# US 12,604,685 B2 · Methods for controlling spin-on self-assembled monolayer (SAM) selectivity

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 12,604,685 B2
- Document ID: US12604685B2
- Status: Granted
- Kind: B2
- Application number: 18/223,881
- Filed: 2023-07-19
- Published: 2025-01-23
- Granted: 2026-04-14
- Earliest claimed: 2023-07-19
- Assignees: Tokyo Electron Limited
- Applicants: Tokyo Electron Limited
- Inventors: Lior Huli; Nathan Antonovich; Dina Triyoso
- Web page: https://patentgrep.com/patent/US12604685B2

## CPC

- H10P 14/6506: {Formation of intermediate materials}
- C23C 16/02: Pretreatment of the material to be coated (C23C16/04 takes precedence)
- C23C 16/04: Coating on selected surface areas, e.g. using masks
- C23C 16/042: {using masks}
- C23C 16/40: Oxides
- C23C 16/403: {of aluminium, magnesium or beryllium}
- C23C 16/45525: {Atomic layer deposition [ALD]}
- H10P 14/61: using masks
- H10P 14/6334: {using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition (deposition by physical ablation of a target H10P14/6329)}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 95/00: Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass
- H10W 20/056: {by filling conductive material into holes, grooves or trenches}
- H10W 20/077: {on sidewalls or on top surfaces of conductors (H10W20/076 takes precedence)}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- 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)
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10

## Abstract

Various embodiments of methods are provided to control formation of self-assembled monolayers (SAMs) used in an area-selective deposition (ASD) process, and thus, prevent defects in the ASD process. In the disclosed embodiments, a SAM structure is formed via a spin-on process that includes: (a) a spin coating step for coating a surface of a semiconductor substrate with a liquid solution containing SAM-forming molecules, the semiconductor substrate having a target material and a non-target material exposed on the substrate surface, and (b) an anneal step for heat treating the semiconductor substrate to chemically bond the SAM-forming molecules to the non-target material exposed on the substrate surface. By controlling and/or varying process parameter(s) utilized during the anneal step, the embodiments disclosed herein improve the selectivity of the SAM structure to the non-target material and prevent defects from occurring when a film is subsequently deposited onto the target material.

## Claims

### Claim 1

A method to reduce edge exclusion defects in a dielectric-on-dielectric (DoD) process, the method comprising:
providing a substrate within a process chamber, the substrate having a metal layer and a dielectric layer exposed on a surface of the substrate;
selectively depositing a self-assembled monolayer (SAM) structure on an exposed surface of the metal layer by:
dispensing a liquid solution onto the surface of the substrate while the substrate is spinning to coat the surface of substrate with the liquid solution, the liquid solution comprising SAM-forming molecules; and
heat treating the substrate to chemically bond the SAM-forming molecules to the exposed surface of the metal layer and form the SAM structure on the exposed surface of the metal layer;
controlling a plurality of process parameters used during said heat treating to ensure that the SAM structure completely covers the exposed surface of the metal layer and prevent the SAM structure from extending beyond boundaries of the metal layer and covering portions of the dielectric layer, wherein the plurality of process parameters controlled during said heat treating comprise a gas, a gas flow rate, a pressure within the process chamber, a temperature and a time; and
selectively depositing a dielectric film on an exposed surface of the dielectric layer without removing the SAM structure selectively deposited on the exposed surface of the metal layer, wherein said controlling the plurality of process parameters during said heat treating reduces edge exclusion defects in the DoD process by ensuring that the dielectric film completely covers the exposed surface of the dielectric layer.

### Claim 2 (depends on 1)

The method of claim 1, wherein said controlling the plurality of process parameters comprises selecting the gas, the gas flow rate, the pressure within the process chamber, the temperature and the time to be used during said heat treating, wherein said selecting is based on experimental results.

### Claim 3 (depends on 1)

The method of claim 1, wherein said controlling the plurality of process parameters comprises selecting the gas from a group of gases comprising nitrogen (N2), ammonia (NH3), helium (He) and argon (Ar).

### Claim 4 (depends on 1)

The method of claim 1, wherein said controlling the plurality of process parameters comprises selecting the gas flow rate from a range of gas flow rates comprising about 4 liters/minute (L/min) to about 7 L/min.

### Claim 5 (depends on 1)

The method of claim 1, wherein said controlling the plurality of process parameters comprises selecting the temperature from a range of temperatures comprising about 130° C. to about 180° C.

### Claim 6 (depends on 1)

The method of claim 1, wherein said controlling the plurality of process parameters comprises selecting the time from a range of times comprising about 60 seconds to about 180 seconds.

### Claim 7 (depends on 1)

The method of claim 1, wherein said controlling the plurality of process parameters comprises varying one or more of the gas, the gas flow rate, the pressure within the process chamber, the temperature and the time during said heat treating based on a predetermined recipe or based on feedback control.

### Claim 8

A method to control formation of a self-assembled monolayer (SAM) structure utilized in an area-selective deposition (ASD) process, the method comprising:
providing a substrate within a process chamber, the substrate having a target material and a non-target material exposed on a surface of the substrate;
forming the SAM structure on an exposed surface of the non-target material by:
dispensing a liquid solution onto the surface of the substrate while the substrate is spinning to coat the surface of substrate with the liquid solution, the liquid solution comprising SAM-forming molecules; and
heat treating the substrate to chemically bond the SAM-forming molecules to the exposed surface of the non-target material and form the SAM structure on the exposed surface of the non-target material; and
controlling a plurality of process parameters used during said heat treating to ensure that the SAM structure completely covers the exposed surface of the non-target material and prevent the SAM structure from extending beyond boundaries of the non-target material and covering portions of the target material, wherein the plurality of process parameters controlled during said heat treating comprise a gas, a gas flow rate, a pressure within the process chamber, a temperature and a time.

### Claim 9 (depends on 8)

The method of claim 8, further comprising selectively depositing a film on an exposed surface of the target material without removing the SAM structure formed on the exposed surface of the non-target material, wherein said controlling the one or more process parameters during said heat treating ensures that the film completely covers the exposed surface of the target material.

### Claim 10 (depends on 9)

The method of claim 9, wherein the non-target material is a conductive material, the target material is a dielectric material and the film is a dielectric film.

### Claim 11 (depends on 10)

The method of claim 10, wherein the SAM-forming molecules have a head group, which bonds to the exposed surface of the conductive material, and a tail group that provides a barrier against the dielectric film.

### Claim 12 (depends on 11)

The method of claim 11, wherein the SAM-forming molecules have a thiol, silane, phosphate, amine or carboxylic acid head group.

### Claim 13 (depends on 8)

The method of claim 8, wherein said controlling the plurality of process parameters comprises selecting one or more of the gas, the gas flow rate, the pressure within the process chamber, the temperature and the time to be used during said heat treating, wherein said selecting is based on experimental results.

### Claim 14 (depends on 8)

The method of claim 8, wherein said controlling the plurality of process parameters comprises selecting the gas from a group of gases comprising nitrogen (N2), ammonia (NH3), helium (He), and argon (Ar).

### Claim 15 (depends on 8)

The method of claim 8, wherein said controlling the plurality of process parameters comprises selecting the gas flow rate from a range of gas flow rates comprising about 4 liters/minute (L/min) to about 7 L/min.

### Claim 16 (depends on 8)

The method of claim 8, wherein said controlling the plurality of process parameters comprises selecting the temperature from a range of temperatures comprising about 130° C. to about 180° C.

### Claim 17 (depends on 8)

The method of claim 8, wherein said controlling the plurality of process parameters comprises selecting the time from a range of times comprising about 60 seconds to about 180 seconds.

### Claim 18 (depends on 8)

The method of claim 8, wherein said controlling the plurality of process parameters comprises varying one or more of the gas, the gas flow rate, the pressure within the process chamber, the temperature and the time during said heat treating based on a predetermined recipe or based on feedback control.