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Solids in which the atoms, ions, or molecules are arranged in a definite repeating pattern are known as crystalline solids. Metals and ionic compounds typically form ordered, crystalline solids. A crystalline solid has a precise melting temperature because each atom or molecule of the same type is held in place with the same forces or energy. Amorphous solids or non-crystalline solids (or, sometimes, glasses) which lack an ordered internal structure and are randomly arranged. Substances that...
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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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Structure and Transport Properties of the BiCuSeO-BiCuSO Solid Solution.

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Materials (Basel, Switzerland)
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Summary

This study explores BiCuSeO and BiCuSO materials, finding a complete solid solution exists. Sulfur substitution significantly increases electrical resistivity and decreases thermal conductivity due to defects.

Keywords:
crystal structureelectrical resistivityelectronic band structurelayered chalcogenidesthermal conductivitythermoelectric materials

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Area of Science:

  • Materials Science
  • Solid State Chemistry
  • Thermoelectrics

Background:

  • Bismuth copper oxychalcogenides (BiCuSeO and BiCuSO) are promising thermoelectric materials.
  • Understanding the impact of chalcogen substitution (Se to S) on their properties is crucial for optimizing performance.

Purpose of the Study:

  • To investigate the crystal structure and electrical/thermal transport properties of the BiCuSe$_{1-x}$S$_{x}$O solid solution series.
  • To determine the effects of sulfur substitution on the band gap, bonding, and defect scattering mechanisms.

Main Methods:

  • Synthesis and characterization of the BiCuSe$_{1-x}$S$_{x}$O series.
  • Analysis of crystal structure evolution with varying sulfur content.
  • Measurement of electrical resistivity and thermal conductivity.

Main Results:

  • A complete solid solution was confirmed between BiCuSeO and BiCuSO.
  • Band gap increased linearly from 0.8 eV to 1.1 eV with increasing sulfur content.
  • Thermal conductivity decreased significantly due to point defect scattering, while electrical resistivity strongly increased.

Conclusions:

  • Sulfur substitution in BiCuSeO leads to a tunable band gap and reduced thermal conductivity.
  • Increased electrical resistivity is attributed to changes in copper vacancy formation energy.
  • Challenges exist in obtaining sulfur-rich samples due to stability and volatilization issues.