SAM Selective Deposition Oxygen Plasma Removal

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Solution Overview

Problem

In semiconductor manufacturing, self-assembled monolayer (SAM) based selective depositions face challenges in achieving high SAM density while minimizing agglomerates, which can lead to voids and degradation of electrical devices due to unwanted SAM deposition on metal surfaces, requiring methods to enhance selectivity and cleanliness for subsequent atomic layer deposition (ALD) processes.

Innovation Solution

The method involves exposing a patterned substrate with a metal and dielectric surface to a SAM molecule to form a protected surface and a carbonized layer on the metal, followed by oxygenation to remove the carbonized layer, and then using reactants for selective deposition, while also employing a dual-stack process flow to remove SAM agglomerates and ensure high-quality ALD film growth by alternating SAM layers and reactant exposure.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If long-chain carbon-based SAM is used to form a sacrificial layer on dielectric surfaces, then selective deposition precision is improved, but unwanted SAM agglomerates may form on metal surfaces degrading device quality

Engineering Contradiction:

Improveselective deposition precisionVSAvoidunwanted SAM agglomerates on metal surfaces

Core Design Contradiction:

Manufacturing precisionVSObject-affected harmful factors

Solution Approach 1:

The patent extracts and removes the harmful carbonized layer and SAM agglomerates from metal surfaces using oxygen plasma treatment. This selective removal process eliminates the unwanted deposits while preserving the SAM layer on dielectric surfaces, thereby resolving the contradiction between achieving high SAM density and preventing harmful agglomerate formation on metal surfaces.

Inventive Principle:

Principle #2Taking out (Extraction)

Solution Approach 2:

The patent changes the chemical state of the SAM layer by converting it to a carbonized layer through controlled oxygen exposure, and then selectively removes this carbonized layer using plasma parameters. By adjusting plasma power, gas flow, and exposure time, the process achieves selective removal of carbonized SAM from metal surfaces while maintaining SAM integrity on dielectric surfaces.

Inventive Principle:

Principle #35Parameter changes

2Manufacturing precision

If high SAM molecular packing density is achieved on dielectric surfaces, then quality of selectively deposited ALD films is improved, but SAM agglomerates increase causing voids in ALD films

Engineering Contradiction:

Improvequality of selectively deposited ALD filmsVSAvoidvoids in ALD films

Core Design Contradiction:

Manufacturing precisionVSReliability

Solution Approach 1:

The patent converts the harmful effect of SAM agglomerates into a beneficial process by using oxygen plasma to selectively carbonize and remove these agglomerates from metal surfaces. The carbonized agglomerates serve as a marker for plasma treatment, and their removal eliminates voids in subsequent ALD films while preserving the high-density SAM layer on dielectric surfaces that enables selective deposition.

Inventive Principle:

Principle #22Blessing in disguise (Convert harm into benefit)

3Manufacturing precision

If SAM molecules are deposited on metal surfaces to form a carbonized layer, then selectivity for dielectric surfaces is improved, but the carbonized layer degrades quality of electrical devices

Engineering Contradiction:

Improveselectivity for dielectric surfacesVSAvoidcarbonized layer on metal surfaces

Core Design Contradiction:

Manufacturing precisionVSObject-affected harmful factors

Solution Approach 1:

The patent applies preliminary oxygen plasma treatment before ALD deposition to convert any SAM or carbonized layer on metal surfaces into a removable form. This preliminary action ensures that metal surfaces are free of carbonaceous contaminants that would degrade device quality, while the SAM layer on dielectric surfaces remains intact to provide selectivity for subsequent ALD processes.

Inventive Principle:

Principle #10Preliminary action

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This approach enhances the quality of ALD films by reducing carbon-based interfacial layers, minimizing granularity, and achieving void-free films, thereby improving the precision and reliability of semiconductor film patterning with reduced manufacturing costs.

Implementation Method 1

The patterned substrate is exposed to an oxygenating agent to remove the carbonized layer from the first surface

Methodology Applied

Scientific EffectOxidation: Oxidation

Implementation Method 2

long-chain carbon-based self-assembled monolayers (SAMs), has been proposed as a method for depositing a sacrificial layer

Methodology Applied

Scientific EffectSelf-assembly: Self-Assembly

Implementation Method 3

A feature of selective deposition process flows based on SAMs is the degree to which a high-quality SAM can be grown on part of the structure

Methodology Applied

Scientific EffectAdsorption: Adsorption

Data Source

PatentUS11515155B2Methods for enhancing selectivity in SAM-based selective deposition

Publication Date: 2022.11.29 APPLIED MATERIALS INC

AI summary

Methods of improved selectively for SAM-based selective depositions are described. Some of the methods include forming a SAM on a second surface and a carbonized layer on the first surface. The substrate is exposed to an oxygenating agent to remove the carbonized layer from the first surface, and a film is deposited on the first surface over the protected second surface. Some of the methods include overdosing a SAM molecule to form a SAM layer and SAM agglomerates, depositing a film, removing the agglomerates, reforming the SAM layer and redepositing the film.