Monomers, polymers and photoresist compositions comprising the same

Abstract

Monomers, polymers, and photoresist compositions comprising the same. A photoresist composition is provided comprising: a) one or more polymers comprising: one or more repeat units of a monomer comprising a tellurophene heterocycle and one or more ethylenically polymerizable groups, or one or more polymers comprising one or more repeat units of a monomer represented by Formula (IIIC); and b) one or more acid generator compounds,

Description

[0001] This invention patent application is a divisional application of the invention patent application with application number 201811552540.5, application date December 18, 2018, and name “Monomers, polymers and photolithographic compositions containing the same”. Technical Field

[0002] The present invention relates to novel monomeric and polymeric materials containing one or more Te atoms. In a preferred aspect, tellurium-containing monomers and polymers are provided that are useful in photoresists and other coating compositions for extreme ultraviolet lithography. Background Art

[0003] Extreme ultraviolet lithography (EUVL) is one of the leading technology options replacing optical lithography for volume semiconductor manufacturing with feature sizes <20nm. Its extremely short wavelength (13.4nm) is a key enabler for the high resolution required for multiple technology generations. Furthermore, the overall system concept—scanning exposure, projection optics, mask formats, and resist technology—is very similar to that used by current optical technologies. Like previous lithography generations, EUVL consists of resist technology, exposure tool technology, and mask technology. The main challenges are EUV source power and throughput. Any improvement in EUV power will directly impact the currently stringent resist sensitivity specifications. In fact, a major issue in EUVL imaging is resist sensitivity; the lower the sensitivity, the higher the source power required or the longer the exposure time needed to fully expose the resist. The lower the power level, the greater the impact of noise on the line edge roughness (LER) of the printed lines.

[0004] Various attempts have been made to modify the composition of EUV photoresist compositions to improve the performance of functional properties. Among others, a variety of polymer compounds have been reported. See US 20040241574 and 5989776. See also WO2017033943A1; WO2017188450; WO2017188451; Fukunaga et al., Journal of Photopolymer Science and Technology, 2017, 30, 103-107; Kudo et al., Chem. Letters, 2011, 40, 762-764.

[0005] Electronic device manufacturers continually seek patterned photoresist images with increased resolution.

[0006] New photoresist compositions that can provide enhanced imaging capabilities are desired, including new photoresist compositions that can be used for EUVL. Summary of the Invention

[0007] We now provide novel monomers and polymers comprising one or more tellurium (Te) atoms. We also provide photolithographic compositions including photoresist compositions and undercoating compositions (eg, antireflective or planarizing compositions) comprising one or more monomers or polymers of the present invention.

[0008] In one preferred aspect, an addition polymer is provided comprising one or more repeating units comprising one or more Te atoms. In another preferred aspect, a polymer is provided comprising one or more moieties pendant to the polymer backbone, wherein the one or more pendant moieties comprise one or more Te atoms. In the polymers of the present invention, the one or more Te atoms of the polymer are suitably divalent or tetravalent.

[0009] In a preferred aspect, there is provided a monomer comprising (a) one or more Te atoms; (b) one or more unsaturated polymerizable groups, including one or more olefinic polymerizable groups. The one or more Te atoms of such monomers are suitably divalent or tetravalent.

[0010] Preferred monomers may further comprise one or more acid-cleavable groups, polar groups and / or base-reactive groups.

[0011] The alkyl alkyl of the present invention can be alkyl ...

[0012] The one or more polymerisable groups may suitably be an ethylenically unsaturated group, for example an optionally substituted acrylate, an optionally substituted acrylamide, an optionally substituted vinyl ether moiety, an optionally substituted acyclic vinyl or cycloolefin moiety.

[0013] More specifically, in certain aspects, preferred monomers may include an acrylate moiety. Preferred acrylate monomers may include a structure corresponding to the following formula (I):

[0014]

[0015] wherein R is hydrogen or substituted non-hydrogen, such as optionally substituted C 1-16 alkyl, including optionally substituted methyl; and

[0016] P contains one or more Te atoms.

[0017] In certain preferred aspects, P may comprise one or more acid-cleavable groups, polar groups, and / or base-reactive groups.

[0018] In certain aspects, preferred acrylate monomers include monomers comprising carbon or heteroaromatic (carbocyclic aryl or heteroaryl) or alicyclic (carbon alicyclic or heteroalicyclic) groups, such as monomers comprising the structure of Formula (IA) below:

[0019]

[0020] wherein in formula (IA), R and each P are the same as defined above in formula (I);

[0021] S is a linking group, such as a chemical bond or a chain having from 1 to 20 or more optionally substituted carbon and heteroatoms (N, O, S), including providing a quaternary carbon atom adjacent to the depicted ester bond;

[0022] Each R 1 are the same or different non-hydrogen substituents and may contain one or more acid-cleavable groups, polar groups or base-reactive groups, or optionally may contain one or more alkyl groups;

[0023] m is an integer equal to 1 to the maximum valence number allowed by G, and m is typically an integer of 1, 2, 4, 5, 6, 7, or 8.

[0024] n is equal to 0 (where R 1 groups) to the maximum valence allowed by G, and m is typically an integer of 0, 1, 2, 3, 4, 5, 6, 7 or 8; and

[0025] represents a monocyclic or polycyclic unsubstituted or substituted C 6-30 Arylene or containing one or more tellurophene heterocyclic or monocyclic or polycyclic unsubstituted or substituted C 3-30 heteroarylene groups, wherein "*" indicates the point of attachment to the adjacent group or atom;

[0026] In certain aspects, preferred acrylate monomers may contain one or more carbocyclic aromatic groups, such as phenyl or naphthyl. Such preferred monomers include monomers containing a structure corresponding to the following formula (IB):

[0027]

[0028] Wherein in formula (IB):

[0029] R is the same as defined in the above formula (I);

[0030] S is a linking group, such as a chemical bond or a chain having from 1 to 20 or more optionally substituted carbon and heteroatoms (N, O, S), including providing a quaternary carbon atom adjacent to the depicted ester bond;

[0031] P comprises one or more Te atoms and optionally further comprises one or more acid-cleavable groups, polar groups or base-reactive groups; and

[0032] Each R 1 are the same or different non-hydrogen substituents and may contain one or more acid-cleavable groups, polar groups or base-reactive groups, or optionally may contain one or more alkyl groups; and

[0033] n is 0 (where R is absent 1 group) is an integer from 1 to 4, and m is an integer from 1 to 4.

[0034] In certain preferred aspects, P or at least one R 1 The group optionally comprises at least one acid-labile, polar or base-reactive group.

[0035] In certain aspects, preferred acrylate monomers may contain one or more carbocyclic aromatic groups, wherein the Te atom is directly substituted by a carbocyclic aromatic ring (without other atoms intervening between Te and the carbocyclic aromatic ring atom). For example, preferred are monomers comprising the structure of the following formula (IC):

[0036]

[0037] Wherein in formula (IC):

[0038] R and S are each the same as defined in the above formula (IB);

[0039] Each R 1 are the same or different non-hydrogen substituents and may contain one or more acid-cleavable groups, polar groups and / or base-reactive groups;

[0040] R 2 is a non-hydrogen substituent, and optionally may contain one or more acid-cleavable groups, polar groups, and / or base-reactive groups; and

[0041] n is 0 (where R is absent 1 group) to an integer of 4.

[0042] In certain preferred embodiments of monomers of formula (IC), at least one R 1 group or an R 2 The group contains at least one acid-labile, polar or base-reactive group.

[0043] In certain other aspects, the preferred monomer may comprise a vinyl ether moiety. The preferred vinyl ether monomer may comprise a structure corresponding to the following formula (II):

[0044]

[0045] wherein in formula (II), R and P are the same as defined in formula (I) above.

[0046] In certain aspects, preferred vinyl ether monomers include monomers comprising carbon or heteroaromatic (carbocyclic aryl or heteroaryl) or alicyclic (carbon alicyclic or heteroalicyclic) groups, for example, monomers comprising the structure of Formula (IIA) below:

[0047]

[0048] Wherein in formula (IIA), R, each P, S, each R 1 , m and n are the same as defined in formula (IA); and

[0049] represents an unsubstituted or substituted monocyclic or polycyclic C 6-30 Arylene or containing one or more tellurophene heterocycles or unsubstituted or substituted monocyclic or polycyclic C 3-30 heteroarylene groups, wherein "*" indicates the point of attachment to the adjacent group or atom;

[0050] Preferred vinyl ether monomers may contain one or more carbocyclic aromatic groups, such as phenyl or naphthyl. Preferred monomers of this type include monomers containing a structure corresponding to the following formula (IIB):

[0051]

[0052] Wherein in formula (IIB), R, S, P, R 1 and n are the same as defined in the above formula (IB).

[0053] Preferred vinyl ether monomers containing one or more carbocyclic aromatic groups include groups in which the Te atom is directly substituted with a carbocyclic aromatic ring. For example, preferred are monomers containing the structure of the following formula (IIC):

[0054]

[0055] In formula (IIC), R, S, R 1 、R 2 and n are the same as defined in the above formula (IC).

[0056] In certain other aspects, preferred monomers may comprise a vinyl moiety and suitably may comprise a structure corresponding to the following formula (III):

[0057]

[0058] wherein in formula (III), R and P are the same as defined in formula (I) above.

[0059] In certain aspects, preferred vinyl monomers include monomers comprising carbon or heteroaromatic (carbocyclic aryl or heteroaryl) or alicyclic (carbon alicyclic or heteroalicyclic) groups, for example, monomers comprising the structure of Formula (IIIA) below:

[0060]

[0061] Wherein in formula (IIIA), R, each P, S, each R 1 , m and n are the same as defined in formula (IA) above; and

[0062] represents a monocyclic or polycyclic unsubstituted or substituted C 6-30 Arylene or containing one or more tellurophene heterocyclic or monocyclic or polycyclic unsubstituted or substituted C 3-30 heteroarylene groups, wherein "*" indicates the point of attachment to the adjacent group or atom;

[0063] In certain aspects, preferred vinyl monomers may contain one or more carbocyclic aromatic groups, such as phenyl or naphthyl. Such preferred monomers include monomers containing a structure corresponding to the following formula (IIIB):

[0064]

[0065] Wherein in formula (IIIA), R, P, R 1 and n are the same as defined in the above formula (IB).

[0066] Preferred vinyl monomers containing one or more carbocyclic aromatic groups include groups in which the Te atom is directly substituted with a carbocyclic aromatic ring. For example, preferred are monomers containing the structure of the following formula (IIIC):

[0067]

[0068] Wherein in formula (IIIC), R, S, R 1 、R 2 and n are the same as defined in the above formula (IC).

[0069] In another preferred embodiment, a cycloolefin monomer comprising one or more Te atoms is provided. As referred to herein, a cycloolefin is a non-aromatic ring structure (e.g., 5 to about 20 ring atoms, preferably 5 or 6 ring atoms in certain embodiments) having at least one endocyclic carbon-carbon single endocyclic multiple bond. In certain aspects, preferred cycloolefin monomers include monomers having the structure of Formula (IV):

[0070]

[0071] Wherein in formula (IV):

[0072] P contains one or more Te atoms;

[0073] Each R 1 are the same or different non-hydrogen substituents and may contain one or more acid-cleavable groups, polar groups or base-reactive groups, or optionally may contain one or more alkyl groups; and

[0074] n is equal to 0 (where R 1 The number of valences of the rings is an integer from 1 to 2, and n is typically 0, 1, 2, 3, 4, or 5. In the above formula (IV), the ring structure depicted can be a variety of structures, including having 5 to about 20 ring atoms in a single, fused, or connected ring structure, and in certain embodiments, 5 or 6 ring atoms may be preferred. Although one or more aromatic rings can be covalently linked (including fused) to the alicyclic (non-aromatic) ring, the ring containing the carbon-carbon double bond depicted in formula (IV) is non-aromatic.

[0075] In yet another preferred aspect, a monomer comprising one or more Te atoms and one or more lactone functional groups is provided. For example, in the above formulas (I), (IA), (IB), (IC), (II), (IIA), (IIB), (IIC), (III), (IIIA), (IIIB), (IIIC) and (IV), any of P, R 1 or R 2 The group may contain one or more lactone moieties, such as a group having one of the following structures (where the wavy line represents a covalent bond to the monomer):

[0076]

[0077] Also provided are polymers comprising one or more reacted Te monomers as disclosed herein, including one or more reacted monomers of one of formula (I), (IA), (IB), (IC), (II), (IIA), (IIB), (IIC), (III), (IIIA), (IIIB), (IIIC), or (IV) above.

[0078] Preferred photoresists of the invention may comprise one or more acid generator compounds and a polymer component comprising one or more Te polymers as disclosed herein.The photoresists of the invention may suitably be positive-acting or negative-acting.

[0079] Positive-acting photoresists may suitably comprise a component comprising an acid-labile group as disclosed herein. The acid-labile group may be present on a polymer containing one or more Te atoms (Te polymer), and / or the acid-labile group may be present on another photoresist component, such as another resist resin that does not contain Te atoms.

[0080] Negative-acting photoresists suitably may include a crosslinker component, either as a separate composition or as a covalently linked portion of the resist component, such as a Te polymer. Suitable photoresist crosslinkers include the amine-based materials discussed below as crosslinkers for the underlying composition.

[0081] Also provided are primer compositions that can be utilized wherein a photoresist is coated onto a primer composition layer. The primer compositions of the present invention comprise one or more Te polymers as disclosed herein and may optionally comprise one or more additional components, such as a crosslinking agent and an acid or acid generator compound. Preferably, the primer coating composition may be a crosslinked organic film and may preferably have a substantially reduced thickness. In certain preferred embodiments, the dry thickness of the primer composition film layer is about or smaller, or approximately or smaller, approximately or smaller, approximately or smaller, approximately or smaller, approximately or smaller or approximately or smaller.

[0082] In one aspect, a method is provided comprising applying a layer of an undercoating composition comprising one or more Te polymers as disclosed to a substrate; and applying a layer of a photoresist composition over the layer of undercoating composition.

[0083] Also provided are methods for forming a relief image of the photoresist composition of the present invention (including pattern lines having a size of less than 50 nm or less than 20 nm). Such methods may comprise, for example: a) applying a photoresist coating of the present invention to a substrate; b) exposing the photoresist composition layer to activating radiation including EUV radiation; and c) developing the exposed photoresist composition coating.

[0084] Also provided are substrates, such as microelectronic wafers, having coated thereon the photoresist compositions of the present invention. Also provided are electronic devices formed by the disclosed methods.

[0085] Other aspects of the invention are discussed below. DETAILED DESCRIPTION

[0086] The term Te polymer refers to a polymer as disclosed herein, which comprises one or more Te atoms.

[0087] As discussed above, in a preferred aspect, an addition polymer is provided, which comprises one or more repeating units comprising one or more Te atoms. Addition polymers as mentioned herein are formed by addition polymerization, such as free radical, cation, anion or coordination polymerization. As mentioned herein, addition polymers can be formed by reaction, wherein small molecule by-products (such as H2O) or MeOH) are not produced by reaction, and are distinguished from condensation-type polymerization. The polymerization of preferred monomers of the above formula (I), (IA), (IB), (IC), (II), (IIA), (IIB), (IIC), (III), (IIIA), (IIIB), (IIIC) and (IV) can provide addition polymers. In some preferred aspects, addition polymers can be formed by any free radical polymerization, nitrogen oxide regulated polymerization (NMP), atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, living anionic polymerization (LAP) and / or atom transfer polymerization (ATP).

[0088] As also discussed, in another preferred aspect, polymers are provided that include one or more moieties pendant to the polymer backbone, wherein one or more pendant moieties include one or more Te atoms. Particularly preferred polymers may include such pendant Te moieties, but lack any Te atoms along the polymer backbone. Polymerization of preferred monomers of formula (I), (IA), (IB), (IC), (II), (IIA), (IIB), (IIC), (III), (IIIA), (IIIB), (IIIC), and (IV) above may provide such Te-containing pendant moieties.

[0089] As referred to herein, the Te-containing moiety will be pendant to the polymer chain, wherein the Te atom or atoms of the moiety are separated from the polymer backbone by any of a number of groups, including, for example, alkyl (alkylene) groups; cyclic groups containing carbon atoms; and / or heteroatoms, such as oxygen or optionally substituted sulfur (e.g., S(O), S(O)2), in a chain containing 1 or more atoms (including carbon atoms), typically 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 atoms (including carbon atoms) inserted between the polymer backbone and the reactive nitrogen-containing moiety.

[0090] As will be understood, the term polymer backbone refers to a series of covalently bonded atoms that together form a continuous linear chain of the polymer. In poly(acrylate) or poly(alkylacrylate) (e.g., poly(methacrylate) resins), the side chain Te atoms may be separated from the polymerized acrylate carboxyl (-CH2-CH(COO-)-) moiety by 1 or more atoms (including carbon atoms), by 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 atoms (including carbon atoms) by 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 atoms (including carbon atoms).

[0091] In certain preferred aspects, 1, 2, 3, 4, or 5 optionally substituted carbon atoms (spacer groups) can be inserted between the polymerized acrylate or alkylacrylate (eg, methacrylate) polymer backbone moiety and the Te atom of the pendant Te-containing moiety.

[0092] In the above formulae (I), (IA), (IB), (IC), (II), (IIA), (IIB), (IIC), (III), (IIIA), (IIIB), (IIIC) and (IV), suitable non-hydrogen substituents may be, for example, halo (F, Cl, Br or I); cyano, nitro, hydroxyl, optionally substituted C1-20 alkyl, optionally substituted C1-20 alkoxy, such as optionally substituted alkyl (e.g., optionally substituted C1-10 alkyl); optionally substituted an alkenyl or alkynyl group, preferably having 2 to about 20 carbon atoms, such as an allyl group; an optionally substituted ketone group, preferably having 1 to about 20 carbon atoms; an optionally substituted alkylthio group, preferably having 1 to about 20 carbon atoms; an optionally substituted alkylsulfinyl group, preferably having 1 to about 20 carbon atoms; an optionally substituted alkylsulfonyl group, preferably having 1 to about 20 carbon atoms; an optionally substituted carboxyl group, preferably having 1 to about 20 carbon atoms (which includes groups such as -COOR', where R' is H or C 1-8 alkyl, including esters that are substantially unreactive with photoacids); optionally substituted alkaryl, such as optionally substituted benzyl; optionally substituted carbocyclic aryl, such as optionally substituted phenyl, naphthyl, acenaphthenyl; or optionally substituted heteroalicyclic or heteroaromatic groups, such as pyridyl, furanyl, pyrrole, thiophene, furan, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, furazol, oxadiazole, thiadiazole, dithiazole, tetrazole, pyran, thiopyran, diazine, oxazine, thiazine, dioxin, dithiane, and triazine, as well as polyaromatic groups containing one or more of these moieties.

[0093] As referred to herein, the term "arylene" refers to a functional group having a valence of at least two obtained by removing two hydrogens from an aromatic ring, which is optionally substituted with one or more substituents as specified, provided that the valence of the arylene group is not exceeded.

[0094] As referred to herein, the term "heteroarylene" refers to a functional group having a valence of at least two obtained by removing two hydrogens from a heteroaromatic ring, which is optionally substituted with the specified substituent(s), with the proviso that the valence does not exceed that of the heteroarylene group.

[0095] As discussed, the group of the above formula can be suitably substituted by one or more acid-labile groups at available position.Suitable acid-labile groups can be various parts, comprise acid-labile ester and acetal, for example optional substituted ethylcyclopentyl ester, methyladamantyl ester, ethyladamantyl ester, tert-butyl ester, phenyl ester, naphthyl ester and other ester.In some preferred aspects, Te polymer of the present invention will contain 1 or 2 covalently bound acid-labile groups.As mentioned herein, in typical photolithography process, comprise during the heat exposure after any radiation exposure, acid-labile part or group (comprising acid-labile ester and acetal) react in the presence of the acid (from the acid generator compound in the resist) of generation.As mentioned herein, acid-labile groups can also be called photoacid-labile groups.

[0096] The Te-containing monomers and polymers of the present invention can be readily prepared. See, for example, the syntheses illustrated in the Examples below.

[0097] Specifically, the monomeric compounds of the present invention include the following:

[0098]

[0099] As discussed, monomers containing acidic or base reactive groups such as alcohol groups (including halohydrins, such as fluoroalcohols, such as hexafluoroalcohol (HFA or hexafluoro-2-propanol)), carboxylic acid groups, sulfonic acid groups, sulfonamide groups or phenolic groups may be preferred. Particularly preferred monomers containing phenolic groups include the following:

[0100]

[0101] Other preferred monomers containing alcohol (including naphthol), carboxylic acid and halohydrin substitutions include the following:

[0102]

[0103] As discussed, compounds containing one or more lactone groups may also be preferred, such as the following:

[0104]

[0105] Compounds containing one or more epoxy groups may also be preferred:

[0106]

[0107] Preferred cyclic olefin monomers include the following:

[0108]

[0109] Preferred compounds containing one or more acid labile groups include the following:

[0110]

[0111] Preferred polymers include the following:

[0112]

[0113] Photoresist composition

[0114] As discussed above, the polymers as disclosed herein are suitable for use in photoresist compositions, including both positive-acting and negative-acting chemically amplified resist compositions.

[0115] The photoresists of the present invention generally comprise a polymer as disclosed herein and one or more photoacid generator compounds.

[0116] The polymers of the present invention may comprise various repeating units, which may or may not contain one or more Te atoms.

[0117] For example, preferred additional monomers for forming the polymers of the present invention include: an acid-labile monomer having the following formula (V), a lactone-containing monomer of formula (VI), an alkali-soluble monomer (for adjusting the dissolution rate in alkaline developers) of formula (VII), and a photoacid-generating monomer of formula (VIII), or a combination comprising at least one of the foregoing monomers:

[0118]

[0119] Each R a are independently H, F, -CN, C 1-10 Alkyl or C 1-10 In the acid-deprotectable monomer of formula (V), R b Independently C 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl or C 7-20 Aralkyl, and each R b are independent or at least one R b Bonded to adjacent R bIn the lactone-containing monomer of formula (VI), L is a monocyclic, polycyclic or fused polycyclic C 4-20 In the alkali-soluble monomer of formula (VII), W is a halogenated or non-halogenated, aromatic or non-aromatic C 2-50 A hydroxyl-containing organic group having a pKa of less than or equal to 12. In the photoacid generating monomer of formula (VIII), Q is ester-containing or non-ester-containing and is fluorinated or non-fluorinated, and is C 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl or C 7-20 Aralkyl, A is ester-containing or non-ester-containing and is fluorinated or non-fluorinated, and is C 1-20 Alkyl, C 3-20 Cycloalkyl, C 6-20 Aryl or C 7-20 Aralkyl, Z - is an anion moiety comprising a carboxylate, sulfonate, sulfonamide anion, or sulfonimide anion, and G + It is a sulfonium or iodonium cation.

[0120] Exemplary acid labile monomers include, but are not limited to:

[0121]

[0122]

[0123] or a combination comprising at least one of the foregoing, wherein R a It is H, F, -CN, C 1-6 Alkyl or C 1-6 Fluoroalkyl.

[0124] Suitable lactone monomers may have the following formula (IX):

[0125]

[0126] where R a It is H, F, -CN, C 1-6 Alkyl or C 1-6 Fluoroalkyl, R is C 1-10 alkyl, cycloalkyl or heterocycloalkyl, and w is an integer from 0 to 5. In formula (IX), R is directly connected to the lactone ring or is usually connected to the lactone ring and / or one or more R groups, and the ester portion is directly connected to the lactone ring or indirectly connected via R.

[0127] Exemplary lactone-containing monomers include:

[0128]

[0129] or a combination comprising at least one of the foregoing monomers, wherein R a It is H, F, -CN, C 1-10 Alkyl or C 1-10 Fluoroalkyl.

[0130] Suitable alkali-soluble monomers may have the following formula (X):

[0131]

[0132] Each R a are independently H, F, -CN, C 1-10 Alkyl or C 1-10 Fluoroalkyl, A is a hydroxyl-containing or non-hydroxyl-containing, ester-containing or non-ester-containing, fluorinated or non-fluorinated C 1-20 Alkylene, C 3-20 Cycloalkylene, C 6-20 Arylene or C 7-20 Aralkylene, and x is an integer from 0 to 4, wherein when x is 0, A is a C containing hydroxyl group 6-20 Arylene.

[0133] Exemplary alkali-soluble monomers include monomers having the following structure:

[0134]

[0135] or a combination comprising at least one of the foregoing, wherein R a It is H, F, -CN, C 1-6 Alkyl or C 1-6 Fluoroalkyl.

[0136] Preferred photoacid generating monomers include monomers of formula (XI) or formula (XII):

[0137]

[0138] Each R a are independently H, F, -CN, C 1-6 Alkyl or C 1-6 Fluoroalkyl, A is C substituted by fluorine 1-30 Alkylene, C substituted by fluorine 3-30 Cycloalkylene, C substituted by fluorine 6-30 Arylene or C substituted by fluorine 7-30 Alkylene-arylene, and G + It is a sulfonium or iodonium cation.

[0139] Preferably, in formula (XI) and formula (XII), A is [(C(R 1 )2) x C(=O)O] b -C((R 2)2) y (CF2) z -group or an ortho-, meta- or para-substituted -C6F4-group, wherein each R 1 and R 2 are independently H, F, -CN, C 1-6 Fluoroalkyl or C 1-6 Alkyl, b is 0 or 1, x is an integer from 1 to 10, y and z are independently integers from 0 to 10, and the sum of y+z is at least 1.

[0140] Exemplary preferred photoacid generating monomers include:

[0141]

[0142]

[0143] or a combination comprising at least one of the foregoing, wherein each R a are independently H, F, -CN, C 1-6 Alkyl or C 1-6 fluoroalkyl, k is suitably an integer from 0 to 5; and G + It is a sulfonium or iodonium cation.

[0144] Preferred photoacid generating monomers may include sulfonium or iodonium cations. Preferably, in formula (IV), G + Having formula (XIII):

[0145]

[0146] Where X is S or I; each R 0 is halogenated or non-halogenated and is independently C 1-30 Alkyl, polycyclic or monocyclic C 3-30 Cycloalkyl, polycyclic or monocyclic C 4-30 Aryl; or a combination comprising at least one of the foregoing, wherein when X is S, R 0 One of the groups is optionally linked to an adjacent R 0 group, and a is 2 or 3, wherein when X is I, a is 2, or when X is S, a is 3.

[0147] Exemplary acid-generating monomers include monomers having the formula:

[0148]

[0149] where R a It is H, F, -CN, C 1-6 Alkyl or C 1-6 Fluoroalkyl.

[0150] Polymers having acid-labile deblocking groups that are particularly suitable for use in the positive-acting chemically amplified photoresists of the present invention have been disclosed in European Patent Application 0829766A2 (polymers having acetals and ketal polymers) and European Patent Application EP0783136A2 (terpolymers and other copolymers comprising units of 1) styrene; 2) hydroxystyrene; and 3) acid-labile groups (specifically, alkyl acrylate acid-labile groups).

[0151] The molecular weight and polydispersity of the Te polymers used in the photoresist and underlayer compositions of the present invention can suitably vary widely. Suitable polymers include weight average M w A polymer having a molecular weight distribution of about 3 or less, more typically a molecular weight distribution of about 2 or less. Te polymers of other molecular weights and molecular weight distributions are also suitable.

[0152] The photoresists of the present invention may also contain other materials. For example, other optional additives include actinic and contrast dyes, anti-striation agents, plasticizers, speed increasers, sensitizers, light-destructible bases, etc. Such optional additives are typically present in smaller concentrations in the photoresist composition.

[0153] Including a basic material, a carboxylate or sulfonate salt of the photodecomposable cation preferably provides a mechanism for neutralizing the acid from the acid decomposable group and limits the diffusion of the photogenerated acid, thereby providing improved contrast in the photoresist.

[0154] Photodestructible bases include those that react with weak (pKa>2) acids, such as C 1-20 The photodecomposable cation of the anion pair of the carboxylic acid, and preferably also a base suitable for preparing the acid generator compound. Exemplary such carboxylic acids include formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexyl carboxylic acid, benzoic acid, salicylic acid and other such carboxylic acids.

[0155] Alternatively or additionally, other additives may include quenchers, which are non-photodestructible bases, such as bases based on hydroxides, carboxylates, amines, imines and amides. Preferably, such quenchers include C 1-30 Organic amines, imines or amides, or C which can be a strong base (such as a hydroxide or alkoxide) or a weak base (such as a carboxylate) 1-30Quaternary ammonium salts. Exemplary quenchers include amines such as tripropylamine, dodecylamine, 1,1′,1″-azotripropan-2-ol, 1,1′,1″,1″′-(ethane-1,2-diylbis(azanetriyl))tetrapropan-2-ol; arylamines such as diphenylamine, triphenylamine, aminophenol, and 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane; Troger's base; hindered amines such as diazabicycloundecene (DBU) or diazabicyclononene (DBN); or ion quenchers including quaternary alkylammonium salts such as tetrabutylammonium hydroxide (TBAH) or tetrabutylammonium lactate.

[0156] Surfactants include fluorinated and non-fluorinated surfactants, and are preferably nonionic. Exemplary fluorinated nonionic surfactants include perfluorinated C4 surfactants, such as FC-4430 and FC-4432 surfactants available from 3M Company; and fluorodiols, such as POLYFOX PF-636, PF-6320, PF-656, and PF-6520 fluorosurfactants from Omnova.

[0157] The photoresist further includes a solvent generally suitable for dissolving, dispensing, and coating the components used in the photoresist. Exemplary solvents include anisole; alcohols including ethyl lactate, 1-methoxy-2-propanol, and 1-ethoxy-2-propanol; esters including n-butyl acetate, 1-methoxy-2-propyl acetate, methoxyethoxypropionate, and ethoxyethoxypropionate; ketones including cyclohexanone and 2-heptanone; and combinations comprising at least one of the foregoing solvents.

[0158] By the gross weight of solid, this type of photoresist can include copolymers in an amount of 50 to 99 wt %, 55 to 95 wt %, more specifically 60 to 90 wt % and more specifically 65 to 90 wt %. By the gross weight of solid, light destructible alkali (if used) can be present in the photoresist in an amount of 0.01 to 5 wt %, 0.1 to 4 wt % and more specifically 0.2 to 3 wt %. By the gross weight of solid, surfactants can be included in an amount of 0.01 to 5 wt %, 0.1 to 4 wt % and more specifically 0.2 to 3 wt %. By the gross weight of solid, quenchers can be included in an amount of relatively small amounts, for example 0.03 to 5 wt %. By the gross weight of solid, other additives can be included in an amount of less than or equal to 30 wt %, less than or equal to 20% or more specifically less than or equal to 10%. The total solids content of the photoresist composition can be 0.5 to 50 wt %, specifically 1 to 45 wt %, more specifically 2 to 40 wt % and more specifically 5 to 30 wt % by the total weight of solid and solvent. The acid generator compound should be present in an amount sufficient to generate a latent image in the resist coating. More specifically, one or more acid generator compounds will suitably be present in an amount of about 1 to 50 wt % of the total solids of the resist. It should be understood that the solids include copolymers, light-destructible bases, quenchers, surfactants, any added PAGs, and any optional additives, excluding solvents.

[0159] Base composition

[0160] As discussed above, primer compositions are also provided that include one or more Te polymers as disclosed herein.

[0161] In certain embodiments, the primer composition of the present invention may also include a crosslinker in addition to or as a component of (i.e., covalently linked to) the Te polymer. For example, the primer composition may include an amine-based crosslinker, such as a melamine material, including, for example, melamine resins manufactured by Cytec Industries and sold under the trade names Cymel 300, 301, 303, 350, 370, 380, 1116, and 1130; glycolurils, including glycolurils available from Cytec Industries; and benzoguanamine and urea-based materials, including resins such as benzoguanamine resins available from Cytec Industries under the names Cymel 1123 and 1125, and urea resins available from Cytec Industries under the names Powderlink 1174 and 1196. In addition to commercially available amino resins, such amino resins can be prepared, for example, by reacting acrylamide or methacrylamide copolymers with formaldehyde in an alcoholic solution, or by copolymerizing N-alkoxymethylacrylamide or methacrylamide with other suitable monomers.

[0162] The coating compositions of the present invention, particularly for reflection control applications, may also contain additional dye compounds which absorb the radiation used to expose the overcoated photoresist layer.

[0163] The primer composition of the present invention may also contain other materials, such as one or more acid generator compounds, including one or more thermal acid generators and / or photoacid generators. Suitable photoacid generators for use in primer compositions include those disclosed herein for use in overcoat photoresist compositions. For a discussion of such uses of photoacid generators in primer compositions, see U.S. Patent No. 6,261,743.

[0164] To prepare the liquid primer composition, the components of the coating composition are dissolved in a suitable solvent, such as one or more oxyisobutyrates, particularly methyl 2-hydroxyisobutyrate, ethyl lactate; or one or more of glycol ethers, such as 2-methoxyethyl ether (diethylene glycol dimethyl ether), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; solvents having ether and hydroxyl moieties, such as methoxybutanol, ethoxybutanol, methoxypropanol, and ethoxypropanol; methyl 2-hydroxyisobutyrate; esters, such as cellosolve methyl acetate, cellosolve ethyl acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and other solvents, such as dibasic esters, propylene carbonate, and gamma-butyrolactone.

[0165] The concentration of the dry components (desirably the entire coating composition of the solvent) in the solvent will depend on several factors, such as the coating method. The solids content of the primer coating composition typically varies from about 0.1 to 20 weight percent, based on the total weight of the coating composition, with a preferred solids content varying from about 0.1 to 10 weight percent of the coating composition.

[0166] Photolithography

[0167] The coated substrate can be formed from a photoresist containing one or more Te polymers as disclosed herein and typically from an acid generator compound, which should be present in an amount sufficient to generate a latent image in the resist and acid generator compound coating. Such coated substrates include: (a) a substrate having one or more layers to be patterned on its surface; and (b) a layer of a photoresist composition comprising an acid generator compound above the one or more layers to be patterned. For EUV or electron beam imaging, the photoresist can suitably have a relatively high acid generator compound content, for example, wherein the one or more acid generator compounds comprise 5 to 10 to about 65% by weight of the total solids of the resist. Typically, smaller amounts of photosensitive components will be suitable for chemically amplified resists.

[0168] The photoresists of the present invention are generally prepared according to known procedures, except that one or more Te polymers of the present invention are included in the photoresist and, in some aspects, replace the previous photosensitive compounds used in such photoresist formulations. The photoresists of the present invention can be used according to known procedures.

[0169] The substrate can be of any size and shape and is preferably a substrate suitable for photolithography, such as silicon, silicon dioxide, silicon-on-insulator (SOI), strained silicon, gallium arsenide; coated substrates, including substrates coated with silicon nitride, silicon oxynitride, titanium nitride, tantalum nitride; ultra-thin gate oxides, such as hafnium oxide; metal or metal-coated substrates, including substrates coated with titanium, tantalum, copper, aluminum, tungsten, alloys thereof; and combinations thereof. Preferably, the substrate surface herein includes a critical dimension layer to be patterned, including, for example, one or more gate layers or other critical dimension layers on the substrate for semiconductor fabrication. Such substrates may preferably include silicon, SOI, strained silicon, and other such substrate materials, formed into circular wafers having a diameter, for example, of 20 cm, 30 cm, or greater, or other sizes suitable for wafer fabrication production.

[0170] In addition, a method of forming an electronic device includes (a) coating a photoresist composition layer on a substrate surface; (b) pattern-wise exposing the photoresist composition layer to activating radiation; and (c) developing the exposed photoresist composition layer to provide a resist relief image.

[0171] In use, the primer composition of the present invention is applied to a substrate as a coating by any of a variety of methods, such as spin coating. The coating composition is typically applied to the substrate and the dried layer thickness is between about 0.001 and 0.5 μm, inclusive, between 0.002 and 0.01 μm. The substrate is preferably any substrate used in methods involving photoresists. For example, the substrate can be silicon, silicon dioxide, or aluminum-aluminum oxide microelectronic wafers. Gallium arsenide, silicon carbide, ceramic, quartz, or copper substrates can also be used.

[0172] In certain aspects, including EUV imaging, it may be desirable to coat the primer composition over the hardmask layer.

[0173] Preferably, the applied primer layer is cured before the photoresist composition is applied to the primer composition. Curing conditions will vary with the components of the primer composition. In particular, the curing temperature will depend on the specific acid or acid (e.g., heat) generator used in the coating composition. Typical curing conditions are at about 60° C. to 225° C. for about 0.5 to 5 minutes. Curing conditions preferably render the coating composition coating substantially insoluble in the photoresist solvent and the developer solution to be used.

[0174] After such curing, a photoresist is applied to the surface of the applied coating composition. As with the application of the base coating composition layer, the overcoat photoresist can be applied by any standard means (e.g., by spin coating, dipping, meniscus coating, or roller coating). After application, the photoresist coating is typically dried by heating to remove the solvent, preferably until the resist layer is tack-free. Optimally, the base composition layer and the overcoat photoresist layer will not substantially intermix.

[0175] The resist layer is then imaged in a conventional manner with activating radiation (e.g., 248 nm, 193 nm, or EUV radiation) through a mask. The exposure energy is sufficient to effectively activate the photosensitive components of the resist system to produce a patterned image in the resist coating. Typically, the exposure energy is between about 3 and 300 mJ / cm 2 The exposure temperature range is within a certain range and depends in part on the exposure tool and the specific resist and resist processing used. If necessary, the exposed resist layer can be subjected to a post-exposure bake to form or enhance the solubility difference between the exposed and unexposed areas of the coating. For example, negative acid-hardening photoresists generally require post-exposure heating to induce the acid-promoted crosslinking reaction, and many chemically amplified positive-acting resists require post-exposure heating to induce the acid-promoted deprotection reaction. Typical post-exposure bake conditions include temperatures of about 50°C or higher, more specifically, temperatures in the range of about 50°C to about 160°C.

[0176] Subsequently, the exposed photoresist layer is developed by treating the exposed layer with a suitable developer capable of selectively removing exposed film portions (where the photoresist is positive-working) or removing unexposed film portions (where the photoresist is crosslinkable in the exposed areas, i.e., negative-working). Preferably, the photoresist is positive-working based on a polymer having acid-sensitive (deprotectable) groups, and the developer is preferably a metal ion-free tetraalkylammonium hydroxide solution, such as a 0.26N aqueous solution of tetramethylammonium hydroxide. A pattern is formed by development.

[0177] Alternatively, for positive photoresists, unexposed areas can be selectively removed by treatment with a nonpolar solvent suitable for negative-tone development. Negative-tone development procedures for positive photoresists are described in US 2011 / 0294069. Typical nonpolar solvents used for negative-tone development are organic developers, such as solvents selected from ketones, esters, hydrocarbons, and mixtures thereof, such as acetone, 2-hexanone, methyl acetate, butyl acetate, and tetrahydrofuran.

[0178] When used in one or more of such patterning processes, photoresists can be used in the manufacture of electronic and optoelectronic devices, such as memory devices, processor chips (CPUs), graphics chips, and other such devices.

[0179] The following examples illustrate the present invention.

[0180] Examples 1-3: Monomer Synthesis

[0181] Example 1: M1 synthesis

[0182] The reaction for the synthesis of monomer M1 is shown in Scheme 1 below. The synthesis of tellurophene derivative 1 is described in Ahmad, Sohail et al., Journal of Organic Chemistry, 80(8), 3880-3890; 2015 and Ahmad, Sohail et al., RSC Advances, 4(7), 3171-3180; 2014. A solution of 2,2'-(tellurophene-2,5-diyl)bis(propan-2-ol) (Compound 1, 15.0 g, 50.7 mmol) in 150 mL of dichloromethane was charged to a reaction flask. The solution was cooled to 0°C. Methacryloyl chloride (3.53 g, 33.8 mmol) and triethylamine (3.54 g, 35.0 mmol) were added to the reaction flask, and the mixture was stirred at room temperature for 16 h. The organic phase was washed with water (3×100 mL) and the solvent was completely removed under reduced pressure. The crude material was purified by silica gel column chromatography. The solvent fractions containing the product were collected and the solvent was completely removed under reduced pressure to yield monomer M1.

[0183] Process 1:

[0184]

[0185] Example 2: M2 synthesis

[0186] The reaction steps for the synthesis of monomer compound M2 are shown in the following flow 2. The synthesis of bis(4-hydroxyphenyl)telluride (2) is described by S. Zhang et al., Tetrahedron Letters, 54(20), 2452-2454; 2013. The synthesis of 1-ethylcyclopentyl bromoacetate (3) is described by Thackeray, James W. et al. in US 20140080062. To a solution of compound 2 (10.0 g, 31.80 mmol) in 75 mL of N,N-dimethylformamide, tert-butyl chloroacetate (6.0 g, 31.50 mmol) and 4.40 g of potassium carbonate are added. The mixture is stirred at 80 ° C. under an inert atmosphere for 6 hours, cooled to room temperature and poured into 150 mL of water to produce a residue containing a mixture of the desired product 4 and other organic components. Product 4 is separated from other components by column chromatography. In the next step, a solution of compound 4 (10.0 g, 21.36 mmol) in 50 mL of dichloromethane was charged into the reaction flask. The solution was cooled to 0 ° C. Methacryloyl chloride (2.23 g, 21.36 mmol) and triethylamine (2.5 g, 24.7 mmol) were added to the reaction flask, and the mixture was stirred at room temperature for 16 h. The organic phase was washed with water (3 × 75 mL), and the solvent was completely removed under reduced pressure. The crude material was purified by silica gel column chromatography. The solvent eluted portion containing the product was collected, and the solvent was completely removed under reduced pressure to produce monomer M2.

[0187] Process 2:

[0188]

[0189] Example 3: M3 synthesis

[0190] The reaction steps for the synthesis of monomer compound M3 are shown in the following flow 3. A solution of compound 2 (10.0 g, 31.86 mmol) in 50 mL of dichloromethane was charged into a reaction flask. The solution was cooled to 0 ° C. Methacryloyl chloride (3.32 g, 31.86 mmol) and triethylamine (2.5 g, 24.7 mmol) were added to the reaction flask, and the mixture was stirred at room temperature for 16 h. The organic phase was washed with water (3 × 75 mL), and the solvent was completely removed under reduced pressure. The crude material was purified by silica gel column chromatography. The solvent eluted portion containing the product was collected, and the solvent was completely removed under reduced pressure to produce monomer M3.

[0191] Process 3

[0192]

[0193] Example 4: Polymer Synthesis

[0194] This example describes the synthesis of the present invention and comparative copolymers. The molar ratio of the monomers used to synthesize each polymer is set forth in Table 1 below. The structure of the monomers is shown in the following flow 4. The following procedure is used to synthesize polymer 1 (P1). Monomer MAMA (10.16 g, 0.058 mol), monomer aGBLMA (8.31 g, 0.066 mol) % and monomer HAMA (5.17 g, 0.022 mol) were added to 48 g of propylene glycol monomethyl ether acetate (" PGMEA ") and initiator azo initiator dimethyl 2,2'-azobis(2-methylpropionate) (2.5 g) under a nitrogen atmosphere and heated for 8 hours. The reaction was cooled to room temperature and poured into methanol to produce polymer P1, which was filtered and dried.

[0195] Additional polymers (P2, P3, P4, P5) set forth in Table 1 below were prepared using a similar procedure as used to prepare Copolymer 1 (P1 ), except that the monomer types and molar feed ratios as specified in Table 1 were used.

[0196] Process 4:

[0197]

[0198] Table 1

[0199]

[0200] Example 5: Preparation of photoresist composition

[0201] General procedure for photoresist preparation for PTD (positive tone development) applications. 38.85 g of polymer solution (15% in PGMEA of polymer, such as P2, P3, P4, or P5 described in Example 4 above), 31.04 g of triphenylsulfonium trifluoromethanesulfonate (TPS Tf) (2% in methyl-2-hydroxyisobutyrate), and 5.03 g of tert-butyl (1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl)carbamate solution (1% in methyl-2-hydroxyisobutyrate) were mixed and filtered with a nylon filter to give a photoresist composition.

[0202] Example 6: Base layer composition

[0203] 0.14 g of polymer P1 described in Example 4 above, 0.012 g of tetramethoxymethyl glycoluril as a crosslinker, and 0.002 g of 2,4,6-trimethylpyridinium p-toluenesulfonate were dissolved in 82 g of methyl-2-hydroxyisobutyrate solvent to obtain a fluid primer composition. The prepared fluid composition was filtered through a PTFE molecular weight polyethylene membrane filter. The filtered primer composition was then spin-coated onto a silicon wafer at 1500 rpm and the coated wafer was heated on a hot plate at 205°C for 1 minute.

[0204] Example 7: Photolithography

[0205] The photoresist composition prepared as in Example 5 was spin-coated on the hardened organic coating on a 300 mm silicon wafer, followed by a soft bake at 100° C. for 60 seconds. The resist coating was exposed to patterned EUV radiation through a mask. The exposed wafer was baked at 100° C. for 60 seconds, and the resist layer was developed in 2.38% tetramethylammonium hydroxide (TMAH) to provide a relief image.

[0206] Example 8: Further photolithography processing

[0207] The photoresist composition prepared as in Example 5 was spin-coated on the baked coating prepared as in Example 6 and then soft-baked at 100° C. for 60 seconds. The resist coating was exposed to patterned EUV radiation through a mask. The exposed wafer was baked at 100° C. for 60 seconds, and the resist layer was developed in 2.38% tetramethylammonium hydroxide (TMAH) to provide a relief image.

[0208] Example 9: EUV transmittance calculation

[0209] Table 2 below shows the compositions of comparative and inventive compositions, each comprising a polymer and a photoacid generator, triphenylsulfonium trifluoromethanesulfonate (TPS Tf), at 20 wt %. Inventive compositions C2, C3, C4, and C5 comprise inventive polymers P2, P3, P4, and P5, respectively. The transmission of films made from the composition examples under EUV exposure (13.5 nm) was calculated by the Center for X-Ray Optics at the Lawrence Berkeley National Laboratory website by inputting the calculated composition formula and assuming a film density of 1.20 g / cm 3 The film thickness is calculated to be 60 nm. As can be seen from Table 2, for the formulations containing the examples of the present invention, less transmission is achieved. These data confirm that the PAG absorption of the tellurium-containing polymer is significantly increased.

[0210] Table 2

[0211]

Claims

1. A photoresist composition comprising: a) one or more polymers comprising one or more repeating units of a monomer represented by formula (IIIC); and b) one or more acid generator compounds, (IIIC) Where, R is hydrogen or optionally substituted C 1-16 alkyl; S is a chemical bond or a chain having 1 to 20 or more optionally substituted carbon and heteroatoms selected from N, O and S; Each R 1 are the same or different non-hydrogen substituents and may contain one or more acid-cleavable groups, polar groups and / or base-reactive groups; R 2 is a non-hydrogen substituent and may contain one or more acid-cleavable groups, polar groups, and / or base-reactive groups; and n is 0 (where R 1 An integer from (group) to 4; The monomer represented by formula (IIIC) includes one or more acid-cleavable groups.

2. A method for providing a photoresist relief image, comprising: a) applying a coating of the photoresist composition according to claim 1 on a substrate; and b) exposing the photoresist composition layer to activating radiation and developing the exposed photoresist composition layer.

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