Germanium ALD Using Sequential Precursor Pulses for Film Growth

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Solution Overview

Problem

Existing atomic layer deposition (ALD) processes have not been successful in depositing germanium, which is a promising material for semiconductor and optoelectronic devices due to its high mobility and transport properties.

Innovation Solution

A process involving sequential exposure of a substrate to a Ge-containing precursor and a reducing precursor, such as tetrakis(dimethylamino)Ge and hydrogen, respectively, within a temperature range of 50°C-350°C, using ALD to achieve self-saturating surface reactions and deposit germanium.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional ALD processes are used for germanium deposition, then the process follows standard ALD methodology, but germanium deposition is not successful

Engineering Contradiction:
Improvedeposition successVSAvoidprocess feasibility
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent changes the chemical parameters of the ALD process by using novel precursor combinations: germanium precursors (such as GeCl4, Ge(OEt)4, or Ge(acac)3) combined with sulfur-based precursors (such as H2S, DS, or DMDS). This parameter change in precursor chemistry enables successful germanium deposition where conventional ALD processes failed.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent introduces sulfur-based compounds as intermediary species that facilitate germanium deposition. The sulfur precursors react with germanium precursors to form intermediate species that enable controlled germanium film growth, acting as a mediator between the germanium source and the substrate.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Reliability

If standard ALD temperature ranges are used, then the process maintains typical ALD conditions, but germanium deposition fails

Engineering Contradiction:
Improvedeposition successVSAvoiddeposition temperature
Core Design Contradiction:
ReliabilityVSTemperature

Solution Approach 1:

The patent optimizes the temperature parameter within a specific range of 60°C to 350°C, with preferred ranges of 80°C to 250°C. This temperature parameter change, combined with the novel precursor system, enables successful germanium deposition at controlled temperatures that prevent precursor decomposition while ensuring adequate reaction kinetics.

Inventive Principle:
Principle #35Parameter changes

3Manufacturing precision

If sequential precursor exposure is implemented, then self-saturating surface reactions occur, but process complexity increases

Engineering Contradiction:
Improvefilm thickness controlVSAvoiddeposition cycle complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent divides the deposition process into distinct sequential segments: germanium precursor pulse, purge, sulfur precursor pulse, and purge. This segmentation of the deposition cycle into discrete, well-defined steps enables precise control over film thickness and composition while maintaining processability through clear process boundaries.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent employs periodic cyclic exposure of germanium and sulfur precursors in alternating pulses. This periodic action creates self-saturating surface reactions where each precursor cycle completes a full reaction sequence, enabling precise thickness control through the number of cycles while maintaining systematic process control.

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 effectively deposits elemental germanium or germanium oxide layers on substrates, overcoming previous ALD process failures and enabling the use of germanium in semiconductor and optoelectronic devices.

Implementation Method 1

Precursor species form a chemical bond to reactive sites of the heated surfaces through chemisorption. Reaction conditions are typically arranged in such a way that no more than a molecular or atomic monolayer of a solid material forms on the surfaces during one precursor pulse. Thus, the growth process is self-terminating, i.e. saturative growth.

Methodology Applied
Scientific EffectChemisorption: Chemisorption

Implementation Method 2

the reducing precursor is H2 or hydrogen plasma

Methodology Applied
Scientific EffectReduction: Reduction

Data Source

PatentEP3114248B1Atomic layer deposition of germanium or germanium oxide
Publication Date: 2025.05.07 PICOSUN OY
  • EP3114248B1 patent drawingFigure 1

AI summary

A process of depositing germanium on a substrate comprising sequentially exposing in at least one deposition cycle the substrate inside a chamber with a Ge-containing precursor and a reducing or oxidizing precursor. The object is to provide an industrially applicable method for depositing germanium and germanium oxide on various substrates. This is achieved by sequentially exposing in at least one deposition cycle the substrate inside a chamber to a Ge-containing precursor and a reducing or oxidizing precursor. The invention also relates to a Ge-deposited article and to the use of tetrakis(dimethylamino)germanium in ALD.