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1.
Low‐energy lead ion implantation and high‐temperature electron beam annealing were used to study the potential of producing Pb nanostructures on Si. Pb+ ions were implanted at high dose into p‐type (100) Si to the depth of 8.0 nm. The implanted samples were annealed under high vacuum conditions with an electron beam at 200–700 °C for 15 s. Rutherford Backscattering Spectrometry (RBS) shows rapid out‐diffusion of Pb atoms above 400 °C. However, some Pb atoms are still present in the near‐surface region after annealing the implanted samples at 700 °C. Lead nanostructures were found on samples annealed above 300 °C. Annealing the samples at 450 °C causes the formation of nanostructures as tall as 4.1 ± 0.1 nm. Many of these are arranged in ‘web‐like’ strings that extend over micrometer distances. Occasionally, much larger nano‐features (as wide as 500 nm in diameter, average height of 1.5 nm) appear in the centre of the strings. Annealing samples well above the melting point of lead results in randomly distributed small nanometer‐sized Si nano‐dots. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

2.
Lead zirconate titanate (PZT) thin films were deposited on Pt/Ti/SiO2/Si and interlayer/Pt/Ti/SiO2/Si substrate by radio frequency (r.f.) magnetron sputtering with a Pb1.1Zr0.53Ti0.47O3 target. The crystallization of the PZT thin films was formed only by substrate temperature. When interlayer (PbO/TiO2) was inserted between the PZT thin film and the Pt electrode, the grain growth and processing temperature of the PZT thin films were considerably improved. Compared to PZT/Pt structure, the dielectric constant and polarization properties of the PZT/interlayer/Pt structure were fairly improved. In particular, PZT/interlayer/Pt at the substrate temperature of 400 °C showed prevalent ferroelectric properties (r=475.97, tanδ=0.0591, Pr=23 μC/cm2). As a result of an X-ray photoelectron spectroscopy (XPS) depth-profile analysis, it was found that PZT/interlayer/Pt deposited only by substrate temperature without the post-annealing process via r.f. magnetron sputtering method remained independent of each other regardless of substrate temperatures.  相似文献   

3.
We report a series of luminescent sandwich‐type clusters [Pt2Pb2(C≡CR)8] (R=Tol, 1 ; C6H4OMe‐3, 2 ; C6H4OMe‐4, 3 ) with a dynamic Pt2Pb2 metallic core, which is key to their intriguing stimuli‐responsive photophysical properties. The solvent‐free solids 1 – 3 display an orange emission ascribed to charge transfer from Pt–alkynyl fragments to a delocalized orbital with mixed Pt2Pb2/C≡CR nature, with a predominant lead contribution and Pb???Pb bonding character (3MLCCT/3IL). They exhibit mechanical, color, and luminescence changes that are reversible and perceivable with the naked eye, which are attributed to small inter‐ and intramolecular structural modifications induced by gentle grinding. Interestingly, 1 and 2 also exhibit remarkable and fast reversible vapochromic responses to donor solvent vapors (acetone, THFMe‐2: yellow; NCMe: green, vs. dry solids: orange). The structures of 1(acetone)2 ?2(Me2CO), 2 ( acetone ) 3 , and 2 ( THFMe ‐ 2 ) 2 allow the vapochromic responses to be ascribed to the fast creation/disruption of solvate clusters [Pt2Pb2(C≡CR)8Sx] (x≥2), with concomitant electronic and geometrical modifications within the Pt2Pb2 core, which are easily accessible through a slight change in the stereochemical activity of the lone pair. The binding of one (or two) solvent molecules to Pb2+ increases the Pb???Pb separation in the metallic core, causing a destabilization of the target orbital and larger energy gaps of the transitions. All the solvates exhibit remarkable rigidochromism upon a decrease in temperature, which is also associated with the gradual increase in the transannular Pb???Pb separation, as revealed by X‐ray crystallography of 1 ( acetone ) 2 at different temperatures. Investigation of the crystal lattice of 1 ?CH2Cl2 and 3 ?2 CH2Cl2 further suggests that the lack of vapor stimuli response of complex 3 could be attributed to the presence of competitive additional secondary intermolecular Pb???O(OMe) contacts, which give rise to a more compact network built up from extended chains of clusters.  相似文献   

4.
Pb2(OH)2[p‐O2C‐C6H4‐CO2]: Synthesis and Crystal Structure Single crystals of Pb2(OH)2[p‐O2C‐C6H4‐CO2] ( 1 ) were obtained by hydrothermal reaction of terephthalic acid and PbCO3 at 180 °C (10 days). 1 crystallizes in the monoclinic space group P21/c with Z = 2 (a = 1115.6(2) pm, b = 380.10(4) pm, c = 1141.3(2) pm, β = 93.39(1)°, V = 0.4831(1) nm3). The crystal structure is characterized by ladder‐type Pb(OH)3/3 double chains, which are connected to a three‐dimensional framework by terephthalate dianions.  相似文献   

5.
Structure‐Behaviour‐Relation of Cu5Pb6O3Cl11, a Good Solid State Ionic Conductor for Cu+‐Ions A new compound within the group of coin metal lead(II) oxide halides is found and characterized by X‐ray single crystal structure determination in a temperature range from 120 K to 400 K. Cu5Pb6O3Cl11 shows a new crystal type structure with a = 21.098(4) Å, b = 10.233(2) Å, c = 12.224(2) Å, β = 124.08(3)°, Z = 4 and space group C 2/c (No. 15) at 120 K. There are found isolated oxidic chains built of OPb4 tetrahedra beside columnar areas consisting of CuCl. In this halidic partial structure are a lot of empty and partially occupied Cl4‐tetrahedra. This structural characteristic seems to be source of a very good conductivity of copper ions, like in microscopic and nanoscaled composites of Al2O3 and AgI.  相似文献   

6.
Chemical solution deposited (CSD) complex oxide thin films attract considerable interest in various emerging fields as for example, fuel cells, ferroelectric random access memories or coated conductors. In the present paper the results of soft-X-ray spectroscopy between 280 and 560 eV on the amorphous to crystalline phase transition of ferroelectric Pb(Zr0.3Ti0.7)O3 (PZT) thin films are presented. Five CSD samples derived from the same wafer coated with a PZT film pyrolyzed at 350 °C were heat treated at different temperatures between 400 and 700 °C. At first the samples were morphologically and electrically characterized. Subsequently the soft-X-ray absorption and emission experiments were performed at the undulator beamline 8.0 of the Advanced Light Source of the Lawrence Berkeley National Laboratory. Soft-X-ray absorption spectra were acquired for the Ti L 2,3-, O K-, and C K-edge thresholds by using simultaneously the total electron yield (TEY) and total fluorescence yield (TFY) detection methods. For two samples, annealed at 400 and 700 °C, respectively, the resonant inelastic soft-X-ray spectroscopy (RIXS) was applied for various excitation energies near the Ti L-, O K-edges. We observed clear evidence of a rutile phase at untypically low temperatures. This rutile phase transforms into the perovskite phase upon increasing annealing temperature. These results are discussed in the framework of current microscopic models of the PZT (111) texture selection.  相似文献   

7.
Fabrication of ferroelectric Pb(Zr0.52Ti0.48)O3 (PZT) thick films on a Pt/Ti/SiO2/Si substrate using powder-mixing sol-gel spin coating and continuous wave CO2 laser annealing technique to treat the specimens with at a relatively low temperature was investigated in the present work. PZT fine powders were prepared by drying and pyrolysis of sol-gel solutions and calcined at temperatures from 400 to 750°C. After fine powder-containing sol-gel solutions were spin-coated on a substrate and pyrolyzed, CO2 laser annealing was carried out to heat treat the specimens. The results show that laser annealing provides an extremely efficient way to crystallize the materials, but an amorphous phase may also form in the case of overheating. Thicker films absorb laser energy more effectively and therefore melt at shorter periods, implying a significant volume effect. A film with thickness of 1 μm shows cracks and rough surface morphology and it was difficult to obtain acceptable electrical properties, indicating importance of controlling interfacial stress and choosing appropriate size of the mixing powders. On the other hand, a thick film of 5 μm annealed at 100 W/cm2 for 15 s exhibits excellent properties (P r = 36.1 μC/cm2, E c = 19.66 kV/cm). Films of 10 μm form a melting zone at the surface and a non-crystallized bottom layer easily at an energy density of 100 W/cm2, showing poor electrical properties. Besides, porosity and electrical properties of thick films can be controlled using appropriate processing parameters, suggesting that CO2 laser annealing of modified sol-gel films is suitable for fabricating films of low dielectric constants and high crystallinity.  相似文献   

8.
Novel Coloring of the α‐Mn Structure Type with Main Group Elements in K5Pb24 – Crystal Structure, Superconductivity, and Structure Property Relationship K5Pb24 was synthesized from the elements in a welded niobium ampoule at 800 °C. The crystal structure was determined from X‐ray single crystal data. Space group I 4 3m, a = 12.358(1) Å, Z = 2, Pearson symbol cI58. The structure of K5Pb24 shows an ordered atomic distribution on the four crystallographic sites of the α‐Mn structure type. The aristotype is decomposed into cluster units consisting of 48 Pb atoms. The structural subunits are built from four 16‐vertex Frank Kasper polyhedra, which consist of 15 Pb and one K atom (K1). The 16‐vertex polyhedra are centered with another K atom (K2). Four such polyhedra share a common corner (K1) and several edges. 18 shared edges form a truncated tetrahedra of twelve Pb atoms. These atoms form together with four K1 atoms (located in the center of the Frank Kasper polyhedra) a Friauf polyhedra. The result is a ‘supratetrahedra‘ of 48 Pb atoms enclosing five K atoms. The body centered arrangement of this units results in a three‐dimensional framework of Pb atoms. The title compound is the lead‐richest phase of the K/Pb system. Superconducting properties are observed from temperature dependent susceptibility measurements. Field dependent measurements reveal a hard type II superconductor. LMTO and EH band structure calculations verify the metallic behavior. An analysis of the density of states with the help of the electron localization function (ELF) shows the presence of lone pairs in this intermetallic phase. The role of lone pairs is discussed with respect to the superconducting property.  相似文献   

9.
This paper addresses the role of Mo coating to modify the interface of SiC fiber reinforced Ti‐6Al‐4V composite (SiCf/Mo/Ti‐6Al‐4V). The formation of microstructure as well as the diffusion of elements in the interface of as‐prepared and heat‐treated SiCf/Mo/Ti‐6Al‐4V composites was investigated. The results show that the phases formed at the interfacial zone are: Mo coating∣TiC∣Mo + β‐Ti∣β‐Ti∣β‐Ti + α‐Tistrip, ordering from fiber to matrix. Mo coating can effectively hinder the diffusion of elements between the matrix and fiber to some extent, thus it can inhibit fiber/matrix interfacial reaction and protect the fiber from damage. It is believed that the β‐Ti layer formed around the interface can improve the formability of composites. Furthermore, it indicates that Mo coating exhibits excellent thermal stability bellow 700 °C according to the heat treatment of the composites at 700 °C for up to 200 h. Copyright © 2012 John Wiley & Sons, Ltd.  相似文献   

10.
"Lead zirconate titanate Pb(Zr0:95Ti0:05)O3 (PZT95/5) antiferroelectric thin films with 300 nm thickness were grown on Pt/Ti/SiO2/Si substrates by a sol-gel method with rapid thermal annealing processing. The X-ray diffraction results showed that the highly (111)-oriented pervoskite PZT95/5 thin films were grown on Pt/Ti/SiO2/Si substrates when annealed at 600-700 oC. Electrical measurements were conducted on PZT95/5 films in metal-ferroelectric-metal capacitor configuration. The PZT95/5 thin films annealed at 600-700 oC showed well-saturated hysteresis loops at an applied voltage of 20 V. At 1 kHz, the dielectric constant and dielectric loss of the films were 519 and 0.028, 677 and 0.029, 987 and 0.025, respectively for the thin films annealed at 600, 650, and 700 oC. The average remanent polarization (Pr) and the coercive electric field (Ec) obtained from the P-E hysteresis loops, were 19.1 1C/cm2 and 135.6 kV/cm, 29.31C/cm2 and 88.57 kV/cm, 45.3 1C/cm2 and 102.1 kV/cm, respectively for PZT95/5 thin films annealed at 600, 650 and 700 oC for 10 min in the oxygen atmosphere. This showed a good ferroelectricity of the prepared PZT95/5 films on Pt/Ti/SiO2/Si substrates by the simple sol-gel processing. The pyroelectric coeocient (p) of antiferroelectric PZT95/5 films was measured by a dynamic technique. At room temperature, the p values of the antiferroelectric PZT95/5 films at 1 kHz were 274, 238, and 212 1C/m2K."  相似文献   

11.
Highly (111) oriented, phase-pure perovskite Pb(Zr0.3Ti0.7)O3 (or PZT 30/70) thin films were deposited on single-crystal, (0001) wurtzite GaN/sapphire substrates using the sol-gel process and rapid thermal annealing. The phase, crystallinity, and stoichiometry of annealed PZT films were evaluated by X-ray diffraction and Rutherford backscattering spectroscopy. The atomic force microscopy revealed a smooth PZT surface (rms roughness ∼1.5 nm) with striations and undulations possibly influenced by the nature of the underlying GaN surface. The cross-sectional field-emission scanning electron microscopic images indicated a sharper PZT/GaN interface compared to that of sol-gel derived PZT on (111) Pt/TiO2/SiO2/(100) Si substrates. The capacitance-voltage (C-V) characteristics for PZT in the Pt/PZT/GaN (metal-ferroelectric-semiconductor or MFS) configuration were evaluated as a function of annealing temperature and applied voltage. The observed C-V hysteresis stemmed from trapped charge at defect sites within PZT. Also, the lower capacitance density (C/A = 0.35 μF/cm2, where A is the area of an electrode) and remnant polarization (P r ∼ 4 μC/cm2) for PZT in the MFS configuration, compared to the values for PZT in the MFM configuration (Pt/PZT/Pt), were attributed to the high depolarization field within PZT.  相似文献   

12.
13.
The title compound, [Pb(C4H3N2S)2]n, was prepared by the reaction of [Pb(OAc)2]·3H2O (OAc is acetate) with pyrimidine‐2‐thione in the presence of triethylamine in methanol. In the crystal structure, the PbII atom has an N4S4 coordination environment with four ligands coordinated by N‐ and S‐donor atoms. This compound shows that the pyrimidine‐2‐thiolate anion can lead to a three‐dimensional network when the coordination number of the metal ion can be higher than 6, as is the case with the PbII ion. This compound presents only covalent bonds, showing that despite the possibility of the hemidirected geometries of PbII, the eight‐coordinated ion does not allow the formation of an isolated molecular structure with pyrimidine‐2‐thiolate as the ligand.  相似文献   

14.
A perovskite lead zirconate titanate was synthesized by the sol‐gel process, using lead glycolate, sodium tris(glycozirconate) and titanium glycolate as the starting precursors. For the mole ratio Pb:Zr:Ti of 1:0.5:0.5 [Pb(Zr0.5Ti0.5)O3], TGA‐DSC thermal analysis indicated that the percentage of ceramic yield was 55.8, close to the calculated chemical composition value of 49.5. The exothermic peak occurred at 268 °C below the theoretical Curie temperature of 400 °C. The pyrolysis of Pb(Zr0.5Ti0.5)O3 of the perovskite phase was investigated in terms of calcination temperature and time. The structure obtained was of the tetragonal form when calcined at temperatures below 400 °C; it transformed to the tetragonal and the cubic forms of the perovskite phase on calcination above the Curie temperature, as verified by X‐ray data. The lead zirconate titanate synthesized and calcined at 400 °C for 1 h had the highest dielectric constant, the highest electrical conductivity and the dielectric loss tangent of 10 190, 0.803 × 10?3 (Ω.m)?1 and 1.513 at 1000 Hz, respectively. The lead zirconate titanate powder synthesized has potential applications as an electronic material. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

15.
The free‐radical polymerization of methyl acrylate (MA) has been studied in the presence of a novel cyclic dixanthate under γ‐ray irradiation (80 Gy min?1) at room temperature (~28 °C), ?30 °C, and ?76 °C respectively. The resultant polymers have controlled molecular weights and relatively narrow molecular weight distributions, especially at low temperatures (i.e., ?30 and ?76 °C). The polymerization control may be associated with the temperature: the lower the temperature is, the more control there is. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analysis of poly(methyl acrylate) (PMA) samples shows that there are at least three distributions: [3‐(MA)n‐H]+ cyclic polymers, [3‐(MA)n‐THF‐H]+, and [3‐(MA)n‐(THF)2‐H]+ linear PMAs. The relative content of the cyclic polymers markedly increases at a lower temperature, and this may be related to the reduced diffusion rate and the suppressed chain‐transfer reaction at the low temperature. It is evidenced that the good control of the polymerization at the low temperature may be associated with the suppressed chain‐transfer reaction, unlike reversible addition–fragmentation chain transfer polymerization. In addition, styrene bulk polymerizations have been performed, and gel permeation chromatography traces show that there is only one cyclic dixanthate moiety in the polymer chain. This article is the first to report the influence of a low temperature on controlled free‐radical polymerizations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2847–2854, 2007  相似文献   

16.
A feasible strategy is reported for the synthesis of a disk‐like Pt/CeO2‐p‐TiO2 catalyst derived from the titanium‐based metal–organic framework (MOF) MIL‐125(Ti) through a few valid steps. To verify the successful synthesis and structural features of the Pt/CeO2‐p‐TiO2 catalyst, as‐prepared samples were characterized using several techniques. The characterizations demonstrated that MOF‐derived porous TiO2 was appropriate for application as a support owing to its moderate surface area (101 m2 g?1) and suitable pore size (6 nm). Moreover, to study the effect of calcination temperature on the catalytic performance, the obtained catalyst was calcined at various temperatures. It was found that Pt/CeO2‐p‐TiO2 calcined at 550 °C exhibited the highest catalytic performance, evaluated by means of the reduction of 4‐nitrophenol monitored by UV–visible spectra. Furthermore, this catalyst showed good reusability with a conversion of 94% even after six cycles. Finally, a possible reaction mechanism was proposed to explain the reduction of 4‐nitrophenol to 4‐aminophenol over the Pt/CeO2‐p‐TiO2 catalyst.  相似文献   

17.
In order to suppress polarization fatigue and decrease the leakage current of the PZT capacitor, composite electrodes consisting of MO2 (RuOx or IrOx) as an effective diffusion barrier and considerably large amounts of Pt were deposited by magnetron co-sputtering to yield heterostructured PZT capacitors, Pt/(Pt+MO2)//PZT(52/48)//(Pt+MO2)/(Pt+M)/M/Pt/Ti(Ta)/SiO2/Si(1 0 0), and the crystallinity and the orientation, the morphology of the surface and the cross section, and the composition depth profile of the PZT capacitor were examined by XRD analysis, SEM and AES, respectively, and the ferroelectric properties were measured. The results indicated that by adjusting the distribution and composition of the RuO2 phase, the polarization loss of the PZT capacitor can be suppressed to as small as 5% after polarization reversals of 109 while maintaining the effective polarization dPr = Pr* – Pr ^ at 15 C/cm2. The suppression of the polarization fatigue was found more effective with (Pt+IrO2) electroding than (Pt+RuO2) electroding. The leakage current of the PZT capacitor electroded with (Pt+MO2) was a little larger than that of the PZT capacitor with Pt electrode. The possible reason was suggested.  相似文献   

18.
In the title compound, [Pb(C12H8NO2)2]n, the Pb atom sits on a crystallographic C2 axis and is six‐coordinate, ligated by two chelating carboxylate groups from two 3‐(pyridin‐4‐yl)benzoate (L) ligands and by two N atoms from another two ligands. Each ligand bridges two PbII centres, extending the structure into a corrugated two‐dimensional (4,4) net. The ligand L is conformationally chiral, with a torsion angle of 27.9 (12)° between the planes of its two rings. The torsion angle has the same sense throughout the structure, so that the extended two‐dimensional polymer is homochiral. Investigation of the thermal stability shows that the network is stable up to 613 K. In the absence of any stereoselective factor in the preparation of the compound, the enantiomeric purity of the crystal studied, based only on the torsional conformation of the ligand, implies that the bulk sample is a racemic conglomerate.  相似文献   

19.
The reaction of Pb(CH3COO)2·3H2O with N‐benzesulfonyl‐L‐glutamic acid in the presence of 2, 2′‐bipyridine (bipy) or 1,10‐phenanthroline (phen) produced two novel complexes [Pb2(Bs‐glu)2(bipy)2] ( 1 ) and [Pb2(Bs‐glu)2(phen)2] ( 2 ) (Bs‐glu = N‐benzesulfonyl‐L‐glutamic acid dianion). In 1 chains bearing alternative 16‐membered rings and Pb2O3 nodes are constructed from the interactions of PbII ions with the carboxylates of Bs‐glu ligands. To the best of our knowledge, this is the first lead(II) complex of carboxylates with the formation of chains of Pb2O3. In 2 the 16‐membered ring units are connected by centrosymmetric Pb2O2 nodes to form chains. Complexes 1 and 2 construct the 3‐D supramolecular architectures through versatile hydrogen bonds and π‐π stacking interactions.  相似文献   

20.
张树芹  侯万国 《中国化学》2007,25(10):1455-1460
Layered double hydroxide (LDH) with a Mg/Al molar ratio of 1 : 1 was synthesized by using a co-precipitation method and its calcined product (CLDH) was obtained by calcination of the MgAl-LDH at 500 ℃. The sorption removal of Pb^2+ from solution was investigated, finding that both LDH and CLDH show good sorption ability and they could be used as a new type of environmental sorbent for the removal of Pb^2+ from water. The sorption kinetics and the sorption isotherms of Pb^2+ on both LDH and CLDH can be described by the pseudo-second order kinetics and Freundlich isotherm, respectively, under the studied conditions. The sorption amounts of Pb^2+ on LDH and CLDH are independent of pH in a pH range of about 3-10. The presence of NaNO3 may inhibit the sorption of Pb^2+ on LDH while hardly affect that on CLDH. The sorption mechanism of Pb^2+ on LDH and CLDH may be attributed to the surface precipitation and the surface complex adsorption. The surface complex adsorption may be further distinguished to the chemical binding adsorption forming the inner-sphere surface complexes and the electrostatic binding adsorption forming the outer-sphere surface complexes. The sorption mechanism of Pb^2+ on LDH may be attributed to the surface precipitation and the electrostatic binding adsorption, while that on CLDH may be attributed to the surface precipitation and the chemical binding adsorption.  相似文献   

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