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Theoretical study of the stability and formation methods of layer diamond-like nanostructures

MetadataDetails
Publication Date2020-01-01
JournalLetters on Materials
AuthorsV. A. Greshnyakov, E. A. Belenkov
InstitutionsChelyabinsk State University
Citations5
AnalysisFull AI Review Included

Theoretical Study of Layer Diamond-Like Nanostructures

Section titled “Theoretical Study of Layer Diamond-Like Nanostructures”

This theoretical study (using Density Functional Theory) investigates the structure, stability, and formation of two novel two-dimensional (2D) diamond-like carbon bilayers, DL3-12 and DL4-6-12.

  • Novel Materials: The study confirms the viability of two new sp3-hybridized 2D carbon structures, DL3-12 and DL4-6-12, derived from specific graphene polymorphs (L3-12 and L4-6-12).
  • Semiconducting Properties: Both bilayers are predicted to be direct band gap semiconductors, with band gaps of 1.7 eV (DL3-12) and 2.3 eV (DL4-6-12).
  • High Density: The calculated surface densities (0.082-0.098 ”g/cm2) are 7-28% greater than that of hexagonal graphene, indicating a highly compact structure.
  • Porous Structure: Despite high density, the structures contain pores with a maximum diameter of approximately 4.5 Angstrom.
  • Synthesis Route: The most probable formation method is strong uniaxial compression of two parallel graphene layers (AA stacking), mimicking known synthesis mechanisms for diamond-like materials.
  • Stability Limits: The structures exhibit thermal stability up to 200 K (DL3-12) and 210 K (DL4-6-12), suggesting low-temperature synthesis is required.
ParameterValueUnitContext
Structure TypeBilayer, HexagonalN/Asp3-hybridized diamond-like carbon
Lattice Parameter (DL3-12)5.8204AngstromUnit cell dimension (a=b)
Lattice Parameter (DL4-6-12)7.5116AngstromUnit cell dimension (a=b)
Surface Density (DL3-12)0.082”g/cm27% greater than hexagonal graphene
Surface Density (DL4-6-12)0.098”g/cm228% greater than hexagonal graphene
Maximum Pore Diameter~4.5AngstromCharacteristic of the porous structure
Direct Band Gap (DL3-12)1.7eVSemiconductor property
Direct Band Gap (DL4-6-12)2.3eVSemiconductor property
Thermal Stability Limit (DL3-12)200KTemperature threshold before destruction
Thermal Stability Limit (DL4-6-12)210KTemperature threshold before destruction
Formation Pressure (DL3-12)> 16.7GPaRequired for phase transition from L3-12 graphene
Formation Pressure (DL4-6-12)8.6GPaRequired for phase transition from L4-6-12 graphene
Bilayer Thickness (h)1.5747 to 1.5946AngstromVaries slightly between the two structures

The research utilized computational methods to predict the structure and properties of the new 2D materials:

  1. Initial Structure Modeling: The diamond-like bilayers (DL3-12 and DL4-6-12) were modeled by cross-linking two identical layers of polymorphic hexagonal graphene (L3-12 or L4-6-12).
  2. Semi-Empirical Optimization: Initial geometric optimization of the modeled structures was performed using the PM7 semi-empirical method.
  3. First-Principle Calculation (DFT): Final geometric optimization and property calculations were conducted using Density Functional Theory (DFT) via the Quantum ESPRESSO software package.
  4. Exchange-Correlation Functional: The Perdew-Burke-Ernzerhof (PBE) formulation was used for the exchange-correlation energy functional.
  5. Basis Set Cutoff: An energy cutoff of 800 eV was applied to limit the dimensionality of the basis set.
  6. Brillouin Zone Integration: Integration was performed using k-point grids of 16x16x8 for structural calculations and 8x8x4 for molecular dynamics simulations.
  7. Simulated Synthesis (Compression): Phase transitions were modeled under uniaxial compression of the graphene precursors (L3-12 or L4-6-12) to determine the critical pressure required for bilayer formation.
  8. Thermal Stability Simulation: Annealing simulations were performed using molecular dynamics (1 fs time step) at temperatures near the stability limits (200 K and 210 K) to assess thermal robustness.

The unique combination of semiconducting behavior, high density, and porous structure makes these materials promising for advanced technological applications:

  • Nanoelectronics: As direct band gap semiconductors, DL3-12 and DL4-6-12 could serve as active components in next-generation 2D electronic devices, potentially replacing or complementing silicon in certain applications.
  • Solar Energy: The materials are suitable for use in solar cells and photovoltaic devices, leveraging their semiconducting properties for efficient light absorption and charge separation.
  • Molecular Sieves/Filtration: The presence of uniform pores (approximately 4.5 Angstrom diameter) suggests potential use as molecular sieves, gas separation membranes, or highly selective filters.
  • Hydrogen Storage: Carbon nanostructures with high surface area and specific pore geometries are often investigated as hydrogen adsorbents, making these bilayers relevant for energy storage research.
  • High-Pressure Synthesis: The study provides critical pressure thresholds (8.6 GPa and 16.7 GPa) necessary for synthesizing these novel diamond-like phases, guiding experimental high-pressure material synthesis efforts.
View Original Abstract

In this article, a theoretical study of the structure, stability, electronic properties and formation process of new two-dimensional diamond-like DL3-12 and DL4‑6‑12 nanostructures is carried out using the density functional theory method. As a result of the calculations, it is established that the structures of these diamond-like bilayers can be obtained in the process of model cross-linking of two identical graphene L3-12 or L4‑6‑12 layers. The DL3-12 and DL4‑6‑12 bilayers have hexagonal unit cells with the lattice parameters of 5.8204 and 7.5116 Å, respectively. The calculated surface density of DL3-12 and DL4‑6‑12 bilayers is 0.082 and 0.098 ÎŒg / cm2, respectively, and exceeds the density of hexagonal graphene by 7 - 28 %. The structure of the studied diamond-like bilayers contains pores with a maximum diameter of ~4.5 Å. The calculation of the electronic properties showed that the DL3-12 and DL4‑6‑12 bilayers should be semiconductors with the direct band gap widths of 1.7 and 2.3 eV, respectively. It is also found that the diamond-like DL3-12 bilayer is stable up to 200 K, whereas the DL4‑6‑12 bilayer stable up to 210 K. In the region of these temperatures, a slight corrugation of the diamond-like bilayers occurs. Destruction of the bilayers is observed at higher temperatures. The most probable method for producing the DL3-12 and DL4‑6‑12 bilayers consists in strong uniaxial compression of two graphene layers. The diamond-like DL3-12 bilayer can be formed from L3-12 graphene at pressures exceeding 16.7 GPa, while the DL4‑6‑12 bilayer can be formed from L4‑6‑12 graphene at 8.6 GPa.