Articles for chemical mechanical polishing processes and chemical mechanical polishing systems containing such articles

Abstract

An article for use in a chemical mechanical polishing process comprises a metal framework and a thermoplastic composition enclosing the metal framework. The metal framework may optionally include a buffer layer between the surface of the framework and the thermoplastic composition. The metal framework, or the buffer layer if present, contains a plurality of pores. A method for manufacturing the article is also described.

Description

Technical Field

[0001] The present invention relates to an article for a chemical mechanical polishing process and a chemical mechanical polishing system including the article.

[0002] (Cross - reference to related applications) This application claims the priority and benefits of European Patent Application No. 23170661.5, filed on April 28, 2023, the content of which is hereby incorporated by reference in its entirety.

Background Art

[0003] Chemical mechanical polishing (CMP), also known as chemical mechanical planarization, refers to a method of removing a solid layer by chemical mechanical polishing performed for the purpose of surface planarization. In a typical CMP process, a rotating polishing pad uses a chemically reactive slurry to polish the outermost surface of a substrate. The substrate is placed on the polishing pad and held in place by a retaining ring. Typically, the substrate and the retaining ring are placed on a carrier or a polishing head. A controlled force is applied to the substrate by the carrier head, and the substrate is pressed against the polishing pad. As the polishing pad moves across the surface of the substrate, material is removed from the substrate surface both chemically and mechanically. The equipment used to perform the CMP process typically includes various components that need to be replaced at some frequency during the polishing process, which can increase the costs associated with CMP. One such component is the retaining ring, which, as mentioned above, contains slurry and functions to maintain the position of the substrate being polished.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Therefore, improved chemical mechanical polishing processes remain necessary in this field. [Means for solving the problem]

[0005] An article for use in a chemical mechanical polishing process is a metal skeleton optionally having a buffer layer on the surface of the metal skeleton, wherein the metal skeleton further includes a plurality of pores on the surface of the metal skeleton or, if present, on the buffer layer, and a thermoplastic composition that encapsulates the metal skeleton.

[0006] A method for manufacturing an article includes the steps of providing a metal framework, optionally depositing a buffer layer on the metal framework, surface treating the metal framework or, if present, the buffer layer to provide a plurality of pores on the metal framework or, if present, on the buffer layer, and forming a thermoplastic composition on the surface-treated metal framework to provide an article.

[0007] Chemical mechanical polishing systems include articles.

[0008] Another aspect of the present disclosure is a polyphenylene sulfide composition comprising 5 to 43.9 weight percent of poly(etherimide-siloxane copolymer), 55 to 85 weight percent of poly(phenylene sulfide), 1 to 10 weight percent of polyaryl ether ketone, 0.1 to 5 weight percent of epoxy resin, and optionally 0.1 to 10 weight percent of an additive composition, where the weight percent is based on the total weight of the thermoplastic composition.

[0009] The above and other features are illustrated in the diagram and detailed explanation below.

[0010] The diagram below shows an exemplary embodiment, and similar elements are numbered similarly. [Brief explanation of the drawing]

[0011] [Figure 1] A bottom view of an article ring according to one aspect of this disclosure is shown. [Figure 2] This is a schematic diagram representing one aspect of the present disclosure. [Figure 3] This is a schematic diagram representing one aspect of the present disclosure. [Figure 4] This is a photograph of a cross-section of an article not described in this disclosure, showing delamination from a metal framework. [Figure 5] This is a photograph of a cross-section of an article according to one aspect of the present disclosure, which does not show delamination from the metal framework. [Modes for carrying out the invention]

[0012] The inventors unexpectedly discovered that improved articles for the CMP process can be provided when the article contains multiple pores on the metal surface of the article. The article can take the form of a retaining ring for use in the CMP process. For convenience, the use of certain articles described herein can provide a structure with good mechanical strength and improved adhesion between the polymer composition and the metal skeleton, resulting in improved flatness and reduced strain observed in the product. The inventors also found that further improvements can be provided even without nanopores when certain polyphenylene sulfide compositions are used as components of the article.

[0013] Accordingly, one aspect of the present disclosure is an article for use in a chemical mechanical polishing process. In a particular aspect, the article is a retaining ring for use in a chemical mechanical polishing process. The article includes a metal skeleton. The metal skeleton may include, for example, aluminum, stainless steel, molybdenum, ceramic, zinc, or an alloy or a combination thereof. In one aspect, the metal skeleton may be an annular metal skeleton.

[0014] The metal framework is optional and may include a buffer layer on its surface. In one embodiment, the buffer layer can cover the entire surface of the metal framework. In other words, the buffer layer can encapsulate the metal framework.

[0015] If present, the buffer layer may include inorganic materials, organic materials, or combinations thereof. In one embodiment, the buffer layer may include inorganic materials such as Al2O3, TiO2, ZnO, SiO2, PbO, Na2O, CaO, MgO, CuO, or alloys thereof. In a particular embodiment, the buffer layer may include Al2O3. In one embodiment, the buffer layer may include organic materials such as thermosetting materials. Exemplary thermosetting materials include thermosetting acrylates, epoxy, polyimide, polyurethane, or combinations thereof. In one embodiment, the buffer layer may include a filled thermosetting material, the filler of which is preferably an inorganic oxide, such as Al2O3, TiO2, ZnO, SiO2, PbO, Na2O, CaO, MgO, CuO, or alloys thereof.

[0016] The buffer layer, if present, can be deposited by any suitable means, which can be determined, for example, based on the chemical composition of the buffer layer. The buffer layer can be deposited in an amount effective to provide a buffer layer having a thickness of 1 to 1000 micrometers, preferably 1 to 750 micrometers, 5 to 750 micrometers, or 5 to 500 micrometers, or 10 to 500 micrometers.

[0017] The metal framework further includes multiple pores on its surface. If a buffer layer is present on the surface of the metal framework, multiple pores are present on the outer surface of the buffer layer. In one embodiment, there is no buffer layer, and multiple pores are present on the surface of the metal framework. In another embodiment, a buffer layer is present, and multiple pores are present on the outer surface of the buffer layer.

[0018] In one embodiment, the pores are preferably nanopores. The term “nanopore” as used herein refers to pores having a diameter of 1 to 100 nanometers. In one embodiment, the pores may have a depth of 1 to 1000 nanometers. In one embodiment, the pores may have a diameter of 1 to 100 nanometers and a depth of 1 to 1000 nanometers. The pores may have any preferred shape, including regular or irregular shapes, or a combination thereof. For example, the pores may be substantially cylindrical. In one embodiment, the pores may be irregular in shape, with an average diameter (e.g., measured by the maximum width dimension of the pore opening on the surface of the metal framework or buffer layer) of 1 to 100 nanometers.

[0019] The articles relating to this disclosure further include a thermoplastic composition for encapsulating a metal skeleton. The thermoplastic composition comprises a thermoplastic polymer. Exemplary thermoplastic polymers include polyetherimide, poly(phenylene sulfide), poly(aromatic ketone), poly(phenylene sulfone), polycarbonate, polyester, polyolefin, or combinations thereof. In one embodiment, the thermoplastic composition may include polyetherimide, poly(phenylene sulfide), poly(aromatic ketone), poly(phenylene sulfone), polyester (e.g., poly(butylene naphthalate)), or combinations thereof.

[0020] In one embodiment, the thermoplastic composition comprises a polyetherimide. The polyetherimide comprises more than 1, for example, 2 to 1000, or 5 to 500, or 10 to 100, structural units of formula (1), [ka] (1) In the formula, each R is either the same or different, substituted or unsubstituted divalent organic group, for example, substituted or unsubstituted C 6-20 Aromatic hydrocarbon groups, substituted or unsubstituted linear or branched chains C 4-20An alkylene group, a substituted or unsubstituted C 3-8 cycloalkylene group, particularly a halogenated derivative of any of the above. In one aspect, R is one or more divalent groups of the following formula (2)

Chemical formula

[0021] In formula (1), further, T is -O- or a group of the formula -O-Z-O-, and the divalent bond of the -O- or -O-Z-O- group is at the 3,3', 3,4', 4,3', or 4,4' position. Z is optionally an aromatic C 1-8 alkyl group having 1 to 6 carbon atoms, a halogen atom having 1 to 8 carbon atoms, or an aromatic C 6-24 monocyclic or polycyclic moiety substituted by a combination containing at least one of the above, provided that the valence of Z is not exceeded. Exemplary Z groups include groups of formula (3),

Chemical formula

[0022] In one embodiment of formula (1), R is m-phenylene, p-phenylene, or a combination comprising at least one of the above, T is -OZO-, where Z is the divalent group of formula (3a). Alternatively, R is m-phenylene, p-phenylene, or a combination comprising at least one of the above, T is -OZO-, where Z is the divalent group of formula (3a), and Q is 2,2-isopropylidene. In one embodiment, R is p-phenylene, T is -OZO-, where Z is the divalent group of formula (3a), and Q is 2,2-isopropylidene. Such materials are available from SABIC under the trade name ULTEM.

[0023] In one embodiment, the polyetherimide is a copolymer that optionally includes additional structural imide units other than polyetherimide units, for example, imide units of formula (4). [ka] (4) In the formula, R is as described in formula (1), and each V is either the same or different, and substituted or unsubstituted C 6-20 Aromatic hydrocarbon groups, for example, tetravalent linkers of the following formula: [ka] In the formula, W represents a single bond, -O-, -S-, -C(O)-, -SO2-, -SO-, C 1-18 Hydrocarbylene group, -P(R a )(=O)-(wherein, R a is C 1-8 Alkyl or C 6-12 (It is an aryl), or -C y H 2y-(y is an integer from 1 to 5) or its halogenated derivative (containing a perfluoroalkylene group). These additional structural imide units may preferably constitute less than 20 mol% of the total number of units, more preferably in amounts of 0 to 10 mol%, or 0 to 5 mol%, or 0 to 2 mol% of the total number of units. In one embodiment, the additional imide units are not present in the poly(etherimide).

[0024] Polyetherimides can be prepared by any method known to those skilled in the art, which includes the reaction of an aromatic bis(ether anhydride) of formula (5) or its chemical equivalent with an organic diamine of formula (6). [ka] (5) H2N-R-NH2 (6) In the formula, T and R are defined as described above. Polyetherimide copolymers can be prepared using a combination of the aromatic bis(ether anhydride) of formula (5) and an additional bis(anhydride) that is not a bis(ether anhydride), such as pyromellitic dianhydride or bis(3,4-dicarboxyphenyl)sulfone dianhydride.

[0025] Examples of aromatic bis(ether anhydrides) include: 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (also known as bisphenol A dianhydride or BPADA), 3,3-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl ether dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4' -Bis(2,3-dicarboxyphenoxy)benzophenone dianhydride, 4,4'-bis(2,3-dicarboxyphenoxy)diphenylsulfone dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl-2,2-propane dianhydride, 4-(2,3-dicarboxyphenoxy)-4'-(3,4-dicarboxyphenoxy)diphenyl ether dianhydride, 4-(2,3 -Dicarboxyphenoxy)-4'-(3,4-Dicarboxyphenoxy)diphenyl sulfide dianhydride, 4-(2,3-Dicarboxyphenoxy)-4'-(3,4-Dicarboxyphenoxy)benzophenone dianhydride, 4,4'-(Hexafluoroisopropylidene)diphthalic acid anhydride, and 4-(2,3-Dicarboxyphenoxy)-4'-(3,4-Dicarboxyphenoxy)diphenyl sulfone dianhydride. Different aromatic bis(ether anhydrides) combinations can be used.

[0026] Examples of organic diamines include: 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5 -Dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis(3-aminopropyl)amine, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy)ethane, bis(3-aminopropyl)sulfide, 1,4-cyclohexanediamine, bis-(4-aminocyclohexyl)methane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2, 6-Diaminotoluene, m-Xylylenediamine, p-Xylylenediamine, 2-Methyl-4,6-Diethyl-1,3-Phenylenediamine, 5-Methyl-4,6-Diethyl-1,3-Phenylenediamine, Benzidine, 3,3'-Dimethylbenzidine, 3,3'-Dimethoxybenzidine, 1,5-Diaminonaphthalene, Bis(4-Aminophenyl)methane, Bis(2-Chloro-4-Amino-3,5-Diethylphenyl)methane, Bis(4-Aminophenyl)propane , 2,4-bis(p-amino-t-butyl)toluene, bis(p-amino-t-butylphenyl) ether, bis(p-methyl-o-aminophenyl)benzene, bis(p-methyl-o-aminopentyl)benzene, 1,3-diamino-4-isopropylbenzene, bis(4-aminophenyl) sulfide, bis-(4-aminophenyl) sulfone (also known as 4,4'-diaminodiphenyl sulfone (DDS)), and bis(4-aminophenyl) ether. Any positional isomer of the above compounds can be used. Any of the above C 1-4 Alkylated or poly(C) 1-4Alkylated derivatives, such as polymethylated 1,6-hexanediamine, can be used. Combinations of these compounds can also be used. In one embodiment, the organic diamine is m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, or a combination comprising at least one of the above.

[0027] The thermoplastic composition may also include a poly(etherimide-siloxane) copolymer comprising a polyetherimide unit of formula (1) and a siloxane block of formula (7). [ka] (7) In the formula, E has a mean value between 2 and 100, 2 and 31, 5 and 75, 5 and 60, 5 and 15, or 15 and 40, and each R' is independently C 1-13 It is a monovalent hydrocarbyl group. For example, each R' independently is C 1-13 Alkyl alkyl group, C 1-13 Alkoxy group, C 2-13 Alkenyl group, C 2-13 Alkenyloxy group, C 3-6 Cycloalkyl groups, C 3-6 Cycloalkoxy group, C 6-14 Aryl group, C 6-10 Aryloxy group, C 7-13 Arylalkyl group, C 7-13 Arylalkoxy group, C 7-13 Alkylaryl group, or C 7-13The group may be an alkylaryloxy group. The group can be fully or partially halogenated with fluorine, chlorine, bromine, or iodine, or a combination of at least one of the above. In one embodiment, bromine or chlorine is absent, and in another embodiment, no halogen is present. The combination of the R groups can be used in the same copolymer. In one embodiment, the polysiloxane block contains an R' group having a minimal hydrocarbon content. In a particular embodiment, the R' group having a minimal hydrocarbon content is a methyl group.

[0028] Poly(etherimide-siloxane) can be formed by polymerization of diamine components including aromatic bis(ether anhydride) of formula (5), a combination of the organic diamine (6) or diamine described above, and polysiloxanediamine of formula (8). [ka] (8) In the formula, R' and E are as shown in formula (7), and R 4 Each is independent of C2-C 20 Hydrocarbons, especially C2-C 20 It is an arylene, alkylene, or arylenealkylene group. In one embodiment, R 4 is C2-C 20 Alkylene group, specifically C2-C 10 The alkylene group is, for example, propylene, and E has an average value of 5 to 100, 5 to 75, 5 to 60, 5 to 15, or 15 to 40. The procedure for producing the polysiloxanediamine of formula (8) is well known in the art.

[0029] In some poly(etherimide-siloxane) copolymers, the diamine components may include 10 to 90 mol percent (mol%), or 20 to 50 mol%, or 25 to 40 mol% of polysiloxanediamine (8), and 10 to 90 mol%, or 50 to 80 mol%, or 60 to 75 mol% of diamine (6), as described, for example, in U.S. Patent No. 4,404,350. The diamine components can be physically mixed with the bis(anhydride)(if any) before reaction, so that a substantially random copolymer is formed. Alternatively, block or alternating copolymers can be formed by the selective reaction of (6) and (8) with aromatic bis(etheranhydride)(5), so that polyimide blocks are produced, which then react together. Thus, poly(etherimide-siloxane) copolymers can be block, random, or graft copolymers. In one embodiment, the copolymer is a block copolymer.

[0030] Examples of specific poly(etherimide-siloxane) are described in U.S. Patents 4,404,350, 4,808,686 and 4,690,997. In one embodiment, the poly(etherimide-siloxane) has units of formula (9), [ka] (9) In the formula, R' and E of the siloxane are as shown in formula (7), and R and Z of the imide are as shown in formula (1), R 4 The formula is as shown in equation (8), where n and m are integers greater than 0, and the sum of n and m is from 5 to 100. In certain embodiments of poly(etherimide-siloxane), R of etherimide is phenylene, Z is a residue of bisphenol A, and R 4 R is n-propylene, E is 2 to 50, 5 to 30, or 10 to 40, n+m is 5 to 100, and each R' in the siloxane is methyl.

[0031] The relative amounts of polysiloxane units and etherimide units in poly(etherimide-siloxane) depend on the desired properties and are selected using the guidelines provided herein. In particular, as described above, block or grafted poly(etherimide-siloxane) copolymers are selected to have a certain average value of E and are selected and used in an amount effective to provide the desired weight percent of polysiloxane units in the composition. In one embodiment, poly(etherimide-siloxane) contains 10 to 50 weight percent, 10 to 40 weight percent, or 20 to 35 weight percent of polysiloxane units based on the total weight of poly(etherimide-siloxane).

[0032] Polyetherimides can have a melt index of 0.1 grams per minute to 10 grams per minute (g / min) when measured using a 6.7 kilogram (kg) load at 340°C to 370°C, according to the American Society for Testing and Materials (ASTM) D1238. In one embodiment, polyetherimides have a weight-average molecular weight (Mw) of 1,000 grams / mol to 150,000 grams / mol (Daltons) when measured by gel permeation chromatography using a poly(styrene) standard. In one embodiment, poly(etherimides) have an Mw of 10,000 Daltons to 80,000 Daltons. Such polyetherimides typically have an intrinsic viscosity of more than 0.2 deciliters per gram (dl / g), or more specifically, 0.35 dl / g to 0.7 dl / g, when measured in m-cresol at 25°C.

[0033] In one embodiment, the thermoplastic composition of the article includes a polyphenylene sulfide composition comprising a polyetherimide-siloxane copolymer, a polyphenylene sulfide, a polyaromatic ketone, and an epoxy.

[0034] The polyetherimide-siloxane copolymer can be as described above. In one embodiment, the polyetherimide-siloxane copolymer may have a siloxane content of 10 to 30 weight percent, or 15 to 25 weight percent, or 18 to 22 weight percent.

[0035] Polyaromatic ketones contain the repeating unit of formula (10), [ka] (10) In the formulas, Ar is independently a substituted or unsubstituted, monocyclic or polycyclic aromatic group having 6-30 carbon atoms in each event. Examples of Ar groups include, but are not limited to, substituted or unsubstituted phenyl, tolyl, naphthyl, and biphenyl. Unsubstituted phenyl may be preferred. In one embodiment, the poly(aromatic ketone) can be a poly(arylene ether ketone) (PAEK) containing repeating units of formulas (10) and (12). [ka] (12) In the formula, Ar is defined as above. In one embodiment, poly(aromatic ketone) includes poly(ether ketone). Poly(ether ketone) includes the repeating unit of formula (13), [ka] (13) In the formula, Ar is defined as above, 1 These are independently substituted or unsubstituted, monocyclic or polycyclic aromatic groups, each having 6-30 carbon atoms. Ar is Ar 1 It may be the same as or different from this. In one embodiment, Ar and Ar 1 This is a phenyl group, preferably an unsubstituted phenyl group.

[0036] In one embodiment, poly(aromatic ketone) includes poly(ether-ether-ketone). Poly(ether-ether-ketone) includes the repeating unit of formula (14), [ka] (14) In the formula, Ar and Ar 1 It is defined as above. Ar 2 These are independently substituted or unsubstituted, monocyclic or polycyclic aromatic groups, each having 6-30 carbon atoms. Ar, Ar 1 , and Ar 2 They can be the same as or different from each other. In addition, Ar, Ar 1 , and Ar 2 The first two can be the same, and the third can be different. In one aspect, Ar, Ar 1 , and Ar 2 This is a phenyl group, preferably an unsubstituted phenyl group.

[0037] Poly(aromatic ketones) are generally well-known, and many examples are commercially available. An example of a commercially available poly(aromatic ketone) is the one sold under the trademark name PEEK (trademark) by VICTREX.

[0038] In one embodiment, poly(aromatic ketone) includes poly(ether ketone), poly(ether ether ketone), poly(ether ketone ketone), or a combination thereof, preferably poly(ether ether ketone) of formula (14).

[0039] Epoxy resins can be produced as a result of the reaction of phenols or polyphenols with epichlorohydrins, forming polyglycidyl ethers. Examples of phenols useful for the production of epoxy resins include substituted bisphenol A, bisphenol F, hydroquinone, resorcinol, tris-(4-hydroxyphenyl)methane, and novolac resins derived from phenols or o-cresol. Epoxy resins can also be produced by the reaction of aromatic amines, such as p-aminophenol or methylenedianiline, with epichlorohydrins, forming polyglycidylamines. In one embodiment, the epoxy resin may include a novolac resin. In one embodiment, the epoxy resin may include a novolac resin derived from cresol.

[0040] The polyphenylene sulfide composition may contain polyetherimide-siloxane copolymer in an amount of 5% to 43.9% by weight, based on the total weight of the composition. Within this range, the polyetherimide-siloxane copolymer may be present in an amount of 5% to 40% by weight, or 5% to 30% by weight, or 5% to 25% by weight, or 10% to 20% by weight, or 12% to 18% by weight.

[0041] A polyphenylene sulfide composition may contain polyphenylene sulfide in an amount of 55 to 85 percent by weight, based on the total weight of the composition. Within this range, polyphenylene sulfide may be present in an amount of 60 to 85 percent by weight, or 70 to 85 percent by weight, or 72 to 85 percent by weight, or 75 to 80 percent by weight.

[0042] A polyphenylene sulfide composition may contain a polyaromatic ketone in an amount of 1% to 10% by weight, based on the total weight of the composition. Within this range, the polyaromatic ketone may be present in an amount of 1% to 8% by weight, or 2% to 8% by weight, or 3% to 7% by weight, or 4% to 6% by weight.

[0043] The polyphenylene sulfide composition may contain epoxy resin in an amount of 0.1 to 5 weight percent based on the total weight of the composition. Within this range, the epoxy may be present in an amount of 0.1 to 4 weight percent, or 0.2 to 3 weight percent, or 0.5 to 3 weight percent, or 1 to 3 weight percent, or 1.5 to 2.5 weight percent.

[0044] The thermoplastic composition of the article may optionally further include, in addition to the thermoplastic polymer, one or more additives selected to achieve desired properties (e.g., improved adhesion, fluidity, processability, miscibility, etc.), provided that the additives(s) are also selected so as not to significantly adversely affect the desired properties of the thermoplastic composition. The additive composition or individual additives may be mixed at a suitable time during the mixing of the components to form the composition. Examples of additive compositions include impact modifiers, flow modifiers, fillers (e.g., particulate polytetrafluoroethylene (PTFE), glass, carbon, minerals, or metals), reinforcing agents (e.g., glass fibers), antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) stabilizers, UV-absorbing additives, plasticizers, lubricants, mold release agents (e.g., mold release agents), antistatic agents, antifogging agents, antimicrobial agents, colorants (e.g., dyes or pigments), surface effect additives, radiation stabilizers, flame retardants, anti-drip agents (e.g., PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)), or combinations thereof. Additives may be used in amounts generally known to be effective. For example, the total amount of additive compositions (other than impact modifiers, fillers, or reinforcing agents) may range from 0.001% to 10% by weight, or from 0.01% to 5% by weight, based on the total weight of the composition. In one embodiment, additives are not intentionally added to the thermoplastic composition of the article.

[0045] Figure 1 shows a bottom view of an exemplary article (e.g., a retaining ring) (101) according to one aspect of the present disclosure. The bottom surface (102) of the article (101) may include a plurality of channels (103) within the bottom surface (102) extending from the inner edge (104) of the article to the outer edge (105) of the article. The channels can facilitate the inflow and outflow of slurry into and out of the article during the polishing process. The depth of the channels can be varied (e.g., deeper or shallower) to regulate or alter the inflow and outflow of fluid (polishing slurry or other liquid) into and out of the article where the substrate is placed. The channel cross-section may be rectangular, radial, or any other suitable shape. The shape of the channel cross-section can be selected to reduce or eliminate low-flow regions or dead volumes within the channels.

[0046] A cross-sectional view of an article according to one aspect of the present disclosure is shown in Figure 2. As shown in Figure 2, the article may include a metal skeleton (201) having a plurality of pores (203) on the surface of the metal skeleton. The metal skeleton having a plurality of pores is encapsulated in a thermoplastic composition (202).

[0047] A cross-sectional view of an article according to another aspect of the present disclosure is shown in Figure 3. As shown in Figure 3, the article may include a metal skeleton (301) (with or without pores) having a buffer layer (303) on its surface (i.e., encapsulating it). The buffer layer (303) has a plurality of pores (304) on its surface. The metal skeleton (301) encapsulated in the buffer layer (303) is further encapsulated in a thermoplastic composition (302).

[0048] The articles of this disclosure can be manufactured by a method comprising the step of surface-treating a metal framework to provide a plurality of pores on the metal framework. If a buffer layer is present on the article, the method comprises the steps of depositing the buffer layer on the metal framework and surface-treating the buffer layer to provide a plurality of pores on the buffer layer. The method further comprises the steps of forming a thermoplastic composition on the metal framework so that the metal framework is encapsulated by the thermoplastic composition. If a buffer layer is present, the thermoplastic composition is formed on a metal framework including the buffer layer.

[0049] Examples of surface treatment steps to provide pores include laser etching, chemical etching, plasma etching, or a combination thereof. In one embodiment, the surface treatment step may include plasma etching.

[0050] In one embodiment, molding is performed by an overmolding process, in which the thermoplastic composition is molded in the presence of a metal framework, optionally including a buffer layer. In other words, the thermoplastic composition can be formed or molded directly on or around a metal framework, optionally including a buffer layer. This process can also be called a metal insert molding process. Overmolding of the thermoplastic composition on a metal framework can be carried out by any molding technique suitable for melting the thermoplastic composition. Exemplary molding techniques include injection molding, injection compression molding, and compression molding. In one embodiment, molding can be carried out by injection molding of the thermoplastic composition.

[0051] The method may further include a step of creating multiple channels on the bottom surface of the article. The multiple channels may be as shown in Figure 1.

[0052] The articles of this disclosure may be particularly useful in chemical mechanical polishing systems. Therefore, another aspect of this disclosure is a chemical mechanical polishing system comprising the articles. In certain aspects, the chemical mechanical polishing system comprises the articles, where the articles are retaining rings.

[0053] Another aspect of the present disclosure is a polyphenylene sulfide composition, independent of its use as a component of an article for use in a chemical mechanical polishing process. The polyphenylene sulfide composition is as described above and comprises a polyetherimide-siloxane copolymer, polyphenylene sulfide, a polyaromatic ketone, and an epoxy resin.

[0054] The polyphenylene sulfide composition may contain polyetherimide-siloxane copolymer in an amount of 5% to 43.9% by weight, based on the total weight of the composition. Within this range, the polyetherimide-siloxane copolymer may be present in an amount of 5% to 40% by weight, or 5% to 30% by weight, or 5% to 25% by weight, or 10% to 20% by weight, or 12% to 18% by weight.

[0055] A polyphenylene sulfide composition may contain polyphenylene sulfide in an amount of 55 to 85 percent by weight, based on the total weight of the composition. Within this range, polyphenylene sulfide may be present in an amount of 60 to 85 percent by weight, or 70 to 85 percent by weight, or 72 to 85 percent by weight, or 75 to 80 percent by weight.

[0056] A polyphenylene sulfide composition may contain a polyaromatic ketone in an amount of 1% to 10% by weight, based on the total weight of the composition. Within this range, the polyaromatic ketone may be present in an amount of 1% to 8% by weight, or 2% to 8% by weight, or 3% to 7% by weight, or 4% to 6% by weight.

[0057] A polyphenylene sulfide composition may contain epoxy in an amount of 0.1 to 5 weight percent based on the total weight of the composition. Within this range, epoxy may be present in an amount of 0.1 to 4 weight percent, or 0.2 to 3 weight percent, or 0.5 to 3 weight percent, or 1 to 3 weight percent, or 1.5 to 2.5 weight percent.

[0058] The polyphenylene sulfide composition may optionally further contain one or more additives selected to achieve desired properties (e.g., improved adhesion, fluidity, processability, miscibility, etc.), provided that the additives(s) are also selected so as not to significantly adversely affect the desired properties of the thermoplastic composition. The additive composition or individual additives may be mixed at a suitable time during the mixing of the components to form the composition. Examples of additive compositions include impact modifiers, flow modifiers, fillers (e.g., fine-particle polytetrafluoroethylene (PTFE), glass, carbon, minerals, or metals), reinforcing agents (e.g., glass fibers), antioxidants, heat stabilizers, light stabilizers, ultraviolet (UV) stabilizers, UV-absorbing additives, plasticizers, lubricants, mold release agents (e.g., mold release agents), antistatic agents, antifogging agents, antimicrobial agents, colorants (e.g., dyes or pigments), surface effect additives, radiation stabilizers, flame retardants, anti-drip agents (e.g., PTFE-encapsulated styrene-acrylonitrile copolymer (TSAN)), or combinations thereof. Additives can be used in amounts generally known to be effective. For example, the total amount of additive compositions (other than impact modifiers, fillers, or reinforcing agents) can range from 0.001% to 10% by weight, or from 0.01% to 5% by weight, based on the total weight of the composition.

[0059] Other components not specifically provided herein can be minimized or excluded from the composition. For example, a polyphenylene sulfide composition can minimize thermoplastic polymers other than polyetherimide-siloxane copolymer, poly(phenylene sulfide), and polyaromatic ketones (e.g., present in amounts of less than 5% by weight, or less than 1% by weight, or less than 0.1% by weight). [Examples]

[0060] This disclosure is non-limiting and will be further illustrated by the following embodiments.

[0061] The materials used in the following examples are summarized in Table 1.

[0062] [Table 1]

[0063] Table 2 summarizes the composition of the test samples for the following examples. The amount of each component is given as a weight percentage based on the total weight of the composition.

[0064] [Table 2]

[0065] The physical properties were characterized according to the following test procedure.

[0066] The adhesive strength ("As") was determined according to ASTM 1002 and measured on a sample prepared from a molded sample of the composition (with an adhesive area of ​​10 × 5 mm) bonded to aluminum with dimensions of 18 × 50 × 1.5 mm. The adhesive strength is reported in MPa. It should be noted that the test articles used to evaluate the adhesive strength were not used in the formation of CMP retaining rings. The adhesive strength was tested independently, because, although we do not wish to be bound by theory, the adhesive strength shown by the test articles is thought to be able to suggest whether the composition would work well when used as a CMP retaining ring.

[0067] The following tests were performed on CMP retaining ring articles, in which case the thermoplastic composition was overmolded onto the metal ring. Flatness ("Fn") was determined by measuring the thickness of the molded sample in the form of a retaining ring at nine points across the entire sample. Flatness was calculated as the average of the standard deviations of the nine thicknesses. Strain ("Dt") was characterized by measuring the flatness of the molded sample in the form of a retaining ring, with a flatness value exceeding 0.01 millimeters (mm) being evaluated as "fail" and a flatness value of 0.01 mm or less being evaluated as "pass".

[0068] The results are summarized in Tables 3A and 3B. Insert metals were used with stainless steel (SUS304) or Al-Zn alloys. Where indicated in the table, an Al2O3 buffer layer was deposited on the insert metal by plasma etching. Where indicated in the table, nanopores were introduced into the insert metal or buffer layer using the plasma etching process.

[0069] [Table 3]

[0070] [Table 4]

[0071] As shown in Tables 3A and 3B, observation of test samples prepared from thermoplastic composition BE revealed improved adhesive strength between the metal and the thermoplastic. In contrast, the adhesive strength between the metal and thermoplastic composition A could not be measured. As described above, the adhesive strength of the test articles may provide insights into the usefulness of the composition in CMP applications.

[0072] Samples containing nanopores (E1-E18) showed significantly lower flatness compared to samples lacking nanopores (e.g., 0.001 to 0.009 for E1-E18 compared to 0.009 or higher for the comparative example). While we do not wish to be bound by theory, it is conceivable that the improvement in flatness may arise from the thermoplastic composition's ability to fill nanopores on metal rings or, if present, on buffer layers. Thus, materials can be interconnected through pore filling, leading to improved flatness of the article.

[0073] Tables 3A and 3B further show that samples containing nanopores did not show any distortion. In contrast, comparative examples without nanopores generally showed more significant distortion.

[0074] CMP retaining ring samples were further characterized for delamination from the thermoplastic composition metal rings. Delamination was determined by visually inspecting the cross-section of the retainer ring product after cutting the product. Inspection of the cut samples revealed that samples prepared from thermoplastic composition A showed delamination. In contrast, samples using thermoplastic composition CE did not show delamination. Examples using thermoplastic composition B were observed to show some delamination, but the performance of the article was not significantly affected, probably due to the lack of flatness and distortion of the article.

[0075] Furthermore, unexpectedly, a specific thermoplastic composition C was found to provide good adhesion, flatness, and strain even in the absence of nanopores, suggesting that this composition may be particularly useful in CMP-retaining ring articles even without nanopores.

[0076] As shown in Figure 4, composition CE1 showed delamination of the thermoplastic composition from the metal insert upon inspection of the cross-section of the ring after cutting. In contrast, as shown in Figure 5, no delamination was observed for composition E5 upon inspection of the cross-section of the ring after cutting.

[0077] The E5 composition was further observed to provide good color uniformity on the surface, and both the E1 and E5 compositions showed good color uniformity between the inner and outer layers of the molded part. These compositions were also found to have good workability, particularly with respect to cutting, slicing, bolting, and tapping, and did not exhibit cracks or chips after aging or during processing. Further advantages of this disclosure include reduction of part dimensions (e.g., thickness, height, weight) and improvement of the strength of the retaining ring structure.

[0078] Therefore, this provides significant advantages for articles used in chemical mechanical polishing processes where good workability and strong adhesion to metals are required.

[0079] This disclosure further encompasses the following aspects:

[0080] Embodiment 1: An article for use in a chemical mechanical polishing process, comprising a metal skeleton, which optionally includes a buffer layer on the surface of the metal skeleton, wherein the metal skeleton further includes a plurality of pores on the surface of the metal skeleton or, if present, on the buffer layer, and a thermoplastic composition for encapsulating the metal skeleton.

[0081] Embodiment 2: The article of Embodiment 1, wherein the thermoplastic composition comprises polyetherimide, poly(phenylene sulfide), poly(phenylene sulfone), poly(aromatic ketone), polyester, or a combination thereof.

[0082] Embodiment 3: An article according to Embodiment 1 or 2, wherein the thermoplastic composition comprises a polyetherimide.

[0083] Embodiment 4: The article of Embodiment 3, wherein the polyetherimide comprises repeating units derived from meta-phenylenediamine and bisphenol A dianhydride.

[0084] Embodiment 5: The article of Embodiment 3, wherein the polyetherimide is a poly(etherimide-siloxane) block copolymer.

[0085] Embodiment 6: An article according to any of Embodiments 1 to 5, wherein the thermoplastic composition comprises 5 to 43.9 weight percent of poly(etherimide-siloxane copolymer), 55 to 85 weight percent of poly(phenylene sulfide), 1 to 10 weight percent of polyaryletherketone, and 0.1 to 5 weight percent of epoxy resin, the weight percent being based on the total weight of the thermoplastic composition.

[0086] Embodiment 7: An article of any of Embodiments 1 to 6, which is present on the surface of a plurality of porous metal skeletons, preferably the metal skeletons comprising aluminum, stainless steel, molybdenum, ceramic, or a combination thereof.

[0087] Embodiment 8: An article according to any of Embodiments 1 to 6, wherein a buffer layer is present and a plurality of pores are located on the buffer layer.

[0088] Embodiment 9: An article according to any of Embodiments 1 to 8, wherein each of the plurality of pores has a diameter of 1 nanometer to 100 nanometers, and preferably each of the plurality of pores further has a depth of 1 nanometer to 100 nanometers.

[0089] Embodiment 10: The buffer layer comprises an inorganic, organic material, or a combination thereof, preferably an article of any of Embodiments 1 to 9, wherein the buffer layer comprises Al2O3, TiO2, ZnO, SiO2, PbO, Na2O, CaO, MgO, CuO, or an alloy thereof, more preferably Al2O3.

[0090] Embodiment 11: An article according to any of Embodiments 1 to 10, wherein the buffer layer has a thickness of 1 micrometer to 1000 micrometers.

[0091] Embodiment 12: An article of any embodiment 1 to 10, wherein the bottom surface of the article includes a plurality of channels within the bottom surface that extend from the inner edge of the article to the outer edge of the article, the channels being effective for moving a slurry during the polishing process.

[0092] Embodiment 13: An article according to any of Embodiments 1 to 12, wherein the metal skeleton is an annular metal skeleton.

[0093] Embodiment 14: The article is a retaining ring for use in a chemical mechanical polishing process, according to any of Embodiments 1 to 11.

[0094] Embodiment 15: A method for manufacturing an article according to any of Embodiments 1 to 14, comprising the steps of: providing a metal skeleton; optionally, depositing a buffer layer on the metal skeleton; surface treating the metal skeleton, or if present, the buffer layer, to provide a plurality of pores on the metal skeleton, or if present, on the buffer layer; and forming a thermoplastic composition on the surface-treated metal skeleton to provide an article.

[0095] Embodiment 16: A chemical mechanical polishing system comprising any article from Embodiments 1 to 14.

[0096] Embodiment 17: A polyphenylene sulfide composition comprising 5 to 43.9 weight percent of poly(etherimide-siloxane copolymer), 55 to 85 weight percent of poly(phenylene sulfide), 1 to 10 weight percent of polyaryl ether ketone, 0.1 to 5 weight percent of epoxy resin, and optionally 0.1 to 10 weight percent of an additive composition, wherein the weight percent is based on the total weight of the thermoplastic composition.

[0097] Embodiment 18: An article for use in a chemical mechanical polishing process, comprising a metal skeleton and a thermoplastic composition for encapsulating the metal skeleton, the thermoplastic composition comprising 5 to 43.9 weight percent of poly(etherimide-siloxane copolymer), 55 to 85 weight percent of poly(phenylene sulfide), 1 to 10 weight percent of polyaryletherketone, 0.1 to 5 weight percent of epoxy resin, and optionally 0.1 to 10 weight percent of an additive composition, the weight percent being based on the total weight of the thermoplastic composition.

[0098] Embodiment 19: The article of Embodiment 18, wherein the metal skeleton further comprises a plurality of pores on the surface of the metal skeleton or, if present, on the buffer layer.

[0099] Compositions, methods, and articles may optionally include, be composed of, or be essentially composed of, any suitable materials, processes, or components disclosed herein. In addition, compositions, methods, and articles may be formulated to lack, or substantially include, any materials (or types), processes, or components that are not otherwise necessary for achieving the function or purpose of the composition, method, and article.

[0100] All scopes disclosed herein include endpoints, which are independently and combinable with one another. “Combinations” include blends, mixtures, alloys, reaction products, etc. Terms such as “first,” “second,” etc., do not indicate order, quantity, or importance, but rather are used to distinguish one element from another. Terms such as “a,” “an,” or “the” do not indicate a limit on quantity and should be interpreted as encompassing both singular and plural forms unless otherwise specified herein or explicitly denied by the context. “Or” means “and / or” unless otherwise explicitly stated. Throughout the specification, references to “one aspect” mean that a particular element described in relation to an aspect is included in at least one aspect described herein, and may or may not be present in other aspects. As used herein, “their combinations” includes, but is not limited to, one or more of the enumerated elements, and the presence of one or more similar elements not specifically named is possible. In addition, it should be understood that the elements described may be combined in any preferred manner in various aspects.

[0101] Unless otherwise specified herein, all test standards are the most current standards in effect as of the filing date of this application, or, if priority is claimed, as of the filing date of the earliest priority application in which the test standard appears.

[0102] Unless otherwise specified, the technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art to which this application pertains. All cited patents, patent applications, and other references are incorporated herein by reference as a whole. However, in the event of any conflict or inconsistency between terms in this application and terms in any incorporated reference, the terms in this application shall prevail over the conflicting terms in the incorporated reference.

[0103] Compounds are described using standard nomenclature. For example, any position not substituted by any indicated group is understood to have an indicated bond or valence filled with a hydrogen atom. A dash ("-") without a space between two letters or symbols is used to indicate a bonding point for a substituent. For example, -CHO is bonded via the carbonyl group.

[0104] In this specification, the term "hydrocarbyl" refers to a residue containing only carbon and hydrogen, whether used alone or as a prefix, suffix, or fragment of another term. The residue may be aliphatic or aromatic, linear, cyclic, bicyclic, branched, saturated, or unsaturated. It may also contain combinations of aliphatic, aromatic, linear, cyclic, bicyclic, branched, saturated, and unsaturated hydrocarbon moieties. However, when a hydrocarbyl residue is described as substituted, it may optionally contain heteroatoms in addition to the carbon and hydrogen members of the substituted residue. Thus, when specifically described as substituted, the hydrocarbyl residue may also contain one or more carbonyl groups, amino groups, hydroxyl groups, etc., or may contain heteroatoms within the hydrocarbyl residue's backbone. The term "alkyl" means branched or linear, saturated aliphatic hydrocarbon groups, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, and n- and s-hexyl. "Alkenyl" refers to a linear or branched monovalent hydrocarbon group having at least one carbon-carbon double bond (e.g., ethenyl (-HC=CH2)). "Alkoxy" refers to an alkyl group linked via oxygen (i.e., alkyl-O-), such as methoxy, ethoxy, and sec-butyloxy groups. "Alkylene" refers to a linear or branched saturated divalent aliphatic hydrocarbon group (e.g., methylene (-CH2-) or propylene (-(CH2)3-)). "Cycloalkylene" refers to a divalent cyclic alkylene group, -C n H 2n-xThis means that, in the formula, x is the number of hydrogens replaced by cyclization(s). "Cycloalkenyl" means a monovalent group having one or more rings and one or more carbon-carbon double bonds within the ring, where all ring members are carbon (e.g., cyclopentyl and cyclohexyl). "Aryl" means an aromatic hydrocarbon group containing a specific number of carbon atoms, e.g., phenyl, tropone, indanyl, or naphthyl. "Arylene" means a divalent aryl group. "Alkylarylene" means an arylene group substituted with an alkyl group. "Arylalkylene" means an alkylene group substituted with an aryl group (e.g., benzyl). The prefix "halo" means a group or compound containing one or more fluoro, chloro, bromo, or iodo substituents. A combination of different halo atoms (e.g., bromo and fluoro), or only a chloro atom, can be present. The prefix "hetero" means that a compound or group contains at least one ring member that is a heteroatom (e.g., 1, 2, or 3 heteroatoms), each of which is independently N, O, S, Si, or P. "Substituting" means that a compound or group contains, in place of hydrogen, each independently C. 1-9 Alkoxy, C 1-9 Haloalkoxy, nitro(-NO2), cyano(-CN), C 1-6 Alkylsulfonyl (-S(=O)2-alkyl), C 6-12 Arylsulfonyl (-S(=O)2-aryl), thiol (-SH), thiocyano (-SCN), tosyl (CH3C6H4SO2-), C 3-12 Cycloalkyl, C 2-12 Alkenil, C 5-12 Cycloalkenyl, C 6-12 Ariel, C 7-13 Arylalkylene, C 4-12 Heterocycloalkyl, and C 3-12 This means that the group is substituted with at least one (e.g., 1, 2, 3, or 4) substituents that can form a heteroaryl group, provided that the number of substituents does not exceed the standard valence of the substituted atoms. The number of carbon atoms shown within the group excludes any substituents. For example, the -CH2CH2CN group is a nitrile-substituted C2 alkyl group.

[0105] While specific embodiments have been described, the applicant or those skilled in the art may conceive of alternatives, modifications, alterations, improvements, and substantial equivalents that are not anticipated or could not be anticipated at this time. Therefore, the filed, potentially amended appended claims are intended to encompass all such alternatives, modifications, alterations, improvements, and substantial equivalents.

Claims

1. Articles for use in chemical mechanical polishing processes, A metal skeleton optionally comprising a buffer layer on the surface of the metal skeleton, wherein the metal skeleton further comprises a plurality of pores on the surface of the metal skeleton or, if present, on the buffer layer. A thermoplastic composition for encapsulating the aforementioned metal skeleton, Articles including.

2. The article according to claim 1, wherein the thermoplastic composition comprises polyetherimide, poly(phenylene sulfide), poly(phenylene sulfone), poly(aromatic ketone), polyester, or a combination thereof.

3. The article according to claim 1 or 2, wherein the thermoplastic composition comprises a polyetherimide, preferably a polyetherimide comprising repeating units derived from meta-phenylenediamine and bisphenol A dianhydride.

4. The article according to claim 3, wherein the polyetherimide is a poly(etherimide-siloxane) block copolymer.

5. The thermoplastic composition, 5 to 43.9 weight percent of poly(etherimide-siloxane copolymer), 55 to 85 weight percent poly(phenylene sulfide), 1 to 10 weight percent of polyarylether ketone, 0.1 to 5% by weight of epoxy resin, Includes, The article according to any one of claims 1 to 4, wherein the weight percentage is based on the total weight of the thermoplastic composition.

6. The article according to any one of claims 1 to 5, wherein the plurality of pores are present on the surface of the metal skeleton, and preferably the metal skeleton comprises aluminum, stainless steel, molybdenum, ceramic, or a combination thereof.

7. The article according to any one of claims 1 to 5, wherein the buffer layer is present and the plurality of pores are located on the buffer layer.

8. The article according to any one of claims 1 to 7, wherein each of the plurality of pores has a diameter of 1 nanometer to 100 nanometers, and preferably each of the plurality of pores further has a depth of 1 nanometer to 100 nanometers.

9. The buffer layer comprises an inorganic, organic material, or a combination thereof, and preferably the buffer layer is Al ２ O ３ , TiO ２ ZnO, SiO ２ PbO, Na ２ O, CaO, MgO, CuO, or alloys thereof, more bluntly Al ２ O ３ The article according to any one of claims 1 to 8, comprising, preferably, the buffer layer having a thickness of 1 micrometer to 1,000 micrometers.

10. The article according to any one of claims 1 to 9, wherein the bottom surface of the article includes a plurality of channels extending from the inner edge of the article to the outer edge of the article, the channels being effective for moving a slurry during the polishing process.

11. The article according to any one of claims 1 to 10, wherein the metal skeleton is an annular metal skeleton.

12. The article according to any one of claims 1 to 11, wherein the article is a retaining ring for use in a chemical mechanical polishing process.

13. A method for manufacturing an article according to any one of claims 1 to 12, Process for providing a metal skeleton, Optionally, a step of depositing a buffer layer on the metal skeleton, The steps include: surface-treating the metal framework, or the buffer layer if present, to provide a plurality of pores on the metal framework, or the buffer layer if present; A step of forming a thermoplastic composition on a surface-treated metal skeleton to provide the article, Methods that include...

14. A chemical mechanical polishing system comprising an article according to any one of claims 1 to 12.

15. 5 to 43.9 weight percent of poly(etherimide-siloxane copolymer), 55 to 85 weight percent poly(phenylene sulfide), 1 to 10 weight percent of polyarylether ketone, 0.1 to 5% by weight of epoxy resin, Optionally, an additive composition in an amount of 0.1 to 10 weight percent, A polyphenylene sulfide composition comprising, A polyphenylene sulfide composition, the weight percentage being based on the total weight of the thermoplastic composition.

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