# US 12,006,442 B2 · Additive manufacturing of polishing pads

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- Number: US 12,006,442 B2
- Document ID: US12006442B2
- Status: Granted
- Kind: B2
- Application number: 16/681,700
- Filed: 2019-11-12
- Published: 2021-03-11
- Granted: 2024-06-11
- Earliest claimed: 2019-09-11
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Atul Bhaskar Chaudhari; Sivapackia Ganapathiappan; Srobona Sen
- Web page: https://patentgrep.com/patent/US12006442B2

## CPC

- C09D 11/102: containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- B24B 37/24: characterised by the composition or properties of the pad materials
- B33Y 70/00: Materials specially adapted for additive manufacturing
- B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
- C08F 290/061: {Polyesters; Polycarbonates}
- C08F 290/067: {Polyurethanes; Polyureas}
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/246: {containing also tin-carbon bonds}
- C08G 18/3876: {containing mercapto groups}
- C08G 18/42: Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G 18/4238: {derived from dicarboxylic acids and dialcohols}
- C08G 18/44: Polycarbonates
- C08G 18/48: Polyethers
- C08G 18/672: {Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen}
- C08G 18/6755: {Unsaturated carboxylic acids}
- C08G 18/73: acyclic
- C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate}
- C08G 18/758: {containing two or more cycloaliphatic rings}
- C08G 18/7621: {being toluene diisocyanate including isomer mixtures}
- C08G 18/7671: {containing only one alkylene bisphenyl group}
- C08L 75/16: having terminal carbon-to-carbon unsaturated bonds
- C09D 11/101: Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
- C09D 11/30: Inkjet printing inks
- B33Y 10/00: Processes of additive manufacturing
- B33Y 30/00: Apparatus for additive manufacturing; Details thereof or accessories therefor
- B33Y 80/00: Products made by additive manufacturing
- 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)
- B24B: MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING (grinding of gear teeth B23F, of screw-threads B23G1/36; by electro-erosion B23H; abrasive or related blasting B24C; tools for grinding, buffing or sharpening B24D; polishing compositions C09G1/00; abrasives C09K3/14; electrolytic etching or polishing C25F3/00; grinding arrangements for use on assembled railway tracks E01B31/17); DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

A system, formulation, and method for additive manufacturing of a polishing layer of a polishing pad. The formulation includes a urethane acrylate oligomer based on a difunctional polyol or difunctional polythiol. The techniques includes selecting the difunctional polyol or the difunctional polythiol to affect a property of the polishing layer. The formulation also includes a monomer and a photoinitiator. The viscosity of the formulation is applicable for 3D printing of the polishing layer.

## Claims

### Claim 1

A method of manufacturing a polishing pad, comprising:
correlating multiple difunctional polyols with a property of a polishing layer of the polishing pad, wherein the property comprises ultimate tensile strength (UTS), storage modulus, glass transition temperature, or melting point, or any combinations thereof, wherein the multiple difunctional polyols comprise linear aliphatic polyester polyols;
selecting a difunctional polyol that is a linear aliphatic polyester polyol of the multiple difunctional polyols to affect the property of the polishing layer of the polishing pad to give a specified value of the property;
performing a catalytic reaction of the difunctional polyol as selected with a difunctional isocyanate to give a urethane oligomer;
capping the urethane oligomer with an acrylate to give a urethane acrylate oligomer, wherein the urethane acrylate oligomer as applied in additive manufacturing of the polishing pad affects the property to give the specified value; and
performing the additive manufacturing including injecting a formulation through a three dimensional (3D) printer nozzle to form the polishing layer of the polishing pad, the formulation comprising 15 weight percent (wt %) to 25 wt % of the urethane acrylate oligomer and 70 wt % to 80 wt % of an acrylic monomer, wherein the polishing layer comprises a storage modulus at 90° C. in a range of 100 megapascal (MPa) to 300 MPa, and wherein the polishing pad comprises a chemical-mechanical planarization (CMP) pad.

### Claim 2 (depends on 1)

The method of claim 1, wherein the acrylic monomer comprises multiple acrylic monomers, and wherein the urethane oligomer comprises a prepolymer, and wherein the urethane acrylate oligomer comprises an ultraviolet (UV) curable oligomer.

### Claim 3 (depends on 1)

The method of claim 1, wherein the linear aliphatic polyester polyol comprises a semi-crystalline polyester.

### Claim 4 (depends on 1)

The method of claim 1, wherein the difunctional isocyanate comprises a diisocyanate, and wherein the acrylic monomer comprises N,N-diethylacrylamide.

### Claim 5 (depends on 1)

The method of claim 1, wherein correlating multiple difunctional polyols with the property comprises synthesizing a urethane acrylate oligomer from a difunctional polyol of the multiple difunctional polyols, incorporating the urethane acrylate oligomer as synthesized into a test formulation comprising monomer and a photoinitiator, curing the test formulation to give a cured formulation, and measuring the property of the cured formulation.

### Claim 6 (depends on 1)

The method of claim 1, wherein a catalyst in the catalytic reaction comprises dibutyltindilaurate (DBTDL), and wherein the catalytic reaction comprises polymerization.

### Claim 7 (depends on 1)

The method of claim 1, wherein the acrylate comprises 2-hydroxyethyl acrylate.

### Claim 8 (depends on 1)

The method of claim 1, wherein the property comprises UTS or storage modulus, and wherein to affect the property comprises to increase the UTS or the storage modulus.

### Claim 9 (depends on 1)

The method of claim 1, wherein to affect the property comprises selecting the difunctional polyol to meet the specified value as a specified numerical range of the property.

### Claim 10 (depends on 1)

The method of claim 1, wherein the formulation comprises a viscosity in a range of 10 centipoise (cP) to 20 cP at a temperature of 70° C. for ejection of the formulation through the 3D printer nozzle, and wherein the urethane acrylate oligomer as applied comprises the urethane acrylate oligomer subjected to UV light to cure or crosslink the urethane acrylate oligomer.

### Claim 11 (depends on 1)

The method of claim 1, wherein the difunctional polyol is selected to decrease viscosity of the formulation, wherein the formulation comprises photoinitiator less than 5 wt %, and wherein the urethane acrylate oligomer as applied comprises the urethane acrylate oligomer subjected to photopolymerization.

### Claim 12 (depends on 1)

The method of claim 1, wherein selecting the difunctional polyol further comprises selecting the difunctional polyol to decrease viscosity of the formulation comprising a three dimensional (3D) printing formulation comprising the urethane acrylate oligomer.

### Claim 13 (depends on 1)

The method of claim 1, wherein selecting the difunctional polyol further comprises selecting the difunctional polyol to meet a specified numerical range of viscosity of the formulation comprising a 3D printer formulation comprising the urethane acrylate oligomer.

### Claim 14 (depends on 1)

The method of claim 1, wherein selecting the difunctional polyol further comprises selecting the difunctional polyol such that viscosity of the formulation comprising the urethane acrylate oligomer is below a maximum value.

### Claim 15 (depends on 14)

The method of claim 14, wherein the maximum value of the viscosity of the formulation as ejected through the 3D printer nozzle in the additive manufacturing comprises 20 centipoise (cP) as measured at 70° C.

### Claim 16

A method of additive manufacturing of a polishing pad, comprising:
choosing a difunctional polyol comprising a linear aliphatic polyester polyol to affect a viscosity of a three dimensional (3D) printing formulation having urethane acrylate oligomer and to affect a property of a polishing layer of the polishing pad, wherein the property comprises ultimate tensile strength (UTS), storage modulus, glass transition temperature, or melting point, or any combinations thereof;
reacting in presence of catalyst the difunctional polyol with a difunctional isocyanate to give a urethane oligomer prepolymer;
incorporating an acrylate as end caps on the urethane oligomer prepolymer to give the urethane acrylate oligomer, wherein the urethane acrylate oligomer affects the property;
preparing the 3D printing formulation comprising 15 wt % to 25 wt % of the urethane acrylate oligomer and 70 wt % to 80 wt % of acrylic monomer; and
injecting the 3D printing formulation through a 3D printer nozzle, thereby forming the polishing layer of the polishing pad, wherein the polishing layer comprises a storage modulus at 90° C. in a range of 100 megapascal (MPa) to 300 MPa, wherein the polishing pad comprises a chemical-mechanical planarization (CMP) pad.

### Claim 17 (depends on 16)

The method of claim 16, wherein to affect the viscosity comprises to give the viscosity of the 3D printing formulation less than 20 centipoise (cP) as measured at 70° C., and wherein the 3D printing formulation comprises photoinitiator less than 5 wt %.

### Claim 18 (depends on 16)

The method of claim 16, wherein the urethane acrylate oligomer comprises an ultraviolet (UV) curable oligomer, and wherein the acrylic monomer comprises N,N-diethylacrylamide.