注册 English

Linear and nonlinear optical responses in perovskite-like formate salts

Lu QI ,  Congjiao RAN ,  Chao WU ,  Zhipeng HUANG ,  Chi ZHANG

downloadPDF
Citation:  Lu QI, Congjiao RAN, Chao WU, Zhipeng HUANG, Chi ZHANG. Linear and nonlinear optical responses in perovskite-like formate salts[J]. Chinese Journal of Inorganic Chemistry, 2024, 40(1): 247-255. doi: 10.11862/CJIC.20230386 shu

类钙钛矿甲酸盐的线性和非线性光学响应

  • .

    同济大学化学科学与工程学院中澳功能分子材料联合研究中心, 上海 200092

  • #共同第一作者。
    • 通讯作者: 吴超, wuc@tongji.edu.cn
    张弛, chizhang@tongji.edu.cn
  • 基金项目:

    国家自然科学基金 51432006

    国家自然科学基金 52002276

    中国教育部长江学者创新团队计划 IRT14R23

    中国教育部和国家外国专家局111计划 B13025

摘要: 采用原位溶剂热法合成了2种混合有机阳离子杂化甲酸盐(CH (NH2)2)[RE (HCOO)4](RE=Y、Er)。这2种材料是同构的(手性空间群C2221)，并具有有趣的类钙钛矿结构。进行了包括线性和非线性光学特性在内的光物理研究。(CH (NH2)2)[Y(HCOO)4]和(CH (NH2)2)[Er (HCOO)4]分别表现出5.59和5.61 eV的宽光学带隙，对应于222和221 nm的紫外吸收边缘。粉末倍频测量表明，(CH (NH2)2)[Y (HCOO)4]和(CH (NH2)2)[Er (HCOO)4]的倍频效应分别是基准KH2PO4(KDP)的0.32和0.37倍。测量得到(CH (NH2)2)[Y (HCOO)4]和(CH (NH2)2)[Er (HCOO)4]的双折射率分别为0.013和0.015。第一性原理研究表明，2个π共轭的(CH (NH2)2)+和HCOO-基团是光学性质的主要贡献者。

English

  • Organic-inorganic hybrid materials are highly attractive in solar cells, photo-detectors, ferroelectrics, optical information processing, and laser frequency conversion due to their excellent performance and versatility[1-5]. Nonlinear optical (NLO) crystals can generate coherent laser light, which is widely used in photolithography and semiconductor manufacturing, and plays an important role in solid-state lasers[6-10]. Recently, a series of excellent organic-inorganic hybrid NLO crystals, such as (o-C5H4NHOH)2[I7O18(OH)]⋅3H2O[11], (C(NH2)3)6(PO4)2·3H2O[12], Cs3Cl(HC3N3S3)[13], and (2cepyH)SbBr4[14], have been developed. It is of great importance and interest to search for new functional building blocks as well as the as-constructed new organic-inorganic hybrid NLO crystals. Organic molecules play an important role in modulating the optical properties when designing organic-inorganic hybrid NLO crystals. π-Conjugated organic cations exemplified by (C(NH2)3)+ cation[15-16], melamine[17], and 4-hydroxypyridine[18], have been discovered and proved to be efficient NLO-active groups owing to their strong hyperpolarizability and polarizability anisotropy. Recently, Lin et al. adopted melamine and synthesized a potential ultraviolet NLO material (C3H7N6)2Cl2·H2O exhibiting a strong second harmonic generation (SHG) response and large birefringence[17]. (C(NH2)2NHNO2)+ is an excellent cationic NLO-active group, and the resultant material showed excellent NLO properties[19]. Inorganic anions are an important component of NLO materials. Significant efforts have been focused on these inorganic salts containing π-conjugated planar groups (e.g. BO33-, CO32-, NO3-), such as KBe2BO3F2[20], LiB3O5[21], β-Ba2B2O4[22], ABCO3F (A=K, Rb, B=Mg, Ca, Sr)[23], LiZn(OH)CO3[24], Bi3TeO6OH(NO3)2[25], RE(OH)2 NO3 (RE=La, Y, and Gd)[26]. However, owing to the intricate multiple inter-anion interactions, the combination of two types of π-conjugated groups into one structure to create new NLO materials is thus far underexploited[27].

    The organic-inorganic hybrid perovskites with general formula ABXn (n=3, 4) have attracted extraordinary attention in physics, chemistry, and materials science[28-30]. The unique structural feature offers tremendous possibilities for optical property tuning owing to the flexible and replaceable A, B, and X sites[31]. We report herein the construction of the NLO-active formate salts (CH(NH2)2)[RE(HCOO)4] (RE=Y, Er) containing the π-conjugated formamidine cation and formate anion. Both two materials are isostructural with perovskite-like structures. The synthesis, UV-Vis-NIR spectroscopy, SHG response, and birefringence are demonstrated. Density functional theory (DFT) calculation was performed to reveal relationships between linear and nonlinear optical properties and electronic states.

    1.   Experimental

    1.1   Reagents

    Yttrium nitrate (Y(NO3)3·6H2O, 99.99%, Xiya Reagent), erbium nitrate (Er(NO3)3·5H2O, 99%, Adamas Reagent), formamide (CH3NO, 99%, Adamas Reagent) were commercially available and used as received without further purification.

    1.2   Synthesis of (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4]

    A mixture of Y(NO3)3·6H2O (0.192 g, 0.50 mmol) and CH3NO (5 mL) was tightly sealed in a 23 mL autoclave equipped with a Teflon liner. The autoclave was heated at 110 ℃ for 72 h and then cooled slowly to room temperature at a rate of 3 ℃·h-1. The product was collected by vacuum filtration, washed with ethanol, and dried in the air. Colorless block crystals of (CH(NH2)2)[Y(HCOO)4] were isolated in a yield of 70% (based on Y) using a microscope. The same process was operated to synthesize compound (CH(NH2)2) [Er(HCOO)4] using Er(NO3)3·5H2O (0.222 g, 0.50 mmol), and CH3NO (5 mL). Pink block crystals were picked out in a yield of 75% (based on Er).

    1.3   Single crystal and powder X-ray diffraction

    Single-crystal X-ray diffraction data collection of (CH(NH2)2)[RE(HCOO)4] (RE=Y, Er) was carried out on a Bruker D8 VENTURE CMOS X-ray diffractometer using graphite-monochromated Mo Kα radiation (λ=0.071 073 nm) at room temperature. APEX Ⅱ software was applied to collect and reduce data. For (CH(NH2)2)[Y(HCOO)4], in a range of 3.25° < θ < 27.12°, a total of 10 270 reflections were collected and 1 150 were independent with Rint=0.049 1, of which 1 089 were observed with I > 2σ(I). For (CH(NH2)2)[Er(HCOO)4], in a range of 3.255° < θ < 27.14°, a total of 9 394 reflections were collected and 1 152 were independent with Rint=0.034 3, of which 1 129 were observed with I > 2σ(I). Semi- empirical absorption corrections based on equivalent reflections were applied for both data sets using the APEX Ⅱ program. The two structures of (CH(NH2)2)[RE(HCOO)4] (RE=Y, Er) were solved by direct methods and refined on F 2 by full-matrix least-squares methods using Olex2 software package[32-33]. All hydrogen atoms were placed in calculated positions and refined with a riding model. The detailed crystallographic data and structural refinement parameters of the two compounds are summarized in Table S1 (Supporting information). Selected bond distances (nm) and angles (°) are given in Table S2 and S3, while hydrogen-bonding interactions are provided in S4 and S5. Powder X-ray diffraction (PXRD) was used to confirm the phase purity of (CH(NH2)2)[RE(HCOO)4] (RE=Y, Er). The PXRD analysis of each sample was carried out on a Bruker D8 X-ray diffractometer equipped with Cu Kα radiation (λ=0.154 18 nm) in a 2θ range of 5°-80° with a step size of 0.02° at room temperature, and the working voltage and current were 40 kV and 40 mA, respectively.

    1.4   Energy-dispersive X-ray spectroscopy

    Elemental analyses were performed using energy-dispersive X-ray spectroscopy (EDS) with a field- emission scanning electron microscope (FESEM, Hitachi S-4800, Japan). The EDS analyses on (CH(NH2)2) [Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] confirm the presence of C, H, O, N, and Y/Er, which are evenly dispersed in both samples (Fig.S1).

    1.5   Infrared and UV-Vis-NIR diffuse reflectance spectra

    The infrared (IR) spectra were recorded on a Nicolet iS10 Fourier transform IR spectrometer (resolution 4 cm-1, spectral range 400-4 000 cm-1). Optical diffuse-reflectance spectra were collected on a Cary 5000 UV-Vis-NIR spectrophotometer over the spectral range 200-800 nm at room temperature and a BaSO4 plate was used as a 100% reflectance standard. Reflectance spectra were converted into absorbance spectra using the Kubelka-Munk function α/S=(1-R)2/(2R), where α is the absorption coefficient, S is the scattering coefficient that is practically wavelength-independent when the particle size is larger than 5 μm, and R is the reflectance[34].

    1.6   Thermal analysis

    A Netzsch STA 409PC thermal analyzer was used to analyze the thermal stabilities of (CH(NH2)2) [Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4]. The samples were heated from 30 to 800 ℃ with a heating rate of 15 ℃·min-1 under a nitrogen atmosphere.

    1.7   Powder SHG measurements

    The SHG intensities of (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] were measured employing the powder measurement method proposed by Kurtz and Perry[35]. A Q-switched Nd∶YAG laser with 1 064 nm radiation was employed for the visible SHG study. Because the SHG efficiency is related to the particle size, the polycrystalline samples of (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] were ground and sieved into several particle size ranges (0-26, 26-50, 50-74, 74-105, 105-150, 150-200, and 200-280 μm). Crystalline KDP with the same particle size ranges was used as references.

    1.8   Birefringence measurements

    The birefringences of (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] were assessed with a polarizing microscope (ZEISS Axio Scope. A1) equipped with a Berek compensator. The wavelength of the light source was 546 nm. The positive and negative rotation of compensation affords the relative retardation.

    1.9   Theoretical calculations

    First-principles calculations on (CH(NH2)2) [Er(HCOO)4] were performed using the CASTEP package[36], a total energy package based on pseudopotential DFT[37]. The correlation-exchange terms in the Hamiltonian were described by the functional developed by Perdew, Burke, and Ernzerhof in the generalized gradient approximation form[38-39]. Optimized norm-conserving pseudopotentials[40] in the Kleinman-Bylander form were adopted to model the effective interaction between the valence electrons and atom cores, which allows the choice of a relatively small plane-wave basis set without compromising the computational accuracy. A kinetic energy cutoff of 850 eV and dense Monkhorst-Pack[41] k-point meshes spanning less than 1.5×10-5 nm3 in the Brillouin zone were chosen.

    2.   Results and discussion

    2.1   Synthesis, phase purity, IR, and thermal stability

    The mixed organic cationic hybrid formates (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] was obtained through a mild solvothermal method. Both two crystals were synthesized directly by employing in situ reactions[42]. The phase purity of crystalline (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] were confirmed by PXRD (Fig.S2). The IR spectra of (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] were similar owing to their isostructural feature. The IR absorption bands and their assignments are shown in Fig.S3, and they are characteristic of N—H vibrations in the formamidine (CH(NH2)2)+ cation and formate HCOO- anion. (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] also exhibited similar thermal behavior (Fig.S4), and taking (CH(NH2)2)[Y(HCOO)4] as representative. The thermal analysis curve of (CH(NH2)2) [Y(HCOO)4] (Fig.S4a) exhibited three weight-loss steps: in the first stage (220-300 ℃), the weight loss of 28.85% was close to the calculated value of 28.57% by loss of 2CO and 2NH3. The second weight loss of 27.62% was close to the calculated value of 28.25% by loss of 1.5H2, 1.5CO, and CO2 in a range of 310-410 ℃. The minor weight loss of 6.38% that occurred in a range of 410-800 ℃ is due to the loss of CO2 (Calcd. 6.98%). The residue of (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] after 800 ℃ was confirmed as Y2O3/Er2O3 by PXRD (Fig.S5).

    2.2   UV-Vis-NIR diffuse reflectance spectra

    The study of optical diffuse reflectance spectra showcases that two crystalline materials could be classified among wide optical bandgap semiconductors possessing bandgaps of 5.59 and 5.61 eV for (CH(NH2)2) [Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4], respectively. (Fig. 1) The bandgaps increased slightly with the increase of atomic number for the lanthanide ions. The UV absorption edge of (CH(NH2)2)[Y(HCOO)4] was 222 nm, and there was no absorption peak ranging from 222 to 800 nm. (CH(NH2)2)[Er(HCOO)4] exhibited sharp absorption bands at 257, 380, 525, and 654 nm. The f-f or d-f typical transitions of the respective lanthanide􀃮 ions lead to these absorption peaks[43].

    Figure 1

    Figure 1.  UV-Vis-NIR diffuse reflectance spectra and the corresponding crystal morphologies (Inset) for (CH(NH2)2)[Y(HCOO)4] (a) and (CH(NH2)2)[Er(HCOO)4] (c); Bandgaps for (CH(NH2)2)[Y(HCOO)4] (b) and (CH(NH2)2)[Er(HCOO)4] (d)
    下载: 全尺寸图片 幻灯片

    2.3   Powder SHG response

    Based on the chiral structure with a space group of C2221, the powder SHG response was measured by the Kurtz-Perry method. The SHG intensities increased with the increasing of particle size in a range of 26-280 μm (Fig. 2a), indicating both (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] are phase-matchable crystals at the 1 064 nm laser. As shown in Fig. 2b, compounds (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2) [Er(HCOO)4] showed the SHG intensity of about 0.32 and 0.37 times that of KDP in a particle size range of 105-150 μm. Because (CH(NH2)2)[RE(HCOO)4] (RE=Y, Er) crystallizes in the C2221 space group, both crystals have one non-zero independent SHG coefficient (d14) under the restriction of Kleinman symmetry. The corresponding calculated SHG values of (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] were 0.71 and 0.29 pm·V-1, respectively. To quantify the specific SHG contributions from all units, a real-space atom-cutting method was employed. As shown in Table S6, the (CH(NH2)2)+ units made the dominant contributions to the SHG coefficient d14 (58.9% and 48.7%) with the HCOO- anions accounting for 25.0% and 28.2% for (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4], respectively. We conclude that (CH(NH2)2)+ and HCOO- groups play a decisive role in the SHG response, and the contributions of Y3+ and Er3+ to the SHG response should not be ignored.

    Figure 2

    Figure 2.  (a) Phase-matching curves of (CH(NH2)2)[Y(HCOO)4], (CH(NH2)2)[Er(HCOO)4], and KDP with 1 064 nm laser radiation; (b) Oscilloscope traces of the SHG signals for polycrystalline (CH(NH2)2)[Y(HCOO)4], (CH(NH2)2)[Er(HCOO)4], and KDP in a particle size range of 105-150 μm at λ=1 064 nm

    KDP sample serves as the reference.

    下载: 全尺寸图片 幻灯片

    2.4   Birefringence

    The birefringence of (CH(NH2)2)[RE(HCOO)4] (RE=Y, Er) single crystal was measured on a polarizing microscope (ZEISS Axio A1), which can achieve complete extinction (Fig. 3). The optical path difference of (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] with thicknesses of 158.1 and 167.3 μm were measured to be 2.055 and 2.510 μm, respectively. Birefringence occurs and causes the polarized light to decompose into two kinds of polarized light, which are fast polarized light and slow polarized light when polarized light enters an anisotropic single crystal. The generation of optical path difference between the fast polarized light and the slow polarized light is inevitable in this process. The optical path difference ΔR can be obtained by the Eq.: ΔR=|Ne-No|δ=δΔn, where ΔR denotes the optical path difference, Δn represents the birefringence, and δ is the thickness of the crystal. The derived birefringences were 0.013 and 0.015 for (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4], respectively, at the wavelength of 546 nm.

    Figure 3

    Figure 3.  Original crystals (a, d), crystal diagrams to achieve complete extinction (b, e), and thickness diagrams (c, f) of compounds (CH(NH2)2)[Y(HCOO)4] (a-c) and (CH(NH2)2)[Er(HCOO)4] (d-f)
    下载: 全尺寸图片 幻灯片

    2.5   Crystal structures and their relationships with optical properties

    Both (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2) [Er(HCOO)4] are isostructural, and we take (CH(NH2)2)[Y(HCOO)4] as representative. In (CH(NH2)2)[Y(HCOO)4], one Y3+ cation, two HCOO- groups, and one formamidinium cation form the asymmetric units. All of the Y atoms in the unit cell are equivalent and located at the origin. The central Y3+ is coordinated with the surrounding eight oxygen atoms to compose a YO813- polyhedron with four different Y—O bond lengths. As shown in Fig. 4a, the lengths of the Y—O bond are 0.228 6, 0.233 8, 0.239 9, and 0.241 0 nm, respectively. The 1D chain structure is composed of YO813- octahedra and π-conjugated HCOO- planar groups (Fig. 4b). The orientation of the C—H bonds in formic acid ligands is diverse, but the alignment in the same direction is consistent when forming 2D and 3D frames. This arrangement can be conducive to the NLO properties of the crystal. Each Y3+ ion links to eight neighboring Y3+ ions via formate bridges, to form the rhombohedral units′ network, and the unit has the two neighboring grids diagonally crossed by one anti-anti HCOO-. The 2D [Y(HCOO)n]∞ layers contain 12- membered rings (MRs) and 16-MRs viewed along the crystallographic c-axis (Fig. 4c). The 3D (CH(NH2)2) [Y(HCOO)4] framework possesses perovskite-like structure. The center of the polyhedron is occupied by the Y atom, and (CH(NH2)2+ cations in situ produced from formamide lie in a cage surrounded by a YO813- polyhedron. (Fig. 4d) The (CH(NH2)2)+ cations connect the adjacent [Y(HCOO)n]∞ layers through N—H…O hydrogen bonds, and the adjacent (CH(NH2)2)+ cations are arranged in opposite directions. It is beneficial to break the symmetry of the structure. However, the parallel and consistent orientation of (CH(NH2)2)+ in the diagonal rhombohedral cell cavity promotes its SHG response, and the strong covalent bonds of the π-conjugated cation (CH(NH2)2)+ can facilitate a relatively wide UV transparency. The combination of π-conjugated formate and formamidine groups can not only enhance the nonlinear optical properties of the compounds but also expand the bandgap. In light of anionic group theory, π-conjugated (CH(NH2)2)+ and HCOO- groups are suggested as possibilities to generate the SHG responses while also retaining the short UV absorption edge.

    Figure 4

    Figure 4.  (a) Coordination environment of Y3+ in (CH(NH2)2)[Y(HCOO)4], HCOO- ligand group and (CH(NH2)2)+ group; (b) 1D chain of [Y(HCOO)n]∞; (c) 2D [Y(HCOO)n]∞ layers containing 12-MRs and 16-MRs viewed from the c-axis direction; (d) 3D structure of the cavity-template units in a (CH(NH2)2)[Y(HCOO)4] crystal

    Symmetry codes: #1: 1-x, y, 3/2-z; #2: 1/2+x, 1/2-y, 1-z; #3: 1/2-x, 1/2-y, 1/2+z.

    下载: 全尺寸图片 幻灯片

    2.6   Theoretical calculations

    Linear and nonlinear optical properties are closely related to the characteristics of band structure, including bandgap and density of state (DOS). To further comprehend the relationships between electronic structure and optical properties, theoretical calculations using pseudopotential DFT methods were carried out to calculate the bandgap and DOS of (CH(NH2)2) [Er(HCOO)4]. As shown in Fig. 5a, the calculated band structure of (CH(NH2)2)[Er(HCOO)4] indicates that it possesses a direct bandgap of 4.52 eV with both the conduction band minimum (CBM) and the valence band maximum (VBM) located at the G point. These calculated values were smaller than the experimental value due to the underestimation of the bandgap with the DFT method. Fig. 5b shows the total and partial densities of states (TDOS and PDOS) of (CH(NH2)2) [Er(HCOO)4]. The VBs are mainly occupied by N2p, C2p, O2p and Er4f states. The CBs are primarily assigned to C2p and O2p states, with slight contributions from the Er4d orbital, which indicates that the electron transition is mainly contributed by inside excitation of (CH(NH2)2)+ and HCOO- groups, and slight contributions from ErO813- polyhedra. These results indicate that optical performance (bandgap, SHG response, and birefringence) of (CH(NH2)2)[Er(HCOO)4] determined by electronic transitions are mostly governed by the interaction of (CH(NH2)2)+ and HCOO- groups.

    Figure 5

    Figure 5.  (a) Energy band structures, (b) TDOS and PDOS of compound (CH(NH2)2)[Er(HCOO)4]
    下载: 全尺寸图片 幻灯片

    3.   Conclusions

    In summary, two isomeric rare-earth formate nonlinear optical materials (CH(NH2)2)[RE(HCOO)4] (RE=Y, Er) were successfully synthesized through an in situ solvothermal method and comprehensively determined by various types of spectroscopic techniques. They exhibit perovskite-like structures where the negatively charged cavity of the [RE(HCOO)4]- anionic framework is occupied by the (CH(NH2)2)+ cations. The powder SHG measurements indicated that (CH(NH2)2)[RE(HCOO)4] (RE=Y, Er) possess phase-matchable SHG responses in the visible regions. Linear optical studies show that (CH(NH2)2)[Y(HCOO)4] and (CH(NH2)2)[Er(HCOO)4] exhibited optical bandgaps of 5.59 and 5.61 eV, and birefringences of 0.013 and 0.015, respectively. DFT calculations show that the optical characteristics are mainly attributed to the synergistic effects of two π-conjugated (CH(NH2)2)+ and HCOO- groups. This work highlights that the introduction of π-conjugated formamidine cations into formate systems may be an effective approach for the development of excellent NLO materials.


    Supporting information is available at http://www.wjhxxb.cn
    #共同第一作者。
    1. [1]

      Parola S, Julián-López B, Carlos L D, Sanchez C. Optical properties of hybrid organic-inorganic materials and their applications[J]. Adv. Funct. Mater., 2016, 26(36):  6506-6544. doi: 10.1002/adfm.201602730

    2. [2]

      Chen X, Wang Y R, Chai R, Xu Y, Li H R, Liu B Y. Luminescent lanthanide-based organic/inorganic hybrid materials for discrimination of glutathione in solution and within hydrogels[J]. ACS Appl. Mater. Interfaces, 2017, 9(15):  13554-13563. doi: 10.1021/acsami.7b02679

    3. [3]

      Wang H L, Dong Z J, Liu H C, Li W P, Zhu L Q, Chen H N. Roles of organic molecules in inorganic CsPbX3 perovskite solar cells[J]. Adv. Energy Mater., 2020, 11(1):  2002940.

    4. [4]

      Jin H L, Li J, Iocozzia J, Zeng X, Wei P C, Yang C, Li N, Liu Z P, He J H, Zhu T J, Wang J C, Lin Z Q, Wang S. Hybrid organic-inorganic thermoelectric materials and devices[J]. Angew. Chem. Int. Ed., 2019, 58(43):  15206-15226. doi: 10.1002/anie.201901106

    5. [5]

      Zhang Z P, Liu X, Liu X M, Lu Z W, Sui X, Zhen B Y, Lin Z S, Chen L, Wu L M. Driving nonlinear optical activity with dipolar 2-aminopyrimidinium cations in (C4H6N3)+(H2PO3)-[J]. Chem. Mater., 2022, 34(4):  1976-1984. doi: 10.1021/acs.chemmater.2c00002

    6. [6]

      Wu C, Jiang C B, Wei G F, Jiang X X, Wang Z J, Lin Z S, Huang Z P, Humphrey M G, Zhang C. Toward large second-harmonic generation and deep-UV transparency in strongly electropositive transition metal sulfates[J]. J. Am. Chem. Soc., 2023, 145(5):  3040-3046. doi: 10.1021/jacs.2c11645

    7. [7]

      Jiang C B, Jiang X X, Wu C, Huang Z P, Lin Z S, Humphrey M G, Zhang C. Isoreticular design of KTiOPO4-like deep-ultraviolet transparent materials exhibiting strong second-harmonic generation[J]. J. Am. Chem. Soc., 2022, 144(44):  20394-20399. doi: 10.1021/jacs.2c08403

    8. [8]

      Wu C, Lin L, Jiang X X, Lin Z S, Huang Z P, Humphrey M G, Halasyamani P S, Zhang C. K5(W3O9F4)(IO3): An efficient mid-infrared nonlinear optical compound with high Laser damage threshold[J]. Chem. Mater., 2019, 31(24):  10100-10108. doi: 10.1021/acs.chemmater.9b03214

    9. [9]

      Mutailipu M, Poeppelmeier K R, Pan S L. Borates: A rich source for optical materials[J]. Chem. Rev., 2021, 121(3):  1130-1202. doi: 10.1021/acs.chemrev.0c00796

    10. [10]

      Becker P. Borate materials in nonlinear optics[J]. Adv. Mater., 1998, 10(13):  979-992. doi: 10.1002/(SICI)1521-4095(199809)10:13<979::AID-ADMA979>3.0.CO;2-N

    11. [11]

      Chen Q Q, Hu C L, Chen J, Li Y L, Li B X, Mao J G. [o-C5H4NHOH]2[I7O18(OH)]⋅3H2O: An organic-inorganic hybrid SHG material featuring an [I7O18(OH)]∞2- branched polyiodate chain[J]. Angew. Chem. Int. Ed., 2021, 60(32):  17426-17429. doi: 10.1002/anie.202106335

    12. [12]

      Wu C, Jiang X X, Wang Z J, Sha H Y, Lin Z S, Huang Z P, Long X F, Humphrey M G, Zhang C. UV solar-blind-region phase-matchable optical nonlinearity and anisotropy in a π-conjugated cation-containing phosphate[J]. Angew. Chem. Int. Ed., 2021, 60(27):  14806-14810. doi: 10.1002/anie.202102992

    13. [13]

      Li M J, Zhang X, Xiong Z Y, Li Y Q, Zhou Y, Chen X, Song Y P, Hong M C, Luo J H, Zhao S G. A hybrid antiperovskite with strong linear and second-order nonlinear optical responses[J]. Angew. Chem. Int. Ed., 2022, 61(42):  e202211151. doi: 10.1002/anie.202211151

    14. [14]

      Qi Z K, Chen Y L, Gao H Z, Zhang F Q, Li S L, Zhang X M. Two SbX5-based isostructural polar 1D hybrid antimony halides with tunable broadband emission, nonlinear optics, and semiconductor properties[J]. Sci. China Chem., 2021, 64:  2111-2117. doi: 10.1007/s11426-021-1076-9

    15. [15]

      Luo M, Lin C S, Lin D H, Ye N. Rational design of the metal-free KBe2BO3F2 (KBBF) family member C(NH2)3SO3F with ultraviolet optical nonlinearity[J]. Angew. Chem. Int. Ed., 2020, 59(37):  15978-15981. doi: 10.1002/anie.202006671

    16. [16]

      Jin C C, Zeng H, Zhang F, Qiu H T, Yang Z H, Mutailipu M, Pan S L. Guanidinium fluorooxoborates as efficient metal-free short-wavelength nonlinear optical crystals[J]. Chem. Mater., 2021, 34(1):  440-450.

    17. [17]

      Liu L H, Hu C L, Bai Z Y, Yuan F F, Huang Y S, Zhang L Z, Lin Z B. 2(C3H7N6)+·2Cl-·H2O: An ultraviolet nonlinear optical crystal with large birefrigence and strong second-harmonic generation[J]. Chem. Commun., 2020, 56(93):  14657-14660. doi: 10.1039/D0CC06558G

    18. [18]

      Lu J, Liu X, Zhao M, Deng X B, Shi K X, Wu Q R, Chen L, Wu L M. Discovery of NLO semiorganic (C5H6ON)+(H2PO4)-: Dipole moment modulation and superior synergy in solar-blind UV region[J]. J. Am. Chem. Soc., 2021, 143(9):  3647-3654. doi: 10.1021/jacs.1c00959

    19. [19]

      Yan D, Ren M M, Liu Q, Mao F F, Ma Y, Tang R L, Huang H B, Zhang B B, Zhang X D, Li S F. [C(NH2)2NHNO2][C(NH2)3](NO3)2: A mixed organic cationic hybrid nitrate with an unprecedented nonlinear-optical-active unit[J]. Inorg. Chem., 2023, 62(12):  4757-4761. doi: 10.1021/acs.inorgchem.3c00556

    20. [20]

      Chen C T, Wang G L, Wang X Y, Xu Z Y. Deep-UV nonlinear optical crystal KBe2BO3F2-discovery, growth, optical properties and applications[J]. Appl. Phys. B, 2009, 97:  9-25. doi: 10.1007/s00340-009-3554-4

    21. [21]

      Chen C T, Wu Y C, Jiang A D, Wu B C, You G M, Li R K, Lin S J. New nonlinear-optical crystal: LiB3O5[J]. J. Opt. Soc. Am. B, 1989, 6(4):  616-621. doi: 10.1364/JOSAB.6.000616

    22. [22]

      Knyrim J S, Römer S R, Schnick W, Huppertz H. High-pressure synthesis and characterization of the alkaline earth borate β-BaB4O7[J]. Solid State Sci., 2009, 11(2):  336-342. doi: 10.1016/j.solidstatesciences.2008.07.015

    23. [23]

      Zou G H, Ye N, Huang L, Lin X S. Alkaline-alkaline earth fluoride carbonate crystals ABCO3F (A=K, Rb, Cs; B=Ca, Sr, Ba) as nonlinear optical materials[J]. J. Am. Chem. Soc., 2011, 133(49):  20001-20007. doi: 10.1021/ja209276a

    24. [24]

      Liu X M, Kang L, Gong P F, Lin Z S. LiZn(OH)CO3: A deep-ultraviolet nonlinear optical hydroxycarbonate designed from a diamond-like structure[J]. Angew. Chem. Int. Ed., 2021, 60(24):  13574-13578. doi: 10.1002/anie.202101308

    25. [25]

      Zhao S G, Yang Y, Shen Y G, Zhao B Q, Li L N, Ji C M, Wu Z Y, Yuan D Q, Lin Z S, Hong M C, Luo J H. Cooperation of three chromophores generates the water-resistant nitrate nonlinear optical material Bi3TeO6OH(NO3)2[J]. Angew. Chem. Int. Ed., 2017, 56(2):  540-544. doi: 10.1002/anie.201609876

    26. [26]

      Song Y X, Luo M, Lin C S, Ye N. Structural modulation of nitrate group with cations to affect SHG responses in RE(OH)2NO3 (RE=La, Y, and Gd): New polar materials with large NLO effect after adjusting pH values of reaction systems[J]. Chem. Mater., 2017, 29(2):  896-903. doi: 10.1021/acs.chemmater.6b05119

    27. [27]

      Li M J, Wang Z Y, Ahmed B, Li Y Q, Wang H, Song Y P, Song X Y, Kuang X J, Luo J H, Zhao S G. A second-order nonlinear optical material consisting of two π-conjugated groups[J]. ChemPlusChem, 2023, 88(3):  e202300094. doi: 10.1002/cplu.202300094

    28. [28]

      Shaw B K, Hughes A R, Ducamp M, Moss S, Debnath A, Sapnik A F, Thorne M F, McHugh L N, Pugliese A, Keeble D S, Chater P, Bermudez-Garcia J M, Moya X, Saha S K, Keen D A, Coudert F X, Blanc F, Bennett T D. Melting of hybrid organic‑inorganic perovskites[J]. Nat. Chem., 2021, 13(8):  778-785. doi: 10.1038/s41557-021-00681-7

    29. [29]

      Gomez-Aguirre L C, Pato-Doldan B, Mira J, Castro-Garcia S, Senaris-Rodriguez M A, Sanchez-Andujar M, Singleton J, Zapf V S. Magnetic ordering-induced multiferroic behavior in [CH3NH3][Co(HCOO)3] metal-organic framework[J]. J. Am. Chem. Soc., 2016, 138(4):  1122-1125. doi: 10.1021/jacs.5b11688

    30. [30]

      Scatena R, Johnson R D, Manuel P, Macchi P. Formate-mediated magnetic superexchange in the model hybrid perovskite [(CH3)2NH2]Cu(HCOO)3[J]. J. Mater. Chem. C, 2020, 8(37):  12840-12847. doi: 10.1039/D0TC03913F

    31. [31]

      Kim S Y, Yun Y, Shin S, Lee J H, Heo Y W, Lee S. Wide range tuning of band gap energy of A3B2X9 perovskite-like halides[J]. Scr. Mater., 2019, 166:  107-111. doi: 10.1016/j.scriptamat.2019.03.009

    32. [32]

      Bourhis L J, Dolomanov O V, Gildea R J, Howard J A K, Puschmann H. The anatomy of a comprehensive constrained, restrained refinement program for the modern computing environment-Olex2 dissected[J]. Acta Crystallogr. Sect. A, 2015, A71(1):  59-75.

    33. [33]

      Dolomanov O V, Bourhis L J, Gildea R J, Howard J A K, Puschmann H. OLEX2: A complete structure solution, refinement and analysis program[J]. J. Appl. Crystallogr., 2009, 42(2):  339-341. doi: 10.1107/S0021889808042726

    34. [34]

      Johnson T J, Bernacki B E, Redding R L, Su Y F, Brauer C S, Myers T L, Stephan E G. Intensity-value corrections for integrating sphere measurements of solid samples measured behind glass[J]. Appl. Spectrosc., 2014, 68(11):  1224-1234. doi: 10.1366/13-07322

    35. [35]

      Kurtz S K, Perry T T. A powder technique for the evaluation of nonlinear optical materials[J]. J. Appl. Phys., 1968, 39(8):  3798-3813. doi: 10.1063/1.1656857

    36. [36]

      Clark S J, Segall M, Pickard C J, Hasnip P J, Probert M J, Refson K, Payne M C. First principles methods using CASTEP[J]. Z. Kristallogr., 2005, 220(5/6):  567-570.

    37. [37]

      Payne M C, Arias T A, Joannopoulos J D. Iterative minimization techniques for ab initio total-energy calculations: Molecular dynamics and conjugate gradients[J]. Rev. Mod. Phys., 1992, 64(4):  1045-1097. doi: 10.1103/RevModPhys.64.1045

    38. [38]

      Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple[J]. Phys. Rev. Lett., 1998, 77(18):  3865-3868.

    39. [39]

      Perdew J P, Yue W. Pair-distribution function and its coupling- constant average for the spin-polarized electron gas[J]. Phys. Rev. B, 1992, 46(20):  12947-12954. doi: 10.1103/PhysRevB.46.12947

    40. [40]

      Hamann D R, Schlüter M, Chiang C. Norm-conserving pseudopotentials[J]. Phys. Rev. Lett., 1979, 43(20):  1494-1497. doi: 10.1103/PhysRevLett.43.1494

    41. [41]

      Monkhorst H J, Pack J D. Special points for Brillouin-zone integrations[J]. Phys. Rev. B, 1976, 13(12):  5188-5192. doi: 10.1103/PhysRevB.13.5188

    42. [42]

      Samarasekere P, Wang X Q, Kaveevivitchai W, Jacobson A J. Reactions of rare earth hydrated nitrates and oxides with formamide: Relevant to recycling rare earth metals[J]. Cryst. Growth Des., 2015, 15(3):  1119-1128. doi: 10.1021/cg501421u

    43. [43]

      Feng J H, Hu C L, Xu X, Kong F, Mao J G. Na2RE2TeO4(BO3)2 (RE=Y, Dy-Lu): Luminescent and structural studies on a series of mixed metal borotellurates[J]. Inorg. Chem., 2015, 54(5):  2447-2454. doi: 10.1021/ic503068s

  • Figure 1  UV-Vis-NIR diffuse reflectance spectra and the corresponding crystal morphologies (Inset) for (CH(NH2)2)[Y(HCOO)4] (a) and (CH(NH2)2)[Er(HCOO)4] (c); Bandgaps for (CH(NH2)2)[Y(HCOO)4] (b) and (CH(NH2)2)[Er(HCOO)4] (d)

    下载: 全尺寸图片 幻灯片

    Figure 2  (a) Phase-matching curves of (CH(NH2)2)[Y(HCOO)4], (CH(NH2)2)[Er(HCOO)4], and KDP with 1 064 nm laser radiation; (b) Oscilloscope traces of the SHG signals for polycrystalline (CH(NH2)2)[Y(HCOO)4], (CH(NH2)2)[Er(HCOO)4], and KDP in a particle size range of 105-150 μm at λ=1 064 nm

    KDP sample serves as the reference.

    下载: 全尺寸图片 幻灯片

    Figure 3  Original crystals (a, d), crystal diagrams to achieve complete extinction (b, e), and thickness diagrams (c, f) of compounds (CH(NH2)2)[Y(HCOO)4] (a-c) and (CH(NH2)2)[Er(HCOO)4] (d-f)

    下载: 全尺寸图片 幻灯片

    Figure 4  (a) Coordination environment of Y3+ in (CH(NH2)2)[Y(HCOO)4], HCOO- ligand group and (CH(NH2)2)+ group; (b) 1D chain of [Y(HCOO)n]∞; (c) 2D [Y(HCOO)n]∞ layers containing 12-MRs and 16-MRs viewed from the c-axis direction; (d) 3D structure of the cavity-template units in a (CH(NH2)2)[Y(HCOO)4] crystal

    Symmetry codes: #1: 1-x, y, 3/2-z; #2: 1/2+x, 1/2-y, 1-z; #3: 1/2-x, 1/2-y, 1/2+z.

    下载: 全尺寸图片 幻灯片

    Figure 5  (a) Energy band structures, (b) TDOS and PDOS of compound (CH(NH2)2)[Er(HCOO)4]

    下载: 全尺寸图片 幻灯片
  • 加载中
WeChat 扫一扫看文章
计量
  • PDF下载量:  12
  • 文章访问数:  2045
  • HTML全文浏览量:  214
文章相关
  • 发布日期:  2024-01-10
  • 收稿日期:  2023-10-16
  • 修回日期:  2023-11-27
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

/

返回文章

All Rights Reserved by the Chinese Chemical Society   中国化学会 版权所有 京ICP备05002797号

本系统由北京仁和汇智信息技术有限公司开发    技术支持: info@rhhz.net