# US 2019/0171106 A1 · Silsesquioxane Resin and Oxaamine Composition

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- Number: US 2019/0171106 A1
- Document ID: US20190171106A1
- Status: Published application
- Kind: A1
- Application number: 16/092,463
- Filed: 2017-04-27
- Published: 2019-06-06
- Earliest claimed: 2016-05-03
- Assignees: Dow Silicones Corporation
- Applicants: Dow Silicones Corporation
- Inventors: Peng-Fei FU; Wonbum JANG
- Web page: https://patentgrep.com/patent/US20190171106A1

## CPC

- G03F 7/0757: {Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)}
- C07F 7/21: Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
- C08G 77/045: {containing less than 25 silicon atoms}
- C08K 5/04: Oxygen-containing compounds {(C08K5/0091 takes precedence)}
- C08K 5/17: Amines; Quaternary ammonium compounds
- C08L 83/06: containing silicon bound to oxygen-containing groups (C08L83/12 takes precedence)
- G03F 7/162: {Coating on a rotating support, e.g. using a whirler or a spinner}
- G03F 7/168: {Finishing the coated layer, e.g. drying, baking, soaking}
- G03F 7/2002: {with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image}
- G03F 7/2004: {characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light}
- G03F 7/2037: {Exposure with X-ray radiation or corpuscular radiation, through a mask with a pattern opaque to that radiation}
- G03F 7/2039: {X-ray radiation}
- G03F 7/322: {Aqueous alkaline compositions}
- G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)}
- H10P 76/2041: {Photolithographic processes}
- C08G 77/14: containing silicon bound to oxygen-containing groups
- C08G 77/70: {Siloxanes defined by use of the MDTQ nomenclature}
- 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)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

A silsesquioxane-containing composition comprising a silsesquioxane resin and an oxaamine of formula (II) (see description), products prepared therefrom, photoresist compositions comprising the silsesquioxane-containing composition and a photoacid generator, products prepared therefrom, methods of making and using same, and manufactured articles and semiconductor devices containing same.

## Claims

### Claim 1

A silsesquioxane-containing composition comprising (A) a silsesquioxane resin and (B) an oxaamine, wherein:
the (A) silsesquioxane resin is of formula (I):
[HSiO3/2]t1[Z-L-SiO3/2]t2[H(R1O)SiO2/2]d[(R1O)xSiO(4-x)/2]y[R2SiO3/2]t3 (I), wherein:
(I), wherein:
subscript t1 is a mole fraction of from 0.4 to 0.9;
subscript t2 is a mole fraction of from 0.1 to 0.6;
subscript d is a mole fraction from 0 to 0.45;
subscript x is an integer of 1, 2, or 3;
subscript y is a mole fraction from 0 to 0.25;
subscript t3 is a mole fraction from 0 to 0.15;
the sum of t1+t2=from ≥0.9 to ≤1 and the sum of t1+t2+d+y+t3=1;
each R1 is independently H or (C1-C6)alkyl;
each R2 is independently HO-L- or HOOC-L-;
each L is independently a divalent (C1-C20)hydrocarbon group that is unsubstituted or substituted with at least 1 substituent independently selected from (C1-C3)alkyl, —OH, and a fluorine atom up to and including perfluoro-substitution; and
each Z is —OH, —COOH, —O-THP, —OCH(R3a)2, —OC(R3b)3, —COOCH(R3a)2, —COOC(R3b)3, —OCOOCH(R3a)2, or —OCOOC(R3b)3,
wherein THP is tetrahydropyran-2-yl;
wherein each R3a is independently a (C1-C6)alkyl, (C3-C12)cycloalkyl, (C6-C10)aralkyl, ((C1-C6)alkyl)3SiCH2CH2-, or 2 R3a together with the carbon atom to which they are both bonded are a (C3-C12)cycloalkyl or a (C6-C12)bicycloalkyl; and
wherein each R3b is independently a (C1-C6)alkyl, (C3-C12)cycloalkyl, (C6-C10)aralkyl, ((C1-C6)alkyl)3SiCH2CH2-; or 2 R3b together with the carbon atom to which they are both bonded are a (C3-C12)cycloalkyl or a (C6-C12)bicycloalkyl and the remaining R3b is independently a (C1-C6)alkyl, (C3-C12)cycloalkyl, (C6-C10)aralkyl, or ((C1-C6)alkyl)3SiCH2CH2-; or all 3 R3b together with the carbon atom to which they are all bonded are a (C7-C12)bicycloalkyl; and
the (B) oxaamine is of formula (II):
RN(3-n)N—[(CH2CH(R4)O)m—R5]n (II),
wherein:
subscript m is an integer from 1 to 10;
subscript n is an integer 1, 2, or 3;
each RN is independently unsubstituted (C1-C12)alkyl;
each R4 is independently H or an unsubstituted (C1-C12)alkyl; and
each R5 is independently H or a (C1-C12)alkyl, which is unsubstituted or independently substituted with 1, 2, or 3 (C1-C12)alkoxy groups.

### Claim 2 (depends on 1)

The silsesquioxane-containing composition of claim 1 wherein in the (A) silsesquioxane resin:
subscript t1 is a mole fraction of from 0.4 to 0.65;
subscript t1 is a mole fraction of from 0.65 to 0.9;
subscript t2 is a mole fraction of from 0.1 to 0.35;
subscript t2 is a mole fraction of from 0.5 to 0.6;
subscript d is 0;
subscript d is a mole fraction from >0 to 0.45;
subscript x is 1;
subscript x is 2;
subscript x is 3;
subscript y is 0;
subscript y is a mole fraction from >0 to 0.25;
subscript t3 is 0;
subscript t3 is a mole fraction from >0 to 0.15;
at least one R1 is H;
subscript d is a mole fraction from >0 to 0.45 or subscript y is a mole fraction from >0 to 0.25 and at least one R1 is H;
at least one R1 is independently (C1-C6)alkyl;
subscript d is a mole fraction from >0 to 0.45 or subscript y is a mole fraction from >0 to 0.25 and at least one R1 is (C1-C6)alkyl;
at least one R2 is independently HO-L-;
subscript t3 is a mole fraction from >0 to 0.15 and at least one R2 is independently HO-L-;
at least one R2 is independently HOOC-L-;
subscript t3 is a mole fraction from >0 to 0.15 and at least one R2 is independently HOOC-L-;
at least one L is independently a divalent (C1-C20)hydrocarbon group that is unsubstituted;
at least one L is independently a divalent (C6-C10)bicycloalkane group that is unsubstituted;
at least one L is a divalent (C1-C20)hydrocarbon group that is substituted with at least 1 (C1-C3)alkyl group;
at least one L is a divalent (C6-C10)bicycloalkane group that is substituted with at least 1 (C1-C3)alkyl group;
at least one L is a divalent (C1-C20)hydrocarbon group that is substituted with at least 1 —OH group;
at least one L is a divalent (C6-C10)bicycloalkane group that is substituted with at least 1 —OH group;
at least one L is independently a divalent (C1-C20)hydrocarbon group that is substituted with at least 1 fluorine atom up to and including perfluoro-substitution;
at least one L is independently a divalent (C6-C10)bicycloalkane group that is substituted with at least 1 fluorine atom up to and including perfluoro-substitution;
at least one Z is —OH;
at least one Z is —COOH;
at least one Z is —O-THP;
at least one Z is —OCH(R3a)2;
at least one Z is —COOCH(R3a)2;
at least one Z is —OCOOCH(R3a)2;
at least one Z is —OC(R3b)3;
at least one Z is —COOC(R3b)3;
at least one Z is —OCOOC(R3b)3;
at least one R3a or R3b is independently a (C1-C6)alkyl;
at least one R3a or R3b is independently (C3-C12)cycloalkyl;
at least one R3a or R3b is independently (C6-C10)aralkyl;
at least one R3a or R3b is independently ((C1-C6)alkyl)3SiCH2CH2-;
2 R3a or 2 R3b together with the carbon atom to which they are both bonded are a (C3-C12)cycloalkyl or a (C6-C12)bicycloalkyl; or
all 3 R3b together with the carbon atom to which they are all bonded are a (C7-C12)bicycloalkyl.

### Claim 3 (depends on 1)

The silsesquioxane-containing composition of claim 1 wherein in the (A) silsesquioxane resin of formula (I) the Z-L- is selected from the following monovalent carboxylic esters: a bicyclo[2.2.1]heptane-5-yl-2-carboxylic acid, secondary aliphatic ester; a bicyclo[2.2.1]heptane-5-yl-2-carboxylic acid, tertiary aliphatic ester; a bicyclo[2.2.1]heptane-6-yl-2-carboxylic acid, secondary aliphatic ester; or a bicyclo[2.2.1]heptane-6-yl-2-carboxylic acid, tertiary aliphatic ester.

### Claim 4 (depends on 3)

The silsesquioxane-containing composition of claim 3 wherein Z-L- is selected from the following monovalent carboxylic esters:
bicyclo[2.2.1]heptane-5-yl-2-carboxylic acid, 1′,1′-dimethylethyl ester;
bicyclo[2.2.1]heptane-6-yl-2-carboxylic acid, 1′,1′-dimethylethyl ester;
bicyclo[2.2.1]heptane-5-yl-2-carboxylic acid, 1′-methylethyl ester;
bicyclo[2.2.1]heptane-6-yl-2-carboxylic acid, 1′-methylethyl ester;
bicyclo[2.2.1]heptane-5-yl-2-carboxylic acid, adaman-1′-yl ester;
bicyclo[2.2.1]heptane-6-yl-2-carboxylic acid, adaman-1′-yl ester;
bicyclo[2.2.1]heptane-5-yl-2-carboxylic acid, 3′-methyladaman-1′-yl ester;
bicyclo[2.2.1]heptane-6-yl-2-carboxylic acid, 3′-methyladaman-1′-yl ester;
bicyclo[2.2.1]heptane-5-yl-2-carboxylic acid, 2′-methyladaman-2′-yl ester;
bicyclo[2.2.1]heptane-6-yl-2-carboxylic acid, 2′-methyladaman-2′-yl ester;
bicyclo[2.2.1]heptane-5-yl-2-carboxylic acid, 2′-ethyladaman-2′-yl ester;
bicyclo[2.2.1]heptane-6-yl-2-carboxylic acid, 2′-ethyladaman-2′-yl ester;
bicyclo[2.2.1]heptane-5-yl-2-carboxylic acid, cyclohexyl ester;
bicyclo[2.2.1]heptane-6-yl-2-carboxylic acid, cyclohexyl ester;
bicyclo[2.2.1]heptane-5-yl-2-carboxylic acid, 1′-ethylcyclopentyl ester;
bicyclo[2.2.1]heptane-6-yl-2-carboxylic acid, 1′-ethylcyclopentyl ester;
bicyclo[2.2.1]heptane-5-yl-2-carboxylic acid, 2′-hydroxy-2′,6′,6′-trimethylbicyclo[3.1.1]heptane-3′-yl ester; and
bicyclo[2.2.1]heptane-6-yl-2-carboxylic acid, 2′-hydroxy-2′,6′,6′-trimethylbicyclo[3.1.1]heptane-3′-yl ester.

### Claim 5 (depends on 1)

The silsesquioxane-containing composition of claim 1 wherein the (A) silsesquioxane resin of formula (I) has a weight average molecular weight (Mw) of 1,000 to 50,000.

### Claim 6 (depends on 1)

The silsesquioxane-containing composition of claim 1 wherein in the (B) oxaamine of formula (II):
subscript m is an integer from 1 to 5.5;
subscript m is an integer from 5.5 to 10;
subscript n is 1;
subscript n is 2;
subscript n is 3;
n is 1 or 2 and RN is unsubstituted (C1-C4)alkyl;
at least one R4 is independently H;
at least one R4 is independently an unsubstituted (C1-C12)alkyl;
at least one R5 is independently H;
at least one R5 is independently a (C1-C12)alkyl, which is unsubstituted;
at least one R4 and R5 is independently an unsubstituted (C1-C5)alkyl;
at least one R4 and R5 is independently an unsubstituted (C6-C12)alkyl;
at least one R5 is independently a (C1-C12)alkyl, which is independently substituted with 1, 2, or 3 (C1-C12)alkoxy groups;
at least one R5 is independently a (C1-C12)alkyl, which is independently substituted with 1 (C1-C12)alkoxy group;
at least one R5 is independently a (C1-C5)alkyl, which is independently substituted with 1 (C1-C5)alkoxy group;
at least one R5 is independently a (C1-C12)alkyl, which is independently substituted with 2 (C1-C12)alkoxy groups;
at least one R5 is independently a (C1-C12)alkyl, which is independently substituted with 3 (C1-C12)alkoxy groups;
at least one R5 is independently a (C1-C5)alkyl, which is independently substituted with 1, 2, or 3 (C1-C5)alkoxy groups; or
at least one R5 is independently a (C1-C5)alkyl, which is independently substituted with 1, 2, or 3 (C6-C12)alkoxy groups.

### Claim 7 (depends on 1)

The silsesquioxane-containing composition of claim 1 wherein the (B) oxaamine of formula (II) is selected from:
tri(2-(ethyloxy)ethyl)-amine;
tri(1-methyl-ethanol-2-yl)-amine;
tri(2-(3′-methylbutyloxy)ethyl)-amine;
tri(2-(hexyloxy)ethyl)-amine;
tri(2-(octyloxy)ethyl)-amine;
tri(2-(methoxymethoxy)ethyl)-amine;
tri(2-(methoxyethoxy)ethyl)-amine;
tri(2-(2′-ethoxyethoxy)ethyl)-amine; and
tri(2-(2′-(2″-methoxyethoxy)ethoxy)ethyl)-amine.

### Claim 8 (depends on 1)

A silsesquioxane-containing composition comprising the silsesquioxane-containing composition of claim 1 and (C) a photoacid generator, wherein the (C) photoacid generator comprises an onium salt, a halogen-containing compound, a diazoketone compound, a glyoxime derivative, a sulfone compound, a sulfonate compound, or a combination of any two or more thereof.

### Claim 9 (depends on 1)

The silsesquioxane-containing composition of claim 1 independently further comprising one or more constituents: (D) a solvent or (E) an adhesion promoter.

### Claim 10 (depends on 1)

A manufactured article comprising the silsesquioxane-containing composition of claim 1.

### Claim 11 (depends on 1)

A method of making a resist image on a substrate, the method comprising:
applying the silsesquioxane-containing composition of claim 1 to a surface of a substrate so as to form an applied film thereof on the surface of the substrate, wherein the silsesquioxane-containing composition comprises the (A) silsesquioxane resin, the (B) oxaamine, and (C) a photoacid generator;
mask exposing the applied film to radiation to produce an exposed film containing a latent pattern;
developing the exposed film to produce a resist image from the latent pattern to give a manufactured article comprising the resist image disposed on the substrate.

### Claim 12 (depends on 11)

The method of making a resist image on a substrate of claim 11, wherein:
the substrate comprises a bare semiconductor wafer;
the substrate comprises a primed semiconductor wafer;
the substrate comprises a primed semiconductor wafer prepared by priming a bare semiconductor wafer with hexamethyldisilazane;
the substrate comprises a semiconductor wafer and the silsesquioxane-containing composition is applied directly on a surface of the semiconductor wafer;
the substrate comprises a semiconductor wafer having a surface portion comprising silicon carbide, silicon carbonitride, silicon nitride, silicon oxide, silicon oxynitride, or silicon oxycarbonitride, and the silsesquioxane-containing composition is applied directly on the surface portion of the semiconductor wafer;
the substrate comprises an underlayer disposed on a surface of a semiconductor wafer and the silsesquioxane-containing composition is applied directly on the underlayer without being applied directly on the semiconductor wafer;
before the applying step the silsesquioxane-containing composition further comprises (D) a solvent and the applying step comprises spin-coating;
the applied film further comprises (D) a solvent and the method further comprises drying the applied film (soft baking) before the mask exposing step;
the applied film has a thickness of from 0.01 to 5 micrometers;
the radiation is selected from ultraviolet (UV) light, X-ray radiation, e-beam radiation, and extreme ultraviolet (EUV) radiation;
the radiation has a wavelength in a range of from 13 nanometers (nm) to 365 nm;
the radiation has a wavelength comprising 365 nm, 248 nm, 193 nm, 157 nm, or 13 nm;
the developing step comprises contacting the mask exposed film with a developer comprising an aqueous base;
the method further comprises heating the mask exposed film at a temperature from 30 degrees Celsius (° C.) to 200° C. and cooling the mask exposed film before the developing step and the developing step comprises contacting the cooled mask exposed film with a developer comprising an aqueous base; or
the developing step comprises contacting the mask exposed film with a developer comprising aqueous tetramethylammonium hydroxide.

### Claim 13 (depends on 11)

The method of making a resist image on a substrate of claim 11, wherein:
the substrate comprises a hardmask layer disposed on a surface of a semiconductor wafer and the silsesquioxane-containing composition is applied directly on the hardmask layer without being applied directly on the semiconductor wafer and the method further comprises oxygen (O2) plasma etching the resist image to etch the hardmask layer by transferring the resist image into the hardmask layer and give a first semiconductor device comprising a bilayer image disposed on the surface of the semiconductor wafer, wherein the bilayer image comprises a resist image layer and a hardmask image layer, and wherein a region of the surface of the semiconductor wafer is covered by the bilayer image and another region of the surface of the semiconductor wafer is uncovered; or
the substrate comprises a hardmask layer disposed on a surface of a semiconductor wafer and the silsesquioxane-containing composition is applied directly on the hardmask layer without being applied directly on the semiconductor wafer and the method further comprises: (i) oxygen (O2) plasma etching the resist image to etch the hardmask layer by transferring the resist image into the hardmask layer to give a first semiconductor device sequentially comprising a bilayer image disposed on the surface of the semiconductor wafer, wherein the bilayer image comprises a resist image layer and a hardmask image layer, and wherein a region of the surface of the semiconductor wafer is covered by the bilayer image and another region of the surface of the semiconductor wafer is uncovered; and (ii) halogen-containing etching the uncovered region of the surface of the semiconductor wafer of the first semiconductor device to transfer the bilayer image into the semiconductor wafer by removing the remaining applied film, at least some of the hardmask layer, and some, but not all, of the uncovered region of the semiconductor wafer to give a second semiconductor device comprising a semiconductor image disposed on a basal semiconductor layer.

### Claim 14 (depends on 13)

A semiconductor device comprising the first or second semiconductor device made by the method of claim 13.