# US 11,307,500 B2 · Method for removing photoresistor layer, method of forming a pattern and method of manufacturing a package

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- Number: US 11,307,500 B2
- Document ID: US11307500B2
- Status: Granted
- Kind: B2
- Application number: 16/379,821
- Filed: 2019-04-10
- Published: 2020-04-30
- Granted: 2022-04-19
- Earliest claimed: 2018-10-30
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Co., Ltd.
- Inventors: Christine Y Ouyang
- Web page: https://patentgrep.com/patent/US11307500B2

## CPC

- G03F 7/427: {using plasma means only}
- G03F 7/0043: {Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof (G03F7/0044 takes precedence)}
- G03F 7/027: Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence)
- G03F 7/423: {containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds}
- G03F 7/426: {containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides}
- G03F 7/70033: {by plasma extreme ultraviolet [EUV] sources}
- H10P 50/283: {by chemical means}
- H10P 50/287: {by chemical means}
- H10P 50/692: {characterised by their composition, e.g. multilayer masks or materials}
- H10P 50/695: {characterised by the process involved to create the mask, e.g. lift-off masks or sidewalls or to modify the mask}
- H10P 76/204: {of organic photoresist masks}
- H10W 20/435: {Cross-sectional shapes or dispositions of interconnections}
- H10W 70/09: extending onto an encapsulation that laterally surrounds the chip or wafer, e.g. fan-out wafer level package [FOWLP] RDLs
- H10W 72/20: Bump connectors, e.g. solder bumps or copper pillars; Dummy bumps; Thermal bumps
- H10W 72/90: Bond pads, in general
- H10W 74/01: Manufacture or treatment
- H10W 74/012: {of encapsulations on active surfaces of flip-chip devices, e.g. forming underfills}
- H10W 74/016: {using moulds}
- H10W 74/117: {the substrate having spherical bumps for external connection}
- H10W 74/15: on active surfaces of flip-chip devices, e.g. underfills
- H10W 70/099: {Connecting interconnections to insulating or insulated package substrates, interposers or redistribution layers}
- H10W 70/60: Insulating or insulated package substrates; Interposers; Redistribution layers (leadframes H10W70/40)
- H10W 70/65: Shapes or dispositions of interconnections
- H10W 70/652: Cross-sectional shapes
- H10W 72/0198: {batch processes}
- H10W 72/073: {of die-attach connectors}
- H10W 72/241: {Dispositions, e.g. layouts}
- H10W 72/29: Bond pads specially adapted therefor
- H10W 72/874: {On different surfaces}
- H10W 72/9413: {on encapsulations}
- H10W 90/722: {between stacked chips}
- H10W 90/734: {between a chip and a stacked insulating package substrate, interposer or RDL}
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

A method for removing a resist layer is provided. A resist layer is formed with a material comprising a metal oxide core with organic ligands. A chlorine-containing compound or a methyl group-containing compound is globally applied onto the resist layer to allow the chlorine-containing compound or the methyl group-containing compound to perform a ligand exchange process with the resist layer so as to remove the resist layer through sublimation.

## Claims

### Claim 1

A method for removing a resist layer, comprising:
forming a resist layer with a material comprising a metal oxide core with organic ligands;
performing a ligand removal process to remove the organic ligands;
perfonning a fluorination process to react the metal oxide core with a fluorine-containing compound to form a metal fluoride core; and
after performing the ligand removal process and the fluorination process, globally applying a chlorine-containing compound or a methyl group-containing compound onto the resist layer to allow the chlorine-containing compound or the methyl group-containing compound to perform a ligand exchange process with the resist layer so as to remove the resist layer through sublimation.

### Claim 2 (depends on 1)

The method of claim 1, wherein the metal oxide core comprises hafnium oxide, titanium oxide, tin oxide, or zirconium oxide.

### Claim 3 (depends on 1)

The method of claim 1, wherein the organic ligands comprise a benzoic acid or a sulfonic acid.

### Claim 4 (depends on 3)

The method of claim 3, wherein the organic ligands further comprise a methacrylic acid.

### Claim 5 (depends on 1)

The method of claim 1,
wherein the chlorine-containing compound comprises tetrachlorosilane, or
wherein the methyl group-containing compound comprises trimethylaluminum or dimethylacetarnide.

### Claim 6 (depends on 1)

The method of claim 1, wherein performing the ligand exchange process comprises replacing oxygen atoms surrounding a metal atom comprised in the metal oxide core with chloro groups provided by the chlorine-containing compound or methyl-groups provided by the methyl group-containing compound to turn resultants thereof into volatiles.

### Claim 7 (depends on 1)

The method of claim 1, wherein the fluorine-containing compound comprises a hydrofluoric acid.

### Claim 8 (depends on 1)

The method of claim 1, wherein performing the ligand removal process comprises performing an ozone plasma process, an oxygen plasma process, or a remote oxygen plasma process.

### Claim 9 (depends on 1)

The method of claim 1, wherein a ratio of an atomic percentage of the organic ligands to an atomic percentage of the metal oxide core being in a range of 10% to 50%.

### Claim 10

A method of forming a pattern, comprising:
forming a resist layer over a base layer;
patterning the resist layer to form a patterned resist layer with openings exposing portions of the base layer, a material of the patterned resist layer comprising a metal oxide core with organic ligands;
patterning the base layer by using the patterned resist layer as a mask to form a pattern; and
removing the patterned resist layer, wherein removing the patterned resist layer comprises:
performing a ligand removal process to remove the organic ligands;
performing a fluorination process to react the metal oxide core with a fluorine-containing compound to form a metal fluoride core; and
after performing the ligand removal process and the fluorination process, globally applying a chlorine-containing compound or a methyl group-containing compound onto the patterned resist layer to allow the chlorine-containing compound or the methyl group-containing compound to perform a ligand exchange process with the patterned resist layer so as to remove the patterned resist layer through sublimation.

### Claim 11 (depends on 10)

The method of claim 10, wherein the base layer comprises a conductive layer, a semiconductor layer, or an insulating layer.

### Claim 12 (depends on 10)

The method of claim 10, wherein patterning the resist layer comprises:
providing a photomask over the resist layer;
globally irradiating the resist layer with an electromagnetic radiation through the photomask to allow part of the resist layer to be exposed portions to the electromagnetic radiation and rest of the resist layer to be unexposed portions to the electromagnetic radiation, wherein the electromagnetic radiation comprises an extreme ultraviolet exposure; and
removing either the exposed portions or the unexposed portions of the resist layer through a developer to form the patterned resist layer with the openings exposing the portions of the base layer.

### Claim 13 (depends on 10)

The method of claim 10, wherein performing the ligand exchange process comprises replacing oxygen atoms surrounding a metal atom comprised in the metal oxide core with chloro groups provided by the chlorine-containing compound or methyl-groups provided by the methyl group-containing compound to turn resultants thereof into volatiles.

### Claim 14 (depends on 10)

The method of claim 10, wherein the fluorine-containing compound comprises hydrofluoric acid.

### Claim 15 (depends on 14)

The method of claim 14, wherein performing the ligand removal process comprises performing an ozone plasma process, an oxygen plasma process, or a remote oxygen plasma process.

### Claim 16 (depends on 10)

The method of claim 10, wherein a ratio of an atomic percentage of the organic ligands to an atomic percentage of the metal oxide core being in a range of 10% to 50%.

### Claim 17

A method of manufacturing a package, comprising:
providing a semiconductor die, wherein the semiconductor die comprises a plurality of metallic posts;
encapsulating the semiconductor die by an insulating encapsulant; and
forming a redistribution circuit structure over the semiconductor die and the insulating encapsulant, comprising:
forming a resist layer with a pattern having openings over the insulating encapsulant, a material of the resist layer comprising a metal oxide core with organic ligands;
forming a metallization layer in the openings of the resist layer over the insulating encapsulant and electrically connected to the plurality of metallic posts;
performing a ligand removal process to remove the organic ligands;
performing a fluorination process to react the metal oxide core with a fluorine-containing compound to form a metal fluoride core; and
after performing the ligand removal process and the fluorination process, globally applying a chlorine-containing compound or a methyl group-containing compound onto the resist layer to allow the chlorine-containing compound or the methyl group-containing compound to perform a ligand exchange process with the resist layer so as to remove the resist layer through sublimation.

### Claim 18 (depends on 17)

The method of claim 17, wherein performing the ligand exchange process comprises replacing oxygen atoms surrounding a metal atom comprised in the metal oxide core with chloro groups provided by the chlorine-containing compound or methyl-groups provided by the methyl group-containing compound to turn resultants thereof into volatiles.

### Claim 19 (depends on 17)

The method of claim 17, wherein the fluorine-containing compound comprises hydrofluoric acid.

### Claim 20 (depends on 19)

The method of claim 19, wherein performing the ligand removal process comprises performing an ozone plasma process, an oxygen plasma process, or a remote oxygen plasma process.