Atomic layer deposition(ALD)is extensively used to fabricate doped dielectrics due to its ability to deposit conformal films with atomic-scale thickness control.Al-doped TiO_(2)(ATO)is a promising high-k dielectric fo...Atomic layer deposition(ALD)is extensively used to fabricate doped dielectrics due to its ability to deposit conformal films with atomic-scale thickness control.Al-doped TiO_(2)(ATO)is a promising high-k dielectric for dynamic random access memory(DRAM)applications,offering a high dielectric constant with a remarkable leakage-lowering effect by Al acceptor doping.However,ATO fabrication via conventional supercycle-based ALD suffers from severe crystallinity loss during the growth of TiO_(2) upon Al doping owing to the dopant-induced lattice disorder.In addition,Al doping cannot reduce any inherent O vacancies(V_(O))of TiO_(2),although the original purpose of doping was to address the n-type nature caused by V_(O).To resolve these limitations,we propose a single-step,in-situ Ar/O_(2) post-doping plasma(PDP)process immediately after the Al dopant incorporation.Using the PDP process,simultaneous atomic-scale dopant migration-mediated crystallization and V_(O) annihilation were successfully initiated.Thus,the surface concentration of the dopant decreased,reducing the dopant-induced lattice distortion,while promoting the highly crystallized seed layer-like surface.Consequently,strong rutile-phase recovery was accompanied by enhanced lattice-matched growth.In addition,the PDP process significantly lowers the V_(O)-to-lattice oxygen ratio by facilitating the recombination between reactive O species and V_(O),increasing the corresponding 0.4 e V of conduction band offset(CBO).Despite the common trade-off between the dielectric constant and leakage,the Pt/PDP-ATO/Ru capacitor exhibited a simultaneous 30%increase in dielectric constant and up to a 1.6-order reduction in leakage current density.展开更多
The garnet-type Li_(7)La_(3)Zr_(2)O_(12)(LLZO)solid electrolyte is regarded as a promising option for all-solid-state batteries owing to its notable features,including high ionic conductivity and wide electrochemical ...The garnet-type Li_(7)La_(3)Zr_(2)O_(12)(LLZO)solid electrolyte is regarded as a promising option for all-solid-state batteries owing to its notable features,including high ionic conductivity and wide electrochemical window.Although aluminum-doped LLZO(Al-LLZO)is crucial for achieving LLZO ceramics with high critical current density,the characteristics of its grain and grain boundary structures remain largely elusive.In this work,the electrochemical impedance spectroscopy(EIS)technique,in conjunction with the distribution of relaxation times(DRT)method,was employed to investigate structural alterations in Al-LLZO ceramics modified by La_(2)Zr_(2)O_(7)(LZO)additives.Additionally,the impact of sintering temperature and electrolyte testing temperature on ceramic structural changes was investigated using the DRT tools.By optimizing experimental conditions such as the concentration of added LZO and the sintering temperature of Al-LLZO,the study was further refined.This enabled us to successfully identify Al-LLZO solid electrolytes exhibiting uniform morphological structures,moderate crystal grain sizes and high density.By adding 6 wt%of LZO to the Al-LLZO solid electrolyte,we achieved the purest cubic phase and optimal lithium-ion conductivity.Under this condition,the sintered Al-LLZO ceramics exhibited exceeding 4.2×10^(-4)S·cm^(-1)conductivity at room temperature and a high critical current density of up to 0.6 mA·cm^(-2).展开更多
The neutral hydrogen evolution reaction(HER)is vital in the chemical industry,and its efficiency depends on the interior character of the catalyst.Herein,work function(WF)engineering is introduced via 3d metal(Fe,Co,N...The neutral hydrogen evolution reaction(HER)is vital in the chemical industry,and its efficiency depends on the interior character of the catalyst.Herein,work function(WF)engineering is introduced via 3d metal(Fe,Co,Ni,and Cu)doping for modulating the Fermi energy level of Mo2C.The defective energy level facilitates the free water molecule adsorption and,subsequently,promotes the neutral HER efficiency.Specifically,at a current density of 10 mA/cm2,Cu-Mo2C exhibits the best HER performance with an overpotential of 78 mV,followed by Ni-Mo2C,Co-Mo2C,Fe-Mo2C,and bare Mo2C with 90,95,100,and 173 mV,respectively,and the corresponding Tafel slope values are 40,43,42,56,and 102 mV/dec.The modified WF can also lead to an enhanced photocatalytic efficiency owing to the lowered Schottky barrier and excellent carrier transition across the electrocatalyst–solution interface.When coupling the metal-doped Mo2C samples with TiO2,enhanced photocatalytic neutral HER rates are obtained in comparison to the case with bare TiO2.Typically,the HER rates are 521,404,275,224,147,and 112μmol/h for Cu,Ni,Co,Fe,bare Mo2C,and bare TiO2,respectively.Time-resolved photoluminescence spectroscopy(TRPS)and ultrafast transient absorption(TA)measurements are carried out to confirm the recombination and migration of the photogenerated carriers.The fittedτvalues from the TRPS curves are 22.6,20.5,10.1,4.7,4.0,2.5,and 1.9 ns for TiO2,TiO2-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,and TiO2-Pt,respectively.Additionally,the fittedτvalues from the TA results are 31,73,and 105 ps for the TiO2-Mo2C,TiO2-Cu-Mo2C,and TiO2-Pt samples,respectively.This work provides in-depth insights into the WF modulation of an electrocatalyst for improving the HER performance.展开更多
A stain-based screening method was developed to screen different catalyst coatings for their germicidal activity. A Baclight dead/live bacteria viability kit （invitrogen, molecular probes） was used for staining the ...A stain-based screening method was developed to screen different catalyst coatings for their germicidal activity. A Baclight dead/live bacteria viability kit （invitrogen, molecular probes） was used for staining the cell. The screening was carried out following a standard procedure. This included loading cell suspension to solid surface and maintaining contact for 30 min, then staining with a mixture containing dyes. The stained cells were observed using an epifluorescent microscope and photographed with a CCD camera under UV. Metal-doped TiO2 coatings on AI plates were prepared and tested for non-UV germicidal activity without using UV. It was tested using model microorganisms such as Bakers Yeast （Saccharomyces cerevisiae）, Bacillus subtilis, Pseudomonas putida, and Escherichia coli. On the basis of the germicidal activity of catalyst and the degree of damage caused to the cells, the stained cells may appear green （viable）, green with red or yellow nuclei and yellow （compromised） or red （nonviable）. According to their stained color, cells were counted to calculate the percentage of dead, live, and compromised cells. Compromised cells are cells that grow very slowly after reculturing indicating a degree of reversible cell damage. Screening the germicidal activity using this staining method is accurate and efficient, and requires less time than the culture-based method. A modification to the procedure for measuring germicidal activity of rough surfaces or fibrous coatings was developed. Both TiO2 and metal-doped TiO2 （Ag, Pt, Au, Cu） possess non-UV based germicidal activity. The germicidal activity of TiO2 was found to be related with its wetting property and can be improved by UV irradiation before testing. It is not greatly affected by contact time, indicating a fast acting germicidal activity.展开更多
In this work, ultrathin pure HfO_2 and Al-doped HfO_2films（about 4-nm thick） are prepared by atomic layer deposition and the crystallinities of these films before and after annealing at temperatures ranging from 550...In this work, ultrathin pure HfO_2 and Al-doped HfO_2films（about 4-nm thick） are prepared by atomic layer deposition and the crystallinities of these films before and after annealing at temperatures ranging from 550℃ to 750℃ are analyzed by grazing incidence x-ray diffraction. The as-deposited pure HfO_2 and Al-doped HfO_2 films are both amorphous. After550-℃ annealing, a multiphase consisting of a few orthorhombic, monoclinic and tetragonal phases can be observed in the pure HfO_2 film while the Al-doped HfO_2 film remains amorphous. After annealing at 650℃ and above, a great number of HfO_2 tetragonal phases, a high-temperature phase with higher dielectric constant, can be stabilized in the Al-doped HfO_2 film. As a result, the dielectric constant is enhanced up to about 35. The physical mechanism of the phase transition behavior is discussed from the viewpoint of thermodynamics and kinetics.展开更多
The electronic structures and elastic properties of Al-doped MoSi2 were calculated using the plane wave pseudo-potential method based on the density functional theory,in which the generalized-gradient approximation(GG...The electronic structures and elastic properties of Al-doped MoSi2 were calculated using the plane wave pseudo-potential method based on the density functional theory,in which the generalized-gradient approximation(GGA) was used to describe the exchange-correlation potential.Starting from the elastic constants,bulk modulus,shear modulus,elastic modulus and Poisson ratio of Al-doped MoSi2 were obtained by using the Hill method.The results indicate that conductivity of Al-doped MoSi2 is improved to some extent in comparison with that of pure MoSi2 due to the orbit hybridization of Mo 4d,Al 3p and Si 3p electrons.In addition,calculations show that the elastic modulus and the brittleness of Al-doped MoSi2 are smaller than those of pure MoSi2,which implies that it is feasible to toughen MoSi2 by doping Al.The agreement of the conclusion with experiment shows that the present theory is reasonable.展开更多
Mesoporous aluminum-doped titanium dioxide(Al-TiO2) materials with high specific surface areas were prepared via a solid-state reaction route.The properties of these materials were characterized by X-ray diffraction(X...Mesoporous aluminum-doped titanium dioxide(Al-TiO2) materials with high specific surface areas were prepared via a solid-state reaction route.The properties of these materials were characterized by X-ray diffraction(XRD),high resolution transmission electron microscopy(HRTEM),energy dispersive spectroscopy(EDS),N2 absorption-desorption,ultraviolet visible light spectroscopy(UV-Vis) and electrochemical spectroscopy.The results show that the mesoporous structure of the product with ethanol is composed of anatase laced crystal walls with amorphous grain boundaries formed gradually by degradation.Compared with those without ethanol,these samples possess larger crystallite size since ethanol decreases the pore size at higher temperature.With the increase of ethanol amount,however,the crystallite size will grow.The amorphous grain boundaries in the mesoporous material,with a large impedance and low incidental cyclic potential,are difficult to effectively degrade and the phase transformation temperature is changed from 500 to 550℃.The growth rate of Al-TiO2 crystallites that obeys the quadratic polynomial equation may be controlled.展开更多
Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolu...Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec^(-1) of Tafel slopes and a higher turnover frequency of 1.72 H2 s^(-1) at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.展开更多
Single phase polycrystalline samples Na0.7Co1-xAlxO2 （x = 0, 0.05, 0.10, 0.15, 0.20, 0.25, 030） were prepared by solid state reaction. The magnetic properties from 5 K to 300 K have been studied by dc and ac magneti...Single phase polycrystalline samples Na0.7Co1-xAlxO2 （x = 0, 0.05, 0.10, 0.15, 0.20, 0.25, 030） were prepared by solid state reaction. The magnetic properties from 5 K to 300 K have been studied by dc and ac magnetic susceptibility measurements. Samples with lower doping quantity （x = 0, 0.05, 0.10） showed paramagnetic behaviors, but those with higher doping quantity （x=0.20, 0.25, 0.30）showed spin-glass behaviors with a freezing temperature （Tf） of about 13 K.展开更多
基金supported by the Samsung Electronics Co.,Ltd.(ISO230414-05954-01)Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(NRF2021R1A6A1A03039981)+2 种基金the Korea Institute for Advancement of Technology(KIAT)Grant,funded by the Korea Government(MOTIE)(P0023703,HRD Program for Industrial Innovation)The computations were performed at the Korea Institute of Science and Technology Information(KISTI)National Supercomputing Center(KSC-2024-CRE-0316)the UNIST Supercomputing Center。
文摘Atomic layer deposition(ALD)is extensively used to fabricate doped dielectrics due to its ability to deposit conformal films with atomic-scale thickness control.Al-doped TiO_(2)(ATO)is a promising high-k dielectric for dynamic random access memory(DRAM)applications,offering a high dielectric constant with a remarkable leakage-lowering effect by Al acceptor doping.However,ATO fabrication via conventional supercycle-based ALD suffers from severe crystallinity loss during the growth of TiO_(2) upon Al doping owing to the dopant-induced lattice disorder.In addition,Al doping cannot reduce any inherent O vacancies(V_(O))of TiO_(2),although the original purpose of doping was to address the n-type nature caused by V_(O).To resolve these limitations,we propose a single-step,in-situ Ar/O_(2) post-doping plasma(PDP)process immediately after the Al dopant incorporation.Using the PDP process,simultaneous atomic-scale dopant migration-mediated crystallization and V_(O) annihilation were successfully initiated.Thus,the surface concentration of the dopant decreased,reducing the dopant-induced lattice distortion,while promoting the highly crystallized seed layer-like surface.Consequently,strong rutile-phase recovery was accompanied by enhanced lattice-matched growth.In addition,the PDP process significantly lowers the V_(O)-to-lattice oxygen ratio by facilitating the recombination between reactive O species and V_(O),increasing the corresponding 0.4 e V of conduction band offset(CBO).Despite the common trade-off between the dielectric constant and leakage,the Pt/PDP-ATO/Ru capacitor exhibited a simultaneous 30%increase in dielectric constant and up to a 1.6-order reduction in leakage current density.
基金supported by the National Natural Science Foundation of China(No.52102284)the Science and Technology Project of Shenzhen(Nos.JCYJ20210324094206019 and JCYJ20210324094000001).
文摘The garnet-type Li_(7)La_(3)Zr_(2)O_(12)(LLZO)solid electrolyte is regarded as a promising option for all-solid-state batteries owing to its notable features,including high ionic conductivity and wide electrochemical window.Although aluminum-doped LLZO(Al-LLZO)is crucial for achieving LLZO ceramics with high critical current density,the characteristics of its grain and grain boundary structures remain largely elusive.In this work,the electrochemical impedance spectroscopy(EIS)technique,in conjunction with the distribution of relaxation times(DRT)method,was employed to investigate structural alterations in Al-LLZO ceramics modified by La_(2)Zr_(2)O_(7)(LZO)additives.Additionally,the impact of sintering temperature and electrolyte testing temperature on ceramic structural changes was investigated using the DRT tools.By optimizing experimental conditions such as the concentration of added LZO and the sintering temperature of Al-LLZO,the study was further refined.This enabled us to successfully identify Al-LLZO solid electrolytes exhibiting uniform morphological structures,moderate crystal grain sizes and high density.By adding 6 wt%of LZO to the Al-LLZO solid electrolyte,we achieved the purest cubic phase and optimal lithium-ion conductivity.Under this condition,the sintered Al-LLZO ceramics exhibited exceeding 4.2×10^(-4)S·cm^(-1)conductivity at room temperature and a high critical current density of up to 0.6 mA·cm^(-2).
文摘The neutral hydrogen evolution reaction(HER)is vital in the chemical industry,and its efficiency depends on the interior character of the catalyst.Herein,work function(WF)engineering is introduced via 3d metal(Fe,Co,Ni,and Cu)doping for modulating the Fermi energy level of Mo2C.The defective energy level facilitates the free water molecule adsorption and,subsequently,promotes the neutral HER efficiency.Specifically,at a current density of 10 mA/cm2,Cu-Mo2C exhibits the best HER performance with an overpotential of 78 mV,followed by Ni-Mo2C,Co-Mo2C,Fe-Mo2C,and bare Mo2C with 90,95,100,and 173 mV,respectively,and the corresponding Tafel slope values are 40,43,42,56,and 102 mV/dec.The modified WF can also lead to an enhanced photocatalytic efficiency owing to the lowered Schottky barrier and excellent carrier transition across the electrocatalyst–solution interface.When coupling the metal-doped Mo2C samples with TiO2,enhanced photocatalytic neutral HER rates are obtained in comparison to the case with bare TiO2.Typically,the HER rates are 521,404,275,224,147,and 112μmol/h for Cu,Ni,Co,Fe,bare Mo2C,and bare TiO2,respectively.Time-resolved photoluminescence spectroscopy(TRPS)and ultrafast transient absorption(TA)measurements are carried out to confirm the recombination and migration of the photogenerated carriers.The fittedτvalues from the TRPS curves are 22.6,20.5,10.1,4.7,4.0,2.5,and 1.9 ns for TiO2,TiO2-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,and TiO2-Pt,respectively.Additionally,the fittedτvalues from the TA results are 31,73,and 105 ps for the TiO2-Mo2C,TiO2-Cu-Mo2C,and TiO2-Pt samples,respectively.This work provides in-depth insights into the WF modulation of an electrocatalyst for improving the HER performance.
基金Project supported by the HK Innovation and Technology Fund.
文摘A stain-based screening method was developed to screen different catalyst coatings for their germicidal activity. A Baclight dead/live bacteria viability kit （invitrogen, molecular probes） was used for staining the cell. The screening was carried out following a standard procedure. This included loading cell suspension to solid surface and maintaining contact for 30 min, then staining with a mixture containing dyes. The stained cells were observed using an epifluorescent microscope and photographed with a CCD camera under UV. Metal-doped TiO2 coatings on AI plates were prepared and tested for non-UV germicidal activity without using UV. It was tested using model microorganisms such as Bakers Yeast （Saccharomyces cerevisiae）, Bacillus subtilis, Pseudomonas putida, and Escherichia coli. On the basis of the germicidal activity of catalyst and the degree of damage caused to the cells, the stained cells may appear green （viable）, green with red or yellow nuclei and yellow （compromised） or red （nonviable）. According to their stained color, cells were counted to calculate the percentage of dead, live, and compromised cells. Compromised cells are cells that grow very slowly after reculturing indicating a degree of reversible cell damage. Screening the germicidal activity using this staining method is accurate and efficient, and requires less time than the culture-based method. A modification to the procedure for measuring germicidal activity of rough surfaces or fibrous coatings was developed. Both TiO2 and metal-doped TiO2 （Ag, Pt, Au, Cu） possess non-UV based germicidal activity. The germicidal activity of TiO2 was found to be related with its wetting property and can be improved by UV irradiation before testing. It is not greatly affected by contact time, indicating a fast acting germicidal activity.
基金Project supported by the National High Technology Research and Development Program of China(Grant No.2015AA016501)the National Natural Science Foundation of China(Grant Nos.61574168 and 61504163)
文摘In this work, ultrathin pure HfO_2 and Al-doped HfO_2films（about 4-nm thick） are prepared by atomic layer deposition and the crystallinities of these films before and after annealing at temperatures ranging from 550℃ to 750℃ are analyzed by grazing incidence x-ray diffraction. The as-deposited pure HfO_2 and Al-doped HfO_2 films are both amorphous. After550-℃ annealing, a multiphase consisting of a few orthorhombic, monoclinic and tetragonal phases can be observed in the pure HfO_2 film while the Al-doped HfO_2 film remains amorphous. After annealing at 650℃ and above, a great number of HfO_2 tetragonal phases, a high-temperature phase with higher dielectric constant, can be stabilized in the Al-doped HfO_2 film. As a result, the dielectric constant is enhanced up to about 35. The physical mechanism of the phase transition behavior is discussed from the viewpoint of thermodynamics and kinetics.
基金Project(20080431025) supported by Chinese Postdoctoral Science FoundationProject(08JJ3005) supported by Hunan Provincial Natural Science Foundation of ChinaProject(2007) supported by Postdoctoral Science Foundation of Central South University,China
文摘The electronic structures and elastic properties of Al-doped MoSi2 were calculated using the plane wave pseudo-potential method based on the density functional theory,in which the generalized-gradient approximation(GGA) was used to describe the exchange-correlation potential.Starting from the elastic constants,bulk modulus,shear modulus,elastic modulus and Poisson ratio of Al-doped MoSi2 were obtained by using the Hill method.The results indicate that conductivity of Al-doped MoSi2 is improved to some extent in comparison with that of pure MoSi2 due to the orbit hybridization of Mo 4d,Al 3p and Si 3p electrons.In addition,calculations show that the elastic modulus and the brittleness of Al-doped MoSi2 are smaller than those of pure MoSi2,which implies that it is feasible to toughen MoSi2 by doping Al.The agreement of the conclusion with experiment shows that the present theory is reasonable.
基金Supported by the National Natural Science Foundation of China （21061006） the Research of Natural Science and Technology Foundation of Guizhou Province （[2010]2006） the Graduate Scientific Innovation Project of Education Department of Guangxi Autonomous Region （1059330901009）
文摘Mesoporous aluminum-doped titanium dioxide(Al-TiO2) materials with high specific surface areas were prepared via a solid-state reaction route.The properties of these materials were characterized by X-ray diffraction(XRD),high resolution transmission electron microscopy(HRTEM),energy dispersive spectroscopy(EDS),N2 absorption-desorption,ultraviolet visible light spectroscopy(UV-Vis) and electrochemical spectroscopy.The results show that the mesoporous structure of the product with ethanol is composed of anatase laced crystal walls with amorphous grain boundaries formed gradually by degradation.Compared with those without ethanol,these samples possess larger crystallite size since ethanol decreases the pore size at higher temperature.With the increase of ethanol amount,however,the crystallite size will grow.The amorphous grain boundaries in the mesoporous material,with a large impedance and low incidental cyclic potential,are difficult to effectively degrade and the phase transformation temperature is changed from 500 to 550℃.The growth rate of Al-TiO2 crystallites that obeys the quadratic polynomial equation may be controlled.
基金support from the European Union Horizon 2020 program(project HERMES,nr.952184)the Ministry of Education,Youth and Sports of the Czech Republic for supporting CEMNAT(LM2023037)+1 种基金Czech-NanoLab(LM2023051)infrastructures for providing ALD,SEM,EDX,XPS,TEM,and XRDCzech Science Foundation(project 23-08019X,EXPRO).
文摘Synergistic interplays involving multiple active centers originating from TiO2 nanotube layers(TNT)and ruthenium(Ru)species comprising of both single atoms(SAs)and nanoparticles(NPs)augment the alkaline hydrogen evolution reaction(HER)by enhancing Volmer kinetics from rapid water dissociation and improving Tafel kinetics from efficient H*desorption.Atomic layer deposition of Ru with 50 process cycles results in a mixture of Ru SAs and 2.8-0.4 nm NPs present on TNT layers,and it emerges with the highest HER activity among all the electrodes synthesized.A detailed study of the Ti and Ru species using different high-resolution techniques confirmed the presence of Ti^(3+)states and the coexistence of Ru SAs and NPs.With insights from literature,the role of Ti^(3+),appropriate work functions of TNT layers and Ru,and the synergistic effect of Ru SAs and Ru NPs in improving the performance of alkaline HER were elaborated and justified.The aforementioned characteristics led to a remarkable performance by having 9mV onset potentials and 33 mV dec^(-1) of Tafel slopes and a higher turnover frequency of 1.72 H2 s^(-1) at 30 mV.Besides,a notable stability from 28 h staircase chronopotentiometric measurements for TNT@Ru surpasses TNT@Pt in comparison.
基金This work was supported by the National Science Foundation of China under Grant No. 50372052, 50430137, 50588201 the National Basic Research Program of China (973 program), under Grant No. 2007CB616906)+1 种基金the Program for Changjiang Scholars and Innovative Research Team in UniversityAustralian Research Council under Grant No. DP0559872, DP0881739.
文摘Single phase polycrystalline samples Na0.7Co1-xAlxO2 （x = 0, 0.05, 0.10, 0.15, 0.20, 0.25, 030） were prepared by solid state reaction. The magnetic properties from 5 K to 300 K have been studied by dc and ac magnetic susceptibility measurements. Samples with lower doping quantity （x = 0, 0.05, 0.10） showed paramagnetic behaviors, but those with higher doping quantity （x=0.20, 0.25, 0.30）showed spin-glass behaviors with a freezing temperature （Tf） of about 13 K.
