Zr-based amorphous alloys have attracted extensive attention because of their large glassy formation ability, wide supercooled liquid region, high elasticity, and unique mechanical strength induced by their icosahedra...Zr-based amorphous alloys have attracted extensive attention because of their large glassy formation ability, wide supercooled liquid region, high elasticity, and unique mechanical strength induced by their icosahedral local structures.To determine the microstructures of Zr–Cu clusters, the stable and metastable geometry of Zr_(n)Cu(n=2–12) clusters are screened out via the CALYPSO method using machine-learning potentials, and then the electronic structures are investigated using density functional theory. The results show that the Zr_(n)Cu(n ≥ 3) clusters possess three-dimensional geometries, Zr_(n)Cu(n≥9) possess cage-like geometries, and the Zr_(12)Cu cluster has icosahedral geometry. The binding energy per atom gradually gets enlarged with the increase in the size of the clusters, and Zr_(n)Cu(n=5,7,9,12) have relatively better stability than their neighbors. The magnetic moment of most Zr_(n)Cu clusters is just 1μB, and the main components of the highest occupied molecular orbitals(HOMOs) in the Zr_(12)Cu cluster come from the Zr-d state. There are hardly any localized two-center bonds, and there are about 20 σ-type delocalized three-center bonds.展开更多
The bulk metallic glass formation in the Cu-Zr-M ternary systems by alloying of a binary basic Cu6Zr5 cluster was inves- tigated, where M stands for Sn, Mo, Ta, Nb, Ag, Al and Ti. The Cu6Zr5 cluster is a capped Archim...The bulk metallic glass formation in the Cu-Zr-M ternary systems by alloying of a binary basic Cu6Zr5 cluster was inves- tigated, where M stands for Sn, Mo, Ta, Nb, Ag, Al and Ti. The Cu6Zr5 cluster is a capped Archimedean antiprism that characterizes the local structure of the Cu10Zr7 crystalline phase. This cluster composition almost superposes with Cu-Zr eutectic Cu0.56Zr0.44. A se- ries of alloys along the cluster line (Cu6Zr5)1-xMx were examined for their glass forming abilities. Alloy rods with a diameter of 3 mm were prepared by copper mould suction casting method and analyzed by XRD and thermal analysis. The Cu-Zr based bulk metallic glasses were discovered with minor Nb, Sn, Mo, Ta additions (≤2at%) and Al, Ti, Ag (8at%≤concentration≤9at%). The alloying mechanism was discussed in the light of atomic size, cluster-linking structure and electron concentration factors.展开更多
The self-assembly reactions of [MOS3]^2- （M = W, Mo） with CuS2COCH3 in DMF produced two novel dodecanuclear Mo（W）/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- （CuS2COCH3）3]·H2O （1： M = W; 2： M = M...The self-assembly reactions of [MOS3]^2- （M = W, Mo） with CuS2COCH3 in DMF produced two novel dodecanuclear Mo（W）/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- （CuS2COCH3）3]·H2O （1： M = W; 2： M = Mo）. Cluster 1 crystallizes in hexagonal, space group P-62c with a = 16.5612（3）, b = 16.5612（3）, c = 16.4660（5）A, Z = 2, V = 3911.13（16）A^3, Dc = 1.935 g/cm^3, μ（MoKα） = 7.269 mm^-1, F（000） = 2192, the final R = 0.0289 and wR = 0.0789 for 2425 observed reflections （I 〉 2σ（I））. Cluster 2 is isomorphous to 1 with similar crystal parameters. X-ray analysis reveals that both clusters consist of three incomplete cubane-like cluster units {MOS3Cu3S2COCH3}, which are linked together by two μ3-S atoms.展开更多
An unusual 3D porous network assembled by tridentate ligand Tbmiz [1,3,5- tris（benzimidazol-1-ylmethyl）-2,4,6-trimethylbenzene] and Cu-I cluster was synthesized by means of hydrothermal process. It crystallizes in t...An unusual 3D porous network assembled by tridentate ligand Tbmiz [1,3,5- tris（benzimidazol-1-ylmethyl）-2,4,6-trimethylbenzene] and Cu-I cluster was synthesized by means of hydrothermal process. It crystallizes in the trigonal system, space group P-3c1 with a = 14.2362（8）, b = 14.2362（8）, c = 36.4017（35）A, γ = 120.00°, V = 6389.1（8）, Dc = 1.976 g/cm^3, Z = 2, μ（MoKα） = 0.71073 and F（000） = 3692.0. Of the 40832 total reflections, 3948 were unique （Rint = 0.0366）. The final R = 0.0460 and wR = 0.1335 for 3948 observed reflections with I 〉 2σ（I）.展开更多
This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<...This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<sub>2</sub>=Me<sub>2</sub>,Et<sub>2</sub>,C<sub>4</sub>H<sub>8</sub>,C<sub>5</sub>H<sub>1</sub>0） yield a series of tetra-,hexa-,and heptanuclear cluster compounds.Their spectroscopic properties and the synthetic reaction mechanism are discussed.展开更多
Deposition and structural characteristics of cadmium sulfide (CdS) thin films by chemical bath deposition (CBD) technique from a bath containing thiourea,cadmium acetate,ammonium acetate and ammonia in an aqueous solu...Deposition and structural characteristics of cadmium sulfide (CdS) thin films by chemical bath deposition (CBD) technique from a bath containing thiourea,cadmium acetate,ammonium acetate and ammonia in an aqueous solution are reported.Researches are made on the influence of the fundamental parameters including pH,temperature,and concentrations of the solution involved in the chemical bath deposition of CdS and titration or dumping of the thiourea solution on the structure characteristic of CdS thin films.The pH of the solution plays a vital role on the characteristic of the CdS thin films.The XRD patterns show that the change in the pH of the solution results in the change in crystal phase from predominant hexagonal phase to predominant cubic phase.The CdS thin films with the two different crystal phases have different influences on CIGS thin film solar cells.The crystal mismatch and the interface state density of the c-CdS(cubic phase CdS) and CIGS are about 1 419% and 8 507×10 12cm -2 respectively,and those of the h-CdS(hexagonal phase CdS) and CIGS are about 32 297% and 2 792×10 12cm -2 respectively.It is necessary for high efficiency CIGS thin film solar cells to deposit the cubic phase CdS thin films.展开更多
基金Project supported by the National Natural Science Foundation of China (Grant Nos.11864040,11964037,and 11664038)。
文摘Zr-based amorphous alloys have attracted extensive attention because of their large glassy formation ability, wide supercooled liquid region, high elasticity, and unique mechanical strength induced by their icosahedral local structures.To determine the microstructures of Zr–Cu clusters, the stable and metastable geometry of Zr_(n)Cu(n=2–12) clusters are screened out via the CALYPSO method using machine-learning potentials, and then the electronic structures are investigated using density functional theory. The results show that the Zr_(n)Cu(n ≥ 3) clusters possess three-dimensional geometries, Zr_(n)Cu(n≥9) possess cage-like geometries, and the Zr_(12)Cu cluster has icosahedral geometry. The binding energy per atom gradually gets enlarged with the increase in the size of the clusters, and Zr_(n)Cu(n=5,7,9,12) have relatively better stability than their neighbors. The magnetic moment of most Zr_(n)Cu clusters is just 1μB, and the main components of the highest occupied molecular orbitals(HOMOs) in the Zr_(12)Cu cluster come from the Zr-d state. There are hardly any localized two-center bonds, and there are about 20 σ-type delocalized three-center bonds.
基金This paper was financially supported by the National Natural Science Foundation of China (No.50401020, 50671018 and 50631010)the Provincial Science and Technology Foundation of Liaoning (No.20061067).
文摘The bulk metallic glass formation in the Cu-Zr-M ternary systems by alloying of a binary basic Cu6Zr5 cluster was inves- tigated, where M stands for Sn, Mo, Ta, Nb, Ag, Al and Ti. The Cu6Zr5 cluster is a capped Archimedean antiprism that characterizes the local structure of the Cu10Zr7 crystalline phase. This cluster composition almost superposes with Cu-Zr eutectic Cu0.56Zr0.44. A se- ries of alloys along the cluster line (Cu6Zr5)1-xMx were examined for their glass forming abilities. Alloy rods with a diameter of 3 mm were prepared by copper mould suction casting method and analyzed by XRD and thermal analysis. The Cu-Zr based bulk metallic glasses were discovered with minor Nb, Sn, Mo, Ta additions (≤2at%) and Al, Ti, Ag (8at%≤concentration≤9at%). The alloying mechanism was discussed in the light of atomic size, cluster-linking structure and electron concentration factors.
基金supported by CAS (SZD08002-2)973 Program (2007CB815306)+1 种基金the NNSFC (20733003 and 20673117)the Young Scientist’s Foundation of Fujian Province (2006F3136)
文摘The self-assembly reactions of [MOS3]^2- （M = W, Mo） with CuS2COCH3 in DMF produced two novel dodecanuclear Mo（W）/Cu/S heterometallic clusters, [Et4N]4[{MOS3}3Cu6S2- （CuS2COCH3）3]·H2O （1： M = W; 2： M = Mo）. Cluster 1 crystallizes in hexagonal, space group P-62c with a = 16.5612（3）, b = 16.5612（3）, c = 16.4660（5）A, Z = 2, V = 3911.13（16）A^3, Dc = 1.935 g/cm^3, μ（MoKα） = 7.269 mm^-1, F（000） = 2192, the final R = 0.0289 and wR = 0.0789 for 2425 observed reflections （I 〉 2σ（I））. Cluster 2 is isomorphous to 1 with similar crystal parameters. X-ray analysis reveals that both clusters consist of three incomplete cubane-like cluster units {MOS3Cu3S2COCH3}, which are linked together by two μ3-S atoms.
基金Supported by the Young Talent Program of Fujian Province (No. 2007F3117)Natural Science Foundation of Fujian Province (No. 2007J0001)
文摘An unusual 3D porous network assembled by tridentate ligand Tbmiz [1,3,5- tris（benzimidazol-1-ylmethyl）-2,4,6-trimethylbenzene] and Cu-I cluster was synthesized by means of hydrothermal process. It crystallizes in the trigonal system, space group P-3c1 with a = 14.2362（8）, b = 14.2362（8）, c = 36.4017（35）A, γ = 120.00°, V = 6389.1（8）, Dc = 1.976 g/cm^3, Z = 2, μ（MoKα） = 0.71073 and F（000） = 3692.0. Of the 40832 total reflections, 3948 were unique （Rint = 0.0366）. The final R = 0.0460 and wR = 0.1335 for 3948 observed reflections with I 〉 2σ（I）.
文摘This paper presents the synthetic and structure studies of molybdenum（tungsten）-copper-sulphur-dialkyldithiocarbamate cluster compounds.The reactions of（M=Mo,W;n=0,2）,CuCl,and R<sub>2</sub>dtc￣-（R<sub>2</sub>=Me<sub>2</sub>,Et<sub>2</sub>,C<sub>4</sub>H<sub>8</sub>,C<sub>5</sub>H<sub>1</sub>0） yield a series of tetra-,hexa-,and heptanuclear cluster compounds.Their spectroscopic properties and the synthetic reaction mechanism are discussed.
文摘Deposition and structural characteristics of cadmium sulfide (CdS) thin films by chemical bath deposition (CBD) technique from a bath containing thiourea,cadmium acetate,ammonium acetate and ammonia in an aqueous solution are reported.Researches are made on the influence of the fundamental parameters including pH,temperature,and concentrations of the solution involved in the chemical bath deposition of CdS and titration or dumping of the thiourea solution on the structure characteristic of CdS thin films.The pH of the solution plays a vital role on the characteristic of the CdS thin films.The XRD patterns show that the change in the pH of the solution results in the change in crystal phase from predominant hexagonal phase to predominant cubic phase.The CdS thin films with the two different crystal phases have different influences on CIGS thin film solar cells.The crystal mismatch and the interface state density of the c-CdS(cubic phase CdS) and CIGS are about 1 419% and 8 507×10 12cm -2 respectively,and those of the h-CdS(hexagonal phase CdS) and CIGS are about 32 297% and 2 792×10 12cm -2 respectively.It is necessary for high efficiency CIGS thin film solar cells to deposit the cubic phase CdS thin films.
