CIGS Nanoparticle Ink Synthesis for Low-Temperature Printing

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Solution Overview

Problem

Current methods for synthesizing Culn x Ga 1-x S 2 nanoparticles are limited by high temperatures, aggregation, poor solubility, and the use of high-boiling capping ligands, which hinder the production of small, monodisperse nanoparticles suitable for low-cost film printing techniques and flexible substrate use in photovoltaic cells.

Innovation Solution

A process involving the reaction of group 11 and group 13 ion sources with an alkane thiol in an organic solvent at lower temperatures (200°C or lower) to produce nanoparticles with a volatile alkyl thiol capping layer, allowing for the formation of small, monodisperse CulnS 2 and Culn x Ga 1-x S 2 nanoparticles that are soluble and can be easily processed into films using conventional printing techniques.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional vapor phase or evaporation techniques are used to deposit copper indium (gallium) disulfide films, then high quality films are produced, but the process is difficult and expensive to scale to large-area depositions and higher process throughputs

Engineering Contradiction:
Improvefilm qualityVSAvoidprocess throughput
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent replaces conventional vapor phase deposition techniques with a solution-based printing process. Nanoparticles of copper indium (gallium) chalcogenide are dispersed in a liquid vehicle to form a printable ink, which is then deposited using low-cost printing techniques such as spin coating, slit coating, or doctor blading. This substitution enables scalable large-area deposition while maintaining film quality, directly resolving the contradiction between manufacturing precision and productivity.

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

2Reliability

If high temperatures are used in nanoparticle synthesis, then complete reaction occurs, but the resulting nanoparticles aggregate and have poor solubility

Engineering Contradiction:
Improvereaction completenessVSAvoidnanoparticle dispersion
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The patent introduces a liquid vehicle as an intermediary medium to disperse the synthesized nanoparticles. The vehicle prevents nanoparticle aggregation by providing steric or electrostatic stabilization, enabling complete reaction at elevated temperatures while maintaining colloidal stability. This resolves the contradiction between reaction completeness and dispersion stability.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent controls synthesis temperature and reaction time parameters to optimize nanoparticle formation. By carefully adjusting these parameters, the process achieves complete reaction without excessive heating that would cause aggregation, while the resulting nanoparticles maintain good solubility in the liquid vehicle.

Inventive Principle:
Principle #35Parameter changes

3Stability of the object's composition

If high-boiling capping ligands are used to stabilize nanoparticles, then nanoparticle stability is improved, but removal of the ligands becomes difficult and leaves carbon impurities

Engineering Contradiction:
Improvenanoparticle stabilityVSAvoidligand removal
Core Design Contradiction:
Stability of the object's compositionVSEase of manufacture

Solution Approach 1:

The patent selects capping ligands with moderate boiling points that balance stability and removability. These ligands provide sufficient colloidal stability during synthesis and processing but can be easily removed by mild thermal treatment or solvent extraction. This parameter optimization resolves the contradiction between nanoparticle stability and ease of ligand removal, minimizing carbon impurities in the final film.

Inventive Principle:
Principle #35Parameter changes

4Manufacturing precision

If small nanoparticle sizes are achieved, then film quality and absorption efficiency are improved, but the synthesis requires precise control and is more difficult to manufacture

Engineering Contradiction:
Improvefilm qualityVSAvoidsynthesis control
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent employs pre-synthesized monodisperse nanoparticle suspensions as starting materials, rather than attempting to control nucleation and growth in situ. This preliminary preparation of standardized nanoparticles simplifies the overall synthesis process while ensuring consistent small particle sizes that improve film quality and absorption efficiency. The pre-formed nanoparticles are simply dispersed in the liquid vehicle and printed, greatly reducing synthesis complexity.

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

The method yields nanoparticles with sizes down to 2.5 nm and narrow size distributions, facilitating improved film quality and enabling lower processing temperatures, which opens up the possibility of using flexible substrates and simplifies the removal of capping ligands, reducing carbon impurities and enhancing solar cell performance.

Implementation Method 1

A process involving the reaction of group 11 and group 13 ion sources with an alkane thiol in an organic solvent at lower temperatures (200°C or lower) to produce nanoparticles with a volatile alkyl thiol capping layer

Methodology Applied
Scientific EffectChemical reaction: Chemical Bonding

Implementation Method 2

simplifies the removal of capping ligands, reducing carbon impurities and enhancing solar cell performance

Methodology Applied
Scientific EffectEvaporation: Evaporation

Implementation Method 3

allowing for the formation of small, monodisperse CulnS 2 and Culn x Ga 1-x S 2 nanoparticles that are soluble and can be easily processed into films

Methodology Applied
Scientific EffectThermal decomposition: Pyrolysis

Data Source

PatentEP2964566B1Copper-indium-gallium-chalcogenide nanoparticle precursors for thin-film solar cells
Publication Date: 2021.02.17 NANOCO TECH LTD
  • EP2964566B1 patent drawingFigure 1~2
  • EP2964566B1 patent drawingFigure 3~4
  • EP2964566B1 patent drawingFigure 5~6

AI summary

Nanoparticles containing lUPAC group 11 ions, group 13 ions and sulfur ions are synthesized by adding metal salts and an alkanethiol in an organic solvent and promoting the reaction by applying heat. Nanoparticles are formed at temperatures as low as 200°C. The nanoparticles may be thermally annealed for a certain amount of time at a temperature lower than the reaction temperature (usually ~40°C lower) to improve the topology and narrow the size distribution. After the reaction is complete, the nanoparticles may be isolated by the addition of a non-solvent and re-dispersed in organic solvents including toluene, chloroform and hexane to form a nanoparticle ink. Additives may be incorporated in the reaction solution to tailor the final ink viscosity.