalkyl group having at least one carbon-carbon double bond; "alkynyl group" means a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" means the conventional concept of aromaticity as defined in the literature, particularly in IUPAC19, and refers to a monocyclic or polycyclic aromatic ring system containing carbon atoms in the ring and optionally containing one or more heteroatoms independently selected from N, O, and S instead of the carbon atoms in the ring; "aryl group" means a monovalent aromatic monocyclic or polycyclic group containing only carbon atoms in the aromatic ring, which may include a group having an aromatic ring fused to at least one cycloalkyl or heterocycloalkyl ring; "arylene group" means an aryl group having at least a valency of 2; "alkylaryl group" means an aryl group substituted with an alkyl group; "arylalkyl group" means an alkyl group substituted with an aryl group; "aryloxy group" means "aryl-O-"; and "arylthio group" means "aryl-S-".

[0012] The prefix "hetero" means that a compound or group contains at least one ring-forming atom (e.g., 1, 2, 3 or 4 or more heteroatoms) that is a heteroatom instead of a carbon atom, where each heteroatom is independently selected from N, O, S, Si, or P; "heteroatom-containing group" means a substituent containing at least one heteroatom; "heteroalkyl group" means an alkyl group having 1 to 4 heteroatoms instead of a carbon atom; "heterocycloalkyl group" means a cycloalkyl group having 1 or more N, O, or S atoms instead of a carbon atom; "heterocycloalkylene group" means a heterocycloalkyl group having at least a valency of 2; "heteroaryl group" means an aryl group having 1 to 3 separate or fused rings having 1 or more N, O, or S atoms as ring-forming atoms instead of a carbon atom; "heteroarylene group" means a heteroaryl group having at least a valency of 2.

[0013] The term "halogen" refers to a monovalent substituent that is fluorine (fluoro), chlorine (chloro), bromine (bromo), or iodine (iodo). The prefix "halo" refers to a group that contains one of the fluoro, chloro, bromo, or iodo substituents instead of a hydrogen atom. A combination of halo groups (e.g., bromo and fluoro) or a fluoro group alone may be present.

[0014] The symbol "*" represents a connection point (i.e., a link point) of a repeating unit.

[0015] "Substituted" means that at least one hydrogen atom on a group is replaced by another group, provided that the valency does not exceed the normal valency of the specified atom. If the substituent is oxo (i.e., =O), two hydrogens on the carbon atom are replaced. Combinations of substituents or variables are permitted. Exemplary groups that may be present in the "substituted" position include nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=O), amino (-NH2), mono- or di-(C) 1~6 ) Alkylamino, alkanoyl (acyl, etc.) 2~6Alkanoyl groups, etc.), formyl (-C(=O)H), carboxylic acids or their alkali metal or ammonium salts, C 2~6 Alkyl ester (-C(=O)O-alkyl or -OC(=O)-alkyl), C 7~13 Aryl esters (-C(=O)O-aryl or -OC(=O)-aryl), amides (-C(=O)NR2 (where R is hydrogen or C) 1~6 Alkyl), carboxamide (-CH2C(=O)NR2 (where R is hydrogen or C) 1~6 Alkyl, halogen, thiol (-SH), C 1~6 Alkylthio(-S-alkyl), thiocyano(-SCN), C1-6 alkyl, C 2~6 Alkenil, C 2~6 Alkinyl, C 1~6 Haloalkyl, C1-9 alkoxy, C 1~6 Haloalkoxy, C 3~12 Cycloalkyl, C 5~18 Cycloalkenyl, a C having at least one aromatic ring (e.g., phenyl, biphenyl, naphthyl, or similar, each ring being either substituted or unsubstituted). 6~12 A C atom having an aryl, 1-3 separate or fused ring and 6-18 ring carbon atoms. 7~19 Arylalkyls, arylalkoxys having 1-3 separated or fused rings and 6-18 ring carbon atoms, C 7~12 Alkylaryl, C 4~12 Heterocycloalkyl, C 3~12 Heteroaryl, C 1~6 Alkylsulfonyl (-S(=O)2-alkyl), C 6~12 Examples include, but are not limited to, arylsulfonyl (-S(=O)2-aryl) or tosyl (CH3C6H4SO2-). If the group is substituted, the number of carbon atoms indicated is the total number of carbon atoms in the group, excluding the carbon atoms of any substituents. For example, the group -CH2CH2CN is a C2 alkyl group substituted with a cyano group.

[0016] As mentioned above, one of the most widely studied novolac resins is the polycondensation product of an activated aromatic derivative with a formaldehyde-type or aromatic aldehyde comonomer. These resins have been widely used in various lithography compositions. However, their rigid and highly aromatic skeletons increase the glass transition temperature and impair gap-fill and planarization properties. There is still a continuing need for novel photoresist underlayer materials that can impart 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.

[0017] 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.

[0018] According to one embodiment, the lower layer composition is formula (1): [ka] (In equation (1), Ar is a monocyclic or polycyclic C) 5~60 The polymer contains an aromatic group, which is an aromatic group comprising a repeating unit of one or more aromatic ring heteroatoms, substituents containing heteroatoms, or combinations thereof. For convenience, this specification refers to monocyclic or polycyclic C 5~60 Aromatic groups are sometimes called "Ar groups." Typically, one or more heteroatoms can be independently selected from N, O, or S. 5~60 When the aromatic group is polycyclic, the ring or ring group may be condensed (e.g., naphthyl), directly bonded (e.g., biaryl, biphenyl), and / or crosslinked by a heteroatom (e.g., triphenylamino or diphenylene ether). In one embodiment, the polycyclic aromatic group may include a combination of a fused ring and a directly bonded ring (e.g., binaphthyl). Monocyclic or polycyclic C5~60 One or more heteroatoms of the aromatic group may be present as ring-constituting atoms of the aromatic ring in place of carbon atoms (e.g., heteroarylene group), as one or more heteroatoms of a heteroatom-containing substituent (e.g., hydroxyl substituent), or in combinations thereof, and this should be understood.

[0019] Monocyclic or polycyclic C 5~60 The aromatic group can 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 alkylaryl, substituted or unsubstituted C 3~30 heteroaryl, substituted or unsubstituted C 4~30 heteroarylalkyl, halogen, -OR 21 、-SR 22 、or -NR 23 R 24 are included, and R 21 ~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.

[0020] In one embodiment, monocyclic or polycyclic C5~60 Aromatic groups are monocyclic or polycyclic carbon groups. 6~60 Arirene group or monocyclic or polycyclic C 5~60 A heteroarylene group may also be used. 5~60 Aromatic groups are monocyclic or polycyclic C 6~60 If it is an arylene group, at least one hydrogen atom is -OR 21 , -SR 22 , or -NR 23 R 24 As described above, R is substituted with a heteroatom-containing substituent. 21 ~R 24 Each of these independently consists of hydrogen, or substituted or unsubstituted carbon. 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 It is a heteroarylalkyl. Preferably, Ar is a polycyclic C 10~60 Arylene group or polycyclic carbon 7~60 It is a heteroarylene group. Examples of Ar groups, though not limited to them, include substituted or unsubstituted carbazole diyl, substituted phenylene, substituted biphenylene, substituted naphthylene, and substituted pyrenylene.

[0021] In one embodiment, a monocyclic or polycyclic C 5~60 Aromatic groups are OR 21 , -SR 22 , or -NR 23 R 24 Monocyclic or polycyclic C substituted with 6~60 It may be an arylene group, R 21 ~R 24 These 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 C6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 3~30 Heteroaryl, or substituted or unsubstituted C 4~30 It is a heteroarylalkyl. For example, a monocyclic or polycyclic C 5~60 Aromatic groups are monocyclic or polycyclic carbon atoms substituted with hydroxyl groups. 6~60 It may be an arylene group.

[0022] "Mono-ring or poly-ring C 6~60 When an "arylene group" is polycyclic, it should be understood that the number of carbon atoms is sufficient to make the group chemically feasible. For example, "monocyclic or polycyclic C 6~60 The "arylene group" is a "monocyclic C 6~60 Arylene group or polycyclic carbon 10~60 It may refer to an "arylene group"; or, for example, a "monocyclic C" 6~30 Arylene group or polycyclic carbon 12~60 It can sometimes refer to the "arylene group".

[0023] "Mono-ring or poly-ring C 5~60 When a heteroarylene group is polycyclic, it should be understood that the number of carbon atoms is sufficient to make the group chemically feasible. For example, "monocyclic or polycyclic C 5~60 "Heterorialene group" is a "monocyclic C5 ~60 Heteroarylene group or polycyclic C 10~60 It may refer to a "heteroarylene group"; or for example, a "monocyclic C 5~30 Heteroarylene group or polycyclic C 12~60 It may refer to a "heteroarylene group".

[0024] In equation (1), X is either C or O. If X is C, R a and R b These are, independently, hydrogen, substituted or unsubstituted C. 1~30 Alkyl, substituted, or unsubstituted C 1~30 Heteroalkyl, substituted, or unsubstituted C 3~30Cycloalkyl, substituted, or unsubstituted C 2~30 Heterocycloalkyl, substituted, or unsubstituted C 2~30 Alkenyl, substituted, or unsubstituted C 2~30 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, or substituted or unsubstituted C 4~30 It is a heteroarylalkyl; R a and R b These may optionally come together to form a 5-7 member ring; R a or R b At least one of them is R, which is optional. 2 They may also form a 5-7 member ring together. If X is O, R a and R b It does not exist. In one embodiment, any of the aforementioned 5- to 7-membered rings may condense with one or more additional rings to form a polyring structure. Preferably, X is C.

[0025] In equation (1), R 1 C is hydrogen, substituted or unsubstituted. 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, or substituted or unsubstituted C 4~30 It is a heteroarylalkyl. Preferably, R 1 is hydrogen, or substituted or unsubstituted C 1~10It is an alkyl group, and hydrogen is a typical example.

[0026] In equation (1), R 2 is a substitution or non-substitution 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Heteroarylalkyl, -NR 11 R 12 And R 11 ~R 12 These 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 It is a heteroarylalkyl. In some embodiments, R 11 ~R 12 At least one of them is R, which is optional. 1 They may also form a 5-7 membered ring together.

[0027] In terms of optional choices, R 1 and R 2 These can combine to form a 5-7 membered ring.

[0028] In one embodiment, the Ar group is represented by formula (2): [ka] (In the formula, A1, A2, and A3 may each be present or absent, and each independently represents 1 to 3 condensed aromatic rings.)

[0029] In equation (2), R 3 and R 4 These are each independently substituted or non-substituted 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, 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 R 3 and R 4 At least one of them is -OR 31 , -SR 32 , or -NR 33 R 34 This is conditional on the following:

[0030] In equation (2), R 31 ~R 34 These 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 3~30Heteroaryl, or substituted or unsubstituted C 4~30 It is a heteroarylalkyl group.

[0031] In equation (2), the condition is that the sum of m and n is an integer greater than 0, where m is an integer between 0 and 4, and n is an integer between 0 and 4. For example, the sum of m and n may be 1, 2, 3, or 4 or greater, typically 1 or 2.

[0032] In another embodiment, the Ar group is of formula (3a), (3b), or (3c): [ka] (In the formula, A4 represents 1 to 3 condensed aromatic rings, and A4 may or may not be present) It is preferable that A4 represents 1 to 3 aromatic rings, more preferably 1 to 2 condensed aromatic rings, and most preferably 1 condensed aromatic ring.

[0033] In formulas (3a), (3b), and (3c), A4 contains at least one heteroaryl ring, or Z 1 and Z 2 On the condition that at least one of them is N, or a combination thereof, Z 1 and Z 2 Each of these is independently either C or N.

[0034] In equations (3a), (3b), and (3c), each R 5 These are, independently, substitutional or non-substitutional 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, or substituted or unsubstituted C 4~30 It is a heteroarylalkyl. In formulas (3a), (3b), or (3c), p is an integer between 0 and 4, typically 0 or 1.

[0035] In another embodiment, the Ar group is represented by formula (4): [ka] The group may be an Ar group, provided that the Ar group contains one or more aromatic ring heteroatoms, substituents containing heteroatoms, or combinations thereof.

[0036] In equation (4), L 1 These are single bonds, -O-, -S-, -S(O)-, -SO2-, -C(O)-, -CR 51 R 52 -, -NR 53 -, or -PR 54 - and R 51 ~R 54 These 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 It is a heteroarylalkyl. Preferably, L 1 is -O- or -NR 53 -and more preferably -NR 53 - is

[0037] In equation (4), L 2 C is either absent, a single bond, -O-, -S-, -S(O)-, -SO2-, -C(O)-, substituted, or unsubstituted. 1~2 Alkylene, substituted, or unsubstituted C6~30 Arylene, or substituted or unsubstituted C 5~30 It is a heteroarylene. Preferably, L 2 It is a single bond.

[0038] In equation (4), R 8 and R 9 These are, independently, substitutional or non-substitutional 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, 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 That is the case.

[0039] In equation (4), R 55 ~R 58 These 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 It is a heteroarylalkyl group.

[0040] In equation (4), a is an integer between 0 and 4, typically between 0 and 2, and more typically between 0; b is an integer between 0 and 4, typically between 0 and 2, and more typically between 0.

[0041] The polymer of the present invention can be formed in the presence of an acidic catalyst and, optionally, in a suitable solvent, by adding one or more monocyclic or polycyclic C compounds. 5~60 Aromatic compounds (aromatic monomers) are given by formula (5): [ka] It can be prepared by reacting with a 1,2-diketone or conjugated aliphatic aldehyde (carbonyl monomer) (wherein X is C or O; R 1 C is hydrogen, substituted or unsubstituted. 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, or substituted or unsubstituted C 4~30 (It is a heteroarylalkyl.)

[0042] In equation (5), R 2 is a substitution or non-substitution 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 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30Arylalkyl, substituted, or unsubstituted C 7~30 Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, substituted, or unsubstituted C 4~30 Heteroarylalkyl, or -NR 11 R 12 And R 11 and R 12 These 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 It is a heteroarylalkyl group.

[0043] In terms of optional choices, R 1 and R 2 These may also form a 5-7 member ring together.

[0044] In terms of optional choices, R 11 or R 12 One of them is R 1 They may also form a 5-7 membered ring together.

[0045] In equation (5), if X is C, then R a and R b These 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 2~30 Alkenyl, substituted, or unsubstituted C 2~30 Alkinyl, substituted, or unsubstituted C 6~30 Aryl, substituted, or unsubstituted C 7~30 Arylalkyl, substituted, or unsubstituted C 7~30Alkylaryl, substituted, or unsubstituted C 3~30 Heteroaryl, or substituted or unsubstituted C 4~30 It is a heteroarylalkyl; R a and R b They may optionally come together to form a 5-7 member ring; R a or R b One of them may be selectively joined together to form a 5-7 member ring; R a or R b One of them is R, which is chosen at will. 2 They may also form a 5-7 membered ring together.

[0046] In equation (5), if X is O, then R a and R b It does not exist.

[0047] Aromatic monomers are monocyclic or polycyclic carbon atoms. 5~60 An aromatic compound comprising one or more aromatic ring heteroatoms, substituents containing heteroatoms, or combinations thereof. Exemplary C 5~60 Aromatic compounds include, but are not limited to, substituted benzene, substituted biphenyl, substituted naphthalene, substituted binaphthyl, substituted anthracene, substituted benz[a]anthracene, substituted fluorene, substituted fluorantene, substituted benzo[b]fluorantene, substituted dibenzo(a,h)anthracene, substituted phenanthrene, substituted phenalene, substituted tetracene, substituted chrysene, substituted triphenylene, substituted pyrene, substituted pentacene, substituted benzo[a]pyrene, substituted corannulene, substituted benzoperylene, and Examples include substituted coronene, substituted ovalen, 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 oxofhenothiazine, and substituted or unsubstituted dioxofhenothiazine.

[0048] Monomers and optional solvents can be mixed in any order. An acid catalyst is typically added to the reaction mixture after the monomers and any optional solvent. Following the addition of the acid catalyst, the reaction mixture can be heated under reflux or other conditions for a time such as 1 to 48 hours. After heating, the reaction products are isolated from the reaction mixture by precipitation or other means, and these 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.

[0049] In one embodiment, the polymer is prepared from the carbonyl monomer of formula (5) without using another aldehyde, ketone, or 1,2-dicarbonyl monomer different from that of formula (5). In one embodiment, the polymer is prepared without using any aldehyde or ketone compounds other than the carbonyl monomer of formula (5). For example, the polymer does not contain repeating units derived from the aldehyde of formula Ar'-CHO, where Ar' is substituted or unsubstituted C. 6~30 It is an aromatic group.

[0050] A variety of solvents, including but not limited to alcohols, glycol ethers, lactones, esters, ethers, ketones, water, and aromatic hydrocarbons, can be used to prepare the polymers of the present invention. Preferably, relatively polar solvents such as alcohols, glycol ethers, lactones, esters, ethers, ketones, or water are used. Mixtures of solvents may also be used. Examples of solvents, but not limited to, include methanol, ethanol, propanol, propylene glycol, propylene glycol monomethyl ether (PGME), propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate (PGMEA), gamma-butyrolactone (GBL), gamma-valerolactone, delta-valerolactone, ethyl lactate, 1,4-dioxane, cyclohexanone, cyclopentanone, methyl ethyl ketone, water, mesitylene, xylene, anisole, and 4-methylanisole. Preferred solvents are methanol, ethanol, propanol, propylene glycol, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, gamma-butyrolactone, gamma-valerolactone, delta-valerolactone, ethyl lactate, 1,4-dioxane, cyclohexanone, and water.

[0051] Various acids can be appropriately used as catalysts in the preparation of 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), mineral acids, and sulfonic acids, with the acid catalyst preferably being a mineral acid or sulfonic acid. Suitable mineral acids include HF, HCl, HBr, HNO3, H2SO4, H3PO4, and HClO4. Suitable sulfonic acids include alkanesulfonic acids and arylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, phenylsulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and cresolsulfonic acid. Preferred acid catalysts are HCl, HBr, HNO3, H2SO4, H3PO4, methanesulfonic acid, ethanesulfonic acid, phenylsulfonic acid, phenolsulfonic acid, and p-toluenesulfonic acid (pTSA).

[0052] In another embodiment, the polymer is based on formulas (6) to (12): [ka] The polymer contains one or more repeating units of any of the following (wherein Ar is defined in formula (1)). Preferably, the polymer contains repeating units of formula (6).

[0053] The polymer of the present invention has a weight-average molecular weight (M) of 500 to 2000 Daltons (Da), preferably 500 to 15000 Da, more preferably 500 to 1000 Da, determined by gel permeation chromatography (GPC) using a polystyrene standard. w ) may have.

[0054] The lower composition may further contain a solvent, and optionally, one or more additives selected from curing agents, crosslinking agents, and surfactants. Those skilled in the art will understand that other additives may be appropriately used in this composition.

[0055] The solvent may be an organic solvent commonly used in the electronics industry, such as PGME, PGMEA, methyl 3-methoxypropionate (MMP), ethyl lactate, n-butyl acetate, anisole, N-methylpyrrolidone, gamma-butyrolactone (GBL), ethoxybenzene, benzyl propionate, benzyl benzoate, cyclohexanone, cyclopentanone, propylene carbonate, xylene, mesitylene, cumene, limonene, and mixtures thereof. Typically, the total solids content of the lower composition is 0.5 to 20% by weight, typically 0.5 to 10% by weight, of the total weight of the lower composition, with the solvent making up the remainder of the lower composition.

[0056] Optionally, the underlying composition of the present invention may further contain one or more curing agents to assist in the curing of the deposited polymer film. The curing agent is any component that causes the underlying composition to cure on the surface of the substrate. Preferred curing agents are thermoacid generators (TAGs). A TAG is any compound that releases acid when exposed to heat. Thermoacid generators are well known in the art and are generally commercially available from King Industries, Norwalk, Connecticut, and others. Exemplary thermoacid generators include, but are not limited to, amine-blocked strong acids, such as amine-blocked dodecylbenzenesulfonic acid. It will also be well understood by those skilled in the art that certain photoacid generators can release acid upon heating and function as thermoacid generators. The amount of such a curing agent useful in the present composition may be, for example, 0 to 10% by weight, typically 0 to 3% by weight, based on the total solids content of the underlying composition.

[0057] Any suitable crosslinking agent can be used in this underlying composition, provided that the crosslinking agent has at least two, preferably at least three, sites that can react with the polymer under appropriate conditions such as acidic conditions. Examples of crosslinking agents, but not limited to them, include novolac resins, epoxy-containing compounds, melamine compounds, guanamine compounds, isocyanate-containing compounds, benzocyclobutene, benzoxazine, and typically methylol, C1~10 Alkoxymethyl, and C 2~10 Examples include any of the aforementioned compounds having two or more substituents, more typically three or fewer, selected from acyloxymethyl. Examples of suitable crosslinking agents are those represented by formulas (13) and (14). [ka]

[0058] Such crosslinking agents are well known in the art and are commercially available from various suppliers. The amount of such a crosslinking agent useful in this composition may be, for example, more than 0 and up to 30% by weight, preferably more than 0 and up to 10% by weight, based on the total solids content of the lower composition.

[0059] The underlying composition may optionally contain one or more surface leveling agents (or surfactants) and antioxidants. Typical surfactants include those exhibiting amphiphilic properties. This means that they may be both hydrophilic and hydrophobic at the same time. Amphiphilic surfactants have a hydrophilic head group with a strong affinity for water and a long, hydrophobic tail that is organic and repels water. Preferred surfactants may be ionic (i.e., anionic, cationic) or nonionic. Further examples of surfactants include silicone surfactants, poly(alkylene oxide) surfactants, and fluorochemical surfactants. Suitable nonionic surfactants include, but are not limited to, octyl and nonylphenol ethoxylates such as TRITON® X-114, X-100, X-45, and X-15, and branched secondary alcohol ethoxylates such as TERGITOL® TMN-6 (The Dow Chemical Company, Midland, Michigan, USA) and PF-656 (Omnova Solutions, Beachwood, Ohio, USA). Further exemplary surfactants include alcohol (primary and secondary) ethoxylates, amine ethoxylates, glucosides, glucamine, polyethylene glycol, poly(ethylene glycol-co-propylene glycol), or other surfactants disclosed by Manufacturers Confectioners Publishing Co. of Glen Rock, NJ. Nonionic surfactants that are acetylenediol derivatives may also be suitable. Such surfactants are commercially available from Air Products and Chemicals, Inc. of Allentown, PA, and are sold under the trade names SURFYNOL® and DYNOL®. Other suitable additional surfactants include other polymer compounds such as the triblock EO-PO-EO copolymers PLURONIC® 25R2, L121, L123, L31, L81, L101, and P123 (BASF, Inc.).When used, such surfactants may be present in the composition in small amounts, for example, more than 0 and up to 1% by weight based on the total solids content of the underlying composition.

[0060] To prevent or minimize the oxidation of organic materials in the composition, antioxidants may be added to the lower layer composition. Suitable antioxidants include, for example, phenolic antioxidants, antioxidants made from organic acid derivatives, sulfur-containing antioxidants, phosphorus-based antioxidants, amine-based antioxidants, antioxidants made from amine-aldehyde condensates, and antioxidants made from amine-ketone condensates.Examples of phenolic antioxidants include 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, butylhydroxyanisole, 2-(1-methylcyclohexyl)-4,6-dimethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2-methyl-4,6-dinonylphenol, and 2,6-di-tert-butylphenol. 4,4'-Dihydroxydiphenyl, 6-(4-hydroxy-3,5-di-tert-butylanilino)2,4-bisoctyl-thio-1,3,5-triazine, n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, octylated phenols, aralkyl-substituted phenols, alkylated p-cresols, and substituted phenols such as hindered phenols; 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-crosslinked polyhydric alkylphenol, 4,4'-butylidenebis-(3-methyl-6-tert-butylphenol), 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 2,2'- Examples of bis, tris, and polyphenols include 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, such as Irganox® antioxidant (Ciba Specialty Chemicals Corp.). When used, the antioxidant may be present in the underlying composition in an amount greater than 0 and up to 1% by weight, based on the total solids content of the underlying composition.

[0061] Another aspect of the present invention provides a coated substrate comprising a layer of an underlying composition disposed on a substrate and a photoresist layer disposed on top of the layer of the underlying composition. The coated substrate may further include a silicon-containing layer and / or an organic anti-reflective coating layer disposed on top of the underlying layer and below the photoresist layer.

[0062] A further aspect of the present invention provides a method for forming a pattern. The method includes (a) coating a layer of a base composition onto a substrate; (b) curing the coated base composition to form a base layer; and (c) forming a photoresist layer on the base layer. The method may further include forming a silicon-containing layer and / or an organic anti-reflective coating layer on the base layer before forming the photoresist layer. The method may further include patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the base layer and the layer below the base layer.

[0063] In this specification, the term “underlayer” refers to all removable processing layers between the substrate and the photoresist layer, such as organic anti-reflective layers, silicon-containing intermediate layers, spin-on carbon layers, and photoresist underlayers.

[0064] A wide variety of substrates can be used in pattern formation methods, with electronic device substrates being 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) such as organic light-emitting diodes (OLEDs); semiconductor wafers; and polycrystalline silicon substrates. Suitable substrates can be in the form of wafers, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, optical integrated circuits, and LEDs. As used herein, the term “semiconductor wafer” is intended to encompass “electronic device substrates,” “semiconductor substrates,” “semiconductor devices,” and various packages for various levels of interconnection, such as single-chip wafers, multiple-chip wafers, packages for various levels, or other assemblies requiring solder connections. Such substrates may be of any suitable size. Typical wafer substrate diameters are 200 mm to 300 mm, but wafers with smaller and larger diameters can be suitably used according to the present invention. As used herein, the term “semiconductor substrate” refers to any substrate having one or more semiconductor layers or structures that may optionally contain an effective or operational portion of a semiconductor device. A semiconductor device means a semiconductor substrate on which at least one microelectronic device is batch manufactured or in the process of being manufactured.

[0065] The substrate is typically composed of one or more of the following materials: 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 one or more conductive layers such as aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys of such metals, nitrides or silicides, doped amorphous silicon, or doped polysilicon layers; one or more dielectric layers such as silicon oxide, silicon nitride, silicon oxynitride, or metal oxide layers; semiconductor layers such as single-crystal silicon; and combinations thereof. The layers can be formed by various techniques, such as chemical vapor deposition (CVD) including plasma-enhanced CVD (PECVD), low-pressure CVD (LPCVD), or epitaxial growth; physical vapor deposition (PVD) including sputtering or evaporation; or electroplating.

[0066] The underlayer coating composition can be coated onto a substrate by any suitable means, such as spin coating, slot die coating, doctor braiding, curtain coating, roller coating, spray coating, immersion coating, etc. In the case of semiconductor wafers, spin coating is preferred. In a typical spin coating method, the underlayer composition is applied to a substrate that is rotating at a speed of 500 to 4000 rpm for a period of 15 to 90 seconds to obtain the desired layer of the underlayer composition on the substrate. It will be understood by those skilled in the art that the thickness of the coated underlayer composition can be adjusted by changing the spin speed and the solid content of the composition. The underlayer formed from the underlayer composition typically has a dry layer thickness of 5 nm to 50 μm, typically 25 nm to 3 μm, and more typically 50 to 500 nm. The underlayer composition can be applied to substantially fill, preferably fill, and more preferably completely fill, multiple gaps on the substrate.

[0067] The coated underlayer composition is optionally soft-baked at a relatively low temperature to remove any solvents and other relatively volatile components from the composition. While other suitable temperatures may be used, a typical bake temperature can be between 60 and 170°C. Such baking to remove residual solvents is performed for 10 seconds to 10 minutes, although longer or shorter times may be used as appropriate. If the substrate is a wafer, such a baking process can be performed by heating the wafer on a hot plate.

[0068] The applied underlayer composition then hardens to form an underlayer, such as a photoresist underlayer. The underlayer composition needs to be hardened sufficiently so that it does not mix with any subsequent layers, such as photoresist or other organic or inorganic layers directly placed on top of it, or mixes only minimally. The underlayer composition can be hardened in an oxygen-containing atmosphere such as air, or in an inert atmosphere such as nitrogen, and under conditions such as heating sufficient to obtain a hardened coating layer. This hardening process is preferably carried out on a hot plate type apparatus, but oven hardening may be used to obtain equivalent results. The hardening temperature needs to be sufficient to harden the entire layer, for example, sufficient to allow a hardening agent such as a free acid to cause crosslinking, or, if the hardening agent is a TAG, sufficient to allow a thermal acid generator to release acid and allow the released acid to cause crosslinking. Typically, hardening is carried out at a temperature of 150°C or higher, preferably 150-450°C. A hardening temperature of 180°C or higher, more preferably 200°C or higher, and even more preferably 200-400°C is preferable. The curing time is typically 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes, more preferably 45 seconds to 5 minutes, and even more preferably 45 to 90 seconds. Optionally, a gradient or multi-stage curing process may be used. A gradient bake typically begins at a relatively low (e.g., ambient) temperature, and the temperature is increased at a constant or variable ramp rate to a higher target temperature. A multi-stage curing process involves curing in two or more temperature planes, typically a first stage at a lower bake temperature and one or more additional stages at higher temperatures. Conditions for such gradient or multi-stage curing processes are known to those skilled in the art and may allow for the omission of a preceding soft bake process.

[0069] After the base layer composition has cured, one or more processing layers, such as a photoresist layer, a hard mask layer including a metal hard mask layer, or an organic or inorganic BARC layer, can be placed on top of the cured base layer. The photoresist layer can be formed directly on the surface of the base layer, or it can be formed on the base layer on top of one or more intervening layers. In this case, the one or more intervening processing layers described above can be formed sequentially on the base layer, followed by the formation of the photoresist layer. Determining appropriate layers, thicknesses, and coating methods is well known to those skilled in the art.

[0070] A wide variety of photoresists can be appropriately used in the method of the present invention, and these are typically positive-toned materials. Suitable photoresists include, for example, materials in the EPIC® series of photoresists available from DuPont Electronics & Imaging (Marlborough, Massachusetts). The photoresist can be applied to the substrate by known coating techniques such as those described above in relation to the underlying composition, spin coating being typical. A typical thickness for the photoresist layer is 500 to 3000 Å. The photoresist layer is typically then soft-baked to minimize the solvent content in the layer, thereby forming a non-stick coating and improving the adhesion of the layer to the substrate. Soft baking can be done 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 to 150°C and for a time of 30 to 90 seconds.

[0071] Optionally, one or more barrier layers may be placed on top of the photoresist layer. Suitable barrier layers include topcoat layers, top anti-reflective coating layers (or TARC layers), etc. Preferably, a topcoat layer 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 OC(trademark)2000 from DuPont Electronics & Imaging. It will be understood by those skilled in the art that a TARC layer is unnecessary when an organic anti-reflective layer is used beneath the photoresist layer.

[0072] The photoresist layer is then exposed to activating radiation through a photomask to create a difference in solubility between exposed and unexposed areas. The reference herein to exposing a photoresist composition to activating radiation for the composition indicates that the radiation can form a latent image in the photoresist composition. The photomask has optically transparent and optically shielding regions, corresponding to the areas of the resist layer that are exposed and unexposed by the activating radiation, respectively. The exposure wavelength is typically less than 400 nm, more typically less than 300 nm, e.g., 248 nm (KrF), 193 nm (ArF), or EUV wavelength (e.g., 13.5 nm). In a preferred embodiment, the exposure wavelength is 193 nm. The exposure energy is typically 10 to 80 mJ / cm², depending, for example, the exposure tool and the components of the photosensitive composition. 2 That is the case.

[0073] After exposure of the photoresist layer, a post-exposure bake (PEB) is typically performed. PEB can be carried out, for example, on a hot plate or in an oven. PEB is typically performed at a temperature of 80–150°C and for 30–90 seconds. This creates a latent image defined by the boundary between the polarity-switched and non-switched regions (corresponding to the exposed and unexposed regions, respectively). The exposed photoresist layer is then developed using a suitable developer to obtain a patterned photoresist layer.

[0074] Next, the pattern of the photoresist layer can be transferred to one or more underlying layers and the substrate, including the underlying layer, by appropriate etching techniques such as plasma etching or wet etching. Plasma etching allows the use of appropriate gas species for each layer being etched. Suitable wet chemical etching chemicals include, for example, mixtures containing ammonium hydroxide, hydrogen peroxide, and water (e.g., SC-1 Clean); mixtures containing hydrochloric acid, hydrogen peroxide, and water (e.g., SC-2 Clean); mixtures containing sulfuric acid, hydrogen peroxide, and water (e.g., SPM Clean); mixtures containing phosphoric acid, hydrogen peroxide, and water; mixtures containing hydrofluoric acid and water; mixtures containing hydrofluoric acid, phosphoric acid, and water; mixtures containing hydrofluoric acid, nitric acid, and water; and mixtures containing tetramethylammonium hydroxide and water.

[0075] Depending on the number and materials of the layers involved, pattern transfer may involve multiple etching steps using different techniques. The patterned photoresist layer, underlying layer, and other optional layers in the lithography stack may be removed after pattern transfer to the substrate using conventional techniques. Optionally, one or more layers of the stack may be removed or consumed after pattern transfer to the underlying layer and before pattern transfer to the substrate. The substrate is then further processed according to known methods for forming electronic devices.

[0076] The underlayer composition can also be used in a self-aligned double patterning process. In such a process, the layer of the underlayer composition described above is coated onto the substrate by spin coating or the like. Any remaining organic solvent is removed and the coating layer hardens to form a photoresist underlayer. A suitable intermediate layer, such as a silicon-containing hard mask layer, may be optionally coated on top of the photoresist underlayer. Subsequently, a suitable layer of photoresist is coated on the intermediate layer by spin coating or the like. The photoresist layer is then imaged (exposed), and the exposed photoresist layer is then developed using a suitable developer to give a patterned photoresist layer. The pattern is then transferred from the photoresist layer to the intermediate and underlayers by a suitable etching technique, exposing multiple portions of the substrate. Typically, the photoresist is also removed during such an etching process. Next, a conformal silicon-containing layer is placed across the patterned underlayer and the exposed portions of the substrate. Such a silicon-containing layer is typically an inorganic silicon layer such as SiON or SiO2, which is conventionally deposited by CVD. Such a conformal coating provides a silicon-containing layer on the exposed portion of the substrate surface and on the underlying pattern. That is, such a silicon-containing layer substantially covers the sides and top of the underlying pattern. Next, the silicon-containing layer is partially etched (deburred) 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 contains multiple features, each feature containing lines or posts of the underlying layer with the silicon-containing layer directly adjacent to the face of the respective underlying feature. Next, the exposed area of ​​the underlying layer is removed by etching or the like to expose the substrate surface that was beneath the underlying pattern, giving the substrate surface a patterned silicon-containing layer where such a patterned silicon-containing layer is twice as numerous as the patterned resist underlying layer (i.e., twice as many lines and / or posts).

[0077] Sublayers formed from the sublayer composition of the present invention, such as photoresist sublayers, exhibit excellent planarization and excellent solvent resistance. The preferred sublayer composition of the present invention may, as a result, be useful in various semiconductor manufacturing processes.

[0078] The concept of the present invention is further illustrated by the following examples. All compounds and reagents used herein are commercially available unless the procedure is given below. [Examples]

[0079] Polymer synthesis Synthesis Example 1 In a round-bottom flask, 8.0 g of 1-naphthol (1 equivalent), 8.34 g of (1R)-(-)-myrthenal (1 equivalent), and 20 mL of PGME were placed. The reaction mixture was heated to 60°C and stirred for 5 minutes, after which 5.33 g of methanesulfonic acid was added all at once. The reaction was then heated at 120°C for 20 hours. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / aqueous solution to obtain a solid polymer product. The product was filtered, washed with methanol, air-dried for 4 hours, and then vacuum-dried at 50°C for a further 20 hours to obtain Synthesis Example 1 (P-1). (Yield 61%, Mw=10¹⁰, PDI=1.2).

[0080] Synthesis Examples 2-6 Synthesis Examples 2(P-2) to 6(P-6) were prepared using the same procedure as above with their respective aromatic monomers to obtain the target polymers shown by the following structures. Citral was used as the aldehyde monomer in Synthesis Examples 5 and 6.

[0081] Synthesis Example 7 In a round-bottom flask, 10.0 g of 4,4'-(9-fluorenylidene)diphenol (1 equivalent), 5.21 g of acenaphthoquinone (1 equivalent), and 40 mL of PGME were placed. The reaction mixture was heated to 60°C and stirred for 5 minutes, after which 2.00 g of methanesulfonic acid was added all at once. The reaction was then heated to 120°C for 24 hours. 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, washed with water and methanol, then air-dried for 4 hours, and further vacuum-dried at 50°C for 20 hours to obtain Synthesis Example 7 (P-7). (Yield 40%, Mw=1120, PDI=1.3).

[0082] Synthesis Examples 8-12 Synthesis Examples 8(P-8) to 12(P-12) were prepared using the same procedure as above with their respective aromatic monomers and diketone monomers to obtain the target polymers shown by the following structures. [ka]

[0083] Synthesis of comparative polymers Comparative Synthesis Example 1 In a round-bottom flask, 5.0 g of 1-naphthol (1 equivalent), 1.04 g of paraformaldehyde (1 equivalent), and 25 mL of propylene glycol monomethyl ether acetate (PGMEA) were placed. The reaction mixture was heated to 60°C and stirred for 5 minutes, after which 0.20 g of methanesulfonic acid was added all at once. The reaction was then heated to 120°C for 16 hours. 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, washed with excess methanol, air-dried for 4 hours, and then vacuum-dried at 50°C for a further 20 hours to obtain Comparative Synthesis Example 1 (CP-1) (Yield 52%, Mw=2240, PDI=2.0).

[0084] Comparative Synthesis Example 2 In a round-bottom flask, 5.0 g of carbazole (1.5 equivalents), 0.60 g of paraformaldehyde (1 equivalent), and 20 mL of propylene glycol monomethyl ether acetate (PGMEA) were placed. The reaction mixture was heated to 60°C and stirred for 5 minutes, after which 1.45 g of methanesulfonic acid was added all at once. The reaction was then heated to 120°C for 16 hours. A solid precipitate formed in the reaction mixture during the reaction. After the allotted 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, washed with excess methanol, air-dried for 4 hours, and then vacuum-dried at 50°C for a further 20 hours to obtain Comparative Synthesis Example 2 (CP-2) (Yield 80%, Mw=2730, PDI=2.5).

[0085] Comparative Synthesis Example 3 In a round-bottom flask, 5.0 g of 1-pyrenol (1 equivalent), 0.69 g of paraformaldehyde (1 equivalent), and 20 mL of propylene glycol monomethyl ether (PGME) were placed. The reaction mixture was heated to 60°C and stirred for 5 minutes, after which 2.20 g of methanesulfonic acid was added all at once. The reaction was then heated to 120°C for 1 hour. After this reaction time, the reaction had almost solidified. The solid was removed from the flask, washed with water and methanol, then air-dried for 4 hours, and further vacuum-dried at 50°C for 20 hours to obtain Comparative Synthesis Example 3 (CP-3).

[0086] Comparative Synthesis Example 4 In a round-bottom flask, 10.0 g of 1-naphthol (1 equivalent), 7.78 g of cyclohexanecarboxaldehyde (1 equivalent), and 30 mL of propylene glycol monomethyl ether (PGME) were placed. The reaction mixture was heated to 60°C and stirred for 5 minutes, after which 6.70 g of methanesulfonic acid was added all at once. The reaction was then heated to 120°C for 20 hours. 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, washed with methanol, air-dried for 4 hours, and then vacuum-dried at 50°C for a further 20 hours. Comparative synthesis example 4 (CP-4) was identified as a small molecule product, not a polymer, by GPC analysis.

[0087] Comparative Synthesis Example 5 In a round-bottom flask, 10.0 g of 1-naphthol (1 equivalent), 7.92 g of heptanal (1 equivalent), and 35 mL of propylene glycol monomethyl ether (PGME) were placed. The reaction mixture was heated to 60°C and stirred for 5 minutes, after which 6.70 g of methanesulfonic acid was added all at once. The reaction was then heated to 120°C for 20 hours. After this reaction time, the reaction mixture was cooled to room temperature and poured into 9 / 1 (v / v) methanol / water. Since no precipitate was observed, the crude mixture was concentrated to obtain oil. Comparative synthesis example 5 (CP-5) was identified as a small molecule product that was not a polymer by GPC analysis. [ka]

[0088] Physical testing The number-average molecular weight and weight-average molecular weight of the polymer, respectively, M n and M w , as well as the value of polydispersity (PDI) (M w / M nThe values ​​were measured by gel permeation chromatography (GPC) on an Agilent 1100 series LC system equipped with an Agilent 1100 series refractive index and a MiniDAWN light scattering detector (Wyatt Technology Co.). Samples were dissolved in HPLC-grade THF at a concentration of approximately 10 mg / mL, filtered through a 0.45 μm syringe filter, and injected into four Shodex columns (KF805, KF804, KF803, and KF802). A flow rate of 1 mL / min and a temperature of 35°C were maintained. The columns were calibrated using a narrow molecular weight PS standard (EasiCal PS-2, Polymer Laboratories, Inc.).

[0089] The glass transition temperature of bulk polymers was determined using differential scanning calorimetry (DSC). Samples (1–3 mg) were heated to 150°C for 10 minutes and held. After removing residual solvent in the first cycle, the samples were cooled to 0°C and then heated back up to 300°C at a rate of 10°C / min. The glass transition temperature was determined using the second heating curve and the reversible heating curve.

[0090] Table 1 shows the molecular weight, solubility, and thermal properties of polymers P-1 to P-12 and comparative polymers CP-1 and CP-5.

[0091] [Table 1]

[0092] As shown in Table 1, the polymer of the present invention has better solubility and a lower glass transition temperature compared to the comparative example.

[0093] compound The base layer composition was prepared by combining the polymers listed in Table 1 with the components described in Table 2 to form the composition. The composition was filtered through a 0.2 μm PTFE syringe filter before coating. The amounts of polymer, additive 1, additive 2, and solvent are listed in grams (g).

[0094] [Table 2]

[0095] The structures of additive B-1, additive C-1, solvent D-1, and solvent D-2 are as follows. [ka]

[0096] Testing of coatings and films The underlying composition was coated to a thickness of 100-200 nm and baked at 240°C for 60 seconds. The film thickness was measured by ellipsometry.

[0097] Solvent resistance Solvent peel resistance was measured as an indicator of film crosslinking. The underlying composition was coated onto an 8-inch silicon wafer using ACT-8 CleanTrack (Tokyo Electron Co.) and baked. Film thickness was measured using Therma-wave Co.'s OptiProbe®. Propylene glycol monomethyl ether acetate (PGMEA) was deposited onto the film for 90 seconds, followed by a pre-peel bake (PSB) at 105°C for 60 seconds. Solvent resistance was calculated according to Equation 1: [(FT before peeling) - (FT after PSB)] / (FT before peeling) * 100% Equation 1 (FT in the formula represents film thickness). Solvent resistance is reported in Table 2, where A is defined as 95-100% solvent resistance and B as less than 95% solvent resistance.

[0098] Flattening test To determine the planarization characteristics, the underlying compositions of the present invention were evaluated. Templates were formed using CNSE Nano-FAB (Albany, NY). The templates had a 100 nm SiO2 film thickness, varying pitches and patterns, and a die size of 1 cm × 1 cm. Each die began with individual step patterns of 100 nm, followed by a 2000 μm unpatterned open area, and then various line / space patterns covering trenches with pitches of 45 nm / 90 nm to 2 μm / 5 μm. The initial step pattern was used to determine the planarization performance. The template coupons were baked at 150°C for 60 seconds as a dehydration bake before coating the coupons with the composition. Each underlying composition was coated onto the template coupons using a spin coater and a spin speed of 1500 rpm + / - 200 rpm. The target film thickness after curing was 100 nm, and the composition dilution was adjusted accordingly to obtain approximately the target film thickness after curing. The film was cured by placing the wafer on a hot plate at 240°C for 60 seconds. The planarization quality of the film throughout the entire step was evaluated using a KLA Tencor P-7 stylus-type surface profile analyzer.

[0099] In Table 2, planarization quality is defined as follows: A represents a height change of less than 30 nm, and B represents a height change of more than 30 nm. A smaller value indicates better planarization performance. Therefore, A represents the best planarization, and B represents the worst planarization performance.

[0100] As can be seen from Table 2, the lower layer composition of the present invention has superior planarization performance compared to the comparative lower layer composition.

[0101] While this disclosure has been described in conjunction with what are currently considered to be practical and exemplary embodiments, it should be understood that the present invention is not limited to the disclosed embodiments, but rather is intended to encompass a variety of modifications and equivalent configurations that fall within the spirit and scope of the appended claims.

Claims

1. An underlayer composition for use with a photoresist to be overcoated, comprising formulas (6), (7), (8), or (9): 【Chemistry 1】 (In the formula, Ar is a monocyclic or polycyclic C ５～６０ (An aromatic group, wherein the aromatic group includes one or more aromatic ring heteroatoms, heteroatom-containing substituents, or combinations thereof.) A lower layer composition comprising a polymer containing repeating units.

2. Ar is a 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 alkylaryl, substituted or unsubstituted C ３～３０ heteroaryl, substituted or unsubstituted C ４～３０ heteroarylalkyl, halogen, -OR ２１ , -SR ２２ , or -NR ２３ R ２４ which is optionally substituted with at least one of, a monocyclic or polycyclic C ５～６０ heteroarylene group or a monocyclic or polycyclic C ６～６０ arylene group, and R ２１ ~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, but The aforementioned single-ring or multi-ring C ６～６０ The lower layer composition according to claim 1, wherein the arylene group is substituted with at least one heteroatom-containing substituent.

3. Ar is given by equation (2): 【Chemistry 2】 (In the formula, A1, A2, and A3 may or may not be present, and each independently represents 1 to 3 condensed aromatic rings; R ３ and R ４ These are each independently substituted or non-substituted 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 Alkylaryl, 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 It represents, R ３ and R ４ At least one of them is -OR ３１ ,-SR ３２ , or -NR ３３ R ３４ Provided that; R ３１ ~R ３４ These 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 It is a heteroarylalkyl; m is an integer between 0 and 4; n is an integer between 0 and 4; (The condition is that the sum of m and n is an integer greater than 0.) The lower layer composition according to claim 1 or 2, comprising the group.

4. Ar is given by equation (3a), (3b), or (3c): 【Transformation 3】 (In the formula, A4 may or may not be present, and represents 1 to 3 condensed aromatic rings; Z １ and Z ２ Each is independently either C or N; Each R ５ These are 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 Alkylaryl, substituted, or unsubstituted C ３～３０ Heteroaryl, or substituted or unsubstituted C ４～３０ It is a heteroarylalkyl; p is an integer between 0 and 4; A4 contains at least one heteroaryl ring, Z １ and Z ２ At least one of them is N, or a combination of these. A lower layer composition according to any one of claims 1 to 3, comprising the base of

5. Ar is in equation (4): 【Chemistry 4】 (In the formula, L １ These are single bonds, -O-, -S-, -S(O)-, -SO ２ -, -C(O)-, -CR ５１ R ５２ -, -NR ５３ - or -PR ５４ - and; L ２ It either does not exist, or it 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 It is a heteroarrene; R ８ and R ９ are each independently a substituted or unsubstituted C １～３０ alkyl, a substituted or unsubstituted C １～３０ heteroalkyl, a substituted or unsubstituted C ３～３０ cycloalkyl, a substituted or unsubstituted C ２～３０ heterocycloalkyl, a substituted or unsubstituted C ２～３０ alkenyl, a substituted or unsubstituted C ２～３０ alkynyl, a substituted or unsubstituted C ６～３０ aryl, a substituted or unsubstituted C ７～３０ arylalkyl, a substituted or unsubstituted C ７～３０ alkylaryl, a substituted or unsubstituted C ３～３０ heteroaryl, or a substituted or unsubstituted C ４～３０ heteroarylalkyl, halogen, -OR ５５ , -SR ５６ , or -NR ５７ R ５８ ; R ５１ ~R ５８ These 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 It is a heteroarylalkyl; a is an integer between 0 and 4; b is an integer between 0 and 4. A lower layer composition according to any one of claims 1 to 4, comprising the group.

6. The aforementioned single-ring or multi-ring C ５～６０ A monocyclic or polycyclic carbon atom whose aromatic group is substituted with a hydroxyl group. ６～６０ A photoresist underlayer composition according to any one of claims 1 to 5, wherein the group is an arylene group.

7. The lower layer composition according to any one of claims 1 to 6, further comprising one or more of a curing agent, a crosslinking agent, and a surfactant.

8. A method for forming a pattern, comprising: (a) coating a layer of the lower layer composition described in any one of claims 1 to 7 onto a substrate; (b) curing the coated lower layer composition to form a lower layer; and (c) forming a photoresist layer on the lower layer.

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

10. The method according to claim 8 or 9, further comprising patterning the photoresist layer and transferring the pattern from the patterned photoresist layer to the lower layer and the layer below the lower layer.

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