Tuning the electronic structure of the trichloride honeycomb lattice by transition metal substitution

Klaproth, Tom; Muller, Eric A.; Habenicht, Carsten; Büchner, B.; Knupfer, M.; Roslova, Maria; Isaeva, Anna; Doert, Thomas; Koitzsch, A.

doi:10.1103/physrevmaterials.6.014001

Cited by 4 publications

(8 citation statements)

References 43 publications

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“…With increasing Cr 3+ content in the solid solution, all of these Mo-related excitations decrease in intensity, as is expected due to the decreasing Mo 3+ content. Finally, the spectra show the excitation spectrum of CrCl 3 in agreement with a previous work. , No major changes of the spectral shape were observed throughout the Cr x Mo 1– x Cl 3 series and support the presence of dimers in the structure up to quite low Mo 3+ concentrations (see Figure and related discussion).…”

Section: Resultssupporting

confidence: 64%

Structural and Magnetic Transitions Caused by Dimer Formation in the CrCl₃–MoCl₃ Solid Solution

Froeschke,

Bestha,

Fucke

et al. 2024

Chem. Mater.

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In this work, we apply the concept of solid solutions to the two 2D transition metal trihalides CrCl 3 and MoCl 3 . While CrCl 3 belongs to the magnetically active CrX 3 family, the magnetism in MoCl 3 is intrinsically suppressed by the formation of aligned Mo−Mo dimers, which also distort the regular honeycomb lattice that is typical for the 2D transition metal trihalides. We report suitable synthesis conditions for the gapless solid solution and crystal growth by chemical vapor transport. The CrCl 3 − MoCl 3 solid solution was initially synthesized at 650 °C for 100 h under addition of MoCl 5 as mineralizer, and bulk crystals were subsequently grown by vapor transport in a temperature gradient from 600 °C → 550 °C for 60 h. The obtained solid solution exhibits multiple composition-dependent phase transitions at room temperature, as confirmed by powder X-ray diffraction measurements. The possible presence of Mo−Mo dimers in the solid solution was further investigated by infrared, Raman, electron energy loss, and nuclear quadrupole resonance spectroscopies. The combined results indicate that the Mo−Mo dimers are present over a wide range of compositions. Their orientation changes from parallel alignment for compositions from 70% ≤ c(Mo 3+ ) ≤ 100% to random orientation for samples with c(Mo 3+ ) < 70% content, which significantly affects the course of lattice parameters. Finally, the magnetic properties of the powder samples show a correlation between the Mo 3+ content and the transition temperature into the low-temperature phase.

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Section: Resultssupporting

confidence: 64%

Structural and Magnetic Transitions Caused by Dimer Formation in the CrCl₃–MoCl₃ Solid Solution

Froeschke,

Bestha,

Fucke

et al. 2024

Chem. Mater.

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“…The cation sites in the crystal structure are randomly occupied by Cr 3+ and Ru 3+ . 8 Besides the very interesting magnetic and optical 11 properties of the bulk solid solution material, which for example features a spin liquid state for intermediate Cr : Ru ratios, 9 one could expect that the properties of the solid solution will change when the height of the crystalline material is scaled from bulk dimensions, over micro-and nanometre heights down to only few-or even monolayer structures, since such exotic behaviour is known for pure CrCl 3 12,13 and RuCl 3 . 14,15 properties, high-quality micro-and nanostructures of the respective material are required, about which to our best knowledge no designated studies were published yet.…”

Section: Introductionmentioning

confidence: 99%

“…Besides the very interesting magnetic and optical 11 properties of the bulk solid solution material, which for example features a spin liquid state for intermediate Cr : Ru ratios, 9 one could expect that the properties of the solid solution will change when the height of the crystalline material is scaled from bulk dimensions, over micro- and nanometre heights down to only few- or even monolayer structures, since such exotic behaviour is known for pure CrCl 3 12,13 and RuCl 3 . 14,15 The investigation of these expectable changes during the downscaling could provide crucial insights on the tuneability of nanomaterial properties by solid solution formation.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of micro- and nanosheets of CrCl₃–RuCl₃ solid solution by chemical vapour transport

et al. 2022

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“…Unfortunately, chemical substitutions in RuCl 3 do not meaningfully modulate electronic structures [14] . The substitution of Cr for Ru in Ru 1− x Cr x Cl 3 does not change the respective electronic density of states [15] …”

Section: Introductionmentioning

confidence: 96%

Electronic Structure Manipulation of the Mott Insulator RuCl₃ via Single‐Crystal to Single‐Crystal Topotactic Transformation

Lee

Cha

et al. 2023

Angew Chem Int Ed

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The core task for Mott insulators includes how rigid distributions of electrons evolve and how these induce exotic physical phenomena. However, it is highly challenging to chemically dope Mott insulators to tune properties. Herein, we report how to tailor electronic structures of the honeycomb Mott insulator RuCl 3 employing a facile and reversible single-crystal to singlecrystal intercalation process. The resulting product (NH 4 ) 0.5 RuCl 3 •1.5 H 2 O forms a new hybrid superlattice of alternating RuCl 3 monolayers with NH 4+ and H 2 O molecules. Its manipulated electronic structure markedly shrinks the Mott-Hubbard gap from 1.2 to 0.7 eV. Its electrical conductivity increases by more than 10 3 folds. This arises from concurrently enhanced carrier concentration and mobility in contrary to the general physics rule of their inverse proportionality. We show topotactic and topochemical intercalation chemistry to control Mott insulators, escalating the prospect of discovering exotic physical phenomena.

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Tuning the electronic structure of the trichloride honeycomb lattice by transition metal substitution

Cited by 4 publications

References 43 publications

Structural and Magnetic Transitions Caused by Dimer Formation in the CrCl₃–MoCl₃ Solid Solution

Structural and Magnetic Transitions Caused by Dimer Formation in the CrCl₃–MoCl₃ Solid Solution

Synthesis of micro- and nanosheets of CrCl₃–RuCl₃ solid solution by chemical vapour transport

Electronic Structure Manipulation of the Mott Insulator RuCl₃ via Single‐Crystal to Single‐Crystal Topotactic Transformation

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Tuning the electronic structure of the trichloride honeycomb lattice by transition metal substitution

Cited by 4 publications

References 43 publications

Structural and Magnetic Transitions Caused by Dimer Formation in the CrCl3–MoCl3 Solid Solution

Structural and Magnetic Transitions Caused by Dimer Formation in the CrCl3–MoCl3 Solid Solution

Synthesis of micro- and nanosheets of CrCl3–RuCl3 solid solution by chemical vapour transport

Electronic Structure Manipulation of the Mott Insulator RuCl3 via Single‐Crystal to Single‐Crystal Topotactic Transformation

Contact Info

Product

Resources

About

Structural and Magnetic Transitions Caused by Dimer Formation in the CrCl₃–MoCl₃ Solid Solution

Structural and Magnetic Transitions Caused by Dimer Formation in the CrCl₃–MoCl₃ Solid Solution

Synthesis of micro- and nanosheets of CrCl₃–RuCl₃ solid solution by chemical vapour transport

Electronic Structure Manipulation of the Mott Insulator RuCl₃ via Single‐Crystal to Single‐Crystal Topotactic Transformation