The preparation of PLZT ceramics from a sol-gel process

Sol-gel process is employed to prepare PLZT ceramic with the composition 9/56/44 (La/Zr/Ti). Complete crystallization of the sol-gel derived powders is achieved after 600°, 1 hr. calcination. The sintered density of the PLZT pellet decreases as the sintering time increases. A ninety-nine percent theoretical density is obtained for samples sintered at 1250° for one hour. The dielectric properties and optical transmission of the sol-gel derived samples are measured and compared with those of the hot-pressed PLZT ceramics reported in the literature. Sol-gel derived powders, when properly sintered, possess sufficient optical transparency for optoelectrical device applications.     

MOCVD epitaxial growth of single crystal GaN,AlN and AlxGa1-xN

Ga begins to deposit from a stream of trimethylgallium (TMG) in H₂ at a minimum temperature of 475‡C. Addition of sufficient amounts of NH₂ results in the growth of textured polycrystalline GaN on basal plane sapphire substrates above 500‡C. A minimum temperature of 800‡C is required for the epitaxial growth of GaN on the substrate. Under similar conditions, but with the TMG replaced with trimethylaluminum (TMA), polycrystalline A1N begins forming at 400‡C (in the absence of NH₃,, the TMA starts pyrolyzing at 300‡C), but single crystal growth of A1N requires a temperature of at least 1200‡C. Epitaxial single crystal layers of Al_x Ga_1-x N can be grown in the temperature range 800−1200‡C, tne minimum temperature being approximately proportional to x, but preferential deposition of A1N on the hot walls of the reactor (>400‡C) precludes precise control of the alloy composition. This predeposition of A1N can be retarded by keeping the walls below 400‡C by using a water-cooled jacket, by rapid flow-rates, or by injecting the TMA through a nozzle close to the surface of the substrate.     

Sintering behavior of a reactively bonded thick film gold ink

The sintering behavior of thick film reactively bonded Au films was studied using electrical re-sistance measurement and scanning electron microscopy. Isothermal firings were conducted at 350‡ to 850‡C for times up to three hours. The sintering process consists of three portions: 1) Burnoff of the binding resin at 350‡ to 450‡C. 2) A second stage involving neck growth between the gold particles with an activation energy of ∼ 15 Kcal/mole and a time exponent of 5.5 to 6.5 corresponding to surface diffusion control and 3) a third stage of densificat ion by pore annihila-tion and grain growth. The activation energy in stage III of 35–45 Kcal/mole agrees closely with bulk diffusion control. Electrical resistance change appears to be a useful method for studying particularly the initial stages of sintering.     

Annealing studies of Be-implanted GaAs0.6P0.4

Differential resistivity and Hall effect measurements and secondary ion mass spectrometry (SIMS) are used to study the annealing behavior of Be-implanted GaAs_0.6P_0.4. Results similar to that previously reported for Be-implanted GaAs are observed, including outdiffusion of Be into the Si₃N₄ encapsulant during 900‡C annealing of high dose implants. Nearly all (85–100%) of the Be remaining after a 900‡C, 1/2 hr anneal is electrically active. However, the electrical activation at low annealing temperatures (600–700‡C) is much lower in GaAs_0.6P_0.4 than in GaAs. A substantial amount of diffusion is observed even for the low fluence Be implants in GaAs_0.6P_0.4 annealed at 900‡C, indicating a greater dependence of the diffusion on defect-related effects in the ternary. This work was supported by the Joint Services Electronics Program (U.S. Army, U.S. Navy, U.S. Air Force) under Contract DAAB-07-72-C-0259, by Monsanto Company, and by the Naval Electronic Systems Command. On leave at Cornell University, Department of Electrical Engineering, Ithaca, NY 14853.     

Raman characterization of hydroxyl in fused silica and thermally grown SiO2

We developed Raman spectroscopy to characterize the hydroxyl (OH) solubility in fused silica and thermally grown steam SiO₂ from 695 to 1000‡C and 1–10 atm steam pressure. The technique was extended to measure the OH diffusion profiles in bulk v-SiO₂, and the derived diffusion coefficients supplement those published in the literature. Fused silicas processed with higner fictive temperatures display larger initial OH solubilities which decrease with time, but saturations at temperatures as low as 600‡C remove much of the prior thermal history as the glass structurally relaxes. The OH solubility appears to be proportional to the square root of external steam pressure; however, the quasiequilibrium temperature dependence is unresolved. The behavior of OH in fused silica and the thermally grown oxide is very similar when the two materials are identically processed.     

Effect of bismuth addition on sintering behavior and microwave dielectric properties of zinc titanate ceramics

The influences of Bi₂O₃ addition on the sintering behavior and microwave dielectric properties of ZnO-TiO₂ ceramics were investigated. ZnO-TiO₂ ceramics were prepared with conventional solid-state method and sintered at temperatures from 950°C to 1,100°C. The sintering temperature of ZnO-TiO₂ ceramics with Bi₂O₃ addition could be effectively reduced to 1,000°C due to the liquidphase effects resulting from the additives. A proper amount of Bi₂O₃ addition could effectively improve the densification and dielectric properties of ZnO-TiO₂ ceramics. The temperature coefficient of resonant frequency could be controlled by varying the sintering temperature and lead to a zero τ_f value. At 1,000°C, 1ZnO-1TiO₂ ceramics with 1 wt.% addition gave better microwave dielectric properties ɛ_r of 29.3, a Q × f value of 22,000 GHz at 8.36 GHz, and a τ_f value of +17.4 ppm/ °C.     

Improvement of Temperature Stability,Dielectric Properties and Nonlinear Current-Electric Field Characteristic of CaCu 3 Ti 4.2−x Sn x O 12 Ceramics

The dielectric properties and the nonlinear current density–electric field (J–E) relationship of CaCu3Ti4.2−xSnxO12 (x = 0.00, 0.05 and 0.10) ceramics at various sintering temperatures are presented. Excellent dielectric properties with a very low tanδ ∼ 0.008–0.020, a giant ε′ ∼ 6495–16,975, and stability of Δε′ of < ± 15% over the temperature range of −60 to 210°C are obtained in a CaCu3Ti4.15Sn0.05O12 ceramic sintered at 1080°C and CaCu3Ti4.10Sn0.10O12 ceramics sintered at both 1080°C and 1100°C. Additionally, all ceramics exhibited a nonlinear J–E relationship. A maximal nonlinear coefficient (α) of ∼ 1044.4 is obtained in the CaCu3Ti4.15Sn0.05O12 sintered at 1080°C. X-ray diffraction and field emission scanning electron microscopy techniques were used for structural and microstructural evaluation of all ceramics. Elemental mapping with energy dispersive X-ray spectroscopy confirmed the presence of Sn4+ dopant at the main CaCu3Ti4O12 site and in minor TiO2 phases of all Sn4+ doped CaCu3Ti4.2O12 ceramics. This mixed phase plays an important role to increase grain boundary resistance (Rgb) and significantly improves the thermal stability of dielectric properties, as well as the nonlinear J-E relationship.     

Structures and physical properties of sputtered amorphous SiC films

Optical and electrical properties have been measured for amorphous SiC films prepared by rf sputtering in a pure Ar atmosphere with a sintered 6H-SiC target. The absorption edge E₀ determined from the relation of αhΝ = B(hΝ-E₀)² ranged from 1.45 to 1.80 eV depending on the film thickness and the substrate temperature. The room temperature electrical conductivity is in the range of 5.4×10⁻¹¹ and 1.4×10⁻⁵ Ω⁻¹cm⁻¹. The absorption edge decreases and the conductivity increases with increasing film thickness. The absorption edge shifts to shorter wavelengths (blue shift) and the conductivity decreases during annealing below 400‡C for 60 min, whereas the absorption edge shifts to the longer wavelength side (red shift) and the conductivity increases during annealing at 800‡C It is proposed that the two annealing processes cause structural changes in amorphous SiC films, one of which involves removal of defects or voids while the other involves rearrangement or rebonding of the component atoms.     

Purification of CdTe from,tellurium-rich solutions

Cadmium telluride was grown from tellurium-rich solutions from 600 ‡C to 900 ‡C. Significant purification occurred during growth. Impurities were intentionally-incorporated into the starting materials and the segregation coefficients were measured. Values at 880 ‡C were Hg - 0.3, Zn - 4, S - 4, Se - 2, O ≈0.02, In - 0.06, Al ≈ 0.1, B <1, Tl <0.01, Co - 0.03, Au - 0.1, Ag - 0. 009, Li - 0. 3, Na ≈0.01, K ≈0. 01, Cl ≈0.005, I <0. 5, Pb < 0.005, C ≈0. 5, N ≈0.4, Bi < 0.001, Mg - 1.5, Pt < 0.01, Cr < 1. Supported in part by the AEC, Division of Applied Technology, and ARPA.     

Liquidus isotherms,solidus lines and LPE growth in the Te-rich corner of the Hg-Cd-Te system

Liquidus isotherms for the Hg_1−xCd_xTe primary phase field in the Te-rich corner of the Hg-Cd-Te ternary system have been determined for temperatures from 425 to 600‡C by a modified direct observational technique. These isotherms were used to help establish conditions for the open-tube liquid phase epitaxial growth of Hg_1−xCd_xTe layers on CdTe_1−ySe_y substrates. Layers with x ranging from 0.1 to 0.8 have been grown from Te-rich HgCdTe solutions under flowing H₂ by means of a horizontal slider technique that prevents loss of Hg from the solutions by evaporation. Growth temperatures and times of 450–550‡C and 0.25–10 min, respectively, have been used. The growth solution equilibration time is typically 1 h at 550‡C. Source wafers, supercooled solutions, and (111)-oriented substrates were employed in growing the highest quality layers, which were between 3 and 15 Μm thick. Electron microprobe analysis was used to determine x for the epitaxial layers, and the resulting data, along with the liquidus isotherms, were used to obtain solidus lines. In addition to EMP data, optical transmission results are given. This work was sponsored by the Department of the Air Force and the U. S. Army Research Office.     

ITO玻璃衬底上PLZT铁电薄膜的制备与电性能

用sol-gel法在掺Sn的In2O3导电透明膜(ITO)衬底上,制备了La掺杂的PbZr0.5Ti0.5O3(PLZT)铁电薄膜。研究了La掺杂量对薄膜的铁电、介电和漏电性质的影响。结果表明,x(La)为5%的PLZT薄膜经650℃退火,有优良的铁电特性,外加15V电压下,剩余极化强度为35.4×10–6C/cm2,矫顽场强为111×103V/cm。100kHz时的εr和tgδ分别为984和0.13。在外加电场小于9V时,薄膜的漏电流密度不超过10–8A/cm2。     

Oxidation through the zirconia substrates of heteroepitaxial silicon films Grown on yttria-stabilized cubic zirconia

We demonstrate the thermal oxidation of the Si side of the interface in epitaxial Si films grown on yttria-stabilized cubic zirconia, 〈Si〉/〈YSZ〉, to form a dual-layer structure of 〈Si〉 /amorphous SiO₂/〈YSZ〉. The SiO₂ films are formed in either dry oxygen (at 1100‡C) or in pyrogenic steam (at 925‡C) by the rapid diffusion of oxidizing species through the 425 Μm thick cubic zirconia substrate. For instance, a 0.17 Μm thick SiO₂ layer is obtained after 100 min in pyrogenic steam at 925‡C. This relatively easy transport of oxidants is unique to YSZ and other insulators which are also superionic oxygen conductors, and cannot be achieved in other existing Si/insulator systems, such as Si-on-sapphire. The present process eliminates the most     

Electron-beam doping-electron radiation effects in impurity overlayers and semiconductor substrates

3-9 MeV electrons were used to introduce impurity Ge atoms into Si wafers from Ge sheets, which are in contact with a Si surface at 20-60‡C in water bath. Concentration-dependent diffusivities of ∼10-18-10^-14 cm²sec^-1 for Ge in Si were measured. Activation energies of sputtering yield for Ge and of the diffusivity of Ge in Si are estimated to be ∼0.3 eV and ∼0.58 eV, respectively. In a case of hot (∼250‡C) irradiation in ∼1x10^-3 Torr vacuum, also the similar concentration profiles of impurity atoms in the substrates were observed.     

Electron microscope studies of InxGav1−xAs/GaAs/Si grown by metalorganic chemical vapor deposition

The microstructure of In_xGa_1−xAs/GaAs (5 nm/5 nm, x < 0 to 1.0), as grown by a metalorganic chemical vapor deposition two-step growth technique on Si(100) at 450‡C, and subsequently annealed at 750‡C, is investigated using plan-view and cross-sectional transmission electron microscopy. The variations in resultant island morphology and strain as a function of the In content were examined through the comparison of the misfit dislocation arrays and moirés observed. The results are discussed in relation to the ways in which the island relaxation process changes for high In content.     

Surface treatment of GaSb substrate and extremely low temperature LPE growth of AlGaSb

After each process of a chemical etching, heat-cleaning, melt-back, or soaking in HC1, the substrate surface of GaSb was characterized by the Auger electron spectroscopy with a simultaneous Ar sputtering to reveal oxide layer structures. An optimum treatment process of GaSb surfaces for low temperature LPE growth of AlGaSb was established. Uniform growth of epitaxial AlGaSb on GaSb is demonstrated for a wide temperature range(from 500‡C to as low as 250‡C).     

Growth and characterization of lattice-matched epitaxial films of GaxIn1−xAs/InP by liquid-phase epitaxy

We determined the conditions for successful lattice-matched growth by liquid-phase epitaxy near T = 620‡ C of Ga_XIn_1−XAs on [111B] InP substrates. We have used the results of the growth of both lattice-matched and intentionally lattice-mismatched epitaxial layers, (0.4 ≤ X ≤ 0.7) to calculate a phase diagram which gives the correct liquidus temperature, (T_L ± 1‡ C), and the correct solid composition, (± 5 % of the nominal composition), for the entire range of growth solutions considered for this important ternary semi-conductor system. The parameters appropriate to this calculation are significantly different from those used to describe the growth of Ga_XIn_1−XAs on GaAs. The results of this calculation play an important part in the better understanding of the quaternary alloy Ga_XIn_1−XAs_yP_1−y. Our measurements show that the ternary alloy lattice-matched to InP is Ga_0.47In_0.53As, semiconductor with a direct band gap about 0.75 eV at room temperature. We have grown p-n junction homostructures and double-heterostructures on InP substrates. These wafers have been used to make detectors in the 1.0 – 1.7/um range of the optical spectrum.     

Miscibility gap in the GaAsy Sb1−y system

Measurements have been made to determine accurately the solidus curve of the pseudobinary section GaAs_ySb_1−y, by annealing samples to equilibrium and determining compositions by x-ray powder photography. It is found that the equilibriui diagram shows a peritectic form with a peritectic temperature of 745 ± 1‡C and a miscibility gap at that temperature extending from y = 0.38 to y = 0.68. It is also shown that as the temperature is lowered the miscibility gap widens rapidly, being from y = 0.30 to y = 0.95 at 700‡C. The form of these phase boundaries is important when growth of GaAs_ySb_1−y alloys by liquid phase epitaxy or similar techniques is considered.     

Au/Ge/Ni ohmic contacts to n-Type InP

The relationship between the electrical properties and microstructure for annealed Au/Ge/Ni contacts to n-type InP, with an initial doping level of 10¹⁷ cm^-3, have been studied. Metal layers were deposited by electron beam evaporation in the following sequence: 25 nm Ni, 50 nm Ge, and 40 nm Au. Annealing was done in a nitrogen atmosphere at 250-400‡C. The onset of ohmic behavior at 325‡C corresponded to the decomposition of a ternary Ni-In-P phase at the InP surface and the subsequent formation of Ni₂P plus Au₁₀In₃, producing a lower barrier height at the InP interface. This reaction was driven by the inward diffusion of Au and outward diffusion of In. Further annealing, up to 400‡C, resulted in a decrease in contact resistance, which corresponded to the formation of NiP and Au₉ln₄ from Ni₂P and Au₁₀In₃,respectively, with some Ge doping of InP also likely. A minimum contact resistance of 10^-7 Ω-cm² was achieved with a 10 s anneal at 400‡C.     

Effects of Zn/Mg Ratio on the Microstructure and Microwave Dielectric Properties of (Zn1?xMgx)2SiO4 Ceramics

Ceramics of nominal composition (Zn_1−x Mg _x )₂SiO₄ were synthesized by the solid-state method. The phase evolution, microstructure, and microwave dielectric characteristics of the (Zn_1−x Mg _x )₂SiO₄ (0 < x < 1.0) ceramics were investigated systematically. The sintering range was widened and the densification temperatures of the present ceramics were much lower compared with the Zn₂SiO₄ and Mg₂SiO₄ end-members. Coexistence of Mg₂SiO₄ and Zn₂SiO₄ phases was observed in the (Zn_1−x Mg _x )₂SiO₄ ceramics with x = 0.4 and 0.6. The MgSiO₃ secondary phase was also observed due to Mg substitution. Changes in grain shapes from equiaxed to rectangular were observed in sintered samples as x varied from 0.7 to 1.0. The microwave characteristics of (Zn_1−x Mg _x )₂SiO₄ ceramics were significantly improved by the suppression of the MgSiO₃ phase, where an enhanced quality factor (Qf) value was obtained. The best microwave characteristics were achieved in the (Zn_1−x Mg _x )₂SiO₄ ceramic with Zn/Mg ratio of 1.5 sintered at 1250°C: ε _r = 6.2, Qf = 148,740 GHz, τ _f = −54.2 ppm/°C.     

Stability of various doping species in trans-polyacetylene

Polyacetylene, a simple conjugated organic polymer, a material of strong interest if doped by various chemical species such as iodine or antimony pentafluoride : its electrical conductivity increases by more than twelve orders of magnitude. By increasing the dopant concentration one obtains a semiconductive or a metallic regime. Such properties allow us to make electronic material and then devices by convenient n or p type doping of polyacetylene. However,it is necessary to determine the thermal stability of the various dopant species. In this paper, we compared the stability of iodine, SbF₅ and CF₃SO₃H dopants by studying the mass loss and the electrical conductivity decrease at various temperatures from 20‡C up to 180‡C. It is shown that only SbF₅ is a relatively stable dopant up to 80‡C, a temperature which may be reached in some active electronic devices. Raman spectroscopy allowed us to measure the ratio of I₋₃ to I₋₅ ions during the desorption process and to propose a possible chemical reaction which produces gaseous iodine from the active dopant species.