Photoresist primer composition

Abstract

A method of forming a pattern, the method comprising: applying a photoresist primer composition on a substrate to provide a photoresist primer; forming a photoresist layer on the photoresist primer; patterning the photoresist layer; and transferring a pattern from the patterned photoresist layer to the photoresist primer. The photoresist primer composition comprises a polymer comprising a repeating unit represented by Formula 1 as described herein, a compound comprising a substituent represented by Formula 2 as described herein, and a solvent.

Description

TECHNICAL FIELD

[0001] The present invention relates to the manufacture of electronic devices, and more particularly, to materials for semiconductor manufacturing. BACKGROUND

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

[0003] Spin-on carbon (SOC) compositions are used in the semiconductor industry for forming an etch resist underlayer film that is used as an etch mask for photolithography in advanced technology nodes of integrated circuit manufacturing. These compositions are typically used in three- and four-layer photoresist integration schemes in which an organic or silicon-containing antireflective coating layer and a patternable photoresist film layer with high carbon content SOC material are disposed on an underlayer.

[0004] An ideal SOC material should have certain specific characteristics: it should be able to be cast onto a substrate by a spin-on process; it should thermally set upon heating with low outgassing and sublimation; it should be soluble in common solvents for good spin bowl compatibility; it should have the appropriate n / k to function in conjunction with the antireflective coating to impart the low reflectivity necessary for photoresist imaging; it should adhere sufficiently to the underlying layer, such as a substrate, to avoid delamination upon immersion during standard cleaning processes, such as the SC-1 process using hydrogen peroxide / ammonium hydroxide baths; and it should have high thermal stability to avoid damage during subsequent processing steps. In addition, the SOC material should have material flow capability (referred to as planarization, PL) on complex topography designs in advanced nodes.

[0005] Accordingly, there remains a need for advanced SOC compositions and resulting photoresist underlayer films / materials that exhibit acceptable adhesion to the underlayer / substrate and acceptable planarization to meet the ever-increasing design requirements in semiconductor manufacturing. SUMMARY

[0006] A method of forming a pattern is provided, the method comprising:

[0007] applying a photoresist underlayer composition on a substrate to provide a photoresist underlayer;

[0008] forming a photoresist layer on the photoresist underlayer;

[0009] patterning the photoresist layer; and

[0010] transferring a pattern from the patterned photoresist layer to the photoresist underlayer;

[0011] wherein the photoresist underlayer composition includes a polymer including a repeating unit represented by Formula 1, a compound including a substituent represented by Formula 2; and a solvent;

[0012]

[0013] wherein in Formula 1

[0014] Ring A represents an aromatic ring group having 1 to 6 independently substituted or unsubstituted aromatic rings, wherein optionally, two or more of the aromatic rings are fused, one or more aromatic rings include a fused optionally substituted cycloalkyl or an optionally substituted fused heterocycloalkyl, or a combination thereof,

[0015] Y is a divalent group including an optionally substituted C 1-4 alkylene, -O-, -S-, C(O)-, an optionally substituted arylene, or an optionally substituted heteroarylene, having one or two aromatic rings, or a combination thereof, and

[0016] o is an integer from 2 to 8;

[0017]

[0018] wherein, in Formula 2:

[0019] R is a substituted or unsubstituted C 1-4 alkylene, -CR A R B -Ar-CH2-, or -Ar-CH2-, wherein Ar is an optionally substituted arylene or heteroarylene having 4 to 10 ring carbons, and R A and R B are independently hydrogen, hydroxyl, an optionally substituted C 1-6 alkyl, an optionally substituted C 1-6 alkoxy, or an optionally substituted C 6-12 aryl;

[0020] R 1 is hydrogen, an optionally substituted C 1-4 alkyl, an optionally substituted C 6-12 aryl, an optionally substituted C 3-8 cycloalkyl, or glycidyl;

[0021] * is a point of attachment to a ring carbon of an aromatic ring system Q, wherein the aromatic ring system Q is Ar 1 or Ar 2 -T-Ar 3 ,

[0022] wherein Ar 1 , Ar 2 and Ar 3 independently comprise a substituted or unsubstituted aromatic group having 4 to 14 ring carbons, and

[0023] T is absent, -O-, -S-, -C(O)-, optionally substituted C 1-4 alkylene, or -NR 2 -, wherein R 2 is hydrogen, optionally substituted C 1-4 alkyl, or optionally substituted C 6-12 aryl; and

[0024] a is 1 to 8, c is 1, 2, or 3, and b + c is 2 or 3.

[0025] Also provided is the above composition, wherein the photoresist primer composition is free of non-polymeric polyphenolic compound and a thermal base generator.

[0026] Also provided is a substrate comprising: a layer of the above photoresist primer composition disposed on a substrate; and a photoresist layer disposed on the layer of the photoresist primer composition.

[0027] Also provided is a photoresist primer composition comprising a polymer comprising repeating units represented by Formula 1 as described herein, a compound comprising a substituent represented by Formula 2 as described herein, and a solvent. DETAILED DESCRIPTION

[0028] Reference will now be made in detail to the example embodiments, examples of which are illustrated in the accompanying drawings. In this regard, the present example embodiments can have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the example embodiments are described below, by referring to the drawings, only to explain aspects of the present description. As used herein, the term "and / or" includes all combinations of one or more of the associated listed items. When expressions such as "at least one of," when preceding a list of elements, modify the entire group of elements, and do not modify the individual elements of the list.

[0029] As used herein, the terms "a," "an," and "the" do not denote a limitation of quantity and can be interpreted to mean either the singular or plural forms, unless otherwise indicated by context or expressly stated otherwise. "Or" means "and / or" unless otherwise indicated by context. All ranges disclosed herein include the 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 term that it modifies, thereby including at least one of that term (in addition to the plural). The term "optional" or "optionally" means that the subsequently described event or circumstance can or can not occur, and that the description includes instances where the event occurs and instances where it does not. The terms "first," "second," and similar terms are used herein to distinguish one element from another, but do not necessarily require or imply a sequence or order unless clearly indicated by context. When one element is referred to as being "on" another element, it can be directly on the other element or intervening elements can also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present. It will be understood that the aspects described herein can be combined in any suitable manner in various aspects.

[0030] 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 this application belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure and will not be interpreted in an overly literal or overly formal sense unless expressly so defined herein.

[0031] 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 at indicated places with one or more substituents; "alkyl" refers to a straight-chain or branched saturated hydrocarbon having the specified number of carbon atoms and having a valence of one; "alkylene" refers to an alkyl group having a valence of two; "hydroxyalkyl" refers to an alkyl group substituted with at least one hydroxyl group (-OH); "alkoxy" refers to "alkyl-O-"; "carboxylic acid group" refers to a group having the formula "-C(=0)-OH"; "cycloalkyl" refers to a monovalent radical having one or more saturated rings in which all ring members are carbon; "cycloalkylene" refers to a cycloalkyl group having a valence of two; "alkenyl" refers to a straight-chain or branched monovalent hydrocarbon group having at least one carbon-carbon double bond; "alkenyloxy" refers to "alkenyl-O-"; "alkenylene" refers to an alkenyl group having a valence of at least two; "cycloalkenyl" refers to a cycloalkyl group having at least one carbon-carbon double bond; "alkynyl" refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond; the term "aromatic group" denotes the conventional aromatic concept as defined in the literature, in particular in IUPAC 19, and refers to a monocyclic or polycyclic aromatic ring system, which includes carbon atoms in one or more rings, and optionally can include one or more heteroatoms independently selected from N, O, and S, instead of one or more carbon atoms in one or more rings; "aryl" refers to a monovalent, monocyclic or polycyclic aromatic group containing only carbon atoms in one or more aromatic rings, and can include groups having aromatic rings fused onto at least one cycloalkyl or heterocycloalkyl ring; "arylene" refers to an aryl group having a valence of at least two; "alkylaryl" refers to an aryl group that has been substituted with an alkyl group; "arylalkyl" refers to an alkyl group that has been substituted with an aryl group; "aryloxy" refers to "aryl-O-"; and "arylthio" refers to "aryl-S-".

[0032] 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 instead of a carbon atom, wherein each of the heteroatoms is 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 instead of carbon atoms; "heterocycloalkyl" refers to a cycloalkyl group having one or more N, O, or S atoms instead of carbon atoms; "heterocycloalkylene" refers to a heterocycloalkyl group having a valence of at least two; "heteroaryl" refers to an aryl group having 1 to 3 separate or fused rings having one or more N, O, or S atoms instead of carbon atoms as ring members; and "heteroarylene" refers to a heteroaryl group having a valence of at least two.

[0033] The symbol "*" represents a bonding site (i.e., a point of attachment).

[0034] "Substituted" or "substituents" means that at least one hydrogen atom on a group is replaced with another group, provided that the normal valency of the designated atom is not exceeded. When the substituent is oxo (i.e., =0), then two hydrogens on a carbon atom are replaced. Combinations of two or more substituents or variables are permissible. For example, the term "substituted" can mean that the hydrocarbon moiety has two, three, or four substituents which are the same or different. Exemplary groups which can be present on a "substituted" position include, but are not limited to, nitro (-NO2), cyano (-CN), hydroxyl (-OH), oxo (=0), amino (-NH2), mono- or di-(C 1-6 alkylamino, alkylacyl (e.g., C 2-6 alkylacyl such as acyl), formyl (-C(=0)H), carboxylic acid or its alkali metal or ammonium salt, C 2-6 alkyl ester (-C(=0)0-alkyl or -OC(=0)-alkyl), C 7-13 aryl ester (-C(=0)0-aryl or -OC(=0)-aryl), amido (-C(=0)NR2, where R is hydrogen or C 1-6 alkyl), formamido (-CH2C(=0)NR2, where R is hydrogen or C 1-6 alkyl), halogen, mercapto (-SH), C 1-6 alkylthio (-S-alkyl), thiocyano (-SCN), C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 haloalkyl, C 1-9 alkoxy, C 1-6 haloalkoxy, C 3-12 cycloalkyl, C 5-18 cycloalkenyl, C 6-12 aryl having 1 to 3 separate or fused rings and 6 to 18 ring carbon atoms (e.g., phenyl, biphenyl, naphthyl, etc., each ring being substituted or unsubstituted aromatic), C 7-19 arylalkyl, C 7-12 alkylaryl, C 4-12 heterocycloalkyl, C 3-12 heteroaryl, C 1-6 alkylsulfonyl (-S(=0)2-alkyl), C 6-12 arylsulfonyl (-S(=0)2-aryl), or tosyl (CH3C6H4SO2-). When a group is substituted, the indicated number of carbon atoms is the total number of carbon atoms in the group, not including those of any substituents. For example, the group -CH2CH2CN is a C2alkyl group which is substituted with a cyano group.

[0035] As used herein, the terms "polymer" and "polymeric" refer to polymeric materials comprising one or more repeating units, wherein the repeating units may be the same as or different from each other. Therefore, the polymers and polymeric materials disclosed herein may be referred to as "polymers" or "copolymers." It should be further understood that the terms "polymer" and "polymeric" further include oligomers. As used herein, each of the one or more different repeating units is present at least twice in the polymeric material. In other words, a polymeric material comprising one repeating unit comprises a first repeating unit present in two or more amounts, and, for example, a polymeric material comprising two repeating units comprises a first repeating unit present in two or more amounts, and a second repeating unit present in two or more amounts.

[0036] As used herein, unless otherwise defined, "divalent linker" means a divalent group comprising one or more of the following: -O-, -S-, -Te-, -Se-, -C(O)-, -N(R)-. a -, -S(O)-, -S(O)2-, -C(S)-, -C(Te)-, -C(Se)-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Arylalkylene, substituted or unsubstituted C 1-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroarylalkylene or combinations thereof, wherein R a It is hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 4-30 Heteroaryl groups. More typically, the divalent linking group includes one or more of the following: -O-, -S-, -C(O)-, -N(R′)-, -S(O)-, -S(O)2-, substituted or unsubstituted C 1-30 Alkylene, substituted or unsubstituted C 3-30 Cycloalkylene, substituted or unsubstituted C 1-30 Heterocyclic alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 7-30 Arylalkylene, substituted or unsubstituted C 1-30 heteroaryl, substituted or unsubstituted C 3-30 Heteroarylalkylene groups or combinations thereof, wherein R' is hydrogen, substituted or unsubstituted C.1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 4-30 heteroaryl.

[0037] Organic underlayer films can be used to protect underlying substrates during various pattern transfer and etching processes. These films are often cast directly and cured on inorganic substrates (e.g., TiN). In these cases, it is desirable for the underlayer film to have sufficient adhesion to the substrate during all subsequent processing steps to protect the substrate from other damaging processing conditions. One commonly used processing step is a wet etch process known as SC-1, which involves submerging the substrate and underlayer in a hydrogen peroxide / ammonium hydroxide bath. Underlayer films that do not adhere sufficiently to the substrate can delaminate upon submersion, resulting in exposure and damage to the underlying inorganic substrate. See SC1 Resistance Evaluation below.

[0038] If the underlying layer or substrate includes various pitches, various line / space patterns, and / or various trench depths, it is also desirable for the underlayer film to have sufficient planarization properties to provide a film with a relatively flat top surface. See PL Evaluation below.

[0039] In embodiments, we provide a composition that can be applied to an underlayer or substrate to form a film layer on the substrate, i.e., as a photoresist underlayer. In one aspect, the photoresist underlayer composition includes a polymer including a repeat unit represented by Formula 1 (e.g., a repeat unit of Formula 1A or Formula IB), a compound including a substituent represented by Formula 2, and a solvent below.

[0040] In embodiments, we provide a method of forming a pattern, the method including:

[0041] applying a photoresist underlayer composition on a substrate to provide a photoresist underlayer;

[0042] forming a photoresist layer on the photoresist underlayer;

[0043] patterning the photoresist layer; and

[0044] transferring a pattern from the patterned photoresist layer to the photoresist underlayer;

[0045] wherein the photoresist underlayer composition includes a polymer including a repeat unit represented by Formula 1, a compound including a substituent represented by Formula 2; and a solvent;

[0046]

[0047] wherein in Formula 1

[0048] Ring A represents an aromatic ring group having 1 to 6 independently substituted or unsubstituted aromatic rings, wherein optionally two or more of the aromatic rings are fused, one or more of the aromatic rings include a fused optionally substituted cycloalkyl or a fused optionally substituted heterocycloalkyl, or a combination thereof,

[0049] Y is a divalent group comprising an optionally substituted C 1-4 alkylene, -O-, -S-, C(O)-, an optionally substituted arylene, or an optionally substituted heteroarylene having one or two aromatic rings, or a combination thereof, and

[0050] o is an integer from 2 to 8;

[0051]

[0052] wherein, in Formula 2:

[0053] R is a substituted or unsubstituted C 1-4 alkylene, -CR A R B -Ar-CH2-, or -Ar-CH2-, wherein Ar is an optionally substituted arylene or heteroarylene having 4 to 10 ring carbons, and R A and R B are independently hydrogen, hydroxyl, an optionally substituted C 1-6 alkyl, an optionally substituted C 1-6 alkoxy, or an optionally substituted C 6-12 aryl;

[0054] R 1 is hydrogen, an optionally substituted C 1-4 alkyl, an optionally substituted C 6-12 aryl, an optionally substituted C 3-8 cycloalkyl, or glycidyl;

[0055] * is a point of attachment to a ring carbon of an aromatic ring system Q, wherein the aromatic ring system Q is Ar 1 or Ar 2 -T-Ar 3 ,

[0056] wherein Ar 1 , Ar 2 , and Ar 3 independently comprise a substituted or unsubstituted aromatic group having 4 to 14 ring carbons, and

[0057] T is absent, -O-, -S-, -C(O)-, an optionally substituted C 1-4 alkylene, or -NR 2 -, wherein R 2is hydrogen, optionally substituted C 1-4 alkyl, or optionally substituted C 6-12 aryl; and

[0058] a is 1 to 8, c is 1, 2, or 3, and b + c is 2 or 3.

[0059] Ring A represents an aromatic group having 1 to 4 independently substituted or unsubstituted aromatic rings, wherein o is an integer from 2 to 8, preferably an integer from 2 to 4. If Ring A includes two or more aromatic rings, the two or more of the aromatic rings can be connected by a single bond or a bivalent linking group, or two or more of the aromatic rings can be fused aromatic rings. Alternatively, two or more of the aromatic rings of Ring A can be connected by a bivalent group, and the remaining aromatic rings can be fused aromatic rings. In one aspect, the bivalent linking group can comprise a single bond, optionally substituted C 1-4 alkylene, -O-, or -C(O)-. As noted above, Ring A can be monocyclic or polycyclic. When the group is polycyclic, the rings or ring groups can be fused (as in naphthyl, anthryl, pyrenyl, etc.), directly linked (as in biphenyl, etc.), bridged by a heteroatom (as in triphenylamino or diphenylene ether). In embodiments, the polycyclic aromatic group can include a combination of fused and directly linked rings (as in the linking of two naphthylene groups, etc.).

[0060] In one aspect, Ring A can be an aromatic group having 5 to 20 ring carbons or 5 to 14 ring carbons, and optionally includes 1 to 4 ring heteroatoms selected from N, O, or S.

[0061] Ring A includes 2 to 8 hydroxyl groups. It is further understood that any one or more ring carbons of Ring A can be substituted as described herein. For example, 1 to 10 ring carbons of Ring A can be substituted.

[0062] In one aspect, a list of exemplary substituents can include, but is not limited to, optionally substituted C 1-18 alkyl, optionally substituted C 1-18 alkoxy, optionally substituted C 1-18 haloalkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted C 1-8 heterocycloalkyl, optionally substituted C 2-18 alkenyl, optionally substituted C 2-18 alkynyl, optionally substituted C 6-14 aryl, optionally substituted C 6-18 aryloxy, optionally substituted C 7-14 arylalkyl, optionally substituted C 7-14 alkylaryl, optionally substituted C3-14 heteroaryl, halogen, -CN, -N02, -C02R 4 wherein R 4 is H, -OH, or C 1-6 alkyl.

[0063] In one aspect, ring A can be represented by Formula 1A or Formula IB:

[0064]

[0065]

[0066] wherein, in Formula 1A and Formula IB:

[0067] A is CR C or N, wherein R C is hydrogen, hydroxyl, optionally substituted C 1-6 alkyl, optionally substituted C 1-6 alkoxy, or optionally substituted C 6-12 aryl;

[0068] ring B represents a fused aromatic group having 1 to 4 aromatic rings;

[0069] L is a divalent group independently comprising 1 to 3 optionally substituted C 1-4 alkylene, 1 to 3 -0-, optionally substituted arylene having one or two aromatic rings, or a combination thereof;

[0070] each Z is independently a substituent, wherein a of Formula 1A is 0 or 1, and b of Formula IB is an integer from 0 to 10;

[0071] i is 2 or 3; j is 0, 1, or 2; and k is an integer from 0 to 6, wherein j+k is 2 or greater.

[0072] Compounds comprising a substituent represented by Formula 2 comprise an aromatic ring system Q, and Q is Ar 1 or Ar 2 -T-Ar 3 wherein T is as defined in Formula 2 above. In one aspect, T is absent, -0-, or optionally substituted -CH2-.

[0073] In one aspect, Ar 1 , Ar 2 , and Ar 3independently substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinolyl, substituted or unsubstituted biphenylenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted fluorenyl, or substituted or unsubstituted carbazolyl, and each of which is optionally substituted with glycidyl.

[0074] In one aspect, the compound comprising a substituent represented by Formula 2 is represented by one of the following compounds:

[0075]

[0076] J is

[0077] wherein k is 1, 2, 3, or 4, and each h is 0, 1, or 2; and

[0078] T is absent, O, S, -C(O)-, optionally substituted C 1-4 alkylene, or -NR 2 -, wherein R 2 is H, optionally substituted C 1-4 alkyl, or optionally substituted C 6-10 aryl.

[0079] In one aspect, the compound comprising a substituent represented by Formula 2 is represented as follows:

[0080] Q is Ar 1 , and Ar 1 is phenyl, R is CH2, a is 1 or 2, and c is 2;

[0081] Q is Ar 1 , and Ar 1 is phenyl substituted with glycidyl, R is CH2, a is 1 or 2, and c is 2;

[0082] Q is Ar 2 -T-Ar 3 , and Ar 2 and Ar 3 are phenyl, and T is absent, -O-, -C(O)-, or -CR B R C -, and for each of Ar 2 and Ar 3 , a is 1 or 2, and c is 2; or

[0083] Q is Ar 2 -T-Ar 3 , and Ar 2 or Ar3 is phenyl substituted with a glycidyl group, and T is absent, -O-, -C(O)-, or -CR D R E -, and for each of Ar 2 and Ar 3 , a is 1 or 2, and c is 2,

[0084] wherein R D and R E are independently hydrogen, optionally substituted C 1-4 alkyl, or optionally substituted phenyl.

[0085] In one aspect, the compound comprising a substituent represented by Formula 2 is represented by one of the following compounds, wherein T is absent, O, S, -C(O)-, optionally substituted C 1-4 alkylene, or -NR 2 -, wherein R 2 is H, optionally substituted C 1-4 alkyl, or optionally substituted C 6-10 aryl.

[0086]

[0087] In one aspect, the repeat unit of Formula 1 is represented by at least one of the following:

[0088]

[0089] wherein

[0090] D is -CR D R E -, wherein R D and R E are independently hydrogen, optionally substituted C 1-18 alkyl, optionally C 6-22 aryl, or optionally C 3-22 heteroaryl, and u is an integer from 0 to 3, v is an integer from 0 to 3, wherein u+v = 2 or greater.

[0091] In one aspect, the repeat unit of Formula 1 is represented by Formula 3A or Formula 3B;

[0092]

[0093]

[0094] wherein, in Formula 3A and 3B:

[0095] W and W 1 are independently optionally substituted C 1-4 alkylene, -O-, or a combination thereof;

[0096] Ar 4 and Ar 5 independently is optionally substituted C 6-14 arylene, or optionally substituted C 3-14 heteroarylene;

[0097] Z is absent, O, -S-, -C(O)-, optionally substituted C 1-4 alkylene;

[0098] m is 0, 1, or 2; n is 0 or 1; q is 2 or 3; and r and s are independently 0, 1, or 2, where r + s is 2 or greater.

[0099] In one aspect, the repeat unit of Formula 3A or Formula 3B, if n is 0, and m is 1 or 2, then W and W 1 independently is -CR F R G -, and Ar 4 is substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl, where R F and R G independently is hydrogen, hydroxyl, optionally substituted C 1-18 alkyl, optionally substituted C 1-18 alkoxy, Ar 6 , -CH2Ar 6 , -OAr 6 , -Ar 6 R 4 , where Ar 6 is optionally substituted C 6-18 aryl, and R 4 is optionally substituted C 1-18 alkyl or optionally substituted C 1-18 alkoxy.

[0100] In one aspect, the repeat unit of Formula 3A or Formula 3B is represented by at least one of the following:

[0101]

[0102]

[0103] Exemplary repeat units of Formula 1A can include one or more of the following.

[0104]

[0105]

[0106] The polymer having repeat units of at least one of Formula 1, Formula 1A, or Formula IB can also include repeat units having a pendant group that includes one or more hydroxyl groups. For example, the repeat units having a pendant group that includes one or more hydroxyl groups can include 1 to 4 hydroxyl groups, preferably 1 to 3 hydroxyl groups, and more typically 1 or 2 hydroxyl groups. In some aspects, the polymer can include two or more different repeat units having a pendant group that includes one or more hydroxyl groups.

[0107] Another exemplary monomer for providing repeat units having a pendant group that includes one or more hydroxyl groups includes an N-hydroxyaryl maleimide monomer of Formula 4 below.

[0108]

[0109] wherein in Formula 4,

[0110] Ar 1 is a hydroxyl-substituted C 6-30 aryl, hydroxyl-substituted C 3-30 heteroaryl, or combinations thereof, each of which can be optionally substituted. For Ar 1 It can be desirable to include a single hydroxyl group or two or more hydroxyl groups.

[0111] Non-limiting examples of N-hydroxyaryl maleimide monomers include the following:

[0112]

[0113] The polymer including repeat units represented by Formula 1, Formula 1A, Formula IB, Formula 3A, or Formula 3B is present in the polymer in an amount from 10 to 100 mole percent (mol%), 20 to 90 mol%, or 20 to 70 mol% based on the total moles of repeat units in the polymer.

[0114] The polymer including repeat units represented by Formula 1, Formula 1A, Formula IB, Formula 3A, or Formula 3B is present in the composition (e.g., photoresist primer composition) in an amount from 5 to 95 weight percent (wt%) based on the total solids of the composition, more typically in an amount from 15 to 85 wt%, 20 to 60 wt%, or 25 to 50 wt% based on the total solids content of the composition. As used herein, the “total solids” of the composition refers to all materials and components of the composition other than solvents.

[0115] As indicated, the composition, for example, a resist underlayer composition, further comprises a compound containing a substituent represented by Formula 2, hereinafter referred to as "Formula 2 compound". The Formula 2 compound is present in the composition in an amount from 5 to 95 wt% based on the total solids of the composition. For example, the Formula 2 compound is present in the composition in an amount from 20 to 80 wt%, 30 to 80 wt%, 40 to 80 wt%, or 50 to 75 wt% based on the total solids content of the composition.

[0116] With respect to the weight ratio of the polymer comprising repeating units having two or more hydroxyl groups of Formula 1 to the compound comprising aromatic substituents represented by Formula 2, the polymer-to-compound weight ratio ranges from 4:1 to 1:20. Exemplary polymer-to-compound weight ratios include, but are not limited to, 3:1, 2:1, 1:1, 1:1.5, 1:2, 1:3, 1:4, 1:6, or 1:10. For example, the polymer-to-compound weight ratio ranges from 2:1 to 1:4, 1:1 to 1:4, or 1:1.2 to 1:4.

[0117] In one aspect, polymers comprising repeating units represented by Formula 1, Formula 1A, Formula 1B, Formula 3A, or Formula 3B may have a weight-average molecular weight (Mg) of 1,000 to 100,000 g / mol and 3,000 to 60,000 g / mol. w or number-average molecular weight (M) of 500 to 100,000 g / mol. n The molecular weight (M) was determined by gel permeation chromatography (GPC) using appropriate polystyrene standards. w Or M n Exemplary polymers comprising repeating units represented by Formula 1, Formula 1A, Formula 1B, Formula 3A, or Formula 3B may have a weight-average molecular weight of 1,000 to 20,000 g / mol, 2,000 to 12,000 g / mol, or 2,000 to 8,000 g / mol.

[0118] In one aspect, an exemplary polymer comprising repeating units represented by Formula 1, Formula 1A, Formula 1B, Formula 3A, or Formula 3B may have a weight-average molecular weight of 1,000 to 8,000 g / mol, and the weight ratio of polymer to compound is in the range of 2:1 to 1:4 or 1:1 to 1:4.

[0119] Compositions, such as photoresist underlayer compositions, may also contain additives having multiple phenolic hydroxyl groups to increase phenol density. Additives can be used in photoresist underlayer compositions to provide even greater adhesion to the substrate or to further enhance the mechanical properties of the resulting underlayer film. It is believed that the multiple phenolic hydroxyl groups of the additives enhance the adhesion of the underlayer film to the substrate, particularly when the film and substrate are immersed in a hydrogen peroxide / ammonium hydroxide (SC-1) bath.

[0120] According to aspects of the present application, a photoresist primer composition is provided that includes a polymer including repeating units represented by Formula 1, Formula 1A, Formula IB, Formula 3A, or Formula 3B, a compound including a substituent represented by Formula 2, and an additive. The additive can include a compound of Formula 5 as described below, a compound of Formula 6 as described below, or a combination thereof.

[0121]

[0122] In Formula 5, AA, X, R 1 , R 2 , Y 2 , a and n

[0123] AA is a single bond or a double bond, and it is understood that "AA" refers to a moiety having a structure represented by (5) in Formula ;

[0124] X is a single bond, -C(O)-, unsubstituted Ci alkylene, or hydroxyl-substituted Ci alkylene. It is understood that "hydroxyl-substituted Ci alkylene" is not further substituted with a group other than a hydroxyl group. For example, X can be -C(O)- or unsubstituted Ci alkylene;

[0125] R 1 and R 2 are each independently hydrogen, substituted or unsubstituted C 1-30 alkyl, substituted or unsubstituted C 3-30 cycloalkyl, -C(O)OR 5a , or glycidyl, wherein R 5a 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 6-30 aryl, substituted or unsubstituted C 7-30 arylalkyl, substituted or unsubstituted C 7-30 alkylaryl, substituted or unsubstituted C 1-30 heteroaryl, substituted or unsubstituted C 2-30 heteroarylalkyl, or substituted or unsubstituted C 2-30 alkylheteroaryl. Typically, R 1 and R 2 can be hydrogen.

[0126] Y 2 is hydrogen, substituted or unsubstituted C6-60 aryl, or substituted or unsubstituted C 1-60 heteroaryl. It is understood that when n is 0, the oxygen atom is bonded directly to the group Y 2 to form the partial structure represented by -O-Y 2 In some aspects, n is 0 and Y 2 is hydrogen. In other aspects, n is 1 and Y 2 is substituted or unsubstituted C 6-30 aryl, preferably C 6-30 aryl optionally can be further substituted with one or more substituents other than hydroxyl. 6-30 aryl optionally can be further substituted with one or more substituents other than hydroxyl.

[0127] and each R A is independently substituted or unsubstituted C 1-10 alkyl, substituted or unsubstituted C 1-10 heteroalkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 2-10 heterocycloalkyl, substituted or unsubstituted C 6-12 aryl, or substituted or unsubstituted C 1-10 heteroaryl; each R B is independently substituted or unsubstituted C 1-10 alkyl, substituted or unsubstituted C 1-10 heteroalkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 2-10 heterocycloalkyl, substituted or unsubstituted C 6-12 aryl, or substituted or unsubstituted C 1-10 heteroaryl; and

[0128] a is 2, 3, or 4, typically 2 or 3; b is 2, 3, 4, or 5, preferably 2, 3, or 4; p is 0, 1, or 2, typically 0 or 1; and q is 0, 1, 2, or 3, typically 0 or 1; m is an integer from 1 to 6, typically 1, 2, or 3; and n is 0 or 1.

[0129] In some aspects, the additive of Formula 5 can be represented by a compound selected from Formula 5A, Formula 5B, or a combination thereof:

[0130]

[0131] wherein in Formula 5A or Formula 5B

[0132] R 6 is hydrogen, substituted or unsubstituted C 1-10 alkyl, substituted or unsubstituted C 1-10Heteroalkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 2-10 Heterocyclic alkyl, substituted or unsubstituted C 6-12 aryl, or substituted or unsubstituted C 1-10 heteroaryl; and

[0133] R 7 It is hydrogen, substituted or unsubstituted C 1-10 Alkyl, substituted or unsubstituted C 1-10 Heteroalkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 2-10 Heterocyclic alkyl, substituted or unsubstituted C 6-12 aryl, or substituted or unsubstituted C 1-10 Mixed aromatic compounds.

[0134] The additive of the exemplary formula 5 may include one or more compounds selected from the following:

[0135]

[0136] In some respects, additives are represented by Formula 6.

[0137]

[0138] In Equation 6, R 2 and R B As defined in Equation 5, R A Same, and R 3 It can be hydrogen, a carboxylic acid group or its derivative, or -C(O)OR 5b Preferably, a carboxylic acid group or a derivative thereof is used. As used herein, "carboxylic acid or a derivative thereof" refers to a carboxylic acid (-COOH) or a carboxylic acid derivative thereof of the following formula: -COO - M + M + It is a cationic organic or inorganic group, such as an alkylammonium cation;

[0139] c and d are each independent integers from 2 to 5, typically 2, 3, or 4; p is 0, 1, or 2, typically 0 or 1; and q is 0, 1, 2, or 3, typically 0 or 1.

[0140] In some respects, the additives of Formula 6 can be represented by compounds of Formula 6a, Formula 6B, or combinations thereof:

[0141]

[0142] In either Equation 6A or Equation 6B;

[0143] R 8is hydrogen, substituted or unsubstituted C 1-10 alkyl, substituted or unsubstituted C 1-10 heteroalkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 2-10 heterocycloalkyl, substituted or unsubstituted C 6-12 aryl, or substituted or unsubstituted C 1-10 heteroaryl; and

[0144] R 9 is hydrogen, substituted or unsubstituted C 1-10 alkyl, substituted or unsubstituted C 1-10 heteroalkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 2-10 heterocycloalkyl, substituted or unsubstituted C 6-12 aryl, or substituted or unsubstituted C 1-10 heteroaryl; and

[0145] each R 3 is the same as defined for Formula 6.

[0146] Exemplary additives of Formula 6 can include one or more compounds selected from the group consisting of:

[0147]

[0148] The additive can be included in the photoresist underlayer composition in an amount from 0.1 to 20 wt%, typically 1 to 20 wt% or 5 to 20 wt%, based on the total solids of the photoresist underlayer composition.

[0149] The composition, e.g., photoresist underlayer composition, can also include an additive that includes a nitrogen atom attached to a thermally cleavable protecting group or an acid cleavable protecting group. At times, such additives are referred to in the art as thermal base generating compounds or thermal base generating polymers. The cleavable protecting group is typically cleaved during curing of the composition and the exposed nitrogen atom can enhance adhesion of the underlayer film to the substrate, particularly when the film and substrate are immersed in a hydrogen peroxide / ammonium hydroxide (SC-1) bath.

[0150] In embodiments, the thermal base generating compound or thermal base generating polymer includes a protected amino group, which can be derived from a primary or secondary amino moiety. Various amine protecting groups are suitable for use in the present application, so long as such protecting groups are removable (cleavable) by heat, acid, or a combination thereof. The amine protecting group is thermally cleavable, such as at temperatures from 75 °C to 350 °C, including from 100 °C to 250 °C.

[0151] Suitable amine protecting groups for use in the present application include carbamates such as 9-fluorenylmethyl carbamate, tert-butyl carbamate, and benzyl carbamate; amides such as acetamide, trifluoroacetamide, and p-toluenesulfonamide; benzylamine; triphenylmethyl amine (tritylamine); and benzylidene amine. Such amine protecting groups, their formation, and their removal are well known in the art. See, e.g., T. W. Green et al., Protective Groups in Organic Synthesis, Wiley-Interscience, New York, 1999.

[0152] In embodiments, the thermal base generating compound is represented by Formula 7. In embodiments, the thermal base polymer can comprise repeat units derived from a monomer of Formula 8. Alternatively, the compositions described herein can comprise a combination of a compound of Formula 7 and a polymer derived from a monomer of Formula 8.

[0153]

[0154] In Formulas 7 and 8, X is C or S, wherein when X is C, then p is 1, and when X is S, then p is 2. Typically, X is C.

[0155] In Formulas 7 and 8, Z 1 , Z 2 , L 1 , and L 2 each independently is a single bond or a divalent linking group. For example, Z 1 , Z 2 , L 1 , and L 2 each independently can be a single bond or a divalent linking group comprising one or more of substituted or unsubstituted C 1-30 alkylene, substituted or unsubstituted C 1-30 heteroalkylene, substituted or unsubstituted C 3-30 cycloalkylene, substituted or unsubstituted C 2-30 heterocycloalkylene, substituted or unsubstituted C 6-30 arylene, substituted or unsubstituted C 1-30 heteroarylene, -0-, -C(O)-, -N(R 4a )-, -S-, or -S(O)2-, wherein R 4a can be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 6-30 aryl, substituted or unsubstituted C 1-30 heteroaryl, or substituted or unsubstituted C 2-30 heteroarylalkyl. Preferably, Z 1 and Z2 Each is O- independently.

[0156] In equations 7 and 8, R 1 and R 2 Each can be 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 6-30 aryl, or substituted or unsubstituted C 1-30 Mixed aryl groups. Optionally, R 1 and R 2 They can form a ring together through divalent linking groups.

[0157] In equations 7 and 8, R 3 and R 5 Each can be 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 6-30 aryl, substituted or unsubstituted C 1-30 Mixed aromatics, -OR 4c 、or -N(R 4d (R) 4e ), where R 4c R 4d and R 4e Each is independently a hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 6-30 aryl, or substituted or unsubstituted C 1-30 Hybrid aryl. Optionally, in Formula 8, L 1 and R 4 A ring can be formed together with a divalent linker (e.g., a divalent linker).

[0158] In Formula 8, P is a polymerizable group. Typically, the polymerizable group can be selected from carboxyl, mercapto, amino, epoxy, alkoxy, amide, vinyl, or combinations thereof.

[0159] The additive may be included in the composition in an amount from 0.1 to 20 wt%, typically 1 to 20 wt%, or 5 to 20 wt%, based on the total solids of the composition.

[0160] In this embodiment, we describe a method for forming a pattern (e.g., a pattern in a semiconductor device). The method includes:

[0161] A photoresist underlayer composition is applied onto a substrate to provide a photoresist underlayer;

[0162] forming a photoresist layer on the photoresist primer layer;

[0163] patterning the photoresist layer; and

[0164] transferring a pattern from the patterned photoresist layer to the photoresist primer layer;

[0165] wherein the photoresist primer layer composition includes a polymer including a repeating unit represented by Formula 1, a compound including a substituent represented by Formula 2; and a solvent;

[0166]

[0167] wherein in Formula 1

[0168] Ring A represents an aromatic ring group having 1 to 6 independently substituted or unsubstituted aromatic rings, wherein optionally, two or more of the aromatic rings are fused, one or more aromatic rings include a fused optionally substituted cycloalkyl or an optionally substituted fused heterocycloalkyl, or a combination thereof,

[0169] Y is a divalent group including an optionally substituted C 1-4 alkylene, -0-, -S-, C(O)-, an optionally substituted arylene, or an optionally substituted heteroarylene, having one or two aromatic rings, or a combination thereof, and

[0170] o is an integer from 2 to 8;

[0171]

[0172] wherein, in Formula 2:

[0173] R is a substituted or unsubstituted C 1-4 alkylene, -CR A R B -Ar-CH2-, or -Ar-CH2-, where Ar is an optionally substituted arylene or heteroarylene having 4 to 10 ring carbons, and R A and R B are independently hydrogen, hydroxyl, an optionally substituted C 1-6 alkyl, an optionally substituted C 1-6 alkoxy, or an optionally substituted C 6-12 aryl;

[0174] R 1 is hydrogen, an optionally substituted C 1-4 alkyl, an optionally substituted C 6-12 aryl, an optionally substituted C 3-8 cycloalkyl, or glycidyl;

[0175] * is the point of attachment to a ring carbon of the aromatic ring system Q, wherein the aromatic ring system Q is Ar 1 or Ar 2 -T-Ar 3 ,

[0176] wherein Ar 1 , Ar 2 , and Ar 3 independently comprise a substituted or unsubstituted aromatic group having 4 to 14 ring carbons, and

[0177] T is absent, -0-, -S-, -C(O)-, optionally substituted C 1-4 alkylene, or -NR 2 -, wherein R 2 is hydrogen, optionally substituted C 1-4 alkyl, or optionally substituted C 6-12 aryl; and

[0178] a is 1 to 8, c is 1, 2, or 3, and b + c is 2 or 3.

[0179] Further, the photoresist primer composition prepared above will be free of non- polymeric polyphenolic compounds and thermal base generators. As will be understood by one of ordinary skill in the art, reference to non-polymeric polyphenolic compounds will include the additive compounds of Formula 5 and Formula 6 described above, and reference to thermal base generators will include the compounds of Formula 7 described above and the polymers of Formula 8 described above, respectively.

[0180] Suitable polymers of the present application can be readily prepared based on the procedures described in the examples of the present application and by analogy to the procedures described in the examples of the present application, as will be readily understood by one of ordinary skill in the art. For example, one or more monomers corresponding to the repeat units described herein can be combined or fed separately using a suitable solvent(s) and initiator(s) and polymerized in a reactor. The monomer composition can further comprise additives, such as solvents, polymerization initiators, cure catalysts (i.e., acid catalysts), and the like. For example, the polymers can be polymerized by the corresponding monomers under any suitable conditions, such as by heating at an effective temperature, irradiation with activating radiation at an effective wavelength, or a combination thereof.

[0181] The photoresist primer composition can further include one or more polymers in addition to the above-described polymers ("additional polymers"). For example, the photoresist primer composition can further include additional polymers as described above but of different composition. Additionally or alternatively, the one or more additional polymers can include those well known in the art, for example, one or more polymers selected from the group consisting of polyacrylates, polyvinylethers, polyesters, polynorbomenes, polyacetals, polyglycols, polyamides, polyacrylamides, polyphenols, novolacs, styrenic polymers, polyvinyl alcohols, copolymers thereof, and combinations thereof.

[0182] In some aspects, the photoresist primer composition can further include one or more curing agents to aid in curing of the photoresist primer composition, for example, after the photoresist primer composition is applied to the surface. Curing agents are any component that causes the photoresist primer composition to cure on the surface of the substrate.

[0183] It can be beneficial for the photoresist primer composition to include an acid generator compound, such as a photoacid generator (PAG) and / or a thermal acid generator (TAG) compound. A preferred curing agent is a thermal acid generator (TAG).

[0184] Suitable PAGs are known in the art of chemically amplified photoresists and include, for example: onium salts, such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; nitrobenzyl derivatives, such as 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, such as 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene, and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, such as bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; glyoxime derivatives, such as bis-0-(p-toluenesulfonyl)-a-dimethylglyoxime, and bis-0-(n-butanesulfonyl)-a-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate; and halogen-containing triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. One or more of such PAGs can be used.

[0185] TAG compounds are any compound that releases an acid upon exposure to heat. Exemplary thermal acid generators include, but are not limited to, amine-terminated strong acids such as amine-terminated sulfonic acids such as amine-terminated dodecylbenzenesulfonic acid. Those skilled in the art will also appreciate that certain photo-acid generators are capable of releasing an acid upon heating and can be used as thermal acid generators.

[0186] Suitable TAG compounds can include, for example, nitrobenzyl tosylates such as 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, 4-nitrobenzyl tosylate; benzenesulfonates such as 2-trifluoromethyl-6-nitrobenzyl 4-chlorobenzenesulfonate, 2-trifluoromethyl-6-nitrobenzyl 4-nitrobenzenesulfonate; phenolsulfonates such as phenyl 4-methoxybenzenesulfonate; alkylammonium salts of organic acids such as triethylammonium salts of 10-camphor sulfonic acid, trifluoromethylbenzenesulfonic acid, perfluorobutanesulfonic acid; and specific onium salts. A variety of aromatic (anthracene, naphthalene, or benzene derivatives) sulfonic acid amine salts can be used as TAGs, including those disclosed in U.S. Patent Nos. 3,474,054, 4,200,729, 4.251,665, and 5,187,019. Examples of TAGs include those sold by King Industries, Norwalk, Conn. USA under the NACURE, CDX, and K-PURE names, such as NACURE 5225, CDX-2168E, K-PURE 2678, and K PURE 2700. One or more of such TAGs can be used.

[0187] The amount of such a curing agent that can be used in the compositions of the present application can be, for example, from greater than 0 to 10 wt%, and typically from greater than 0 to 3 wt%, based on the total solids of the photoresist underlayer composition.

[0188] In some aspects, the photoresist underlayer composition does not include a photoacid generator. Thus, in these embodiments, the photoresist underlayer composition can be substantially free of PAG compounds and / or polymeric PAGs, for example, free of PAG compounds or polymeric PAGs.

[0189] The photoresist underlayer composition can further include one or more crosslinking agents, for example, crosslinking agents including non-epoxy crosslinking agents. Any suitable crosslinking agent can further be used in the coating compositions of the present application, provided that such crosslinking agents have at least 2, and preferably at least 3 moieties capable of reacting with functional groups in the photoresist underlayer composition. Exemplary crosslinking agents can include novolac resins, melamine compounds, guanamine compounds, isocyanate-containing compounds, benzocyclobutene, benzoxazine, and the like, and typically are those having 2 or more, more typically 3 or more, moieties selected from the group consisting of hydroxymethyl, C 1-10alkyl groups, and C 2-10 any of the substituents of acyloxy groups. Examples of suitable crosslinkers include those shown below:

[0190]

[0191] Additional crosslinkers are well known in the art and commercially available from a number of sources. The amount of such additional crosslinkers for use in the coating compositions of the present application can be, for example, in the range of from greater than 0 to 30 wt%, and preferably from greater than 0 to 10 wt%, based on the total solids of the coating composition.

[0192] The photoresist primer composition can include one or more optional additives, including, for example, surfactants, antioxidants, and the like, or combinations thereof. When present, each optional additive can be used in the photoresist primer composition in small amounts, such as from 0.01 to 10 wt%, based on the total solids of the photoresist primer composition.

[0193] Typical surfactants include those that exhibit amphiphilic properties, by which is meant 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 a long hydrophobic tail, which is organophilic and repels water. Suitable surfactants can be ionic (i.e., anionic, cationic) or non-ionic. Further examples of surfactants include silicone surfactants, poly(oxyalkylene) surfactants, and fluorosurfactants. Suitable non-ionic surfactants include, but are not limited to, octyl and nonyl phenol ethoxylates, such as TRITON X-114, X-100, X-45, X-15, and branched secondary alcohol ethoxylates, such as TERGITOL TMN-6 (Dow Chemical Company, Midland, MI). Still further 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 McCutcheon's Emulsifiers and Detergents, North American Edition, 2000, published by Manufacturers Confectioners Publishing Co., Glen Rock, N.J. Non-ionic surfactants that are acetylenic diol derivatives can also be suitable. Such surfactants are commercially available from Air Products and Chemicals, Inc., Allentown, PA and sold under the trade names SURFYNOL and DYNOL. Additional suitable surfactants include other polymeric compounds, such as the triblock EO-PO-EO copolymers PLURONIC 25R2, L121, L123, L31, L81, L101, and P123 (BASF, Inc.).

[0194] Antioxidants can be added to prevent or minimize oxidation of the organic materials in the photoresist underlayer 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 hydroxyltoluene, 2-(1 -methylcyclohexyl)-4,6-dimethylphenol, 2,4-dimethyl-6-tert-butylphenol, 2-methyl-4,6-dinonylphenol, 2,6-di-tert-butyl-alpha-dimethylamino-p-cresol, 6-(4-hydroxy-3,5-di-tert-butylanilino)-2,4-bis-octyl-thio-1,3,5-triazine, n-octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, octylated phenol, aralkyl-substituted phenols, alkylated p-cresols, and hindered phenols; bisphenols, triphenols, and polyphenols such as 4,4'-biphenol, 4,4'-methylene-bis-(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-alpha-methyl-benzyl-p-cresol), methylene-crosslinked polyvalent alkylphenols, 4,4'-butylidene-bis-(3-methyl-6-tert-butylphenol), 1,1 -bis-(4-hydroxyphenyl)- cyclohexane, 2,2'-dihydroxy-3,3'-di-(alpha-methylcyclohexyl)-5,5'-dimethyl diphenylmethane, 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 tetra-[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane. Suitable antioxidants are commercially available, for example, Irganox 1076® (Ciba Specialty Chemicals Corp.). TM Irganox 1010® (Ciba Specialty Chemicals Corp.).

[0195] The photoresist primer composition includes a solvent. The solvent component can be a single solvent or can include a mixture of two or more different solvents. Suitably, each of the plurality of solvents can be miscible with one another. Suitable solvents include, for example, one or more oxo-isobutyric acid esters, particularly methyl-2-hydroxyisobutyrate, 2-hydroxyisobutyric acid, and ethyl lactate; one or more glycol ethers, particularly 2-methoxyethyl ether (diethylene glycol dimethyl ether), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; one or more solvents having both ether and hydroxyl moieties, particularly methoxybutanol, ethoxybutanol, methoxypropanol, and ethoxypropanol; one or more alkyl esters, particularly methylcellosolve acetate, ethylcellosolve acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl ether acetate, as well as other solvents such as one or more dibasic esters; and / or other solvents, such as one or more of propylene carbonate and gamma-butyrolactone.

[0196] The total solids of the desired photoresist primer composition will depend on a variety of factors, such as the desired final layer thickness. Typically, the total solids of the photoresist primer composition can be from 0.1 to 20 wt%, based on the total weight of the coating composition, for example, from 0.1 to 10 wt%, more typically from 0.11 to 5 wt%.

[0197] The photoresist primer composition can be prepared according to known procedures. For example, the photoresist primer composition can be prepared by combining the first material, the second material, the additive, the solvent, and any optional components, in any order. The photoresist primer composition can be used as is, or can be subjected to purification or dilution prior to being coated on a substrate. Purification can involve, for example, one or more of centrifugation, filtration, distillation, decantation, evaporation, treatment with ion exchange beads, and the like.

[0198] The patterning method of the present application includes applying a layer of the photoresist primer composition on a substrate; curing the applied photoresist primer composition to form a coated primer; and forming a photoresist layer on the coated primer. The method can further include the step of exposing the photoresist layer to activating radiation in a pattern; and developing the exposed photoresist layer to provide a resist relief image. In some aspects, the method can further include forming a silicon-containing layer, an organic anti-reflective coating, or a combination thereof on the coated primer prior to forming the photoresist layer. In some aspects, the method can further include transferring the pattern to the silicon-containing layer, the organic anti-reflective coating, or a combination thereof after developing the exposed photoresist layer and prior to the step of transferring the pattern to the coated primer.

[0199] A wide variety of substrates can be used in these patterning methods, with electronic device substrates being typical. Suitable substrates include, for example, package 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; polysilicon substrates; and the like. Suitable substrates can be in the form of wafers, such as those used in the manufacture of integrated circuits, optical sensors, flat panel displays, integrated optical circuits, and LEDs. As used herein, the term "semiconductor wafer" is intended to encompass "electronic device substrates," "semiconductor substrates," "semiconductor devices," as well as various packages for various levels of interconnection, including single-die wafers, multi-die wafers, packages for various levels, or other assemblies requiring solder connections. Such substrates can be of any suitable size. Typical wafer substrates are 200 mm to 300 mm in diameter, although wafers having smaller and larger diameters can be suitably employed in accordance with the present application. As used herein, the term "semiconductor substrate" includes any substrate having one or more semiconductor layers or structures, which can 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- fabricated.

[0200] 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 can include one or more layers as well as patterned features. The layers can include, for example, one or more electrically conductive layers such as layers of aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys, nitrides, or silicides of such metals, doped amorphous or doped polysilicon; one or more dielectric layers such as layers of silicon oxide, silicon nitride, silicon oxynitride, or metal oxide; a semiconductor layer such as monocrystalline silicon; and combinations thereof. In some aspects, the substrate includes titanium nitride. The layers can 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.

[0201] In certain patterning methods of the present application, it can be desirable to provide one or more lithographic layers, such as a hard mask layer, e.g., a spin-on carbon (SOC), amorphous carbon, or metal hard mask layer, a CVD layer, such as a silicon nitride (SiN) layer, a silicon oxide (SiO) layer, or a silicon oxynitride (SiON) layer, an organic or inorganic BARC layer, or combinations thereof, on the upper surface of the substrate prior to forming the photoresist underlayer of the present application. Such layers, in combination with the layer of the photoresist underlayer composition of the present application, and the photoresist layer, form a lithographic stack. Typical lithographic stacks useful in the patterning methods of the present application include, for example, the following: SOC layer / underlayer / photoresist layer; SOC layer / SiON layer / underlayer / photoresist layer; SOC layer / SiARC layer / underlayer / photoresist layer; SOC layer / metal hard mask layer / underlayer / photoresist layer; amorphous carbon layer / underlayer / photoresist layer; and amorphous carbon layer / SiON layer / underlayer / photoresist layer.

[0202] It should be understood that "photoresist underlayer" as used herein refers to one or more layers disposed between the substrate and the photoresist layer (i.e., "on the substrate"). Thus, the coated underlayer of the present application (i.e., the layer of the photoresist underlayer composition) can be used alone as the photoresist underlayer, or the coated underlayer of the present application (i.e., the layer of the photoresist underlayer composition) can be used in combination with other underlayers, including those as described herein.

[0203] The photoresist underlayer composition can be coated on the substrate by any suitable means such as spin coating, slot die coating, blade coating, curtain coating, roller coating, spray coating, dip coating, and the like. In the case of a semiconductor wafer, spin coating is preferred. In a typical spin coating process, the composition of the present application is applied to a substrate rotating at a rate of 500 to 4000 revolutions per minute (rpm) for a period of 15 to 90 seconds to obtain the desired condensed polymer layer on the substrate. Those skilled in the art will appreciate that the thickness of the coated layer can be adjusted by varying the rate of rotation as well as the solids content of the composition. The underlayer formed from the photoresist underlayer composition typically has a dry layer thickness of from 1 to 50 nanometers (nm), more typically from 1 to 10 nm.

[0204] The coated photoresist underlayer composition is optionally soft baked at a relatively low temperature to remove any solvent and other relatively volatile components. Typically, the substrate is baked at a temperature of less than or equal to 150 °C, preferably from 60 °C to 125 °C, and more preferably from 90 °C to 115 °C. The baking time is typically from 10 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, and more preferably from 6 to 90 seconds. When the substrate is a wafer, this baking step can be performed by heating the wafer on a hot plate. This soft baking step can be performed as part of the curing of the coating, or can be omitted entirely.

[0205] The photoresist underlayer composition is then cured to form a coated underlayer. The coating composition should be cured sufficiently that the coated underlayer film does not, or minimally, intermix with another underlayer component or photoresist layer to be formed on the underlayer. The coated 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 performed on a hot plate apparatus, but equivalent results can be obtained using oven curing. Typically, curing can be performed at a temperature of 150 °C or higher, and preferably from 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 from 200 °C to 400 °C. The curing time is typically from 10 seconds to 10 minutes, preferably from 30 seconds to 5 minutes, more preferably from 45 seconds to 2 minutes, and still more preferably from 45 to 90 seconds. Optionally, a ramp or multi-stage curing process can be used. Ramp baking typically begins at a relatively low (e.g., ambient) temperature that is increased to a higher target temperature at a constant or varying ramp rate. A multi-stage curing process involves curing at two or more temperature plateaus, typically a first stage at a lower baking temperature, and one or more additional stages at a higher temperature. The conditions for such ramp or multi-stage curing processes are known to those skilled in the art, and can allow for the omission of a previous soft bake process.

[0206] After the applied photoresist underlayer composition is cured, a photoresist layer is formed on the coated underlayer. As noted above, other intermediate layers can be applied between the coated underlayer and the overcoated photoresist layer. In some aspects, the method can further include forming a silicon-containing layer, an organic anti-reflective coating, or a combination thereof, on the coated underlayer prior to forming the photoresist layer.

[0207] A wide variety of photoresists can be suitably used in the methods of the present application, and are typically positive materials. The particular photoresist to be used will depend on the exposure wavelength used, and generally comprises an acid-sensitive base polymer, a photoactive component such as a photoacid generator, a solvent, and optionally additional components. Suitable photoresists are well known to those skilled in the art, and are commercially available, for example, UV TM and EPIC TMThe photoresist can be applied to the substrate by known coating techniques, such as described above for the underlayer composition, with spin coating being typical. Typical thicknesses of the photoresist layer are from 10 to 300 nm. Next, the photoresist layer is typically soft baked to minimize the solvent content in the layer, to form a tack-free coating and to improve the adhesion of the layer to the substrate. Soft baking can be performed on a hot plate or in an oven, with a hot plate being typical. Typical soft baking is performed at temperatures from 70 °C to 150 °C, and for times from 30 to 90 seconds.

[0208] Next, the photoresist layer is exposed through a photomask to activating radiation to create a solubility differential between exposed and unexposed areas. Reference herein to exposing a photoresist composition to radiation that is activating to the composition indicates that the radiation is capable of forming a latent image in the photoresist composition. The photomask has optically transparent and optically opaque areas corresponding to the areas in the resist layer that are to be exposed and not exposed, respectively, by the activating radiation. The exposure wavelength is typically 400 nm or less, and more typically 300 nm or less, such as 248 nm (KrF), 193 nm (ArF), or EUV wavelengths (e.g., 13.5 nm). In preferred aspects, the exposure wavelength is 193 nm or an EUV wavelength. The exposure energy is typically 10 to 100 millijoules per square centimeter (mJ / cm2), depending on, for example, the exposure tool and the components of the photosensitive composition. 2 ), depending on, for example, the exposure tool and the components of the photosensitive composition.

[0209] After the photoresist layer is exposed, a post-exposure bake (PEB) is typically performed. The PEB can be performed, for example, on a hot plate or in an oven. The PEB is typically performed at temperatures from 70 °C to 150 °C, and for times from 30 to 90 seconds. Thereby a latent image is formed defined by the boundaries between the polar converted and unconverted areas corresponding to the exposed and unexposed areas, respectively. Next, the photoresist layer is developed to remove the exposed areas of the layer, leaving the unexposed areas to form a patterned photoresist layer. The developer is typically an aqueous alkaline developer, for example, a solution of tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide (TMAH) solution, typically a 0.26 normal (N) (2.38 wt%) TMAH solution. The developer can be applied by known techniques, for example, spin coating or puddle coating.

[0210] A patterned photoresist layer can be transferred to one or more underlying layers, including a coated underlayer, and then to a substrate using appropriate etching techniques, such as plasma etching of each etched layer using an appropriate type of gas. Depending on the number of layers and materials involved, pattern transfer may include multiple etching steps using different etching gases. After the pattern has been transferred to the substrate using conventional techniques, the patterned photoresist layer, the coated underlayer, and other optional layers in the photolithographic stack can be removed. Optionally, one or more layers of the stack may be removed or consumed during the process of pattern transfer to the underlying layer and before pattern transfer to the substrate. For example, pattern transfer to one or more of a silicon-containing layer, an organic antireflective coating, etc., may occur after the exposed photoresist layer has been developed and before pattern transfer to the coated underlayer. The substrate is then further processed according to methods known in the art to form an electronic device.

[0211] A coated substrate is also provided, comprising: a layer of the photoresist underlay composition of the present invention on the substrate; and a photoresist layer disposed on the layer of the photoresist underlay composition. As used herein, the term "cured layer" refers to a layer derived from the composition after the photoresist underlay composition has been disposed on the substrate and subsequently cured to form a coating or film. In other words, curing the photoresist underlay composition forms a cured layer derived from the photoresist underlay composition.

[0212] Other aspects provide a layered article comprising a coated underlayer derived from the photoresist underlayer composition of the present invention. In embodiments, the layered article may include a substrate; a coated underlayer disposed on the substrate; and a photoresist layer disposed on the coated underlayer.

[0213] Photoresist underlayers, including coated underlayers prepared from the photoresist underlayer compositions of the present invention, exhibit excellent photosensitivity and improved pattern collapse. The preferred photoresist underlayer compositions of the present invention can therefore be used in a variety of semiconductor manufacturing processes.

[0214] The inventive concept is further illustrated by the following examples, which are intended to be non-limiting. All compounds and reagents used herein are commercially available, except for the procedures provided below.

[0215] Example

[0216] Example A-1, which is referred to in the art as catechol phenolic varnish (A1-CN), wherein M w (GPC) = 2,290 g / mol, obtained from commercial sources.

[0217] Synthesis Example A2:

[0218]

[0219] Catechol (15.00 g) and 4,4'-oxybis[(methoxymethyl)benzene] (17.59 g) were dissolved in propylene glycol methyl ether (70 mL). Methanesulfonic acid (1.96 g) was added and the solution was heated to 120 °C for 26 hours. The solution was then cooled to room temperature and precipitated into 1 L of water. The liquid was decanted and the solution was re-dissolved in 50 mL of tetrahydrofuran and precipitated into 500 mL of water. The liquid was decanted and the solution was re-dissolved in 50 mL of tetrahydrofuran and precipitated into 500 mL of heptane. The liquid was decanted and the polymer was dried under vacuum at 50 °C overnight to yield 23.80 g of Polymer A-3. Mw(by GPC): 2549 g / mol.

[0220] Synthesis Example A3:

[0221]

[0222] Catechol (15.00 g) and 4,4'-oxybis[(methoxymethyl)benzene] (17.59 g) were dissolved in propylene glycol methyl ether (70 mL). Methanesulfonic acid (1.96 g) was added and the solution was heated to 120 °C for 26 hours. The solution was then cooled to room temperature and precipitated into 1 L of water. The liquid was decanted and the solution was re-dissolved in 50 mL of tetrahydrofuran and precipitated into 500 mL of water. The liquid was decanted and the solution was re-dissolved in 50 mL of tetrahydrofuran and precipitated into 500 mL of heptane. The liquid was decanted and the polymer was dried under vacuum at 50 °C overnight to yield 23.80 g of Polymer A-3. Mw(by GPC): 2549 g / mol.

[0223] Synthesis Example A4:

[0224]

[0225] Pyrogallol (10.03 g) and 1,4-benzenedimethanol (10.21 g) were dissolved in propylene glycol methyl ether (40 mL). Methanesulfonic acid (0.76 g) was added and the solution was heated to 120 °C for 8 hours. The solution was then cooled to room temperature and precipitated into 1 L of a 70% water / 30% methanol (v / v) mixture. The liquid was decanted and the polymer was dried under vacuum at 50 °C overnight to yield 11.89 g of Polymer A-4. Mw(by GPC): 3754 g / mol.

[0226] Synthesis Example A5:

[0227]

[0228] Catechol (5.01 g) and 4,4'-biphenyldimethanol (6.49 g) were dissolved in propylene glycol methyl ether (25 mL). Methanesulfonic acid (0.44 g) was added and the solution was heated to 120 °C for 8 hours. The solution was then cooled to room temperature and precipitated into 1 L of 70% water / 30% methanol (v / v) mixture. The liquid was decanted and the polymer was re-dissolved in 50 mL of tetrahydrofuran and precipitated in 1 L of 50% water / 50% methanol (v / v). The liquid was decanted and the polymer was dried under vacuum at 50 °C overnight to yield 6.44 g of Polymer A-5. Mw (by GPC): 4365 g / mol.

[0229] Compound X-PHS was obtained from a commercial source with Mw (by GPC) = 4,299 g / mol. X-PHS = poly(hydroxystyrene).

[0230]

[0231] Compounds A1 to A6 are shown below for reference.

[0232]

[0233] An exemplary list of B-epoxide compounds including substituents represented by Formula 2 and an exemplary list of comparative C-epoxide compounds are shown below. The B-epoxide and C-epoxide compounds were prepared according to procedures known in the art.

[0234]

[0235]

[0236] Substrate composition preparation

[0237] The substrate composition formulations of Examples 1-7 and Comparative Examples 1-6 were prepared by mixing the components in Table 1 in the relative mass amounts provided.

[0238] Table 1: Composition components

[0239]

[0240] CN = catechol novolac (M w (GPC) = 2,290 g / mol); X-PHS = poly(hydroxystyrene) (M w (GPC) = 4,299 g / mol); GMA = poly(glycidyl methacrylate) (M w(GPC) = 3,922 g / mol); 3 epoxide = N,N-diglycidyl-4-glycidoxyaniline; 4 epoxide = 4,4'-methylenebis(N,N-diglycidylaniline); BADE = bisphenol A diglycidyl ether; TMTE = tris(4-hydroxyphenyl)methane triglycidyl ether; PGMEA = propylene glycol methyl ether acetate; GBL = gamma-butyrolactone; numerical values for components are relative mass amounts (or weight percent).

[0241] Solvent resistance peel evaluation

[0242] Each composition in Table 1 was spin-coated onto a respective 200 mm silicon wafer on an ACT-8 Clean Track (Tokyo Electron Co.) at 1500 rpm and then cured at 215 °C for 60 seconds to form a film. The films were then evaluated for solvent resistance by applying PGMEA remover to each film for 90 seconds, followed by a post-peel bake at 105 °C for 60 seconds. The thickness of each film was again measured to determine the amount of film thickness loss. The difference in film thickness before and after contact with PGMEA remover is listed in Table 2 as the percentage of film remaining on the wafer (% film remaining). This value is indicative of the degree of crosslinking of the polymer layer. TM The initial film thickness was measured with a metrology tool. PGMEA remover was then applied to each film for 90 seconds, followed by a post-peel bake at 105 °C for 60 seconds. The thickness of each film was again measured to determine the amount of film thickness loss. The difference in film thickness before and after contact with PGMEA remover is listed in Table 2 as the percentage of film remaining on the wafer (% film remaining). This value is indicative of the degree of crosslinking of the polymer layer.

[0243] Table 2: Solvent resistance of cured films

[0244]

[0245] As seen in Table 2, with the exception of the C1 epoxide of GMA and the amino epoxide, e.g., B1 or B2, the non-polymeric epoxides are not completely resistant to peeling (see, Comparative Examples 5-8), which precludes their use as photoresist underlayers. All of the examples with N-epoxides become completely resistant to peeling. Although Comparative Examples 1-4 also exhibit favorable resistance to peeling, as shown below, these comparative compositions exhibit significantly less favorable planarization ability. In addition, Comparative Example 2 failed during the SC1 resistance evaluation (see below).

[0246] SC1 resistance evaluation

[0247] Each composition in Table 1 was spin-coated onto a respective 200 mm silicon wafer on an ACT-8 Clean Track (Tokyo Electron Co.) at 1500 rpm and then cured at 215 °C for 60 seconds to form a film. The films were then evaluated for solvent resistance by applying PGMEA remover to each film for 90 seconds, followed by a post-peel bake at 105 °C for 60 seconds. The thickness of each film was again measured to determine the amount of film thickness loss. The difference in film thickness before and after contact with PGMEA remover is listed in Table 2 as the percentage of film remaining on the wafer (% film remaining). This value is indicative of the degree of crosslinking of the polymer layer.

[0248] Table 3. Bottom SC1 Resistance Evaluation

[0249]

[0250] A: original film, B: partial film degradation visible to the naked eye, C: completely delaminated film

[0251] As can be seen in Table 3, each of Examples 1-6 exhibited a longer time until delamination occurred as compared to Comparative Example 2. Comparative Example 2 had partial film degradation after 5 minutes, Comparative Example 9 was completely delaminated after 5 minutes, and Comparative Example 1 was completely delaminated after 8 minutes. In contrast, Examples 4 and 6 showed partial degradation after 8 minutes, Example 1 showed degradation after 11 minutes, and Examples 2, 3, and 5 were all original films even after 11 minutes in the SC1 bath. Although Comparative Examples 3 and 4 exhibited good SC1 performance, the comparative examples had relatively poor planarization performance (see Table 4).

[0252] PL Evaluation

[0253] The photoresist bottom layer compositions of the present invention were evaluated to determine their planarization characteristics. The templates had a 100 nm Si02film thickness, and various pitch and patterns with a die size of 1 cm x 1 cm. Each die started with a 100 nm single step pattern, followed by a 2000 μm non-patterned open area, followed by various line / space patterns covering 45 nm / 90 nm to 2 μm / 5 μm pitch trenches. The first step pattern was used to judge planarization performance. The template samples were baked at 150 °C for 60 seconds as a dehydration bake prior to coating the samples with the compositions of the present invention. Each photoresist bottom layer composition was coated on the template samples using a spin coater and a spin rate of 1500 rpm + / - 200 rpm. The target film thickness after curing was 100 nm, and the composition dilution was adjusted accordingly to approximately achieve the target film thickness after curing. The films were cured by placing the wafer on a hot plate at 240 °C for 60 seconds. The films were evaluated for planarization quality throughout the steps by a KLA Tencor P-7 stylus profilometer.

[0254] In Table 4, the planarization quality was defined as follows:

[0255] Single step area: A indicates a material flow transition width of greater than 15 microns (μm), B indicates a material flow transition width between 10-15 μm, and C indicates a material flow transition width of less than 10 μm.

[0256] Local Area: A indicates less than 25 nanometers (nm) of height variation, B indicates between 25-35 nm of height variation, and C indicates greater than 35 nm of height variation. Lower numbers indicate superior planarization performance, so A represents the best planarization, followed by B, and C represents the worst planarization performance. Thus, Examples 1, 2, 3, and 6 each show improved planarization compared to each of Comparative Examples 1-4 and 9.

[0257] Table 4. PL Evaluation

[0258]

[0259] While the disclosure has been described in connection with what is presently considered to be the best example embodiment, it is to be understood that the application is not limited to the disclosed embodiment, 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 method of forming a pattern, the method comprising: applying a photoresist underlayer composition on a substrate to provide a photoresist underlayer; forming a photoresist layer on the photoresist underlayer; patterning the photoresist layer; and transferring a pattern from the patterned photoresist layer to the photoresist underlayer; wherein the photoresist underlayer composition comprises a polymer comprising a repeating unit represented by Formula 1A, a compound comprising a substituent represented by Formula 2; and a solvent; wherein in Formula 1A each Z is independently a substituent, wherein in Formula 1A, a is 0 or 1, i is 2 or 3; A is CR C wherein R C is hydrogen, hydroxy, optionally substituted C 1-6 alkyl, or optionally substituted C 1-6 alkoxy; L is a divalent radical independently comprising an optionally substituted C 1-4 alkylene, -0-, an optionally substituted arylene having one or two aromatic rings, or a combination thereof; wherein, in Formula 2: a is an integer from 1 to 8, c is 1, 2, or 3, and b + c is 2 or 3. R is substituted or unsubstituted C 1-4 alkylene; R 1 is hydrogen or optionally substituted C 1-4 alkyl; * is the point of attachment to the ring carbon of the aromatic ring system Q, wherein the aromatic ring system Q is Ar 1 or Ar 2 -T-Ar 3 , wherein Ar 1 , Ar 2 , and Ar 3 independently comprise a substituted or unsubstituted aromatic group having 4 to 14 ring carbons, and T is optionally substituted C 1-4 alkylene; and substituted phenyl, substituted naphthyl, substituted anthryl, substituted pyrenyl, substituted pyridyl, substituted quinolyl, substituted biphenylene, substituted benzophenyl, substituted fluorenyl, or substituted carbazolyl is substituted with a glycidyl group.

2. The method of claim 1, wherein, Ar 1 , Ar 2 , and Ar 3 are independently substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinolyl, substituted or unsubstituted biphenylenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, or substituted or unsubstituted carbazolyl.

3. The method of claim 2, wherein, 4. The method of claim 1, wherein, the polymer comprising a repeating unit represented by Formula 1 comprises a repeating unit represented by Formula 3A or Formula 3B; Q is Ar 1 and Ar 1 is phenyl, R is CH2, a is 1 or 2, and c is 2; Q is Ar 1 and Ar 1 is phenyl substituted with glycidyl, R is CH2, a is 1 or 2, and c is 2; Q is Ar 2 -T-Ar 3 and Ar 2 and Ar 3 is phenyl and T is absent, -O-, or -C(O)-, and for each of Ar 2 and Ar 3 a is 1 or 2 and c is 2; or Q is Ar 2 -T-Ar 3 , and Ar 2 or Ar 3 is phenyl substituted with glycidyl, and T is absent, -O-, -C(O)-, or -CR D R E -, and for each of Ar 2 and Ar 3 a is 1 or 2, and c is 2; wherein R D and R E are independently hydrogen, optionally substituted C 1-4 alkyl, or optionally substituted phenyl.

5. The method of claim 1 or 2, wherein, wherein, in Formula 3A and 3B: m is 0, 1, or 2, n is 0 or 1, and m + n is 1, 2, or 3; and W and W 1 independently is optionally substituted C 1-4 alkylene, -O-, or a combination thereof; Ar 4 and Ar 5 independently optionally substituted C 6-14 arylene, or optionally substituted C 3-14 heteroarylene; Z is absent, O, -S-, -C(O)-, or optionally substituted C 1-4 alkylene; q is 2 or 3; and r and s are independently 0, 1, or 2, wherein r + s is 2 or greater.

6. The method of claim 5, wherein, the compound comprising a substituent represented by Formula 2 comprises at least one of the following compounds if n is 0 and m is 1 or 2, then W and W 1 independently -CR F R G -; and Ar 4 is substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted biphenyl, or substituted or unsubstituted naphthyl, wherein R F and R G are independently hydrogen, hydroxyl, optionally substituted C 1-18 alkyl, optionally substituted C 1-18 alkoxy, Ar 6 , -CH2Ar 6 , -OAr 6 , -Ar 6 R 4 , wherein Ar 6 is optionally substituted C 6-18 aryl and R 4 is optionally substituted C 1-18 alkyl or optionally substituted C 1-18 alkoxy.

7. The method of claim 1 or 2, wherein, wherein T is as defined in claim 1. a weight ratio of the polymer to the compound comprising a substituent represented by Formula 2 is in a range of 4: 1 to 1:

20.

8. The method of claim 1 or 2, wherein, the photoresist underlayer composition further comprises an additive represented by a compound of Formula 5, a compound of Formula 6, or a combination thereof 9. The method of claim 1 or 2, wherein, wherein in Formula 5, X is a single bond, -C(O)-, unsubstituted Ci alkylene, or hydroxyl-substituted Ci alkylene; AA is a single or double bond, and it is understood that "AA" refers to a moiety having the structure represented by formula (5) ; a is 2, 3, or 4; b is 2, 3, 4 or 5; p is 0, 1, or 2; q is 0, 1, 2, or 3; and n is 0 or 1; R 1 and R 2 are each independently hydrogen, substituted or unsubstituted C 1-22 alkyl, substituted or unsubstituted C 3-14 cycloalkyl, -C(O)OR 5a , or glycidyl, wherein R 5a is hydrogen, substituted or unsubstituted C 1-22 alkyl, substituted or unsubstituted C 1-22 heteroalkyl, substituted or unsubstituted C 3-14 cycloalkyl, substituted or unsubstituted C 2-14 heterocycloalkyl, substituted or unsubstituted C 2-22 alkenyl, substituted or unsubstituted C 6-24 aryl, substituted or unsubstituted C 7-24 arylalkyl, substituted or unsubstituted C 7-24 alkylaryl, or substituted or unsubstituted C 3-24 heteroaryl; Y 2 is hydrogen, substituted or unsubstituted C 6-24 aryl, or substituted or unsubstituted C 3-24 heteroaryl; and each R A and each R B is independently substituted or unsubstituted C 1-10 alkyl, substituted or unsubstituted C 1-10 heteroalkyl, substituted or unsubstituted C 3-10 cycloalkyl, substituted or unsubstituted C 2-10 heterocycloalkyl, substituted or unsubstituted C 6-12 aryl, or substituted or unsubstituted C 1-10 heteroaryl; and c and d are each independently an integer from 2 to 5. In Equation 6, R 2 R A R B p and q are the same as those defined for Equation 5, and R 3 It is a hydrogen group, a carboxylic acid group or a derivative thereof, and the photoresist underlayer composition is free of non-polymeric polyphenol compounds and a thermal base generator.

10. The method of claim 1 or 2, wherein, 11. A composition comprising: a polymer comprising a repeating unit represented by Formula 1A; a compound comprising a substituent represented by Formula 2; and a solvent; wherein in Formula 1A each Z is independently a substituent, wherein in Formula 1A, a is 0 or 1, i is 2 or 3; A is CR C wherein R C is hydrogen, hydroxy, optionally substituted C 1-6 alkyl, or optionally substituted C 1-6 alkoxy; L is a divalent radical independently comprising an optionally substituted C 1-4 alkylene, -0-, an optionally substituted arylene having one or two aromatic rings, or a combination thereof; in Formula 2: wherein a is an integer from 1 to 8, c is 1, 2, or 3, and b + c is 2 or 3; R is substituted or unsubstituted C 1-4 alkylene; R 1 is hydrogen or optionally substituted C 1-4 alkyl; * is the point of attachment to the ring carbon of the aromatic ring system Q, wherein the aromatic ring system Q is Ar 1 or Ar 2 -T-Ar 3 , wherein Ar 1 , Ar 2 , and Ar 3 independently comprise a substituted or unsubstituted aromatic group having 4 to 14 ring carbons, and T is optionally substituted C 1-4 alkylene; and wherein the composition is a photoresist underlayer composition. the polymer comprising a repeating unit represented by Formula 1 comprises a repeating unit represented by Formula 3A or Formula 3B; 12. The composition of claim 11, wherein, wherein, in Formula 3A and 3B: m is 0, 1, or 2, n is 0 or 1, and m + n is 1, 2, or 3; and W and W 1 independently optionally substituted C 1-4 alkylene, -O-, or a combination thereof; Ar 4 and Ar 5 independently optionally substituted C 6-14 arylene, or optionally substituted C 3-14 heteroarylene; Z is absent, O, -S-, -C(O)-, or optionally substituted C 1-4 alkylene; q is 2 or 3; and r and s are independently 0, 1, or 2, wherein r + s is 2 or greater. ​ 13. The composition of claim 11 or 12, wherein, The photoresist composition is free of non-polymeric polyphenolic compounds and a thermal base generator. The photoresist composition is free of non-polymeric polyphenolic compounds and a thermal base generator.

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