Synthesis of micro- and nanosheets of CrCl<sub>3</sub>–RuCl<sub>3</sub> solid solution by chemical vapour transport

Froeschke, Samuel; Wolf, Daniel; Hantusch, Martin; Giebeler, Lars; Wels, Martin; Gräßler, Nico; Büchner, B.; Schmidt, Peer; Hampel, Silke

doi:10.1039/d2nr01366e

Cited by 5 publications

(13 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To increase the number of potentially available nanoplatelets and to further reduce the number of layers, a subsequent delamination of the as-grown material on the substrate was performed by simple ultrasonication of the substrate in an appropriate solvent, as shown in some previous works. , This process peels off a large portion of excess microcrystals from the substrate, leaving behind only those platelets that are more strongly attached to the surface. Selected results of ethanol as the solvent are displayed in Figure .…”

Section: Results and Discussionmentioning

confidence: 99%

“…Commercial powder of CrCl 3 (99.9% metal basis, Alfa Aesar) was purified by CVT as described elsewhere …”

Section: Experimental Sectionmentioning

confidence: 99%

“…Commercial powder of CrCl 3 (99.9% metal basis, Alfa Aesar) was purified by CVT as described elsewhere. 25 For the synthesis of CrBr 3 , 350−550 mg of liquid bromine (99.6%, Acros Organics) was sealed in a mark-tube capillary (Hilgenberg), which was placed in a 2-chamber ampoule together with the corresponding amount of chromium powder (99.2%, <10 μm, Alfa Aesar) and sealed. The amount of chromium was chosen so that at least an excess of 3 mg (∼0.037 mmol) bromine remains for the complete formation of CrBr 3 .…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

See 2 more Smart Citations

Controlled Nanoplatelet Deposition of 2D Chromium Trihalide Solid Solutions

Froeschke,

Yasmen,

Popov

et al. 2023

Chem. Mater.

Self Cite

View full text Add to dashboard Cite

The two-dimensional (2D) chromium trihalides CrCl 3 , CrBr 3 , and CrI 3 are most famous for their exotic magnetic properties when their crystals get downscaled to nanometer dimensions. One way to tune the properties of such materials and to further increase their potential utility, e.g., in spintronics, is the formation of solid solutions. Here, we present a detailed theoretical and experimental study on the synthesis and nanoplatelet growth of CrBr x Cl 3−x and CrBr x I 3−x solid solutions. Phase pure powder was obtained by tempering the respective parent compounds at 600 and 550 °C, using additional iodine in the case of CrBr x I 3−x . The dominant stacking order changes at x = 1.8 for CrBr x Cl 3−x while remaining similar to CrI 3 for the whole CrBr x I 3−x series. A consecutive chemical vapor transport from 575 → 525 °C for 2 h (CrBr x Cl 3−x ) or 600 → 550 °C for 3 h with 0.1 mmol additional iodine (CrBr x I 3−x ) resulted in the deposition of high-quality nanoplatelets on a substrate with only several nanometers in height. The composition can be controlled by the choice of the starting material, since only small shifts in the anion ratio occur during the transport. The deposited CrBr x Cl 3−x nanoplatelets can then be easily delaminated by ultrasonication in ethanol to reduce the height even further to few-layer dimensions. These nanoplatelets could potentially be used to investigate the property changes (e.g., in terms of magnetic response) for the downscaling of these solid solutions. We further demonstrate the quality of the deposited material by transmission electron microscopy, selected area electron diffraction, and X-ray photoelectron spectroscopy. Raman spectroscopy of the solid solution series reveals a complex evolution of vibrational modes. Photoluminescence measurements on solid solution samples show emission peaks in the near-infrared energy range with the specific energy and intensity being composition and temperature dependent.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

“…Commercial powder of CrCl 3 (99.9% metal basis, Alfa Aesar) was purified by CVT as described elsewhere …”

Section: Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

See 1 more Smart Citation

Controlled Nanoplatelet Deposition of 2D Chromium Trihalide Solid Solutions

Froeschke,

Yasmen,

Popov

et al. 2023

Chem. Mater.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Atomic chlorine species of both isotopes, 35 Cl and 37 Cl, were detected in the ratio 1 to 3 at the beginning of the decomposition of K x Ru 2 Cl 6 , while the molecular chlorine species did not occur. The observed mass traces of 36 HCl and 38 HCl in the ratio of 1 to 3 can be explained by the reaction of formed gaseous 35 Cl/ 37 Cl with the small traces of water (< 0.02 ppm) from the purge gas.…”

Section: Resultsmentioning

confidence: 93%

“…[34,35] The mechanism of CVT for α-RuCl 3 is described in details in Ref. [31] α-RuCl 3 used for thermogravimetric analysis was purchased from Aldrich Chemistry (45-55 % Ru content), and purified according to Froeschke et al [36] Intercalation was performed at room temperature in a three-electrode electrochemical cell filled with 0.5 M KCl (99 %, Sigma-Aldrich) aqueous solution. A rectangular piece of α-RuCl 3 with the sizes of about 2×3 mm was placed onto the Pt mesh (99.9 %, Goodfellow GmbH) that was then folded around the crystal and clamped.…”

Section: Methodsmentioning

confidence: 99%

Microstructural evolution of layered K‐doped RuCl₃ during annealing traced by thermogravimetric analysis and 3D electron diffraction

Vinokurova,

Knorr,

Efimova

et al. 2023

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

Nanoscale phase separation was induced in the K‐doped RuCl3 van der Waals material by annealing, and studied with the goal to find a natural design strategy for the formation of two‐dimensional architectures as an alternative to the costly and time‐consuming experimental artificial growth methods. Phase conversion was traced by means of thermogravimetric analysis combined with mass spectrometry. The local crystal structure of co‐existing K3Ru2Cl9 domains with the sizes of about 100 nm was solved by 3D electron diffraction.

show abstract

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

Froeschke,

Bestha,

Fucke

et al. 2024

Chem. Mater.

Self Cite

View full text Add to dashboard Cite

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.

show abstract

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

Abstract: Solid solutions of 2D transition metal trihalides are rapidly growing in interest for the search for new 2D materials with novel properties at nanoscale dimensions. In this regard, we present...

Cited by 5 publications

References 29 publications

Controlled Nanoplatelet Deposition of 2D Chromium Trihalide Solid Solutions

Controlled Nanoplatelet Deposition of 2D Chromium Trihalide Solid Solutions

Microstructural evolution of layered K‐doped RuCl₃ during annealing traced by thermogravimetric analysis and 3D electron diffraction

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

Contact Info

Product

Resources

About

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

Abstract: Solid solutions of 2D transition metal trihalides are rapidly growing in interest for the search for new 2D materials with novel properties at nanoscale dimensions. In this regard, we present...

Cited by 5 publications

References 29 publications

Controlled Nanoplatelet Deposition of 2D Chromium Trihalide Solid Solutions

Controlled Nanoplatelet Deposition of 2D Chromium Trihalide Solid Solutions

Microstructural evolution of layered K‐doped RuCl3 during annealing traced by thermogravimetric analysis and 3D electron diffraction

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

Contact Info

Product

Resources

About

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

Microstructural evolution of layered K‐doped RuCl₃ during annealing traced by thermogravimetric analysis and 3D electron diffraction

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