Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

Elimelech, Orian; Liu, Jing; Płonka, Anna M.; Frenkel, Anatoly; Banin, Uri

doi:10.1002/ange.201702673

Cited by 16 publications

(19 citation statements)

References 45 publications

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“…2 Recently, it has been disclosed that LSPR emerges not only in metals but also in heavily doped semiconductors with appreciable free carrier density, including aliovalent doped/selfdoped metal oxides, metal chalcogenides, metal nitrides and many others. 3 For example, tin doped indium oxide (ITO), 4 aluminum doped zinc oxide (AZO), 5 niobium doped titanium oxide (NTO), 6 oxygen-deficient molybdenum oxide (MoO 3Àx ) 7,8 and tungsten oxide (WO 3Àx ), 9 titanium nitride (Ti x N) 10 as well as nonstoichiometric copper chalcogenide (Cu 2Àx E, E = S, Se and Te) [11][12][13][14][15][16][17][18] NPs exhibit intense LSPR. In particular, copper vacancy (hole) doped Cu 2Àx S NPs have attracted numerous attention…”

Section: Introductionmentioning

confidence: 99%

Plasmonic Cu_2−xS nanoparticles: a brief introduction of optical properties and applications

Chen

et al. 2021

Mater. Adv.

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Section: Introductionmentioning

confidence: 99%

Plasmonic Cu_2−xS nanoparticles: a brief introduction of optical properties and applications

Chen

et al. 2021

Mater. Adv.

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“…As shown in Figure 1h, the absorption spectrum of the initial copper sulfide characterized by a localized surface plasmon resonance peak in the near-infrared range (orange curve in Figure 1h), which is consistent with the literature results. [41][42][43] The ZnS hexagonal nanoplates show an absorption edge with its maximum at 310 nm from which a band gap of 4.0 eV was extracted.…”

Section: Znsmentioning

confidence: 99%

Dominant Polar Surfaces of Colloidal II–VI Wurtzite Semiconductor Nanocrystals Enabled by Cation Exchange

Wang

Chen

et al. 2020

J. Phys. Chem. Lett.

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Polar surfaces of ionic crystals are of growing technological importance, with implications for the efficiency of photocatalysts, gas sensors and electronic devices. Creation of ionic nanocrystals with large percentages of polar surfaces is an option to improve their efficiency in aforementioned applications but is hard to be accomplished because they are less thermodynamically stable and prone to vanish during the growth process. Herein we developed a strategy that is capable of producing polar surface dominated II-VI semiconductor nanocrystals including ZnS and CdS, from copper sulfide hexagonal nanoplates through cation exchange reactions. The obtained hexagonal prism-shaped wurtzite ZnS hexagonal nanoplates have dominant {002} polar surfaces, occupying up to 97.8% of all surfaces. Density functional calculations reveal the polar surfaces can be stabilized by a charge transfer of 0.25 eV/formula from the anion-terminated surface to the cation-terminated surface, which also explains the presence of polar surfaces in the initial Cu1.75S hexagonal nanoplates with cation deficiency prior to cation exchange reactions. Experimental results showed that the HER activity could be boosted by the surface polarization of polar surface dominated ZnS hexagonal nanoplates. We anticipate this strategy is general and could be used to other systems to prepare nanocrystals with dominant polar surfaces. Furthermore, the availability of colloidal semiconductor nanocrystals with dominant polar surfaces produced through this strategy open a new avenue for improving their efficiency in catalysis, photocatalysis, gas sensing and other applications.

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“…27,36 Typically, the emergence of an LSPR optical feature is also coupled with an increase in the optical band gap of Cu 2 − x Se NPs known as the Moss− Burstein effect. 19,20,22,23,26,36−39 In addition, the LSPR is known to be influenced by the NP size, 40,41 surrounding medium such as solvent and surface ligands, 26,42 and environment temperature. 43 The Cu atoms in the cubic phase of Cu 2−x Se are known to be partially disordered 44,45 and have been characterized as superionic due to high Cu mobility.…”

Section: ■ Introductionmentioning

confidence: 99%

Theoretical Study of the Impact of Vacancies and Disorder on the Electronic Properties of Cu_2–xSe

et al. 2021

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Copper selenide (Cu 2−x Se) is a promising material for plasmonic nanoparticle applications. Cu 2−x Se becomes plasmonically active in the oxidized state (x > 0), where free carrier density increases with increasing oxidation. It also has considerable cation (Cu) disorder. To date, there has not been a theoretical study of the impact of the degree of oxidation and cation disorder on the electronic and optical properties of Cu 2−x Se. We used density functional theory (DFT) to investigate the effects of the concentration of Cu vacancies and disorder on the properties of Cu 2−x Se. We used both generalized gradient approximation (GGA) and hybrid-GGA functionals to compute the structural, electronic, and optical properties of the cubic phase of Cu 2−x Se for x = 0, 0.25, 0.5, and 0.75. We performed ab initio molecular dynamics simulations at 300 K to simulate disorder, taking snapshots sampled from simulations of periodic supercells with different levels and arrangements of defects. The HSE06+U hybrid-GGA functional was used to calculate the electronic properties, including the optical band gaps, for a total of 400 different configurations. We found that the average optical band gap increases with increasing oxidation. We also found that only the stoichiometric, x = 0, materials are semiconductors, and the electronic band gap generally increases, increasing disorder.

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Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

Cited by 16 publications

References 45 publications

Plasmonic Cu_2−xS nanoparticles: a brief introduction of optical properties and applications

Plasmonic Cu_2−xS nanoparticles: a brief introduction of optical properties and applications

Dominant Polar Surfaces of Colloidal II–VI Wurtzite Semiconductor Nanocrystals Enabled by Cation Exchange

Theoretical Study of the Impact of Vacancies and Disorder on the Electronic Properties of Cu_2–xSe

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Size Dependence of Doping by a Vacancy Formation Reaction in Copper Sulfide Nanocrystals

Cited by 16 publications

References 45 publications

Plasmonic Cu2−xS nanoparticles: a brief introduction of optical properties and applications

Plasmonic Cu2−xS nanoparticles: a brief introduction of optical properties and applications

Dominant Polar Surfaces of Colloidal II–VI Wurtzite Semiconductor Nanocrystals Enabled by Cation Exchange

Theoretical Study of the Impact of Vacancies and Disorder on the Electronic Properties of Cu2–xSe

Contact Info

Product

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Plasmonic Cu_2−xS nanoparticles: a brief introduction of optical properties and applications

Plasmonic Cu_2−xS nanoparticles: a brief introduction of optical properties and applications

Theoretical Study of the Impact of Vacancies and Disorder on the Electronic Properties of Cu_2–xSe