Table of Content

15 October 2023, Volume 52 Issue 10

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Review

Research Status of Preparation and Processing of Large-Size Single Crystal Diamond Substrates for Semiconductors

LIU Junjie, GUAN Chunlong, YI Jian, SONG Hui, JIANG Nan, KAZUHITO Nishimura

2023, 52(10):  1733-1744. 

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Single crystal diamond has ultra-wide band gap, low dielectric constant, high breakdown voltage, high thermal conductivity, high intrinsic electron and hole mobility, and excellent radiation resistance, making it the most promising wide band gap high temperature semiconductor material known so far, known as the “ultimate semiconductor”. However, there are still many technical problems to be solved in the large-scale application of single crystal diamond on semiconductors. This paper focuses on the chemical vapor deposition synthesis, stripping section and grinding and polishing technology of large size (inch) single crystal diamond substrates. By sorting out the relevant literature in recent years, the related research status at home and abroad are reviewed. On this basis, the preparation, stripping, grinding and polishing of single crystal diamond semiconductor materials in the future are prospected.

Research Articles

Effect of Step Porosity Distribution of Stacked Silicon on Seed Crystal Melting During Quasi-Single Crystalline Silicon Casting Process

SUN Yinglong, ZHENG Lili, ZHANG Hui

2023, 52(10):  1745-1757. 

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This paper presents numerical studies of the melting process of stacked silicon with step porosity distribution, specifically its effect on seed crystal melting during quasi-single crystalline silicon casting for photovoltaic applications. The results show that an axial step porosity distribution in stacked silicon leads to a reduced melting ratio of the seed crystal. And the interface shape after seed crystal melting is mainly determined by the porosity at the lower part of the stacked silicon. In a specific range of the porosity, the axial step porosity distribution has little effect on the interface shape when the porosity difference between the upper and lower parts is small. For the situation with a similar melting ratio in the seed crystal, the interface shape of the seed crystal is flatter for a smaller average porosity. For the situation with a constant average porosity, a smaller porosity in the lower part of the stacked silicon is beneficial to the retention of the edge area of the seed crystal. The radial step porosity distribution dramatically influences the interface shape after seed crystal melting. As the porosity in the inner part of the stacked silicon increases, the interface shape changes from convex to concave after the seed crystal melting. To effectively retain the seed crystal, it is preferred to have the porosity in the outer part of the stacked silicon smaller than that of the inner part. And the size of the melting ratio of the seed crystal is directly related to the difference between the porosity at the outer and inner parts. The smaller the difference between the porosity at the outer and inner parts is, the smaller the melting ratio of seed crystals is. The melting ratio of seed crystal with axial step porosity distribution exhibits a certain symmetry, while that with radial step porosity distribution shows a certain periodicity. The interface shape after seed crystal melting is better under the uniform porosity distribution than others. Under the actual working conditions, the porosity distribution in the stacked silicon can be reasonably configured according to the contour map drawn by the melting state data of seed crystals obtained under different porosity distribution conditions. These findings provide guidelines for the optimal design of silicon stacking for the casting process.

Growth of TbYO₃ Crystal by Laser Floating Zone Method

ZHAO Peng, WU Jialing, XIA Cong, MA Shihui, HU Zhanggui

2023, 52(10):  1758-1765. 

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With the development of high-power solid-state lasers and fiber lasers, the demand for optical isolators in the visible and near-infrared regions is gradually increasing. At present, equipment components are tending towards miniaturization. The most widely used terbium gallium garnet (TGG) crystal in industry cannot meet the needs of future high-power lasers due to its small Verdet constant. Tb₂O₃ has a high Verdet constant, but its high melting point and phase transition mechanism make it difficult to achieve single crystals by Czochralski. The crystal growth of (Tb_xY_1-x)₂O₃ at different doping concentrations was explored by doping Y₂O₃ into Tb₂O₃ in this study. When the ratio of n(Tb)∶n(Y) was 1∶1, TbYO₃ single crystals were grown by laser floating zone (LFZ) method, while undoped Tb₂O₃ and (Tb_0.3Y_0.7)₂O₃ single crystals cannot be synthesized by this method. The TbYO₃ crystal has high Verdet constants (529 rad·T^-1·m^-1 at 445 nm and 116 rad·T^-1·m^-1 at 880 nm), which is 1.51 to 2.37 times that of terbium gallium garnet (TGG) crystal (350 rad·T^-1·m^-1 at 445 nm and 49 rad·T^-1·m^-1 at 880 nm). Therefore, the TbYO₃ crystal can effectively reduce the medium length for constructing optical isolators or decrease the magnetic field intensity required for embedding optical isolators. In addition, TbYO₃ crystal also has a moderate thermal conductivity of 11 W·m^-1·K^-1 and a high laser induced damage threshold of 1.67 GW·cm^-2. These advantages make TbYO₃ crystal an attractive magneto-optical material.

Effect of Chitosan on Color Fastness of SiO₂@PDA Photonic Crystals

ZHANG Fei, YANG Hui

2023, 52(10):  1766-1772. 

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The purpose of this paper is to obtain a coating structure with stable structure and bright color on the silk substrate. Monodisperse SiO₂@PDA microspheres were used as the precursor to construct SiO₂@PDA photonic crystals on the silk. The effect of chitosan solution with different mass fraction of chitosan on the color fastness of structured colored silk was investigated. The microstructure of SiO₂@PDA photonic crystals was observed by field emission scanning electron microscopy (SEM), the elemental composition of SiO₂ microspheres was characterized by energy dispersive spectroscopy (EDS), the phase structure of SiO₂ and SiO₂@PDA microspheres was characterized by X-ray diffraction, and the color fastness of structural colored silk was investigated by friction test and washing test. The results show that the SiO₂ and SiO₂@PDA microspheres prepared in this experiment have uniform particle size and good monodispersity. The structures of SiO₂@PDA photonic crystals are closely and periodically arranged. Compared with the structural colored fabric which has not been treated with chitosan solution, the structure color of the fabric treated with 3% (mass fraction) chitosan solution has less shedding after tribological test and water washing test, and still keep its original color. The results show that chitosan solution treatment can improve the color fastness of colored fabric effectively.

Numerical Simulation of CuSbS₂ Thin Film Solar Cells

TONG Lei, GUO Jiarong, LI Qing, MIAO Jiayi, LI Chunran, ZHONG Min

2023, 52(10):  1773-1779. 

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The model of copper-antimony-sulfur (CuSbS₂) thin film solar cell was constructed, and the performance of the device was calculated by SCAPS. The effects of absorption layer thickness, carrier concentration, defect density, and back contact work function on the device performance were investigated. The results show that the green and red light are not fully absorbed by too thin absorption layer, and the absorption layer with the thickness of 1.5 μm to 3 μm can meet spectral absorption requirements. When the acceptor concentration is 2×10¹⁸ cm^-3, the photoelectricity conversion efficiency (PCE) of the device is the highest. When the defect density is larger than 10^-14 cm^-3, the PCE of the device decreases sharply. CuSbS₂ prepared in a copper-poor and sulfur-rich atmosphere can increase the accepter concentration, reduce the open circuit voltage defect, and inhibit the formation of sulfur vacancy defects, thus improving the PCE of the device. High work function materials can decrease the back contact barrier and reduce carrier recombination. After the material parameters have been optimized, the highest PCE of the device is 21.74%.

First-Principles Study on Thermoelectric Properties of Monolayer BiSbTeSe₂

ZHANG Qian, BI Yajun, LI Jia

2023, 52(10):  1780-1786. 

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Based on the first-principles calculation and Boltzmann transport equation, a new Bi₂Te₃-based material with excellent thermoelectric properties, namely monolayer BiSbTeSe₂, is predicted. By systematically calculating the electronic band structure and thermoelectric transport properties of monolayer BiSbTeSe₂, it is found that the maximum Seebeck coefficient of monolayer BiSbTeSe₂ reaches the highest value (522 μV·K^-1) at 300 K, and the maximum ratio of power factor to relaxation time at 500 K is 5.78 W·m^-1·K^-2·s^-1. In addition, the monolayer BiSbTeSe₂ has lower lattice thermal conductivity and higher mobility. Under the optimum p-type doping, the thermoelectric figure of merit ZT of monolayer BiSbTeSe₂ at 500 K is as high as 3.95. The excellent performance of monolayer BiSbTeSe₂ shows that it has potential application value in the field of medium-temperature electrical devices in the temperature range of 300~500 K, which can provide design basis for further developing high-performance Bi₂Te₃-based thermoelectric materials.

Rapid Preparation and Structural Characterization of Two-Dimensional Layered In₂Se₃ Materials

YU Shuxin, JIN Zexin, CHEN Rong, LI Tao, ZU Xiangyu, WU Haifei

2023, 52(10):  1787-1792. 

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In₂Se₃ 2D layered materials have excellent photoelectric, thermoelectric and ferroelectric properties. At present, most of the In₂Se₃ materials are obtained by mechanical exfoliation of bulk In₂Se₃ prepared by the complicated chemical vapor transport (CVT) method with long time and high cost. Compared with CVT method, the Bridgman (B-S) method has the advantages of simple preparation process, high efficiency and low cost. In this paper, the bulk In₂Se₃ prepared by CVT and B-S method were mechanically exfoliated and transferred to SiO₂/Si(111) substrates to obtain the corresponding two-dimensional layered In₂Se₃ samples. The surface morphology, lattice vibration spectrum and crystalline quality of both samples were also measured by atomic force microscopy (AFM), laser Raman and X-ray diffraction (XRD). The results show that the samples prepared and exfoliated by B-S method have almost the same surface atomic level flatness and single crystal crystalline quality as those prepared and exfoliated by CVT method. This paper provides a more economical and practical way to obtain high-quality two-dimensional layered In₂Se₃ materials.

First-Principles Study on the Electronic Structure and Optical Properties of X(PO₃)₂ (X=Zn, Cd, Hg)

ZHOU Xinyuan, JIANG Bao, WANG Yunjie, ZHAO Can, SU Xin

2023, 52(10):  1793-1800. 

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The microstructure of crystal materials plays a decisive role in macroscopic properties. An important fundamental direction in the synthesis of new materials is to investigate the relationship between electronic structure and optical properties. This study uses the first-principles based on density functional theory to systematically study the electronic structure and optical properties of X(PO₃)₂(X=Zn, Cd, Hg), the three cationic ternary phosphate crystals containing d¹⁰ electron configuration. The band gap width of other three materials Zn(PO₃)₂, Cd(PO₃)₂, and Hg(PO₃)₂ gradually reduces, which are 5.089, 4.065 and 2.942 eV, respectively. By analyzing the attribution of the band orbital near the band gap, it can be seen that the top of the valence band of X(PO₃)₂ is occupied by P atoms, O atoms and d orbitals of cations, while the bottom of the conduction band is mainly composed of P atoms, O atoms and occupied by the s, and p orbitals of cations. The charge density distribution maps of P and adjacent O atoms overlap significantly, which prove that P—O bonds have strong covalence. The static permittivities of X(PO₃)₂ are 3.13, 2.76, 3.24, respectively. It can be calculated that the birefringence index of Zn(PO₃)₂ at 1 064 nm is 0.032, the birefringence index of Cd(PO₃)₂ is 0.025, and the birefringence index of Hg(PO₃)₂ is 0.024. By calculating the birefringence magnitude of the compound and the anion group respectively, it is found that the birefringence is the result of the synergistic action of P—O group and cations. At the same time, the local analysis of the material is carried out, and the loss of electrons of the element is calculated, which further verify that the P—O group has strong covalence compared with Zn—O, Cd—O, and Hg—O.

First-Principles Study on Adsorption of SF₆ Decomposition Components on the Pd-Doped SnP₃ Monolayer

ZHANG Ruien, CHEN Lincong, ZHAO Hailong, FAN Xiaozhou

2023, 52(10):  1801-1808. 

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Information on SF₆ decomposition components can be detected using gas-sensitive sensor methods to assess the operational status of GIS equipment and detect the insulation defects early. Metal-doped SnP₃ monolayer has good adsorption properties, which makes it promising for gas detection applications. Based on the first-principles, the parameters of adsorption energy, density of states, energy gap and desorption time of the system after the adsorption of SO₂, H₂S, SOF₂ and SO₂F₂ by Pd-SnP₃ monolayer were calculated and analyzed to explore the possibility of using this material for gas sensors. The results show that, in terms of adsorption performance, Pd-SnP₃ monolayer only chemisorb SO₂F₂. Combined with the results of density of states, differential charge density and transfer charge analysis, it is verified that the adsorption of SO₂F₂ is significantly better than that of SO₂, H₂S and SOF₂. In terms of sensing characteristics, only the adsorption of SO₂F₂ causes significant change in the energy gap of the system, and desorption of SO₂F₂ from the Pd-SnP₃ monolayer surface rapidly occur at temperature of 398 K and above. Therefore, the Pd-SnP₃ monolayer has the potential to become a gas-sensitive material for the detection of SO₂F₂ for its high selectivity and detectability to SO₂F₂. This study provides a theoretical basis for the application of Pd-SnP₃ monolayers in the field of gas-sensitive materials.

Synthesis and Luminescence Property of Dy³⁺ Doped Y₂MgTiO₆ Phosphor

JIANG Xiaokang, ZHANG Wangxiyue, GAO Feng, ZHOU Hengwei

2023, 52(10):  1809-1815. 

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A series of Dy³⁺ doped Y₂M_gTiO₆ phosphors (YMT∶Dy³⁺) were synthesized by sol-gel method. The morphology, crystal structure and luminescence properties of these phosphors were characterized and analyzed by XRD, SEM and fluorescence analyzer. The results show that YMT∶Dy³⁺ phosphor has a double perovskite structure, and Dy³⁺ doping does not change the crystal structure of the sample. Under the excitation of near UV light (352 nm), the emission spectrum of the sample shows typical Dy³⁺characteristic emission, which is located at 485 nm in blue light region, 578 nm in yellow region and 650~700 nm in red region respectively. The concentration quenching occurred when the molar concentration of Dy³⁺ x=0.03 for YMT∶Dy³⁺phosphor and its mechanism is ascribed to dipole-dipole interaction (d-d). The CIE color coordinates of YMT∶Dy³⁺ phosphors are significantly affected by the concentration of Dy³⁺. Among them, the CIE color coordinate for YMT∶0.02Dy³⁺ phosphor is (0.406, 0.407), which is located in the warm white light region, and shows potential application for the n-UV excited warm white light emitting diodes (w-LEDs).

Preparation and Luminescence Properties of LaNbO₄∶Dy³⁺, Ca²⁺ Phosphors

LU Qin, FANG Chuanli, WANG You, WU Dongni, WANG Yujie, LOU Chenglong

2023, 52(10):  1816-1821. 

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To improve the luminescence property of blue-green phosphors, the conventional high-temperature solid-phase method was used to synthesize LaNbO₄∶Dy³⁺ and LaNbO₄∶Dy³⁺,Ca²⁺ phosphors in this paper. The XRD, fluorescence spectra and CIE chromaticity coordinates of the samples were tested to investigate the effects of Dy³⁺ doping and Dy³⁺,Ca²⁺ co-doping on the performance of niobate phosphors. The results show that the diffraction peaks of LaNbO₄∶Dy³⁺ as well as LaNbO₄∶Dy³⁺,Ca²⁺ phosphors all match the diffraction peaks of standard card. The excitation spectra of the samples are composed of two broadband excitation peaks and a series of sharp excitation peaks, the strongest excitation peaks of LaNbO₄∶Dy³⁺ and LaNbO₄∶Dy³⁺,Ca²⁺ are 387 and 472 nm, respectively. Under excitation at a wavelength of 387 nm, the strongest emission peaks of the sample are 575 and 477 nm, respectively. The best luminescence intensity is obtained when the concentration of Dy³⁺doping is 0.05. When Dy³⁺ and Ca²⁺ are co-doped, the sample has the best luminescence property when the concentration of Ca²⁺ is 0.05. Through the color card coordinates, it can be observed that LaNbO₄∶Dy³⁺,Ca²⁺ is more concentrated in the blue-green region than LaNbO₄∶Dy³⁺,which shows that Dy³⁺ and Ca²⁺ co-doped LaNbO₄ have better luminescence effect, and the co-doped samples show more stable luminescence property, indicating that the phosphor is a more stable blue-green phosphor that can be excited by UV light.

Synthesis and Luminescence Properties of Broadened Red Light La₂MgTiO₆∶Pr³⁺, Mn⁴⁺ Phosphors for Plant Illumination

HU Yifan, CHEN Jiating, WANG Yanhui, WANG Weihao, LU Yonghong

2023, 52(10):  1822-1828. 

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La₂MgTiO₆∶Mn⁴⁺, La₂MgTiO₆∶Pr³⁺, La₂MgTiO₆∶Pr³⁺, Mn⁴⁺ single-doped and co-doped phosphors were synthesized by high-temperature solid-state method. The phase structure, morphology, and luminescence properties of the phosphors were characterized and analyzed by means of X-ray diffraction, scanning electron microscopy, and fluorescence spectrophotometer. The results show that, La₂MgTiO₆∶Mn⁴⁺, La₂MgTiO₆∶Pr³⁺, La₂MgTiO₆∶Pr³⁺, Mn⁴⁺ phosphors with pure phase were successfully synthesized. The particle size of the samples is 1~2 μm. The red emission of La₂MgTiO₆∶Mn⁴⁺ at 650~750 nm is attributed to the ²E_g→⁴A_2g transition of Mn⁴⁺. La₂MgTiO₆∶Pr³⁺ exhibits strong emission in the red light range between 600 nm and 660 nm, which is attributed to the ³P₀→³H₆ and ³P₀→³F₂ transition of Pr³⁺. Because of the different red light emission regions of Mn⁴⁺and Pr³⁺, when they are co-doped in La₂MgTiO₆, the emission spectra of the co-doped phosphors closely match with the absorption spectra of phytochromes P_r and P_fr. The results indicate that, compared to the single-doped phosphors, the red light emission region of the Mn⁴⁺, Pr³⁺ co-doped phosphors are widely extended. The red light emission region of the co-doped phosphors are more tally with the needs for plants grow. The La₂MgTiO₆∶Pr³⁺, Mn⁴⁺ phosphors has potential application in LED plant illumination.

Synthesis, Crystal Structure, and Luminescence Properties of Eu (III) Complex with Two Pyridinedicarboxylic Acids

WANG Hongsheng, LI Hui, LIU Zhan, LIANG Cailian

2023, 52(10):  1829-1835. 

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A new Eu(III) complex {[Eu₂(3,5-pdc)(3,4-pdc)₂(H₂O)₄]·3H₂O}_n was synthesized by reacting 3,5-pyridinedioic acid (3,5-H₂pdc) and 3,4-pyridinedioic acid (3,4-H₂pdc) with Eu(ClO₄)₃ water solution at 170 ℃ by hydrothermal method. X-ray single crystal diffraction shows that the complex is a two-dimensional structure. The complex crystallized in monoclinic crystal system and P2₁/m space group. Its crystal cell parameters are a=0.598 20(4) nm,b=2.639 21(19) nm, c=1.147 58(9) nm, α=γ=90°,β=102.628 0(10)°. The complex was characterized by elemental analysis, infrared spectroscopy. The excitation and emission spectrum, fluorescence lifetime and luminescence quantum yield of the complex were tested. The results indicate that the complex can emit characteristic spectra of Eu (III). The fluorescence lifetime of ⁵D₀→⁷F₂ transition is 338 μs, and the absolute luminescence quantum yield is 24% under the excitation of 313 nm ultraviolet light.

Cu(I) Organic Framework Based on Semi-Rigid Imidazolium Carboxylate Ligand: Synthesis, Crystal Structure and Property

PAN Huibin, WU Tingting, GAO Xia, LU Jiufu

2023, 52(10):  1836-1841. 

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Under solvothermal conditions, a new Cu(I) coordination polymer [Cu(H₂O)(MIBA)]_n was synthesized by using semi-rigid imidazole carboxylic acid ligand 4-(2-methylimidazole) benzoic acid and copper, in which MIBA is the negative monovalent anionic coordination polymer of 4-(2-methylimidazole) benzoic acid. The solid-state fluorescence properties of Cu(I) organic skeleton coordination polymer based on semi-rigid imidazole carboxylic acid ligands were studied at room temperature. The maximum emission peak of MIBA ligand is 433 nm, and the maximum emission peak of coordination polymer [Cu(H₂O)(MIBA)]_n is 412 nm, all of which show fluorescence properties. In addition, its crystal structure was characterized by X-ray single crystal diffractometer, infrared spectrum, thermogravimetric analysis and elemental analysis. X-ray single crystal diffraction shows that the polymer is a 3D→3D double interpenetrating network with a (6⁴·8²) four-connected single-node topology.

Synthesis of Polypyridyl Palladium (Ⅱ) Complexes Modified with Morpholine Group and Its Antibacterial Activity Anti-Staphylococcus Aureus

WANG Runbin, HAN Tianzhi, LI Zhimin, YAO Zhiling, LIAO Xiangwen, WANG Jintao

2023, 52(10):  1842-1849. 

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One Polypyridyl Pd(Ⅱ) complex (Pd1) containing modified morpholine group was synthesized from 4’-[4-(4-morpholinobutyloxy) phenyl]-2,2’∶6’,2’-tripyridine and characterized by ¹H NMR, element analysis and single crystal X-ray diffraction. The antibacterial activity of Pd1 was investigated against S. aureus with the MIC (minimum inhibition concentration) value of 62.48 μg/mL and the effect of Pd1 complex on S. aureus growth was investigated by growth curves. Bacteria resistance development assay indicate that the S. aureus cannot easily develop drug-resistance to Pd1. In addition, Pd1 complex can strengthen the susceptibility of S. aureus to clidamycin hydrochloride when it is combined with clidamycin hydrochloride. Meanwhile, Pd1 has a significant inhibitory effect on biofilms related to drug resistance, and show obviously inhibitory activity against the toxins from S. aureus.

Synthesis, Structure, HSA Binding and Cytotoxic Activity of Complex {[Cu(pcba)₂]₂·(MeOH)₂}

ZENG Zhenfang, CAI Jiehui, HUANG Qiuping, PANG Huayu, YANG Daqin, HUANG Qiuchan

2023, 52(10):  1850-1857. 

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In this paper, a copper complex {[Cu(pcba)₂]₂·(MeOH)₂} (pcba=p-chlorbenzoic acid, MeOH=methanol) was synthesized. The structure of the complex was characterized using elemental analysis, IR and X-ray single crystal diffraction. The complex belongs to triclinic, P1 space group, with a=6.591 80(10) Å, b=10.769 0(2) Å, c=12.472 2(2) Å, α=90.198 0(10)°, β=104.076(2)°, γ=99.673(2)°, Z=1, D_c=1.593 mg/m³, F(000)=408. The final R₁=0.040 0, wR₂=0.114 5. The complex and its interaction with human serum albumin (HSA) were studied by UV-Vis absorption and fluorescence spectroscopy. The higher the concentration of complex, the lower the UV-Vis and fluorescence intensity. The quenching constant (K_sv) of the complex to HSA is 5.78×10³ L·mol^-1, the quenching rate constant (K_q) is 5.78×10¹¹ L·mol^-1·s^-1, the binding constant (K_a) is 1.38×10² L·mol^-1, the number of binding bits (n) is 0.592. And the anti-proliferation abilities of the complex on A549, Hela, HepG2, and LO2 were studied. It was found that the proliferation inhibition effect of the complex is similar to that of cisplatin, and the toxicity to LO2 is less than that of cisplatin.

Synthesis, Crystal Structure, and CT-DNA Binding Activity of a 3-Methylpyridyl Pendant-Arms Cu(II)-Zn(II) Hetero-Binuclear Complex

WANG Yang, LI Ming, GUAN Jintao, ZHANG Zhiyong, YAN Juntao, XIONG Lan, MAO Jiawei

2023, 52(10):  1858-1866. 

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A new 3-methylpyridyl pendant-arms Cu(II)-Zn(II) hetero-binuclear complex was synthesized by condensation reaction of 3,3′-((ethane-1,2-diylbis((pyridin-2-ylmethyl)azanediyl))bis(methylene))bis(2-hydroxy-5-methylbenzaldehyde) (H₂L) and propane diamine in the presence of metal ions. The structure was characterized by IR spectroscopy, UV-Vis spectroscopy, ES-MS spectroscopy and X-ray single-crystal diffraction. The crystal structure reveals that the complex crystallizes in hexagonal, space group P6₃/m, with a=1.982 18(17) nm, b=1.982 18(17) nm and c=1.839 4(2) nm. The coordination environment of Zn(II) and Cu(II) in complex can be described as approximately square pyramid, where the apical positions are occupied by acetate radical. Two metal centers are equivalently bridged by the phenolic oxygens and an acetate radical with the intermetallic separation of 0.289 7 nm. The interaction between the complex and calf thymus DNA (CT-DNA) was measured by cyclic voltammetry and viscosity studies, which shows a weak binding activity of 6.92×10³mol/L.

Effect of Tartaric Acid Addition on Luminescence Properties of Ce³⁺ Activated Borogermanate Scintillating Glass

ZHANG Meilun, CAO Zhenbo, YANG Shengyun, ZHANG Yang, LI Zijin, ZHOU You, ZHENG Jingming, JIA Jinsheng

2023, 52(10):  1867-1871. 

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In this paper, colorless and transparent Ce³⁺ activated borogermanate scintillating glass was prepared in air atmosphere by traditional melt-quenching method. The total content of GeO₂ and Gd₂O₃ in the borogermanate scintillating glass is 85%, and the measured density is about 5.82 g/cm³. The linear transmittance of the glass scintillator is more than 80% in the wavelength range of 450 nm to 800 nm. A small amount of tartaric acid (C₄H₆O₆) was added as a strong reducing agent to reduce the production of Ce⁴⁺. The fluorescence decay characteristics of Ce³⁺ in the borogermanate scintillating glass at 340 nm excitation wavelength were studied under different dosage of tartric acid, and the optimal dosage of tartric acid was also determined. In addition, the light yield of borogermanate scintillating glass was rarely reported before. In this work, the light yield of the prepared Ce³⁺ activated borogermanate scintillating glass is measured as 27 ph/MeV, and the high density Ce³⁺ activated borogermanate scintillating glass has a minimum decay time of about 14.40 ns. It can be predicted that the prepared borogermanate scintillation glass with high density and fast decay time has great development potential in the fields of high energy physics and medicine imaging.

Preparation of RuO₂/BiOCl Composite Photocatalysts and Its Nitrogen Fixation Performance

TIAN Ye, YAN Zhe, LIU Jianxin, FAN Caimei

2023, 52(10):  1872-1879. 

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BiOCl has wide application in the photocatalytic nitrogen fixation field. However, rapid recombination of photogenerated electron-hole pairs limited its development. In this paper, a novel RuO₂/BiOCl composite catalyst with abundant oxygen vacancies was firstly obtained by a simple hydrolysis method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) were used to analyze the chemical composition and morphology of the composite photocatalyst. In addition, the optical properties of RuO₂/BiOCl catalyst were tested by UV-Vis diffuse reflectometry spectroscopy (UV-Vis DRS) and photoluminescence spectroscopy (PL). The synthetic process of photocatalyst was monitored by EPR characterization, indicating that interaction between RuO₂ and BiOCl during the synthesis reaction leads to numerous oxygen defects. The photocatalytic nitrogen fixation performance was evaluated by a 300 W Xe lamp as a simulated sunlight source. The results reveal that the composite catalyst exhibits better nitrogen fixation activity than pure BiOCl, with optimum activity of 131.9 μmol/L after 1 h irradiation when the RuO₂ loading reaches 0.2% (mass fraction), which is 3.5 times of the pure BiOCl. Finally, the underlying photocatalytic reaction mechanism of the catalyst was explored. The improved nitrogen fixation activity may be attributed to the fact that RuO₂NCs could accelerate the transfer and consumption of holes. Besides, the oxygen defects are conducive to the adsorption and activation of nitrogen. The results clarify that the oxygen defects led by the inter-component contact can also act as N₂ catalytic activity sites, resulting in higher nitrogen fixation activity. This work provides ideas for the preparation of photocatalysts with higher nitrogen fixation activity.

Preparation and Photocatalytic Properties of Core-Shell TiO₂ Microspheres

DU Jingjing, ZHAO Junwei, SHI Fei, ZHAO Zhong, LU Qianjie, CHENG Xiaomin

2023, 52(10):  1880-1886. 

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The core-shell structured nano-TiO₂ microspheres were successfully prepared by one-step solvothermal method with titanium tetrachloride as raw material, ammonium sulfate as dispersant, and urea as precursor. The structural parameters of TiO₂ microspheres (including core-shell size, grain size, specific surface area, pore size, etc.) were controlled by the solvothermal temperature. The photocatalytic degradation of gaseous benzene was investigated. The results show that the core and shell of microspheres gradually separates with the increase of solvothermal temperature, and the hollow structure become more obvious, and displays a secondary structure composed of nanoparticles below 20 nm. The specific surface area of the microspheres is up to 265.4 m²/g, the porosity is up to 0.247 8 cm³/g, the light absorption performance is higher than P25 TiO₂, and the edge of the light absorption band shows "blue shift". The core-shell structure microspheres exhibit adsorption synergistic photocatalytic degradation of benzene, especially the sample prepared at 180 ℃ has the highest photocatalytic activity, the excellent performance may ascribe to the sufficient scattering and absorption of light by the core-shell structure, its excellent crystallinity and high specific surface area.

Microreactor Strategy for Morphology Modulation of γ-CuI

ZHAN Sijin, YOU Li, LIU Fei, WANG Shihan, HU Guotao, YANG Xiaojian, ZHANG Dan, WANG Xianwei

2023, 52(10):  1887-1896. 

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Owing to its wide energy band gap, fast ionic conductivity at high temperatures, the ability to maintain a stable p-type conductivity at room temperature and poor spin-orbit splitting, γ-CuI is widely used in optical energy applications and ultrafast scintillation materials. The morphology of γ-CuI is determined by its synthesis conditions. In this paper,γ-CuI with different morphology were synthesized by microreaction method through controlling different NH₃·H₂O dosage, Cu source, in-tube reaction residence time, and temperature in the reaction. The crystalline phase and morphology of these γ-CuI were investigated by SEM, XRD and FT-IR. The γ-CuI prepared by the traditional liquid phase precipitation method was taken as a comparison. The results show that, the highest yield of 90.5% is achieved when the amount of NH₃·H₂O used (C_NH3·H2O/C_N2H4) is 0.4, the residence time in the tube is 10 s, and the reaction temperature is 20 ℃. Among them, the amount of NH₃·H₂O used (which has the greatest effect on the morphology) is 0.4, the rod-shaped γ-CuI with homogeneous morphology is synthesized. Comparing different Cu sources, except for Cu(CH₃COO)₂·H₂O that is prepared to obtain the rod-shaped γ-CuI, all the remaining Cu sources mainly produce the granular γ-CuI. Increasing the in-tube time contribute to the rod-shaped γ-CuI CuI formation, but further increase time will lead to sample loss in the tube. In addition, too high reaction temperature will cause the gradual conversion of rod γ-CuI to granular γ-CuI.

Effect of Mg²⁺ on Crystallization Habit of Calcium Sulfate Hemihydrate Whiskers

WANG Qing, DIAO Huali, LIU Dongmei, ZHANG Dian, XU Gang

2023, 52(10):  1897-1906. 

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In this paper, calcium sulfate hemihydrate whiskers were prepared by autoclaving using phosphogypsum as raw material. Digital microscope, X-ray diffraction (XRD) and X-ray photoelectron spectrometer (XPS) were used to investigate the microscopic morphology, composition and crystal surface development of calcium sulfate hemihydrate whiskers under the effect of Mg²⁺. Using molecular dynamics technology to simulate the interaction energy and radial distribution function of Mg²⁺ in the crystal surface of the calcium sulfate crystal. The effect of Mg²⁺ on the crystallization habits of calcium sulfate crystals was explored by combining the two techniques. The results show that the interaction energies of Mg²⁺ and different crystal faces of calcium sulfate hemihydrate crystals from smallest to largest are listed below: ΔE₍₂₀₀₎<ΔE₍₀₀₂₎<ΔE₍₄₀₀₎<ΔE₍₀₂₀₎<ΔE₍₂₀₄₎, which illustrates that Mg²⁺ is mainly adsorbed on the (200), (400) and (002) crystal faces of calcium sulfate hemihydrate crystals. The interaction distance between Mg²⁺ and SO^2-₄ is smaller than that between Ca²⁺ and SO^2-₄. There is an obvious electronic effect between Mg and S, and the electronic effect is enhanced with the increase of magnesium sulfate content. The position of XRD diffraction peak is more obvious to the right with the increase of magnesium sulfate. All indicate that a small amount of Mg²⁺is embedded in the crystal lattice of calcium sulfate hemihydrate. At 0.15% (mass fraction, the same as below) of magnesium sulfate content, the growth of c-axis direction was preferentially promoted, resulting in slender needle-like calcium sulfate hemihydrate whiskers with an average length of 47.29 μm and an average L/D ratio of 36.07. At 0.30% of magnesium sulfate content, the growth of c-axis and radial direction was inhibited, resulting in slender needle-like calcium sulfate hemihydrate whiskers with an average length of 39.72 μm and an average L/D ratio of 28.91.