# US 10,118,989 B2 · Methods of forming block polymers for directed self-assembly

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- Number: US 10,118,989 B2
- Document ID: US10118989B2
- Status: Granted
- Kind: B2
- Application number: 15/397,391
- Filed: 2017-01-03
- Published: 2017-04-27
- Granted: 2018-11-06
- Earliest claimed: 2014-05-16
- Assignees: International Business Machines Corporation
- Applicants: International Business Machines Corporation
- Inventors: Anindarupa Chunder; Daniel P. Sanders; Ankit Vora
- Web page: https://patentgrep.com/patent/US10118989B2

## CPC

- C08G 64/18: Block or graft polymers
- C08F 293/00: Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule (on to polymers modified by introduction of unsaturated end groups C08F290/02)
- C08G 64/30: using carbonates
- C09D 169/00: Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
- G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping}
- B82Y 40/00: Manufacture or treatment of nanostructures
- C08F 2438/01: Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES

## Abstract

Block polymers are formed by ring opening polymerization (ROP) of a cyclic carbonate monomer using a polymeric initiator for the ROP that comprises repeating functionalized ethylene units. The block polymers are free of, or substantially free of, any polymer having a chemical structure that does not comprise the polymer backbone of the polymeric initiator. The block polymers are capable of directed self-assembly.

## Claims

### Claim 1

A method, comprising:
i) providing a mathematical function F(t) for a ring opening polymerization (ROP) of a cyclic carbonyl monomer, wherein
F(t) expresses an amount of consumed cyclic carbonyl monomer as a function of ROP duration time t for a given set of reaction conditions,
the ROP utilizes a reaction mixture initially comprising the cyclic carbonyl monomer, a polymeric initiator for the ROP, a ROP catalyst, and a solvent,
the polymeric initiator comprises i) a polymer backbone comprising repeating functionalized ethylene units and ii) 1 to 2 nucleophilic groups linked to respective end groups of the polymer backbone, the nucleophilic groups capable of initiating the ROP of the cyclic carbonyl monomer,
F(t) has a duration time t1>0 corresponding to 50% consumption of the cyclic carbonyl monomer,
F(t) has duration times t2 and t3 wherein t3>t2>t1,
F(t) has a first derivative designated F′(t),
F′(t) at t1 has a value F′(t1)=m, wherein m is a number >0
F′(t) at t2 has a value F′(t2)=0.9m, and
F′(t) at t3 has a value F′(t3)=0.8m;
ii) conducting the ROP of the cyclic carbonyl monomer using the given set of reaction conditions; and
iii) stopping the ROP at a ROP duration time of about t1 to about t3, thereby forming a second mixture comprising a block polymer, wherein the block polymer comprises a first block linked to a second block, the first block comprises the polymer backbone comprising repeating functionalized ethylene units, the second block comprises a backbone derived from ROP of the cyclic carbonyl monomer, the first block is substantially immiscible with the second block, the second mixture is free of, or substantially free of, any polymer having a chemical structure that contains none of the polymer backbone of the polymeric initiator, and the block copolymer is capable of self-assembly to form a phase separated domain pattern comprising alternating domains of the first block and the second block.

### Claim 2 (depends on 1)

The method of claim 1, wherein said stopping the ROP comprises treating a living end group of the second block with an alcohol protecting agent.

### Claim 3 (depends on 2)

The method of claim 2, wherein the alcohol protecting agent is a compound selected from the group consisting of active esters, acid halides, acid anhydrides, isocyanates, ether forming agents, perfluorinated derivatives of any of the foregoing compounds, and combinations thereof.

### Claim 4 (depends on 1)

The method of claim 1, wherein said stopping the ROP comprises precipitating the block polymer in a solvent mixture, the solvent mixture comprising i) a first solvent that is a non-solvent for the first block and a non-solvent for the second block and ii) a second solvent comprising a nitrile group, the second solvent a non-solvent for the first block and a solvent for the second block, wherein the first solvent: second solvent volume ratio is about 40:60 to about 60:40.

### Claim 5 (depends on 4)

The method of claim 4, wherein the first solvent is an alcohol.

### Claim 6 (depends on 4)

The method of claim 4, wherein the second solvent is acetonitrile.

### Claim 7 (depends on 1)

The method of claim 1, wherein the ROP is performed at ambient temperature.

### Claim 8 (depends on 1)

The method of claim 1, wherein the polymeric initiator is a polystyrene comprising one hydroxy end group.

### Claim 9 (depends on 1)

The method of claim 1, wherein the block polymer is capable of self-assembly to form cylindrical domains of the second block in a matrix of the first block.

### Claim 10 (depends on 1)

The method of claim 1, wherein the block polymer is capable of self-assembly to form spherical domains of the second block in a matrix of the first block.

### Claim 11 (depends on 1)

The method of claim 1, wherein the block polymer is capable of self-assembly to form lamellar structures comprising alternating domains of the first block and the second block.

### Claim 12 (depends on 1)

The method of claim 1, wherein the ROP catalyst is a phosphate diester.

### Claim 13 (depends on 1)

The method of claim 1, wherein the ROP catalyst is diphenylphosphate (DPP).

### Claim 14 (depends on 1)

The method of claim 1, wherein the cyclic carbonyl monomer is a cyclic ester.

### Claim 15 (depends on 1)

The method of claim 1, wherein the cyclic carbonyl monomer is lactide.

### Claim 16 (depends on 15)

The method of claim 15, wherein the cyclic carbonyl monomer is a cyclic carbonate.

### Claim 17 (depends on 16)

The method of claim 16, wherein the cyclic carbonyl monomer is trimethylene carbonate:

### Claim 18 (depends on 16)

The method of claim 16, wherein the cyclic carbonyl monomer is MTC-Me:

### Claim 19 (depends on 1)

The method of claim 1, wherein no cyclic carbonyl monomer is added to the reaction mixture after the ROP is initiated.

### Claim 20

A method, comprising:
i) providing a mathematical function F(t) for a ring opening polymerization (ROP) of a cyclic carbonyl monomer, wherein
F(t) expresses an amount of consumed cyclic carbonyl monomer as a function of ROP duration time t for a given set of reaction conditions,
the ROP utilizes a reaction mixture initially comprising the cyclic carbonyl monomer, a polymeric initiator for the ROP, a ROP catalyst, and a solvent,
the polymeric initiator comprises i) a polymer backbone comprising repeating functionalized ethylene units and ii) 1 to 2 nucleophilic groups linked to respective end groups of the polymer backbone, the nucleophilic groups capable of initiating the ROP of the cyclic carbonyl monomer, and
F(t) has a first derivative F′(t);
ii) providing a mathematical function D(t) expressing change in F′(t) between adjacent ROP duration times, designated ΔF′(t), as a function of ROP duration time t, wherein i) ΔF′(tn)=F′(tn)−F′(tn-1) for adjacent duration times tn and tn-1, tn>tn-1, and n is a positive integer greater than or equal to 1, ii) D(t) has a first derivative designated D′(t), and iii) D′(t) has a duration time t′>0 wherein D′(t′)=0;
iii) conducting the ROP of the cyclic carbonyl monomer using the given set of reaction conditions; and
iv) stopping the ROP at a polymerization duration time of 0.8t′ to t′, thereby forming a second mixture comprising a block polymer capable of self-assembly, wherein the block polymer comprises a first block comprising the polymer backbone comprising repeating functionalized ethylene units, the first block being linked by a polymer chain end group to a second block comprising a polymer backbone derived from the cyclic carbonyl monomer, the first block is substantially immiscible with the second block, the second mixture is substantially free of any polymer having a chemical structure that contains none of the polymer backbone of the polymeric initiator, and the block copolymer is capable of self-assembly to form a phase separated domain pattern comprising alternating domains of the first block and the second block.

### Claim 21 (depends on 20)

The method of claim 20, wherein the D(t) is a polynomial expression having an R-squared value of about 0.85 to 1.0.