Chemically amplified resist composition without dnq

Abstract

The disclosed subject matter relates to a resist composition comprising: (A) an acetal-functionalized acrylic polymer component comprising recurring units selected from recurring units having structures (1), (2), (3), (4), (5), (6), and (7); (B) a tertiary alkyl-functionalized acrylic polymer component comprising recurring units selected from recurring units having structures (1a), (2a), (3a), (4a), (5a), (6a), and (7a); (C) a phenolic resin component comprising a novolak-based resin; (D) a photoacid generator (PAG) component, and (E) a solvent component, wherein the resist composition does not include a diazonaphthoquinone (DNQ) component.

Description

Technical Field

[0001] The disclosed subject matter relates to positive-working radiation-sensitive aqueous alkali-soluble photoresist compositions for use in the fabrication of integrated circuits (ICs), light emitting diode (LED) devices, and display devices. Background Art

[0002] Photoresist compositions are used in microlithographic etching processes for manufacturing miniaturized electronic components, such as those used in the manufacture of computer chips, integrated circuits, light-emitting diode (LED) devices, and displays. Generally speaking, in these processes, a film of the photoresist composition is first applied to a substrate material, such as a silicon wafer used to manufacture integrated circuits. The coated substrate is then baked to evaporate the solvent in the photoresist composition and to fix the coating on the substrate. The baked, coated surface of the substrate is then subjected to imagewise exposure to imaging radiation.

[0003] This radiation exposure causes a chemical transformation in the exposed areas of the coated surface. Visible light, ultraviolet (UV) light, electron beam, and X-ray radiant energy are common types of imaging radiation used in today's photolithography processes. Following this image-wise exposure, the coated substrate is treated with a developer solution to dissolve and remove either the radiation-exposed or unexposed areas of the coated surface of the substrate.

[0004] There are two types of photoresist compositions, negative-working and positive-working. When a positive-working photoresist composition is imagewise exposed to radiation, the areas of the resist composition exposed to the radiation become more soluble in a developer solution (e.g., by release of base-solubilizing groups or photolysis of a solubility inhibitor), while the unexposed areas of the photoresist coating remain relatively insoluble in such solutions. Thus, treatment of an exposed positive-working resist with a developer removes the exposed areas of the photoresist coating and produces a positive-working image in the coating, thereby leaving uncoated the desired portions of the underlying substrate surface on which the photoresist composition was deposited.

[0005] The use of positive-working, sensitive photoresist compositions that can be developed with aqueous alkaline solutions is well known. Most of these compositions are chemically amplified photoresists based on phenolic or (meth)acrylate resins, or non-chemically amplified photoresists based on novolac / diazide naphthoquinone (DNQ). In novolac / DNQ photoresists, the positive image is formed via photolysis of a diazide naphthoquinone compound (PAC) in the exposed resist areas, which causes relatively rapid dissolution of the novolac resin in aqueous alkaline solutions. These types of photoresists operate at longer UV wavelengths, such as i-line (365 nm), and have been the workhorse photoresists used in integrated circuit (IC) manufacturing for many years.

[0006] In chemically amplified positive photoresists, alkali-soluble resins (typically phenolic or (meth)acrylate resins) are released in areas of the resist exposed to radiation by acid-catalyzed cleavage of protective groups on these resins (which initially mask the alkali-solubilizing moieties), making them aqueous-alkali developable. In these chemically amplified photoresists, the catalytic acid is formed by photolysis of the photoacid generator (PAG) component. These types of resists are typically employed at shorter wavelengths to achieve higher resolution in IC fabrication.

[0007] For thick film applications, conventional novolac / DNQ resist platforms produce a sloped profile, especially at thicker films, due to their higher film absorptivity. Positive-tone chemically amplified (CA) platforms, on the other hand, can provide adequate performance within film thicknesses of 5 to 10 μm. However, the polymers conventionally used in these resists are much more expensive than conventional novolac resins. Furthermore, certain designs of positive-tone chemically amplified resists that require a post-exposure bake can negatively impact IC device throughput due to poor post-exposure delay tolerance between exposure and the post-exposure bake prior to development in aqueous alkaline solution. Cost and device throughput are also issues for applications related to display manufacturing; however, in this application, the thickness requirements for the resists are relatively low (1 to 3 μm). A potential impact on device throughput issues arises in certain chemically amplified resists where the protecting groups shielding the base-solubilizing moiety have high activation energy acids for their cleavage, in turn leaving the base-solubilizing moiety unshielded. Although these high activation energy groups can be removed catalytically by acid, this removal requires a post-exposure bake (PEB) step. However, in positive-type high activation energy chemically amplified resists, there is sensitivity to airborne alkaline contamination. This is because, in order to achieve good resolution, these resists have a high nonlinearity between the degree of cleavage of the high activation energy groups and the dissolution of the exposed resist film. Therefore, even the low consumption of acid at the surface after exposure will cause a lower degree of deprotection of these groups at the surface, which manifests itself as an insoluble resist layer, during the delay time between exposure and baking. Because the resulting positive image formed has a large, undesirable T-shape, this post-exposure delay (PED) effect is called "T-topping," which causes manufacturing defects and lower device yields. Another aspect of the disclosed and claimed subject matter is a reduction in the time of the post-exposure delay (PED).

[0008] One aspect of the disclosed subject matter is to provide a cost-competitive resist formulation based on a conventional novolac-based resist blended with two different types of chemically amplified resists that do not use DNQ compounds, which can be used for relatively thin film (1 to 2 μm) applications in display manufacturing, but are also flexible enough for thick film applications (3 to 10 μm) that show little or no effect on post-exposure delay (PED) for up to 48 hours. Specifically, these novel formulations comprise three polymer components, the first being an aqueous base-soluble (e.g., 0.26N TMAH) novolac polymer, the second being a (meth)acrylate polymer comprising (meth)acrylic acid repeating units terminated by acetal low activation energy, acid-labile groups, and the third being a (meth)acrylate polymer comprising (meth)acrylic acid repeating units protected by high activation energy tertiary alkyl protecting groups.

[0009] In applications where thinner resist films are required, the novel hybrid resist systems described herein can be formulated using a large number of novolac polymers since absorbance is not critical. Advantageously, this approach provides thin film photoresists with high resolution and contrast but can withstand extremely long post-exposure delays (PEDs) of up to 48 hours between exposure and post-exposure baking. This increases manufacturing throughput and reduces the likelihood of adverse post-exposure delay (PED) effects, such as the formation of large T-tops or line slimming. While not being bound by theory, the large PED tolerance of these materials may be due to the low activation energy acetal protecting groups and high activation energy protecting groups in the two polymers compensating for each other. In formulations containing only acetal-protected (meth)acrylate polymers, although these protecting groups are fully deprotected during the exposure phase before the post-exposure bake and exhibit no T-tops, the increased PED can lead to diffusion from exposed areas to unexposed areas, resulting in line slimming and a reduction in the exposure dose of L / S features. It was unexpectedly shown that adding a tertiary alkyl protected (meth)acrylate polymer to the formulation compensates for this diffusion problem and yields good PED latitude for line thinning without imparting the T-top PED effect typically associated with high activation energy positive chemically amplified resist compositions.

[0010] Finally, in either thick or thin film variants of this novel hybrid resist system, these are low-cost resist platforms that are simple to prepare.

[0011] The resist composition disclosed and claimed herein is a chemically amplified resist composition comprising:

[0012] (A) an acetal-functional acrylic polymer component comprising repeating units selected from repeating units having structures (1), (2), (3), (4), (5), (6), and (7):

[0013]

[0014] Wherein PG is an acid-cleavable acetal protecting group,

[0015] wherein said repeating units constitute 100 mol% of the repeating units in the acetal functional acrylic polymer,

[0016] The repeating units of structure (1) range from about 10 mol% to about 35 mol% of the acrylic polymer,

[0017] The repeating units of structure (2) range from about 0 mol% to about 20 mol% of the acrylic polymer,

[0018] The repeating units of structure (3) range from about 15 mol% to about 55 mol% of the acrylic polymer,

[0019] wherein the repeating units of structure (4) range from about 0 mol% to about 30 mol% of the acrylic polymer,

[0020] The repeating units of structure (5) range from about 15 mol% to about 55 mol% of the acrylic polymer,

[0021] The repeating units of structure (6) range from about 0 mol% to about 40 mol% of the acrylic polymer,

[0022] The repeating units of structure (7) range from about 0 mol% to about 25 mol% of the acrylic polymer,

[0023] R1, R2, R3, R4, R5, R6 and R7 are independently selected from H, F, C-1 to C-4 perfluoroalkyl or C-1 to C-4 alkyl,

[0024] R8 and R9 are independently selected from H, C-1 to C-4 alkyl, C-1 to C-4 alkyloxyalkyl and halogen,

[0025] R 10 is selected from the group consisting of a C-1 to C-8 primary alkyl group, a C-3 to C-8 secondary alkyl group, a C-3 to C-8 cyclic secondary alkyl group, and a C-7 to C-14 alicyclic secondary alkyl group,

[0026] R 11 is a C-2 to C-8 (hydroxy)alkylene moiety,

[0027] R 12 is a tertiary alkyl acid cleavable group,

[0028] R 13 is a C-3 to C-12 (alkyloxy)alkylene moiety; and

[0029] The acrylic polymer preferably comprises from about 0.5 wt% solids to about 70 wt% solids;

[0030] (B) a tertiary alkyl functional acrylic polymer component comprising repeating units selected from repeating units having structures (1a), (2a), (3a), (4a), (5a), (6a), and (7a):

[0031]

[0032] wherein said repeating unit constitutes 100 mol% of the repeating units in the tertiary alkyl functional acrylic polymer;

[0033] The repeating units of structure (1a) range from about 0 mol% to about 15 mol% of the acrylic polymer,

[0034] The repeating units of structure (2a) range from about 0 mol% to about 20 mol% of the acrylic polymer,

[0035] The repeating units of structure (3a) range from about 0 mol% to about 30 mol% of the acrylic polymer,

[0036] The repeating units of structure (4a) range from about 0 mol% to about 30 mol% of the acrylic polymer,

[0037] wherein the repeating units of structure (5a) range from about 15 mol% to about 40 mol% of the acrylic polymer,

[0038] wherein the repeating units of structure (6a) range from about 30 mol% to about 45 mol% of the acrylic polymer,

[0039] The repeating units of structure (7a) range from about 0 mol% to about 20 mol% of the acrylic polymer,

[0040] R 1a 、R 2a 、R 3a 、R 4a 、R 5a 、R 6a and R 7a individually selected from H, F, C-1 to C-4 perfluoroalkyl or C-1 to C-4 alkyl,

[0041] R 8a and R 9a individually selected from H, C-1 to C-4 alkyl, C-1 to C-4 alkyloxyalkyl and halogen,

[0042] R10a is selected from the group consisting of a C-1 to C-8 primary alkyl group, a C-3 to C-8 secondary alkyl group, a C-3 to C-8 cyclic secondary alkyl group, and a C-7 to C-14 secondary alicyclic alkyl group,

[0043] R 11a is a C-2 to C-8 (hydroxy)alkylene moiety,

[0044] R 12a is a tertiary alkyl acid cleavable group, and

[0045] R 13a is a C-3 to C-12 (alkyloxy)alkylene moiety;

[0046] (C) a phenolic resin component comprising a novolac-based resin;

[0047] (D) a photoacid generator (PAG) component; and

[0048] (E) a solvent component,

[0049] The resist composition does not include a diazonaphthoquinone (DNQ) component.

[0050] The resist composition may further include one or more optional components, such as but not limited to an acid quencher, an auxiliary resin, a thiol, a plasticizer, a surface leveling agent, and a stabilizer.

[0051] In yet another embodiment, the resist composition disclosed and claimed herein consists essentially of the aforementioned ingredients in varying concentrations, without the presence of added DNQ. In such embodiments, the combined amounts of the ingredients do not equal 100 wt % and may include other ingredients that do not materially change the effectiveness of the resist composition.

[0052] In another embodiment, the resist composition disclosed and claimed herein consists of varying concentrations of ingredients (A), (B), (C), (D), and (E). In such embodiments, the combined amount of ingredients (A), (B), (C), (D), and (E) equals approximately 100 wt%, but may include other minor and / or trace amounts of impurities present in such minor amounts that they do not materially alter the effectiveness of the resist composition.

[0053] Notably, the resist compositions disclosed and claimed herein do not require or include any type of diazonaphthoquinone (DNQ) component, such as a DNQ photosensitive dissolution inhibitor compound, or a DNQ compound that simultaneously acts as a photosensitive dissolution inhibitor compound and also as a source of sulfonic acid that can deprotect acid-labile groups on the acrylate polymer component (A) or (B). Furthermore, when used in a photolithographic process, the disclosed resists eliminate and / or minimize the need for a post-exposure bake (PEB) step and increase the post-exposure delay (PED) time tolerance.

[0054] The disclosed subject matter also relates to methods of applying the resist composition to a substrate as part of a photolithographic process. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] The accompanying drawings are included to provide a further understanding of the disclosed subject matter and are incorporated in and constitute a part of this specification, illustrating embodiments of the disclosed subject matter and together with the description serve to explain the principles of the disclosed subject matter.

[0056] Figure 1 The PED latitude of Formulation 8 is shown, where 180 mJ / cm2 is visible after a 48 hour delay between exposure and post-exposure bake prior to development in aqueous base. 2 There is no change in the resist profile of the 5μm L / S feature at the resolution dose of 100 nm.

[0057] Detailed description

[0058] It should be understood that both the foregoing general description and the following detailed description are illustrative and explanatory and are not restrictive of the subject matter as claimed. In this application, unless specifically stated otherwise, the use of the singular includes the plural, the word "a" or "an" means "at least one", and the use of "or" means "and / or". In addition, the use of the term "including" as well as other forms (such as "includes" and "included") is not limiting. In addition, unless specifically stated otherwise, terms such as "element" or "component" encompass elements or components comprising one unit as well as elements or components comprising more than one unit. As used herein, unless otherwise indicated, the conjunction "and" is intended to be inclusive and the conjunction "or" is not intended to be exclusive. For example, the phrase "or, alternatively" is intended to be exclusive. As used herein, the term "and / or" refers to any combination of the preceding elements, including the use of a single element.

[0059] The section headings used herein are for organizational purposes and should not be construed as limiting the subject matter described. All documents or portions of documents cited in this application (including but not limited to patents, patent applications, articles, books, and treatises) are hereby expressly incorporated by reference in their entirety for any purpose. In the event that one or more of the incorporated references and similar materials define a term in a manner that contradicts a definition of the term in this application, the present application controls.

[0060] The term "point of attachment" when referring to any of the inventive polymers refers to a point of branching to another polymer chain and / or a point of cross-linking to another polymer chain, wherein the extent of branching and / or cross-linking is such that the resulting branched and / or cross-linked polymer still has a sufficiently low molecular weight so as to avoid reaching a gel point where the polymer would become insoluble in a solvent such as a spin casting solvent.

[0061] Unless otherwise indicated, alkyl refers to a hydrocarbon group that can be straight chain, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), or polycyclic (e.g., norbornyl, adamantyl, etc.). These alkyl moieties may be substituted or unsubstituted as described below. The term alkyl refers to such moieties having C-1 to C-20 carbons. It should be understood that for structural reasons, straight chain alkyl groups begin with C-1, while branched and cyclic alkyl groups begin with C-3 and polycyclic alkyl groups begin with C-5. In addition, it should be further understood that, unless otherwise indicated, moieties derived from alkyl groups such as alkyloxy and haloalkyloxy described below have the same carbon number range. If an alkyl length is specified other than as described above, the above-described definition of alkyl still holds true with respect to its inclusion of all types of alkyl moieties as described above, and structural considerations regarding the minimum carbon number for a given type of alkyl group still apply.

[0062] Alkyloxy (also known as Alkoxy) refers to an alkyl group attached through an oxy (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentoxy, cyclohexyloxy, etc.). These alkyloxy moieties can be substituted or unsubstituted as described below.

[0063] Halogen or halide refers to a halogen, such as F, Cl, Br, or I, attached to an organic moiety by a bond.

[0064] Haloalkyl refers to a linear, cyclic or branched saturated alkyl group such as defined above, wherein if more than one halo moiety is present, at least one of the hydrogens has been replaced by a halo group selected from the group consisting of F, Cl, Br, I or mixtures thereof. Fluoroalkyl is a specific subset of these moieties.

[0065] Fluoroalkyl refers to a linear, cyclic, or branched saturated alkyl group as defined above in which hydrogen atoms are partially or fully replaced by fluorine atoms (e.g., trifluoromethyl, perfluoroethyl, 2,2,2-trifluoroethyl, perfluoroisopropyl, perfluorocyclohexyl, etc.). These fluoroalkyl moieties, if not perfluorinated, may be substituted or unsubstituted as described below.

[0066] Fluoroalkyloxy refers to a fluoroalkyl group as defined above attached via an oxy (—O—) group, which may be fully fluorinated (also referred to as perfluorinated) or alternatively partially fluorinated (e.g., trifluoromethoxy, perfluoroethoxy, 2,2,2-trifluoroethoxy, perfluorocyclohexyloxy, etc.). These fluoroalkyl moieties, if not perfluorinated, may be substituted or unsubstituted as described below.

[0067] Herein, when reference is made to an alkyl, alkoxy, fluoroalkyl, fluoroalkyloxy group having a possible range of carbon atoms starting at C-1 (such as, for example, "C-1 to C-20 alkyl" or "C-1 to C-20 fluoroalkyl") as a non-limiting example, this range encompasses straight-chain alkyl, alkyloxy, fluoroalkyl, and fluoroalkyloxy groups starting at C-1, but only refers to branched-chain alkyl, branched-chain alkyloxy, cycloalkyl, cycloalkyloxy, branched-chain fluoroalkyl, branched-chain fluoroalkyloxy, cyclic fluoroalkyl, and cyclic fluoroalkyloxy groups starting at C-3.

[0068] The term "alkylene" refers to a hydrocarbon group that can be linear, branched, or cyclic, with two or more points of attachment (e.g., with two points of attachment: methylene, ethylene, 1,2-isopropylene, 1,4-cyclohexylene, etc.; with three points of attachment: 1,1,1-substituted methane, 1,1,2-substituted ethane, 1,2,4-substituted cyclohexane, etc.). Herein, as a non-limiting example, when a possible range of carbons is indicated (such as C-1 to C-20), this range encompasses linear alkylene groups starting with C-1, but only branched or cycloalkylene groups starting with C-3 are indicated. These alkylene moieties may be substituted or unsubstituted as described below.

[0069] The terms monoalkyleneoxyalkylene and oligoalkyleneoxyalkylene encompass simple alkyleneoxyalkylene moieties such as ethyleneoxyethylene (—CH2—CH2—O—CH2—CH2—), propyleneoxypropylene (—CH2—CH2—CH2—O—CH2—CH2—CH2—), and the like, as well as oligomeric materials such as tris(ethyleneoxyethylene) (—CH2—CH2—O—CH2—CH2—O—CH2—CH2—), tris(propyleneoxypropylene) (—CH2—CH2—CH2—O—CH2—CH2—O—CH2—CH2—CH2—), and the like.

[0070] The term "aryl" or "aromatic group" refers to such groups containing 6 to 24 carbon atoms, including phenyl, tolyl, xylyl, naphthyl, anthracenyl, biphenyl, biphenyl, triphenyl, etc. These aryl groups may be further substituted with any suitable substituents (e.g., the alkyl, alkoxy, acyl or aryl groups mentioned above).

[0071] The term "novolac," when used herein without any other structural modifiers, refers to a novolac resin that is soluble in aqueous base, such as tetramethylammonium hydroxide and the like.

[0072] The term "arylene" refers to an aromatic hydrocarbon moiety having two or more points of attachment (e.g., 2-5). This moiety can be a single benzene moiety (e.g., two points of attachment: 1,4-phenylene, 1,3-phenylene, and 1,2-phenylene; three points of attachment: 1,2,4-substituted benzene, 1,3,5-substituted benzene, etc.); a polycyclic aromatic moiety with two points of attachment, such as those derived from naphthalene, anthracene, pyrene, etc.; or multiple benzene rings in a chain with two points of attachment (e.g., biphenylene). In those cases where the aromatic moiety is a fused aromatic ring, these may be referred to as fused-ring arylenes, and more specifically, such as naphthylene, anthracenylene, pyrenylene, etc. Fused-ring arylene groups may be substituted or unsubstituted as described below, and additionally, these fused-ring arylene groups may also contain hydrocarbon substituents having two sites of attachment on the fused ring forming an additional aliphatic or unsaturated ring formed by attaching a ring having 5 to 10 carbon atoms to the fused ring.

[0073] Unless otherwise specified, the term "PAG" refers to a photoacid generator that generates an acid (also referred to as a photoacid) under deep UV or UV irradiation, such as 200-300 nm, i-line, h-line, g-line, and / or broadband radiation. The acid can be sulfonic acid, HCl, HBr, HAsF6, etc.

[0074] The term "arene" encompasses aromatic hydrocarbon moieties comprising one ring or two to eight carbon-based aromatic rings fused together.

[0075] The term "heteroarene" refers to an aromatic hydrocarbon containing one or more trivalent or divalent heteroatoms, respectively, in such a manner as to retain its aromaticity. Examples of such heteroatoms are N, O, P, and S. As non-limiting examples, such heteroaromatic hydrocarbons may contain from 1 to 3 such heteroatoms.

[0076] Unless otherwise indicated, throughout this text, the term "substituted" when referring to an aryl, alkyl, alkyloxy, fluoroalkyl, fluoroalkyloxy, a fused aromatic ring, an arene, a heteroarene, refers to one of these moieties that further contains one or more substituents selected from the group consisting of unsubstituted alkyl, substituted alkyl, unsubstituted aryl, alkyloxyaryl (alkyl-O-aryl-), dialkyloxyaryl ((alkyl-O-)2-aryl), haloaryl, alkyloxy, alkaryl, haloalkyl, halo, hydroxy, cyano, nitro, acetyl, alkylcarbonyl, formyl, vinyl (CH2=CH-), phenylvinyl (Ph-CH=CH-), arylvinyl (aryl-CH=CH-), and substituents comprising a vinylenearylene moiety, such as Ar (-CH=CH-Ar-). z , wherein z is 1-3). Specific non-limiting examples of substituted aryl and substituted arylvinyl substituents are as follows, wherein Indicates the attachment point:

[0077] and In addition, substituted aryl and substituted vinyl, wherein the substituents are selected from any of the above substituents. Similarly, the term "unsubstituted" refers to these same moieties wherein no substituents are present except hydrogen.

[0078] The term "acid quencher" and / or "quencher system" refers to one or more base components, such as amines, that can be used in a resist formulation to harvest acid generated by a photoacid generator during exposure to i-line or broadband radiation.

[0079] The term "solid components" refers to components of a photoresist formulation that are not solvents. Such components may be solid or liquid.

[0080] The term "phenolic resin component" includes all phenolic-containing polymeric materials, including novolac polymers / resins.

[0081] The term "acid cleavable acetal protecting group" encompasses groups that can be hydrolyzed by acid (H + + HO catalyzed hydrolysis) cleavage of an acetal wherein the acetal group protecting the carboxylic acid is cleaved by hydrolytic cleavage, allowing the tertiary carbonium ion formed by acid cleavage to form an olefin which regenerates the acid catalyst as follows, wherein Rac1 and Rac2 are alkyl groups and Rac3 is alkyl or H:

[0082]

[0083] The term "tertiary alkyl acid cleavable group" encompasses tertiary alkyl acid cleavable groups that can be cleaved by acid +catalytically) cleaved tertiary alkyl esters wherein the tertiary alkyl moiety (branched, cyclic, or alicyclic) has at least one hydrogen attached to a carbon attached to a tertiary carbon of a protected carboxylic acid; this allows for the release of the tertiary carbenium ion formed by the carboxylic acid by acid cleavage to form an olefin which regenerates the acid catalyst as follows:

[0084]

[0085] This tertiary alkyl group can be part of a C-4 to C-8 acyclic alkyl group (e.g., tert-butyl, tert-pentyl), a C6-C12 cyclic group (e.g., 1-methylcyclopentyl, 1-methylcyclohexyl), or a cycloalkyl group.

[0086] Resist composition

[0087] The resist composition disclosed and claimed herein is a chemically amplified resist composition comprising:

[0088] (A) an acetal-functional acrylic polymer component comprising repeating units selected from repeating units having structures (1), (2), (3), (4), (5), (6), and (7):

[0089]

[0090]

[0091] Wherein PG is an acid-cleavable acetal protecting group,

[0092] wherein said repeating units constitute 100 mol% of the repeating units in the acetal functional acrylic polymer,

[0093] The repeating units of structure (1) range from about 10 mol% to about 35 mol% of the acrylic polymer,

[0094] The repeating units of structure (2) range from about 0 mol% to about 20 mol% of the acrylic polymer,

[0095] The repeating units of structure (3) range from about 15 mol% to about 55 mol% of the acrylic polymer,

[0096] The repeating units of structure (4) range from about 0 mol% to about 30 mol% of the acrylic polymer,

[0097] The repeating units of structure (5) range from about 15 mol% to about 55 mol% of the acrylic polymer,

[0098] The repeating units of structure (6) range from about 0 mol% to about 40 mol% of the acrylic polymer,

[0099] The repeating units of structure (7) range from about 0 mol% to about 25 mol% of the acrylic polymer,

[0100] R1, R2, R3, R4, R5, R6 and R7 are independently selected from H, F, C-1 to C-4 perfluoroalkyl or C-1 to C-4 alkyl,

[0101] R8 and R9 are independently selected from H, C-1 to C-4 alkyl, C-1 to C-4 alkyloxyalkyl and halogen,

[0102] R 10 is selected from the group consisting of a C-1 to C-8 primary alkyl group, a C-3 to C-8 secondary alkyl group, a C-3 to C-8 cyclic secondary alkyl group, and a C-7 to C-14 alicyclic secondary alkyl group,

[0103] R 11 is a C-2 to C-8 (hydroxy)alkylene moiety,

[0104] R 12 is a tertiary alkyl acid cleavable group, and

[0105] R 13 is a C-3 to C-12 (alkyloxy)alkylene moiety; and

[0106] Preferably, wherein the acrylic polymer comprises from about 0.5 wt% solids to about 70 wt% solids;

[0107] (B) a tertiary alkyl functional acrylic polymer component comprising repeating units selected from repeating units having structures (1a), (2a), (3a), (4a), (5a), (6a), and (7a):

[0108]

[0109] wherein said repeating unit constitutes 100 mol% of the repeating units in the tertiary alkyl functional acrylic polymer;

[0110] The repeating units of structure (1a) range from about 0 mol% to about 15 mol% of the acrylic polymer,

[0111] The repeating units of structure (2a) range from about 0 mol% to about 20 mol% of the acrylic polymer,

[0112] wherein the repeating units of structure (3a) range from about 0 mol% to about 30 mol% of the acrylic polymer,

[0113] wherein the repeating units of structure (4a) range from about 0 mol% to about 30 mol% of the acrylic polymer,

[0114] wherein the repeating units of structure (5a) range from about 15 mol% to about 40 mol% of the acrylic polymer,

[0115] The repeating units of structure (6a) range from about 30 mol% to about 45 mol% of the acrylic polymer,

[0116] The repeating units of structure (7a) range from about 0 mol% to about 20 mol% of the acrylic polymer,

[0117] R 1a 、R 2a 、R 3a 、R 4a 、R 5a 、R 6a and R 7a individually selected from H, F, C-1 to C-4 perfluoroalkyl or C-1 to C-4 alkyl,

[0118] R 8a and R 9a individually selected from H, C-1 to C-4 alkyl, C-1 to C-4 alkyloxyalkyl and halogen,

[0119] R 10a is selected from the group consisting of a C-1 to C-8 primary alkyl group, a C-3 to C-8 secondary alkyl group, a C-3 to C-8 cyclic secondary alkyl group, and a C-7 to C-14 secondary alicyclic alkyl group,

[0120] R 11a is a C-2 to C-8 (hydroxy)alkylene moiety, and

[0121] R 12a is a tertiary alkyl acid cleavable group,

[0122] R 13a is a C-3 to C-12 (alkyloxy)alkylene moiety;

[0123] (C) a phenolic resin component comprising a novolac-based resin;

[0124] (D) a photoacid generator (PAG) component; and

[0125] (E) Solvent component.

[0126] And further wherein the resist composition does not include a diazonaphthoquinone (DNQ) component.

[0127] The resist composition may further include one or more optional components, such as but not limited to an acid quencher, an auxiliary resin, a thiol, a plasticizer, a surface leveling agent, and a stabilizer.

[0128] In yet another embodiment, the resist composition disclosed and claimed herein consists essentially of the aforementioned ingredients in varying concentrations, without the presence of additional DNQ. In such embodiments, the combined amounts of the ingredients do not equal 100 wt % and may include other ingredients that do not materially change the effectiveness of the resist composition.

[0129] In another embodiment, the resist composition disclosed and claimed herein consists of varying concentrations of ingredients (A), (B), (C), (D), and (E). In such embodiments, the combined amount of ingredients (A), (B), (C), (D), and (E) equals approximately 100 wt%, but may include other minor and / or trace amounts of impurities present in such minor amounts that they do not materially alter the effectiveness of the resist composition.

[0130] Notably, the resist compositions disclosed and claimed herein do not require or include any kind of diazonaphthoquinone (DNQ) component, such as a DNQ photosensitive dissolution inhibitor compound, or a DNQ compound that acts both as a photosensitive dissolution inhibitor compound and also as a source of sulfonic photoacid that can deprotect acid-labile groups on the acrylate polymer component (A) or (B).

[0131] Component (A)

[0132] In one embodiment of the above composition, component (A) the acetal functional acrylic polymer component comprises from about 15 mol% to about 35 mol% of repeating units of structure (1), from about 15 mol% to about 45 mol% of repeating units of structure (3), from about 15 mol% to about 35 mol% of repeating units of structure (5), and from about 10 mol% to about 25 mol% of repeating units of structure (7), wherein these repeating units constitute 100 mol% of the repeating units in the acetal functional acrylic polymer. In another aspect of this embodiment, the repeating units of structure (1) have structure (1b), wherein R 1b is H or CH3; the repeating units of structure (3) have structure (3b); the repeating units of structure (5) have structure (5b), the repeating units of structure (7) have structure (7b), and further wherein these repeating units constitute 100 mol% of the acetal-functional acrylic polymer.

[0133]

[0134] In another embodiment of the above composition, component (A) the acetal functionalized polymer component comprises from about 15 mol% to about 20 mol% of repeating units of structure (1), from about 5 mol% to about 25 mol% of repeating units of structure (2), from about 15 mol% to about 35 mol% of repeating units of structure (5), from about 10 mol% to about 40 mol% of repeating units of structure (6), wherein these repeating units constitute 100 mol% of the repeating units in the acetal functionalized acrylic polymer. In another aspect of this embodiment, the repeating units of structure (1) have structure (1b), wherein R 1b is H or CH3; the repeating unit of structure (2) has structure (2b); the repeating unit of structure (5) has structure (5b), and the repeating unit of structure (6) has structure (6b) or (6c), wherein R 1c is H or CH3, and further wherein these repeating units constitute 100 mol% of the repeating units in the acetal-functional acrylic polymer. In another aspect of this embodiment, the repeating units of structure (6) have structure (6b), and in yet another aspect, the repeating units of structure (6) have structure (6c). In yet another aspect of this embodiment, the repeating units of structure (6) have structure (6d). In yet another aspect of this embodiment, the repeating units of structure (6) have structure (6e). In yet another aspect of this embodiment, the repeating units of structure (6) have structure (6f). In yet another aspect of this embodiment, the repeating units of structure (6) have structure (6g):

[0135]

[0136] In another embodiment of the above composition, component (A) the acetal functional acrylic polymer component comprises from about 20 mol% to about 35 mol% of repeating units of structure (1), from about 15 mol% to about 50 mol% of repeating units of structure (3), from about 15 mol% to about 30 mol% of repeating units of structure (5), from about 10 mol% to about 35 mol% of repeating units of structure (7), wherein these repeating units constitute 100 mol% of the repeating units in the acetal functional acrylic polymer. In another aspect of this embodiment, the repeating units of structure (1) have structure (1b), wherein R 1b is H or CH3; the repeating unit of structure (3) has structure (3b), the repeating unit of structure (4) has structure (4b) or (4c), and the repeating unit of structure (5) has structure (5b). In another aspect of this embodiment, the repeating unit of structure (4) has structure (4b). In another aspect of this embodiment, the repeating unit of structure (4) has structure (4c):

[0137]

[0138] In another embodiment of the above composition, component (A) acetal functionalized polymer component, part of the PG acid cleavable acetal protecting group can have the general structure (AC), wherein Rac1 is selected from C-1 to C-8 unsubstituted primary alkyl, unsubstituted C-3 to C-8 branched secondary alkyl, unsubstituted C-3 to C-8 cyclic secondary alkyl and unsubstituted C-7 to C-14 secondary alicyclic alkyl, Rac2 is selected from unsubstituted C-1 to C-8 primary alkyl, halogen substituted C-1 to C-8 primary alkyl, unsubstituted C-3 to C-8 branched secondary alkyl, halogen-substituted C-3 to C-8 branched secondary alkyl, unsubstituted C-3 to C-8 cyclic secondary alkyl, unsubstituted C-7 to C-14 secondary alicyclic alkyl, and halogen-substituted C-7 to C-14 secondary alicyclic alkyl, and Rac3 is selected from H, unsubstituted C-1 to C-8 primary alkyl, unsubstituted C-3 to C-8 branched secondary alkyl, unsubstituted C-3 to C-8 cyclic secondary alkyl, and unsubstituted C-7 to C-14 secondary alicyclic alkyl. In another aspect of this embodiment, Rac3 is selected from H, unsubstituted C-1 to C-8 primary alkyl, unsubstituted C-3 to C-8 branched secondary alkyl, unsubstituted C-3 to C-8 cyclic secondary alkyl, and unsubstituted C-7 to C-14 secondary alicyclic alkyl. In one specific aspect of this embodiment, Raci is an unsubstituted C-1 to C-8 primary alkyl group, Rac2 is an unsubstituted C-1 to C-8 primary alkyl group, and Rac3 is H. In another specific aspect of this embodiment, Raci is an unsubstituted C-1 to C-8 primary alkyl group, Rac2 is a C-1 to C-8 primary alkyl group substituted with halogen, and Rac3 is H. In another more specific aspect of this embodiment, Raci is CH3, and Rac2 is an unsubstituted C-1 to C-8 primary alkyl group, and Rac3 is H. In yet another more specific aspect of this embodiment, Raci is CH3, and Rac2 is a C-1 to C-8 primary alkyl group substituted with halogen, and Rac3 is H:

[0139]

[0140] In another embodiment of the above composition, component (A) is a component (A) in which the repeating units of structure (1) have a specific structure. In one such embodiment, it has structure (1c). In another aspect, it has structure (1d). In yet another aspect, it has structure (1e). In yet another aspect, it has structure (1f).

[0141]

[0142] Component (B)

[0143] In another embodiment of the above composition, the tertiary alkyl functionalized acrylic polymer component of component (B) comprises from about 2 mol% to about 15 mol% of repeating units of structure (1a), from about 10 mol% to about 25 mol% of repeating units of structure (3a), from about 15 mol% to about 30 mol% of repeating units of structure (5a), from about 30 mol% to about 45 mol% of repeating units of structure (6a), and from about 2 mol% to about 15 mol% of repeating units of structure (7a), wherein these repeating units constitute 100 mol% of the repeating units in the tertiary alkyl functionalized acrylic polymer. In a more specific aspect of this embodiment, the repeating units of structure (1a) have structure (1e), wherein R 1d is H or CH3; the repeating unit of structure (3a) has structure (3b); the repeating unit of structure (5a) has structure (5b); the repeating unit of structure (6a) has structure (6b) or (6c), wherein R 1c is H or CH3; the repeating unit of structure (7a) has structure (7b):

[0144]

[0145] In another embodiment of the above composition, the tertiary alkyl functionalized acrylic polymer component of component (B) comprises from about 2 mol% to about 15 mol% of repeating units of structure (1a), from about 10 mol% to about 25 mol% of repeating units of structure (3a), from about 10 mol% to about 25 mol% of repeating units of structure (4a), from about 25 mol% to about 35 mol% of repeating units of structure (5a), and from about 30 mol% to about 45 mol% of repeating units of structure (6a), wherein these repeating units constitute 100 mol% of the repeating units in the tertiary alkyl functionalized acrylic polymer. In a more specific aspect of this embodiment, the repeating units of structure (1a) have structure (1e), wherein R 1d is H or CH3; the repeating unit of structure (3a) has structure (3c); the repeating unit of structure (4a) has structure (4c) or (4b); the repeating unit of structure (5a) has structure (5b); and the repeating unit of structure (6a) has structure (6b) or (6c), wherein R 1c For H or CH3:

[0146]

[0147] In another embodiment of the above composition, the tertiary alkyl functionalized acrylic polymer component of component (B) comprises from about 5 mol% to about 10 mol% of repeating units of structure (1a), from about 10 mol% to about 25 mol% of repeating units of structure (3a), from about 25 mol% to about 35 mol% of repeating units of structure (5a), and from about 35 mol% to about 45 mol% of repeating units of structure (6a), wherein these repeating units constitute 100 mol% of the repeating units in the tertiary alkyl functionalized acrylic polymer. In a more specific aspect of this embodiment, the repeating units of structure (1a) have structure (1e), wherein R 1d is H or CH3; the repeating unit of structure (3a) has structure (3b); the repeating unit of structure (5a) has structure (5b); the repeating unit of structure (6a) has structure (6b) or (6c), wherein R 1c For H or CH3:

[0148]

[0149] In another embodiment of the above composition, the component (B) tertiary alkyl functional acrylic polymer component described above is a tertiary alkyl functional acrylic polymer component wherein the repetitions of structure (1a) or (1e) are repetitions of structure (1g) and preferably constitute from about 5 mol% to about 10 mol% of this total component:

[0150]

[0151] In another embodiment of the above composition, the component (B) tertiary alkyl functional acrylic polymer component described above is a tertiary alkyl functional acrylic polymer component wherein the repetitions of structure (1a) or (1e) are repetitions of structure (1h) and preferably constitute from about 5 mol% to about 10 mol% of this total component:

[0152]

[0153] In another embodiment of the above composition, the tertiary alkyl functionalized acrylic polymer component of component (B) comprises from about 10 mol% to about 25 mol% of repeating units of structure (3a), from about 25 mol% to about 35 mol% of repeating units of structure (5a), from about 30 mol% to about 45 mol% of repeating units of structure (6a), and from about 8 mol% to about 15 mol% of repeating units of structure (7a), wherein these repeating units constitute 100 mol% of the repeating units in the tertiary alkyl functionalized acrylic polymer. In a more specific aspect of this embodiment, the repeating units of structure (3a) have structure (3c); the repeating units of structure (5a) have structure (5c); and the repeating units of structure (6a) have structure (6b) or (6c), wherein R 1c is H or CH3; the repeating unit of structure (7a) has structure (7c). In another aspect of this embodiment, the repeating unit of structure (6a) has structure (6c). In yet another aspect of this embodiment, the repeating unit of structure (6a) has structure (6d). In another aspect of this embodiment, the repeating unit of structure (6a) has structure (6f). In another aspect of this embodiment, the repeating unit of structure (6a) has structure (6g).

[0154]

[0155] In another embodiment of the above composition, component (A) the acetal functional polymer component and component (B) the tertiary alkyl functional acrylic polymer component are present in an (A) / (B) weight ratio ranging from about 10 to about 2.3.

[0156] In another embodiment of the above composition, component (A) the acetal functional polymer component and component (B) the tertiary alkyl functional acrylic polymer component are present in an (A) / (B) weight ratio ranging from about 9 to about 2.3.

[0157] In another embodiment of the above composition, component (A) the acetal functional polymer component and component (B) the tertiary alkyl functional acrylic polymer component are present in an (A) / (B) weight ratio ranging from about 9 to about 3.

[0158] In another embodiment of the above composition, component (A) the acetal functional polymer component and component (B) the tertiary alkyl functional acrylic polymer component are present in an (A) / (B) weight ratio ranging from about 8 to about 3.5.

[0159] In another embodiment of the above composition, it is a composition wherein the (A) acetal functional polymer component and the (B) tertiary alkyl functional acrylic polymer component are present in an (A) / (B) weight ratio ranging from about 7 to about 4.

[0160] Component (C)

[0161] In another embodiment of the above composition, component (C) the novolac-based resin component comprises repeating units of structure (I); wherein Ra1, Ra2, and Ra3 are each independently (i) hydrogen, (ii) unsubstituted C-1 to C-4 alkyl, (iii) substituted C-1 to C-4 alkyl, (iv) unsubstituted -X-phenol group, wherein X is -O-, -C(CH3)2-, -CH2-, -(C=O)-, or -SO2-, or (v) substituted -X-phenol group, wherein X is -O-, -C(CH3)2-, -CH2-, -(C=O)-, or -SO2-. In a more specific aspect of this embodiment, Ra1 and Ra2 are each hydrogen and Ra3 is unsubstituted C-1 to C-4 alkyl. In yet another more specific aspect of this embodiment, Ra1 and Ra2 are each hydrogen and Ra3 is -CH3. In another aspect of this embodiment, it is one wherein Ra1 and Ra2 are each hydrogen and Ra3 is -CH3.

[0162]

[0163] In another aspect of the above composition embodiment, wherein component (C) is a novolac-based resin component comprising repeating units of structure (I) having structure (IA):

[0164]

[0165] In another aspect of the above composition embodiment, wherein component (C) is a novolac-based resin component comprising repeating units of structure (I), or having the more specific structure (IA), it is a component wherein the novolac-based resin component further comprises one or more repeating units of structure (II), wherein (i) Ra1, Ra2, and Ra3 are each independently hydrogen, unsubstituted C-1 to C-4 alkyl, or substituted C-1 to C-4 alkyl, (ii) X is -O-, -C(CH3)2-, -CH2-, (C=O)-, or -SO2-, and (iii) each Ra4 is independently hydrogen, unsubstituted C-1 to C-4 alkyl, or substituted C-1 to C-4 alkyl. In another aspect of this embodiment, it is a component wherein the novolac-based resin component further comprises repeating units of structure (II), which repeating units are repeating units having the more specific structure (IIA):

[0166]

[0167] Component (D)

[0168] Component (D) The PAG component may be any PAG component known to those skilled in the art, including but not limited to aromatic imide N-oxysulfonate derivatives of organic sulfonic acids, aromatic sulfonium salts of organic sulfonic acids, and trihalotriazine derivatives, or mixtures thereof.

[0169] For example, the PAG component can be a component that generates a photoacid at 365 nm and / or broadband irradiation, such as a sulfonic acid, such as an alkylsulfonic acid, an arylsulfonic acid, or a fluoroalkylsulfonic acid, a perfluorosulfonic acid, an inorganic acid, such as HAsF6, HSbF6, HPF6, or an acid H(perf-Ph)4B derived from tetrakis(perfluorophenyl)borate or an acid H(perf-Aryl)4B derived from a similar tetrakis(perfluoroaryl)borate. Non-limiting examples of such PAGs include various photoacid generators, such as onium salts, sulfonic acid dicarboximido esters, oxime sulfonic acid esters, diazo(sulfonylmethyl) compounds, disulfonylmethylenehydrazine compounds, sulfonic acid nitrobenzyl esters, biimidazole compounds, diazomethane derivatives, glyoxime derivatives, β-ketosulfone derivatives, disulfone derivatives, sulfonic acid ester derivatives, sulfonic acid imido ester derivatives, diazonaphthoquinonesulfonic acid esters, or combinations thereof. Such photoacid generators can be inherently sensitive to 365 nm and / or broadband radiation by appropriate substitution as known in the art. More specifically, for example, as a non-limiting example, these can be substituted or unsubstituted with triarylsulfonium salts of organic sulfonic acids, wherein in the triarylsulfonium salt moiety or its corresponding acid, the anion contains at least one aryl moiety, the at least one aryl moiety having a conjugated aryl group, wherein the conjugated aryl moiety is selected from at least one benzene ring having a substituent selected from the following: aryloxy, alkyloxy, nitro, cyano, acetyl, aryl, alkenyl, alkyloxyaryl (alkyl-O-aryl-), dialkyloxyaryl ((alkyl-O-)2-aryl), or the conjugated aryl moiety thereof can alternatively be a substituted or unsubstituted fused aromatic ring moiety comprising 2 to 4 rings. Such substituents may be attached via a difunctional moiety capable of resonance delocalization, such as arylene (including arylene derived from a fused aromatic or, for example, vinylene (-C=C-) moiety), vinyl (CH2=CH-), phenylvinyl (Ph-CH=CH-), arylvinyl (aryl-CH=CH-), and vinylenearylene moieties such as Ar (-CH=CH-Ar-) z , wherein z is 1 to 3).

[0170] Specific non-limiting examples of substituted aryl and substituted arylvinyl substituents include:

[0171] and

[0172] in Indicates an attachment point.

[0173] Other examples of common PAGs sensitive to 365 nm and / or broadband radiation are substituted or unsubstituted 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl esters of organic sulfonic acids. These PAGs may also have substituents as described above. One example is 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate (also known as naphthaleneimide trifluoromethanesulfonate, NIT) (NIT PAG).

[0174] In another aspect of this novel composition, the PAG component may be one in which the photoacid generator itself is not directly sensitive to i-line or broadband radiation but has been sensitized to such radiation with a photosensitizer that extends the effective wavelength and / or energy range. Such photosensitizers may be, but are not limited to, substituted and unsubstituted anthracenes, substituted and unsubstituted phenothiazines, substituted and unsubstituted perylenes, substituted and unsubstituted pyrenes, and aromatic carbonyl compounds such as benzophenones and thioxanthones, fluorenes, carbazoles, indoles, benzocarbazoles, acridonium chloride, equivalents thereof, or combinations of any of the foregoing.

[0175] In other embodiments of the present invention, the PAG component may be a trihalomethyl derivative, and it may be a component containing 1 to 3 trihalomethyl substituents. In another embodiment of this aspect of the invention, the trihalomethyl derivative is an arene or substituted arene containing 1 to 3 trihalomethyl substituents. In another aspect of this embodiment, the trihalomethyl derivative may be a trihalomethyl derivative containing 1 to 3 trihalomethyl substituents attached to the arene or substituted arene portion via a sulfone spacer (-SO2-).

[0176] In another embodiment of the present invention, wherein the PAG component is a trihalomethyl group, the component can be one of a heteroarene or a substituted heteroarene comprising 1 to 3 trihalomethyl moieties.

[0177] In another embodiment of the present invention, wherein the PAG component is a trihalomethyl group, it can be a derivative of a heteroarene or substituted heteroarene comprising 1 to 3 trihalomethyl substituents attached to the heteroarene or substituted heteroarene via a sulfone spacer (-SO2-).

[0178] In another embodiment of the above composition, the photoacid generator (PAG) component of component (D) is an aromatic imide N-oxysulfonate derivative of an organic sulfonic acid, an aromatic sulfonium salt of an organic sulfonic acid, a trihalotriazine derivative, or a mixture thereof. In a more specific aspect of this embodiment, the photoacid generator (PAG) component is one or more of the following compounds:

[0179] (i) Structure (IXa), wherein R 1pis a fluoroalkyl moiety and R 2p is H, alkyl, oxyalkyl, thioalkyl or aryl moiety;

[0180]

[0181] (ii) Structure (IXb), wherein R 3p is a fluoroalkyl, alkyl or aryl moiety and R4p is H, alkyl, oxyalkyl, thioalkyl or aryl moiety:

[0182]

[0183] (iii) Structure (IXc), wherein X is Cl or Br, R 5p is an aryl or alkyl moiety and n is 0 or 1:

[0184]

[0185] (iv) Structure (IXd), wherein R 6p is substituted or unsubstituted alkenyl or substituted or unsubstituted aryl, or a substituted or unsubstituted fused aromatic ring moiety comprising 2 to 4 rings, Y is oxygen or nitrogen and X is Cl or Br:

[0186]

[0187] (v) Structure (IXe), wherein R 7p is a substituted or unsubstituted alkenyl or a substituted or unsubstituted aryl, and X is Cl or Br:

[0188]

[0189] (vi) Structure (IXf) wherein X is Br or Cl and R 8p is an unsubstituted or substituted alkenyl, an unsubstituted aryl, a substituted aryl moiety, or a substituted or unsubstituted fused aromatic ring moiety comprising 2 to 4 rings:

[0190]

[0191] (vii) Structure (IXg), wherein R 9p is an unsubstituted or substituted alkenyl or an unsubstituted or substituted aryl moiety.

[0192]

[0193] In another embodiment of the above composition, component (C) is wherein the photoacid generator (PAG) component comprises 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate (NIT PAG).

[0194] Component (E)

[0195] In another embodiment of the above composition, component (E) solvent component comprises one or more of butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl amyl ketone, cyclohexanone, cyclopentanone, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl tert-valerate, ethyl tert-valerate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monomethyl ... In one aspect of this embodiment, the solvent component comprises propylene glycol monomethyl ether (PGME). In another aspect of this embodiment, the solvent component comprises propylene glycol monomethyl ether acetate (PGMEA). In another aspect of this embodiment, the solvent component comprises propylene glycol monomethyl ether acetate (PGMEA).

[0196] Optional components

[0197] In another embodiment of the composition described herein, it further comprises one or more optional ingredients selected from the group consisting of an acid quencher, an auxiliary resin, a thiol (preferably a heterocyclic thiol), a plasticizer, a surface leveling agent, and a stabilizer.

[0198] Heterocyclic thiols

[0199] In one embodiment of the above-described composition of the present invention, it further comprises at least one optional heterocyclic thiol component. In one aspect of this embodiment, the heterocyclic thiol component is at least one heterocyclic thiol compound comprising a ring structure selected from the general structure (H1), (H2) or (H3) or tautomers thereof; and

[0200]

[0201] in,

[0202] The ring structure is a monocyclic structure having 4 to 8 atoms or a polycyclic structure having 5 to 20 atoms; and wherein the monocyclic structure or the polycyclic structure comprises an aromatic, non-aromatic or heteroaromatic ring, and

[0203] In the structure (H1), Xt is selected from the group consisting of C (Rt1) (Rt2), O, S, Se, and Te;

[0204] In this structure (H2), Y is selected from the group consisting of C(Rt3) and N;

[0205] In this structure (H3), Z is selected from the group consisting of C(Rt3) and N; and Rt1, Rt2 and Rt3 are independently selected from the group consisting of H, substituted alkyl having 1 to 8 carbon atoms, unsubstituted alkyl having 1 to 8 carbon atoms, substituted alkenyl having 2 to 8 carbon atoms, unsubstituted alkenyl having 2 to 8 carbon atoms, substituted alkynyl having 2 to 8 carbon atoms, unsubstituted alkynyl having 2 to 8 carbon atoms, substituted aromatic having 6 to 20 carbon atoms, substituted heteroaromatic having 3 to 20 carbon atoms, unsubstituted aromatic having 6 to 20 carbon atoms, and unsubstituted heteroaromatic having 3 to 20 carbon atoms.

[0206] In another embodiment wherein the composition of the present invention comprises at least one heterocyclic thiol selected from the general structures (H1), (H2) or (H3) above or tautomers thereof, these heterocyclic thiols may be selected from, but are not limited to, substituted or unsubstituted triazole thiols, substituted or unsubstituted imidazole thiols, substituted or unsubstituted triazinethiols, substituted or unsubstituted mercaptopyrimidines, substituted or unsubstituted thiadiazole-thiols, substituted or unsubstituted indazole thiols, tautomers thereof, or combinations thereof. Substituents may include, but are not limited to, saturated or unsaturated hydrocarbon groups, substituted or unsubstituted aromatic rings, aliphatic, aromatic or heteroaromatic alcohols, amines, amides, imide carboxylic acids, esters, ethers, halide groups, and the like. Such substituents may be used in conjunction with heterocyclic thiols to improve solubility, modify interactions with substrates, facilitate exposure to light, or act as antihalation dyes.

[0207] In another embodiment wherein the composition of the present invention comprises at least one heterocyclic thiol selected from the above general structures (H1), (H2) or (H3) or tautomers thereof, such heterocyclic thiols may be selected from, but are not limited to, the following compounds (H4) to (H34) in unsubstituted or substituted form:

[0208]

[0209]

[0210] In another embodiment wherein the composition of the present invention comprises at least one heterocyclic thiol selected from the above general structures (H1), (H2) or (H3) or tautomers thereof, such heterocyclic thiols may be selected from thiouracil derivatives, such as 2-thiouracil as another example.These include, but are not limited to, 5-methyl-2-thiouracil, 5,6-dimethyl-2-thiouracil, 6-ethyl-5-methyl-2-thiouracil, 6-methyl-5-n-propyl-2-thiouracil, 5-ethyl-2-thiouracil, 5-n-propyl-2-thiouracil, 5-n-butyl-2-thiouracil, 5-n-hexyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dihydroxy-2-thiouracil, 5-hydroxy-6-n-propyl-2-thiouracil, 5-methoxy-2-thiouracil, 5-n-butoxy-2-thiouracil, 5-methoxy-6-n-propyl-2-thiouracil 2-thiouracil, 5-bromo-2-thiouracil, 5-chloro-2-thiouracil, 5-fluoro-2-thiouracil, 5-amino-2-thiouracil, 5-amino-6-methyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5,6-diamino-2-thiouracil, 5-allyl-2-thiouracil, 5-allyl-3-ethyl-2-thiouracil, 5-allyl-6-phenyl-2-thiouracil, 5-benzyl-2-thiouracil, 5-benzyl-6-methyl-2-thiouracil, 5-acetylamino-2-thiouracil, 6-methyl-5-nitro-2-thiouracil, 6-amino-2-thiouracil, 6-amino-5-methyl-2 -thiouracil, 6-amino-5-n-propyl-2-thiouracil, 6-bromo-2-thiouracil, 6-chloro-2-thiouracil, 6-fluoro-2-thiouracil, 6-bromo-5-methyl-2-thiouracil, 6-hydroxy-2-thiouracil, 6-acetylamino-2-thiouracil, 6-n-octyl-2-thiouracil, 6-dodecyl-2-thiouracil, 6-tetradodecyl-2-thiouracil, 6-hexadecyl-2-thiouracil, 6-(2-hydroxyethyl)-2-thiouracil, 6-(3-isopropyloctyl)-5-methyl-2-thiouracil, 6-(m-nitrophenyl)-2-thiouracil, 6-(m-nitrophenyl)-5-n-propyl-2-thiouracil Uracil, 6-α-naphthyl-2-thiouracil, 6-α-naphthyl-5-tert-butyl-2-thiouracil, 6-(p-chlorophenyl)-2-thiouracil, 6-(p-chlorophenyl)-2-ethyl-2-thiouracil, 5-ethyl-6-icosyl-2-thiouracil, 6-acetylamino-5-ethyl-2-thiouracil, 6-icosyl-5-allyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5-amino-6-(p-chlorophenyl)-2-thiouracil, 5-methoxy-6-phenyl-2-thiouracil, 5-ethyl-6-(3,3-dimethyloctyl)-2-thiouracil, 6-(2-bromoethyl)-2-thiouracil.

[0211] In another embodiment wherein the composition of the present invention comprises at least one heterocyclic thiol selected from the above general structures (H1), (H2) or (H3) or tautomers thereof, such heterocyclic thiol may be selected from the group consisting of unsubstituted triazole thiols, substituted triazole thiols, unsubstituted imidazole thiols, substituted imidazole thiols, substituted triazine thiols, unsubstituted triazine thiols, substituted mercaptopyrimidines, unsubstituted mercaptopyrimidines, substituted thiadiazole-thiols, unsubstituted thiadiazole-thiols, substituted indazole thiols, unsubstituted indazole thiols, tautomers thereof, and combinations thereof.

[0212] In another embodiment wherein the composition of the present invention comprises at least one heterocyclic thiol selected from the above general structures (H1), (H2) or (H3) or tautomers thereof, such heterocyclic thiol may be selected from the group consisting of: 1,3,5-triazine-2,4,6-trithiol, 2-mercapto-6-methylpyrimidin-4-ol, 3-mercapto-6-methyl-1,2,4-triazine-5-ol, 2-mercaptopyrimidine-4,6-diol, 1H-1,2,4-triazole-3-thiol, 1H-1,2,4-triazole-5-thiol. , 1H-imidazole-2-thiol, 1H-imidazole-5-thiol, 1H-imidazole-4-thiol, 2-azabicyclo[3.2.1]oct-2-ene-3-thiol, 2-azabicyclo[2.2.1]hept-2-ene-3-thiol, 1H-benzo[d]imidazole-2-thiol, 2-mercapto-6-methylpyrimidin-4-ol, 2-mercaptopyrimidin-4-ol, 1-methyl-1H-imidazole-2-thiol, 1,3,4-thiadiazole-2,5-dithiol, 1H-indazole-3-thiol, tautomers thereof, and combinations thereof.

[0213] Surface leveling agent

[0214] In one embodiment of the above-mentioned composition of the present invention, it further comprises at least one optional surface leveling agent, which may include a surfactant. In this embodiment, there is no particular limitation on the surfactant, and examples thereof include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene cetyl ether, and polyoxyethylene olein ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate; nonionic surfactants of polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorinated surfactants such as F-Top EF301, EF303, and EF352 (manufactured by Jemco Inc.), Megafac F171, F172, F173, R08, R30, R90 and R94 (manufactured by Dainippon Ink & Chemicals, Inc.), Florad FC-430, FC-431, FC-4430 and FC-4432 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-381, S-382, S-386, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10, KH-20, KH-30 and KH-40 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymers such as KP-341, X-70-092 and X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.); and acrylic or methacrylic polymers such as Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0215] Acid quencher

[0216] Suitable acid quenchers include, but are not limited to, basic materials or combinations of materials, such as amine compounds or mixtures of amine compounds having a boiling point above 100° C. at atmospheric pressure and a pK ais at least 1. Such acid quenchers include, but are not limited to, amine compounds having structures (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), (XIIk), and (XIII), or mixtures of compounds from this group; wherein R b1 is a C-1 to C-20 saturated alkyl chain or a C-2 to C-20 unsaturated alkyl chain; R b2 、R b3 、R b4 、R b5 、R b6 、R b7 、R b8 、R b9 、R b10 、R b11 、R b12 and R b13 Independently selected from the group consisting of H and C-1 to C-20 alkyl groups as shown below:

[0217]

[0218] Other suitable acid quenchers are tetraalkylammonium or trialkylammonium salts of carboxylic acids. Specific non-limiting examples are mono(tetraalkylammonium), di(tetraalkylammonium) salts of dicarboxylic acids, mono(trialkylammonium) or di(trialkylammonium) salts of dicarboxylic acids. Non-limiting examples of suitable dicarboxylic acids for these salts are oxalic acid, maleic acid, malonic acid, fumaric acid, phthalic acid, and the like. Structures (XIIma) to (XIImd) provide the general structure of this material, wherein Rqa to Rqc are independently C-4 to C-8 alkyl, and Rqe is a valence bond, an arylene moiety, a C-1 to C-4 alkylene moiety, an alkenyl moiety (-C(Rqf)=C(Rqg)-, wherein Rqf and Rqg are independently H or C-1 to C-4 alkyl). Structure (XIImd) provides a specific example of this material.

[0219]

[0220] deal with

[0221] Another aspect of the present invention is a method of coating a substrate, comprising applying any of the above-described compositions of the present invention to the substrate.

[0222] Another aspect of the invention is a method for imaging a resist comprising the steps of:

[0223] i) applying any of the compositions of the present invention described herein onto a substrate to form a resist film;

[0224] ii) selectively exposing the resist film to UV light using a mask to form a selectively exposed resist film;

[0225] iii) developing the selectively exposed film to form a positive-imaged resist film over the substrate.

[0226] Another aspect of the invention is a method for imaging a resist comprising the steps of:

[0227] ia) applying any of the compositions of the present invention described herein onto a substrate to form a resist film;

[0228] iia) selectively exposing the resist film to UV light using a mask to form a selectively exposed resist film;

[0229] iiia) baking the selectively exposed resist film to form a baked selectively exposed resist film;

[0230] iva) developing the selectively exposed and baked resist film to form a positive image resist film over the substrate.

[0231] Another aspect of the present invention is the use of the above-described composition of the present invention for coating a substrate.

[0232] Yet another aspect of the present invention is the use of the above-mentioned composition of the present invention for forming a resist film, preferably an imaged resist film, on a substrate. Example

[0233] Reference will now be made to more specific embodiments of the present disclosure and to experimental results supporting these embodiments.The following examples are given to more fully illustrate the disclosed subject matter and should not be construed as limiting the disclosed subject matter in any way.

[0234] It will be apparent to those skilled in the art that various modifications and variations can be made in the disclosed subject matter and the specific examples provided herein without departing from the spirit or scope of the disclosed subject matter. Therefore, the disclosed subject matter (including the description provided by the following examples) is intended to cover modifications and variations of the disclosed subject matter that appear within the scope of any claims and their equivalents.

[0235] Material

[0236] APS-437 is a surfactant from Shinetsu (Tokyo, Japan).

[0237] NIT PAG, N-hydroxynaphthalimide trifluoromethanesulfonate, sold under the trade name (NIT PAG, 100%, Tech, pdr), is sold by Heraeus PM NA Daychem LLC. Monotributylammonium oxalate was prepared according to US20190064662A1 as described in Synthesis Example 1.

[0238] Acrylic polymer P11 (Structure P11) (CPR215)

[0239]

[0240] Structure P11

[0241] Poly[methacrylic acid-co-benzyl methacrylate-co-tricyclo(5.2.1.0 / 2.6)decyl methacrylate-co-2-hydroxypropyl methacrylate] was obtained from Miwon Commercial Co., Ltd. (Miwon Bldg, 464 Anyang-ro, Manan-gu, Anyang-si, Gyeonggi-do, 430-806, Korea). This polymer has a dissolution rate in 0.26N aqueous TMAH:

[0242] MTA: The additive (1H-1,2,4-triazole-3-thiol) was purchased from Sigma Aldrich, a subsidiary of Merck KGaA (Darmstadt, Germany).

[0243] PGME (1-methoxy-2-propanol) was obtained from Sigma-Aldrich, a subsidiary of Merck KGaA (Darmstadt, Germany).

[0244] PGMEA (1-Methoxy-2-propanyl acetate) was obtained from Sigma-Aldrich, a subsidiary of Merck KGaA, Darmstadt, Germany.

[0245] Dissolution test

[0246] Dissolution experiments measuring the dissolution rate of films of acrylate polymer coatings or unexposed resist formulation coatings (also known as dark etching) were performed at 23°C using AZ 300MIF developer (also known as 0.26N aqueous TMAH). The dissolution rate was obtained by measuring the film thickness before and after development. The dissolution rate was obtained by dividing the difference in film thickness by the development time.

[0247] Application of the formulation:

[0248] All formulations were tested on 6 or 8" diameter Si and Cu wafers. The Si wafers were rehydration baked and primed with hexamethyldisilazane (HMDS) vapor. The Cu wafers were silicon wafers coated with 5,000 angstroms of silicon dioxide, 250 angstroms of tantalum nitride, and 3,500 angstroms of Cu (PVD deposited).

[0249] The resist coating was prepared by spin coating the resist sample and applying a soft bake for 120 seconds at 110° C. on a standard wafer track hot plate in contact mode. The spin speed was adjusted to obtain a 5 to 10 μm thick resist film. All film thickness measurements were performed on Si wafers using optical measurement.

[0250] Imaging:

[0251] Wafers were exposed on a SUSS MA200 CC mask aligner or an ASML 250i line stepper. Without a post-exposure bake, the resist was allowed to stand for 10-60 minutes and then puddle developed in AZ 300MIF (0.26N aqueous tetramethylammonium hydroxide = TMAH) at 23°C for 120 to 360 seconds. The developed resist image was examined using a Hitachi S4700 or AMRAY 4200L electron microscope.

[0252] Novolac polymer

[0253] For the following formulation examples, three novolac polymers were used: Novolac-1 is a meta-cresol and formaldehyde novolac and is available from Allnex (Alpharetta, Ga) under the trade designation "ALNOVOLTMSPN 560 / 47 MPAC SLOW" with a Mw of 24010, D: 7.3 and a bulk dissolution rate in 0.26N aqueous TMAH developer of Novolac-2 is a meta-cresol and formaldehyde novolac and is available from Allnex (Alpharetta, Ga) under the trade name "ALNOVOLTMSPN 560 / 47MPAC FAST" with a Mw of 7,245, D: 4.8 and a bulk dissolution rate in 0.26N aqueous TMAH developer of Novolac-3 is a 1 / 1 wt / wt blend of Novolac-1 and Novolac-2, wherein the bulk dissolution rate in 0.26N aqueous TMAH developer is Novolac CL23 is a novolac polymer (sold by Asahi Yukizai Corporation under the trade name CL23F10G) comprising 50% m-cresol, 20% p-cresol, 30% 2,5-dimethylphenol, formaldehyde, M w = 4,000 and the dissolution rate in 0.26N aqueous TMAH is

[0254] AZ 300MIF developer was obtained from EMD Performance Materials Corp, a subsidiary of Merck KGaA, Darmstadt, Germany (also known as 2.38% tetramethylammonium hydroxide (TMAH)).

[0255] Unless otherwise stated, all other chemicals were obtained from Sigma-Aldrich, a subsidiary of Merck KGaA (Darmstadt, Germany).

[0256] The molecular weight of the polymers was measured by gel permeation chromatography (GPC).

[0257] Description of the Synthesis of Acrylate-Initiated Polymers and Starting with Commercially Available Acrylates

[0258] Synthesis Example 1:

[0259]

[0260] 10.81 g of acrylic acid, 9.76 g of methoxyethyl acrylate, 17.62 g of benzyl methacrylate, and 25.23 g of hydroxypropyl methacrylate were mixed in 95.2 g of propylene glycol monomethyl ether (PGME) solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.35 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 ° C to obtain 63.0 g (99.3% yield) of acrylic resin P1 with a weight average molecular weight of 25003 and a number average molecular weight of 12470. Dissolution rate:

[0261] Synthesis Example 2:

[0262]

[0263] 9.00 g of acrylic acid, 9.76 g of methoxyethyl acrylate, 22.03 g of benzyl methacrylate, and 25.23 g of hydroxypropyl methacrylate were mixed in 101 g of propylene glycol monomethyl ether (PGME) solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.35 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 ° C to obtain 66.0 g (99.3% yield) of acrylic resin P2 with a weight average molecular weight of 30035. Dissolution rate:

[0264] Synthesis Example 3:

[0265]

[0266] 28.82 g of acrylic acid, 39.04 g of methoxyethyl acrylate, 105.73 g of benzyl methacrylate, and 100.92 g of hydroxypropyl methacrylate were mixed in 420 g of propylene glycol monomethyl ether (PGME) solvent. The polymerization reaction was carried out at 90° C. under nitrogen for 18 hours in the presence of 5.42 g of AIBN. After cooling to room temperature, the reaction mixture was used as is (appropriately 40% solid content). The weight average molecular weight of acrylic resin P3 was 21305 and the number average molecular weight was 9798. Dissolution rate:

[0267] Synthesis Example 4:

[0268]

[0269] 5.40 g of acrylic acid, 39.65 g of hydroxypropyl methacrylate, and 21.33 g of tert-butyl methacrylate were mixed in 126.3 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.64 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 ° C to obtain 64.58 g (97% yield) of acrylic resin P4 with a weight average molecular weight of 18734 and a number average molecular weight of 8321. Dissolution rate:

[0270] Synthesis Example 5:

[0271]

[0272] 9.01 g of acrylic acid, 5.28 g of styrene, 21.62 g of hydroxypropyl methacrylate, and 24.89 g of tert-butyl methacrylate were mixed in 115.8 g of PGME solvent. The polymerization reaction was carried out at 80 ° C under nitrogen for 18 hours in the presence of 1.64 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 ° C to obtain 59.67 g (98% yield) of acrylic resin P5 with a weight average molecular weight of 21457 and a number average molecular weight of 9377. Dissolution rate:

[0273] Synthesis Example 6:

[0274]

[0275] 8.11 g of acrylic acid, 6.51 g of styrene, 21.62 g of hydroxypropyl methacrylate, and 24.89 g of tert-butyl methacrylate were mixed in 76.2 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.23 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 ° C to obtain 60.50 g (99% yield) of acrylic resin P6 with a weight average molecular weight of 18672 and a number average molecular weight of 10817. Dissolution rate:

[0276] Synthesis Example 7:

[0277]

[0278] 7.21 g of acrylic acid, 21.62 g of hydroxypropyl methacrylate, and 44.05 g of benzyl methacrylate were mixed in 138.4 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.6 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 ° C to obtain 71.4 g (98% yield) of acrylic resin P7 with a weight average molecular weight of 15929 and a number average molecular weight of 8007. Dissolution rate:

[0279] Synthesis Example 8:

[0280]

[0281] 9.01 g of acrylic acid, 5.21 g of styrene, 21.62 g of hydroxypropyl methacrylate, and 30.84 g of benzyl methacrylate were mixed in 126.9 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.64 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 ° C to obtain 64.9 g (97% yield) of acrylic resin P8 with a weight average molecular weight of 15314 and a number average molecular weight of 7843. Dissolution rate:

[0282] Synthesis Example 9:

[0283]

[0284] 10.81 g of acrylic acid, 16.67 g of methylisobornyl acrylate, 17.62 g of benzyl methacrylate, and 25.23 g of hydroxypropyl methacrylate were mixed in 105.7 g of propylene glycol monomethyl ether (PGME) solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.35 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 ° C to obtain 70.0 g (99.5% yield) of acrylic resin P9 with a weight average molecular weight of 25535 and a number average molecular weight of 11607. Dissolution rate:

[0285] Commercially available acrylic polymer P10 (CPR215)

[0286]

[0287] Poly[methacrylic acid-co-benzyl methacrylate-co-tricyclo(5.2.1.0 / 2.6)decyl methacrylate-co-2-hydroxypropyl methacrylate] was obtained from Miwon Commercial Co., Ltd. (Miwon Bldg, 464 Anyang-ro, Manan-gu, Anyang-si, Gyeonggi-do, 430-806, Korea). This polymer has a dissolution rate in 0.26N aqueous TMAH: It has a weight average molecular weight of 15,470 and a number average molecular weight of 8,594.

[0288] Synthesis of acetal-protected acrylates:

[0289] Acetalization Example 1: (3044-49A):

[0290]

[0291] 13.2.0 g of polymer P1, 3.58 g of 2-chloroethyl vinyl ether and 0.01 g of citric acid were mixed in 19.8 g of PGMEA. The reaction was carried out at 50°C for 24 hours. The weight average molecular weight of the obtained polymer was 27503 and the number average molecular weight was 12570. The obtained solution was used for formulation. The dissolution rate in AZ 300MIF developer was Acetal-terminated polymer AB-1.

[0292] Acetalization Example 2:

[0293]

[0294] 100 g of polymer P3 solution and 7.1 g of ethyl vinyl ether were mixed in a flask. The reaction was carried out at 50°C for 24 hours. The resulting polymer had a weight average molecular weight of 23354 and a number average molecular weight of 9878. The resulting solution was used for formulation. Dissolution rate: Acetal terminated polymer AB-2.

[0295] Acetalization Example 3:

[0296]

[0297] 100 g of polymer P3 solution and 7.5 g of 2-chloroethyl vinyl ether were mixed in a flask. The reaction was carried out at 50°C for 24 hours. The weight average molecular weight of the resulting polymer was 29,305 and the number average molecular weight was 10,594. The resulting solution was used for formulation. Dissolution rate: Acetal terminated polymer AB-3.

[0298] Acetalization Example 4:

[0299]

[0300] 37.1 g of polymer P6, 8.0 g of 2-chloroethyl vinyl ether, and 37.6 g of PGMEA were mixed in a flask. The reaction was carried out at 40°C for 24 hours. The resulting polymer had a weight average molecular weight of 20,539 and a number average molecular weight of 10,903. The resulting solution was used for formulation. Dissolution rate: Acetal terminated polymer AB-4.

[0301] Acetalization Example 5:

[0302]

[0303] 42.11 g of polymer P8, 8.4 g of 2-chloroethyl vinyl ether, and 42.11 g of PGMEA were mixed in a flask. The reaction was carried out at 50°C for 24 hours. The resulting polymer had a weight average molecular weight of 16845 and a number average molecular weight of 7906. The resulting solution was used for formulation. Dissolution rate: Acetal terminated polymer AB-5.

[0304] Acetalization Example 6:

[0305]

[0306] 16.7 g of CPR215P10 (Miwon, Korea), 2.47 g of ethyl vinyl ether, and 0.03 g of citric acid were mixed in 25.7 g of PGMEA in a flask. The reaction was carried out at 50°C for 24 hours. The resulting polymer had a weight average molecular weight of 17018 and a number average molecular weight of 8663. The resulting solution was used for formulation. Dissolution rate: Acetal terminated polymer AB-6.

[0307] Synthesis of Tertiary Alkyl Protected Acrylates

[0308] Tert-butyl-terminated acrylic polymer synthesis example 1:

[0309]

[0310] The monomer repeat unit percentage is given in molar percentage. In this embodiment, 6.46g methacrylic acid, 35.24g benzyl methacrylate, 43.25g hydroxypropyl methacrylate, 54.47g t-butyl acrylate are mixed in 209.1g PGME solvent. The polymerization reaction is carried out at 90°C under nitrogen for 18 hours in the presence of 2.3g AIBN. After cooling to room temperature, the reaction mixture is precipitated in DI water. The polymer solid is washed and dried under vacuum at 45°C to obtain 137.1g (98% yield), wherein the GPC (using polystyrene standards) weight average molecular weight is 15,072 daltons and the number average molecular weight is 7345 daltons.

[0311] Tert-butyl-terminated acrylic polymer synthesis example 2:

[0312]

[0313] 1.8 g of acrylic acid, 6.5 g of methoxyethyl acrylate, 22.0 g of benzyl methacrylate, 21.6 g of hydroxypropyl methacrylate, and 21.3 g of tert-butyl methacrylate were mixed in 179.6 g of PGME solvent. The polymerization reaction was carried out at 80 ° C under nitrogen for 18 hours in the presence of 3.3 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 45 ° C to obtain 73.5 g (> 99% yield), wherein the GPC (using polystyrene standards) weight average molecular weight was 11,868 Daltons and the number average molecular weight was 5382.

[0314] Synthesis Example 3 of Tert-Butyl-Terminated Acrylic Polymer

[0315]

[0316] 1.8 g of acrylic acid, 6.5 g of methoxyethyl acrylate, 17.6 g of benzyl methacrylate, 21.6 g of hydroxypropyl methacrylate, and 24.9 g of tert-butyl methacrylate were mixed in 172.9 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.6 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 45 ° C to obtain 71.6 g (99% yield), wherein the GPC (using polystyrene standards) weight average molecular weight was 17,205 Daltons and the number average molecular weight was 8407.

[0317] Tert-Butyl-Terminated Acrylic Polymer Synthesis Example 4:

[0318]

[0319] 2.7 g of acrylic acid, 6.5 g of methoxyethyl acrylate, 15.4 g of benzyl methacrylate, 21.6 g of hydroxypropyl methacrylate, and 24.9 g of tert-butyl methacrylate were mixed in 135.2 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.6 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 45 ° C to obtain 70.3 g (99% yield), wherein the GPC (using polystyrene standards) weight average molecular weight was 17,153 Daltons and the number average molecular weight was 9424.

[0320] Tert-Butyl-Terminated Acrylic Polymer Synthesis Example 5:

[0321]

[0322] 3.6 g of acrylic acid, 6.5 g of methoxyethyl acrylate, 13.2 g of benzyl methacrylate, 21.6 g of hydroxypropyl methacrylate, and 24.9 g of tert-butyl methacrylate were mixed in 135.8 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 3.3 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 45 ° C to obtain 70.8 g (> 99% yield), wherein the GPC (using polystyrene standards) weight average molecular weight was 11,913 Daltons and the number average molecular weight was 5564.

[0323] Tert-Butyl-Terminated Acrylic Polymer Synthesis Example 6:

[0324]

[0325] 1.8 g of acrylic acid, 10.0 g of methyl methacrylate, 28.8 g of hydroxypropyl methacrylate, and 24.9 g of tert-butyl methacrylate were mixed in 124.7 g of PGME solvent. The polymerization reaction was carried out at 90° C. under nitrogen for 18 hours in the presence of 1.6 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 45° C. to obtain 64.4 g (98% yield), with a GPC (using polystyrene standards) weight average molecular weight of 16,650 Daltons and a number average molecular weight of 7919.

[0326] Tert-Butyl-Terminated Acrylic Polymer Synthesis Example 7:

[0327]

[0328] 1.8 g of acrylic acid, 3.3 g of methoxyethyl acrylate, 17.6 g of benzyl methacrylate, 21.6 g of hydroxypropyl methacrylate, and 28.4 g of tert-butyl methacrylate were mixed in 138.2 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.6 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 45 ° C to obtain 71.9 g (99% yield) with a weight average molecular weight of 15,843 Daltons and a number average molecular weight of 7642 Daltons.

[0329] Tert-Butyl-Terminated Acrylic Polymer Synthesis Example 8:

[0330]

[0331] 6.5 g of methoxyethyl acrylate, 15.4 g of benzyl methacrylate, 21.6 g of hydroxypropyl methacrylate, and 30.2 g of tert-butyl methacrylate were mixed in 140.0 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.6 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 45 ° C to obtain 72.45 g (98% yield), wherein the GPC (using polystyrene standards) weight average molecular weight was 17,525 Daltons and the number average molecular weight was 8695 Daltons.

[0332] Synthesis Example 9 of Ethylcyclopentyl-terminated Acrylic Polymer

[0333]

[0334] The monomer repeat unit percentages are given as molar percentages. In this example, 7.16 g of methoxyethyl acrylate, 15.86 g of benzyl methacrylate, 25.23 g of hydroxypropyl methacrylate, and 32.78 g of 1-ethylcyclopentyl methacrylate were mixed in 152.6 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 1.2 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The polymer solids were washed and dried under vacuum at 45 ° C to obtain 79.3 g (98% yield), wherein the GPC (using polystyrene standards) weight average molecular weight was 17,888 Daltons and the number average molecular weight was 9502.

[0335] Synthesis Example 10 of Ethylcyclopentyl-Terminated Acrylic Polymer

[0336]

[0337] 4.32 g of acrylic acid, 14.32 g of methoxyethyl acrylate, 22.91 g of benzyl methacrylate, 50.46 g of hydroxypropyl methacrylate, and 63.75 g of 1-ethylcyclopentyl methacrylate were mixed in 158.5 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 2.71 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The polymer solid was washed and dried under vacuum at 45 ° C to obtain 153.45 g (98.5% yield), wherein the GPC (using polystyrene standards) weight average molecular weight was 17,103 Daltons and the number average molecular weight was 8316.

[0338] Synthesis Example 11 of Ethylcyclopentyl-Terminated Acrylic Polymer

[0339]

[0340] 5.76 g of acrylic acid, 14.32 g of methoxyethyl acrylate, 19.38 g of benzyl methacrylate, 50.46 g of hydroxypropyl methacrylate, and 63.75 g of 1-ethylcyclopentyl methacrylate were mixed in 156.4 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 2.71 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The polymer solid was washed and dried under vacuum at 45 ° C to obtain 150.2 g (97.7% yield), wherein the GPC (using polystyrene standards) weight average molecular weight was 15,557 Daltons and the number average molecular weight was 7795.

[0341] Synthesis Example 12 of Tert-Butyl-Terminated Acrylic Polymer

[0342]

[0343] 8.61 g of methacrylic acid, 22.23 g of isobornyl methacrylate, 26.43 g of benzyl methacrylate, 43.25 g of hydroxypropyl methacrylate, and 44.36 g of tert-butyl acrylate were mixed in 156.4 g of PGME solvent. The polymerization reaction was carried out at 90 ° C under nitrogen for 18 hours in the presence of 2.46 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The polymer solids were washed and dried under vacuum at 45 ° C to obtain 142.5 g (98.3% yield), wherein the GPC (using polystyrene standards) weight average molecular weight was 25,535 Daltons and the number average molecular weight was 12,215.

[0344] Formulation Examples

[0345] Application of the formulation:

[0346] All formulations were tested on 8" diameter Si and Cu wafers. The Si wafers were dehydration baked and vapor primed with hexamethyldisilazane (HMDS).

[0347] All formulations were tested on 6 or 8" diameter Si and Cu wafers. The Si wafers were rehydration baked and primed with hexamethyldisilazane (HMDS) vapor. The Cu wafers were silicon wafers coated with 5,000 angstroms of silicon dioxide, 250 angstroms of tantalum nitride, and 3,500 angstroms of Cu (PVD deposited).

[0348] The resist coating was prepared by spin coating the resist sample and applying a soft bake for 120 seconds at 110°C on a standard wafer track hot plate in contact mode. The spin speed was adjusted to obtain a 17 micron thick resist film. All film thickness measurements were performed on Si wafers using optical measurement.

[0349] Imaging:

[0350] Wafers were exposed on a SUSS MA200 CC mask aligner or an ASML 250i line stepper. Without a post-exposure bake, the resist was allowed to stand for 10-60 minutes and then bath-developed in AZ 300MIF (0.26N aqueous solution of tetramethylammonium hydroxide = TMAH) at 23°C for 120 to 360 seconds. The developed resist image was examined using a Hitachi S4700 or AMRAY 4200L electron microscope.

[0351] Imaging results

[0352] Formulation Example 1: 33.16 g (45.87% solution) of acetal acrylic polymer resin (acetalization example 1), 26.38 g of Novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of tributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 40.06 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film and dried at 110°C for 120 seconds. The resist was processed to produce a patterned image, with a post-exposure bake at 70°C for 60 seconds and development for 180 seconds.

[0353] Formulation Example 2: 34.59 g (43.98% solution) of acetal acrylic polymer resin (acetalization example 2), 26.38 g of Novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 38.63 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0354] Formulation Example 3: 34.42 g (44.19% solution) of acetal acrylic polymer resin (acetalization example 3), 26.38 g of Novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 38.80 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0355] Formulation Example 4: 27.90 g (54.53% solution) of acetal acrylic polymer resin (acetalization example 4), 26.38 g of novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 45.32 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0356] Formulation Example 5: 27.90 g (54.53% solution) of acetal acrylic polymer resin (acetalization example 5), 26.38 g of novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 45.32 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0357] Formulation Example 6: 35.61 g (42.72% solution) of acetal acrylic polymer resin (acetalization example 6), 26.38 g of novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 37.61 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0358] Formulation Example 7: 24.80 g (54.53% solution) of acetal acrylic polymer resin (acetalization example 4 (AB-4)), 2.02 g of tert-butyl terminated acrylic polymer synthesis example 12, 26.38 g of novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 46.40 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0359] Formulation Example 8: 23.03 g (54.53% solution) of acetal acrylic polymer resin (acetalization example 4 (AB-4)), 2.95 g of tert-butyl terminated acrylic polymer synthesis example 12, 26.38 g of novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 47.24 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0360] Formulation Example 9: 15.40 g (54.53% solution) of acetal acrylic polymer resin (acetalization example 4 (AB-4)), 6.08 g of tert-butyl terminated acrylic polymer synthesis example 12, 26.38 g of novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 51.74 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0361] Formulation Example 10: 28.50 g (44.19% solution) of acetal acrylic polymer resin (acetalization example 3 (AB-3)), 2.95 g of tert-butyl terminated acrylic polymer synthesis example 12, 26.38 g of novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 41.77 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0362] Formulation Example 11: 23.03 g (54.53% solution) of acetal acrylic polymer resin (acetalization example 4 (AB-4)), 2.95 g of tert-butyl terminated polymer synthesis example 5, 26.38 g of novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 47.24 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0363] Formulation Example 12: 23.03 g (54.53% solution) of acetal acrylic polymer resin (acetalization example 4 (AB-4)), 2.95 g of tert-butyl terminated polymer synthesis example 9, 26.38 g of novolac-3, 0.32 g of 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl trifluoromethanesulfonate [also known as naphthalene dicarboximido trifluoromethanesulfonate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 47.24 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0364] Formulation Example 13: 23.03 g (54.53% solution) of acetal acrylic polymer resin (acetalization example 4 (AB-4)), 2.95 g of tert-butyl terminated polymer synthesis example 11, 26.38 g of novolac-3, 0.32 g of trifluoromethanesulfonic acid 1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl ester [also known as trifluoromethanesulfonic acid naphthalene dicarboximidate, NIT] (NIT PAG), 0.03 g of 1H-1,2,4-triazole-3-thiol, 0.02 g of monotributylammonium oxalate, and 0.03 g of APS-437 were dissolved in 47.24 g of PGMEA solvent to obtain a resist solution at 42.0% solids. This solution was coated onto a copper wafer to produce a 12 μm film, which was dried at 110° C. for 120 seconds. The resist was processed to produce a patterned image, post-exposure baked at 70°C for 60 seconds and developed for 180 seconds.

[0365] Formulations 1 to 6 containing only acetal-terminated polymer (also referred to as component (A) only) did not exhibit T-tops of the L / S features after a 48-hour PED delay. However, these formulations did result in a significant reduction in the size of the L / S features (also referred to as line thinning) after this 48-hour post-exposure time delay at the same exposure size dose as used at time 0. Therefore, to obtain the same target feature size after a 48-hour PED time, a very low exposure dose, for example, 60 mJ / cm2 lower, was required. 2 or more.

[0366] However, by using a formulation having a mixture of tert-butyl or ethylcyclopentyl terminated acrylate polymers (also referred to as component (B)) [tert-butyl terminated acrylic polymer synthesis examples 1 to 12] and acetalization examples 1 to 6 (also referred to as component (A)), the 48-hour PED delay latitude was greatly improved. Specifically, resolution of L / S features at a PED time of 48 hours was achieved at the same resolution dose as a PED time of 0 hours, with greatly reduced or completely eliminated line thinning. In those cases where these acrylate formulations exhibited some slight line thinning after a PED delay of 48 hours, this could be achieved by slightly reducing the dose required to resolve features of the same size after a 48-hour PED delay (20 mJ / cm 2 As an example, Formulation Example 8 shows no change in resolution dose for a 5 micron L / S feature after a 48 hour post-exposure delay (PED), thereby showing no change in T-top or line thinning after this delay time ( Figure 1 ), similar results were seen for formulations 11 to 13.

[0367] For all formulations using a mixture of acetal- and tert-butyl-protected acrylates, none of these formulations showed any signs of T-tops after a 48-hour PED delay (Table 1 formulations). Furthermore, these mixture formulations demonstrated very good dose latitude for resolving L / S features ranging in size from 2.4 to 10 microns at the same resolution dose. In general, a weight ratio of component (A) to component (B) of 2.3 to 9 was found to provide acceptable PED latitude improvements.

[0368] However, it was found that when too low a ratio of component (A) to component (B) was used in the mixture (where there was too much tert-butyl or 1-ethylcyclopentyl terminated acrylate polymer), the photo-speed was seen to decrease too much after a PED equal to 48 hours (also referred to as mJ / cm 2 The dose increment is 100 mJ / cm 2or greater). This particular example is demonstrated by formulation Example 9 using a ratio of 1.38, which shows a decrease in photospeed after 48 hours of PED (increased resolution dose of 120 mJ / cm 2 )(Table 1). In contrast, too high a ratio of component (A) to component (B), wherein the ratio is much greater than 9, results in an excessive increase in photospeed, making it difficult to control line thinning under PED retardation.

[0369] Other formulations comprising a mixture of component (A) and component (B) achieve similar results as described above.

[0370] While the present invention has been described and illustrated with a certain degree of particularity, it is to be understood that the invention is made by way of example only and that those skilled in the art may make numerous changes in conditions and step sequences without departing from the spirit and scope of the invention.

[0371] result

[0372] Table 1. Blended acetal-terminated polymers and tertiary alkyl-terminated acrylate polymers.

[0373]

[0374]

Claims

1. A composition comprising (A) an acetal-functional acrylic polymer component comprising repeating units selected from repeating units having structures (1), (2), (3), (4), (5), (6), and (7): Wherein PG is an acid-cleavable acetal protecting group, wherein these repeating units constitute 100 mol% of the repeating units in the acetal functional acrylic polymer. wherein the repeating unit of structure (1) is in the range of 10 mol% to 35 mol% of the acrylic polymer, The repeating unit of structure (2) is in the range of 0 mol% to 20 mol% of the acrylic polymer, The repeating unit of structure (3) is in the range of 15 mol% to 55 mol% of the acrylic polymer, The repeating unit of structure (4) is in the range of 0 mol% to 30 mol% of the acrylic polymer, The repeating unit of structure (5) is in the range of 15 mol% to 55 mol% of the acrylic polymer, The repeating unit of structure (6) is in the range of 0 mol% to 40 mol% of the acrylic polymer, The repeating unit of the structure (7) is in the range of 0 mol% to 25 mol% of the acrylic polymer, R1, R2, R3, R4, R5, R6 and R7 are independently selected from H, F, C-1 to C-4 perfluoroalkyl or C-1 to C-4 alkyl, R8 and R9 are independently selected from H, C-1 to C-4 alkyl, C-1 to C-4 alkyloxyalkyl and halogen, R 10 selected from the group consisting of C-1 to C-8 primary alkyl, C-3 to C-8 secondary alkyl, and C-7 to C-14 alicyclic secondary alkyl, R 11 is a C-2 to C-8 (hydroxy)alkylene moiety, R 12 is a tertiary alkyl acid cleavable group, and further wherein, R 13 is a C-3 to C-12 (alkyloxy)alkylene moiety; (B) a tertiary alkyl functional acrylic polymer component comprising repeating units selected from repeating units having structures (1a), (2a), (3a), (4a), (5a), (6a), and (7a): wherein these repeating units constitute 100 mol% of the repeating units in the tertiary alkyl functional acrylic polymer. The repeating unit of structure (1a) is in the range of 0 mol% to 15 mol% of the acrylic polymer, wherein the repeating unit of structure (2a) is in the range of 0 mol% to 20 mol% of the acrylic polymer, The repeating unit of the structure (3a) is in the range of 0 mol% to 30 mol% of the acrylic polymer, The repeating unit of the structure (4a) is in the range of 0 mol% to 30 mol% of the acrylic polymer, The repeating unit of the structure (5a) is in the range of 15 mol% to 40 mol% of the acrylic polymer, The repeating unit of the structure (6a) is in the range of 30 mol% to 45 mol% of the acrylic polymer, The repeating unit of the structure (7a) is in the range of 0 mol% to 20 mol% of the acrylic polymer, R 1a 、R 2a 、R 3a 、R 4a 、R 5a 、R 6a and R 7a individually selected from H, F, C-1 to C-4 perfluoroalkyl or C-1 to C-4 alkyl, R 8a and R 9a individually selected from H, C-1 to C-4 alkyl, C-1 to C-4 alkyloxyalkyl and halogen, R 10a selected from the group consisting of C-1 to C-8 primary alkyl, C-3 to C-8 secondary alkyl, and C-7 to C-14 secondary alicyclic alkyl, R 11a is a C-2 to C-8 (hydroxy)alkylene moiety, R 12a is a tertiary alkyl acid cleavable group, and R 13a is a C-3 to C-12 (alkyloxy)alkylene moiety; (C) a phenolic resin component comprising a novolac-based resin; (D) a photoacid generator (PAG) component; and (E) a solvent component, And in addition, The composition does not include a diazonaphthoquinone (DNQ) component.

2. The composition according to claim 1, wherein R 10 is selected from C-3 to C-8 cyclic secondary alkyl groups.

3. The composition according to claim 1, wherein R 10a Selected from C-3 to C-8 cyclic secondary alkyl groups.

4. The composition according to claim 1, wherein (A) the acetal-functional acrylic polymer component comprises 15 mol% to 35 mol% of repeating units of the structure (1), 15 mol% to 45 mol% of repeating units of the structure (3), 15 mol% to 35 mol% of repeating units of the structure (5), and 10 mol% to 25 mol% of repeating units of the structure (7), wherein these repeating units constitute 100 mol% of the repeating units in the acetal-functional acrylic polymer.

5. The composition according to claim 1, wherein (A) the acetal-functionalized polymer component comprises 15 mol% to 20 mol% of repeating units of the structure (1), 5 mol% to 25 mol% of repeating units of the structure (2), 15 mol% to 35 mol% of repeating units of the structure (5), and 10 mol% to 40 mol% of repeating units of the structure (6), wherein these repeating units constitute 100 mol% of the repeating units in the acetal-functionalized acrylic polymer.

6. The composition according to claim 1, wherein (A) the acetal-functional acrylic polymer component comprises 20 mol% to 35 mol% of repeating units of the structure (1), 15 mol% to 50 mol% of repeating units of the structure (3), 15 mol% to 30 mol% of repeating units of the structure (5), and 10 mol% to 35 mol% of repeating units of the structure (7), wherein these repeating units constitute 100 mol% of the repeating units in the acetal-functional acrylic polymer.

7. The composition according to any one of claims 1 to 6, wherein (B) the tertiary alkyl functionalized acrylic polymer component comprises 2 mol% to 15 mol% of repeating units of structure (1a), 10 mol% to 25 mol% of repeating units of structure (3a), 15 mol% to 30 mol% of repeating units of structure (5a), 30 mol% to 45 mol% of repeating units of structure (6a), and 2 mol% to 15 mol% of repeating units of structure (7a), wherein these repeating units constitute 100 mol% of the repeating units in the tertiary alkyl functionalized acrylic polymer.

8. The composition according to any one of claims 1 to 6, wherein (B) the tertiary alkyl functionalized acrylic polymer component comprises 2 mol% to 15 mol% of repeating units of structure (1a), 10 mol% to 25 mol% of repeating units of structure (3a), 10 mol% to 25 mol% of repeating units of structure (4a), 25 mol% to 35 mol% of repeating units of structure (5a), and 30 mol% to 45 mol% of repeating units of structure (6a), wherein these repeating units constitute 100 mol% of the repeating units in the tertiary alkyl functionalized acrylic polymer.

9. The composition according to any one of claims 1 to 6, wherein (B) the tertiary alkyl functionalized acrylic polymer component comprises 5 mol% to 10 mol% of repeating units of structure (1a), 10 mol% to 25 mol% of repeating units of structure (3a), 25 mol% to 35 mol% of repeating units of structure (5a), and 35 mol% to 45 mol% of repeating units of structure (6a), wherein these repeating units constitute 100 mol% of the repeating units in the tertiary alkyl functionalized acrylic polymer.

10. The composition according to any one of claims 1 to 6, wherein (B) the tertiary alkyl functionalized acrylic polymer component comprises 10 mol% to 25 mol% of repeating units of the structure (3a), 25 mol% to 35 mol% of repeating units of the structure (5a), 30 mol% to 45 mol% of repeating units of the structure (6a), and 8 mol% to 15 mol% of repeating units of the structure (7a), wherein these repeating units constitute 100 mol% of the repeating units in the tertiary alkyl functionalized acrylic polymer.

11. The composition of any one of claims 1 to 6, wherein (A) the acetal-functional polymer component and (B) the tertiary alkyl-functional acrylic polymer component are present in an (A) / (B) weight ratio ranging from 10 to 2.

3.

12. The composition of any one of claims 1 to 6, wherein (A) the acetal-functional polymer component and (B) the tertiary alkyl-functional acrylic polymer component are present in an (A) / (B) weight ratio ranging from 9 to 2.

3.

13. The composition of any one of claims 1 to 6, wherein (A) the acetal-functional polymer component and (B) the tertiary alkyl-functional acrylic polymer component are present in an (A) / (B) weight ratio ranging from 9 to 3.

14. The composition of any one of claims 1 to 6, wherein (A) the acetal functional polymer component and (B) the tertiary alkyl functional acrylic polymer component are present in an (A) / (B) weight ratio ranging from 8 to 3.

5.

15. The composition of any one of claims 1 to 6, wherein (A) the acetal functional polymer component and (B) the tertiary alkyl functional acrylic polymer component are present in an (A) / (B) weight ratio ranging from 7 to 4.

16. The composition according to any one of claims 1 to 6, wherein (C) the novolac-based resin component comprises repeating units (I): wherein Ra1, Ra2 and Ra3 are each independently (i) hydrogen, (ii) unsubstituted C-1 to C-4 alkyl, (iii) substituted C-1 to C-4 alkyl, (iv) an unsubstituted -X-phenol group, wherein X is -O-, -C(CH3)2-, -CH2-, -(C=O)- or -SO2-, or (v) a substituted -X-phenol group, wherein X is -O-, -C(CH3)2-, -CH2-, -(C=O)- or -SO2-.

17. The composition according to any one of claims 1 to 6, wherein the photoacid generator (PAG) component is an aromatic imide N-oxysulfonate derivative of an organic sulfonic acid, an aromatic sulfonium salt of an organic sulfonic acid, a trihalotriazine derivative, or a mixture thereof.

18. The composition according to any one of claims 1 to 6, further comprising one or more optional ingredients selected from the group consisting of an acid quencher, an auxiliary resin, a thiol, a plasticizer, a surface leveling agent, and a stabilizer.

19. The composition according to claim 18, wherein the thiol is a heterocyclic thiol.

20. A method of coating a substrate comprising applying a composition according to any one of claims 1 to 19 onto the substrate.

21. A method for imaging a resist comprising the steps of: i) applying the composition according to any one of claims 1 to 19 on a substrate to form a resist film; ii) selectively exposing the resist film to UV light using a mask to form a selectively exposed resist film; iii) developing the selectively exposed film to form a positive-imaged resist film over the substrate.

22. A method for imaging a resist comprising the steps of: ia) applying the composition according to any one of claims 1 to 19 on a substrate to form a resist film; iia) selectively exposing the resist film to UV light using a mask to form a selectively exposed resist film; iiia) baking the selectively exposed resist film to form a baked selectively exposed resist film; iva) developing the selectively exposed and baked resist film to form a positive image resist film over the substrate.

Images