# US 12,119,220 B2 · Methods for filling a gap feature on a substrate surface and related semiconductor structures

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- Number: US 12,119,220 B2
- Document ID: US12119220B2
- Status: Granted
- Kind: B2
- Application number: 18/079,160
- Filed: 2022-12-12
- Published: 2023-06-01
- Granted: 2024-10-15
- Earliest claimed: 2019-12-19
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Leo Salmi; Mikko Ritala; Markku Leskelä
- Web page: https://patentgrep.com/patent/US12119220B2

## CPC

- H10P 14/665: {Porous materials}
- H10P 14/6302: {Non-deposition formation processes}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/6529: {by exposure to a gas or vapour}
- H10W 10/014: {using trench refilling with dielectric materials, e.g. shallow trench isolations}
- H10W 10/17: formed using trench refilling with dielectric materials, e.g. shallow trench isolations
- H10P 14/2925: {Surface structures}
- H10P 14/3426: {Oxides}
- H10P 14/3452: {Microstructure}
- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- H10P 14/69391: {the material containing aluminium, e.g. Al2O3}
- H10P 14/69395: {the material containing zirconium, e.g. ZrO2}
- 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 filling a gap feature on a substrate surface is disclosed. The method may include: providing a substrate comprising a non-planar surface including one or more gap features; depositing a metal oxide film over a surface of the one or more gap features by a cyclical deposition process; contacting the metal oxide with an organic ligand vapor; and converting at least a portion of the metal oxide film to a porous material thereby filling the one or more gap features. Semiconductor structures including a metal-organic framework material formed by the methods of the disclosure are also disclosed.

## Claims

### Claim 1

A method for filling a gap feature on a substrate surface, the method comprising:
providing a substrate comprising a non-planar surface comprising one or more gap features;
conformally depositing a metal oxide film over a surface of the one or more gap features by a cyclical deposition process, wherein the metal oxide comprises Zr, Cu, Fe, or Al;
contacting the metal oxide film with an organic ligand vapor; and
converting at least a portion of the metal oxide film to a porous material thereby filling the one or more gap features;
wherein the cyclical deposition process comprises at least one unit cycle, one unit cycle comprising:
contacting the substrate with a metal vapor phase precursor; and
contacting the substrate with an oxidizing precursor.

### Claim 2 (depends on 1)

The method of claim 1, wherein, the contacting of the metal oxide film with the organic ligand vapor produces a conversion of at least a portion of the metal oxide film to the porous material.

### Claim 3 (depends on 1)

The method of claim 1, wherein the metal vapor phase precursor is selected from one or more of the group consisting of (MeCp)Zr(OMe)2, (MeCp)2Zr(OMe)Me, tetrakis(ethylmethyl)aminozirconium (TEMAZr), tetrakis(dimethyl)aminozirconium (TDMAZr), tetrakis(diethyl)aminozirconium (TDEAZr), tris(dimethylamino)cyclopentadienylzirconium, or derivatives thereof.

### Claim 4 (depends on 1)

The method of claim 1, wherein the oxidizing precursor comprises at least one of water (H2O), hydrogen peroxide (H2O2), ozone (O3), an organic alcohol, or an oxygen based plasma.

### Claim 5 (depends on 1)

The method of claim 1, wherein the non-planar surface comprises a material selected from the group consisting of silicon (Si), germanium (Ge), germanium tin (GeSn), silicon germanium (SiGe), silicon germanium tin (SiGeSn), silicon carbide (SiC), and a group III-V semiconductor material.

### Claim 6 (depends on 1)

The method of claim 1, wherein the metal oxide film is deposited to a thickness of less than 20 nanometers.

### Claim 7 (depends on 1)

The method of claim 1, wherein the organic ligand vapor comprises a carboxylic acid vapor.

### Claim 8 (depends on 7)

The method of claim 7, wherein the carboxylic acid vapor comprises a vapor of at least one of 1,4-benzenedicarboxylic acid, 2,6-napthalenedicarobxylic acid, or 1,3,5-benezenetricarboxylic acid.

### Claim 9 (depends on 1)

The method of claim 1, wherein the organic ligand vapor comprises an azole vapor.

### Claim 10 (depends on 9)

The method of claim 9, wherein the azole vapor comprises a vapor of at least one of 2-methylimidazole, 3-(2-Pyridyl)-5-(4-pyridyl-1,2,4-triazole), or 4,5-dichloroimidazole.

### Claim 11 (depends on 1)

The method of claim 1, wherein the porous material comprises a metal-organic framework material.

### Claim 12 (depends on 11)

The method of claim 11, wherein the metal-organic framework material is continuous.

### Claim 13 (depends on 11)

The method of claim 11, wherein the metal-organic framework material has a thickness of less than 50 nanometers.

### Claim 14 (depends on 1)

The method of claim 1, wherein the porous materials fills the one or more gap features without the formation of a seam.

### Claim 15 (depends on 1)

The method of claim 1, wherein converting at least a portion of the metal oxide film comprises fully converting the metal oxide film to the porous material.

### Claim 16 (depends on 1)

The method of claim 1, further comprising repeating the steps of conformally depositing the metal oxide film and contacting the metal oxide with the organic ligand vapor one or more times.

### Claim 17 (depends on 1)

The method of claim 1, wherein the metal oxide film has an initial thickness and converting at least a portion of the metal oxide film to the porous material produces the porous material with a thickness greater than the initial thickness without additional deposition.

### Claim 18 (depends on 1)

The method of claim 1, wherein the steps of contacting the substrate with a metal vapor phase precursor and contacting the substrate with an oxidizing precursor are separated by a step of providing an inert gas.

### Claim 19 (depends on 1)

The method of claim 1, wherein a temperature during the cyclical deposition process is between 300° C. and 750° C.