Transition Metal Dichalcogenide Layer Deposition via Surface Functionalization

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Solution Overview

Problem

Current methods for producing transition metal dichalcogenide layers on substrates are inefficient for large-scale semiconductor manufacturing, often resulting in uncontrolled multi-layer deposits, high temperatures, long annealing times, and contamination issues, making it difficult to achieve high-purity, flat, and oriented layers suitable for industrial integration.

Innovation Solution

A method involving surface functionalization with silicon-hydrogen or boron-hydrogen compounds, or sulphidization, followed by atomic layer deposition (ALD) using metal halide and chalcogen precursors, which eliminates the need for catalysts like Zn, allowing for precise control of thin layer deposition at lower temperatures and achieving high-purity, flat, and oriented transition metal dichalcogenide layers on large substrates.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional vapor phase deposition methods are used, then transition metal dichalcogenide layers can be deposited, but the layers are uncontrolled multi-layer deposits with poor flatness and orientation

Engineering Contradiction:
Improvelayer control precisionVSAvoiddeposition process complexity
Core Design Contradiction:
Manufacturing precisionVSEase of manufacture

Solution Approach 1:

The deposition process is segmented into distinct sequential steps: surface functionalization followed by controlled ALD deposition. This segmentation allows precise control over layer formation, enabling monolayer or limited multi-layer deposits with flat morphology and proper orientation, eliminating the uncontrolled multi-layer deposits of conventional methods.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

Surface functionalization is performed as a preliminary action before deposition. The substrate surface is pre-treated with silicon-hydrogen or boron-hydrogen compounds or sulphidization to create optimal nucleation sites. This preliminary action ensures that subsequent ALD deposition produces flat, well-oriented layers with controlled thickness from the outset.

Inventive Principle:
Principle #10Preliminary action

2Reliability

If high temperature annealing is used for deposition, then material crystallization is improved, but processing time increases and energy consumption increases

Engineering Contradiction:
Improvematerial crystallization qualityVSAvoidannealing time
Core Design Contradiction:
ReliabilityVSLoss of time

Solution Approach 1:

The deposition temperature parameter is changed from conventional high temperatures (650-1000°C) to lower temperatures (250-450°C). This parameter change is enabled by the surface functionalization step, which creates reactive sites that allow crystallization and proper material formation at lower temperatures, thereby reducing processing time and energy consumption while maintaining crystallization quality.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The conventional thermal annealing mechanism is replaced with a chemical mechanism. Surface functionalization creates chemically active sites that facilitate low-temperature crystallization. The chemical reactions at the functionalized surface enable material formation and crystallization without requiring high thermal energy input, thus eliminating long annealing times.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

3Ease of manufacture

If catalysts like Zn are used during deposition, then deposition initiation is facilitated, but contamination of the layer occurs

Engineering Contradiction:
Improvedeposition initiation easeVSAvoidlayer purity
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The catalyst (Zn) is completely removed from the deposition process. Surface functionalization with silicon-hydrogen or boron-hydrogen compounds or sulphidization provides alternative nucleation mechanisms that do not require metallic catalysts. This extraction of the catalyst eliminates the source of contamination while maintaining easy deposition initiation through the chemically active functionalized surface.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

Surface functionalization acts as an intermediary between the substrate and the depositing material. The functionalized surface (with Si-H, B-H, or S groups) serves as a mediating layer that facilitates deposition initiation and material crystallization without requiring Zn catalysts. This intermediary provides the necessary chemical activity for easy deposition while preventing catalyst contamination of the final layer.

Inventive Principle:
Principle #24Intermediary (Mediator)

4Manufacturing precision

If exfoliation technique is used to produce single layers, then monolayer material is obtained, but the flake dimensions are limited to 1-10 μm

Engineering Contradiction:
Improvelayer thickness controlVSAvoidsubstrate coverage area
Core Design Contradiction:
Manufacturing precisionVSArea of stationary object

Solution Approach 1:

The mechanical exfoliation process is replaced with a chemical vapor deposition process (ALD). Instead of mechanically separating layers from bulk material, the transition metal dichalcogenide is deposited chemically from vapor phase precursors onto a functionalized substrate. This substitution enables atomic-layer precision thickness control while covering large substrate areas continuously, producing uniform films rather than small flakes.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

Solution Approach 2:

The production method parameter is changed from mechanical separation to chemical deposition. ALD deposition parameters (temperature 250-450°C, precursor exposure time, cycle number) provide precise control over layer thickness and uniformity across large areas, eliminating the size limitations inherent in mechanical exfoliation while maintaining monolayer or limited multi-layer precision.

Inventive Principle:
Principle #35Parameter changes

5Area of stationary object

If conventional deposition methods are used on large substrates, then area coverage is achieved, but film uniformity and thickness control deteriorate

Engineering Contradiction:
Improvesubstrate area coverageVSAvoidfilm thickness uniformity
Core Design Contradiction:
Area of stationary objectVSManufacturing precision

Solution Approach 1:

The ALD deposition process uses periodic cyclic actions: alternating exposure to metal precursor and chalcogen precursor, with purging steps in between. Each cycle deposits a controlled amount of material, and the number of cycles precisely controls final thickness. This periodic action ensures uniform deposition across large substrates because each cycle is self-limiting and reproduces the same thin layer uniformly over the entire surface area.

Inventive Principle:
Principle #19Periodic action

Solution Approach 2:

Surface functionalization is performed as a preliminary action across the entire large substrate area before deposition. This creates a uniformly reactive surface that ensures consistent nucleation and growth conditions throughout the large area. The preliminary functionalization eliminates variations in deposition behavior that would otherwise occur on untreated large substrates, enabling both large area coverage and high film uniformity.

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 method enables the production of high-purity, flat, and oriented transition metal dichalcogenide layers with excellent film thickness control and uniformity, suitable for large-area substrates, reducing processing time and cost, and avoiding contamination, making it suitable for high-volume semiconductor manufacturing.

Implementation Method 1

functionalizing said surface with silicon-hydrogen or boron-hydrogen compounds

Methodology Applied
Scientific EffectSurface functionalization: Chemical Bonding

Implementation Method 2

by sulphidizing the surface

Methodology Applied
Scientific EffectSulphidization: Chemical Bonding

Implementation Method 3

depositing the transition metal dichalcogenide layer on the surface using ALD deposition, starting from a metal halide precursor and a chalcogen source

Methodology Applied
Scientific EffectAtomic layer deposition: Chemical Vapour Deposition

Implementation Method 4

strong in-plane bonding and weak out-of plane interactions (the layers are only weakly bonded by van der Waals forces)

Methodology Applied
Scientific EffectVan der Waals forces: Van der Waals Force

Data Source

PatentEP3084033B1Method of producing transition metal dichalcogenide layer and materials
Publication Date: 2023.05.10 INTERUNIVERSITAIR MICRO ELECTRONICS CENT (IMEC VZW)
  • EP3084033B1 patent drawingFigure 1~2
  • EP3084033B1 patent drawingFigure 3
  • EP3084033B1 patent drawingFigure 4

AI summary

Method of producing one or more transition metal dichalcogenide (MX2) layers on a substrate, comprising the steps of: obtaining a substrate having a surface and depositing MX2 on the surface using ALD deposition, starting from a metal halide precursor and a chalcogen source (H2X), at a deposition temperature of about 300°C. Suitable metals are Mo and W, suitable chalcogenides are S, Se and Te. The substrate may be (111) oriented. Also mixtures of two or more MX2 layers of different compositions can be deposited on the substrate, by repeating at least some of the steps of the method.