ASbF3Cl (A = Rb, Cs): Structural Evolution from Centrosymmetry to

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ASbF3Cl (A= Rb, Cs): Structural Evolution from Centrosymmetry to Noncentrosymmetry Pifu Gong, Yi Yang, Fengguang You, Xinyuan Zhang, Gaomin Song, Shengzi Zhang, Qian Huang, and Zheshuai Lin Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 24 Jan 2019 Downloaded from http://pubs.acs.org on January 24, 2019

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Crystal Growth & Design

ASbF3Cl (A= Rb, Cs): Structural Centrosymmetry to Noncentrosymmetry

Evolution

from

Pifu Gong,†,# Yi Yang,†,‖,# Fengguang You,†, ‖ Xinyuan Zhang,‡ Gaomin Song,†, ‖ Shengzi Zhang,†, ‖ Qian Huang,§ and Zheshuai Lin†,‖,* † Technical

Institute of Physics and Chemistry, CAS, Beijing 100190, China. College of Functional Crystals, Tianjin University of Technology, Tianjin 300384, China § Institute of Engineering Thermophysics, CAS, Beijing 100190, China. ‡

‖

University of the Chinese Academy of Sciences, Beijing 100049, China.

ABSTRACT: The alkali metals Rb+ and Cs+ involving structural evolution from centrosymmetric (CS) to noncentrosymmetric (NCS) is investigated in the ASbF3Cl compounds. RbSbF3Cl crystallizes in orthorhombic centrosymmetric space group of Pbca, while CsSbF3Cl crystallizes in tetragonal noncentrosymmetric space group of I-42m, although they both consist of [SbF3Cl2] units and alkali metal cations. The CS to NCS evolution is originated from the structural dimensional reduction owing to the accommodation the relatively larger alkali metal cations. RbSbF3Cl and CsSbF3Cl are stable under 195 °C and 205°C, respectively, and their energy band-gaps are about 3.30 eV and 3.05 eV. Powder second harmonic generation (SHG) measurements show that CsSbF3Cl is phase-matchable with response of 0.3 times of KH2PO4. Moreover, first-principles calculations are performed to investigate the origin of SHG effects in CsSbF3Cl.

1. Introduction Metal halides have played more and more important roles in photoelectronic functional materials.1-3 They have been widely used in photovoltaics, light emitting diodes (LEDs), nonlinear optical (NLO) materials, lasers, and photodetectors.4-6 For example, the organic-inorganic hybrid halides perovskites, especially CH3NH3PbI3, as the light absorbing materials in solar cells, have successfully improved the power conversion efficiency to ~ 22.7% in late 2017.7 In these compounds the flexible connecting modes of fundamental building units [MXk], where M is the central metal cation and X is the halide anion with k varying from 2 to 6, result in large structural diversity. Due to the remarkable structural diversity and photoelectric functions, it is important and valuable to explore new metal halide compounds. Owing to the relatively large energy band-gaps and excellent infrared (IR) transparency, metal halides can be considered as good candidates for IR NLO performances.8-13 The Sb-based metal halides possess stereoactive lone-pair electrons (LPE) whose ordered arrangement would produce large NLO responses and they are beneficial to achieve high efficiencies of laser frequency conversion.14-16 In 1978, Bergman firstly reported the structure and NLO properties of Na2SbF5,17 whose band-gap is about 5.0 eV and SHG effect is 0.17 × KDP. Afterwards, structure modification and halogen replacement were carried out and many new NLO materials, such as SbF3,18 NaSb3F10,19 and K2SbF3Cl20 were obtain with enhanced SHG effects. However, the frameworks of the mentioned compounds are constructed by the isolated fundamental building units ([SbF3] or [SbF3Cl2] units) and the monotonous arrangement is unfavorable for the research of structural diversity and relationships of structure-properties.

In order to serve as NLO materials, metal halides must crystallize in the NCS space groups. Therefore, molecular engineers to construct NCS structures have become important in this field. Attributed to the difference of radius, replacement of alkali metal cations will result in the structural modification and further lead to the construction of NCS space groups. In general, the large structural evolutions in alkali metal compounds would happen when the cation replacement occur between Li+ and Na+ or between Na+ and K+ for their large inconsistence in radius (>20%). In comparison, those between the larger alkali metal cations, especially between Rb and Cs, rarely result in the evolution between CS and NCS structures due to their relatively small radius difference (~10%). Our group has been carrying out new material explorations and performance characterizations for the metal halide compounds in order to enrich their structural diversity and photoelectric functions.21-24 ASbF3Cl compounds were reported in 1976 and only their thermal properties were studied.25, 26 In this work, RbSbF3Cl and CsSbF3Cl are synthesized and systematically investigated. Interestingly, RbSbF3Cl crystallizes in a CS structure, while CsSbF3Cl crystallizes in a NCS structure, despite of their similar chemical constitutions. The alkali metal involving structural evolution is elucidated and the second-order NLO performance of CsSbF3Cl is evaluated. Moreover, experimental and ab-initio studies are carried out to characterize these two compounds. 2. Experimental Section 2.1. Synthesis Hydrothermal method are carried out to obtain the single crystals of RbSbF3Cl and CsSbF3Cl with RbCl or CsCl (Aladdin, 99.0%), SbF3 (SCR, 98.0%) and HCl (Aladdin, 40%)

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as the raw materials. RbCl (0.0238 mol), SbF3 (0.0044 mol), and 0.5ml HCl were mixed and dissolved in H2O (1.0 mL) to obtain RbSbF3Cl. The solution was fully mixed and further sealed into an autoclave equipped with a Teflon liner (25 ml). Hold at 240 °C for 1 day, the temperature was slowly cooled to the room temperature at a rate of 3 °C/h. For CsSbF3Cl, about 1g (0.0238 mol) CsCl, 2g (0.0044 mol) SbF3, and 0.5ml HCl were dissolved in H2O (1.5 mL) and the following operations were same with that as synthesized RbSbF3Cl. Their chemical reaction equations were: Rb(Cs)Cl + SbF3→ Rb(Cs)SbF3Cl↓. After reactions, the reaction products were washed with ethanol and dried in air and Colorless single crystals of RbSbF3Cl and CsSbF3Cl (see Figure S1) were obtained. 2.2. Single-Crystal Structure Determination A Rigaku AFC10 diffractometer equipped with a graphitemonochromated Kα (λ= 0.71073 Å) radiation was chosen for the data collection of single crystal X-ray diffraction (XRD) measurements. Single crystals of RbSbF3Cl and CsSbF3Cl with suitable sizes were selected on a 'multiwire proportional diffractometer for diffraction data collection at 298.3 K. The face-indexed absorption corrections is carried out based on the XPREP program. Using Olex2,27 the structures were solved using Intrinsic Phasing with the ShelXT28 structure solution program and refined using Least Squares minimization with the ShelXL29 refinement package. The ADDSYM algorithm from the program PLATON was used for structural verified,30 and no higher symmetries were found. 2.3. Powder X-ray Diffraction An automated Bruker D8 Focus X-ray diffractometer equipped with a diffracted monochromator set for Cu Kα ( λ = 1.5418 Å) radiation was used for the powder X-ray diffraction (PXRD) of the polycrystalline RbSbF3Cl and CsSbF3Cl at about 300K. Scanning step width of 0.02° and the scanning rate of 0.1° s-1 were chosen to record the patterns in the 2 theta range of 5-70°. After measurement, the experimental PXRD patterns agree well with the simulated ones deduced from the single crystal crystallographic data (shown in Figure 1). 2.4. UV-Vis-NIR Diffuse Reflectance Spectroscopy SolidSpec-3700 DUV spectrophotometer was used for the collection of UV−vis−NIR diffuse reflectance spectra of RbSbF3Cl and CsSbF3Cl. The measured wavelength range was set to be 200 - 1400 nm and fluororesin was applied as the standard. 2.5. Thermal Stability Measurement About 10 mg of RbSbF3Cl and CsSbF3Cl were used for the differential thermal analysis (DTA) and thermogravimetric (TG) analysis. These measurements are carried out by the NETZSCH STA-2500 thermal analyzer. The measured temperature range is from room temperature to 900°C with the rate of 20 C/min. 2.6 Nonlinear Optical Property The Kuttz-Perry method was chosen for the powder SHG measurements for CsSbF3Cl.31 The fundamental 1064 nm laser source generated by a pulsed Q-switched Nd:YAG laser with a pulse width of 5 ns was applied. In order to measure the particle size dependent SHG effect, the CsSbF3Cl single crystals were ground and sieved into 30-50，50-61，61-76， 76-150, 150-212, and 212-300 um particle size ranges. As references, KDP were grounded and sieved into the same particle size ranges and used for powder SHG measurements. 2.7. Computational Method

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The theoretical calculations for electronic and optical properties of RbSbF3Cl and CsSbF3Cl were performed using CASTEP package.32 The Perdew, Burke and Ernzerhof (PBE) functionals33 based on the generalized gradient approximation (GGA)34 and the optimized norm-conserving KleinmanBylander pseudopotentials 35 are chosen for the calculations. Then Rb 4s24p65s1, Cs 5s25p66p1, Sb 5s25p3, F 2s22p5, and Cl 3s23p electrons were treated as valence electrons. The kinetic cutoff energy of 900 eV and the Monkhorst–Pack k-point meshes36 of 2×2×2 were chosen in the calculations. To rationalize the structural evolution, geometric optimizations are carried out to evaluate the total energy of both the experimental and hypothetical structures. According to our previous work, these computational parameters can guarantee the accuracy of present purpose.37

Figure 1. The experimental and calculated PXRD patterns of (a) RbSbF3Cl and (b) CsSbF3Cl.

3. Results and Discussion 3.1. Crystal structure Based on the single crystal XRD data, the crystal structures of RbSbF3Cl and CsSbF3Cl were solved and refined. The crystal data and structure refinement for RbSbF3Cl and CsSbF3Cl are exhibited in Table 1 and the atomic coordinates, atomic displacement parameters, bond distances and angles are shown in Table S1-S4. The PXRD patterns (Figure 1) for the obtained crystals and the calculated results derived from the single crystal data show good agreement, indicating the validity of structure determination. Table 1. Crystal data and structure refinement for RbSbF3Cl and CsSbF3Cl. Empirical formula

RbSbF3Cl

CsSbF3Cl

Formula weight Temperature/K Crystal system Space group a/Å b/Å c/Å Volume/Å3 Z ρcalcg/cm3 2 θ for collection/

299.67 298(2) orthorhombic Pbca 8.1372(5) 8.3717(6) 15.0823(11) 1027.44(12) 8 3.875 5.39 - 59.52 -13 ≤ h ≤ 13, -13 ≤ k ≤ 13, -14 ≤ l ≤ 15

347.11 298(3) tetragonal I-42m 9.9406(2) 9.9406(2) 11.6351(5) 1149.73(7) 8 4.011 7.368 - 54.99 -10 ≤ h ≤ 9, -10 ≤ k ≤ 10, -19 ≤ l ≤ 19

Index ranges


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Crystal Growth & Design

Reflections collected Data/restraints/parameters GOF on F2 Final R [I≥2σ (I)] Final R [all data]

8525 856/0/35 1.088 R1 = 0.0326, wR2 = 0.0657 R1 = 0.0380, wR2 = 0.0677

5702 1173/0/56 1.099 R1 = 0.0332, wR2 = 0.0705 R1 = 0.0344, wR2 = 0.0771

The structure of RbSbF3Cl is illustrated in Figure 2. This compound is isostructural with the reported homolog, KSbF3Cl and NH4SbF3Cl,38 and it crystallizes in the CS orthorhombic space group Pbca (No. 61). There are one Rb, one Sb, three F, and one Cl crystallographically unique positions in the symmetric unit and all the atoms are located at Wyckoff positions of 8c in RbSbF3Cl. All Sb atoms are fivefold coordinated with three fluorine anions and two chlorine anions to form the [SbF3Cl2] anionic groups. The Sb-F bonds vary from 1.933(3) Å to 1.948(3) Å and the Sb-Cl bonds are between 3.100(3) Å and 3.035(4) Å, both of which are comparable to those in Rb2SbCl3F2.39 These [SbF3Cl2] anionic groups further connected with each other by sharing the Cl anions and construct the [SbF3Cl]1 ∞ chains along the a-axis as shown in Figure 2b. These [SbF3Cl]1 ∞ chains are parallel in the a-b plane, while the adjacent chain are reserved arranged with each other, which cancels the macro polarity of RbSbF3Cl. The Rb+ cations are inserted in the spaces between the chains to balance the charges and each coordinates with five F- and three Cl- anions with the Rb-F bonds varying from 2.811(4) Å to 2.980(3) Å and the Rb-Cl ones from 3.3956(13) Å to 3.4622(15) Å (see Figure 2c).

Figure 2. (a) The crystal structure of RbSbF3Cl, (b) the arrangement of [SbF3Cl2] groups in [SbF3Cl]1 ∞ chain along aaxis, and (c) the coordinating environment of Rb cation.

Although possessing the similar chemical formula, CsSbF3Cl crystallizes in a totally different structure compared with RbSbF3Cl. As shown in Figure 3a, CsSbF3Cl crystallizes in the NCS tetragonal space group I-42m with unit cell parameters a = b = 9.9406(2) Å, c = 11.6351(5) Å. In the symmetric unit, Cs, Sb, F, and Cl occupy two, one, two, and one crystallographically unique positions, respectively, with Sb(1), Cs(2), Cs(3), Cl(4), F(5), and F(6) located at the Wyckoff positions of 8i, 4e, 4d, 8f, 8i, and 16j. Same as RbSbF3Cl, all the Sb atoms in CsSbF3Cl are five-fold coordinated with three fluorine anions and two chlorine anions to form the [SbF3Cl2] anionic groups. The Sb-F bond lengths vary from 1.920(9) Å to 1.972(6) Å and all the Sb-Cl bond lengths are equal of 2.9359(6) Å, both of which are

comparable to those reported before.40 In this structure, every four [SbF3Cl2] anionic groups connect with each other to construct the [Sb4F12Cl4] ring by sharing with the bridging Cl atom. These [Sb4F12Cl4] rings are dispersed located in the structure and parallelly arranged along the a-b plane. The Cs+ cations are inserted into the interval between the pseudo-plane consisted of the [Sb4F12Cl4] rings with the Cs(2) and Cs(3) cations are 10-fold and 7-fold coordinated with F- and Clanions, respectively (see Figure 3c and 3d). The Cs-F bonds vary from 3.148(7) Å to 3.611(2) Å and the Cs-Cl bonds are 3.575(2) Å or 3.661(3) Å.

Figure 3. (a) The crystal structure of CsSbF3Cl, (b) the [Sb4F12Cl4] ring consisted of four [SbF3Cl] groups sharing the bridging Cl, the local coordination environment of (c) Cs(2) and (d) Cs(3) cations in CsSbF3Cl.

3.2 Structural evolution It is interesting to investigate the influence of the A-site alkali metal cations to the structure evolution in the ASbF3Cl series. We carried out the first-principles calculations to obtain the energy difference between the total energies of orthorhombic(EO) and tetragonal-phases (ET) structures with different A-site alkali metal cations. In the simulation models, the alkali metal cations, K+, NH4+, Rb+ to Cs+ are incorporate into the orthorhombic- and tetragonal-phases ASbF3Cl structures, respectively, and then the geometry optimizations were performed. The energy differences between these phases (ETEO) with respect to alkali metal cations are exhibited in Figure 4a. The positive (or negative) value means that the orthorhombic (or tetragonal) phase structure is more stable. Clearly, for KSbF3Cl, NH4SbF3Cl and RbSbF3Cl the orthorhombic phase structures possess lower total energies than the tetragonal phase, while for CsSbF3Cl the tetragonal phase structure has lower energy. The calculated results are consistent with the experimental observations that the former three compounds are in the orthorhombic phase and the latter compound is in the tetragonal phase. Interestingly, the energy difference ET-EO decreases as the radius of alkali metal cation increases, indicating that the orthorhombic structure becomes gradually unfavorable as the size of alkali metal cations becomes larger.



Figure 6a exhibit the UV−vis−NIR diffuse-reflectance spectra for RbSbF3Cl and CsSbF3Cl. As the results shown, the shortest optical absorption edges are about 375 nm and 405 nm for RbSbF3Cl and CsSbF3Cl, respectively, corresponding to the energy band-gaps of 3.30 eV and 3.05 eV. The relatively large band gap also indicates the high laser damage thresholds for practical applications.41-43 The result of powder SHG measurements for NCS CsSbF3Cl is shown in Figure 6b. It is clear that SHG intensities grow gradually until it reaches a plateau with the particle sizes above 150 μm. As the results shown, CsSbF3Cl exhibit phasematchable powder SHG effect about 1/3 times as strong as that of KDP. Figure 4. (a) The calculated energy difference between the orthorhombic and tetragonal phases in ASbF3Cl and (b) comparison of atomic geometries between RbSbF3Cl and CsSbF3Cl from the viewpoint of structural evolution (scissors mean bond broken and red dash lines mean bond built).

Figure 4b exhibit the sketch map of structural evolution from RbSbF3Cl to CsSbF3Cl. As shown, the frameworks of ASbF3Cl are both composed of homologous [SbF3Cl2] units, and these units construct the pseudo-planes along the a-c and a-b planes in RbSbF3Cl and CsSbF3Cl, respectively, with the cations located between these layers. Owing to the relatively small size of Rb+ cations, in RbSbF3Cl there exists enough space to accommodate the [SbF3Cl]1 ∞ 1D infinite chains and Rb+, both of which exhibit the zigzag arrangement along the aaxis. When Rb+ cations are substituted by bigger Cs+ cations, the interstitial spaces are drastically compressed. Consequently, the Cs+ are pushed in lines along the a-axis and the [SbF3Cl]1 ∞ chains are broken in CsSbF3Cl. Specifically, one Sb-Cl bond in every two [SbF3Cl2] units (black scissors in Figure 4b) is broken to build the [Sb2F6Cl2] group with the whole unit rotating along the a-axis. Further, the resulted [Sb2F6Cl2] units connect with the ones in the neighboring chains to form the [Sb4F12Cl4] rings, which construct the frameworks in CsSbF3Cl. With this structural modification, the CS to NCS evolution occurs from RbSbF3Cl to CsSbF3Cl. 3.3. Thermal properties The thermal properties of the titled compounds are measured and the results are shown in Figure 5. As the picture shown, the thermal behaviors of these two compounds are similar. DTA analysis curves (blue lines in Figure 5) exhibit clear endothermic peaks at 195 °C and 205°C, which agree well with the decomposition temperatures shown in the TG curves (red lines in Figure 5). These test results indicate that RbSbF3Cl and CsSbF3Cl are stable under 195 °C and 205°C, respectively.

Figure 6. (a) The UV-vis-NIR diffuse reflectance spectra of ASbF3Cl and (b) particle size dependence of SHG intensity for CsSbF3Cl.

3.5. Electronic structures and SHG mechanism The electronic structure in RbSbF3Cl and CsSbF3Cl are investigated by the theoretical calculations based on the CASTEP package. As Figure 7a and 7c shown, RbSbF3Cl and CsSbF3Cl are indirect band-gap semiconductors with the calculated valued of 4.34 eV and 3.41 eV, respectively, both of which are comparable with the experimental values of 3.05 eV and 3.30 eV. It should be mentioned that these deviations between the calculated and experimental values are attributed to the discontinuity of exchange-correlation energy as used in GGA.44 Figure 7b and 7d exhibit the partial density of states (PDOS) nearby the band-gap of RbSbF3Cl and CsSbF3Cl and these two compounds show great similarities: (i) The states lower than -7 eV are mainly consisted of the localized innershell s- and p-orbitals of the constituent elements, which have little interaction with the neighboring atoms. (ii) The regions between the band-gap (-6 eV to 5 eV) are composed of not only the p- orbitals of F- (2p) and Cl- (3p) anions but also the 5s- and 5p- orbitals of Sb3+ cations, indicating the hybridization between these atoms. As shown in Figure S2, the Sb 5s orbitals occupy the topmost parts of the valence bands (VB), indicting the unneglectable effects of the lone pairs electrons. The Sb 5p orbitals exhibit strong hybridization with F- 2p and Cl- 3p. Therefore, the [SbF3Cl2] groups contribute most to the electronic states between the band-gap and further determine optical properties of RbSbF3Cl and CsSbF3Cl, which are in good agreement with the anionic group theory proposed by Chen.45

Figure 5. The DTA and TG curves for (a) RbSbF3Cl and (b) CsSbF3Cl.

3.4. Optical properties


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Crystal Growth & Design for the first time. Moreover, theoretical calculations reveal the origin of SHG effects and optical anisotropy in CsSbF3Cl. The researches of RbSbF3Cl and CsSbF3Cl can provide representative cases in the investigation of structuresproperties relationships and are beneficial for further NLO materials exploration in metal halides.

ASSOCIATED CONTENT Supporting Information. The Supporting Information is available free of charge on the ACS Publications website at http://pubs.acs.org. CIF files and additional data. Deposition CCDC number 1866955 for RbSbF3Cl and 1866956 for CsSbF3Cl.

AUTHOR INFORMATION Corresponding Author * [email protected].

Author Contributions. #

Figure 7. The electronic band structure and PDOS plot of RbSbF3Cl and CsSbF3Cl.

Table2 exhibit the calculated linear and nonlinear optical properties of CsSbF3Cl. As the results shown, the calculated NLO coefficient deff is about 0.10 pm/V, which agree well with the experimental value (~ 0.3KDP). At the wavelength () of 1064 nm and 2090 nm, the calculated birefringence for CsSbF3Cl are larger than 0.2, which is guaranteed by the phase-matchability based on the powder SHG measurements. Consider the relationship between structure and property, the large optical anisotropy of CsSbF3Cl may be originated from the pseudo-layered arrangement of the [Sb4F12Cl4] rings in the a-b plane. Nevertheless, the [SbF3Cl2] units in the [Sb4F12Cl4] rings point to the opposite orientations, which almost attenuates the polarity and thus results in the relatively weak NLO effect. Table 2. The calculated refractive indices, birefringence and NLO coefficients in CsSbF3Cl. Refractive indices and birefringence  (nm)

1064

2090

no ne

1.9231 1.6412

1.8975 1.6352

∆n

0.2819

0.2623

NLO coefficients (pm/V) d14 dpow

0.12 ~0.10 (~0.3KDP)

4. Conclusions Two Sb-based alkali metal mixed halide compounds, RbSbF3Cl and CsSbF3Cl, are successfully synthesized by hydrothermal method. Interestingly, the [SbF3Cl2] units in RbSbF3Cl construct the 1D chains while those in CsSbF3Cl form 0D [Sb4F12Cl4] rings. The CS to NCS evolution is originated from the structural dimensional reduction to accommodate the relatively larger Cs+ cations, which is revealed by the structural analysis combined with firstprinciples calculations. Both RbSbF3Cl and CsSbF3Cl exhibit high thermal stability up to 195 °C and 205°C, respectively, and their band-gap are about 3.30 eV and 3.05 eV. Powder SHG measurement show that CsSbF3Cl is phase-matchable with response about 0.3 times of KH2PO4, which is measured

These authors contributed equally.

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China under Grant (51702330, 51802321, and 51890864) and Fujian Institute of Innovation, Chinese Academy of Science. ZL acknowledges the support from Youth Innovation Promotion Association, Chinese Academy of Science.

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For Table of Contents Only ASbF3Cl (A= Rb, Cs): Structural Evolution from Centrosymmetry to Noncentrosymmetry Pifu Gong,†,# Yi Yang,†,‖,# Fengguang You,†,b Xinyuan Zhang,‡ Gaomin Song,†, ‖ Shengzi Zhang,†, ‖ Qian Huang,§ and Zheshuai Lin†,‖,*

Centrosymmetric RbSbF3Cl and noncentrosymmetric CsSbF3Cl are synthesized. Although they are both consisted of [SbF3Cl2] units and alkali metal cations, the [SbF3Cl2] units in RbSbF3Cl construct 1D chains, while those in CsSbF3Cl form 0D [Sb4F12Cl4] rings. The alkali metal involving structural evolution is analyzed. Moreover, the experimental and ab-initio studies are carried out for these two compounds.


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ASbF3Cl (A = Rb, Cs): Structural Evolution from Centrosymmetry to

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