Redox Atomic Layer Deposition Using Aqueous Solutions

Resolve Bottlenecks,
Find Innovative Solutions
Generate Solutions

Solution Overview

Problem

Current Atomic Layer Deposition (ALD) techniques face limitations, including the need for expensive and unstable gas-phase precursors, restricted applicability to conductive substrates, and requirement for sophisticated equipment and anhydrous conditions, which hinder efficient and scalable deposition of inorganic films.

Innovation Solution

A liquid-phase ALD method using aqueous solutions with organic compounds and inorganic ions or ion complexes, where each cycle involves adsorption of an organic compound followed by oxidation with an inorganic ion complex, allowing for self-limiting deposition of inorganic materials like metal or metal oxides without the need for vacuum equipment or electrical potentials.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If gas-phase ALD is used, then deposition precision is improved, but equipment complexity and cost increase

Engineering Contradiction:
Improvedeposition precisionVSAvoidequipment complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent changes the phase parameter of precursors from gas to liquid, enabling ALD deposition without vacuum equipment. Liquid precursors are delivered through simple pumping systems, dramatically reducing device complexity while maintaining monolayer-level deposition precision through the self-limited surface reaction mechanism

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent replaces the complex vacuum mechanical system with a liquid delivery system using simple pumps and flow controllers. The liquid-phase precursors are delivered through capillary action or pressure-driven flow, eliminating the need for vacuum chambers, throttle valves, and complex pumping systems while preserving ALD precision

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

2Adaptability or versatility

If electrochemical ALD is used, then substrate applicability is improved, but device complexity increases

Engineering Contradiction:
Improvesubstrate applicabilityVSAvoiddevice complexity
Core Design Contradiction:
Adaptability or versatilityVSDevice complexity

Solution Approach 1:

The patent extracts and removes the electrochemical power supply system (potentiostat, reference electrode, counter electrode) from the ALD process. Instead of using electrochemical reduction, the invention employs simple liquid-phase chemical reduction with stoichiometric control, eliminating complex electrical hardware while maintaining broad substrate compatibility including dielectrics and semiconductors

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The patent implements self-limited surface reactions where the substrate surface itself controls the reaction extent. The liquid-phase precursors react autonomously with surface sites until saturation, providing self-regulating deposition without external electrical control. This self-service mechanism simplifies the device while enabling deposition on diverse substrates

Inventive Principle:
Principle #25Self-service

3Stability of the object's composition

If anhydrous conditions are used, then deposition stability is improved, but process complexity increases

Engineering Contradiction:
Improvedeposition stabilityVSAvoidprocess complexity
Core Design Contradiction:
Stability of the object's compositionVSDevice complexity

Solution Approach 1:

The patent changes the solvent parameter from anhydrous organic solvents to aqueous solutions. This parameter change eliminates the need for moisture-exclusion equipment (glove boxes, molecular sieves, dried gas systems) while maintaining stable deposition. The aqueous precursors are designed with hydrolysis resistance or controlled hydrolysis, providing stable monolayer formation in ambient conditions

Inventive Principle:
Principle #35Parameter changes

4Ease of operation

If liquid-phase ALD is used, then ease of operation is improved, but growth rate decreases

Engineering Contradiction:
Improveease of operationVSAvoidgrowth rate
Core Design Contradiction:
Ease of operationVSProductivity

Solution Approach 1:

The patent employs periodic pulsed delivery of liquid precursors to maintain high surface concentration during each pulse, maximizing reaction rate. The cyclic immersion and withdrawal of the substrate, combined with pulsed precursor flow, creates periodic high-rate deposition events that increase overall growth rate while maintaining the simplicity of liquid-phase operation

Inventive Principle:
Principle #19Periodic 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 stable, scalable, and conformal deposition of inorganic films at ambient conditions, with growth rates close to one monolayer per cycle, suitable for a variety of substrates, and eliminates the risks of air-induced ignition and organic solvent use, offering precise thickness control and environmental benefits.

Implementation Method 1

contacting the substrate surface with a first aqueous liquid solution comprising an organic compound having a functional group permitting its adsorption on the substrate

Methodology Applied
Scientific EffectAdsorption: Adsorption

Implementation Method 2

contacting the substrate surface having the organic compound adsorbed thereon with a second liquid aqueous solution comprising an inorganic ion or an ion complex suitable for oxidizing the organic compound

Methodology Applied
Scientific EffectOxidation: Oxidation

Implementation Method 3

The redox replacement is possible thanks to the sufficiently high difference between the reduction potential of zinc and copper

Methodology Applied
Scientific EffectRedox Reactions: Redox Reactions

Implementation Method 4

having an insoluble reduction product which is the inorganic material

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Data Source

PatentEP3575004B1Redox atomic layer deposition
Publication Date: 2023.06.28 INTERUNIVERSITAIR MICRO ELECTRONICS CENT (IMEC VZW)
  • EP3575004B1 patent drawingFigure 1
  • EP3575004B1 patent drawingFigure 2
  • EP3575004B1 patent drawingFigure 3

AI summary

Method to deposit a layer of inorganic material on a substrate surface, comprising one or more cycles, each cycle comprising the steps of: a) contacting the substrate surface with a first aqueous liquid solution comprising an organic compound having a functional group permitting its adsorption on the substrate, followed by b) contacting the substrate surface having the organic compound adsorbed thereon with a second liquid aqueous solution comprising an inorganic ion or an ion complex suitable for oxidizing the organic compound and having an insoluble reduction product which is the inorganic material.