CZTS Nanoparticle Core-Shell Synthesis for Solar Absorption Layers

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Solution Overview

Problem

CZTS-based solar cells have lower photoelectric efficiency compared to CIGS-based solar cells due to challenges in forming large crystal sizes in thin films, leading to electron loss and instability issues from oxidation, particularly when using CZTS/Se nanoparticles.

Innovation Solution

A method for synthesizing metal chalcogenide nanoparticles with a core-shell structure, comprising a copper-tin chalcogenide core and a zinc chalcogenide shell, using a solution process that includes specific ratios of copper, zinc, and selenium, ensuring a uniform composition and stability against oxidation, which are then used to form a light absorption layer in solar cells.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If CZTS/Se nanoparticles are used to form thin films, then the manufacturing cost is reduced and the process is simplified, but the crystal size remains small leading to extended interfaces and electron loss

Engineering Contradiction:
Improvemanufacturing costVSAvoidelectron loss
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent changes the chemical composition parameters by incorporating excess sulfur or selenium (Group VI elements) into the nanoparticle structure. This compositional modification enables the nanoparticles to form larger crystals with fewer interfaces during thin film formation, reducing electron loss while maintaining the low-cost solution process advantage.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates composite nanoparticles with a core-shell structure where the core contains Cu-Zn-Sn-chalcogenide and the shell contains excess S or Se. This composite structure provides both the desired low-cost processing and improved crystal growth characteristics that reduce interface-related electron loss.

Inventive Principle:
Principle #40Composite materials

2Device complexity

If metal nanoparticles are used instead of chalcogenide nanoparticles, then the synthesis process is simplified, but oxidation stability deteriorates requiring oxygen removal processes

Engineering Contradiction:
Improvesynthesis processVSAvoidoxidation stability
Core Design Contradiction:
Device complexityVSStability of the object's composition

Solution Approach 1:

The patent incorporates sulfur or selenium (Group VI elements) into the nanoparticle structure, which creates an inherently oxidation-resistant environment. The chalcogenide composition acts as a protective layer that prevents oxidation of the metal cores, eliminating the need for separate oxygen removal processes while maintaining synthesis simplicity.

Inventive Principle:
Principle #39Inert atmosphere (Inert environment)

Solution Approach 2:

The patent creates composite nanoparticles where metal cores are combined with sulfur or selenium shells. This composite structure provides both the synthesis simplicity of metal nanoparticles and the oxidation stability of chalcogenides, as the S or Se shell protects the metal core from oxidation.

Inventive Principle:
Principle #40Composite materials

3Adaptability or versatility

If chalcogenides including each metal are synthesized separately and mixed, then the synthesis flexibility is increased, but composition uniformity deteriorates

Engineering Contradiction:
Improvesynthesis flexibilityVSAvoidcomposition uniformity
Core Design Contradiction:
Adaptability or versatilityVSManufacturing precision

Solution Approach 1:

The patent merges the synthesis of multiple metal chalcogenides into a single simultaneous reaction process. By combining Cu, Zn, and Sn salts with sulfur or selenium sources in one pot under ultrasonic irradiation, the method produces uniformly composed CZTS or CZTSe nanoparticles in one step, maintaining synthesis flexibility while achieving excellent composition uniformity.

Inventive Principle:
Principle #5Merging (Combining)

Solution Approach 2:

The patent develops a universal synthesis method using ultrasonic irradiation that can simultaneously produce multiple metal chalcogenide nanoparticles with controlled compositions. This single methodology replaces multiple separate synthesis and mixing steps, providing both flexibility in composition control and uniformity in the final product.

Inventive Principle:
Principle #6Universality (Multi-functionality)

4Reliability

If CIGS-based light absorption layers are used, then the photoelectric efficiency is improved to greater than 19%, but the manufacturing cost increases and In supply becomes insufficient

Engineering Contradiction:
Improvephotoelectric efficiencyVSAvoidmanufacturing cost
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent replaces expensive and scarce indium with abundant and cheap elements (Cu, Zn, Sn, S, Se). The developed nanoparticle synthesis method produces low-cost CZTS or CZTSe light absorption layers that can achieve competitive photoelectric efficiency without relying on expensive indium materials.

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

Solution Approach 2:

The patent changes the material composition parameters by eliminating indium and using earth-abundant elements instead. The optimized nanoparticle synthesis conditions and excess chalcogenide incorporation enable this alternative composition to achieve photoelectric efficiency comparable to CIGS while dramatically reducing material costs.

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 method results in a thin film with enhanced uniformity and stability, increasing the amount of Group VI elements, leading to superior photoelectric efficiency and reduced production costs by eliminating the need for harmful hydrazine and vacuum processes.

Implementation Method 1

Cu 2 ZnSnS 4 nanoparticles are synthesized by sonochemical reactions under multibubble sonoluminescence conditions

Methodology Applied
Scientific EffectSonochemistry: Sonochemistry

Implementation Method 2

Cu 2 ZnSnS 4 nanoparticles are synthesized by sonochemical reactions under multibubble sonoluminescence conditions

Methodology Applied
Scientific EffectMultibubble sonoluminescence: Sonoluminescence

Implementation Method 3

formation of a thin film through heat treatment of ink including CZTS/Se nanoparticles on a base

Methodology Applied
Scientific EffectHeat treatment: Heat Treatment

Data Source

PatentEP3026714B1Method for preparing metal chalcogenide nanoparticles for manufacturing optical absorption layer for solar cell
Publication Date: 2020.11.04 LG CHEM LTD
  • EP3026714B1 patent drawingFigure 1~2
  • EP3026714B1 patent drawingFigure 3
  • EP3026714B1 patent drawingFigure 4

AI summary

Disclosed are metal chalcogenide nanoparticles forming a light absorption layer of solar cells including a first phase including copper (Cu)-tin (Sn) chalcogenide and a second phase including zinc (Zn) chalcogenide, and a method of preparing the same.