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Reversed size-dependent stabilization of ordered nanophases.

J Pirart¹, A Front², D Rapetti³

¹Université d'Orléans, CNRS, ICMN UMR7374, 1b rue de la Férollerie, 45071, Orléans Cedex 2, France.

Nature Communications

|May 2, 2019

Summary

Small AgPt nanoparticles exhibit enhanced stability of the ordered L1₁ phase, contrary to typical size-stability trends. A silver shell forms, preventing surface defects in smaller nanoparticles.

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Area of Science:

Materials Science
Nanotechnology
Physical Chemistry

Background:

Nanoparticle stability often increases with size.
Ordered phases in nanomaterials are crucial for their properties.
Understanding size-dependent phase stability is key for designing advanced materials.

Purpose of the Study:

To investigate the phase stability of L1₁ ordered AgPt nanoparticles.
To determine the influence of particle size on the formation of the defect-free L1₁ phase.
To elucidate the mechanisms governing phase stabilization in small nanoparticles.

Main Methods:

Utilized a multiscale modelling approach.
Employed full-DFT global optimization calculations.
Applied atomistic modelling techniques.

Main Results:

Demonstrated that smaller AgPt nanoparticles (≤2.5 nm) stabilize the defect-free L1₁ phase better than larger ones.
Observed that larger nanoparticles exhibit phase domain fragmentation and faults.
Identified a segregated silver monolayer (Ag-skin) as the driving force for L1₁ phase formation in small nanoparticles.
Found that the Ag-skin induces internal stress in larger nanoparticles, limiting the ordered phase domain size.

Conclusions:

The study presents a counterexample to the common trend of increasing stability with nanoparticle size.
The Ag-skin formation is critical for stabilizing the L1₁ phase in small AgPt nanoparticles.
Internal stress due to the Ag-skin limits the critical size for the stable L1₁ phase in AgPt nanoparticles.