Low temperature metal oxide film deposition and reaction kinetics in supercritical carbon dioxide

An effective method is developed for low temperature metal oxide deposition through thermal decomposition of metal diketonates in supercritical carbon dioxide (scCO₂) solvent. The rates of Al(acac)₃ (Aluminum acetyl acetonate) and Ga(acac)₃ (Gallium acetyl acetonate) thermal decomposition in scCO₂ to form conformal Al₂O₃ and Ga₂O₃ thin films on planar surfaces were investigated. The thermal decomposition reaction of Al(acac)₃ and Ga(acac)₃ was found to be initialized at  150 °C and 160 °C respectively in scCO₂ solvent, compared to  250 °C and 360 °C in analogous vacuum-based processes. By measuring the temperature dependence of the growth rates of metal oxide thin films, the apparent activation energy for the thermal decomposition of Al(acac)₃ in scCO₂ is found to be 68 ± 6 kJ/mol, in comparison with 80–100 kJ/mol observed for the corresponding vacuum-based thermal decomposition reaction. The enhanced thermal decomposition rate in scCO₂ is ascribed to the high density solvent which effectively reduces the energy of the polar transition states in the reaction pathway. Preliminary results of thin film deposition of other metal oxides including ZrO_x, FeO_x, Co₂O₃, Cr₂O₃, HfO_x from thermal decomposition of metal diketonates or fluorinated diketonates in scCO₂ are also presented.     

Langmuir–Blodgett films of substituted bis(naphthalocyaninato) rare earth complexes: structure and interaction with nitrogen dioxide

Ordered molecular assemblies of novel alkylthio-substituted bis(naphthalocyaninato) rare earth complexes M[2,3-Nc(SC₁₂H₂₅)₈]₂ (M=Gd, Er) have been fabricated by Langmuir–Blodgett (LB) technique and characterized by surface pressure-area isotherm measurements, electronic absorption and polarized electronic absorption spectroscopy and low-angle X-ray diffractometry. The interaction between the thin films and NO₂ gas was investigated. The experimental results indicate that the bis(naphthalocyaninato) rare earth molecules form well-ordered stable monolayers with face-to-face orientation for the macrocycles and edge-on configuration for the molecules at the air–water interface and lamellar multilayers on solid substrates. The orientation angles of naphthalocyanine rings with respect to the quartz plate surface in the LB films for M[2,3-Nc(SC₁₂H₂₅)₈]₂ with M of Gd and Er have been determined based on the polarized absorbance and found to be 50° and 54°, respectively. The adsorption–desorption process of NO₂ on LB films of M[2,3-Nc(SC₁₂H₂₅)₈]₂ has been monitored by electronic absorption spectroscopy. A process of gas desorption was found to obey the Elovich equation.     

Preparation of cobalt oxide nanoparticles and cobalt powders by solvothermal process and their characterization

Co₃O₄ nanoparticles and cobalt (fcc-Co) powders were successfully synthesized by solvothermal process from a single precursor. The reaction of Co(Ac)₂ with sodium dodecylbenzenesulfonate (SDBS) shows evident-dependent temperature effect. At 180 °C, Co(Ac)₂ reacts with SDBS to produce precursor CoCO₃ plate structures, which are assembled by small nanoparticles. At the temperature of 250 °C, the precursor CoCO₃ can be gradually decomposed to form Co₃O₄ nanoparticles with diameter of ca. 70 nm. While, at 250 °C, the reaction of Co(Ac)₂ with SDBS also produce precursor CoCO₃ nanoparticles/plates, but the CoCO₃ nanoparticles/plates would only decompose to give metal Co. In this process, SDBS acts as not only a surfactant but also a reagent. Magnetic measurements reveal that the as-prepared Co₃O₄ nanoparticles exhibit weak ferromagnetic properties and Co powders show ferromagnetic properties. In addition, a possible formation mechanism was elaborately discussed.     

Characterization of Cat-CVD grown Si–C and Si–C–O dielectric films for ULSI applications

Si–C films with the Si compositions ranging from 40 to 70% have been grown by Cat-CVD using dimethylsilane [DMSi, Si(CH₃)₂H₂] compounds. Tetraethoxysilane [TEOS, Si(OC₂H₅)₄] and dimethyldimethoxysilane [DMDMOS, Si(CH₃)₂(OCH₃)₂] gas source gave us Si–C–O (C-doped SiO_x) films with wide ternary alloy compositions. The dielectric constant of a Si–C film has been evaluated by C–V measurements (at 1 MHz) using Al/Si–C/n-Si(001)/Cu MIS structure. The relative dielectric constant value of a Si–C film was estimated to be 3.0. The resistivity of the Si–C layer with 1 mm diameter and 0.24 μm thickness was estimated to be more than 24.5 Gohm·cm. These results gave us promising characteristics of Si–C and Si–C–O films grown by alkylsilane- and alcoxysilane-based Cat-CVD.     

Atomic layer deposition of calcium oxide and calcium hafnium oxide films using calcium cyclopentadienyl precursor

Calcium oxide and calcium hafnium oxide thin films were grown by atomic layer deposition on borosilicate glass and silicon substrates in the temperature range of 205–300 °C. The calcium oxide films were grown from novel calcium cyclopentadienyl precursor and water. Calcium oxide films possessed refractive index 1.75–1.80. Calcium oxide films grown without Al₂O₃ capping layer occurred hygroscopic and converted to Ca(OH)₂ after exposure to air. As-deposited CaO films were (200)-oriented. CaO covered with Al₂O₃ capping layers contained relatively low amounts of hydrogen and re-oriented into (111) direction upon annealing at 900 °C. In order to examine the application of CaO in high-permittivity dielectric layers, mixtures of Ca and Hf oxides were grown by alternate CaO and HfO₂ growth cycles at 230 and 300 °C. HfCl₄ was used as a hafnium precursor. When grown at 230 °C, the films were amorphous with equal amounts of Ca and Hf constituents (15 at.%). These films crystallized upon annealing at 750 °C, showing X-ray diffraction peaks characteristic of hafnium-rich phases such as Ca₂Hf₇O₁₆ or Ca₆Hf₁₉O₄₄. At 300 °C, the relative Ca content remained below 8 at.%. The crystallized phase well matched with rhombohedral Ca₂Hf₇O₁₆. The dielectric films grown on Si(100) substrates possessed effective permittivity values in the range of 12.8–14.2.     

Microstructures in Advanced Materials Characterized by HREM and Nanoscale Analysis

Segregation of yttrium induces the formation of Y_0.25Zr_0.75O_2-x and Y_0.5Zr_0.5O_2-y microdomains, with L1₂- and L1₀-like ordered structures, in ZrO₂–6mol%Y₂O₃ ceramics in both the sintered and annealed states. The compositions of precipitates such as χ_L, χ_S, χ_SS, and small precipitates formed inside χ_L, in Cu–11.88Al–5.06Ni–1.63Mn–0.96Ti (wt.%) shape memory alloys have been determined. Under electron beam irradiation, four types of dynamic behavior of the G.P. zones were observed in the Al–6.58Zn–2.33Mg–2.40Cu (wt.%) alloy. The G.P. zone and “G.P. zone-like” defect structures were also distinguished. Lattice distortion profile in the GaAs/In_xGa_1-xAs superlattice and two-dimensional lattice distortion around a 60° dislocation core in the InAs_xP_1-x/InP superlattice were determined.     

Direct liquid injection metal-organic chemical vapor deposition of HfO2 thin films using Hf(dimethylaminoethoxide)4

Hf(OCH₂CH₂NMe₂)₄, [Hf(dmae)₄] (dmae=dimethylaminoethoxide) was synthesized and used as a chemical vapor deposition precursor for depositing Hf oxide (HfO₂). Hf(dmae)₄ is a liquid at room temperature and has a moderate vapor pressure (4.5 Torr at 80 °C). It was found that HfO₂ film could be deposited as low as 150 °C with carbon level not detected by X-ray photoelectron spectroscopy. As deposited film was amorphous but when the deposition temperature was raised to 400 °C, X-ray diffraction pattern showed that the film was polycrystalline with weak peak of monoclinic (020). Scanning electron microscope analysis indicated that the grain size was not significantly changed with the increase of the annealing temperature. Capacitance–voltage measurement showed that with the increase of annealing temperature, the effective dielectric constant was increased, but above 900 °C, the effective dielectric constant was decreased due to the formation of interface oxide. For 500 Å thin film, the dielectric constant of HfO₂ film annealed at 800 °C was 20.1 and the current–voltage measurements showed that the leakage current density of the HfO₂ thin film annealed at 800 °C was 2.2×10⁻⁶ A/cm² at 5 V.     

La2Zr2O7 films on Cu–Ni alloy by chemical solution deposition process

Films of La₂Zr₂O₇ (=LZO) have been formed by chemical solution deposition technique (CSD) on new bi-axially textured Cu–Ni alloy tapes based on rolled constantan (Cu₅₅Ni₄₅) Rabits. The precursor used was acetylacetonates treated in propionic acid (0.1–0.87 mol/l) and then deposited by spin-coating. The LZO film starts to crystallize above 850 °C, the film nucleates bi-axially textured on the substrate (with unit cell axis rotated 45° from those of the substrate). The top part of the film is not textured even after long annealing time at 1100 °C, but the interfacial part is bi-axially textured. Thus, synthesis of bi-axially textured films on Cu₅₅Ni₄₅ Rabits seems possible but more works are needed to optimize its properties.     

Effects of Co and Ni addition on reactive diffusion between Sn–3.5Ag solder and Cu during soldering and annealing

The reactive diffusion between Sn–Ag solders and Cu was experimentally examined during soldering and isothermal annealing. Three sorts of solders with compositions of Sn–3.5Ag, Sn–3.5Ag–0.1Ni and Sn–3.5Ag–0.1Co were used for the experiment. Each solder was soldered on a Cu plate at 523 K (250 °C) for 1–60 s in a pure nitrogen gas, and then the solder/Cu diffusion couple was isothermally annealed at 423 K (150 °C) for 168–1008 h. Due to soldering, only Cu₆Sn₅ is formed at the interface in each diffusion couple. On the other hand, Cu₃Sn is produced between Cu₆Sn₅ and Cu owing to the isothermal annealing. The composition of Cu₆Sn₅ is (Cu_0.8Ni_0.2)₆Sn₅ and (Cu_0.93Ni_0.07)₆Sn₅ on the solder and Cu₃Sn sides, respectively, in the (Sn–3.5Ag–0.1Ni)/Cu diffusion couple, and it is (Cu_0.9Co_0.1)₆Sn₅ and (Cu_0.99Co_0.01)₆Sn₅ on the solder and Cu₃Sn sides, respectively, in the (Sn–3.5Ag–0.1Co)/Cu diffusion couple. Different rate-controlling processes were suggested for the (Sn–3.5Ag)/Cu, (Sn–3.5Ag–0.1Ni)/Cu and (Sn–3.5Ag–0.1Co)/Cu diffusion couples. Finally, thermodynamic models were herein adopted to explore influences of the additives on the thermodynamic interaction of the component elements and the driving force for the growth of intermetallics.     

Chemical vapour deposition of praseodymium oxide films on silicon: influence of temperature and oxygen pressure

Metal-organic chemical vapour deposition (MOCVD) of various phases in PrO_x system has been studied in relation with deposition temperature (450–750 °C) and oxygen partial pressure (0.027–100 Pa or 0.2–750 mTorr). Depositions were carried out by pulsed liquid injection MOCVD using Pr(thd)₃ (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate) precursor dissolved in toluene or monoglyme. By varying deposition temperature and oxygen partial pressure amorphous films or various crystalline PrO_x phases (Pr₂O₃, Pr₇O₁₂, Pr₆O₁₁) and their mixtures can be grown. The pure crystalline Pr₂O₃ phase grows only in a narrow range of partial oxygen pressure and temperature, while high oxygen pressure (40–100 Pa) always leads to the most stable Pr₆O₁₁ phase. The influence of annealing under vacuum at 750 °C on film phase composition was also studied. Near 90% step coverage conformity was achieved for PrO_x films on structured silicon substrates with aspect ratio 1:10. In air degradation of Pr₂O₃ films with transformation to Pr(OH)₃ was observed in contrast to Pr₆O₁₁ films.     

Thaumasite––direct, woodfordite and other possible formation routes

Two main formation routes for thaumasite exist below 15 °C. One is the direct route from C–S–H reacting with appropriate carbonate, sulfate, Ca²⁺ ions and excess water. The other route is the woodfordite route from ettringite reacting with C–S–H, carbonate, Ca²⁺ ions and excess water, in which thaumasite arises through the intermediate formation of the solid solution woodfordite. The woodfordite route for thaumasite formation appears to be relatively quicker (although still slow) than the direct route, presumably because with the former the ettringite already has the octahedral [M(OH)₆] units that can facilitate the critical change from [Al(OH)₆]³⁻ to [Si(OH)₆]²⁻ groupings. Both routes are mutually dependent on each other. The presence of magnesium salts can modify the path to thaumasite formation. High pressure might be able to stabilise [Si(OH)₆]²⁻ groupings and allow thaumasite to become formed above 15 °C. This possibility is discussed.     

Deposition of Sm2O3 doped CeO2 thin films from Ce(DPM)4 and Sm(DPM)3 (DPM=2,2,6,6-tetramethyl-3,5-heptanedionato) by aerosol-assisted metal–organic chemical vapor deposition

Samarium-doped ceria (SDC) thin films were prepared from Sm(DPM)₃ (DPM = 2,2,6,6-tetramethyl-3,5-heptanedionato) and Ce(DPM)₄ using the aerosol-assisted metal–organic chemical vapor deposition method. -Al₂O₃ and NiO-YSZ (YSZ = Y₂O₃-stabilized ZrO₂) disks were chosen as substrates in order to investigate the difference in the growth process on the two substrates. Single cubic structure could be obtained on either -Al₂O₃ or NiO-YSZ substrates at deposition temperatures above 450 °C; the similar structure between YSZ and SDC results in matching growth compared with the deposition on -Al₂O₃ substrate. A typical columnar structure could be obtained at 650 °C on -Al₂O₃ substrate and a more uniform surface was produced on NiO-YSZ substrate at 500 °C. The composition of SDC film deposited at 450 °C is close to that of precursor solution (Sm : Ce = 1 : 4), higher or lower deposition temperature will both lead to sharp deviation from this elemental ratio. The different thermal properties of Sm(DPM)₃ and Ce(DPM)₄ may be the key reason for the variation in composition with the increase of deposition temperature.     

Formation of Transparent and Photo Conducting Films by High Temperature Chemical Conversion of Solution Grown Precursor Films

The formation of photoconducting ZnO and transparent conducting CdO films by high temperature oxidation and thermal decomposition of chemically deposited ZnS and Cd(OH)₂ precursor films respectively is reported. The ZnS to ZnO and Cd(OH)₂ to CdO conversions were confirmed by x-ray diffraction (XRD)₂ electrical and optoelectronic studies. As deposited ZnS and Cd(OH)₂ films exhibited very low dark conductivity and no photoconductivity. Air oxidation of ZnS films at about 400°C for at least 15 minutes converted them to ZnO films with higher dark and photoconductivity. Cd(OH)₂ to CdO conversion occurred at about 300°C. CdO films exhibited a dark conductivity of the order of 10³ (Ωcm)^-1 and an optical transmittance in the range of 90%. These characteristics of ZnO and CdO films make them suitable candidates for the development of low cost photoconductors and solar cell structures.     

Microstructure, crystallinity, and properties of low-pressure MOCVD-grown europium oxide films

A study of growth, structure, and properties of Eu₂O₃ thin films were carried out. Films were grown at 500–600 °C temperature range on Si(1 0 0) and fused quartz from the complex of Eu(acac)₃·Phen by low pressure metalorganic chemical vapor deposition technique which has been rarely used for Eu₂O₃ deposition. These films were polycrystalline. Depending on growth conditions and substrates employed, these films had also possessed a parasitic phase. This phase can be removed by post-deposition annealing in oxidizing ambient. Morphology of the films was characterized by well-packed spherical mounds. Optical measurements exhibited that the bandgap of pure Eu₂O₃ phase was 4.4 eV. High frequency 1 MHz capacitance–voltage (C–V) measurements showed that the dielectric constant of pure Eu₂O₃ film was about 12. Possible effects of cation and oxygen deficiency and parasitic phase on the optical and electrical properties of Eu₂O₃ films have been briefly discussed.     

Catalytic CVD growth of Si–C and Si–C–O alloy films by using alkylsilane and related compounds

Cat-CVD method has been applied to the growth of Si–C and Si–C–O alloy thin films. Growth mechanism has been studied with emphasis on the effects of filament materials. Growth rates and alloy compositions were measured for W, Ta, Mo and Pt filaments at the filament temperatures ranging from 1300 to 2000 °C. Si_1−xC_x films with x ranging from 0.38 to 0.7 could be grown by using single molecule source Si(CH₃)₂H₂ (dimethylsilane). Si–C–O ternary alloy films was successfully prepared by using Si(OC₂H₅)₄ (tetraethoxysilane) and Si(CH₃)₂(OCH₃)₂ (dimethyldimethoxysilane) molecules.     

Interface phenomena in the Y2O3/(Al–Cu) system

Wetting behavior and the interface reaction in the Y₂O₃/(Cu–Al) system were investigated at 1423 K. A contact angle of about 130° was measured in the Y₂O₃/Cu system. Aluminum addition to copper improves wetting and the transition from non-wetting to wetting (θ ≤ 90°) was observed for the alloy with 50 at.% Al. The microstructure examination of the interface indicates that Al reacts with yttria, yttrium dissolves in the melt and a crater of AlYO₃ is formed at the substrate. The interface interaction in the Y₂O₃/(Cu–Al) system is in a good agreement with the results of a thermodynamic analysis in the Y–Al–Cu–O system. The crater depth and the macroscopic final contact angles are correlated with the Y and Al activities in the melt.     

An investigation of graphite PEEK composite under compression with a centrally located circular discontinuity

The failure characteristic of graphite polyetheretherketone (Gr/PEEK) under compression with a centrally located circular discontinuity was investigated through experimentation and a nonlinear ply-by-ply finite element technique. The stacking sequence of the laminates investigated were: [0 °₁₆], [90 °₁₆], [±45 °]_4S [0 °/90 °]_4S, and [0 °/ ± 45 0°/90 °]_2S. In the experimentation, [90 °]₁₆, [0 °/90 °]_4S, and [0 °/ ±45 °/90 °]_2S laminates, as well as three of the [0 °]₁₆, failed due to a crack that was normal to the loading direction and initiated from the edge of the hole progressing to the outer edges of the specimen. The [±45 °]_4S specimens failed to support the load due to an internal crack that originated from the hole's edge and then traveled at an angle of about 42% to the direction of loading. The finite element method used to analytically model the failure of Gr/PEEK accurately modeled the response of the specimens tested experimentally.     

Controllable formation of Er–Yb codoped Al2O3 films by the non-aqueous sol–gel method

1 mol%Er³⁺–10 mol%Yb³⁺ codoped Al₂O₃ thin films have been prepared on thermally oxidized SiO₂/Si(110) substrates by a dip-coating process in the non-aqueous sol–gel method from the hydrolysis of aluminum isopropoxide [Al(OC₃H₇)₃] under isopropanol environment. Addition of N,N-dimethylformamide (DMF) as a drying control chemical additive (DCCA) into the sol suppresses formation of the cracks in the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films when the rare-earth ion is doped with a high doping concentration. Homogeneous, smooth and crack-free Er³⁺–Yb³⁺ codoped Al₂O₃ thin films form at the conditions by a molar ratio of 1:1 for DMF:Al(OC₃H₇)₃. A strong photoluminescence spectrum with a broadband extending from 1.400 to 1.700 µm centered at 1.533 µm is obtained for the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films, which is unrelated to the addition of DMF. Controllable formation of the Er³⁺–Yb³⁺ codoped Al₂O₃ thin films may be explained by the fact that the DMF assisted the deprotonation process of Al–OH at the surfaces of gel particles, resulting in enhancement of the degree of polymerization of sols and improvement of the mechanical properties of gel thin films.     

Sol–gel deposition and characterization of Mn-doped silicate phosphor films

Mn²⁺-doped Zn₂SiO₄ and Mg₂Gd₈(SiO₄)₆O₂ phosphor films were deposited on silicon and quartz glass substrates by sol–gel process (dip-coating). The variations of sol viscosity with time and film thickness with the number of layers were investigated in Zn₂SiO₄: Mn system. The results of XRD and IR showed that the Zn₂SiO₄: Mn films remained amorphous below 700°C and crystallized completely around 1000°C. From AFM studies, it was observed that the grains with 0.5–0.8 μm size packed closely in Zn₂SiO₄: Mn films, which were uniform and crack free. The luminescence properties of Zn₂SiO₄: Mn films were characterized by absorption, excitation and emission spectra as well as luminescence decay. These properties were discussed in detail by a comparison with those of Mn²⁺ (and Pb²⁺)-doped Mg₂Gd₈(SiO₄)₆O₂ phosphor films.     

Pyrolytic Trifluoromethylation of [76]-, [78]-, [84]-, and Aza[60]Fullerenes with Silver Trifluoroacetate; Evidence for Coordination of Fullerenes to Silver

Pyrolytic trifluoromethylation of [76], [78], [84], and aza[60]fullerenes with silver trifluoroacetate at 300°C results in extensive polyaddition of up to 18, 18, 20 and 20 CF₃ groups, respectively. In contrast to trifluoromethylation of [60]- and [70]fullerenes that give a full range of derivatives ranging upwards from C_n(CF₃)₂, [76]-, [78]-, and [84]-fullerenes only give C_n(CF₃)_6-18 derivatives, largely in the 10-12 CF₃ range; reaction with [76]fullerene is accompanied by formation of C₆₀(CF₃)₆ attributed to cage fragmentation. For aza[60]fullerene the hexa-addition level dominates, in contrast to its other reactions which give predominantly penta-addition products. All the compounds showed peaks at 1256±2 and 1180-1190 cm^-1, due to the CF₃ group, and peaks in this region are shown also by the soluble extract obtained on trifluoromethylation of nanotubes. As in trifluoromethylation of [60]- and [70]-fullerenes, the products obtained initially are involatile, attributed to formation os silver complexes; these are decomposed on subsequent solution in toluene. Mixed isomeric trifluoromethylated C₆₀F₈ derivatives viz. C₆₀F₇CF₃, C₆₀F₆(FG₃)₂, C₆₀F₅(CF₃)₃ and C₆₀F₄(CF₃)₄, and C₆₀F₄CF₃CF₂CF₃ (a C₆₀F₆ derivative) have been isolated from fluorination of [60]fullerene with MnF₃/K₂NilF₆ at 510°C.