Spin-on metal organic formulations

Abstract

The disclosed and claimed subject matter relates to spin-on metal organic formulations including zirconium.

Description

Technical Field

[0001] The disclosed and claimed subject matter relates to newly identified polymorphs of zirconium propionate (IV), spin-coated organometallic formulations including these new polymorphs, and their use in forming spin-coated metal oxide hard masks. Background Technology

[0002] Metal oxide films are suitable for a variety of applications in the semiconductor industry, serving as the underlayer for anti-reflective coatings in photolithographic hard masks and / or electro-optic devices. In this regard, spin-coated metal-organic formulations have been developed to replace CVD / PVD ALD hard masks in semiconductor manufacturing processes due to their simplification of multiple stacks, their ability to allow high throughput, and their lower cost of ownership. Furthermore, the trend of replacing planar NAND with 3D NAND has spurred the development of novel hard mask materials, particularly those capable of high aspect ratio etching. Spin-coated metal oxide films offer excellent etch resistance in oxidized plasmas, and their low argon sputtering rates make them excellent solutions for photolithographic patterning of multiple passes.

[0003] A base layer containing a high refractory element content can be used as a hard mask (and anti-reflective coating). Hard masks are useful when the overlay photoresist cannot provide sufficiently high resistance to dry etching (used to transfer images to the underlying semiconductor substrate). In particular, such cases benefit from utilizing a hard mask with sufficient etch resistance to transfer any pattern created thereon to the underlying semiconductor substrate. This is made possible because organic photoresists differ from the underlying hard mask and it is possible to find etching gas mixtures that allow the image in the photoresist to be transferred to the underlying hard mask. This patterned hard mask can then be used with appropriate etching conditions and gas mixtures to transfer the image from the hard mask to the semiconductor substrate, a task that is impossible for the photoresist itself to achieve through a single etching process. One approach has incorporated silicon, zirconium, or other metallic materials into the hard mask layer base, while other approaches utilize high-carbon content layers (e.g., a three-layer structure of high-carbon film / hard mask film / photoresist) to improve lithography performance.

[0004] Conventional hard masks can be coated using vapor deposition techniques (e.g., CVD / PVD / ALD). However, as mentioned above, simpler coating methods (e.g., spin coating) are desirable for depositing hard masks or anti-reflective coatings with high concentrations of metallic materials.

[0005] Substrate compositions containing metal oxides for semiconductor applications have been shown to provide dry etch resistance and anti-reflective properties. Improved etch resistance and thermal conductivity can be obtained when higher concentrations of metal oxides are present in the substrate. However, conventional metal oxide compositions have been found to be highly unstable in air due to moisture, causing issues with shelf-life stability, coating, and performance drawbacks. Therefore, there is a significant need to prepare spin-coated hard masks, anti-reflective coatings, and other substrates containing high concentrations of stable, soluble metal oxides (either soluble or colloidal).

[0006] The use of zirconium (IV) precursors in spin-coating formulations / coatings is well known in the art. For example, U.S. Patent No. 9,201,305 describes how to formulate zirconium propionate, zirconium acetate, zirconium (IV) 2-ethylhexanoate, and zirconium (IV) acetylated pyruvate with crosslinkable polymers (with or without wetting agents), surfactants, defoamers, etc., in organic solvents such as PGME, PGMEA, or ArF diluents to form spin-coating compositions.

[0007] Given the properties of such zirconium (IV) precursors, the objective of this study is to identify novel zirconium (IV) precursors for spin-coating formulations. As mentioned above, the disclosed and claimed subject matter relates to newly identified polymorphs of zirconium (IV) propionate and their use in spin-coating hard mask formulations.

[0008] Besides the novel material described herein, other known zirconium propionate (IV) materials exist. For example, the Russian Journal of Inorganic Chemistry, 12(10), pp. 1348-1350 (1967) describes the following reaction:

[0009]

[0010] The predicted tetrameric structure of the side-oxy-zirconium propionate product is as follows: Figure 8 As shown.

[0011] In Eur. J. Inorg. Chem., 3283-3293 (2006), the authors described a structure with the following characteristics: Figure 9 The structure shown is [Zr6O4(OH)4(OOCCH2Me)]. 12 Synthesis of 2·6MeCH2COOH.

[0012] The Journal of Analytical and Applied Pyrolysis, 97, 137-142 (2012) describes the reaction of zirconium acetylacetonate (IV) with propionic acid to form a compound with the following properties: Figure 10The structure shown is [Zr6O4(OH)4(CH3CH2COO)]. 12 ]2·11H2O.

[0013] Regardless of the above, there remains a need for zirconium propionate (IV) compounds and formulations thereof suitable for spin-coating applications that produce robust ZrOx films. This invention addresses these needs. Invention Overview

[0015] In one embodiment, the disclosed and claimed subject matter relates to zirconium propionate polymorph S1 (“ZPPA”), the characteristics of which are described in more detail below.

[0016] In another embodiment, the disclosed and claimed subject matter relates to a method for synthesizing ZPPA. In another aspect of this embodiment, ZPPA is prepared by reacting (tert-butanol)4 zirconium(IV) with propionic anhydride and propionic acid in a 3:1 molar ratio, followed by reacting it with propylene glycol monomethyl ether (PGME) in a solvent-free environment.

[0017] In another embodiment, the disclosed and claimed subject matter relates to formulations comprising ZPPA or zirconium propionate (IV) (“ZPP”) and their preparation. In another aspect of this embodiment, the formulation includes other additives suitable for managing the properties of the film after baking in a photolithography process.

[0018] In one embodiment, the formulation comprises (i) ZPP and / or ZPPA, (ii) one or more etch-resistant modifier additives, and (iii) one or more solvents. In other embodiments, the formulation further comprises (iv) one or more surfactants and (v) one or more water-resistant enhancers, or both.

[0019] In another embodiment, the disclosed and claimed subject matter relates to the use of formulations of ZPP and / or ZPPA to form a highly crosslinked ZrOx film on a substrate under thermal decomposition. In another aspect, the ZrOx film exhibits a crosslinking density greater than approximately [missing information]. Etching resistance and / or less than approximately The Ar sputtering rate. On the other hand, the ZrOx film exhibits a rate greater than approximately Etching resistance and / or less than approximately The Ar sputtering rate. On the other hand, the ZrOx film exhibits a rate greater than approximately to approximately The etch resistance is high. On the other hand, the ZrOx film exhibits a greater than approximately [missing information]. to approximately The etch resistance is high. On the other hand, the ZrOx film exhibits a greater than approximately [missing information]. to approximately Etching resistance.

[0020] The disclosed and claimed subject matter also relates to a process of filling (e.g., “gap filling”) photolithographic features on a substrate using the aforementioned ZPP and / or ZPPA formulations, which, after processing, produces a substrate containing a patterned high ZrOx film.

[0021] In particular, the disclosed and claimed subject matter further relates to the coating of patterned substrates with novel air-stabilized compositions having ZPP and / or ZPPA, the patterned substrate being a patterned photoresist, patterned spin-coated carbon, or patterned semiconductor containing vias, trenches, holes, or other hollow morphological features that fill these voids with low porosity; and the formation of a patterned ZrOx film on the substrate using these filled patterns in the process.

[0022] This overview does not specify every embodiment and / or incremental novelty aspect of the disclosed and claimed subject matter. Rather, this overview provides only a preliminary discussion of different embodiments and corresponding novelty points relative to conventional and known technologies. Additional details and / or possible perspectives regarding the disclosed and claimed subject matter and embodiments are described in the detailed description and corresponding figures of this disclosure, as further discussed below.

[0023] For clarity, the order in which the different steps described herein are presented has been shown. In general, the steps disclosed herein can be performed in any suitable order. Furthermore, although each of the different features, techniques, configurations, etc., disclosed herein may be discussed at different points in the invention, it is intended that each of the concepts can be performed independently or, where appropriate, in combination with each other. Therefore, the disclosed and claimed subject matter can be implemented and viewed in many different ways. Attached Figure Description

[0024] The accompanying drawings, included to provide a further understanding of the disclosed subject matter and incorporated into and forming part of this specification, illustrate embodiments of the disclosed subject matter and, together with this specification, serve to explain the principles of the disclosed subject matter. In the drawings:

[0025] Figure 1 The powder X-ray diffraction (XRD) pattern of zirconium propionate polymorph S1 (ZPPA) is shown.

[0026] Figure 2 Thermogravimetric analysis (TGA) of ZPPA prepared in Example 1 is shown;

[0027] Figure 3 Dynamic light scattering (DLS) analysis of the ZPPA formulation in Example 1 is shown;

[0028] Figure 4The FTIR of ZPP with -OH absorption band is shown;

[0029] Figure 5 The integral proton NMR of ZPP is shown;

[0030] Figure 6 This demonstrates the effect of D2O addition on proton NMR; and

[0031] Figure 7 Dynamic light scattering (DLS) analysis of ZPP.

[0032] Figure 8-10 The structures of zirconium propionate known in the art above are shown; and

[0033] Figure 11 The crystal structure of zirconium propionate polymorph S1 (ZPPA) is shown.

[0034] definition

[0035] Unless otherwise stated, the following terms used in this specification and claims shall have the following meanings for the purposes of this application.

[0036] In this application, unless otherwise specified, the use of the singular includes the plural, and the words “a” and “the” mean “at least one.” Furthermore, the use of the term “including” and other forms such as “include / includes / included” is not restrictive. Similarly, unless otherwise specified, terms such as “element” or “component” cover both elements or components that include one unit and elements or components that include more than one unit. As used herein, unless otherwise specified, 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.

[0037] When used in conjunction with measurable numerical variables, the term "about / approximately" refers to the indicated variable and all variable values ​​within the experimental error of the indicated value (e.g., within the 95% confidence limit of the mean) or as a percentage of the indicated value (e.g., ±10%, ±5%), whichever is greater.

[0038] As used in this article, "C" x-y "" indicates the number of carbon atoms in the chain. For example, C 1-6Alkyl refers to an alkyl chain having between 1 and 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl). Unless otherwise specified, the chain can be straight or branched.

[0039] Unless otherwise specified, "alkyl" means a hydrocarbon group that can be straight-chain, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, and the like), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, and the like), or polycyclic (e.g., norbornyl, adamantyl, and the like). Suitable acyclic groups may be methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl or tert-butyl, straight-chain or branched pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, and hexadecyl. Unless otherwise specified, alkyl means a moiety of 1 to 10 carbon atoms. Cyclic alkyl groups may be monocyclic or polycyclic. Suitable examples of monocyclic alkyl groups include substituted cyclopentyl, cyclohexyl, and cycloheptyl. Substituents may be any acyclic alkyl group described herein.

[0040] "Alkoxy" (also known as "alkyloxy") refers to an alkyl group as defined above, which is linked via an oxygen (-O-) moiety (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentoxy, cyclohexyloxy, and the like). These alkoxy moiety may be substituted or unsubstituted.

[0041] "alkylcarbonyl" refers to an alkyl group as defined above, which is linked via a carbonyl (-C (=O-)) moiety (e.g., methyl carbonyl, ethyl carbonyl, propyl carbonyl, butyl carbonyl, cyclopentyl carbonyl, and the like). These alkyl carbonyl moiety may be substituted or unsubstituted.

[0042] "Hydroxy" (also known as "hydroxyl") refers to the -OH group.

[0043] Unless otherwise indicated, when referring to alkyl, alkoxy, fluorinated alkyl, and the like, the term "substituted" means one of these moieties that also contains one or more substituents, including but not limited to: alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxyl, amino, and aminoalkyl. Similarly, the term "unsubstituted" means the same moieties in which no substituents other than hydrogen are present.

[0044] Alkylenes are divalent alkyl groups derived from any of the alkyl groups mentioned above. When referring to alkylenes, these include those with a (C1-C2) alkyl group in the main carbon chain. 18Alkyl-substituted alkylene chains. Alkylenes may also include one or more alkynyl groups in the alkylene moiety, where alkynyl refers to a triple bond. Essentially, alkylenes have a divalent hydrocarbon group as the main chain. Therefore, the divalent acyclic group can be methylene, 1,1-ethylene or 1,2-ethylene, 1,1-propylene, 1,2-propylene or 1,3-propylene, 2,5-dimethyl-hexene, 2,5-dimethyl-hex-3-yne, etc. Similarly, the divalent cycloalkyl group can be 1,2-cyclopentylene or 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene or 1,4-cyclohexylene, and the like. Divalent tricycloalkyl groups can be any of the tricycloalkyl groups mentioned above. An example of a tricycloalkyl group is 4,8-bis(methylene)-tricyclo[5.2.1.0]. 2,6 Decane. When referring to perfluoroalkylene, these include materials described above as alkylene but in which hydrogen atoms have been replaced by fluorine. Similarly, when describing partially fluorinated alkylene, this refers to alkylene in which some hydrogen atoms have been replaced by fluorine.

[0045] Aryl groups contain 6 to 24 carbon atoms and include phenyl, tolyl, xylyl, naphthyl, anthracene, biphenyl, diphenyl, triphenyl, and the like. These aryl groups may be further substituted with any suitable substituents (e.g., alkyl, alkoxy, acyl, or aryl groups mentioned above). Similarly, suitable polyvalent aryl groups may be used as needed in the subject matter disclosed and claimed herein. Representative examples of divalent arylarylene groups include phenylene, diphenylenedimethyl, naphthylene, biphenylene, and the like. As used herein and unless otherwise stated, the term "aromatic" refers to an unsaturated cyclic hydrocarbon (aromatic C4-C) having a non-localized conjugated π system and having 4 to 20 carbon atoms. 20 Hydrocarbons). Exemplary aromatic substances include, but are not limited to, benzene, toluene, xylene, mesitylene, ethylbenzene, cumene, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, acenaphthene, anthracene, phenanthrene, benzene, tetraphenylene, benzene, fluoranthene, pyrene, etc. Triphenylene oxides and similar compounds, and combinations thereof. Aromatic compounds may optionally be substituted, for example, by one or more alkyl groups, alkoxy groups, halogens, etc. For example, aromatic compounds may include anisole. Additionally, aromatic compounds may contain one or more heteroatoms. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, phosphorus, boron, and / or sulfur. Aromatic compounds having one or more heteroatoms include, but are not limited to, furans, benzofurans, thiophenes, benzothiophenes, oxazoles, thiazoles, and similar compounds, and combinations thereof. Aromatic compounds may contain monocyclic, bicyclic, tricyclic, and / or polycyclic compounds (in some embodiments, at least monocyclic, only monocyclic and bicyclic, or only monocyclic) and may be fused rings.

[0046] The term “non-aromatic” means four or more carbon atoms linked in at least one ring structure, wherein at least one of the four or more carbon atoms in the ring structure is not an aromatic carbon atom.

[0047] The term (meth)acrylate refers to methacrylate or acrylate, and similarly, (meth)acrylic acid class refers to methacrylic acid class or acrylic acid class.

[0048] The concentrations of the organic polymer and zirconate compounds, based on total solids, can vary depending on the desired zirconium content in the final substrate film. The concentration of zirconium in the composition and during the curing process determines the final zirconium content of the cured film. In novel compositions, the concentration of the organic polymer, based on total solids, can vary from about 0.1 wt% to about 90 wt%; the concentration of the zirconate compound, based on total solids, can vary from about 10 wt% to about 99.9 wt%. As an example, for non-polymeric zirconates, the concentration can be between about 10 wt% and about 50 wt% of total solids. For polymeric / oligomeric zirconates, the concentration can be between about 10 wt% and about 99.9 wt% of total solids, or 50% to 97%. Mixtures of non-polymeric and polymeric zirconates can also be used.

[0049] After curing at 250°C, the zirconium content of the cured film can range from approximately 3 to 80% by weight, or approximately 10 to 70% by weight, or approximately 20 to 60% by weight, as measured by elemental analysis. The zirconium content of the film is determined by the curing conditions; higher curing temperatures and / or longer curing times result in higher zirconium content.

[0050] In embodiments of the disclosed and claimed subject matter, the substrate can also serve as an anti-reflective layer, i.e., it contains sufficient chromophores, and the refractive index n (refractive index) of the substrate is in the range of about 1.4 to about 2.7, and the absorptivity k (absorbance) is in the range of about 0.1 to about 0.7 at a 193 nm exposure wavelength. The novel film is suitable as an anti-reflective coating and as a hard mask at this wavelength. Materials such as JAWoollam VUV-VASE VU-32 can be used. TM The ellipsometer calculates the n and k values. The exact values ​​of the optimal range for k and n depend on the exposure wavelength used and the type of application. Typically, for 193 nm, the preferred range for k is from about 0.1 to about 0.6, and for 248 nm, the preferred range for k is from about 0.03 to about 0.8.

[0051] The compositions of the disclosed and claimed subject matter may contain 1% to about 50% total solids in solution, or 2% to 30% total solids in solution. The solid components of the undercoating composition are mixed with a solvent or a mixture of one or more solvents that dissolve the solid components of the antireflective coating. Suitable solvents may include, for example, lower alcohols (C1-C6), such as isopropanol, n-butanol, tert-butanol, 1-pentanol, and 4-methyl-2-pentanol; glycols, such as ethylene glycol and propylene glycol; glycol ether derivatives, such as ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol dimethyl ether, propylene glycol n-propyl ether, or diethylene glycol dimethyl ether; glycol ether ester derivatives, such as ethyl cellosolve acetate, methyl cellosolve acetate, or propylene glycol monomethyl ether acetate; carboxylic acid esters, such as ethyl acetate, n-butyl acetate, and amyl acetate; carboxylates of dicarboxylic acids, such as diethyl oxalate and diethyl malonate; and dicarboxylic acid esters of glycols, such as ethylene glycol diacetate and diethyl propylene glycol diacetate. Esters; and hydroxycarboxylic acid esters, such as methyl lactate, ethyl lactate, ethyl glycolate and ethyl 3-hydroxypropionate; ketone esters, such as methyl pyruvate or ethyl pyruvate; alkoxy esters, such as 2-methoxyethanol, ethoxyethanol; alkoxycarboxylic acid esters, such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-hydroxy-2-methylpropionate or methyl ethoxypropionate; ketone derivatives, such as methyl ethyl ketone, acetylacetone, cyclopentanone, cyclohexanone or 2-heptanone; ketone ether derivatives, such as diacetone alcohol methyl ether; ketone alcohol derivatives, such as acetone alcohol or diacetone alcohol; lactones, such as butyrolactone and γ-valerolactone; amide derivatives, such as dimethylacetamide or dimethylformamide, anisole and mixtures thereof.

[0052] Other components can be added to enhance the coating's performance, such as lower alcohols (C 1- C6 alcohols), alkoxy alcohols, lactones, C 1- C 20 Alkyl carboxylic acids, surface leveling agents (<5% by weight of total solids), dialkoxybis(β-diketone esters) (1 to 20% by weight or 5 to 10% by weight of total solids), dialkoxybis(β-diketone) (1 to 20% by weight or 5 to 10% by weight of total solids), thermal acid generators, photoacid generators, etc. Examples of dialkoxybis(β-diketone esters) and dialkoxybis(β-diketone) include acetylacetone, benzoylacetone, and 4,4,4-trifluoro-1-phenyl-1,3-butanedione, and ethyl acetoacetate surface leveling agents or surfactants can be nonionic, cationic, or anionic surfactants, such as surfactants based on polyoxyalkylene ethers, surfactants based on fluoroalkyl groups, and surfactants based on organosilicones.

[0053] When referring to the composition of ZPP and / or ZPPA described herein (in weight % (wt%)), it should be understood that in any case, the total weight % of all components, including non-essential components (such as impurities), should not exceed 100% by weight. In compositions “consisting substantially of the described components,” such components may total 100% by weight or may total less than 100% by weight. When the total weight of components is less than 100% by weight, such compositions may include small amounts of non-essential contaminants or impurities. For example, in one such embodiment, the ZPP or ZPPA formulation may contain 2% by weight or less of impurities. In another embodiment, the ZPP or ZPPA formulation may contain 1% by weight or less of impurities. In yet another embodiment, the ZPP or ZPPA formulation may contain 0.05% by weight or less of impurities. In other of these embodiments, the components may form at least 90 wt%, more preferably at least 95 wt%, more preferably at least 99 wt%, more preferably at least 99.5 wt%, most preferably at least 99.9 wt%, and may include other components that will not substantially affect the performance of the wet etchant. Otherwise, if no significant non-essential impurity components are present, it should be understood that the composition of all essential components will essentially total 100 wt%.

[0054] The section headings used herein are for organizational purposes and should not be construed as limiting the subject matter described. All references or portions thereof cited in this application (including, but not limited to, patents, patent applications, articles, books, and papers) are hereby expressly incorporated in their entirety for any purpose. In the event that any terminology defined in any of the incorporated references and similar materials in a manner that contradicts the definitions used in this application, the definitions used in this application shall prevail. Detailed Implementation

[0055] It should be understood that the foregoing general description and the following detailed description are illustrative and explanatory in nature, and do not limit the subject matter as claimed. Those skilled in the art will readily recognize the objectives, features, advantages, and concepts of the disclosed subject matter based on the description provided herein, and will be able to readily implement the disclosed subject matter based on the description presented herein. Descriptions of any “preferred embodiments” and / or examples demonstrating preferred modes of practice for the disclosed subject matter are included for illustrative purposes, and such “preferred embodiments” and / or examples are not intended to limit the scope of the claims.

[0056] Those skilled in the art will also appreciate that various modifications can be made to how the disclosed and claimed subject matter is practiced, based on the aspects described herein, without departing from the spirit and scope of the disclosed subject matter.

[0057] As described above, the disclosed and claimed subject matter relates to (i) zirconium propionate polymorph S1 (“ZPPA”), (ii) a method for preparing ZPPA, (iii) a formulation comprising ZPP and / or ZPPA, and (iv) the formation of a ZrOx film from a formulation comprising ZPP and / or ZPPA.

[0058] I. Zirconium propionate polymorph S1 (ZPPA)

[0059] In one aspect, the disclosed and claimed subject matter relates to zirconium propionate polymorph S1 (“ZPPA”) and a method for preparing the same.

[0060] A.ZPPA molecule

[0061] ZPPA has demonstrated that it features C 72 H 128 O 64 Zr 12 ×4(C3H5O2)×2(H2O) and Figure 11 The structure shown:

[0062] Characterization of B.ZPPA

[0063] Table 1 below describes the characteristics of ZPPA.

[0064]

[0065]

[0066]

[0067] Table 1

[0068] As shown in Table 1, ZPPA has a molecular weight of 3447.72 g / mol.

[0069] Figure 1 The powder X-ray diffraction (XRD) pattern of ZPPA is shown. (As shown...) Figure 1 As shown, ZPPA has characteristic peaks at approximately 4.8, 6.5, 7.8, 8.1, 8.4, 9.4, 9.7, 10.9, 11.7, 12.0, 12.6 and 22.6 ± 0.2 degrees 2θ.

[0070] Figure 2 The TGA analysis of the ZPPA prepared in Example 1 is shown. Figure 2As shown, the thermal behavior of the material under air and inert conditions is consistent with temperatures up to approximately 300°C. The mass loss at temperatures above 300°C shows different values ​​at the minimum of the first derivative, indicating that the processes must be different. Additionally, a mass increase was detected at approximately 800°C. This can be attributed to possible oxidation. The residual mass after 1000°C can be considered consistent for both measurements.

[0071] II.ZPP

[0072] Zirconium propionate (“ZPP”) is a white powder with a complex structure generally believed to be based on hydroxyl-bridged zirconium polymers, in which the propionate carboxyl groups are bonded to zirconium. Although ZPP with CAS number 84057-80-7 is described as Zr(CH3CH2COO)4, ZPP is hydrolyzable and can react with zirconium having the formula Zr(CH3CH2COO). 4-x (OH) x ZPP exists in combinations of several hydrolysates / protonates, where x = 1 to 3. Furthermore, ZPP can also exist in oligomeric or polymeric forms containing repeating units of various hydrolysates linked to each other by bridging hydroxyl groups (i.e., propionates with 1 and 3 bonds to each zirconium are present in Table 2). Such oligomeric or polymeric forms can also exist as mixtures with multiple monomer classes (e.g., Zr(CH3CH2COO)4).

[0073]

[0074]

[0075] Table 2

[0076] In Table 2, This refers to the actual or potential direct valence bond between a protonated or deprotonated oxygen atom in an oligomeric or polymeric zirconium complex and another zirconium atom, or alternatively, the direct valence bond with H to form a Zr-OH moiety (i.e., it can also exist in equilibrium with a free propionate ester group or propionic acid molecule). Therefore, oligomeric or polymeric types include the bonded / bridging moiety Zr-(OH). + -Zr and / or Zr-(O)-Zr, and this oligomer or polymer class may also include combinations of these linking portions that are structurally present together with some free ZrOH moiety.

[0077] In one embodiment, ZPP as used herein comprises a monomer. In one embodiment, ZPP as used herein comprises oligomers or polymers (or mixtures thereof) wherein the ZPP is from about 10-mers to about 15-mers. In one embodiment, ZPP as used herein comprises oligomers or polymers (or mixtures thereof) of ZPP with a molecular weight of from about 10-mers to about 15-mers. In another embodiment, the ZPP has an average molecular weight of from about 4,000 Da to about 10,000 Da.

[0078] In one embodiment, ZPP as used herein includes oligomers or polymers (or mixtures thereof) comprising repeating units in any order (where the monomers are defined by the structures in Table 2 corresponding to the letters of the respective rows and the numbers of the respective columns, for example, A2 corresponds to the structure in column 2 of row A):

[0079] (A2) n (B2) m (C2) o (D2) p (A3) n1 (B3) m1 (C3) o1 (D3) p1

[0080] Wherein each of n, n1, m, m1, o, o1, p, and p1 = 0 to 10, and the sum of n, n1, m, m1, o, o1, p, and p1 is between 2 and 10. In another aspect of this embodiment, the ZPP oligomers and / or polymers constitute a mixture having one or more of ZPP monomer classes A1, B1, C1, and D1. In another aspect of this embodiment, n = 0. In another aspect of this embodiment, m = 0. In another aspect of this embodiment, o = 0. In another aspect of this embodiment, m = 0. In another aspect of this embodiment, p = 0. In another aspect of this embodiment, n1 = 0. In another aspect of this embodiment, m1 = 0. In another aspect of this embodiment, o1 = 0. In another aspect of this embodiment, m1 = 0. In another aspect of this embodiment, p1 = 0. In another aspect of this embodiment, the ZPP oligomers and / or polymers will include one of classes A2 and A3 at the terminal chain position.

[0081] In one embodiment, the ZPP comprises an oligomer or polymer class comprising repeating units derived from free monomer classes B1 and C1. In another embodiment, the repeating units derived from free monomer classes B1 and C1 are in a wt% ratio of approximately 3:1.

[0082] The ratio of hydroxyl groups (including (i) bridging hydroxyl groups (i.e., protonated hydroxyl groups) and (ii) any -OH groups from existing monomers or polymers) to propionate ligands can be estimated by proton NMR. This can be achieved by comparing the integral values ​​of the -OH peak and the -O (C=O)CH2-CH3 peak (attributable to propionate ligands) in the proton NMR, and subsequently adjusting for the amount of water in a given ZPP sample due to elemental analysis of the ZPP material being used (e.g., by Karl-Fischer measurement). Figure 4 The FTIR spectra of ZPP are shown before (bottom) and after (top) heat treatment (approximately >100°C). After heat treatment, the spectra are approximately 3400 to 3600 cm⁻¹. -1 The -OH absorption band decreases. This indicates that water, propionic acid, and possibly ZrOH will be removed by this heat treatment. Water will be removed by evaporation, while some ZrOH can be removed by the formation of Zr-O-Zr bridging groups and free water. Water formed by any Zr-O-Zr bridging groups will then be evaporated after this heat treatment.

[0083] For example, a ZPP sample with elemental analysis of C: 21.1, H: 3.91, Zr: 32 is most closely associated with oligomeric or polymeric materials that primarily consist of ZPP monomer class B1 (where B1 may exist in free form and B2 or B3 are part of the oligomeric or polymeric sample). Based on this estimate, ZPP monomer class B1 has calculated elemental analysis of C: 26.56, H: 4.46, Zr: 33.16 and Mw of 271.38. If the ZPP sample has a water content of approximately 4.64 wt%, it would imply that the ZPP sample comprises at most approximately 95 to 96 wt% ZPP classes B1 to B3. This is equivalent to approximately 58 mol% hydroxyl groups (i.e., bridging hydroxyl groups from existing monomers or polymers and any -OH groups) and approximately 42 mol% water (due to the much greater effect of the two -OH groups in the much higher Mw B1 to B3ZPP molecules compared to the single -OH group in the much lower Mw H2O molecule). This value is then used to adjust the integrated value of the proton NMR obtained using a suitable proton NMR solvent (e.g., CDCl3, pyridine-d5 with a small amount of D2O, or THF-d8), where the solvent does not truncate the spectrum of the -OH peak. A preferred solvent is pyridine-d5 with a small amount of D2O.

[0084] For example, Figure 5The proton NMR of ZPP in pyridine-d5 with a small amount of D2O added (a blank control corrected for H2O impurities in D2O, integrated intensity approximately 42.3) is shown, with the -OH peak between approximately 5.5 and 6 ppm (integral = 156) and the integration of the propionate ligand (i.e., -CH2CH3) peak at approximately 0.5 to 2.5 ppm (integral = 539.5 / 5 protons = 107.9). Figure 6 (Compare the effect of D2O addition on proton NMR). The -OH peak was then adjusted to exclude H2O by multiplying by the estimated mol% hydroxyl content (i.e., 113.7 × 0.58 = 65.9). This resulted in a -OH to propionate ligand ratio of approximately 0.61 (i.e., 65.9 / 107.9 = 0.61). As those skilled in the art will recognize, the -OH to propionate ligand ratio will be somewhat variable because ZPP samples are oligomers or polymers and may contain more than one of the ZPP classes shown in Table 2. This will therefore affect the estimation of the molar percentage of non-H2O hydroxyl groups to water and the ratio of derived hydroxyl groups to propionate ligands in a given sample. However, this value allows for better characterization of ZPP used in its formulations and is suitable for adjusting the ZPP in a given formulation as needed in a specific application setting.

[0085] Using the aforementioned measurement method, in one embodiment, ZPP comprises oligomers or polymers with a hydroxyl to propionate ligand ratio of about 0.5 to about 1.1, as measured by proton NMR. In another embodiment, the hydroxyl to propionate ligand ratio is about 0.55 to about 1.05, as measured by proton NMR. In another embodiment, the hydroxyl to propionate ligand ratio is about 0.6 to about 0.9, as measured by proton NMR. In another embodiment, the hydroxyl to propionate ligand ratio is about 0.7 to about 0.8, as measured by proton NMR. In another embodiment, the hydroxyl to propionate ligand ratio is about 0.5, as measured by proton NMR. In another embodiment, the hydroxyl to propionate ligand ratio is about 0.55, as measured by proton NMR. In another embodiment, the hydroxyl to propionate ligand ratio is about 0.6, as measured by proton NMR. In another aspect of this embodiment, the ratio of hydroxyl to propionate ligands is about 0.65, as measured by proton NMR. In another aspect of this embodiment, the ratio of hydroxyl to propionate ligands is about 0.7, as measured by proton NMR. In another aspect of this embodiment, the ratio of hydroxyl to propionate ligands is about 0.75, as measured by proton NMR. In another aspect of this embodiment, the ratio of hydroxyl to propionate ligands is about 0.8, as measured by proton NMR. In another aspect of this embodiment, the ratio of hydroxyl to propionate ligands is about 0.85, as measured by proton NMR. In another aspect of this embodiment, the ratio of hydroxyl to propionate ligands is about 0.9, as measured by proton NMR. In another aspect of this embodiment, the ratio of hydroxyl to propionate ligands is about 0.55, as measured by proton NMR. In another aspect of this embodiment, the ratio of hydroxyl to propionate ligands is about 1.0, as measured by proton NMR. In another embodiment, the ratio of hydroxyl to propionate ligand is about 1.05, as measured by proton NMR. In another embodiment, the ratio of hydroxyl to propionate ligand is about 1.1, as measured by proton NMR.

[0086] In one embodiment, ZPP comprises zirconium propionate with CAS number 84057-80-7.

[0087] In one embodiment, ZPP comprises about 0.5 wt% to about 6 wt% water. In one embodiment, ZPP comprises about 1 wt% to about 5 wt% water. In one embodiment, ZPP comprises about 2 wt% to about 5 wt% water. In one embodiment, ZPP comprises about 3 wt% to about 5 wt% water. In one embodiment, ZPP comprises about 4 wt% to about 5 wt% water. In one embodiment, ZPP comprises about 5 wt% water or less. In one embodiment, ZPP comprises about 4 wt% water or less. In one embodiment, ZPP comprises about 3 wt% water or less. In one embodiment, ZPP comprises about 2 wt% water or less. In one embodiment, ZPP comprises about 1 wt% water or less.

[0088] In one embodiment, ZPP comprises about 0.5 wt% to about 6 wt%, preferably about 5 wt% of propionic acid. In one embodiment, ZPP comprises about 1 wt% to about 5 wt% of propionic acid. In one embodiment, ZPP comprises about 2 wt% to about 5 wt% of propionic acid. In one embodiment, ZPP comprises about 3 wt% to about 5 wt% of propionic acid. In one embodiment, ZPP comprises about 4 wt% to about 5 wt% of propionic acid. In one embodiment, ZPP comprises about 5 wt% or less of propionic acid. In one embodiment, ZPP comprises about 4 wt% or less of propionic acid. In one embodiment, ZPP comprises about 3 wt% or less of propionic acid. In one embodiment, ZPP comprises about 2 wt% or less of propionic acid. In one embodiment, ZPP comprises about 1 wt% or less of propionic acid.

[0089] like Figure 7As shown, the average diameter (nm) of the ZPP can be measured by dynamic light scattering (DLS). In one embodiment, the ZPP has an average diameter (nm) of about 7.0 nm to about 12.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 7.5 nm to about 11.5 nm. In one embodiment, the ZPP has an average diameter (nm) of about 8.0 nm to about 11.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 8.5 nm to about 10.5 nm. In one embodiment, the ZPP has an average diameter (nm) of about 9.0 nm to about 10.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 7.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 7.5 nm. In one embodiment, the ZPP has an average diameter (nm) of about 8.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 8.5 nm. In one embodiment, the ZPP has an average diameter (nm) of about 9.0 nm. In one embodiment, the ZPP has an average diameter (nm) of about 9.5 nm. In one embodiment, the ZPP has an average diameter of about 10.0 nm. In one embodiment, the ZPP has an average diameter of about 10.5 nm. In one embodiment, the ZPP has an average diameter of about 11.0 nm. In one embodiment, the ZPP has an average diameter of about 11.5 nm. In one embodiment, the ZPP has an average diameter of about 12.0 nm.

[0090] ZPP and ZPPA formulations

[0091] In another aspect, the disclosed and claimed subject matter relates to formulations including ZPP and / or ZPPA and their preparation.

[0092] In one embodiment, the formulation comprises (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more etch resist additives, and (iii) one or more solvents. In another embodiment, the formulation essentially comprises: (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more etch resist additives, and (iii) one or more solvents. In yet another embodiment, the formulation comprises: (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more etch resist additives, and (iii) one or more solvents. In each of these embodiments, a preferred etch resist additive is 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, a preferred solvent is... ArF diluent (i.e., a mixture of PGMEA and PGME).

[0093] In another embodiment, the above formulation further includes (iv) one or more surfactants and (v) one or more water-resistant enhancers or both.

[0094] Therefore, in another embodiment, the formulation comprises (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more anti-etching modifier additives, and (iii) one or more solvents and (iv) one or more surfactants. In another aspect, the formulation is substantially composed of: (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more anti-etching modifier additives, and (iii) one or more solvents and (iv) one or more surfactants. In another aspect, the formulation comprises: (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more anti-etching modifier additives, and (iii) one or more solvents and (iv) one or more surfactants. In each of these embodiments, the preferred anti-etching modifier additive is 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, the preferred solvent is ArF diluent (i.e., a mixture of PGMEA and PGME). In each of these embodiments, the surfactant is preferably an organosilicone polymer, and in particular an organosilicone polymer sold under the trade name X-22-4952 (manufactured by Shin-Etsu Chemical Co.; see https: / / www.shinetsusilicone-global.com / products / type / oil / detail / search / deg25.shtml).

[0095] In another embodiment, the formulation comprises (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (v) one or more water-resistant reinforcing agents. In another aspect, the formulation essentially comprises: (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (v) one or more water-resistant reinforcing agents. In another aspect, the formulation comprises: (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (v) one or more water-resistant reinforcing agents. In each of these embodiments, the preferred etch-resistant modifier additive is 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, the preferred solvent is... ArF diluent (i.e., a mixture of PGMEA and PGME). In each of these embodiments, the preferred water-resistant enhancer is isobutyric acid.

[0096] In another embodiment, the formulation comprises (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more anti-etching modifier additives, (iii) one or more solvents, (iv) one or more surfactants, and (v) one or more water-resistant reinforcing agents. In another aspect, the formulation essentially comprises: (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more anti-etching modifier additives, (iii) one or more solvents, (iv) one or more surfactants, and (v) one or more water-resistant reinforcing agents. In yet another aspect, the formulation comprises: (i) a zirconium-containing material selected from the group consisting of (a) ZPPA, (b) ZPP, and (c) combinations thereof, (ii) one or more anti-etching modifier additives, (iii) one or more solvents, (iv) one or more surfactants, and (v) one or more water-resistant reinforcing agents. In each of these embodiments, the preferred etch-resistant modifier additive is 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, the preferred solvent is... ArF diluent (i.e., a mixture of PGMEA and PGME). In each of these embodiments, the preferred surfactant is X-22-4952. In each of these embodiments, the preferred water-resistant enhancer is isobutyric acid.

[0097] In one embodiment, the formulation comprises (i) ZPPA, (ii) one or more etch resist additives, and (iii) one or more solvents. In another embodiment, the formulation is substantially composed of (i) ZPPA, (ii) one or more etch resist additives, and (iii) one or more solvents. In yet another embodiment, the formulation comprises (i) ZPPA, (ii) one or more etch resist additives, and (iii) one or more solvents. In each of these embodiments, the preferred etch resist additive is 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, the preferred solvent is... ArF diluent (i.e., a mixture of PGMEA and PGME).

[0098] In another embodiment, the above formulation further includes (iv) one or more surfactants and (v) one or more water-resistant enhancers or both.

[0099] Therefore, in another embodiment, the formulation comprises (i) ZPPA, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (iv) one or more surfactants. In another aspect, the formulation is substantially composed of (i) ZPPA, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (iv) one or more surfactants. In another aspect, the formulation comprises (i) ZPPA, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (iv) one or more surfactants. In each of these embodiments, the etch-resistant modifier additive is preferably 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, the solvent is preferably... ArF diluent (i.e., a mixture of PGMEA and PGME). In each of these embodiments, the surfactant is preferably an organosilicone polymer, and in particular an organosilicone polymer sold under the trade name X-22-4952 (manufactured by Shin-Etsu Chemical Co.; see https: / / www.shinetsusilicone-global.com / products / type / oil / detail / search / deg25.shtml).

[0100] In another embodiment, the formulation comprises (i) ZPPA, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (v) one or more water-resistant enhancers. In another aspect, the formulation is substantially composed of (i) ZPPA, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (v) one or more water-resistant enhancers. In another aspect, the formulation comprises (i) ZPPA, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (v) one or more water-resistant enhancers. In each of these embodiments, the etch-resistant modifier additive is preferably 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, the solvent is preferably... ArF diluent (i.e., a mixture of PGMEA and PGME). In each of these embodiments, the preferred water-resistant enhancer is isobutyric acid.

[0101] In another embodiment, the formulation comprises (i) ZPPA, (ii) one or more etch-resistant modifier additives, and (iii) one or more solvents, (iv) one or more surfactants, and (v) one or more water-resistant enhancers. In another aspect, the formulation comprises essentially the following: (i) ZPPA, (ii) one or more etch-resistant modifier additives, and (iii) one or more solvents, (iv) one or more surfactants, and (v) one or more water-resistant enhancers. In each of these embodiments, the etch-resistant modifier additive is preferably 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, the solvent is preferably... ArF diluent (i.e., a mixture of PGMEA and PGME). In each of these embodiments, the preferred surfactant is X-22-4952. In each of these embodiments, the preferred water-resistant enhancer is isobutyric acid.

[0102] In one embodiment, the formulation comprises (i) ZPP, (ii) one or more etch resist additives, and (iii) one or more solvents. In another embodiment, the formulation is substantially composed of (i) ZPP, (ii) one or more etch resist additives, and (iii) one or more solvents. In yet another embodiment, the formulation comprises (i) ZPP, (ii) one or more etch resist additives, and (iii) one or more solvents. In each of these embodiments, the preferred etch resist additive is 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, the preferred solvent is... ArF diluent (i.e., a mixture of PGMEA and PGME).

[0103] In another embodiment, the above formulation further includes (iv) one or more surfactants and (v) one or more water-resistant enhancers or both.

[0104] Therefore, in another embodiment, the formulation comprises (i) ZPP, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (iv) one or more surfactants. In another aspect, the formulation is substantially composed of (i) ZPP, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (iv) one or more surfactants. In another aspect, the formulation comprises (i) ZPP, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (iv) one or more surfactants. In each of these embodiments, the etch-resistant modifier additive is preferably 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, the solvent is preferably... ArF diluent (i.e., a mixture of PGMEA and PGME). In each of these embodiments, the preferred surfactant is X-22-4952.

[0105] In another embodiment, the formulation comprises (i) ZPP, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (v) one or more water-resistant enhancers. In another aspect, the formulation is substantially composed of (i) ZPP, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (v) one or more water-resistant enhancers. In another aspect, the formulation comprises (i) ZPP, (ii) one or more etch-resistant modifier additives, (iii) one or more solvents, and (v) one or more water-resistant enhancers. In each of these embodiments, the etch-resistant modifier additive is preferably 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, the solvent is preferably... ArF diluent (i.e., a mixture of PGMEA and PGME). In each of these embodiments, the preferred water-resistant enhancer is isobutyric acid.

[0106] In another embodiment, the formulation comprises (i) ZPP, (ii) one or more etch-resistant modifier additives, and (iii) one or more solvents, (iv) one or more surfactants, and (v) one or more water-resistant enhancers. In another aspect, the formulation comprises essentially the following: (i) ZPP, (ii) one or more etch-resistant modifier additives, and (iii) one or more solvents, (iv) one or more surfactants, and (v) one or more water-resistant enhancers. In each of these embodiments, the etch-resistant modifier additive is preferably 4,4',4”-trihydroxytriphenylmethane (“THTPM”). In each of these embodiments, the solvent is preferably... ArF diluent (i.e., a mixture of PGMEA and PGME). In each of these embodiments, the preferred surfactant is X-22-4952. In each of these embodiments, the preferred water-resistant enhancer is isobutyric acid.

[0107] (ii) Etching resistance modifiers

[0108] One or more etch-resistant modifiers are added to improve the coating formation characteristics of the coating to be formed, prevent mixing with the upper layers (such as silicon interlayers and resists), and / or prevent the diffusion of low molecular weight components into the upper layers.

[0109] Exemplary embodiments of etch-resistant modifiers include: melamine, guanidine, glycourea, and urea compounds substituted with at least one group selected from hydroxymethyl, alkoxymethyl, and acyloxymethyl groups; epoxy compounds; thioepoxide compounds; isocyanate compounds; azide compounds; and compounds having double-bonded groups (such as alkenyl ether groups). These can be used as additives or alternatively introduced as side groups into polymer side chains. Preferably, compounds containing one or more hydroxyl groups can be used as etch-resistant modifiers.

[0110] Examples of epoxy compounds include tris(2,3-epoxypropyl) isocyanurate, trimethylolpropane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether. Examples of melamine compounds include hexamethylolmelamine, hexamethoxymethylmelamine, and any mixture of any such compounds. Examples of guanidine compounds include tetramethylolguanidine, tetramethoxymethylguanidine, and any mixture of any such compounds. Examples of urea compounds include tetramethylolurea, tetramethoxyurea, tetramethoxymethylurea, and any mixture of any such compounds. Examples of urea compounds include tetramethylolurea and tetramethoxymethylurea.

[0111] Examples of compounds containing an alkenyl ether group include ethylene glycol diethylene ether and triethylene glycol diethylene ether.

[0112] Examples of etch-resistant modifiers containing one or more hydroxyl groups include those represented by structure (1).

[0113]

[0114] In structure (1), R 11 It is a hydrogen or methyl group with L3 being a direct bond, substituted or unsubstituted C. 1-3 Alkyl or substituted or unsubstituted C 7-16 Aryl group. L3 is preferably a direct bond, C1 alkyl group, or C2 alkyl group. 15 Aryl alkyl group. The substituents of the alkyl or aryl alkyl group are preferably hydrogen, methyl, or C. 6-11 Aryl group or structure (1a):

[0115]

[0116] Or structure (1b):

[0117]

[0118] Substituents.

[0119] In one preferred aspect, L3 is unsubstituted C. 1-3 Alkyl or unsubstituted C 1-3 Aryl group.

[0120] The following are exemplary embodiments of an etch-resistant conditioning additive represented by structure (1). The disclosed and claimed subject matter is not limited to these examples.

[0121]

[0122]

[0123] Table 3

[0124] Other examples of etch-resistant modifiers containing one or more hydroxyl groups include those having monomers, dimers (dimers) or more (such as trimeric phenolic compounds, tetrameric phenolic moieties, or higher (e.g., 10 phenolic moieties)), wherein the phenolic moieties in these compounds are linked together via linking groups (such as alkylene moieties, oxy moieties, -SO2- moieties, and the like). Non-limiting examples of such compounds are shown in structures (2), (2A), (2B), (3), (3A), (3B), (3C), (3D), and (4) through (18), wherein the linking groups Xp and Xpa are independently selected from -O-, -CH2-, -C(CH3)2-, and -SO2-; Rp1 is a hydrogen or alkyl moiety, and Rp2, Rp3, Rp4, and Rp5 are independently selected from hydrogen or alkyl moieties.

[0125]

[0126]

[0127]

[0128] Table 4

[0129] In one embodiment, the etch resistance modifier has the structure (3) described above. In another embodiment, the etch resistance modifier has the structure (3C) described above (i.e., 4,4',4”-trihydroxytriphenylmethane; THTPM).

[0130] In another aspect of this embodiment, the etch resistance modifier has a structure (3D) as described above. In one aspect of this embodiment, R 1 and R 2 Each of them is a propionyl group (i.e., 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP; 3D1)):

[0131]

[0132] In another aspect of this implementation scheme, R 1 and R 2 One of them is propionyl and R 1 and R 2 The other one is hydrogen (i.e., 3D2):

[0133]

[0134] In another aspect of this implementation scheme, R 1 and R 2 Each of them is hydrogen (i.e., 3D3).

[0135]

[0136] In yet another embodiment, the etch resist modifier is a mixture of more than one etch resist modifier. In another aspect of this embodiment, the mixture comprises an etch resist modifier having the structure (3C) (i.e., 4,4',4”-trihydroxytriphenylmethane; THTPM). In one aspect of this embodiment, the mixture comprises an etch resist modifier having the structure (3D1) (i.e., 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP)). In one aspect of this embodiment, the mixture comprises an etch resist modifier having the structure (3C) (i.e., 4,4',4”-trihydroxytriphenylmethane; THTPM) and (3D1) (i.e., 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP)). In another aspect of this embodiment, the mixture includes an etch modifier having a structure (3C) (i.e., 4,4',4”-trihydroxytriphenylmethane; THTPM) and one or more of etch modifiers 3D1 (THTPM-TP), 3D2 and 3D3.

[0137] Other polyphenolic compounds or polymers may also be used. Examples of suitable polyphenolic compounds or polymers include those disclosed in U.S. Patent No. 9,274,426 and / or U.S. Patent Application Publication No. 2012 / 0251956. The phenolic OH group may be protected by acid-unstable groups (such as ester or acetal groups), and heterocyclic structures may also be included in the structure.

[0138] Other etch-resistance modifiers are also included. In some embodiments, etch-resistance modifiers (19) or (20) may be included. These crosslinking agents may be available, for example, from Sanwa Chemical Co., Ltd., Honshu Chemical Industry Co., Ltd., Asahi Yukizai Corporation and Nippon Carbide Industries Co., Inc.

[0139]

[0140] Table 5

[0141] In one embodiment of the disclosed and claimed subject matter, the amount of the etch-resistant additive is preferably from about 0.1 wt% to about 30 wt% of the total solids in the composition. In another aspect of this embodiment, the amount of the etch-resistant additive is from about 1 wt% to about 20 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is from about 2 wt% to about 15 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is from about 5 wt% to about 12 wt%. In one embodiment of the disclosed and claimed subject matter, the amount of the etch-resistant additive is preferably from about 0.1 wt% to about 1 wt% of the total solids in the composition. In one embodiment of the disclosed and claimed subject matter, the amount of the etch-resistant additive is preferably from about 0.5 wt% to about 1 wt% of the total solids in the composition. In one embodiment of the disclosed and claimed subject matter, the amount of the etch-resistant additive is preferably from about 0.5 wt% to about 0.75 wt% of the total solids in the composition. In another aspect of this embodiment, the amount of the etch-resistant additive is about 0.5 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 0.6 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 0.7 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 0.8 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 0.9 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 1 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 2 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 3 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 4 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 5 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 6 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 7 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 8 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 9 wt%. In another aspect of this embodiment, the amount of the etch-resistant additive is about 10 wt%.

[0142] In one embodiment, the formulation comprises about 0.5 wt% to about 5 wt% of 4,4',4"-trihydroxytriphenylmethane (THTPM). In another embodiment, the formulation comprises about 2 wt% to about 5 wt% of 4,4',4"-trihydroxytriphenylmethane (THTPM). In another embodiment, the formulation comprises about 0.5 wt% to about 0.75 wt% of 4,4',4"-trihydroxytriphenylmethane (THTPM). In another embodiment, the formulation comprises about 0.5 wt% to about 1 wt% of 4,4',4"-trihydroxytriphenylmethane (THTPM). In another embodiment, the formulation comprises about 1 wt% to about 2 wt% of 4,4',4"-trihydroxytriphenylmethane (THTPM). In another embodiment, the formulation comprises about 3 wt% to about 4 wt% of 4,4',4"-trihydroxytriphenylmethane (THTPM).

[0143] In another aspect of this embodiment, the formulation comprises about 0.5 wt% of 4,4',4”-trihydroxytriphenylmethane (THTPM). In another aspect of this embodiment, the formulation comprises about 0.6 wt% of 4,4',4”-trihydroxytriphenylmethane (THTPM). In another aspect of this embodiment, the formulation comprises about 0.7 wt% of 4,4',4”-trihydroxytriphenylmethane (THTPM). In another aspect of this embodiment, the formulation comprises about 0.8 wt% of 4,4',4”-trihydroxytriphenylmethane (THTPM). In another aspect of this embodiment, the formulation comprises about 0.9 wt% of 4,4',4”-trihydroxytriphenylmethane (THTPM). In another aspect of this embodiment, the formulation comprises about 1 wt% of 4,4',4”-trihydroxytriphenylmethane (THTPM).

[0144] In one embodiment, the formulation comprises about 0.5 wt% to about 5 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In another embodiment, the formulation comprises about 2 wt% to about 5 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In another embodiment, the formulation comprises about 0.5 wt% to about 0.75 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In yet another embodiment, the formulation comprises about 0.5 wt% to about 1 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In another aspect of this embodiment, the formulation comprises about 0.5 wt% to about 1 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In another aspect of this embodiment, the formulation comprises about 1 wt% to about 2 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In another aspect of this embodiment, the formulation comprises about 3 wt% to about 4 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In another aspect of this embodiment, the formulation comprises about 0.5 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In another aspect of this embodiment, the formulation comprises about 0.6 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In another aspect of this embodiment, the formulation comprises about 0.7 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In another aspect of this embodiment, the formulation comprises about 0.8 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In another aspect of this embodiment, the formulation comprises about 0.9 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP). In another aspect of this embodiment, the formulation comprises about 1 wt% of 4,4',4”-tripropionyloxytriphenylmethane (THTPM-TP).

[0145] In one embodiment, the formulation comprises about 0.5 wt% to about 0.75 wt% of any one of NF0327, NF0A28, NF71A7, or NF0127, as shown in Table 4 above. In another embodiment, the formulation comprises about 0.6 wt% of any one of NF0327, NF0A28, NF71A7, or NF0127, as shown in Table 4 above.

[0146] In some implementations, the formulation includes more than one anti-etching modifier.

[0147] (iii) one or more solvents

[0148] As mentioned above, ZPP and / or ZPPA formulations include one or more solvents suitable for spin casting. In this regard, the one or more solvents may include glycol ether derivatives, glycol ether ester derivatives, carboxylic acid esters, carboxylic acid esters of diacids, dicarboxylic acid esters of diols, hydroxycarboxylic acid esters, ketone esters, alkoxycarboxylic acid esters, ketone derivatives, ketone ether derivatives, ketone alcohol derivatives, amide derivatives, and mixtures thereof.

[0149] In some embodiments, the one or more solvents are glycol solvents selected from the following: alkylene glycols, oligomeric ((alkoxide)alkylene)glycolide [HO-(alkylene-O-alkylene-O]] n The solvent comprises alkyl dialkyl ethers and monoalkyl diols, alkyl carboxylic acid esters / alkyl ether derivatives of monoalkyl diols, and mixtures of at least two of these solvents. In a more specific embodiment, one or more solvents comprise alkyl diols. In another more specific embodiment, one or more solvents comprise oligomeric ((alkoxy)alkylene)diols [HO-(alkylene-O-alkylene-O)nH] (n = 1 to 4). In another more specific embodiment, one or more solvents comprise monoalkyl carboxylic acid esters of alkylene diols. In yet another more specific embodiment, one or more solvents comprise monoalkyl carboxylic acid esters of oligomeric ((alkoxy)alkylene)diols [HO-(alkylene-O-alkylene-O)nH] (n = 1 to 4). In a more specific embodiment in this respect, the alkylene portion of these diol derivatives may be a C-2 to C-6 straight-chain alkylene, or a C-3 to C-7 branched alkylene, or, in the case of oligomeric ((alkoxy)alkylene), a mixture of these. In a more specific embodiment, the alkyl portion of these monoalkyl ethers and dialkyl ethers is individually selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, and isobutyl. In a more specific embodiment, these glycol solvents contain alkyl carboxylic acids selected from acetates, propionates, isobutyrates, and butyrates. In a more specific embodiment, the glycol derivative solvent is selected from ethylene glycol, propylene glycol, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and di(propylene glycol)methyl ether (DPGME), or a mixture of at least two of these solvents. In a more specific embodiment, the glycol derivative solvent is selected from propylene glycol, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and di(propylene glycol)methyl ether (DPGME), or a mixture of at least two of these solvents.

[0150] The term "dipropylene glycol," also named by dipropylene glycol dimethyl ether or the abbreviation DPGDME, refers to a mixture having the general formula CH3OC3H6OC3H6OCH3. This mixture also has synonyms such as bis(methoxypropyl) ether, DMFG, and Proglyde. TM DMM and Proglyme TM .

[0151] In some embodiments, the formulation preferably includes one or both of PGMEA (propylene glycol monomethyl ether acetate) and PGME (propylene glycol monomethyl ether). A preferred solvent is... ArF diluent. ArF diluent is a common name for a mixture of 70 wt% PGMEA and 30 wt% PGME. Another preferred solvent is... EBR7030 is a mixture of 30 wt% PGMEA and 70 wt% PGME. Other weight ratio mixtures of PGMEA and PGME can also be used, such as a mixture of 60 wt% PGMEA and 40 wt% PGME, or 100% PGMEA.

[0152] In one embodiment, the formulation comprises about 70 wt% to about 98 wt% of one or more solvents. In another embodiment, the formulation comprises about 70 wt% to about 80 wt% of one or more solvents. In another embodiment, the formulation comprises about 80 wt% to about 90 wt% of one or more solvents. In another embodiment, the formulation comprises about 90 wt% to about 95 wt% of one or more solvents. In another embodiment, the formulation comprises about 90 wt% to about 98 wt% of one or more solvents. In another embodiment, the formulation comprises about 90 wt% of one or more solvents. In another embodiment, the formulation comprises about 91 wt% of one or more solvents. In another embodiment, the formulation comprises about 92 wt% of one or more solvents. In another embodiment, the formulation comprises about 93 wt% of one or more solvents. In another embodiment, the formulation comprises about 94 wt% of one or more solvents. In another embodiment, the formulation comprises about 95 wt% of one or more solvents. In another embodiment, the formulation comprises about 96 wt% of one or more solvents. In another aspect of this embodiment, the formulation comprises about 97 wt% of one or more solvents. In another aspect of this embodiment, the formulation comprises about 98 wt% of one or more solvents.

[0153] In one embodiment, the formulation comprises approximately 93 wt% ArF diluent.

[0154] In one embodiment, the formulation comprises approximately 94 wt% ArF diluent.

[0155] In one embodiment, the formulation comprises approximately 95 wt% ArF diluent.

[0156] In one embodiment, the formulation comprises approximately 93 wt% PGMEA.

[0157] In one embodiment, the formulation comprises approximately 94 wt% PGMEA.

[0158] In one embodiment, the formulation comprises approximately 95 wt% PGMEA.

[0159] (iv) one or more surfactants

[0160] As mentioned above, in some embodiments, the ZPP and / or ZPPA formulation may optionally include one or more surfactants. In some embodiments, the amount of surfactant is from about 0.001 wt% to about 5 wt% of the composition, preferably from about 0.01 wt% to about 2.5 wt% of the composition, and more preferably from about 0.1 wt% to about 1.0 wt%. In some embodiments, the ZPP and / or ZPPA formulation may include about 1.0 wt% or less of surfactant.

[0161] There are no specific limitations on surfactants, and examples include: polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers, such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene polyoxypropylene block copolymers; sorbitol fatty acid esters, such as sorbitol monolaurate, sorbitol monopalmitate, and sorbitol monostearate; nonionic surfactants of polyoxyethylene sorbitol fatty acid esters, such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyethylene sorbitol trioleate, and polyoxyethylene sorbitol tristearate; fluorinated surfactants, such as Brij 30, Brij 32 (Croda, USA), and Triton X-100 (Trion Chemical, USA), F-Top EF301, EF303 and EF352 (Jemco Inc. Japan), Megaface F171, F172, F173, R08, R30, R90 and R94 (DIC Corp, Japan), Florad FC-430, FC-431, FC-4430 and FC-4432 (3M, USA), 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 (Asahi Glass) (ShinEtsuSilicone Co., Ltd., Japan); organosiloxane polymers or those containing organosilicone surfactants, such as KF53, KP-341, KP-351, X22-4952, X70-092 and X70-093 (ShinEtsuSilicone Co., Ltd., Japan); and acrylic or methacrylic acid polymers, such as Polyflow No. 75 and No. 95 (Kyoeisha Yushikagaku Kogyo KKapan).

[0162] In some embodiments, the ZPP and / or ZPPA formulations comprise one or more silicone-containing surfactants. In one aspect of these embodiments, the surfactant is preferably an organosiloxane polymer, and particularly an organosiloxane polymer sold under the trade name X-22-4952.

[0163] In one embodiment, the formulation comprises about 0.1 wt% to about 0.2 wt% of X-22-4952.

[0164] In one embodiment, the formulation comprises about 0.1 wt% to about 0.15 wt% of X-22-4952.

[0165] In one embodiment, the formulation comprises about 0.1 wt% of X-22-4952.

[0166] In one embodiment, the formulation comprises about 0.15 wt% of X-22-4952.

[0167] In one embodiment, the formulation comprises about 0.025 wt% to about 0.2 wt% of KF53.

[0168] In one embodiment, the formulation comprises about 0.025 wt% to about 0.1 wt% of KF53.

[0169] In one embodiment, the formulation comprises about 0.1 wt% KF53.

[0170] In one embodiment, the formulation comprises about 0.05 wt% KF53.

[0171] In one embodiment, the formulation comprises about 0.025 wt% KF53.

[0172] In one embodiment, the formulation comprises about 0.1 wt% to about 0.5 wt% of KF353A.

[0173] In one embodiment, the formulation comprises about 0.1 wt% KF353A.

[0174] In one embodiment, the formulation comprises about 0.13 wt% KF353A.

[0175] In one embodiment, the formulation comprises about 0.2 wt% KF353A.

[0176] In one embodiment, the formulation comprises about 0.3 wt% KF353A.

[0177] In one embodiment, the formulation comprises about 0.001 wt% to about 0.1 wt% of KP341.

[0178] In one embodiment, the formulation comprises about 0.001 wt% KP341.

[0179] In one embodiment, the formulation comprises about 0.05 wt% KP341.

[0180] In one embodiment, the formulation comprises about 0.1 wt% KP341.

[0181] In some embodiments, the compositions of the disclosed and claimed subject matter will be free of or substantially free of surfactants.

[0182] (v) Water-resistant reinforcing agent

[0183] As mentioned above, ZPP and / or ZPPA formulations optionally include one or more water-resistant enhancers to influence or improve moisture resistance.

[0184] In one embodiment, one or more water-resistant reinforcing agents comprise one or more alkyl monocarboxylic acids having 3 to 20 carbon atoms, wherein the alkyl group may be a straight-chain alkyl group, a branched alkyl group, or a cyclic alkyl group. In another embodiment, one or more alkyl monocarboxylic acids have 3 to 10 carbon atoms.

[0185] In another embodiment, one or more water-resistant reinforcing agents include one or more of the following: carboxylic acids, such as propionic acid (PA), n-butyric acid, isobutyric acid (IBA), valeric acid, 2-methylbutyric acid, 3-methylbutyric acid, tert-butylacetic acid, hexanoic acid, 2-methylvaleric acid, 3-methylvaleric acid, 4-methylvaleric acid, heptanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2,2-dimethylvaleric acid, 2,3-dimethylvaleric acid, 2,4-dimethylvaleric acid, 3,3-dimethylvaleric acid, 4,4-dimethylvaleric acid, octanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 4-methylheptanoic acid, 5-methylheptanoic acid, 6-methylheptanoic acid, 2,2-dimethylhexanoic acid, 2,3-dimethylhexanoic acid, 2,4-dimethyl... Hexanoic acid, 2,5-dimethylhexanoic acid, 3,3-dimethylhexanoic acid, 4,4-dimethylhexanoic acid, 5,5-dimethylhexanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 4-ethylhexanoic acid, 2-propylvaleric acid, nonanoic acid, 1-methyloctanoic acid, 2-methyloctanoic acid, 3-methyloctanoic acid, 4-methyloctanoic acid, 5-methyloctanoic acid, 6-methyloctanoic acid, 7-methyloctanoic acid, 2,2-dimethylheptanoic acid, 2,3-dimethylheptanoic acid, 2,4-dimethylheptanoic acid, 2,5-dimethylheptanoic acid, 3,3-dimethylheptanoic acid, 4,4-dimethylheptanoic acid, 5,5-dimethylheptanoic acid, 2-ethyl-2-methylhexanoic acid, 3-ethyl-3-methylhexanoic acid, 4-ethyl-4-methylhexanoic acid, 5,5-dimethylheptanoic acid, 2,2,5-trimethylhexanoic acid 2,2,4-Trimethylhexanoic acid, 2,2,3-Trimethylhexanoic acid, 2,4,4-Trimethylhexanoic acid, 2,5,5-Trimethylhexanoic acid, 2-Propylhexanoic acid, 3-Propylhexanoic acid, 3-Isopropylhexanoic acid, 2-Isopropylhexanoic acid, 4-Ethyl-5-methylhexanoic acid, 5,6-Dimethylheptanoic acid, 2,3,4-Trimethylhexanoic acid, 2,3,5-Trimethylhexanoic acid, 3,4,5-Trimethylhexanoic acid, 2-Isopropyl-3,3-Dimethylbutanoic acid, 2-(tert-butyl)valerate, 3-Ethyl-4,4-Dimethylvalerate, 4,4,5-Trimethylhexanoic acid, 3-Ethyl-3,4-Dimethylvalerate, 2-Isopropyl-2-methylvalerate, Decanoic acid, 2-Methylnonanoic acid, 3-Methylnonanoic acid, 4-Methylnonanoic acid, 5-Methylnonanoic acid, 6 2,2-Dimethylnonanoic acid, 7-methylnonanoic acid, 8-methylnonanoic acid, 2,2-dimethyloctanoic acid, 3,3-dimethyloctanoic acid, 4,4-dimethyloctanoic acid, 5,5-dimethyloctanoic acid, 6,6-dimethyloctanoic acid, 7,7-dimethyloctanoic acid, 2,2,3-trimethylheptanoic acid, 2,2,4-trimethylheptanoic acid, 2,2,5-trimethylheptanoic acid, 2,2,6-trimethylheptanoic acid, 2,3,3-trimethylheptanoic acid, 2,4,4-trimethylheptanoic acid, 2,5,5-trimethylheptanoic acid, 2,6,6-trimethylheptanoic acid, 3,3,4-trimethylheptanoic acid, 3,3,5-trimethylheptanoic acid, 3,3,6-trimethylheptanoic acid, 4,5,5-trimethylheptanoic acid, 4,6,6-trimethylheptanoic acid, 5,6,6-trimethylheptanoic acid, 2,3,4,5-Tetramethylhexanoic acid, 2-ethyl-3,4-dimethylhexanoic acid, 4-ethyl-2,3-dimethylhexanoic acid, 3-ethyl-2,4-dimethylhexanoic acid, 2,3,4-trimethylheptanoic acid, 2-isopropyl-3,3-dimethylvaleric acid, 2-isopropyl-3,4-dimethylvaleric acid, 2,3-diethyl-4-methylvaleric acid, 2,2-diethyl-4-methylvaleric acid, 3,3-diethyl-4-methylvaleric acid, 2-ethyl-2-isopropylvaleric acid, 2-ethyl-2-isopropyl-3-methylbutyric acid, 3-isopropyl-3,4-dimethylvaleric acid, 3-ethyl-3,4,4-trimethylvaleric acid, 2,2-diethyl-3,3-dimethylbutyric acid, 2-isopropyl-2,3,3-trimethylbutyric acid, maleic acid, trans-butyric acid, and combinations thereof. In one aspect of this embodiment, one or more water-resistant reinforcing agents include propionic acid, n-butyric acid, isobutyric acid, tert-butylacetic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, maleic acid, trans-butenedioic acid, and combinations thereof. In one aspect of this embodiment, one or more water-resistant reinforcing agents include valeric acid. In another aspect of this embodiment, one or more water-resistant reinforcing agents include isobutyric acid. In another aspect of this embodiment, one or more water-resistant reinforcing agents include 2-methylbutyric acid. In another aspect of this embodiment, one or more water-resistant reinforcing agents include propionic acid.

[0186] In one embodiment, the amount of the water-resistant reinforcing agent is from about 1 wt% to about 15 wt% of the formulation. In another embodiment, the amount of the water-resistant reinforcing agent is from about 2 wt% to about 10 wt% of the formulation. In another embodiment, the amount of the water-resistant reinforcing agent is from about 3 wt% to about 8 wt% of the formulation. In another embodiment, the amount of the water-resistant reinforcing agent is from about 4 wt% to about 6 wt% of the formulation. In another embodiment, the amount of the water-resistant reinforcing agent is from about 5 wt% to about 6 wt% of the formulation. In another embodiment, the amount of the water-resistant reinforcing agent is about 5 wt% of the formulation. In another embodiment, the amount of the water-resistant reinforcing agent is about 5.6 wt% of the formulation. In another embodiment, the amount of the water-resistant reinforcing agent is about 6 wt% of the formulation.

[0187] In one embodiment, the formulation comprises about 0.1 wt% to about 2.0 wt% of one or more water-resistant enhancers.

[0188] In one embodiment, the formulation includes about 0.1 wt% to about 1.0 wt% of one or more water-resistant enhancers.

[0189] In one embodiment, the formulation includes about 0.1 wt% to about 0.5 wt% of one or more water-resistant enhancers.

[0190] In one embodiment, the formulation includes about 0.1 wt% to about 0.75 wt% of one or more water-resistant enhancers.

[0191] In one embodiment, the formulation includes about 1.0 wt% to about 2.0 wt% of one or more water-resistant enhancers.

[0192] In one embodiment, the formulation comprises about 1.0 wt% to about 1.5 wt% of one or more water-resistant enhancers.

[0193] In one embodiment, the formulation includes about 1.5 wt% to about 2.0 wt% of one or more water-resistant enhancers.

[0194] In one embodiment, the formulation includes about 0.1 wt% of one or more water-resistant enhancers.

[0195] In one embodiment, the formulation includes about 0.2 wt% of one or more water-resistant enhancers.

[0196] In one embodiment, the formulation includes about 0.3 wt% of one or more water-resistant enhancers.

[0197] In one embodiment, the formulation includes about 0.4 wt% of one or more water-resistant enhancers.

[0198] In one embodiment, the formulation includes about 0.5 wt% of one or more water-resistant enhancers.

[0199] In one embodiment, the formulation includes about 0.6 wt% of one or more water-resistant enhancers.

[0200] In one embodiment, the formulation includes about 0.7 wt% of one or more water-resistant enhancers.

[0201] In one embodiment, the formulation includes about 0.8 wt% of one or more water-resistant enhancers.

[0202] In one embodiment, the formulation includes about 0.9 wt% of one or more water-resistant enhancers.

[0203] In one embodiment, the formulation includes about 1.0 wt% of one or more water-resistant enhancers.

[0204] In one embodiment, the formulation includes about 1.1 wt% of one or more water-resistant enhancers.

[0205] In one embodiment, the formulation includes about 1.2 wt% of one or more water-resistant enhancers.

[0206] In one embodiment, the formulation includes about 1.3 wt% of one or more water-resistant enhancers.

[0207] In one embodiment, the formulation includes about 1.4 wt% of one or more water-resistant enhancers.

[0208] In one embodiment, the formulation includes about 1.5 wt% of one or more water-resistant enhancers.

[0209] In one embodiment, the formulation includes about 1.6 wt% of one or more water-resistant enhancers.

[0210] In one embodiment, the formulation includes about 1.7 wt% of one or more water-resistant enhancers.

[0211] In one embodiment, the formulation includes about 1.8 wt% of one or more water-resistant enhancers.

[0212] In one embodiment, the formulation includes about 1.9 wt% of one or more water-resistant enhancers.

[0213] In one embodiment, the formulation includes about 2.0 wt% of one or more water-resistant enhancers.

[0214] In one embodiment, the formulation comprises about 0.1 wt% to about 2.0 wt% isobutyric acid.

[0215] In one embodiment, the formulation comprises about 0.1 wt% to about 1.0 wt% isobutyric acid.

[0216] In one embodiment, the formulation comprises about 0.1 wt% to about 0.5 wt% isobutyric acid.

[0217] In one embodiment, the formulation comprises about 0.2 wt% isobutyric acid.

[0218] In one embodiment, the formulation comprises about 0.3 wt% isobutyric acid.

[0219] In one embodiment, the formulation comprises about 0.4 wt% isobutyric acid.

[0220] In one embodiment, the formulation comprises about 1.6 wt% isobutyric acid.

[0221] In one embodiment, the formulation comprises about 1.7 wt% isobutyric acid.

[0222] In one embodiment, the formulation comprises about 1.8 wt% isobutyric acid.

[0223] In one embodiment, the formulation comprises about 0.1 wt% to about 2.0 wt% of propionic acid.

[0224] In one embodiment, the formulation comprises about 0.1 wt% to about 1.0 wt% of propionic acid.

[0225] In one embodiment, the formulation comprises about 0.1 wt% to about 0.5 wt% of propionic acid.

[0226] In one embodiment, the formulation comprises about 0.2 wt% propionic acid.

[0227] In one embodiment, the formulation comprises about 0.3 wt% propionic acid.

[0228] In one embodiment, the formulation comprises about 0.4 wt% propionic acid.

[0229] In one embodiment, the formulation comprises about 0.1 wt% to about 2.0 wt% of 2-methylbutyric acid.

[0230] In one embodiment, the formulation comprises about 0.1 wt% to about 1.0 wt% of 2-methylbutyric acid.

[0231] In one embodiment, the formulation comprises about 0.1 wt% to about 0.5 wt% of 2-methylbutyric acid.

[0232] In one embodiment, the formulation comprises about 0.2 wt% of 2-methylbutyric acid.

[0233] In one embodiment, the formulation comprises about 0.3 wt% of 2-methylbutyric acid.

[0234] In one embodiment, the formulation comprises about 0.4 wt% of 2-methylbutyric acid.

[0235] III. Methods for preparing ZPPA-based membranes

[0236] Another aspect of the disclosed and claimed subject matter relates to the use of ZPPA and its formulations for forming ZrOx membranes.

[0237] A solution comprising ZPPA can be applied to a substrate using techniques well known to those skilled in the art, such as dip coating, spin coating, or spray coating. Spin coating is preferred. The thickness of the undercoat is in the range of about 5 nm to about 400 nm, preferably about 10 nm to about 120 nm. The coating is further heated on a hot plate or convection oven for a sufficient time to remove any residual solvent and induce curing, thereby preventing the antireflective coating from dissolving and preventing intermixing between the antireflective coating and the layers applied above it. Preferably, the temperature is generally below about 450°C and can be, for example, between about 90°C and about 300°C, or between about 160°C and about 250°C. The coating can be applied over layers of other antireflective coatings, such as antireflective coatings with a high carbon content (above about 80%, about 85%, or about 90%).

[0238] The substrate on which the undercoat is formed can be any of those typically used in the semiconductor industry. Suitable substrates include, but are not limited to, low-dielectric-constant materials, silicon, silicon substrates with metal-coated surfaces, copper, aluminum, polymeric resins, silicon dioxide, metals, doped silicon dioxide, silicon nitride, tantalum, polycrystalline silicon, ceramics, aluminum / copper mixtures, gallium arsenide, and other such Group III / V compounds. The substrate can also be other anti-reflective coatings or undercoats, such as high-carbon undercoats coated on the aforementioned substrates. The substrate can contain any number of layers made of the materials described above.

[0239] A photoresist film can be applied on top of an undercoat and baked to substantially remove the photoresist solvent. Following the coating step, an edge bead remover can be applied to clean the substrate edges using methods well-known in the art. The photoresist can be of any type used in the semiconductor industry, provided that the photoresist and the photosensitive compounds in the antireflective coating are substantially absorbed at the exposure wavelength used in the imaging method. Photoresists suitable for immersion lithography are preferred. Typically, photoresists suitable for immersion lithography imaging can be used, wherein the photoresist has a refractive index greater than 1.85 and is also hydrophobic, having a water contact angle in the range of about 75° to about 95°.

[0240] Several major deep ultraviolet (UV) exposure techniques exist, offering significant advancements in miniaturization and radiation at 248 nm, 193 nm, and 13.5 nm. Chemically amplified photoresists are frequently used. Photoresists for 248 nm are typically based on substituted polyhydroxystyrene and its copolymers / onium salts, such as those described in US Patent Nos. 4,491,628 and 5,350,660. On the other hand, photoresists for exposure at 193 nm and 157 nm require non-aromatic polymers because aromatic substances are opaque at these wavelengths. US Patent Nos. 5,843,624 and 6,866,984 disclose photoresists suitable for 193 nm exposure. Typically, polymers containing alicyclic hydrocarbons are used for photoresists exposed below 200 nm. Alicyclic hydrocarbons are incorporated into polymers for many reasons, primarily because they have a relatively high carbon-to-hydrogen ratio (improved etch resistance), offer transparency at low wavelengths, and have relatively high glass transition temperatures. U.S. Patent No. 5,843,624 discloses photoresist polymers obtained by the free radical polymerization of maleic anhydride with unsaturated cyclic monomers. Any known type of 193 nm photoresist, such as those described in U.S. Patent Nos. 6,447,980 and 6,723,488, is permitted to be used, and is hereby incorporated herein by reference. Photoresists absorbing far-ultraviolet (EUV) radiation at 13.5 nm are also suitable and known in the art. Therefore, photoresists absorbing light in the range of about 12 nm to about 250 nm are suitable. Novel coatings can also be used in conjunction with nanoimprint and electron beam resists in the process.

[0241] Following the coating process, the photoresist can be exposed image by image. Typical exposure equipment can be used for exposure. The exposed photoresist is then developed in an aqueous developer to remove the treated photoresist. The developer is preferably an alkaline aqueous solution, including, for example, tetramethylammonium hydroxide (TMAH), typically 2.38 wt% TMAH. The developer may further include one or more surfactants. Optional heating steps can be incorporated into the process before development and after exposure.

[0242] Methods for coating and imaging photoresist are well known to those skilled in the art and are optimized for the specific type of photoresist used. The photoresist-patterned substrate can then be dry-etched in a suitable etching chamber using an etching gas or gas mixture to remove the exposed portions of the underlayer and optionally other anti-reflective coatings. Various etching gases for etching the underlayer coating are known in the art, such as those containing O2, CF4, CHF3, Cl2, HBr, SO2, CO, etc. In one embodiment, the article comprises a semiconductor substrate having a high-carbon anti-reflective film coated with a novel zirconium metal layer. A photoresist layer is coated over this metal layer. The photoresist is imaged as disclosed above, and the metal underlayer is dry-etched using a gas containing fluorocarbons. After etching the metal underlayer, the high-carbon film can be dry-etched using oxygen or an oxygen mixture.

[0243] In one embodiment, ZPPA and ZPP formulation can be coated onto a substrate using the following steps:

[0244] a. Pour ZPPA or ZPP formulation onto a silicon substrate and spin-coat at an adjusted rotation speed to obtain the desired thickness; and

[0245] b. The coated silicon wafer is baked on a hot plate at different temperatures for different durations depending on the desired characteristics.

[0246] In one embodiment, the baking temperature is from about 200°C to 600°C and the baking time is selected from 30 seconds to 1 hour. Typically, the baking temperature is from about 250°C to about 500°C and the baking time is from about 60 seconds to about 300 seconds.

[0247] In another embodiment, baking may be a single-step baking or a multi-step baking (e.g., baking at about 250°C for about 60 seconds, followed by baking at about 450°C for about 120 seconds).

[0248] Example

[0249] Reference will now be made to more specific embodiments of the invention and experimental results supporting these embodiments. Examples are given below to illustrate the disclosed subject matter more fully and should not be construed as limiting the disclosed subject matter in any way.

[0250] Those skilled in the art will appreciate that various modifications and variations can be made to the disclosed subject matter and the specific embodiments 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 embodiments) is intended to cover modifications and variations of the disclosed subject matter that appear within the scope of any claims and their equivalents.

[0251] Materials and methods:

[0252] The reaction was carried out in an air- and moisture-free environment. Propionic acid (Millipore Sigma), propionic anhydride (Millipore Sigma), and 1-methoxy-2-propanol (PGME; EMD Performance Materials) were contained within a molecular sieve. Then, it is distilled under an inert atmosphere and atmospheric pressure.

[0253] X-ray crystallography was determined using a SuperNova (Oxford Diffraction) diffractometer equipped with an Atlas CCD detector. Radiation: Cu Ka Monochromator: X-ray microscope; Measurement software: CrysAlisPro 39.46; Evaluation software: OLEX 2 1.2.8.

[0254] From Netzsch Simultaneous thermal analysis (STA) was performed on GmbH's STA 449F3 Jupiter at a heating rate of 10 °C / min from 30 °C to 1000 °C under inert and air conditions.

[0255] Dynamic light scattering (DLS) measurements for measuring the size of ZPP and ZPPA were performed at 25°C using a Malvern Zetasizer Nano-S-Model, model number ZEN1600.

[0256] Tokyo Electron Ltd Clean Track ACT 8, ACT 12, or Mark 8 are used for coating and baking ZPPA or ZPP formulations. Elemental analysis was performed using Intertek at Whitehouse, NJ to determine the C, H, and Zr content (wt%).

[0257] The refractive index (n) and extinction coefficient (k) were measured using a JAWoollam VUV-VASE VU-302 spectroelastic ellipsometry. The sample was coated onto a Si wafer at the target film thickness and baked at 250°C / 60 sec + 450°C / 90 sec, and the optical parameters were measured.

[0258] The overall etching rate was measured using a TRION DUAL CHAMBER MINILOCK III as follows: ZPPA or ZPP formulation was spin-coated onto a silicon wafer and baked at 250°C / 60 sec + 450°C / 90 sec. The spin speed was adjusted to the desired film thickness. The coated sample wafer was loaded into the Trion etcher and etched at Ar 80 sccm, CF4 20 sccm, pressure 50 mT, top RF 1000 W, bottom RF 400 W, and etching time 120 sec. The film thickness of the sample was measured before and after etching to obtain the overall etching rate.

[0259] XPS measurements were performed on a Thermo Fisher Scientific K-α X-ray photoelectron spectroscopy (XPS) KA1191 using the following protocol: Wafers coated with MHM of the target film thickness were baked at 250°C / 60 sec + 450°C / 90 sec. The wafers were then used for XPS analysis. Based on the film thickness of each wafer, the Ar sputtering rate and atomic percentages were reported after the XPS measurements were completed.

[0260] Moisture sensitivity was assessed using a humidity control chamber (Ets Electro-tech Systems Inc.). Samples in glass vials were placed in a humidity chamber at 45% RH, which was kept open, and changes were observed for 24 hours.

[0261] The contact angle with water was measured using the OCA 20L data physics contact angle measurement system.

[0262] I. Zirconium propionate polymorph S1 (ZPPA) and related compounds

[0263] A. Synthesis of Zirconium propionate polymorph S1 (ZPPA) 1

[0264] The reaction was carried out in an air- and moisture-free environment. Propionic acid (Millipore Sigma), propionic anhydride (Millipore Sigma), and 1-methoxy-2-propanol (PGME; EMD Performance Materials) were contained within a molecular sieve. The mixture was then distilled under an inert atmosphere and atmospheric pressure. Propionic acid (19.48 g; 0.263 mol) was added all at once to propionic anhydride (103.08 g; 0.792 mol) while the mixture was stirred for 2 minutes. Then, 100.93 g (0.263 mol) (tert-butanol) 4-zirconium (IV) (Millipore Sigma) was added dropwise over 45 minutes. During this addition, the temperature was controlled to reach approximately 60°C. The mixture was then stirred at 62–65°C for 18 hours. Next, 118.50 g (1.315 mol) of 1-methoxy-2-propanol was added dropwise to the solution, and the crude ZPPA was stirred at 62°C for an additional 5 hours. The mixture was transferred to a dry round-bottom flask filled with nitrogen. The flask was placed on a vacuum rotary evaporator with a heating bath to distill off the volatile components. The removal of volatiles yielded 81.9 g of solid and residual PGME (approximately 20% by 1H NMR). The PGME was removed by drying in a vacuum oven at 90°C for 3 days.

[0265] ZPPA features are described above.

[0266] B. Synthesis of Zirconium propionate polymorph S2

[0267] (tert-butanol)zirconium(IV) (32.65 g; 0.085 mol) was added to 2-methylpropionic acid (7.50 g; 0.085 mol) and propionic anhydride (33.22 g; 0.255 mol) over 34 min, followed by stirring for 20 h. Then, 1-methoxy-2-propanol (22.9 g; 0.254 mol) was added as described in Example 1. 27.43 g of isobutyrato-zirconium(IV) solid solvate I was obtained, with a residual volatile matter content of 6.92 wt%.

[0268] C. Synthesis of Zirconium propionate polymorph S3

[0269] (tert-butanol)-zirconium(IV) (27.48 g; 0.0716 mol) was added to 2-methylpropionic acid (12.94 g; 0.146 mol) and propionic anhydride (27.85 g; 0.214 mol) over 25 min, followed by stirring for 20 h. Then, 1-methoxy-2-propanol (12.96 g; 0.144 mol) was added as described in Example 1. 22.92 g of isobutyrate-zirconium(IV) solid solvate II was obtained, with a residual volatile matter content of 11.33 wt%.

[0270] D. Synthesis of zirconium propionate polymorph S4

[0271] (tert-butanol)-zirconium(IV) (19.77 g; 0.0515 mol) was added to methacrylic acid (4.43 g; 0.0515 mol) and propionic anhydride (19.97 g; 0.153 mol) over 41 min, followed by stirring for 20 h. Then, 1-methoxy-2-propanol (13.96 g; 0.155 mol) was added as described in Example 1. 17.28 g of methacrylato-zirconium(IV) solid solvate was obtained, with a residual volatile matter content of 21.7 wt%.

[0272] E. Synthesis of Zirconium propionate polymorph S5

[0273] (tert-butanol)-zirconium(IV) (28.43 g; 0.074 mol) was added to 2-(2-methoxyethoxy)acetic acid (9.94 g; 0.074 mol) and propionic anhydride (28.93 g; 0.222 mol) over 52 min, followed by stirring for 18 h as described in Example 1. 30.7 g of 2-(2-methoxyethoxy)acetate-zirconium(IV) as a glassy solvate was obtained, with a residual volatile content of 17.24 wt%.

[0274] F. Synthesis of zirconium propionate polymorph S6

[0275] (tert-butanol)-zirconium(IV) (24.24 g; 0.0618 mol) was added to 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (11.26 g; 0.063 mol) and propionic anhydride (24.67 g; 0.190 mol) over 35 min, followed by stirring for 22 h as described in Example 1. 30.7 g of 2-[2-(2-methoxyethoxy)ethoxy]acetate-zirconium(IV) was obtained as a low-temperature molten solvate, with a residual volatile content of 28.58 wt%.

[0276] Synthesis of G. Zirconium propionate polymorph S7

[0277] (tert-butanol)-zirconium(IV) (30.11 g; 0.0785 mol) was added to benzoic acid (9.77 g; 0.08 mol) and propionic anhydride (30.79 g; 0.236 mol) over 29 min, followed by stirring for 19.7 h. Then, 1-methoxy-2-propanol (21.36 g; 0.237 mol) was added as described in Example 1. 29.08 g of benzoato-zirconium(IV) solid solvate was obtained, with a residual volatile content of 19.8 wt%.

[0278] Synthesis of H. zirconium propionate polymorph S8

[0279] (tert-butanol)-zirconium(IV) (31.43 g; 0.082 mol) was added to 4-methoxybenzoic acid (8.97 g; 0.059 mol) and propionic anhydride (31.24 g; 0.240 mol) over 53 min, followed by stirring for 21 h as described in Example 1. 35.15 g of 4-methoxybenzoate-zirconium(IV) in glassy solvate form was obtained, with a residual volatile content of 16.71 wt%.

[0280] I. Synthesis of Zirconium propionate polymorph S9

[0281] (tert-butanol)-zirconium(IV) (24.37 g; 0.0635 mol) was added to phenylacetic acid (8.69 g; 0.0638 mol) and propionic anhydride (24.73 g; 0.19 mol) over 50 min, followed by stirring for 19 h. Then, 1-methoxy-2-propanol (17.17 g; 0.191 mol) was added as described in Example 1. 23.95 g of phenylacetate-zirconium(IV) in glassy solvate form was obtained, with a residual volatile content of 5.6 wt%.

[0282] Synthesis of Zirconium propionate polymorph S10 10

[0283] (tert-butanol)-zirconium(IV) (19.44 g; 0.0507 mol) was added to propionic anhydride (19.78 g; 0.152 mol) over 44 min, followed by stirring for 15.5 h. Then, DI water (1.11 g; 0.062 mol) was added, and stirring was performed as in Example 1. 12.71 g of hydroxo-zirconium(IV) solid solvate was obtained, with a residual volatile content of 13.1 wt%.

[0284] II. Synthesis of THTPM tri-propionate (THTPM-TP)

[0285] A. Reactions in solvent synthesis

[0286] 4,4',4”-trihydroxytriphenylmethane (THTPM, 5.04 g, 17.24 mmol) and propionic anhydride (13.46 g, 103.44 mmol) were refluxed in toluene (50 ml) for 6.5 hours. 1 ¹H NMR (DMS-d6) showed the completion of the reaction. After cooling to room temperature, the volatiles were removed from the crude material by distillation using a rotary evaporator. Removal of the volatiles gave 7.9 g of solid, which was subsequently crystallized from 25.8 g of isopropanol. After drying in a vacuum oven at 95 °C, 7.39 g (93.1% yield) of the triester was obtained as a green crystalline powder.

[0287] B. Solvent-free synthesis

[0288] 4,4',4”-trihydroxytriphenylmethane (THTPM, 3.03 g, 10.36 mmol) and propionic anhydride (7.19 g, 55.25 mmol) were stirred at 120 °C for 6.5 h. After cooling to room temperature, the crude material was poured into 400 mL of DI water, and the resulting crystalline material was recovered by filtration the next day. After drying in a vacuum oven at 95 °C, 4.53 g (94.9% yield) was obtained. 1 The purity of the 1H NMR was 95.6% (DMS-d6).

[0289] Characterization: MP 100.7℃; 1 H NMR (400Mz, CDCl3) δ7.08 (d, J=8.54Hz, 6H, Ar-H), 6.99 (d, J=8.54Hz, 6H, Ar-H), 5.51(s,1H,CH),2.56(q,J=7.48Hz,6H,C-H2),1.24(t,J=7.48Hz,9H,C-H3)ppm; 13 C NMR (400Mz, CDCl3) δ172.9,149.4,140.9,130.3,121.5,55.1,27.8,9.1ppm; FTI R(KBr)3044,2982,2944,2882,1756,1604,1593,1505,1462,1417,1357,1269cm -1 C 28 H 28 Calculated values ​​of O6: C 73.03, H 6.13; experimental values: C 72.86, H 6.06.

[0290] III. Exemplary Formulations

[0291] ZPPA formulation

[0292] A. Preparation 1

[0293] The formulation comprising ZPPA is prepared by (i) 246.8 g of a 15.4% ZPPA solution in ArF diluent, (ii) 2 g of isobutyric acid (Millipore Sigma), (iii) 4 g of 4,4',4”-trihydroxytriphenylmethane (Asahi Yukizai), and (iv) 8.25 g of... 10% X22-4952 (ShinEtsu) solution in ArF diluent and (v) 289g The mixture was prepared by mixing with ArF diluent. The components were mixed overnight and then filtered through a 0.2 μm filter.

[0294] Performance: Film uniformity (3sigma%) 3.8; etching rate (A / sec) 1.37; and moisture resistance (h) 15. Refractive index (n) and extinction coefficient (k): n 2.44 and k 0.54 at 193nm, and n 2.11 and k 0.03 at 248nm.

[0295] B. Formulation 2

[0296] The formulation containing ZPPA is prepared by (i) 388.6 g of a 15.4% ZPPA solution in ArF diluent, (ii) 1.43 g of isobutyric acid (Millipore Sigma), (iii) 28.64 g of a 10% 4,4',4”-trihydroxytriphenylmethane (Asahi Yukizai) solution in ArF diluent, and (iv) 6.75 g of... ArF diluent containing 10% X22-4952 (ShinEtsu) solution, (v) 12.56 g of γ-valerolactone, and (vi) 12 g of The mixture was prepared by mixing with ArF diluent. The components were mixed overnight and then filtered through a 0.2 μm filter.

[0297] Performance: Film uniformity (3sigma%) 3.5; etching rate (A / sec) 1.38; and moisture resistance (h) 13. Refractive index (n) and extinction coefficient (k): n 2.49 and k 0.60 at 193 nm, and n 2.15 and k 0.03 at 248 nm.

[0298] ZPP formulation

[0299] ZPP used in these formulations has an average molecular weight of about 4,000 Da to about 10,000 Da.

[0300] C. Preparation 3

[0301] 32.39g of ZPP, 2g of isobutyric acid (Millipore Sigma), 3.409g of 4,4',4”-trihydroxytriphenyl-methane (Asahi Yukizai), and 7.5g of 10% X22-4952 (ShinEtsu) were mixed with 455g of... ArF diluent combination. The solution was mixed overnight and then filtered through a 0.2 μm filter.

[0302] Performance: Film uniformity (3sigma%) 3.6; etching rate (A / sec) 1.34; and moisture resistance (h) 12. Refractive index (n) and extinction coefficient (k): n 2.55 and k 0.63 at 193 nm, and n 2.20 and k 0.04 at 248 nm.

[0303] D. Preparation 4

[0304] 431.8g of ZPP, 17.05g of isobutyric acid (Millipore Sigma), 454.55g of 10% 4,4',4”-trihydroxytriphenylmethane (Asahi Yukizai), 80g of 10% X22-4952 (ShinEtsu), and 285g of γ-valerol were mixed with 8.656kg of... ArF diluent combination. The solution was mixed overnight and then filtered through a 0.2 μm filter.

[0305] Performance: Film uniformity (3sigma%) 3.7; etching rate (A / sec) 1.36; and moisture resistance (h) 12. Refractive index (n) and extinction coefficient (k): n 2.53 and k 0.62 at 193 nm, and n 2.19 and k 0.03 at 248 nm.

[0306] E. Preparation of 5 to 45

[0307] Additional exemplary formulations are described in Tables 6 through 9. In these embodiments, the Zr material, etch-resistant modifier additive, one or more solvents, surfactant, and water-resistant enhancer were mixed overnight and then filtered through a 0.2 μm filter.

[0308]

[0309]

[0310] Table 6

[0311]

[0312]

[0313] Table 7

[0314]

[0315]

[0316] Table 8

[0317]

[0318]

[0319] Table 9

[0320] V. Membrane Preparation and Properties

[0321] As illustrated in Examples 1 to 4 and 5 to 45, the present invention provides spin-coated organometallic formulations. All formulations in Examples 1 to 45 are spin-coated and exhibit excellent etch resistance and Ar sputtering etch rates. Furthermore, these formulations demonstrate good stability in humid environments.

[0322] All formulations exhibit good film thickness uniformity with 3 sigma% ranging from <10% to 3.2% to 6.5%. The overall etch rate is low at 0.6 to 0.8 A / sec under the given conditions and exhibits good resistance. The Ar sputtering rate is approximately 1.2 to 1.6 A / sec. The ratio of Ar sputtering rate to overall etch rate is generally high, >1.5, and exhibits good etch selectivity. The formulations are stable to moisture and show no changes in a moisture chamber for >8 hours.

[0323] Although the disclosed and claimed subject matter has been described and illustrated with a certain degree of specificity, it should be understood that the invention is carried out only by means of embodiments, and those skilled in the art can make various changes to the conditions and order of steps without departing from the spirit and scope of the disclosed and claimed subject matter.

Claims

1. A formulation comprising: (i) Zirconium propionate ZPP; (ii) One or more anti-etching modifier additives. Wherein, one or more anti-etching modifier additives comprise compounds of structure (1): (1) in R 11 It is hydrogen or methyl; and L3 is a direct bond, substituted or unsubstituted C. 1-3 Alkyl or substituted or unsubstituted C 7-16 Aryl groups, or Wherein (ii) one or more etch resistance modifier additives comprise one or more of the following: A.4,4',4''-Trihydroxytriphenylmethane (THTPM): ； B.4,4',4''-Tripropionyloxytriphenylmethane (THTPM-TP); 3D1: ； C.3D2: ;and D.3D3: ； (iii) One or more solvents (iv) one or more surfactants; and (v) One or more water-resistant reinforcing agents.

2. The formulation according to claim 1, wherein the ZPP comprises ZPP designated with CAS number 84057-80-7.

3. The formulation according to claim 1, wherein the ZPP comprises Zr(CH3CH2COO). 4-x (OH) x , where x = 1 to 3.

4. The formulation of claim 1, wherein the ZPP comprises an oligomer or polymer class comprising repeating units in any order thereof: (A2) n (B2) m (C2) o (D2) p (A3) n1 (B3) m1 (C3) o1 (D3) p1 Where each of n, n1, m, m1, o, o1, p, and p1 is between 0 and 10. The sum of n, n1, m, m1, o, o1, p, and p1 is between 2 and 10; and Repeating cells are shown in the table below, where " "" indicates a protonated or deprotonated oxygen atom in an oligomer or polymeric zirconium complex that has an actual or potential direct valence bond with another zirconium atom, or alternatively, forms a direct valence bond with H to form a Zr-OH moiety: 。 5. The formulation of claim 1, wherein the ZPP comprises an oligomer or polymer having a hydroxyl to propionate ligand ratio of 0.5 to 1.1, as measured by proton NMR.

6. The formulation according to claim 1, wherein the ZPP contains 0.5 wt% to 6 wt% water.

7. The formulation according to claim 1, wherein the ZPP comprises 0.5 wt% to 6 wt% propionic acid.

8. The formulation according to claim 1, wherein the ZPP has an average diameter (nm) of 7.0 nm to 12.0 nm, as measured by dynamic light scattering (DLS).

9. The formulation of claim 1, wherein the formulation comprises 0.1 wt% to 1 wt% of (ii) one or more anti-etching modifier additives.

10. The formulation according to claim 1, wherein the (iii) one or more solvents comprise one or more of the following: glycol ether derivatives, glycol ether ester derivatives, carboxylic acid esters, ketone derivatives, amide derivatives, and mixtures thereof.

11. The formulation according to claim 10, wherein the carboxylic ester is selected from carboxylic esters of dicarboxylic acids, dicarboxylic esters of diols, hydroxycarboxylic esters, ketone esters or alkoxycarboxylic esters.

12. The formulation according to claim 10, wherein the ketone derivative is selected from ketone ether derivatives or ketone alcohol derivatives.

13. The formulation according to claim 1, wherein one or more solvents in (iii) comprise diol derivatives.

14. The formulation according to claim 1, wherein the (iii) one or more solvents comprises a diol derivative selected from the group consisting of ethylene glycol, propylene glycol, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), dipropylene glycol monomethyl ether (DPGME), and mixtures thereof.

15. The formulation according to claim 1, wherein one or more solvents in (iii) comprise propylene glycol monomethyl ether acetate (PGMEA).

16. The formulation according to claim 1, wherein one or more solvents in (iii) comprise propylene glycol monomethyl ether (PGME).

17. The formulation according to claim 1, wherein the (iii) one or more solvents comprise a mixture of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME).

18. The formulation of claim 1, wherein the formulation comprises 70 wt% to 98 wt% of one or more solvents.

19. The formulation of claim 1, wherein the one or more surfactants comprise an organosiloxane polymer.

20. The formulation of claim 1, wherein the formulation comprises 0.001 wt% to 5 wt% of one or more surfactants.

21. The formulation according to claim 1, wherein the one or more water-resistant enhancers comprise one or more of the following: propionic acid, n-butyric acid, isobutyric acid, tert-butylacetic acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, maleic acid, trans-butenedioic acid, and combinations thereof.

22. The formulation of claim 1, wherein the one or more water-resistant enhancers comprise propionic acid.

23. The formulation of claim 1, wherein the one or more water-resistant enhancers comprise isobutyric acid.

24. The formulation of claim 1, wherein the formulation comprises 1 wt% to 15 wt% of one or more water-resistant enhancers.

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