Core-Gap-Shell Nanoparticles via Selective Dealloying

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Solution Overview

Problem

Current methods for synthesizing plasmonic nanostructures with nanogaps face challenges in reproducibility and scalability due to complex synthesis processes, structural precision, and limited applicability in biosensing and bioimaging, particularly in generating uniform and tunable surface-enhanced Raman scattering (SERS) signals.

Innovation Solution

A method for preparing core-gap-shell nanoparticles with a hollow nanogap using selective-interdiffusive dealloying (SID), where a shell made of an alloy of two metals is introduced onto a core particle modified with a Raman-active material, and the second metal is selectively removed using an etchant, creating a nanogap without an interlayer, allowing for the deposition of a Raman-active material within the gap.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Adaptability or versatility

If conventional methods are used to synthesize plasmonic nanostructures with nanogaps, then structural diversity can be achieved, but manufacturing precision and reproducibility deteriorate due to complex synthesis processes

Engineering Contradiction:
Improvestructural diversityVSAvoidnanogap uniformity
Core Design Contradiction:
Adaptability or versatilityVSManufacturing precision

Solution Approach 1:

The synthesis process is segmented into distinct stages: first forming a core particle with Raman-active material on its surface, then depositing an alloy shell containing two different metals, and finally selectively removing one metal through etching. This segmentation allows precise control over nanogap formation while maintaining structural versatility.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The Raman-active material is pre-deposited on the core particle surface before shell formation. This preliminary action ensures that when the shell is formed and subsequently etched, the Raman-active material is already positioned to fill the resulting nanogap, guaranteeing both precision and reproducibility.

Inventive Principle:
Principle #10Preliminary action

2Manufacturing precision

If complex synthesis processes are employed to achieve precise nanogaps, then manufacturing precision improves, but device complexity increases

Engineering Contradiction:
Improvenanogap uniformityVSAvoidsynthesis process complexity
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

An alloy shell containing two different metals serves as an intermediary structure. This shell is deposited over the core particle and then selectively etched to create the nanogap. The intermediary alloy shell simplifies the overall process by providing a straightforward path to precise nanogap formation without requiring complex direct fabrication techniques.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The synthesis process utilizes parameter changes in the alloy composition and etching conditions to control nanogap formation. By adjusting the ratio of metals in the alloy shell and controlling the etching parameters, precise and uniform nanogaps are achieved through simple, scalable steps rather than complex procedures.

Inventive Principle:
Principle #35Parameter changes

3Manufacturing precision

If interlayers are introduced to form intra-nanogaps, then structural precision improves, but ease of manufacture deteriorates due to additional synthesis steps

Engineering Contradiction:
Improvenanogap controlVSAvoidsynthesis simplicity
Core Design Contradiction:
Manufacturing precisionVSEase of manufacture

Solution Approach 1:

Instead of introducing an interlayer material to form the nanogap, the invention extracts one metal from the alloy shell through selective etching. This extraction creates the nanogap space directly, eliminating the need for separate interlayer deposition steps and simplifying the overall manufacturing process while maintaining precise nanogap control.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The alloy shell structure is designed to self-generate the nanogap through selective metal removal. The differential etching rates of the two metals in the alloy shell automatically create the desired nanogap structure without requiring additional interlayer materials or complex multi-step synthesis procedures.

Inventive Principle:
Principle #25Self-service

4Ease of operation

If conventional SERS substrates are used, then ease of operation is maintained, but measurement precision deteriorates due to untunable reproducibility

Engineering Contradiction:
Improveusage simplicityVSAvoidSERS signal reproducibility
Core Design Contradiction:
Ease of operationVSMeasurement precision

Solution Approach 1:

The nanogap regions are designed with localized high electromagnetic field enhancement properties, creating distinct 'hot spots' for SERS signal generation. This local quality enhancement ensures highly reproducible and tunable SERS signals from specific regions of the nanoparticle, improving measurement precision while maintaining ease of operation through simple nanoparticle incorporation into assays.

Inventive Principle:
Principle #3Local quality

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 approach enables the production of nanoparticles with uniform nanogaps, enhancing SERS signals for ultrasensitive biosensing and bioimaging, offering high yield, stability, and scalability, while maintaining the gap through metal bridges, thus overcoming previous limitations in reproducibility and structural precision.

Implementation Method 1

surface-enhanced Raman scattering (SERS) is receiving much attention due to its ultra-high sensitivity

Methodology Applied
Scientific EffectSurface-enhanced Raman scattering (SERS):

Implementation Method 2

the extinction of localized surface plasmon resonance (LSPR) in nanoparticles (NP) of a noble metal (e.g., gold and silver) can significantly increase and localize electromagnetic (EM) field at a specific location between NPs

Methodology Applied
Scientific EffectLocalized surface plasmon resonance (LSPR):

Data Source

PatentUS12109620B2Plasmonic nanoparticles with intra-nanogap produced by dealloying, method for preparing the same and use thereof
Publication Date: 2024.10.08 BIONANO HEALTH GUARD RES CENT
  • US12109620B2 patent drawing
  • US12109620B2 patent drawing
  • US12109620B2 patent drawing

AI summary

The present invention relates to a method for preparing a core-gap-shell nanoparticle having an average height of 0.1 nm to 10 nm, in which a Raman-active material is disposed between a core and a shell, and more specifically, to a method for preparing a core-gap-shell nanoparticle, which comprises introducing a shell made of an alloy of a second metal and a third metal, on the core particles of the first metal, the surface of which is modified with a Raman-active material; selectively removing the second metal by treating with a second metal etchant, followed by dealloying; the core-gap-shell nanoparticle prepared by the above method comprising a Raman-active material disposed in the gap, and uses of the core-gap-shell nanoparticle for biosensing and/or bioimaging.