Solid-state structure and electronic properties of a mixed-valence two-dimensional metal, potassium copper sulfide (KCu4S3)

Brown, David B.; Zubieta, Jon; Vella, P.; Wrobleski, James T.; Watt, Timothy; Hatfield, William E.; Day, Peter

doi:10.1021/ic50209a024

Cited by 83 publications

(51 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It contains corner-sharing CuS 4 tetrahedra, reminiscent of a double-layer version of the ThCr 2 Si 2 -type structure that exhibits superconductivity in alkaliiron-pnictide compounds (33). KCu 4 S 3 is mixed valence and exhibits holes in the S p-band, but modification/doping reactions to induce a superconducting state have yet to be demonstrated (34). A small amount of digenite Cu 2-δ S is formed at higher temperatures.…”

Section: Hidden Compounds Upon Heating Cu In K 2 Smentioning

confidence: 99%

In situ studies of a platform for metastable inorganic crystal growth and materials discovery

Shoemaker

Chung

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

134

152

View full text Add to dashboard Cite

Rapid shifts in the energy, technological, and environmental demands of materials science call for focused and efficient expansion of the library of functional inorganic compounds. To achieve the requisite efficiency, we need a materials discovery and optimization paradigm that can rapidly reveal all possible compounds for a given reaction and composition space. Here we provide such a paradigm via in situ X-ray diffraction measurements spanning solid, liquid flux, and recrystallization processes. We identify four new ternary sulfides from reactive salt fluxes in a matter of hours, simultaneously revealing routes for ex situ synthesis and crystal growth. Changing the flux chemistry, here accomplished by increasing sulfur content, permits comparison of the allowable crystalline building blocks in each reaction space. The speed and structural information inherent to this method of in situ synthesis provide an experimental complement to computational efforts to predict new compounds and uncover routes to targeted materials by design.D iscovering new materials is a crucial step to address largescale problems of energy conversion, storage, and transmission and other technological needs whether seeking bulk phases or thin films. Dense inorganic materials are desired for their tunable transport, magnetism, optical absorption, and stability, but their existence in general cannot be predicted with the near certainty of that of metastable organic and organometallic compounds. Whereas the desire to efficiently locate and assemble inorganic materials is great, it is hindered by traditional solid-state synthetic methods-at high temperatures often only the energy-minimum thermodynamic product is obtained. To strive toward an arena where metastable compounds can be discovered rapidly and made systematically, here we conduct reactions within liquid fluxes and use in situ monitoring to capture signatures of new phases, even when they quickly dissolve in the melt.Convective liquid fluxes (salts, metals, or oxides) can serve as reaction media that aid diffusion and enable rapid formation of compounds at temperatures far below their melting points (1-6). The flux can be nonreactive or reactive; in the latter case the flux itself becomes incorporated into the product (7,8). This wellestablished approach has demonstrated the prolific discovery of novel inorganic materials grown out of low-melting fluxes, from oxides and other chalcogenides (9-12), to pnictides (13,14), to intermetallics (15), many of which cannot be attained by direct combinations of the elements. Despite the variety of metastable phases formed in these reactions, the classical approach is to predetermine a given set of reaction conditions (e.g., time, temperature, and heating and cooling rates) and wait for completion to isolate and identify the formed compounds. It is not possible to observe how the reaction system itself has arrived at the isolated compound, whether the crystalline material formed on heating, on cooling, or on soaking at the given high temperature,...

show abstract

Section: Hidden Compounds Upon Heating Cu In K 2 Smentioning

confidence: 99%

In situ studies of a platform for metastable inorganic crystal growth and materials discovery

Shoemaker

Chung

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

134

152

View full text Add to dashboard Cite

show abstract

“…Many of the copper-containing chalcogenides show various * Corresponding author. unique properties such as a metallic behavior, unlike oxides of which many are insulators [8][9][10][11]. Additionally, the copper-containing chalcogenides exhibit a large variety of crystal structures and phase transitions [12,13].…”

Section: Introductionmentioning

confidence: 99%

Electrical properties of β-BaCu2S2

Kurosaki

Uneda

Muta

et al. 2004

Journal of Alloys and Compounds

View full text Add to dashboard Cite

“…Therefore, the mixed-valent thiocuprates are to be classified as semimetals. In accordance they show Pauli paramagnetism [58,60]. They are not transparent and have a blue to black lustre.…”

Section: Physical Propertiesmentioning

confidence: 91%

“…For KCu 4 S 3 conductivities 4.1 × 10 3 −1 cm −1 at room temperature and 6 × 10 4 −1 cm −1 at 20 K were measured [58]. Other authors report a σ = 1.6 × 10 3 −1 cm −1 for KCu 4 S 3 and a σ = 0.7 × 10 3 −1 cm −1 for Na 3 Cu 4 S 4 at room temperature [59], also with a metal-like temperature dependence.…”

Section: Physical Propertiesmentioning

confidence: 99%

Thiocuprates—Interesting anisotropic solids

Boller

2007

Journal of Alloys and Compounds

View full text Add to dashboard Cite

Solid-state structure and electronic properties of a mixed-valence two-dimensional metal, potassium copper sulfide (KCu4S3)

Cited by 83 publications

References 3 publications

In situ studies of a platform for metastable inorganic crystal growth and materials discovery

In situ studies of a platform for metastable inorganic crystal growth and materials discovery

Electrical properties of β-BaCu2S2

Thiocuprates—Interesting anisotropic solids

Contact Info

Product

Resources

About