# US 10,372,032 B2 · Method and device for permanently repairing defects of absent material of a photolithographic mask

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- Number: US 10,372,032 B2
- Document ID: US10372032B2
- Status: Granted
- Kind: B2
- Application number: 15/441,678
- Filed: 2017-02-24
- Published: 2017-08-31
- Granted: 2019-08-06
- Earliest claimed: 2016-02-26
- Assignees: Carl Zeiss SMT GmbH
- Applicants: Carl Zeiss SMT GmbH
- Inventors: Jens Oster; Kinga Kornilov; Tristan Bret; Horst Schneider; Thorsten Hofmann
- Web page: https://patentgrep.com/patent/US10372032B2

## CPC

- G03F 1/72: Repair or correction of mask defects
- C23C 14/048: {using irradiation by energy or particles}
- C23C 14/083: {of refractory metals or yttrium}
- C23C 14/085: {of iron group metals}
- C23C 14/10: Glass or silica
- C23C 14/221: {Ion beam deposition (C23C14/46, C23C14/48 take precedence)}
- C23C 14/28: by wave energy or particle radiation (C23C14/32 - C23C14/48 take precedence)
- C23C 14/30: by electron bombardment
- C23C 14/548: {Controlling the composition}
- C23C 14/5873: {Removal of material}
- C23C 16/047: {using irradiation by energy or particles}
- C23C 16/16: from metal carbonyl compounds
- C23C 16/18: from metallo-organic compounds
- C23C 16/402: {Silicon dioxide}
- C23C 16/405: {of refractory metals or yttrium}
- C23C 16/483: {using coherent light, UV to IR, e.g. lasers}
- C23C 16/486: {using ion beam radiation}
- C23C 16/56: After-treatment
- G03F 1/26: Phase shift masks [PSM]; PSM blanks; Preparation thereof
- G03F 1/74: by charged particle beam [CPB], e.g. focused ion beam
- H01J 37/30: Electron-beam or ion-beam tubes for localised treatment of objects
- H01J 37/3178: {for applying thin layers on objects}
- H01J 2237/006: Details of gas supplies, e.g. in an ion source, to a beam line, to a specimen or to a workpiece, (H01J37/3244 takes precedence; environmental cells for electron microscopes H01J2237/2003; microscopes with environmental specimen chamber H01J2237/2608)
- H01J 2237/30466: Detecting endpoint of process
- H01J 2237/31744: introducing gas in vicinity of workpiece
- 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)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)

## Abstract

The present application relates to a method for permanently repairing defects of absent material of a photolithographic mask, comprising the following steps: (a) providing at least one carbon-containing precursor gas and at least one oxidizing agent at a location to be repaired of the photolithographic mask; (b) initiating a reaction of the at least one carbon-containing precursor gas with the aid of at least one energy source at the location of absent material in order to deposit material at the location of absent material, wherein the deposited material comprises at least one reaction product of the reacted at least one carbon-containing precursor gas; and (c) controlling a gas volumetric flow rate of the at least one oxidizing agent in order to minimize a carbon proportion of the deposited material.

## Claims

### Claim 1

A method for repairing defects of absent material of a photolithographic mask, wherein the method comprises the following steps:
a. providing at least one carbon-containing precursor gas and at least one oxidizing agent at a location to be repaired of the photolithographic mask, in which the at least one carbon-containing precursor gas comprises a mixture of at least one metal carbonyl and at least one main group element alkoxide at the location to be repaired, wherein providing the at least one metal carbonyl at the location of absent material is carried out in a partial pressure range of 10−6 mbar to 10−4 mbar, providing the at least one main group element alkoxide is carried out in a partial pressure range of 10−6 mbar to 10−4 mbar, and providing the at least one oxidizing agent is carried out in a partial pressure range of 10−5 mbar to 10−2 mbar;
b. initiating a reaction of the at least one carbon-containing precursor gas with the aid of at least one energy source at the location of absent material in order to deposit material at the location of absent material, wherein the deposited material comprises at least one reaction product of the reacted at least one carbon-containing precursor gas; and
c. controlling a gas volumetric flow rate of the at least one oxidizing agent in order to reduce a carbon proportion of the deposited material, wherein the deposited material comprises a carbon proportion of <20 atom %.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the deposited material comprises a carbon proportion of <15 atom %.

### Claim 3 (depends on 1)

The method according to claim 1, wherein the at least one metal carbonyl comprises at least one element from the group: chromium hexacarbonyl (Cr(CO)6), molybdenum hexacarbonyl (Mo(CO)6), tungsten hexacarbonyl (W(CO)6), dicobalt octacarbonyl (Co2(CO8), triruthenium dodecacarbonyl (Ru3(CO)12), and iron pentacarbonyl (Fe(CO)5).

### Claim 4 (depends on 1)

The method according to claim 1, wherein the at least one main group element alkoxide comprises at least one element from the group: tetraethyl orthosilicate (Si(OC2H5)4), tetramethyl orthosilicate (Si(OCH3)4) and titanium tetraisopropoxide (Ti(OCH(CH3)2)4).

### Claim 5 (depends on 1)

The method according to claim 1, wherein the at least one oxidizing agent comprises at least one element from the group: oxygen (O2), ozone (O3), water vapor (H2O), hydrogen peroxide (H2O2), dinitrogen monoxide (N2O), nitrogen monoxide (NO), nitrogen dioxide (NO2) and nitric acid (HNO3).

### Claim 6 (depends on 1)

The method according to claim 1, wherein the at least one energy source comprises at least one particle beam.

### Claim 7 (depends on 1)

The method according to claim 1, wherein the absent material comprises at least one element from the group: absent material of at least one structure element of a binary mask, absent material of at least one structure element of a phase mask, absent material of at least one structure element of a photomask for the extreme ultraviolet wavelength range, absent material of a substrate of a transmissive photolithographic mask, and absent material of at least one structure element of a nanoimprint lithography mask.

### Claim 8 (depends on 1)

The method according to claim 1, wherein providing the at least one precursor gas and the at least one oxidizing agent at the location of absent material is carried out with a mixture ratio of 1:10.

### Claim 9 (depends on 1)

The method according to claim 1, wherein providing the at least one metal carbonyl and the at least one main group element alkoxide is carried out with a mixture ratio of 1:5.

### Claim 10 (depends on 1)

The method according to claim 1, wherein providing the at least one main group element alkoxide and the at least one oxidizing agent at the location of absent material is carried out with a mixture ratio of 1:10.

### Claim 11 (depends on 1)

The method according to claim 1, wherein providing the at least one oxidizing agent is carried out with a gas volumetric flow rate in the range of 0.3 sccm to 10 sccm.

### Claim 12 (depends on 1)

The method according to claim 1, wherein providing the at least one metal carbonyl at the location of absent material is carried out in a temperature range of −50° C. to +35° C.

### Claim 13 (depends on 1)

The method according to claim 1, wherein providing the at least one main group element alkoxide at the location of absent material is carried out in a temperature range of −40° C. to +15° C.

### Claim 14 (depends on 1)

The method according to claim 1, wherein material is deposited at a rate of 0.01 nm/s to 1.0 nm/s.

### Claim 15 (depends on 1)

The method according to claim 1, wherein the photolithographic mask comprises a phase mask, and providing the at least one precursor gas comprises simultaneously providing chromium hexacarbonyl (Cr(CO6)) and tetraethyl orthosilicate (Si(OC2H5)4).

### Claim 16

A method for repairing defects of absent material of a photolithographic mask, the method comprising:
a. providing a mixture of at least one metal carbonyl, at least one main group element alkoxide, and at least one oxidizing agent at a location to be repaired of the photolithographic mask, wherein providing the at least one metal carbonyl at the location of absent material is carried out in a partial pressure range of 10−6 mbar to 10−4 mbar, providing the at least one main group element alkoxide is carried out in a partial pressure range of 10−6 mbar to 10−4 mbar, and providing the at least one oxidizing agent is carried out in a partial pressure range of 10−5 mbar to 10−2 mbar; and
b. initiating a reaction of the at least one metal carbonyl and the at least one main group element alkoxide with the aid of at least one energy source at the location of absent material in order to deposit material at the location of absent material, wherein the deposited material comprises at least one reaction product of the reacted at least one metal carbonyl and the at least one main group element alkoxide.

### Claim 17 (depends on 16)

The method of claim 16, comprising controlling a gas volumetric flow rate of the at least one oxidizing agent in order to reduce a carbon proportion of the deposited material to be less than 15 atom %.

### Claim 18

A method for repairing defects of absent material of a photolithographic mask, the method comprising:
a. providing at least one carbon-containing precursor gas and at least one oxidizing agent at a location to be repaired of the photolithographic mask, in which the at least one oxidizing agent comprises at least one of H2O2 or HNO3, in which the at least one carbon-containing precursor gas comprises a mixture of at least one metal carbonyl and at least one main group element alkoxide at the location to be repaired, wherein providing the at least one metal carbonyl at the location of absent material is carried out in a partial pressure range of 10−6 mbar to 10−4 mbar, providing the at least one main group element alkoxide is carried out in a partial pressure range of 10−6 mbar to 10−4 mbar, and providing the at least one oxidizing agent is carried out in a partial pressure range of 10−5 mbar to 10−2 mbar;
b. initiating a reaction of the at least one carbon-containing precursor gas with the aid of at least one energy source at the location of absent material in order to deposit material at the location of absent material, wherein the deposited material comprises at least one reaction product of the reacted at least one carbon-containing precursor gas; and
c. controlling a gas volumetric flow rate of the at least one oxidizing agent in order to reduce a carbon proportion of the deposited material to be less than 15 atom %.

### Claim 19 (depends on 18)

The method of claim 18 in which the at least one carbon-containing precursor gas comprises tantalum hexacarbonyl (Ta(CO)6).