Plasma Post-Discharge Deposition for Crystalline Metal Oxide Coatings

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Solution Overview

Problem

Existing methods for atmospheric pressure plasma enhanced chemical vapour deposition of metal oxide coatings on substrates often require high temperatures, which is detrimental for heat-sensitive materials, and result in amorphous films, limiting their application in crystalline coatings for photocatalytic, photovoltaic, or sensing purposes.

Innovation Solution

A plasma post-discharge deposition device and method that uses a microwave surface wave launcher with a dielectric tube to create a post-discharge zone at low temperatures, allowing for the deposition of crystalline metal oxide derivatives on heat-sensitive substrates, such as polymers and glass, using a chemical precursor and metal nanoparticles, achieving crystalline coatings at temperatures below 150°C.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Stability of the object's composition

If high temperature is used for chemical vapour deposition, then crystalline coating is obtained, but heat-sensitive substrates are damaged

Engineering Contradiction:
Improvecrystalline structureVSAvoidsubstrate damage
Core Design Contradiction:
Stability of the object's compositionVSObject-affected harmful factors

Solution Approach 1:

The device segments the plasma discharge into two distinct zones: a high-temperature plasma zone for generating reactive species, and a low-temperature post-discharge zone for substrate deposition. This spatial segmentation allows crystalline coating formation without exposing heat-sensitive substrates to damaging temperatures.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

A dielectric tube acts as an intermediary between the plasma source and substrate, confining the plasma discharge while allowing thermal isolation. The tube enables the plasma to generate reactive species that deposit on the substrate without direct thermal contact, preserving substrate integrity while achieving crystalline structure.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Object-affected harmful factors

If low temperature is used for deposition, then substrate integrity is maintained, but amorphous films are formed instead of crystalline coatings

Engineering Contradiction:
Improvesubstrate damageVSAvoidcrystalline structure
Core Design Contradiction:
Object-affected harmful factorsVSStability of the object's composition

Solution Approach 1:

The invention changes the plasma parameters by operating in a post-discharge regime with specific power density and residence time conditions. This allows sufficient thermal energy for crystallization at low substrate temperatures, producing crystalline films without substrate damage.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The plasma discharge preliminarily activates the chemical precursors and heats the depositing species before they reach the substrate. This preliminary action provides the necessary energy for crystalline structure formation, eliminating the need for high substrate temperatures.

Inventive Principle:
Principle #10Preliminary action

3Temperature

If corona discharge or dielectric barrier discharge is used, then low temperature deposition is achieved, but the resulting films are amorphous

Engineering Contradiction:
Improvesubstrate temperatureVSAvoidfilm crystallinity
Core Design Contradiction:
TemperatureVSStability of the object's composition

Solution Approach 1:

The invention uses a dynamic plasma discharge that evolves into a post-discharge state, creating time-varying conditions with high reactive species concentration followed by a cooler deposition phase. This dynamic process enables crystalline structure formation at low temperatures.

Inventive Principle:
Principle #15Dynamics

Solution Approach 2:

The method combines microwave plasma with chemical vapour deposition in a composite process, creating a synergistic effect where plasma-generated reactive species enhance deposition rate and crystallinity while maintaining low substrate temperature.

Inventive Principle:
Principle #40Composite materials

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

The method enables the deposition of crystalline metal oxide layers on heat-sensitive substrates without damaging them, allowing for applications in photocatalytic, photovoltaic, and sensing technologies, while maintaining the substrates' integrity and enhancing the coatings' crystallinity and adhesion.

Implementation Method 1

a microwave surface wave launcher with a frequency comprised between 300 MHz and 300 GHz, preferentially with a frequency of 2.45 GHz

Methodology Applied
Scientific EffectMicrowave radiation: Microwave Radiation

Implementation Method 2

plasma post-discharge deposition device

Methodology Applied
Scientific EffectPlasma: Plasma

Implementation Method 3

a dielectric tube to create a post-discharge zone

Methodology Applied
Scientific EffectDielectric heating: Dielectric Heating

Implementation Method 4

plasma enhanced chemical vapour deposition

Methodology Applied
Scientific EffectChemical vapour deposition: Chemical Vapour Deposition

Implementation Method 5

deposition of crystalline metal oxide derivatives

Methodology Applied
Scientific EffectCrystallization: Crystallisation

Data Source

PatentEP3513423B1Device and method for performing atmospheric pressure plasma enhanced chemical vapour deposition at low temperature
Publication Date: 2020.11.18 LUXEMBOURG INSTITUTE OF SCIENCE AND TECHNOLOGY (LIST)
  • EP3513423B1 patent drawingFigure 1~3
  • EP3513423B1 patent drawingFigure 4~5b
  • EP3513423B1 patent drawingFigure 6~7

AI summary

The invention is directed to a plasma post-discharge deposition device (100) for depositing crystalline metal oxide derivative on a substrate (112), said device comprising a gas source (116) with a substrate inlet (102), a post-discharge deposition chamber (110) with a substrate outlet (104), said substrate inlet and said substrate outlet defining a longitudinal central axis, and a dielectric tube (108) placed between said gas source and said deposition chamber on said longitudinal central axis; configured to confine a plasma discharge and comprising a discharge zone lying on the internal surface of said dielectric tube and a central zone centred on said longitudinal central axis. Said deposition device is remarkable in that said central zone is located at a distance comprised between 1 mm and 2.5 mm from the internal surface of said dielectric tube. The invention is also directed to a plasma-enhanced chemical vapour deposition method.