A Nonlinear Optical Switchable Sulfate of Ultrawide Bandgap

Open AccessCCS ChemistryRESEARCH ARTICLE1 Jul 2021A Nonlinear Optical Switchable Sulfate of Ultrawide Bandgap Yanqiang Li, Congling Yin, Xiaoyan Yang, Xiaojun Kuang, Jie Chen, Lunhua He, Qingran Ding, Sangen Zhao, Maochun Hong and Junhua Luo Li State Key Laboratory Structural Chemistry, Fujian Institute Research on the Structure Matter, Chinese Academy Sciences, Fuzhou, 350002 University Beijing 100049 Google Scholar More articles by this author , Yin MOE New Processing Technology for Nonferrous Metals Materials, Guangxi Electronic Materials Devices, College Science Engineering, Guilin Technology, Guilin, 541004 Yang Kuang *Corresponding author: E-mail Address: [email protected] Chen National Condensed Matter Physics, 100190 Songshan Lake Laboratory, Dongguan, Guangdong 523808 He Ding Zhao Innovation Optoelectronic Information China, 350108 https://doi.org/10.31635/ccschem.020.202000436 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesTrack Citations ShareFacebookTwitterLinked InEmail optical (NLO) switchable materials have attracted intense attention because their promising applications in optoelectronic devices. However, previous studies are mainly limited molecular-based compounds that usually exhibit narrow bandgaps. Here, we report all-inorganic Li9Na3Rb2(SO4)7 as an ultrawide-bandgap NLO material. To best our knowledge, sulfate shows widest bandgap (6.70 eV) among materials. Furthermore, it undergoes a reversible phase transition with high switching contrast about 180, which is almost highest known Variable-temperature X-ray neutron powder diffractions reveal exceptional can be attributed NLO-active [SO4]2− anions translating rotating local scale. This work will provide insights into development materials, may open up unprecedented opportunities emerging applications, such switches, sensors, optoelectronics. Download figure PowerPoint Introduction responses reversibly converted diverse stable states under external stimulation, considerable interest owing prospective application devices, data storage, information processing smart communication.1–5 Over past decades, researchers devoted great effort studying found number liquid phase.6,7 Meanwhile, variety efficient strategies been put forward explore solid-state crystalline cation exchange, conformational reorganization, “push–pull” molecules via photochromism.8–10 The resultant include metal–organic framework [(H2NMe2)2Cd3(C2O4)4]·MeOH·2H2O NH2-MIL-53 (Al), anil crystals N-(4-hydroxy)-salicylidene-amino-4-(methylbenzoate) N-(3,5-di-tert-butylsalicylidene)-4-aminopyridine, well complexes.8,9,11,12 Unfortunately, these show low contrasts reversibility. A new scheme, relying structural transitions, especially those from centrosymmetric (CS) structures noncentrosymmetric (NCS) structures, has recently employed inspire sharp changes responses. In 2006, Mercier et al.13 first reported transformation-induced phenomenon compound, [{H3N(CH2)2SS(CH2)2NH3}PbI5]·H3O. Subsequently, series were discovered, [α-(H3N(CH2)2S-S(CH2)2NH3)BiI5,14 (Hdabco+)(CF3COO−),15 bis(imidazolium) L-tartrate,16,17 2-(hydroxymethyl)-2-nitro-1,3-propanediol,18 (C4H10N)(CdCl3),19 dipropylammonium trichloroacetate,20 (R-CTA)2CuCl4,21 (S-CTA)2CuCl4.21 despite excellent performance, bandgaps relatively account π-conjugated electrons, d-d or f-f transition, [α-(H3N(CH2)2S-S(CH2)2NH3]BiI5 (∼1.84 eV),14 L-tartrate (∼5.21 eV),17 trichloroacetate (∼3.82 eV).20 As result, merely used visible ultraviolet spectral regions. With respect deep region (bandgap more than 6.20 eV), they play unique crucial role modern instruments, but approaches theoretical limit materials.22,23 Hence, date, there still huge opening Recently, group sulfates, Li8NaRb3(SO4)6•2H2O24 (NH4)2NaLi(SO4)2.25 Particularly, (NH4)2NaLi(SO4)2 exhibits aroused nearly parallel nonbonding O 2p orbitals groups, not switchable.25 result continuous successfully synthesized high-temperature melt, namely ( I) ultrawide 6.70 eV, presents working range ever known. Uniquely, I NCS state (P3) CS (P 3 ¯ ) 180. Experimental Methods Synthesis Polycrystalline was traditional method using Li2SO4•H2O (99.0%), Rb2SO4 Na2SO4 (99.0%) stoichiometric molar ratio. mixture fully ground transferred muffle furnace. After that, preheated at 723 K 24 h. products gradually heated 823 sintered 96 h several intermediate mixings grindings. purity as-synthesized polycrystalline samples checked diffraction (XRD) analyses, performed Rigaku MiniFlex 600 diffractometer Cu Kα radiation (λ = 1.5418 Å) 2θ 10°–70° scan rate 1° min−1 room temperature. Crystal growth Single grown top-seeded solution method. powders Φ 45 × mm platinum crucible melted 973 temperature-programmable melt held form transparent solution. Then, quickly cooled 900 K, wire dipped rapidly saturation temperature, then formed cooling 2 h−1. crystal process completed, drawn out served seed crystals. following procedure, determined crystallized temperature tentative strategy as-grown good quality introduced 10 above 60 min dropped min. centimeter-grade single down 0.2–0.5 per day. Finally, pulled characterization variable (VT)-XRD analyses carried Panalytical X’Pert PRO Anton Parr HTK 1200 N attachment. VT-XRD over 10–80° collected 783 increment 100 except 733–783 close interval K. Time-of-flight (NPD) temperatures general-purpose China Spallation Neutron Source. time-of-flight NPD both refined Rietveld methods TOPAS-Academic software26 Jana2006 software.27 100(2) single-crystal XRD Bruker APEX II CCD monochromatic Mo radiation. program APEX3 perform cell refinements reductions.28 structure established direct SHELXS least-squares SHELXL.29 Final included anisotropic displacement parameters. solved verified PLATON,30 no higher symmetries recommended. Property measurements Elemental Jobin Yvon Ultima inductively coupled plasma emission spectrometer. thermal stability investigated differential scanning calorimetric (DSC) thermogravimetric (TG) NETZSCH STA 449C simultaneous analyzer instrument. About 22 mg placed Al2O3 crucibles, heating 660 820 dependence dielectric constant TongHui TH2828 680–790 min−1. transmittance spectrum acquired PerkinElmer LAMBDA 950 UV/Vis/NIR spectrophotometer wavelength 185–800 nm plate. Powder second harmonic generation (SHG) Kurtz–Perry Q-switched Nd:YAG laser λ 1064 nm.31 sieved particle size ranges: 53–75, 75–125, 125–180, 180–250, 250–300 μm. Infrared spectra obtained infrared instrument wavenumber 400–4000 cm−1. bands ranging 1006 1223 cm−1 stretching vibrations tetrahedra Supporting Figure S2). absorption 423 646 assigned bending modes Results Discussion Pure (Figure 1a). element gave ratio Li:Na:Rb:S 9.16∶2.71∶2.21∶6.78, consistent compositions data. illustrated 2a, DSC curves imply melts congruently around 874.8 bulk its top-seed technique. sizes 18 mm3 1b). Interestingly, heating/cooling curves, pair small peaks observed 771.7 (Tc) 759.4 2a). At same time, obvious weight loss TG analysis Thus, speculated Tc, additional analyses. indicated 2b, reproducible, proving occurs. For convenience, Tc denoted (HTP), below marked low-temperature (LTP). We also measured various frequencies. shown Figures 2c 2d, evident peak anomalies near Tc. 1 | patterns photograph I. (a) Calculated experimental (b) Photograph crystal. Scale bar, mm. further confirm Considering neutrons sensitive atoms, atoms negative scattering lengths Na, Rb, S [neutron (fm) are: −1.90; 3.63; 7.09; 5.803; 2.847],32 possible positions better different temperatures. method.33 3a, seen process. It significant reorganization course transition. 4a, situ plots similar 763 changed dramatically Several reflections including (361), (171), (161), (251), (440) disappeared. Also, background profiles displayed broad d 1.5 Å within 2.0–2.7 disorder occurs initially 1.0–1.5 expands larger increasing view large length absence patterns, conclude most probably related thermally activated motion anions. addition, fitted lattice parameters volumes 3b) 4b) abrupt 743 Tables S1–S12 list detailed crystallographic information. “Film plot” heating. VT against vertical dashed line marks occurrence crystallizes space P3 (No. 143) LTP P 147) HTP. 5a, features three-dimensional (3D) tetrahedral framework, basal plane ab apical bonds c-axis, composed LiO4 tetrahedra. Na+ Rb+ distributed well-ordered manner cavities maintain balance. There nine crystallographically independent sites LTP. [S4O4]2− [S6O4]2− alternatively linked sharing corners construct hexagonal pillars 5b) three-fold axis. [S5O4]2− occupy central pillars. HTP considered locally HTP, all partially occupied two equivalent positions, disturbing ordered alignment units. arrangements retain feature LTP, one arrangement 5c. compared 5d), tilted away plane. axis translate along c-axis. Due shift, strains plane, leads noticeable elongated c-axis (Figures 5e 5f). order reduce strain, cavity, reflected radius R 3.87 (LTP) 4.03 (HTP). Owing reminiscent anionic Li+, Na+, cations confined likely move become highly disordered melting behavior called quasi-melting 5 viewing tetrahedra, highlighted yellow circle (a). terahedra (c) (e) b-axis, comparison (d) (f) b-axis. green represent denotes pillar. clarify, omitted 5c–5f. obtain accurate bandgap, polished (the inner picture 6a) test. demonstrated 6a, 185 nm, corresponds eV. far aware, exceeds many [α-(H3 N(CH2)2 S-S(CH2)2NH3]BiI5 2-(hydroxymethyl)-2-nitro-1,3-propanediol (∼6.20 eV),18 6 properties Transmittance spectrum. sample measurements. SHG intensity versus nm. red curve guide eyes does fit VT-SHG between SHG-on SHG-off signal state. Completely recoverable intensity. Given expected properties, is, First, intensities tested method31 6b, increase sizes, showing phase-matchable. Besides, size, 1.3 times benchmark material KH2PO4 S3), some NH4NaLi2(SO4)2 (1.1 KH2PO4),25 (NH4)2Na3Li9(SO4)7 (0.5 Li8NaRb3(SO4)6·2H2O KH2PO4).24 sample. 6c, stay wide until When continues increase, drop completely disappear quite weak noise errors. According reports,9,18 defined states. Therefore, Notably, (∼1.75)8 (Al) (∼38),9 ionic salts (Hdabco+)CF3COO−) (∼35),15 bis(imidazolium hydrochlorate) dihydrate 18-crown-6 (∼12),34 NH4[(CH3)4N]SO4·H2O (∼24),35 single-component plastic (∼150)18 [CH3C(NH2)2]ClO4 (∼62),36 organic–inorganic hybrid [C6H11NH3]2[CdCl4] (∼1.3)37 [C4H10N][CdCl3] (∼8).19 sole appears imidazolium-FCrO3 (∼250).38 Moreover, recover without any attenuation after cycles, indicating reversibility 6d). Evidently, fascinating candidate facile growth, stability, 4 Temperature-dependent Because disordered, difficult carry popular first-principle calculations. understand structure–property relationships contrast, calculated dipole moments bond-valence instead.39 Based famous theory,40 should groups determining I, proved studies,24 so only calculated. Detailed results provided Table S13. vector summation geometry gives rise overall moment 4.60 D unit z direction, microscopic susceptibilities constructive generate increases occurs, makes rotate scale becomes CS, canceled zero, leading rationalized ascribed resulting translation rotation 623 black box panel indicates where appear. Temperature frequencies run kHz. Conclusion summary, Li9Na3Rb2(SO4)7. eV 180 primary suggest outstanding originates These highlight sulfates source believe inspiration exploring contrasts, potential future, available. Conflict Interest conflict report. Funding research supported Nature Foundation (21833010, 61975207, 21622101, 21921001, 21525104, 51662013), Strategic Priority Program Sciences (XDB20000000 XDB20010200), Natural Province (2018H0047), Frontier (ZDBS-LY-SLH024), (2018GXNSFDA281015), Development (2019YFA0210400), Functional Crystals Laser TIPC, CAS (FCLT 202003), Metal & Ministry Education/Guangxi Devices (20KF-11). References 1. Itkis M. E.; Chi X.; Cordes A. W.; Haddon R. C.Magneto-Opto-Electronic Bistability Phenalenyl-Based Neutral Radical.Science2002, 296, 1443–1445. 2. Stuart C.; Huck W. T. S.; Genzer J.; Müller M.; Ober Stamm Sukhorukov G. B.; Szleifer I.; Tsukruk V. V.; Urban Winnik F.; Zauscher Luzinov Minko S.Emerging Applications Stimuli-Responsive Polymer Materials.Nat. Mater.2010, 9, 101–113. 3. Champagne Plaquet A.; Pozzo J.-L.; Rodriguez Castet F.Nonlinear Molecular Switches Selective Cation Sensors.J. Am. Chem. Soc.2012, 134, 8101–8103. 4. 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