# US 9,040,659 B2 · Methods and materials for removing metals in block copolymers

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- Number: US 9,040,659 B2
- Document ID: US9040659B2
- Status: Granted
- Kind: B2
- Application number: 14/175,203
- Filed: 2014-02-07
- Published: 2014-06-05
- Granted: 2015-05-26
- Earliest claimed: 2012-03-09
- Assignees: Az Electronic Materials (Luxembourg) S.A.R.L.
- Applicants: Jian Yin; Hengpeng Wu; Muthiah Thiyagarajan; SungEun Hong; Mark Neisser; Yi Cao
- Inventors: Jian Yin; Hengpeng Wu; Muthiah Thiyagarajan; SungEun Hong; Mark Neisser; Yi Cao
- Web page: https://patentgrep.com/patent/US9040659B2

## CPC

- B01D 15/361: {Ion-exchange}
- B05D 5/00: Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B01J 39/05: in the strongly acidic form
- B01J 41/07: in the weakly basic form
- B01J 45/00: Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties (ion-exchange chromatography processes B01D15/36)
- B05D 1/005: {Spin coating}
- B05D 3/00: Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials (successively applying liquids or other fluent materials B05D1/36; drying ovens F26B)
- C08F 6/02: Neutralisation of the polymerisation mass, e.g. killing the catalyst (short-stopping C08F2/42 ){also removal of catalyst residues}
- C08J 3/00: Processes of treating or compounding macromolecular substances
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)

## Abstract

The present invention relates to a method for treating a block copolymer solution, wherein the method comprises: providing a solution comprising a block copolymer in a non aqueous solvent; and, treating the solution to remove metals using an ion exchange resin. The invention also relates to a method of forming patterns using the treated block copolymer.

## Claims

### Claim 1

A method of forming a directed self assembly pattern comprising the steps of;
a. coating a substrate with a solution with reduced metal ion contamination content, wherein the solution comprises a block copolymer where the block copolymer is derived from monomers which are arranged in blocks which are different compositionally, structurally or both and are capable of phase separating and forming domains, and further wherein the blocks have differing etch properties which can be used to remove one block while keeping the other block intact on the surface of the substrate, thus providing a pattern on the surface of the substrate and further where the solution with reduced metal ion contamination is produced by,
i. treating the solution with a basic ion exchange to form a slurry; and,
ii. filtering the slurry to remove the ion exchange resin;
b. heating the substrate to form a directed self assembly polymer layer; and
c. removing one block of the block copolymer and thereby forming a pattern.

### Claim 2 (depends on 1)

The method of claim 1, where one block is removed by wet or dry etching step.

### Claim 3 (depends on 1)

The method of claim 1, wherein the basic ion exchange resin has a morphology chosen from gel type, macroreticular or porous; and wherein, as a result of treating the block copolymer solution, one or more metal ion contaminants chosen from aluminum, calcium, chromium, copper, iron, magnesium, manganese, nickel, potassium, sodium, zinc, tin, cadmium, cobalt, germanium, lead, lithium, silver, or titanium are reduced by at least 5% from their initial pretreatment values.

### Claim 4 (depends on 1)

The method of claim 1, wherein the solution comprises a concentration of 0.1%-20% w/w of the block copolymer.

### Claim 5 (depends on 1)

The method of claim 1, wherein, as a result of treating the block copolymer solution, the percent exposure latitude of the block copolymer is increased by at least 2 percentage points.

### Claim 6 (depends on 1)

The method of claim 1, further comprising adding a sulfonic acid cation exchange resin to form a mixed slurry.

### Claim 7 (depends on 6)

The method of claim 6, wherein the sulfonic acid cation exchange resin has a morphology chosen from gel-type, macroreticular or porous; and wherein, as a result of treatment, one or more metal ion contaminants chosen from aluminum, calcium, chromium, copper, iron, magnesium, manganese, nickel, potassium, sodium, zinc, tin, cadmium, cobalt, germanium, lead, lithium, silver, or titanium are reduced by at least 5% from their initial values.

### Claim 8 (depends on 6)

The method of claim 6, wherein, as a result of treating the block copolymer solution, the percent exposure latitude is increased by at least 2 percentage points.

### Claim 9 (depends on 1)

The method of claim 1 where the basic ion exchange resin is dehydrated by contact with an organic solvent prior to contact with the solution.

### Claim 10 (depends on 6)

The method of claim 6 where the sulfonic acid cation exchange resin is dehydrated by contact with an organic solvent prior to contact with the solution.

### Claim 11 (depends on 1)

The method of claim 1, wherein the block copolymer is chosen from poly(styrene-b-methyl (meth)acrylate), poly(styrene-b-vinyl pyridine), poly(styrene-b-polyethylene glycol), poly(styrene-b-dimethylsiloxane), poly(styrene-b-ethyl methylsiloxane), poly(styrene-b-lactide), poly(styrene-b-2-hydroxyethyl (meth)acrylate), poly(styrene-b-2-hydroxypropyl (meth)acrylate), poly(dimethylsiloxane-b-n-butyl (meth)acrylate), poly(dimethylsiloxane-b-t-butyl (meth)acrylate), poly(dimethylsiloxane-b-hydroxy ethyl (meth)acrylate), poly(dimethylsiloxane-b-methylmethacrylate-co-t-butyl methyl acrylate), poly(dimethylsiloxane-b-1-ethoxy ethyl (meth)acrylate), poly(dimethylsiloxane-b-ε-caprolactone), poly(dimethylsiloxane-b-lactide), or poly(propylene oxide-b-styrene-co-4-vinyl pyridine).

### Claim 12 (depends on 1)

The method of claim 1, wherein the etch properties are plasma etching.

### Claim 13 (depends on 1)

The method of claim 1, wherein the etch properties are solvent etching.

### Claim 14 (depends on 1)

The method of claim 1, wherein the etch properties are developer etching.