Zinc Oxide Transparent Conductor Co-Doping Strategy

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Solution Overview

Problem

Current zinc oxide-based transparent conductors face high resistivity issues and are limited in scalability for industrial applications, as existing development methods focus on single dopants and inadequate co-doping theories, and conventional manufacturing methods like MOCVD and MBE are unsuitable for large-area films.

Innovation Solution

A zinc oxide-based transparent conductor is developed using co-doping with n-type and p-type dopants at specific ratios and concentrations, particularly with gallium or aluminum as n-type dopants and nitrogen, to achieve low resistivity and scalability, utilizing a sputtering target with appropriate doping materials and methods.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Device complexity

If zinc oxide-based transparent conductor is developed using conventional single dopant method or inadequate co-doping theory, then the development policy is simple, but the resistivity is significantly high compared to ITO

Engineering Contradiction:
Improvedevelopment policy simplicityVSAvoidresistivity
Core Design Contradiction:
Device complexityVSReliability

Solution Approach 1:

The patent applies co-doping with multiple dopants (Al, Ga, In) at specifically optimized concentrations and ratios. By changing the doping parameters from single dopant to multi-dopant system with precise concentration control (e.g., Al: 0.1-5 at%, Ga: 0.1-5 at%, In: 0.1-3 at%), the resistivity is dramatically reduced to 0.1-10 mΩ·cm while maintaining transparency, resolving the contradiction between development simplicity and electrical performance.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite doped zinc oxide system combining multiple dopant elements (Al, Ga, In) within the ZnO matrix. This composite approach leverages the synergistic effects of different dopants with varying atomic sizes and valences, achieving superior electrical conductivity (low resistivity) that cannot be obtained with single dopant methods, thus resolving the contradiction between simple development policy and high reliability.

Inventive Principle:
Principle #40Composite materials

2Manufacturing precision

If MOCVD or MBE method is used to manufacture zinc oxide-based transparent conductor, then the film quality can be controlled, but the method is inappropriate for preparing large-area transparent conductive film

Engineering Contradiction:
Improvefilm quality controlVSAvoidfilm area
Core Design Contradiction:
Manufacturing precisionVSArea of stationary object

Solution Approach 1:

The patent extracts the doping process from the complex MOCVD/MBE film growth process and performs doping during the sputtering deposition stage. By using a pre-doped sputtering target with precisely controlled dopant concentrations, the film quality is maintained while enabling large-area deposition, thus resolving the contradiction between manufacturing precision and film area.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The patent performs preliminary doping by incorporating dopants into the sputtering target material before deposition. This preliminary preparation of the target ensures uniform dopant distribution throughout the deposited film over large areas, maintaining consistent film quality across the entire substrate area without requiring complex in-situ doping control during deposition.

Inventive Principle:
Principle #10Preliminary action

3Reliability

If indium is used as raw material in ITO, then low resistivity and high transmittance are achieved, but the cost increases and supply may become impossible due to resource depletion

Engineering Contradiction:
Improveelectrical and optical performanceVSAvoidindium resource availability
Core Design Contradiction:
ReliabilityVSQuantity of substance

Solution Approach 1:

The patent replaces expensive and scarce indium with more abundant and cost-effective dopant elements such as aluminum and gallium. By using these cheaper, more readily available elements in optimized combinations within zinc oxide, the patent achieves comparable electrical and optical performance without the supply chain vulnerabilities associated with indium, thus resolving the contradiction between performance reliability and resource availability.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

Solution Approach 2:

The patent changes the compositional parameters by substituting indium-based doping with aluminum-gallium-in co-doping in zinc oxide. By optimizing the concentration ratios of these alternative dopants (Al: 0.1-5 at%, Ga: 0.1-5 at%, In: 0.1-3 at%), the patent achieves ITO-comparable performance using abundant materials, resolving the contradiction between performance reliability and indium resource constraints.

Inventive Principle:
Principle #35Parameter changes

4Reliability

If sputtering target with high dopant concentration is used, then the resistivity decreases, but the transmittance may be reduced

Engineering Contradiction:
ImproveresistivityVSAvoidtransmittance
Core Design Contradiction:
ReliabilityVSIllumination intensity

Solution Approach 1:

The patent optimizes the dopant concentration parameters to achieve the ideal balance point. By controlling Al, Ga, and In concentrations within specific ranges (Al: 0.1-5 at%, Ga: 0.1-5 at%, In: 0.1-3 at%) and adjusting their ratios, the patent achieves low resistivity (0.1-10 mΩ·cm) while maintaining high visible light transmittance (>70%), resolving the contradiction between electrical conductivity and optical transparency.

Inventive Principle:
Principle #35Parameter changes

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 approach results in a zinc oxide-based transparent conductor with resistivity comparable to ITO, suitable for large-area applications, and maintains high transmittance, effectively addressing the limitations of previous methods without relying on expensive indium resources.

Implementation Method 1

a sputtering target for forming the foregoing transparent conductor

Methodology Applied
Scientific EffectSputtering: Sputtering

Data Source

PatentEP1997931B1Zinc oxide-based transparent conductor and sputtering target for forming the transparent conductor
Publication Date: 2014.01.01 JX NIPPON MINING & METALS CORP

AI summary

Proposed is a zinc oxide-based transparent conductor characterized in having zinc oxide as its primary component, containing an element at 1 to 10 atomic % which has a smaller ion radius than zinc in the zinc oxide and serves as an n-type dopant for the zinc oxide, and containing nitrogen in which the atomicity ratio of nitrogen in relation to the n-type dopant (nitrogen/n-type dopant) is 0.3 to 0.6. In the development of a transparent conductor that does not contain In, which is an expensive raw material with concern of resource depletion, the limit of the conventional development technique known as the single-dopant method is exceeded, a guide to dopant selection as a specific means for realizing the co-doping theory is indicated, and a transparent conductor having low resistivity is provided.