US20150144557A1 - Organic Solvent Purifier And Method Of Using - Google Patents

Organic Solvent Purifier And Method Of Using Download PDF

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Publication number
US20150144557A1
US20150144557A1 US14/397,566 US201314397566A US2015144557A1 US 20150144557 A1 US20150144557 A1 US 20150144557A1 US 201314397566 A US201314397566 A US 201314397566A US 2015144557 A1 US2015144557 A1 US 2015144557A1
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Prior art keywords
membrane
ion
purifier
microporous
exchange resin
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Saksatha Ly
Wai Ming Choi
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Entegris Inc
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Entegris Inc
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Publication of US20150144557A1 publication Critical patent/US20150144557A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
    • B01D15/361—Ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/14—Pleat-type membrane modules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/10—Monohydroxylic acyclic alcohols containing three carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/20—Specific housing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/20—Specific housing
    • B01D2313/201—Closed housing, vessels or containers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2313/00—Details relating to membrane modules or apparatus
    • B01D2313/40—Adsorbents within the flow path
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/42—Ion-exchange membranes

Definitions

  • the standard wet bench configuration includes a couple of isopropyl alcohol (IPA) rinse steps, but the final rinse step, often called the IPA dry step, is a critical step.
  • the final rinse is provided by a thin film of clean, distilled IPA, which condenses on the wafer surface from the vapors located above the IPA liquid.
  • the IPA can be directly sprayed onto the wafer as a liquid. This thin layer of IPA solvent prepares the wafer for final drying.
  • a low capacity version of an IPA purifier using a standard, surface-modified microporous membrane cleaned with IPA is known for low temperature and high temperature applications, but the ion-exchange capacity is very low. If severe metal spikes occurred, this filter would have difficulty with adequate capacity.
  • Some microporous filters have been modified with ion-exchange material and used to remove metal contaminants from deionized (DI) water. These filters show high removal of metals without selectivity to any one metal. This technology is limited because some sulfonic acid functionality can break down and be shed over time due to degradation of the ion-exchange (IEC) media. This breakdown, which has also been observed in pellet media, causes non-volatile residue (NVR) and sulfonic acid ions to shed downstream of the media. The shed residue can then be deposited on a wafer, which can be a problem for semiconductor manufacturers or end-users.
  • IEC ion-exchange
  • U.S. Pat. No. 7,172,694 discloses a filter assembly adapted for use in filtering fluid flow in turbomachinery.
  • the filter assembly includes a cylindrical housing, and a filter element disposed within the housing.
  • the housing is adapted for fluid connection to a turbomachine.
  • the filter element is adapted to filter fluid passing to the turbomachine.
  • the filter element includes a fluid permeable core element defining a central core element flow channel through the filter element, a fluid permeable ion exchange resin layer disposed about the core element and adapted to remove mineral and organic acids from the fluid passing through the filter element, and a pleated filter media disposed about the ion exchange resin layer and core element.
  • the filter element has the pleated filter media disposed about the core element, and the fluid permeable ion exchange resin layer disposed about the core element and pleated filter media.
  • the present invention relates to point-of-use purifiers for removing metal and, in particular, chromium from an organic solvent, for example, isopropanol, in a single pass.
  • the purifiers of the present invention provide higher purity isopropanol for wafer spray process tools, thereby improving semiconductor device performance and overall process yield.
  • the purifier comprises a housing having a fluid inlet and a fluid outlet in fluid communication with the fluid inlet.
  • a volume of ion-exchange resin is disposed within the housing downstream of the fluid inlet.
  • a filtration member is disposed downstream of the volume of ion-exchange resin and comprises at least one microporous membrane having a substantially neutral surface and a polytetrafluoroethylene (PTFE) membrane downstream of the at least one microporous membrane.
  • PTFE polytetrafluoroethylene
  • the purifier comprises a cylindrical housing having a longitudinal axis, a fluid inlet and a fluid outlet in fluid communication with the fluid inlet.
  • a volume of ion-exchange resin is disposed within the cylindrical housing downstream of the fluid inlet.
  • the ion-exchange resin is adapted to remove metal species from the organic solvent.
  • a pleated filtration member is disposed concentrically around the longitudinal axis within the cylindrical housing and downstream of the volume of ion-exchange resin.
  • the pleated filtration member comprises at least one microporous membrane having a substantially neutral surface and adapted to remove chromium from the organic solvent and a microporous PTFE membrane downstream of the at least one microporous membrane.
  • the purifier for removing metal, such as chromium, from an organic solvent.
  • the purifier comprises a cylindrical housing having a longitudinal axis, a fluid inlet and a fluid outlet in fluid communication with the fluid inlet; a volume of ion-exchange resin disposed within the cylindrical housing downstream of the fluid inlet, the ion-exchange resin being adapted to remove metal species from the organic solvent; and a pleated filtration member disposed concentrically around the longitudinal axis within the cylindrical housing and downstream of the volume of ion-exchange resin.
  • the pleated filtration member comprises at least three microporous membranes, each having a substantially neutral surface; and a microporous polytetrafluoroethylene ion-exchange membrane downstream of the at least three microporous membranes, wherein each microporous membrane is modified with amide and has a pore size rating greater than the pore size rating of the microporous polytetrafluoroethylene ion-exchange membrane; and the microporous polytetrafluoroethylene ion-exchange membrane has a surface modified with sulfonic acid and a pore size rating of about 1 nanometer to about 25 nanometers.
  • Each of the at least three microporous membranes can be a microporous polytetrafluoroethylene membrane.
  • the purifiers of the invention can also remove other trace metals and reduce non-volatile residue in an organic solvent. Therefore, another embodiment of the invention is a method of removing metal from an organic solvent, the method comprising passing a flow of the organic solvent through a purifier described herein, thereby removing metal, such as chromium, from the organic solvent.
  • a filtration member comprising a microporous PTFE membrane downstream of at least one microporous membrane having a substantially neutral surface is to capture any particles and ions that may be shed by or pass through the at least one microporous membrane, and is demonstrated by the purifier described in Example 2 herein, which can be used to remove greater than about 85% of the chromium from a solution of IPA containing 1.5 ppb chromium in a single pass (see Example 2 herein).
  • FIG. 1 shows an exemplary configuration of an IPA filter in an IPA dry process.
  • FIG. 2 is a cross-sectional view of an exemplary IPA purifier showing the fluid flow path.
  • FIG. 3 is a cross-sectional view of an exemplary IPA purifier.
  • FIG. 4 is a graph of chromium removal efficiency as a function of flow rate, and shows the chromium removal efficiency from IPA of a PRS-45 membrane coated with sulfonic acids (available from Tomoegawa Inc.) and four 0.2 ⁇ m PTFE membranes coated with amides.
  • FIG. 5 is a graph of chromium removal efficiency as a function of flow rate, and shows the chromium removal efficiency from IPA of an exemplary IPA purifier of the invention, the IPA purifier described in Example 2 herein.
  • compositions and methods are described in terms of “comprising” various components or steps (interpreted as meaning “including, but not limited to”), the compositions and methods can also “consist essentially of” or “consist of” the various components and steps; such terminology should be interpreted as defining essentially closed or closed member groups.
  • One embodiment of the invention is a purifier for removing metal, such as chromium, from an organic solvent, comprising a housing having a fluid inlet and a fluid outlet in fluid communication with the fluid inlet; a volume of ion-exchange resin disposed within the housing downstream of the fluid inlet; and a filtration member downstream of the volume of ion-exchange resin and comprising at least one microporous membrane having a substantially neutral surface.
  • the filtration member further includes a microporous polytetrafluoroethylene (PTFE) membrane downstream of the at least one microporous membrane.
  • PTFE microporous polytetrafluoroethylene
  • the purifiers of the invention can be installed within a process tool at a point-of-use (POU) application.
  • a common set-up for an IPA dry step includes installing a purifier in a process tool or in the fluid supply pathway of IPA feeding the tool.
  • a purifier of the invention can be installed at the outlet of an IPA tank and/or at the point-of-use just before the nozzle or spray tip (not shown in FIG. 1 ).
  • the purifiers of the invention are particularly useful in point-of-use applications because they can remove metal and specifically, chromium, contaminants from a solvent stream in a single pass through the purifier.
  • the purifiers of the invention can be used to remove metal, such as chromium, from organic solvents, or mixtures of organic solvents.
  • Organic solvents include alcohols (e.g., methanol, ethanol, isopropanol, ethyl lactate, ethylene glycol, propylene glycol monomethyl ether, cylcohexanol and mixtures thereof), polar aprotic solvents (e.g., acetonitrile, acetone, dimethylformamide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate and mixtures thereof), aromatic solvents (e.g., benzene, polyarylethers, and mixtures thereof) and non-polar solvents (e.g., hexamethyldisilazane).
  • alcohols e.g., methanol, ethanol, isopropanol, ethyl lactate, ethylene glycol, propylene glycol monomethyl ether,
  • the purifiers of the present invention can be used to purify anhydrous organic solvents or organic solvents containing some weight percentage of water (e.g., less than or equal to about 1 weight percent, less than or equal to about 0.25 weight percent, less than or equal to about 0.1 weight percent).
  • the organic solvent is an alcohol.
  • the alcohol is isopropanol.
  • Organic solvents are commonly transferred through the fab and tool via stainless steel lines. This transfer process can result in trace chromium impurities (e.g., chromium salts, chromium complexes, chromium particles) in the organic solvent. Therefore, in some embodiments, the purifier housing is plastic.
  • the purifiers of the invention are useful in removing chromium, including chromium salts and chromium complexes, from organic solvents, such as isopropanol.
  • the purifier in embodiments of the invention can also remove other metal ions and complexes, such as, but not limited to, ions and complexes containing sodium, iron, aluminum, nickel, and combinations of these.
  • the ion-exchange resin in the purifiers of the invention is composed of particles.
  • the particles can be thermoplastic particles that can be extruded, which is advantageous because the thermoplastic nature of the ion-exchange particles optionally allows them to be bonded to a netting or other support.
  • Optional bonding of the ion-exchange particles to a support in some embodiments allows more uniform packing of the particles in the housing and can eliminate channeling of a fluid being purified.
  • the ion-exchange resin can be NAFION®.
  • the ion-exchange particles can be non-porous and should be of a size that does not plug or reduce flow through a downstream filtration member.
  • the ion-exchange particles should be of a size that does not pass through the microporous PTFE membrane downstream of the at least one microporous membrane.
  • the particles which can be in the form of pellets, beads, combinations of these, or the like, can have a size of less than about 2 millimeters. However, particles in the range of 2 mm to 0.1 mm, or 0.5 millimeters to 0.1 millimeters can also be used, depending on the pore size of the membranes in the filtration member.
  • the ion-exchange particles can be ground. Smaller particles provide higher surface area and capacity.
  • Particle shedding of the ion-exchange resin in versions of the invention is less than 15 particles/mL at 0.05 microns.
  • the ion-exchange resin is approximately 15 mesh to approximately 40 mesh, approximately 15 mesh to approximately 30 mesh, or approximately 15 mesh to approximately 20 mesh. Ion-exchange resins having particles of these size ranges advantageously reduce or eliminate fluid channeling through the volume of ion-exchange resin.
  • the purifier further comprises an ion-exchange resin vessel that contains the volume of ion-exchange resin.
  • the ion-exchange resin vessel can comprise a net material (e.g., mesh net) or a frit (e.g., a porous frit).
  • the particles must be large enough to be retained by the net material or frit, or the pores in the net material or frit must be small enough to retain the particles.
  • the net material or frit, as well as the volume of ion-exchange resin, should be fluid-permeable.
  • the filtration member is disposed downstream of the volume of ion-exchange resin and comprises at least one microporous membrane having a substantially neutral surface and a microporous PTFE membrane downstream of the at least one microporous membrane. In some embodiments, the filtration member is disposed within the housing. In some embodiments, the filtration member is disposed within the housing and upstream of the fluid outlet.
  • the filtration member comprises more than one microporous membrane having a substantially neutral surface.
  • the filtration member can comprise two, at least two, three, at least three, four, at least four or five microporous membranes having a substantially neutral surface.
  • the arrangement of the microporous membranes in the filtration member can vary.
  • the at least one microporous membrane having a substantially neutral surface and the microporous PTFE membrane are disposed adjacent to one another.
  • Each microporous membrane can independently be a pleated flat sheet membrane, a hollow fiber, or a flat sheet membrane.
  • the at least one microporous composite membrane having a substantially neutral surface and the microporous PTFE membrane are each pleated flat sheet membranes.
  • the microporous membranes can further be bonded to one another. Therefore, in some embodiments of the invention, the at least one microporous membrane having a substantially neutral surface and the microporous PTFE membrane are bonded to one another. More specifically, each of the at least one microporous membranes having a substantially neutral surface and the microporous PTFE membrane are bonded to at least one of the at least one microporous membranes having a substantially neutral surface and/or the microporous PTFE membrane.
  • the pore size of the microporous membranes or the filtration member can be characterized by IPA bubble point or hydrofluoroether (HFE) bubble point.
  • a microporous membrane or filtration member can have an IPA bubble point of over about 70 pounds per square inch (psi).
  • a microporous membrane or filtration member can have a pore size characterized by an HFE bubble point that is 70 psi or more, or 100 psi or more.
  • a microporous membrane or filtration member can also be characterized by its ability to remove 25 nanometer particles, and may be referred to as a 15 nanometer membrane or 10 nanometer membrane.
  • the bubble point refers to a mean IPA bubble point using an air flow porisometer.
  • microporous membrane bubble points refers to a mean bubble point measured in HFE-7200 (available from 3MTM, St. Paul, Minn.).
  • HFE-7200 bubble points can be converted into IPA bubble point values by multiplying the HFE-7200 measured bubble point by 1.5, or about 1.5.
  • 3MTM HFE-7200 is ethoxy-nonafluorobutane and has a reported surface tension of 13.6 mN/m at 25° C.
  • microporous membrane will be used to include porous membranes that may also be described by terms such as ultraporous membranes, nanoporous membranes, and microporous membranes. These microporous membranes retain feed stream components (retentate) such as, but not limited to gels, particles, colloids, cells, and poly-oligomers, while components substantially smaller than the pores pass through the pores into a permeate steam. Retention of components in the feed stream by the microporous membrane can be dependent upon operating conditions, for example face velocity and use of surfactants, pH and combinations of these, and can be dependent upon the size and structure (hard particle or gel) of the particle relative to the size, structure and distribution of the microporous membrane pores.
  • feed stream components retentate
  • Retention of components in the feed stream by the microporous membrane can be dependent upon operating conditions, for example face velocity and use of surfactants, pH and combinations of these, and can be dependent upon the size and structure (hard particle or gel) of the particle relative to the size, structure and distribution
  • the microporous PTFE membrane is a microporous PTFE ion-exchange membrane, such as a phobic microporous membrane, for example, QC (QUICK CHANGE®, Entegris Inc.), including Q-1500 and Q-3000.
  • QC QUICK CHANGE®, Entegris Inc.
  • Microporous PTFE ion-exchange membranes, and methods of making the same, are disclosed in U.S. Pat. No. 6,179,132 to Moya and in International Publication No. WO 2010/117845, the teachings of which are incorporated herein by reference in their entirety.
  • the microporous PTFE membrane has a pore size rating by bubble point of about 1 nanometer to about 100 nanometers, about 1 nanometer to about 50 nanometers, or about 1 nanometer to about 25 nanometers.
  • a surface of the microporous PTFE ion-exchange membrane is modified with sulfonic acid. Sulfonic acid-modified membranes, and methods of making the same are disclosed, for example, in International Publication No. WO 2010/117845, the teachings of which are incorporated herein by reference in their entirety.
  • a microporous PTFE ion-exchange membrane has an ion-exchange capacity (IEC) of between about 60 nanomole/centimeter squared and about 80 nanomole/centimeter squared and/or a zeta potential of about ⁇ 20 millivolts to about ⁇ 30 millivolts at a pH of between about 1 and about 7.
  • IEC ion-exchange capacity
  • microporous membranes having a substantially neutral surface are disclosed in U.S. Pat. No. 4,618,533, to Steuck, and in International Publication No. WO 01/51170, the contents of which are incorporated herein by reference in their entirety.
  • the microporous membrane having a substantially neutral surface is adapted to remove chromium (e.g., chromium salts, chromium complexes) from an organic solvent (e.g., IPA).
  • chromium e.g., chromium salts, chromium complexes
  • the microporous membrane having a substantially neutral surface is a microporous PTFE membrane having a substantially neutral surface, for example, a surface modified with amide groups, or a polymer comprising amide groups.
  • Amide-modified membranes, and methods of making the same are disclosed, for example, in International Publication No. WO 01/51170, the contents of which are incorporated herein by reference in their entirety.
  • the surface of the membrane modified with amide groups advantageously also reduces the amount of non-volatile residue in the organic solvent.
  • a substantially neutral surface, or a weakly charged surface is a surface having an electrostatic potential of or near 0 mV. Electrostatic potential is proportional to zeta potential.
  • a substantially neutral surface can be formed through proper selection of a membrane material or by surface modification of a membrane.
  • a substantially neutral surface, or weakly charged surface can advantageously retain particles, for example, chromium particles, through non-sieving retention mechanisms.
  • a microporous membrane having a substantially neutral surface can be used to remove chromium from isopropanol.
  • Non-sieving retention includes retention mechanisms, such as interception, diffusion and adsorption, that remove particles from a fluid stream without being related to the pressure drop or bubble point of the filter or microporous membrane.
  • Particle adsorption to membrane surfaces can be mediated by, for example, intermolecular Van der Waals and electrostatic forces.
  • Interception occurs when a particle travelling through a tortuous membrane cannot change direction fast enough to avoid contact with the membrane.
  • Particle transport due to diffusion results from random or Brownian motion of predominantly small particles, which creates a certain probability that the particles will collide with the filter media.
  • Non-sieving retention mechanisms can be active when there is an absence of repulsive forces between the particle and the filter or membrane.
  • the microporous membrane having a substantially neutral surface has a pore size rating greater than the pore size rating of the microporous PTFE membrane.
  • the microporous membranes having a substantially neutral surface can have a particle size rating of less than or equal to about 10 ⁇ m, less than or equal to about 5 ⁇ m, less than or equal to about 1 ⁇ m, or less than or equal to about 0.5 ⁇ m.
  • the microporous membrane having a substantially neutral surface can have a particle size rating of less than or equal to about 0.2 ⁇ m, or less than or equal to about 0.1 ⁇ m.
  • a purifier can further include a liquid distributor downstream of the volume of ion-exchange resin and upstream of the filtration member.
  • the liquid distributor, the ion-exchange resin and the filtration member are each disposed within the housing of the purifier.
  • the liquid distributor collects a flow of fluid from the ion-exchange resin and distributes it outwardly around the periphery of a cylindrical housing.
  • Exemplary liquid distributor 11 collects a flow of fluid from ion-exchange resin 9 and distributes it outwardly around the periphery of cylindrical body portion 2 , as illustrated in FIGS. 2 and 3 .
  • FIGS. 2 and 3 depict exemplary purifiers of the invention.
  • the purifiers depicted in FIGS. 2 and 3 comprise housing 1 .
  • Housing 1 includes cylindrical body portion 2 , first housing endcap 3 and second housing endcap 4 .
  • cylindrical body portion 2 is bonded to first and second housing endcaps 3 and 4 .
  • the housing endcaps 3 and 4 depicted in FIGS. 2 and 3 include process fluid or liquid inlet 5 , drain 6 , purified process fluid or liquid outlet 7 and gas vent 8 .
  • Inlet 5 and outlet 6 are in fluid communication, as indicated by the flow arrows shown in FIG. 2 .
  • a volume of ion-exchange resin 9 is contained in ion-exchange resin vessel 10 in housing 1 in the purifiers of FIGS. 2 and 3 .
  • Ion-exchange resin vessel 10 includes bottom portion 10 a which, in the purifiers depicted in FIGS. 2 and 3 , is bonded to first housing endcap 3 .
  • Ion-exchange resin vessel 10 also includes top portion 10 b which, in the purifiers depicted in FIGS. 2 and 3 , is bonded to optional liquid distributor 11 .
  • Ion-exchange resin vessel 10 also includes cylindrical body portion 10 c .
  • Ion-exchange resin 9 is downstream of inlet 5 and upstream of optional liquid distributor 11 .
  • top portion 10 b and bottom portion 10 a each include a frit for retaining ion-exchange resin 9 in ion-exchange resin vessel 10 .
  • ion-exchange resin 9 can be retained in ion-exchange resin vessel 10 by a mesh bag.
  • Filter cartridge 12 is downstream of optional liquid distributor 11 in the purifiers depicted in FIGS. 2 and 3 .
  • Filter cartridge 12 includes first filter cartridge endcap 13 which, in the purifiers depicted in FIGS. 2 and 3 , is bonded to second housing endcap 4 .
  • Filter cartridge 12 includes second filter cartridge endcap 14 which, in the purifiers depicted in FIGS. 2 and 3 , is bonded to optional liquid distributor 11 .
  • filter cartridge 12 houses first filter membrane 15 and second filter membrane 16 downstream of first filter membrane 15 .
  • the purifiers depicted in FIGS. 2 and 3 can be inserted into a fluid supply pathway feeding a process tool, such as a spray processor.
  • Inlet 5 can be connected to a fluid supply, such as a tank (not shown), and outlet 6 can be connected to a component, such as a pipe, that feeds the fluid to a processing chamber in the tool.
  • Fluid enters the purifier through inlet 5 , flows through ion-exchange resin 9 contained in ion-exchange resin vessel 10 and enters optional liquid distributor 11 .
  • optional liquid distributor 11 collects a flow of fluid from ion-exchange resin 9 and distributes it outwardly around the periphery of cylindrical housing 1 .
  • the fluid then enters filter cartridge 12 and passes through first filter membrane 15 , then second filter membrane 16 before flowing out of the purifier via outlet 7 .
  • FIGS. 2 and 3 depict a specific configuration of an exemplary purifier of the invention, other configurations of a purifier are possible.
  • optional liquid distributor 11 could direct a flow of fluid centrally along the longitudinal axis of housing 1 , such that the fluid traverses the filters in the opposite order than that depicted in FIG. 2 (i.e., second filter membrane 16 , then first filter membrane 15 ).
  • second filter membrane 16 second filter membrane 16
  • first filter membrane 15 first filter membrane 15
  • a purifier for removing metal, such as chromium from an organic solvent comprising a cylindrical housing having a longitudinal axis, a fluid inlet and a fluid outlet in fluid communication with the fluid inlet.
  • a volume of ion-exchange resin is disposed within the cylindrical housing downstream of the fluid inlet and the ion-exchange resin is adapted to remove metal species from the organic solvent.
  • a pleated filtration member is disposed concentrically around the longitudinal axis within the cylindrical housing and downstream of the volume of ion-exchange resin.
  • the pleated filtration member comprises at least one microporous membrane having a substantially neutral surface and adapted to remove chromium from the organic solvent, and a microporous polytetrafluoroethylene membrane downstream of the at least one microporous membrane.
  • a purifier for removing metal, such as chromium, from an organic solvent comprises a cylindrical housing having a longitudinal axis, a fluid inlet and a fluid outlet in fluid communication with the fluid inlet; a volume of ion-exchange resin disposed within the cylindrical housing downstream of the fluid inlet, the ion-exchange resin being adapted to remove metal species from the organic solvent; and a pleated filtration member disposed concentrically around the longitudinal axis within the cylindrical housing and downstream of the volume of ion-exchange resin.
  • the pleated filtration member comprises at least three microporous membranes, each having a substantially neutral surface; and a microporous polytetrafluoroethylene ion-exchange membrane downstream of the at least three microporous membranes, wherein each microporous membrane is modified with amide and has a pore size rating greater than the pore size rating of the microporous polytetrafluoroethylene ion-exchange membrane; and the microporous polytetrafluoroethylene ion-exchange membrane has a surface modified with sulfonic acid and a pore size rating of about 1 nanometer to about 25 nanometers.
  • Each of the at least three microporous membranes can be a microporous polytetrafluoroethylene membrane.
  • one embodiment of the invention is a method of removing metal, such as chromium, from an organic solvent using a purifier of the invention.
  • the method comprises passing a flow of an organic solvent through a purifier of the invention, thereby removing the metal from the organic solvent.
  • the method comprises passing a flow of an organic solvent through a purifier of the invention one time to remove metal, including chromium, from the organic solvent.
  • the purifier removes chromium from the organic solvent and the chromium removal is greater than about 70%, or greater than about 75% at a flow rate of about 20 mL/min, as ascertainable under the test conditions of Example 2. Specifically, the chromium removal is greater than about 80% or greater than about 85% at a flow rate of about 10 mL/min, as ascertainable under the test conditions of Example 2.
  • the pressure drop of the purifier in some embodiments of the invention, is about 0.1 kgf/cm (kilogram force per centimeter) to about 0.3 kgf/cm.
  • a microporous PTFE ion-exchange membrane coated with sulfonic acid functional groups (sulfonic acid-modified PRS-45, a non-woven PTFE membrane having a pore size of about 20 microns) (available from Tomoegawa Inc.) and a coupon including four 0.2- ⁇ m PTFE membranes coated with amide functional groups, and having an IEC of between about 60 nanomole/centimeter squared and about 80 nanomole/centimeter squared and a zeta potential of about ⁇ 20 millivolts to about ⁇ 30 millivolts at a pH of between about 1 and about 7 (GUARDIAN® DEV, available from Entegris, Inc.) were challenged with a solution of isopropanol having 15 ppb chromium (from a stock solution of chromium nitrate in nitric acid) at a variety of flow rates.
  • sulfonic acid-modified PRS-45 a non-woven PT
  • Each membrane was 47 mm in diameter. The challenge was continued for approximately 20 minutes at each flow rate. The concentration of chromium in the permeate stream was then measured by inductively-coupled plasma mass spectrometry (ICPMS), and the chromium removal efficiency calculated.
  • ICPMS inductively-coupled plasma mass spectrometry
  • FIG. 4 is a graph of the chromium removal efficiency from IPA of a sulfonic acid-modified PRS-45 membrane coated with sulfonic acid functional groups and four 0.20- ⁇ m PTFE membranes coated with amides as a function of flow rate.
  • FIG. 4 shows that the GUARDIAN® DEV membranes were very effective at removing chromium from the challenge solution, removing greater than about 75% of the chromium at a flow rate of about 8 mL/min, while the sulfonic acid-modified PRS-45 membrane was ineffective at removing chromium from the isopropanol, removing less than 5% of the chromium at all of the flow rates tested.
  • An exemplary purifier was constructed and evaluated for its ability to remove chromium from a solution of IPA containing 1.5 ppb chromium. 8 g of a pellet of an ion-exchange resin ground to 16 mesh was put into a cyclindrical housing having a diameter of 47 mm.
  • the filtration member also disposed within the housing downstream of the ion-exchange resin, included three 0.2- ⁇ m PTFE membranes coated with amide functional groups (GUARDIAN® DEV, available from Entegris, Inc.) and a 15-nm microporous PTFE ion-exchange membrane coated with sulfonic acid functional groups (TORRENTOTM, available from Entegris, Inc.) downstream of the GUARDIAN® DEV membranes.
  • amide functional groups (GUARDIAN® DEV, available from Entegris, Inc.)
  • TORRENTOTM sulfonic acid functional groups
  • the purifier was challenged with a solution of isopropanol having 1.5 ppb chromium (from a stock solution of chromium nitrate in nitric acid) at a variety of flow rates. The challenge was continued for approximately 20 minutes at each flow rate. The concentration of chromium in the permeate stream was then measured by ICPMS, and the removal efficiency calculated.
  • FIG. 5 is a graph showing the chromium removal efficiency from IPA of the purifier as a function of flow rate. FIG. 5 shows that nearly 90% of the chromium content was removed from the isopropanol in just one pass through the purifier.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
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US10464058B2 (en) 2015-07-14 2019-11-05 Fujifilm Manufacturing Europe B.V. Ion exchange membranes
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US11693321B2 (en) 2016-03-31 2023-07-04 Fujifilm Corporation Treatment liquid for manufacturing semiconductor, storage container storing treatment liquid for manufacturing semiconductor, pattern forming method, and method of manufacturing electronic device
US11305272B2 (en) 2016-12-13 2022-04-19 Organo Corporation Ion exchanger filled cartridge and metal removing column
US9855534B1 (en) 2016-12-28 2018-01-02 Pall Corporation Porous PTFE membranes for metal removal
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US11833475B2 (en) * 2018-03-22 2023-12-05 Fujifilm Corporation Filtering device, purification device, and method for manufacturing chemical liquid
US11759749B2 (en) * 2018-03-22 2023-09-19 Fujifilm Corporation Filtering device, purification device, and method for manufacturing chemical liquid
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TWI554328B (zh) 2016-10-21
SG11201407134SA (en) 2014-12-30
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WO2013165602A1 (en) 2013-11-07
US10150087B2 (en) 2018-12-11
EP2844374B1 (de) 2018-09-19
KR20140147148A (ko) 2014-12-29
US20150343391A1 (en) 2015-12-03
EP2844374A1 (de) 2015-03-11
CN104470625A (zh) 2015-03-25

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