The Rb7Bi3−3xSb3xCl16 Family: A Fully Inorganic Solid Solution with Room‐Temperature Luminescent Members

Benin, Bogdan M.; McCall, Kyle M.; Wörle, Michael; Morad, Viktoriia; Aebli, Marcel; Yakunin, Sergii; Shynkarenko, Yevhen; Kovalenko, Maksym V.

doi:10.1002/ange.202003822

Cited by 13 publications

(10 citation statements)

References 57 publications

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“…Sb3 exhibits a trigonal lone pair distortion and Sb4 (the Sb V site) possesses a nearly perfect octahedron ( Figure 2 d). The average Sb–Cl bond lengths of Sb1 (2.660 Å), Sb2 (2.644 Å), and Sb3 (2.647 Å) are consistent with those of other Sb III Cl 6 octahedra in the literature (e.g., 2.637 Å in Rb 7 Sb 3 Cl 16 34 ), while that of Sb4 is significantly smaller at 2.345 Å, supporting the assignment of Sb V on this site ( Table S7 ). Within slabs I and III the [Sb V Cl 6 ] − octahedra of Sb4 are surrounded by six [SbCl 6 ] 3– octahedra, with an average Sb···Sb distance of 7.50 Å and no Rb cations directly between them ( Figure S1 ).…”

Section: Resultssupporting

confidence: 87%

“…Instead, the resistivity of Rb 23 Bi III 7 Sb V 2 Cl 54 is on par with values measured for other low-dimensional n s 2 -based pnictogen-halides such as Rb 7 Sb 3 Cl 16 or the A 3 M 2 X 9 series. 34 , 48 , 49 Following these measurements, visible light photoconductivity was also examined but, similarly to previously reported mixed-valent compounds, no significant response could be detected.…”

Section: Resultsmentioning

confidence: 63%

“…The Sb III octahedra in Rb 23 Sb III 7 Sb V 2 Cl 54 are slightly more distorted than those in Rb 7 Sb 3 Cl 16 , suggesting greater lone-pair stereoactivity. 34 …”

Section: Resultsmentioning

confidence: 99%

“…Upon closer examination, it became evident that in these cases two phases were present and that colorless Rb 7 Bi 3–3 x Sb 3 x Cl 16 crystals had nucleated and served as a substrate for the intergrowth of smaller, red crystals ( Figure 3 a). 34 …”

Section: Resultsmentioning

confidence: 99%

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Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb₂₃Bi^III_xSb^III_7–xSb^V₂Cl₅₄ (0 ≤ x ≤ 7)

et al. 2021

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Mixed-valent metal-halides containing n s 2 lone pairs may exhibit intense visible absorption, while zero-dimensional (0D) n s 2 -based metal-chlorides are generally colorless but have demonstrated promising optoelectronic properties suitable for thermometry and radiation detection. Here, we report solvothermally synthesized mixed-valent 0D metal-halides Rb 23 Bi III x Sb III 7– x Sb V 2 Cl 54 (0 ≤ x ≤ 7). Rb 23 Sb III 7 Sb V 2 Cl 54 crystallizes in an orthorhombic space group ( Cmcm ) with a unique, layered 0D structure driven by the arrangement of the 5s 2 lone pairs of the Sb III Cl 6 octahedra. This red material is likely the true structure of a previously reported monoclinic “Rb 2.67 SbCl 6 ” phase, the structure of which was not determined. Partially or fully substituting Sb III with isoelectronic Bi III yields the series Rb 23 Bi III x Sb III 7– x Sb V 2 Cl 54 (0 < x ≤ 7), which exhibits a similar layered 0D structure but with additional disorder that yields a trigonal crystal system with an enantiomorphic space group ( R 32). Second harmonic generation of 532 nm light from a 1064 nm laser using Rb 23 Bi III 7 Sb V 2 Cl 54 powder confirms the noncentrosymmetry of this space group. As with the prototypical mixed-valent pnictogen halides, the visible absorption bands of the Rb 23 Bi III x Sb III 7– x Sb V 2 Cl 54 family are the result of intervalent Sb III –Sb V and mixed-valent Bi III –Sb V charge transfer bands (CTB), with a blueshift of the absorption edge as Bi III substitution increases. No PL is observed from this family of semiconductors, but a crystal of Rb 23 Bi III 7 Sb V 2 Cl 54 exhibits a high resistivity of 1.0 × 10 10 Ω·cm and X-ray photoconductivity wi...

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Section: Resultssupporting

confidence: 87%

Section: Resultsmentioning

confidence: 63%

“…The Sb III octahedra in Rb 23 Sb III 7 Sb V 2 Cl 54 are slightly more distorted than those in Rb 7 Sb 3 Cl 16 , suggesting greater lone-pair stereoactivity. 34 …”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb₂₃Bi^III_xSb^III_7–xSb^V₂Cl₅₄ (0 ≤ x ≤ 7)

et al. 2021

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“…Recently, Kovalenko and co-workers reported a Rb 7 Bi 3x Sb 3−3x Cl 16 material family. [28] First, they presented Rb 7 Sb 3 Cl 16 and make a thorough inquiry into the origin of luminescence. PL spectra were measured under different excitation wavelength and an additional blue emission was observed excited by 290 nm.…”

Section: Photoluminescence Of Cs 2 Agsbcl 6 and Rb 7 Sb 3 CL 16mentioning

confidence: 99%

Photoluminescence of Singlet/Triplet Self‐Trapped Excitons in Sb³⁺‐Based Metal Halides

Jing

Liu

et al. 2021

Advanced Optical Materials

182

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these alternatives with varied crystal structures improved the water/thermal stability and optimized the optical performance of metal halide materials group. [7] ns 2 metal ion-based metal halides have always been regarded as the mainstream materials owing to their excellent optical properties and the facile synthesis procedure. [8] Moreover, ns 2 metal ion-based halides with broad-band emission and large Stokes shift, which can avoid selfabsorption effectively, are desirable for phonic applications. And, the self-trapped excitons (STEs) herein are ascribed to the strong electronphonon coupling in the distorted excited structure. [9] To generate diverse STEs emission in the visible light region, different ns 2 metal ions like Ge 2+ , Sn 2+ , Te 4+ , Bi 3+ , and Sb 3+ are selected to adjust emission peaks due to their different coordination environment and special crystal/local structures. [10] Among ns 2 metal halides, Sb 3+ -based halides with blue, green, and red tunable luminescence have been explored extensively as low-toxic and highly stable candidates, moreover, their luminescence mechanisms are discussed by combined experimental and theoretical methods, as well as their unique singlet and triplet excitonic emission. [5d,e,11] In this review, we first look back the electronic energy levels of ground state and excited state for ns 2 ions and the luminescence of Sb 3+ in transition metal oxides. Next, we summarize the recent progresses of the crystal structures, optical properties, and luminescence mechanisms of some Sb 3+ -based halides and Sb 3+ -doped metal halides including all-inorganic and hybrid organic-inorganic perovskite derivatives. Then, we discuss the current achievements of these materials in the emerging applications. And finally, we offer the perspective and some suggestions on the possible development of luminescent Sb 3+ -based metal halides. Electronic Energy Levels of Sb 3+The luminescence and radiation process of ns 2 ions in solidstate compounds have been widely investigated. [10a,b,d,12] A free Emerging lead-free metal halides with low toxicity and unparalleled optoelectronic properties have attracted growing research interests, also demonstrating extensive application potentials. Among these, Sb 3+ -based allinorganic/organic-inorganic hybrid metal halides become a vital group due to the special energy level distribution along with diverse optical properties. However, there remains a gap in understanding the relationship between the crystal structure and the radiation process of involved Sb 3+ emission. Herein, the existing reports about Sb 3+ -based luminescent metal halides are revisited and their structure-luminescence-application relationship is explored, and it is further established that the triplet self-trapped excitons (STEs) emission of Sb 3+ varies in different crystallographic environments and endows tunable luminescent performance. This work aims to provide constructive strategies in the further exploitation of Sb 3+ -based metal halides, and also guides the structura...

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Sb³⁺–Er³⁺‐Codoped Cs₂NaInCl₆ for Emitting Blue and Short‐Wave Infrared Radiation

et al. 2022

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Cs 2 NaInCl 6 double perovskite is stable, environmentally benign and easy to prepare. But it has a wide band gap (5.1 eV), and therefore, does not show optical and optoelectronic properties in the visible and short-wave infrared (SWIR) region. Here we introduce such functionalities in Cs 2 NaInCl 6 by codoping Sb 3 + (s-electron doping) and Er 3 + (f-electron doping) ions. Sb 3 + doping introduces optically allowed 5s 2 !5s 1 5p 1 electronic absorption at the sub-band gap level, which then emits blue photoluminescence with � 93 % quantum yield. But f-f electronic absorption of Er 3 + is parity forbidden. Codoping Sb 3 + -Er 3 + , leads to transfer of excitation energy from Sb 3 + to Er 3 + , yielding SWIR emission at 1540 nm. Temperature (6 to 300 K) dependent photoluminescence measurements elucidate the excitation and emission mechanism. A phosphor converted light emitting diode (pc-LED) fabricated by using the codoped sample emits stable blue and SWIR radiation over prolonged (84 hours) operation at 5.1 V.

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The Rb₇Bi_3−3xSb_3xCl₁₆ Family: A Fully Inorganic Solid Solution with Room‐Temperature Luminescent Members

Cited by 13 publications

References 57 publications

Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb₂₃Bi^III_xSb^III_7–xSb^V₂Cl₅₄ (0 ≤ x ≤ 7)

Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb₂₃Bi^III_xSb^III_7–xSb^V₂Cl₅₄ (0 ≤ x ≤ 7)

Photoluminescence of Singlet/Triplet Self‐Trapped Excitons in Sb³⁺‐Based Metal Halides

Sb³⁺–Er³⁺‐Codoped Cs₂NaInCl₆ for Emitting Blue and Short‐Wave Infrared Radiation

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The Rb7Bi3−3xSb3xCl16 Family: A Fully Inorganic Solid Solution with Room‐Temperature Luminescent Members

Cited by 13 publications

References 57 publications

Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb23BiIIIxSbIII7–xSbV2Cl54 (0 ≤ x ≤ 7)

Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb23BiIIIxSbIII7–xSbV2Cl54 (0 ≤ x ≤ 7)

Photoluminescence of Singlet/Triplet Self‐Trapped Excitons in Sb3+‐Based Metal Halides

Sb3+–Er3+‐Codoped Cs2NaInCl6 for Emitting Blue and Short‐Wave Infrared Radiation

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Product

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The Rb₇Bi_3−3xSb_3xCl₁₆ Family: A Fully Inorganic Solid Solution with Room‐Temperature Luminescent Members

Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb₂₃Bi^III_xSb^III_7–xSb^V₂Cl₅₄ (0 ≤ x ≤ 7)

Lone-Pair-Induced Structural Ordering in the Mixed-Valent 0D Metal-Halides Rb₂₃Bi^III_xSb^III_7–xSb^V₂Cl₅₄ (0 ≤ x ≤ 7)

Photoluminescence of Singlet/Triplet Self‐Trapped Excitons in Sb³⁺‐Based Metal Halides

Sb³⁺–Er³⁺‐Codoped Cs₂NaInCl₆ for Emitting Blue and Short‐Wave Infrared Radiation