Porous poly(cyclic olefin) membrane

Abstract

The present disclosure provides certain porous membranes comprised of cyclic polyolefin polymers such as poly(norbornene). In one embodiment, the poly(norbornene) polymer is dissolved in tetrahydrofuran, cast into a film, and subjected to solvent-induced phase separation to obtain a porous filter membrane (i.e., a film).

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates generally to the field of liquid purification using membrane technology. [Background technology]

[0002] Filter products are essential tools in modern industry, used to remove unwanted materials from useful fluid streams. Useful fluids treated using filters include water used in manufacturing or processing (e.g., in semiconductor manufacturing), liquid industrial solvents and process fluids, and liquids with medical or pharmaceutical applications. Unwanted materials removed from fluids include impurities and contaminants such as particles, microorganisms, and dissolved chemical species. Specific examples of filter applications include use with liquid materials for semiconductor and microelectronic device manufacturing.

[0003] Filters can remove unwanted materials through a variety of different methods, such as by size exclusion or by chemical and / or physical interaction with materials. Some filters are defined by the structural material that provides the filter with a porous structure, allowing the filter to capture particles of a size that cannot pass through the pores. Some filters are defined by the ability of the filter's structural material, or chemicals associated with the structural material, to associate and interact with materials passing through the filter. For example, the chemical characteristics of the filter can allow it to associate with unwanted materials from the stream passing through the filter and capture these unwanted materials through ionic, coordination, chelation, or hydrogen-bonding interactions, etc. Some filters can utilize both size exclusion and chemical interaction characteristics to remove materials from the filtered stream.

[0004] In some cases, to perform the filtering function, the filter includes a filter membrane responsible for removing unwanted materials from the fluid passing therethrough. The filter membrane may optionally be in the form of a flat sheet, which may be wound (e.g., spiral), flat, pleated, or disk-shaped. Alternatively, the filter membrane may be in the form of a hollow fiber. The filter membrane may be contained within a housing or otherwise supported such that the fluid being filtered enters the filter inlet and is required to pass through the filter membrane before passing through the filter outlet.

[0005] Removing ionic materials, such as dissolved anions or cations, from solution is important in many industries, such as the microelectronics industry, where ionic contaminants and very low concentrations of particles can adversely affect the quality and performance of microprocessors and memory devices. In particular, it may be desirable to remove metal-containing materials, including metal ions, from liquid compositions used in device fabrication. Metal-containing materials can be found in various types of liquids used in microelectronics fabrication.

[0006] Various unresolved technical challenges remain for the removal of metal-containing materials from fluids. A wide variety of different liquid materials are used as process solvents, cleaning agents, and other processing solutions in microelectronic device processing. Many, if not most, of these materials require very high levels of purity. As an example, liquid materials (e.g., solvents) used in photolithography processing of microelectronic devices must be of very high purity. Specific examples of liquids used in microelectronic device processing include spin-on-glass (SOG) technology, bottom antireflective coating (BARC) methods, photolithography, wet chemical etching methods, and process solutions for cleaning operations after chemical-mechanical polishing, ashing, and etching methods. One option for solving these technical challenges is new film materials. Summary of the Invention

[0007] In summary, the present disclosure provides certain filter membranes composed of cyclic polyolefin polymers. Despite their relatively high molecular weights and glass transition temperatures (Tg), these polymers are soluble in certain solvents, such as hydrocarbons and cyclic ethers such as tetrahydrofuran (THF). Once in solution, these polymer solutions can be cast into films and subjected to non-solvent-induced phase separation to ultimately obtain porous membranes. Water and certain protic water-miscible organic solvents, either alone or in combination with other non-solvents, can be used as non-solvents (for the polymer) in this membrane formation. In this regard, the non-solvent must be miscible with the first solvent. In one embodiment, a norbornene polymer (homopolymer or copolymer) is dissolved in a solvent such as tetrahydrofuran, and then a non-solvent such as isopropanol is added. The polymer solution is cast into a film on a flat surface, such as a glass plate, and then immersed in water to form a norbornene polymer membrane. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a scanning electron micrograph (SEM) of a filter membrane of the present invention prepared from poly(norbornene) at 5000x magnification (see Example 2 below). DETAILED DESCRIPTION OF THE INVENTION

[0009] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the content clearly dictates otherwise. As used in this specification and the appended claims, the term "or" is generally used in its sense including "and / or" unless the content clearly dictates otherwise.

[0010] The term "about" generally refers to a range of numbers that are considered equivalent to the recited value (i.e., having the same function or result). In many cases, the term "about" can include numbers that are rounded to the nearest significant figure.

[0011] Numerical ranges expressed using endpoints include all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0012] Filter membranes can be constructed from porous structures with average pore sizes that can be selected based on the use of the filter, i.e., the type of filtration to be performed by the filter. Typical pore sizes are in the micron or submicron range, such as from about 0.001 micron to about 10 microns. Membranes with average pore sizes of about 0.001 to about 0.05 microns are sometimes classified as ultrafiltration membranes. Membranes with pore sizes between about 0.05 and 10 microns are sometimes called microporous membranes.

[0013] Filter membranes with pore sizes in the micron or submicron range, or simply referred to herein as "membranes," can be effective in removing unwanted materials from a fluid stream by either a sieving or non-sieving mechanism, or both. A sieving mechanism is a type of filtration that removes particles from a liquid stream by mechanically retaining them on the surface of the filter membrane, which acts to mechanically interfere with the movement of the particles, retaining them within the filter, and mechanically impeding the flow of particles through the filter. Typically, particles can be larger than the pores of the filter. A "non-sieving" filtration mechanism is a type of filtration in which a filter membrane retains suspended particles or dissolved materials contained in a fluid stream passing through the filter membrane in a manner that is not exclusively mechanical, for example, including an electrostatic mechanism in which particles or dissolved impurities are electrostatically attracted to and retained on the filter surface and removed from the fluid stream; the particles can be dissolved or solid with a particle size smaller than the pores of the filter material.

[0014] In certain embodiments of the filter membranes and methods of the present disclosure, the filter comprises a porous filter membrane in the form of a polymer film composed of certain poly(cyclic olefins). As used herein, a "porous filter membrane" is a porous polymer solid containing porous (e.g., microporous) interconnected passages extending from one surface of the membrane to the opposite surface of the membrane. The passages generally provide tortuous tunnels or paths through which the liquid to be filtered must pass.

[0015] The filter membranes and methods of the present disclosure can also function to prevent any particles (e.g., metal-containing particles) present in the liquid composition that are larger than the pores from entering the microporous membrane, or to trap the particles within the pores of the microporous membrane (i.e., the particles are removed by a sieving-type filtration mechanism). The liquid to be treated can pass through the membrane to provide a flow-through having a reduced amount of metals, such as a reduced amount of ionic metal species, a reduced amount of metal-containing particles, or both.

[0016] Thus, the porous polymer membranes of the present disclosure are capable of removing metal and metal ion contaminants in a solution passing through the membrane, as well as any material too large in size to pass through the pores of the membrane.

[0017] Liquid compositions that require purification can be passed through the filter membrane of the present disclosure to effectively remove metal contaminants to a level suitable for the desired application.One application that the filter material and method of the present disclosure can be used for is semiconductor manufacturing, for example, for purifying metals from solutions used in etching and cleaning semiconductor materials.Given the selectivity of their purification capabilities, the filter material and method of the present disclosure are particularly useful in photolithography in general.Advantageously, the filter membrane and method of the present disclosure are expected to effectively remove undesirable amounts of particulate materials, such as metal particles, and ionic contaminants and organic contaminants from such fluids.

[0018] In one embodiment, the metal contaminants removed using the filter materials and methods of the present disclosure include Li, B, Na, Mg, Al, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Mo, Cd, Sn, Ba, and Pb ions, individually or in combination of two or more thereof. In one embodiment, the metal ions removed are selected from iron, chromium, manganese, aluminum, and nickel cations.

[0019] In a first aspect, the present disclosure provides a porous membrane comprising a poly(cyclic olefin) polymer having a thickness of about 40 μm to about 300 μm and an average pore size of about 5 nm to about 100 nm, the porous membrane exhibiting an isopropanol flow time of greater than about 200 seconds / 500 ml when measured at 14.2 psi. The porous membrane may also have a bubble point of about 5 to about 250 psi when measured using ethoxynonafluorobutane HFE7200 at a temperature of about 22° C. In one embodiment, the bubble point is about 5 to about 180 psi when measured using ethoxynonafluorobutane HFE7200 at a temperature of about 22° C.

[0020] Poly(cyclic olefins) useful in the present disclosure include the reaction polymerization products of cyclic alkenes. In one embodiment, the poly(cyclic olefin) has the structure: TIFF0007739459000001.tif34170 (wherein n represents the number of repeating units, p is 0 or 1, and R is: (i) C1 to C 10 alkyl groups; (ii) C1-C substituted 1 to 3 times with a group selected from halo, nitro, C1-C4 alkoxy, cyano, amine, sulfonamide, sulfonic acid, trifluoromethanesulfonamide, phosphonic acid, carboxyl, hydroxyl, and salts thereof. 10 alkyl groups; (iii) an aryl group, (iv) a carboxyl acid, ester, or amide group; (v) sulfonic acid groups, (vi) a sulfonamide group, (vii) a trifluoromethanesulfonamide group, (viii) an alkoxy group, and (ix) heteroaryl group (selected from The repeat unit may comprise one or more crosslinked monomeric repeat units, such as a repeat unit having the following structure:

[0021] In one embodiment, the salts are selected from alkali metal and ammonium salts.

[0022] The poly(cyclic olefin) may be a homopolymer containing one repeat unit of the structure shown above, or may be a copolymer containing two or more different repeat units having the above structure. For example, the poly(cyclic olefin) may be a copolymer containing cyclic olefin repeat units shown above substituted with R and cyclic olefin repeat units that are not substituted with R, such as norbornene. An exemplary random copolymer has the structure: TIFF0007739459000002.tif37170 (wherein n and m represent the number of repeating units of each type, and n and m may be the same or different) Poly(cyclic olefins) containing both substituted and unsubstituted cyclic olefin repeat units have been found to have improved viscosity, particularly in solvent systems used to provide porous polymer membranes.

[0023] In certain embodiments, the filter membrane material can have a chemistry suitable for attaching chelating or ion-exchange functionality. This functionality can be introduced via a coating that can be applied to the membrane, with such coating having functional groups suitable for chelating and / or ion-exchange mechanisms for removing impurities. Alternatively, the "R" groups of the repeating units can be modified to contain such functional groups, which can then be utilized for non-sieving purification mechanisms without applying a coating or other surface treatment to the membrane, such as sulfonic acid groups or other groups used in ion-exchange purification methods. Examples of various methodologies for grafting or otherwise attaching desired functional groups to polymer membrane surfaces for purposes of non-sieving filtration can be found in U.S. Pat. No. 10,792,620, which is incorporated herein by reference in its entirety, and U.S. Patent Application Publication Nos. 2020 / 0406201; 2020 / 0254398; 2020 / 0206691; 2019 / 0329185; and 2018 / 0185835, which are incorporated herein by reference in their entirety.

[0024] As used herein, the term "aryl" refers to a carbocyclic aromatic ring such as phenyl, naphthyl, biphenyl, etc. Similarly, the term "heteroaryl" refers to a carbocyclic aromatic ring having one or more heteroatoms selected from sulfur, oxygen, or nitrogen. Examples of heteroaryl groups include pyridyl, pyrimidyl, furyl, thienyl, pyrrolyl, benzofuryl, and benzothienyl groups. Aryl and heteroaryl groups may be substituted one or more times with groups such as C1-C6 alkyl, C1-C6 alkoxy, cyano, halo, sulfonamide, sulfonic acid, phosphonic acid, carboxyl, and hydroxyl groups, as well as alkali metal and ammonium salts thereof.

[0025] In another embodiment, the poly(cyclic olefin) is a poly(norbornene) polymer, i.e., a polymer having the structure: TIFF0007739459000003.tif34170 (wherein R is hydrogen or C1 to C 10 alkyl) For example, poly(cyclic olefins) contain only repeating units where R is hydrogen, or where R is C1-C 10 Alternatively, the poly(cyclic olefin) may be a homopolymer containing only repeating units that are alkyl. TIFF0007739459000004.tif37170 (wherein n and m represent the number of repeating units, and n and m are the same or different) The poly(norbornene) may be a copolymer containing a combination of these repeating units, such as a copolymer having the repeating units (R = 1, R = 2, R = 1). Some poly(norbornene) homopolymers are commercially available, and their synthesis is known. For example, poly(norbornene) can be obtained by the Diels-Alder reaction of cyclopentadiene and ethylene. Therefore, derivatization of the R groups described above can be achieved by changing the corresponding R groups on the starting materials.

[0026] Thus, in one embodiment, the present disclosure provides a porous membrane comprising a poly(norbornene) polymer having a thickness of about 40 μm to about 300 μm and an average pore size of about 10 nm to about 100 nm, the porous membrane exhibiting an isopropanol flow time of about 200 seconds / 500 ml to about 8000 seconds / 500 ml when measured at 14.2 psi. The porous membrane may also have a bubble point of about 5 to about 250 psi when measured using ethoxynonafluorobutane HFE7200 at a temperature of about 22° C. In one embodiment, the bubble point is about 5 to about 180 psi when measured using ethoxynonafluorobutane HFE7200 at a temperature of about 22° C.

[0027] As described above, the membranes of the present invention can be prepared by an immersion casting process. In this process, a poly(cyclic olefin) is dissolved in a water-miscible solvent. A suitable solvent for a particular poly(cyclic olefin) for this purpose can be determined using Hansen solubility parameter analysis or empirically by trial and error. In certain embodiments, such solvents include water-miscible cyclic ether solvents such as tetrahydrofuran, dioxane, or tetrahydropyran. Polymer nonsolvents are another class of materials commonly added to polymer solutions to alter their phase separation behavior and produce the desired membrane morphology. Liquids such as water and certain water-miscible organic materials can be used alone, in combination, or sequentially as nonsolvents in this membrane formation. Once in solution, these polymer solutions can be cast into films and immersed in a nonsolvent / coagulant to induce phase separation and form the porous asymmetric membranes of the present disclosure.

[0028] In one embodiment, the water-miscible material (i.e., the non-solvent) is a C1-C ethanol, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, etc. 10 Further non-solvents include glycols and glycol ethers, C2-C6 10 Diols and C2-C 10Triol, tetrahydrofurfuryl alcohol, ethyl benzoate, acetonitrile, acetone, ethylene glycol, propylene glycol, 1,3-propanediol, dioxane, butyryl lactone, butylene carbonate, ethylene carbonate, propylene carbonate, dipropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol phenyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether The alkyl ether may be selected from ethylene glycol ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl ether, propylene glycol n-propyl ether, dipropylene glycol n-propyl ether, tripropylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, propylene glycol phenyl ether, ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, hexaethylene glycol monophenyl ether, dipropylene glycol methyl ether acetate, tetraethylene glycol dimethyl ether dibasic ester, glycerin carbonate, N-formylmorpholine, triethyl phosphate, and combinations thereof.

[0029] The addition of a non-solvent results in the formation of a membrane (i.e., porous membrane) morphology having a desired microstructure in terms of porosity, average pore size, and pore size distribution. Thus, the desired morphology is provided through selection of the non-solvent, concentration, temperature, etc. In one embodiment, a poly(norbornene) polymer is dissolved in tetrahydrofuran, blended with isopropanol, cast into a film, and then immersed in water to induce phase separation and the formation of a porous filter membrane (i.e., film).

[0030] Thus, in a further aspect, the present disclosure provides a porous membrane comprising a poly(norbornene) homopolymer or copolymer having a thickness of about 40 μm to about 300 μm and an average pore size of about 5 nm to about 100 nm, the porous membrane exhibiting an isopropanol flow time of about 200 seconds / 500 ml to about 8000 seconds / 500 ml when measured at 14.2 psi. The porous membrane may also have an initial bubble point of about 5 to about 250 psi when measured using an ethoxynonafluorobutane HFE7200 at a temperature of about 22° C. The porous membrane is prepared by dissolving the polymer in a water-miscible solvent to form a solution, followed by adding at least one first non-solvent, followed by casting the solution onto a flat surface to thereby form a coated surface, and subsequently immersing the coated surface in at least one second non-solvent, thereby forming a porous membrane.

[0031] In one embodiment, the bubble point is from about 5 to about 180 psi when measured using ethoxynonafluorobutane HFE7200 at a temperature of about 22°C.

[0032] In one embodiment, the first non-solvent is isopropanol and the second non-solvent is water.

[0033] In another embodiment, the poly(cyclic olefin) solution can be subjected to filtration through an ion exchange resin or membrane to remove trace metal ions that may be entrained within the starting poly(cyclic olefin) material. For example, a tetrahydrofuran solution of poly(norbornene) can be passed through an ion exchange membrane or column containing ion exchange resin beads to remove trace metal ions prior to formation of the membranes of the present disclosure.

[0034] As used herein, "filter" refers to an article having a structure that includes a filter membrane.

[0035] In some embodiments, the filter of the present disclosure comprises a composite filter arrangement. For example, a filter having a composite arrangement can comprise two or more filter materials, such as two or more filter articles. For example, the filter can comprise a first porous polymer membrane comprising the membrane of the present disclosure, and a second filter material that does not comprise the membrane of the present disclosure or is different in some way from the membrane of the present disclosure. The second filter material can also be in the form of a porous membrane, or can be different, such as having a non-porous form, or can be another filter material, such as a woven or non-woven material. The second filter material can be made from the same or different polymer material as the first membrane.

[0036] Thus, in another embodiment, the present disclosure provides: First filter material and second filter material A composite filter comprising: an output side of the first filter material in contact with an input side of the second filter material; the first filter material comprises the membrane of the present disclosure shown herein; The second filter material is different from the first filter material. A composite filter is provided.

[0037] As described above, filter membranes can be used to remove particulate materials (such as metal particles), metal ions, and organic contaminants from organic solvents. Specific, non-limiting examples of solvents used in photolithography that can be filtered using the described filter membranes include n-butyl acetate (nBA), isopropyl alcohol (IPA), 2-ethoxyethyl acetate (2EEA), cyclohexanone, ethyl lactate, gamma butyrolactone, isopentyl ether, methyl 2-hydroxyisobutyrate, methyl isobutyl carbinol (MIBC), methyl isobutyl ketone (MIBK), isoamyl acetate, propylene glycol methyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), and a mixed solution of propylene glycol monomethyl ether (PGME) and PGMEA (7:3 mixture ratio, surface tension of 27.7 mN / m). Because porous membranes comprising poly(cyclic olefins), particularly those comprising copolymeric poly(norbornene) homopolymers, are hydrophobic and essentially non-reactive, these membranes can be particularly useful for removing impurities from highly reactive solvents, which may include aqueous acids (e.g., hydrochloric acid), aqueous bases (e.g., aqueous ammonia), peroxy compounds such as hydrogen peroxide, and the like.

[0038] For example, in some embodiments, a solvent may be obtained that has a higher amount of metal ions and / or metal-containing impurities (i.e., particles) than is desirable for the target application, such as a cleaning solvent for forming integrated circuits, or a solvent for resist stripping applications in lithography. For example, metal impurities may be present in the solvent in total amounts at ppm or ppb levels. Therefore, the solvent is passed through a filter membrane of the present disclosure to remove the metal contaminants, resulting in a filtered solvent that has a lower amount of metal than the amount of metal in the starting solvent. In certain embodiments, the filters of the present disclosure can remove any one or more metals from the starting solvent in an amount of about 25% (wt) or more, about 30% (wt) or more, about 35% (wt) or more, about 40% (wt) or more, about 45% (wt) or more, about 50% (wt) or more, about 55% (wt) or more, about 60% (wt) or more, about 65% (wt) or more, about 70% (wt) or more, about 75% (wt) or more, about 80% (wt) or more, about 85% (wt) or more, about 90% (wt) or more, or about 95% (wt) or more.

[0039] The solvent being treated to remove metal contaminants can be passed through the filter under desired conditions, such as conditions that enhance the removal of metal contaminants from the fluid stream. In some embodiments, the solvent is passed through the filter at a temperature of about 120° C. or less, 80° C. or less, or 40° C. or less.

[0040] The passage of solvent through the filter membranes of the present disclosure is not limited to any particular flow rate.

[0041] With reference to the porous polymeric filter membranes described herein, such membranes can be characterized by physical characteristics including pore size, bubble point, and porosity. In this regard, the porous polymeric filter membranes can have any pore size that allows the filter membrane to be effective in functioning as a filter membrane, including pores of a size (average pore size) that may be considered, for example, a microporous filter membrane or an ultrafiltration membrane, as described herein. In certain embodiments, the porous membrane can have an average pore size ranging from about 5 nm to about 100 nm, with the pore size selected based on one or more factors, including the particle size or type of impurities to be removed, the pressure and pressure drop requirements, and the viscosity requirements of the liquid to be processed by the filter. Pore size is often reported as the average pore size of the porous material, which can be measured by known techniques such as mercury porosimetry (MP), scanning electron microscopy (SEM), liquid displacement spectroscopy (LLDP), or atomic force microscopy (AFM).

[0042] Bubble point is also a known characteristic of porous membranes. According to the bubble point test, a sample of porous polymeric filter membrane is immersed in a liquid with a known surface tension, thereby wetting it, and gas pressure is applied to one side of the sample. The gas pressure is gradually increased. The minimum pressure at which gas flows through the sample is called the bubble point. To determine the bubble point of a porous material, a sample of the porous material is immersed in ethoxy-nonafluorobutane HFE7200 (available from 3M) at a temperature of 20-25°C (e.g., 22°C), thereby wetting it. Gas pressure is applied to one side of the sample using compressed air, and the gas pressure is gradually increased. If the membrane is asymmetric, the gas pressure is applied to the side of the membrane sample with the larger pore size. All bubble point values ​​provided herein are initial bubble points, measured using the procedure described above. Examples of useful bubble points of porous polymer filter membranes useful or preferred according to the present invention, as measured using the above procedure, can be about 5 to about 250 psi, about 5 to about 225 psi, about 5 to about 200 psi, about 5 to about 180 psi, about 5 to about 150 psi, about 30 to about 250 psi, about 30 to about 225 psi, about 30 to about 200 psi, about 30 to about 180 psi, about 30 to about 150 psi, about 50 to about 250 psi, about 50 to about 225 psi, about 50 to about 200 psi, about 50 to about 180 psi, and all ranges and subranges therebetween. The described porous polymer filter layers can have any porosity that enables the porous polymer filter layer to be effective as described herein. Exemplary porous polymer filter layers can have a relatively high porosity, for example, at least 60, 70, or 80% porosity. As used herein, and in the art of porous bodies, the "porosity" (sometimes called porosity) of a porous body is a measure of the void (i.e., "empty") space within the porous body as a percentage of the total volume of the porous body, calculated as the ratio of the volume of the voids in the porous body to the total volume of the porous body. A body with 0% porosity is completely solid.

[0043] Advantageously, the balance between bubble point and IPA flow time (which is influenced by pore size and interconnectivity, ie, morphology) is optimized for the desired overall performance.

[0044] The described porous polymer filter membranes can be in the form of sheets or hollow fibers having any useful thickness, for example, thicknesses ranging from about 40 μm to about 300 μm, from about 80 μm to about 250 μm, or from about 120 μm to about 200 μm, from about 140 μm to 180 μm, and all ranges or subranges therebetween.

[0045] In certain embodiments, the membranes of the present disclosure are asymmetric, with one surface of the membrane having a larger pore size than the opposite surface of the membrane.

[0046] The membrane isopropanol (IPA) flow time reported herein is 13.8 cm for 500 ml of isopropyl alcohol (IPA) fluid at 14.2 psi and a temperature of 21°C. 2The water flow time is determined by measuring the time it takes for the isopropanol to pass through a membrane having a 47 mm membrane disk with an effective surface area of ​​1000 s. The water flow time can be measured using the same procedure as the IPA flow time, except that water is used instead of IPA. In some embodiments, the isopropanol flow time is greater than about 200 s / 500 mL. In other embodiments, the isopropanol flow time is greater than about 200 seconds / 500 mL and less than about 50,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 20,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 15,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 8,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 1,000 seconds / 500 mL, greater than about 500 seconds / 500 mL and less than about 50,000 seconds / 500 mL, greater than about 500 seconds / 500 mL and less than about 20,000 seconds / 500 mL, or less than about 500 seconds / 500 mL. seconds / 500 mL and less than about 15,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 8,000 seconds / 500 mL, greater than about 500 seconds / 500 mL and less than about 1,000 seconds / 500 mL, greater than about 1,000 seconds / 500 mL and less than about 50,000 seconds / 500 mL, greater than about 1,000 seconds / 500 mL and less than about 20,000 seconds / 500 mL, greater than about 1,000 seconds / 500 mL and less than about 15,000 seconds / 500 mL, greater than about 200 seconds / 500 mL and less than about 8,000 seconds / 500 mL, and all ranges and subranges therebetween.

[0047] The described filter membranes can be contained within a larger filter structure, such as a multi-layer filter assembly or filter cartridge, used in a filtration system. The filtration system places the filter membrane within a filter housing, for example, as part of a multi-layer filter assembly or filter cartridge, so that the filter membrane removes a certain amount of impurities or contaminants from a liquid chemical, exposing the filter membrane to a flow path of the liquid chemical and allowing at least a portion of the liquid chemical flow to pass through the filter membrane. The structure of the multi-layer filter assembly or filter cartridge can include one or more various additional materials and structures that support the filter membrane within the filter assembly or filter cartridge and allow fluid to flow from the filter inlet through the membrane (including the filter layer) and through the filter outlet, thereby passing through the filter membrane as it passes through the filter. The filter membrane supported by the filter assembly or filter cartridge can be of any useful shape, such as a pleated cylinder, a cylindrical pad, one or more non-pleated (flat) cylindrical sheets, a pleated sheet, etc.

[0048] Furthermore, the described filter membrane can be characterized by membrane flux, which is defined as the volumetric flow rate of a liquid passing through a unit area of ​​the membrane at a certain pressure. The membrane flux must be high enough so that a membrane filter device with a certain membrane area can deliver the required flow rate of liquid for a certain application. The flow characteristic of a membrane can be considered as the membrane resistance to liquid flow, which is 13.8 cm at 21 ° C and 14.2 psi. 2 The membrane flow rate can also be measured by membrane flow time, which is defined as the time required for 500 ml of liquid to flow through a 47 mm disk membrane having an effective surface area of ​​1000 μm. The filter membranes described herein can, in certain embodiments, have a relatively low flow time, e.g., in combination with a relatively high bubble point, to exhibit good filtration performance (e.g., as measured by particle retention).

[0049] In a further aspect, the present disclosure provides a method for removing one or more particulate materials, and / or metal ions, and / or organic contaminants from a liquid composition, wherein the liquid composition comprises at least one particulate material, and / or metal ions, and / or organic contaminants, the method comprising: (i) passing a liquid composition through a membrane of the present disclosure; and (ii) reducing the amount of one or more particulate materials, and / or metal ions, and / or organic contaminants in the liquid composition, thereby providing a purified liquid composition. The present invention provides a method comprising: [Example]

[0050] Example 1 A 5 g sample of poly(norbornene) PNB polymer in powder form was added to 50 g of tetrahydrofuran (THF) solvent under stirring with an overhead stirrer. After the polymer was completely dissolved, 6.5 g of isopropanol (IPA) was added to the solution as a non-solvent. A PNB membrane was fabricated by casting a thin film of the polymer solution having a thickness of approximately 200 microns onto a glass plate and then immersing it in a room temperature water bath. The water flow time and bubble point of the formed membrane were measured according to the procedures described above. The formed membrane exhibited a wet membrane water flow time of 1700 seconds / 500 ml and a bubble point of 22 psi.

[0051] Example 2 Five grams of PNB polymer in powder form was added to 50 grams of THF solvent under stirring with an overhead stirrer. After the polymer was completely dissolved, 5-6.5 grams of IPA was added to the solution as a non-solvent. A thin film of the polymer solution approximately 200 microns thick was cast onto a glass plate and then immersed in a room-temperature water bath to create a PNB membrane. The membrane was then dried at room temperature for 24 hours. The IPA flow time and bubble point of the membrane were then measured according to the procedure described above. The results are shown in the table below. TIFF0007739459000005.tif34170

[0052] Example 3 structure: TIFF0007739459000006.tif37170 (wherein R is hexyl) Two poly(cyclic olefin) (PCO) copolymers were prepared, with n = 92 and m = 8 for copolymer A and n = 80 and m = 20 for copolymer B. Additionally, a poly(cyclic olefin) homopolymer with n = 100 and m = 0 was prepared.

[0053] A polymer solution containing Copolymer A, Copolymer B and a homopolymer was prepared using the procedure described in Example 1. The ratios of each material are shown in the table below.

[0054] PNB membranes were fabricated by casting thin films of these polymer solutions with a thickness of approximately 200 microns onto glass and then immersing them in a room temperature water bath. The IPA flow time and bubble point of the formed membranes were measured according to the procedures described above, and the results are shown in the table below. TIFF0007739459000007.tif31170

[0055] Aspects In a first aspect, the present disclosure provides a method for manufacturing a semiconductor device comprising: A poly(cyclic olefin) polymer having a thickness of about 40 μm to about 300 μm and an average pore size of about 5 nm to about 100 nm. A porous membrane comprising: A porous membrane is provided that exhibits an isopropanol flow time of greater than about 200 seconds / 500 ml when measured at 14.2 psi and a temperature of about 21°C.

[0056] In a second aspect, the present disclosure provides the membrane of the first aspect, having a bubble point of about 5 to about 250 psi when measured using ethoxynonafluorobutane HFE7200 at a temperature of about 22°C.

[0057] In a third aspect, the present disclosure provides a membrane of the first or second aspect, wherein the poly(cyclic olefin) comprises crosslinked monomer repeat units.

[0058] In a fourth aspect, the present disclosure provides a poly(cyclic olefin) comprising a poly(cyclic olefin) having the moiety: TIFF0007739459000008.tif34170 (wherein n represents the number of repeating units, p is 0 or 1, and R is: (i) C1 to C 10 alkyl groups; (ii) C1-C substituted 1 to 3 times with a group selected from halo, nitro, C1-C4 alkoxy, cyano, amine, sulfonamide, sulfonic acid, trifluoromethanesulfonamide, phosphonic acid, carboxyl, hydroxyl, and salts thereof. 10 alkyl groups; (iii) an aryl group, (iv) a carboxylic acid, ester, or amide group; (v) sulfonic acid groups, (vi) a sulfonamide group, (vii) a trifluoromethanesulfonamide group, (viii) an alkoxy group, and (ix) heteroaryl group (selected from The membrane of any of the first to third aspects is provided, wherein the membrane is a polymer having

[0059] In a fifth aspect, the present disclosure provides the porous membrane of any of the first to fourth aspects, wherein the poly(cyclic olefin) polymer is a poly(norbornene) homopolymer or copolymer.

[0060] In a sixth aspect, the present disclosure provides a porous membrane of any of the first to fifth aspects, exhibiting an isopropanol flow time in the range of about 200 seconds / 500 ml to about 50,000 seconds / 500 ml when measured at 14.2 psi and a temperature of about 21° C.

[0061] In a seventh aspect, the present disclosure provides a porous membrane of any of the first to sixth aspects, exhibiting an isopropanol flow time in the range of about 200 seconds / 500 ml to about 8,000 seconds / 500 ml when measured at 14.2 psi and a temperature of about 21° C.

[0062] In an eighth aspect, the present disclosure provides a porous membrane of any of the first to seventh aspects, having an incipient bubble point of about 5 to about 180 psi when measured using ethoxynonafluorobutane HFE7200 at a temperature of about 22°C.

[0063] In a ninth aspect, the present disclosure provides a porous membrane comprising a poly(cyclic olefin) polymer having a thickness of about 40 μm to about 300 μm, the porous membrane exhibiting an isopropanol flow time of greater than about 200 seconds / 500 ml when measured at 14.2 psi and a temperature of about 21° C., and a bubble point of about 5 to about 250 psi when measured using ethoxynonafluorobutane HFE7200 at a temperature of about 22° C.

[0064] In a tenth aspect, the present disclosure provides a porous membrane of any of the first to ninth aspects, prepared by dissolving a polymer in a water-miscible solvent to form a solution, subsequently adding at least one first non-solvent, subsequently casting the solution onto a flat surface, thereby forming a coated surface, and subsequently immersing the coated surface in at least one second non-solvent, thereby effecting formation of the porous membrane.

[0065] In an eleventh aspect, the present disclosure provides the porous membrane of the tenth aspect, further comprising purifying the solution by filtration through an ion exchange resin or membrane prior to casting the solution onto the flat surface, thereby removing trace metal ion contaminants.

[0066] In a twelfth aspect, the present disclosure provides the porous membrane of the tenth or eleventh aspect, wherein the first non-polar solvent comprises isopropanol.

[0067] In a thirteenth aspect, the present disclosure provides the porous membrane of any of the tenth to twelfth aspects, wherein the second non-solvent comprises water.

[0068] In a fourteenth aspect, the present disclosure provides the porous membrane of any of the tenth to thirteenth aspects, wherein the water-miscible solvent comprises tetrahydrofuran.

[0069] In a fifteenth aspect, the present disclosure provides the porous membrane of any of the tenth to fourteenth aspects, wherein the poly(cyclic olefin) polymer is a poly(norbornene) polymer.

[0070] In a sixteenth aspect, the present disclosure provides the porous membrane of the fifteenth aspect, wherein the poly(norbornene) polymer is a norbornene homopolymer.

[0071] In a seventeenth aspect, the present disclosure provides the porous membrane of the fifteenth aspect, wherein the poly(norbornene) polymer is a norbornene copolymer.

[0072] In an eighteenth aspect, the present disclosure provides a method for removing one or more contaminants from a liquid composition, wherein the liquid composition comprises at least one particulate material, metal ions, organic contaminants, or a combination thereof, the method comprising passing the liquid composition through the porous membrane of any of the first to seventeenth aspects and reducing the amount of contaminants in the liquid composition, thereby providing a purified liquid composition.

[0073] In a nineteenth aspect, the present disclosure provides the method of the eighteenth aspect, wherein the particulate material comprises one or more metal particles.

[0074] In a twentieth aspect, the present disclosure provides the method of the eighteenth or nineteenth aspect, wherein the liquid is a liquid used in semiconductor device manufacturing.

[0075] In a twenty-first aspect, the present disclosure provides a filter comprising the porous membrane of any one of the first to seventeenth aspects.

[0076] In a twenty-second aspect, the present disclosure provides a composite filter comprising a first filter material and a second filter material, wherein an output side of the first filter material is in contact with an input side of the second filter material, the first filter material comprising the porous membrane of any one of the first to seventeenth aspects, and the second filter material is different from the first filter material.

[0077] Having thus described several exemplary embodiments of the present disclosure, those skilled in the art will readily appreciate that still other embodiments may be made and used within the scope of the appended claims. Numerous advantages of the disclosure encompassed by this document have been set forth in the foregoing description. It will be understood, however, that this disclosure is in many respects merely illustrative. The scope of the disclosure is, of course, defined in the language in which the appended claims are expressed.

Claims

1. Poly(cyclic olefin) polymer having a thickness of about 40 μm to about 300 μm and an average pore size of about 10 nm to about 100 nm. A porous membrane comprising: exhibiting an isopropanol flow time of greater than about 200 seconds / 500 ml when measured at 14.2 psi and a temperature of about 21° C.; The poly(cyclic olefin) has the structure: (In the formula, n represents the number of repeating units; R is hydrogen or C 1 -C 10 alkyl, or (In the formula, n and m represent the number of repeating units, and n and m are the same or different; R is: (i) a C 1 to C 10 alkyl group; (ii) a C 1 -C 10 alkyl group substituted one to three times with a group selected from halo, nitro, C 1 -C 4 alkoxy, cyano, amine, sulfonamide, sulfonic acid, trifluoromethanesulfonamide, phosphonic acid, carboxyl, hydroxyl, and salts thereof; (iii) an aryl group, (iv) a carboxylic acid, ester, or amide group; (v) sulfonic acid groups, (vi) a sulfonamide group, (vii) a trifluoromethanesulfonamide group, (viii) an alkoxy group, and (ix) heteroaryl group (selected from A porous membrane that is a polymer consisting of one or more monomer repeat units having the formula:

2. 10. The porous membrane of claim 1, having a bubble point of about 5 to about 250 psi when measured using ethoxynonafluorobutane HFE 7200 at a temperature of about 22°C.

3. 3. The porous membrane of claim 1 or 2, exhibiting an isopropanol flow time in the range of about 200 seconds / 500 ml to about 50,000 seconds / 500 ml when measured at 14.2 psi and a temperature of about 21°C.

4. 3. The porous membrane of claim 1 or 2, exhibiting an isopropanol flow time in the range of about 200 seconds / 500 ml to about 8,000 seconds / 500 ml when measured at 14.2 psi and a temperature of about 21°C.

5. 3. The porous membrane of claim 1 or 2, having an initial bubble point of about 5 to about 180 psi when measured using ethoxynonafluorobutane HFE 7200 at a temperature of about 22°C.

6. A method for preparing the porous membrane of claim 1 or 2, comprising the step of: (In the formula, n represents the number of repeating units; R is hydrogen or C 1 -C 10 alkyl, or (In the formula, n and m represent the number of repeating units, and n and m are the same or different; R is: (i) a C 1 to C 10 alkyl group; (ii) a C 1 -C 10 alkyl group substituted one to three times with a group selected from halo, nitro, C 1 -C 4 alkoxy, cyano, amine, sulfonamide, sulfonic acid, trifluoromethanesulfonamide, phosphonic acid, carboxyl, hydroxyl, and salts thereof; (iii) an aryl group, (iv) a carboxylic acid, ester, or amide group; (v) sulfonic acid groups, (vi) a sulfonamide group, (vii) a trifluoromethanesulfonamide group, (viii) an alkoxy group, and (ix) heteroaryl group (selected from in a water-miscible solvent to form a solution, followed by adding at least one first non-solvent, followed by casting the solution onto a flat surface, thereby forming a coated surface, and followed by immersing the coated surface in at least one second non-solvent, thereby effecting the formation of a porous membrane.

7. 7. The method of claim 6, further comprising purifying the solution by filtration through an ion exchange resin or membrane prior to casting the solution onto the flat surface, thereby removing trace metal ion contaminants.

8. 7. The method of claim 6, wherein the first non-solvent comprises isopropanol.

9. The method of claim 6 , wherein the second non-solvent comprises water.

10. 7. The method of claim 6, wherein the water-miscible solvent comprises tetrahydrofuran.

11. 1. A method for removing one or more contaminants from a liquid composition, said liquid composition comprising at least one particulate material, metal ions, organic contaminants or combinations thereof, said method comprising: Passing a liquid composition through a porous membrane according to claim 1 or 2; and Reducing the amount of contaminants in a liquid composition, thereby providing a purified liquid composition A method comprising:

12. The method of claim 11 , wherein the particulate material comprises one or more metal particles.

13. The method of claim 11 , wherein the liquid composition is a liquid used in semiconductor device manufacturing.

14. A filter comprising the porous membrane of claim 1 or 2.

15. First filter material and second filter material A composite filter comprising: an output side of the first filter material in contact with an input side of the second filter material; The first filter material comprises the porous membrane of claim 1 or 2; the second filter material is different from the first filter material; Composite filter.

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