Synthesis and Electronic Structure of Mid-Infrared Absorbing Cu3SbSe4 and CuxSbSe4 Nanocrystals

Moser, Annina; Yarema, Olesya; Garcia, Gregorio; Luisier, Mathieu; Longo, Filippo; Billeter, Emanuel; Borgschulte, Andreas; Yarema, Maksym; Wood, Vanessa

doi:10.1021/acs.chemmater.3c00911

Cited by 5 publications

(1 citation statement)

References 45 publications

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“…Among all of the group I–V–VI elements, environmentally friendly ternary copper-based chalcogenides, such as Cu 3 SbSe 4 , have been reported as promising candidates for photovoltaic devices as well as thermoelectric power generation purposes, resulting from its superiority of cheap and nontoxic constituents as well as its unique carrier transport behavior caused by its special atomic arrangement. Many studies investigate Cu 3 SbSe 4 for thermoelectrics due to its low thermal conductivity and high Seebeck coefficient, − whereas its thermoelectric conversion efficiency is restricted by its relatively low PF and electrical conductivity resulting from its low carrier concentration and low carrier mobility. To overcome this limitation, many investigations have been made to optimize its carrier concentration by doping at Cu sites with elements such as Zn and Ag and substitution of Sb by elements like Pb, Sn, , and Bi. ,, Other strategies include Sn and Zr or Hf codoping, Sn and Bi double doping, and Sn and La codoping .…”

Section: Introductionmentioning

confidence: 99%

2D Self-Assembly of Large-Sized Inorganic Nanosheets Leading to Enhanced Power Factors in Earth-Abundant Cu₃SbSe₄-Based Flexible Hybrid Films

Dou,

Yao,

et al. 2024

ACS Appl. Mater. Interfaces

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Fabrication of large-sized inorganic nanosheets is an efficient strategy to promote carrier transportation in flexible thermoelectric (TE) films. Herein, we report the self-assembly of large-sized Cu 3 SbSe 4 nanosheets by using a Se nanowire template via wet chemical synthesis and then vacuum-assisted filter these plate-like microcrystals on nylon to prepare Cu 3 SbSe 4 flexible thermoelectric (TE) hybrid films. SEM reveals that the as-synthesized Cu 3 SbSe 4 powders by using Se nanowires as selenium sources presented 2D plate-like micron structures uniformly and tightly selfassembled by acute triangle-like nanoparticles. Furthermore, XPS evidences that extra Sb vacancies are generated in the unit cell of Cu 3 SbSe 4 crystals synthesized by using the Se NW template, resulting in the shrinkage of the unit cell and the narrowing interplanar spacing, which are characterized by XRD and TEM. As a result, both carrier concentration and carrier mobility have been significantly improved. The high carrier concentration is proved to originate from the extra carriers induced by Sb vacancies, and the high carrier mobility of the film is mainly ascribed to its continuous grain boundaries in the plate-like microcrystal morphology. The large-sized nanosheet Cu 3 SbSe 4 /nylon hybrid film (CSS MPs) exhibits a high power factor (PF) of 235.45 μW m −1 K −2 at 400 K, which is 4.23 times higher than that of the Cu 3 SbSe 4 /nylon hybrid film (CSS NPs) where Cu 3 SbSe 4 crystals are synthesized by using raw Se particles. This work reveals a novel approach to prepare plate-like Se-based semiconductors, which requires both high carrier concentration and high carrier mobility.

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Section: Introductionmentioning

confidence: 99%

2D Self-Assembly of Large-Sized Inorganic Nanosheets Leading to Enhanced Power Factors in Earth-Abundant Cu₃SbSe₄-Based Flexible Hybrid Films

Dou,

Yao,

et al. 2024

ACS Appl. Mater. Interfaces

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Palladium Zinc Nanocrystals: Nanoscale Amalgamation Enables Multifunctional Intermetallic Colloids

Yarema,

Moser,

Chang

et al. 2023

Adv Funct Materials

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Intermetallic nanocrystals are emerging materials for energy, catalysis, and biomedical applications, but combining two or more metals at the nanoscale remains challenging. The amalgamation reaction represents a convenient method for hundreds of intermetallic compositions, as it relies on fast and efficient alloying of liquid metals into presynthesized metallic seeds. Here, Pd–Zn nanocrystals, prepared via Zn amide thermolysis on the surface of Pd nanocrystals and subsequent amalgamation alloying, are investigated. Size‐uniform nanocrystals and control over a wide range of Pd–Zn compositions are achieved. This allows deriving a phase diagram at the nanoscale, in which miscibility gaps and three phases with broad solid solutions are detected. Furthermore, the formation of homogeneous ZnO shells for Pd–Zn compositions extending beyond phase solubility limits is observed. Full chemistry control for Pd–Zn nanocrystals enables a rational choice of materials for selected energy applications, achieveing an extended lifetime of Zn‐ion batteries for Zn‐rich PdZn2 stoichiometry, superior electrocatalytic properties for nearly stoichiometric PdZn halite phase, and the stability and efficiency of high‐voltage cathodes benefiting from ZnO shell protection around Pd3Zn10 nanocrystals are reported. This paper exemplifies the multifunctionality of intermetallics Pd–Zn nanocrystals, while this methodology can be extended to many other bimetallic nanomaterials.

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Band Engineering Through Pb‐Doping of Nanocrystal Building Blocks to Enhance Thermoelectric Performance in Cu₃SbSe₄

Wan,

Xiao,

et al. 2023

Small Methods

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Developing cost‐effective and high‐performance thermoelectric (TE) materials to assemble efficient TE devices presents a multitude of challenges and opportunities. Cu3SbSe4 is a promising p‐type TE material based on relatively earth abundant elements. However, the challenge lies in its poor electrical conductivity. Herein, an efficient and scalable solution‐based approach is developed to synthesize high‐quality Cu3SbSe4 nanocrystals doped with Pb at the Sb site. After ligand displacement and annealing treatments, the dried powders are consolidated into dense pellets, and their TE properties are investigated. Pb doping effectively increases the charge carrier concentration, resulting in a significant increase in electrical conductivity, while the Seebeck coefficients remain consistently high. The calculated band structure shows that Pb doping induces band convergence, thereby increasing the effective mass. Furthermore, the large ionic radius of Pb2+ results in the generation of additional point and plane defects and interphases, dramatically enhancing phonon scattering, which significantly decreases the lattice thermal conductivity at high temperatures. Overall, a maximum figure of merit (zTmax) ≈ 0.85 at 653 K is obtained in Cu3Sb0.97Pb0.03Se4. This represents a 1.6‐fold increase compared to the undoped sample and exceeds most doped Cu3SbSe4‐based materials produced by solid‐state, demonstrating advantages of versatility and cost‐effectiveness using a solution‐based technology.

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Synthesis and Electronic Structure of Mid-Infrared Absorbing Cu₃SbSe₄ and Cu_xSbSe₄ Nanocrystals

Cited by 5 publications

References 45 publications

2D Self-Assembly of Large-Sized Inorganic Nanosheets Leading to Enhanced Power Factors in Earth-Abundant Cu₃SbSe₄-Based Flexible Hybrid Films

2D Self-Assembly of Large-Sized Inorganic Nanosheets Leading to Enhanced Power Factors in Earth-Abundant Cu₃SbSe₄-Based Flexible Hybrid Films

Palladium Zinc Nanocrystals: Nanoscale Amalgamation Enables Multifunctional Intermetallic Colloids

Band Engineering Through Pb‐Doping of Nanocrystal Building Blocks to Enhance Thermoelectric Performance in Cu₃SbSe₄

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Synthesis and Electronic Structure of Mid-Infrared Absorbing Cu3SbSe4 and CuxSbSe4 Nanocrystals

Cited by 5 publications

References 45 publications

2D Self-Assembly of Large-Sized Inorganic Nanosheets Leading to Enhanced Power Factors in Earth-Abundant Cu3SbSe4-Based Flexible Hybrid Films

2D Self-Assembly of Large-Sized Inorganic Nanosheets Leading to Enhanced Power Factors in Earth-Abundant Cu3SbSe4-Based Flexible Hybrid Films

Palladium Zinc Nanocrystals: Nanoscale Amalgamation Enables Multifunctional Intermetallic Colloids

Band Engineering Through Pb‐Doping of Nanocrystal Building Blocks to Enhance Thermoelectric Performance in Cu3SbSe4

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Product

Resources

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Synthesis and Electronic Structure of Mid-Infrared Absorbing Cu₃SbSe₄ and Cu_xSbSe₄ Nanocrystals

2D Self-Assembly of Large-Sized Inorganic Nanosheets Leading to Enhanced Power Factors in Earth-Abundant Cu₃SbSe₄-Based Flexible Hybrid Films

2D Self-Assembly of Large-Sized Inorganic Nanosheets Leading to Enhanced Power Factors in Earth-Abundant Cu₃SbSe₄-Based Flexible Hybrid Films

Band Engineering Through Pb‐Doping of Nanocrystal Building Blocks to Enhance Thermoelectric Performance in Cu₃SbSe₄