An Illuminating Framework:  Understanding the Photoluminescence of α-CuAlCl<sub>4</sub>

and, Roger M. Sullivan; Martin, James D.

doi:10.1021/ja9925204

Cited by 18 publications

(15 citation statements)

References 38 publications

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“…Cu(I) is only present in the CmCm material, which had only one sample showing significant PL; the luminescence in this sample could have been due to Pnma impurities in the batch. An alternative explanation is that the emission comes from CuCl 4 complexes in the NPs as CuCl 4 has been seen to luminesce at roughly 500 nm in CuAlCl 4 . This seems unlikely as it is still slightly bluer than what we observe, but the absorption maximum of the absorption of the CuCl 4 2– ion coincides with the maximum we see in Figure a .…”

Section: Resultssupporting

confidence: 47%

“…An alternative explanation is that the emission comes from CuCl 4 complexes in the NPs as CuCl 4 has been seen to luminesce at roughly 500 nm in CuAlCl 4 . 34 This seems unlikely as it is still slightly bluer than what we observe, but the absorption maximum of the absorption of the CuCl 4 2− ion coincides with the maximum we see in Figure 4a. 35 There have been a large number of studies, which have investigated copper defects in other systems.…”

Section: ■ Methodsmentioning

confidence: 99%

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Synthesis, Characterization, and Morphological Control of Cs₂CuCl₄ Nanocrystals

et al. 2019

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Recently, there has been an increase in research relating to the search for new optoelectronic materials for photovoltaic devices and light-emitting diodes. This research focuses on developing materials that not only possess the required optoelectronic properties (high absorption, efficient photon emission, and high charge-carrier mobilities) but are also solution-processable, which can reduce fabrication costs. Ternary ionic crystal structures, such as lead-halide perovskites, have emerged as a class of such suitable materials. However, the most promising structures, which exhibit the highest device efficiencies, rely on toxic lead as a cationic species, thereby hindering commercial application. Here, we synthesize and characterize CsCuCl3 and Cs2CuCl4 nanocrystals. These nanocrystals exhibit bright broad band green emission from copper defects when excited below 300 nm. We show that by employing a variety of ratios of coordinating solvents during synthesis, we can tailor the morphology of the nanoparticles produced, allowing us to produce structures such as dots, platelets, and rods. These materials represent a new class of nontoxic, solution-processable ternary semiconductors for optoelectronic applications.

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Section: Resultssupporting

confidence: 47%

Section: ■ Methodsmentioning

confidence: 99%

Synthesis, Characterization, and Morphological Control of Cs₂CuCl₄ Nanocrystals

et al. 2019

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“…Metal halides of III(A) elements in the periodic table that act as Lewis acid sites can bind arenes to form XR 3 ·arene complexes (X = B, Al, Ga; R = F, Cl, Br). − XYR 4 ·arene complexes (X = B, Al, Ga; Y = Cu(I), Ag(I), Hg(II); R = F, Cl, Br) can be obtained by adding transition-metal halides to XR 3 –arene solutions. − Haase was the first to synthesize a CuAlCl 4 –toluene solution, , which was discovered as an alternative absorbent for the recovery of carbon monoxide (CO) , and light alkenes. − A well-known process for recovering pure CO is the COSORB process . Most of the reports focused on the study of the kinetics and thermodynamics of the absorption process using AlCl 3 –CuCl–toluene solution. − CuAlCl 4 could be synthesized and existed stably. − Turner suggested that AlCl 3 –CuCl–arene solutions were formed by CuAlCl 4 and arenes . The interactions between arenes and CuAlCl 4 were charge-transfer bonds, confirmed by Toshima …”

Section: Introductionmentioning

confidence: 97%

Aluminum Species and the Synthesis Mechanism of AlCl₃–CuCl–Arene Solutions

Luo

Zhang

et al. 2021

Ind. Eng. Chem. Res.

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Aluminum species in AlCl3–arene and AlCl3–CuCl–arene solutions (including benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene) were investigated using 27Al NMR and infrared (IR) spectroscopy. The AlCl3·arene and Al2Cl6·arene complexes were demonstrated experimentally. AlCl3 could not coordinate with benzene and toluene at a low temperature (40 °C) but could form complexes at a high temperature (80 °C). AlCl3 could coordinate with xylene and mesitylene to form Al2Cl6·arene complexes at both low and high temperatures (40 and 80 °C). As for AlCl3–CuCl–arene solutions with a molar ratio of 1:1:2, two signals were observed in 27Al NMR spectra. The signal at around 101 ppm was assigned to CuAlCl4·2arene complexes, and the other signal at around 96 ppm belonged to AlCl3·arene complexes. The characteristic peaks of AlCl3–CuCl–arene solutions in IR spectra moved toward the low field due to the strong π-back-bonding. The CuAlCl4·2arene complexes would convert to CuAl2Cl7·2arene complexes with a further increase in AlCl3 content when the molar ratio of AlCl3/CuCl exceeded 1. The synthesis mechanism of AlCl3–CuCl–arene solutions was analyzed by in situ Fourier transform IR (FTIR) spectroscopy. Three reaction pathways originating from different aluminum species were proposed.

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“…33 Another report described the emission due to the generation of the CuCl4 complex in CuAlCl4. 37 On the other hand, Xu et al have achieved the emission in non-emissive ZnO nanorods on Cu 2+ doping where Cu defects were observed as the cause of the emission band. 38 In this concern, Davis and co-workers suggested that the origin of Cu 2+ defects could be responsible for the emission in Cs2CuCl4 nanoparticles.…”

Section: Resultsmentioning

confidence: 99%