Structural and magnetic properties of SmCo5/Co exchange coupled nanocomposite thin films

We investigated the structural and magnetic properties of SmCo5/Co exchange coupled nanocomposite thin films grown by magnetron sputtering from Sm and Co multitargets successively. The growth of the films was carried out at elevated substrate temperature followed by in situ annealing. On Si (100) substrate, X-ray diffraction confirms the formation of textured (110) SmCo5 hard phase, whereas on MgO (110) substrate, the diffraction pattern shows the epitaxial growth of SmCo5 phase with crystalline orientation along 100] direction. Secondary Ion Mass Spectroscopy reveals the structural transformation from multilayered (Sm/Co) to SmCo5/Co nano-composite films due to high reactivity of Sm at elevated temperature. Transmission electron microscopy indicates the existence of nanocrystalline phase of SmCo5 along with unreacted Co. Observed single phase behavior in magnetic hysteresis measurements indicates well exchange coupling between the soft and the hard phases in these nano-composite films. For samples with samarium layer thickness, t(sm)=3.2 nm and cobalt layer thickness, t(Co)= 11.4 nm, the values of (BH)(max) were obtained as 20.1 MGOe and 12.38 MGOe with H-c value similar to 3.0 kOe grown on MgO and Si substrates, respectively.

Nanoscale compositional analysis of NiTi shape memory alloy films deposited by DC magnetron sputtering

The formation of surface oxide layer as well as compositional changes along the thickness for NiTi shape memory alloy thin films deposited by direct current magnetron sputtering at substrate temperature of 300 degrees C in the as-deposited condition as well as in the postannealed (at 600 degrees C) condition have been thoroughly studied by using secondary ion mass spectroscopy, x-ray photoelectron spectroscopy, and scanning transmission electron microscopy-energy dispersive x-ray spectroscopy techniques. Formation of titanium oxide (predominantly titanium dioxide) layer was observed in both as-deposited and postannealed NiTi films, although the oxide layer was much thinner (8 nm) in as-deposited condition. The depletion of Ti and enrichment of Ni below the oxide layer in postannealed films also resulted in the formation of a graded microstructure consisting of titanium oxide, Ni3Ti, and B2 NiTi. A uniform composition of B2 NiTi was obtained in the postannealed film only below a depth of 200-250 nm from the surface. Postannealed film also exhibited formation of a ternary silicide (NixTiySi) at the film-substrate interface, whereas no silicide was seen in the as-deposited film. The formation of silicide also caused a depletion of Ni in the film in a region similar to 250-300 nm just above the film substrate interface. (C) 2013 American Vacuum Society.

Sputtering by multiply-charged ions, and preferential sputtering of isotopic mixtures

Collector-type experiments have been conducted to investigate two different aspects of sputtering induced by keV ions. The first study looked for possible ejection mechanisms related to the primary charge state of the projectile. Targets of CsI and LiNbO_3 were bombarded with 48 keV Ar^(q+), and a Au target was bombarded with 60 keV Ar^(q+), for q = 4, 8, and 11. The collectors were analyzed using heavy-ion Rutherford backscattering spectroscopy to determine the differential angular sputtering yields; these and the corresponding total yields were examined for variations as a function of projectile charge state. For the Au target, no significant changes were seen, but for the insulating targets slight (~10%) enhancements were observed in the total yields as the projectile charge state was increased from 4+ to 11+.

In the second investigation, artificial ^(92)Mo/^(100)Mo targets were bombarded with 5 and 10 keV beams of Ar^+ and Xe^+ to study the isotopic fractionation of sputtered neutrals as a function of emission angle and projectile fluence. Using secondary ion mass spectroscopy to measure the isotope ratio on the collectors, material ejected into normal directions at low bombarding fluences (~ 10^(15) ions cm^(-2)) was found to be enriched in the light isotope by as much as ~70‰ compared to steady state. Similar results were found for secondary Mo ions sputtered by 14.5 keV O^-. For low-fluence 5 keV Xe^+ bombardment, the light-isotope enrichment at oblique angles was ~20‰ less than the corresponding enrichment in the normal direction. No angular dependence could be resolved for 5 keV Ar^+ projectiles at the lowest fluence. The above fractionation decreased to steady-state values after bombarding fluences of a few times 10^(16) ions cm^(-2) , with the angular dependence becoming more pronounced. The fractionation and total sputtering yield were found to be strongly correlated, indicating that the above effects may have been related to the presence of a modified target surface layer. The observed effects are consistent with other secondary ion measurements and multiple-interaction computer simulations, and are considerably larger than predicted by existing analytic theory.

Isotopic fractionation in sputtering

Isotopic fractionation due to sputtering has been investigated via a collector type experiment in which targets of known isotopic composition have been bombarded with several keV Ar⁺ and Xe⁺ ions with fluences down to 3.0x10¹⁴ ions/cm² , believed to be the lowest fluences for which such detailed measurements have ever been made. The isotopes were sputtered onto carbon collectors and analyzed with Secondary Ion Mass Spectroscopy (SIMS.) There is clear indication of preferential effects several times that predicted by the dominant analytical theory. Results also show a fairly strong angular variation in the fractionation. The maximum effect is usually seen in the near normal direction, measured from the target surface, falling continuously, by a few percent in some cases, to a minimum in the oblique direction. Measurements have been made using Mo isotopes: ¹⁰⁰Mo and ⁹²Mo and a liquid metal system of In:Ga eutectic. The light isotope of Mo is found to suffer a 53 ± 5‰ (note: 1.0‰ ≡ 0.1%) enrichment in the sputtered flux in the near normal direction, compared to the steady state near normal sputtered composition, under 5.0 keV Xe⁺ bombardment of 3.0 x 10¹⁴ ions/cm². In the liquid metal study only the angular dependence of the fractionation could be measured due to the lack of a well defined reference and the nature of the liquid surface, which is able to 'repair' itself during the course of a bombardment. The results show that ¹¹³In is preferentially sputtered over ¹¹⁵In in the near normal direction by about 8.7 ± 2.7‰ compared to the oblique direction. ⁶⁹Ga, on the other hand, is sputtered preferentially over ⁷¹Ga in the oblique direction by about 13 ± 4.4‰ with respect to the near normal direction.

Solubility and Diffusivity of Water in Lunar Basalt, and Chemical Zonation in Olivine-Hosted Melt Inclusions

I report the solubility and diffusivity of water in lunar basalt and an iron-free basaltic analogue at 1 atm and 1350 °C. Such parameters are critical for understanding the degassing histories of lunar pyroclastic glasses. Solubility experiments have been conducted over a range of fO₂ conditions from three log units below to five log units above the iron-wüstite buffer (IW) and over a range of pH₂/pH₂O from 0.03 to 24. Quenched experimental glasses were analyzed by Fourier transform infrared spectroscopy (FTIR) and secondary ionization mass spectrometry (SIMS) and were found to contain up to ~420 ppm water. Results demonstrate that, under the conditions of our experiments: (1) hydroxyl is the only H-bearing species detected by FTIR; (2) the solubility of water is proportional to the square root of pH₂O in the furnace atmosphere and is independent of fO₂ and pH₂/pH₂O; (3) the solubility of water is very similar in both melt compositions; (4) the concentration of H₂ in our iron-free experiments is <3 ppm, even at oxygen fugacities as low as IW-2.3 and pH₂/pH₂O as high as 24; and (5) SIMS analyses of water in iron-rich glasses equilibrated under variable fO₂ conditions can be strongly influenced by matrix effects, even when the concentrations of water in the glasses are low. Our results can be used to constrain the entrapment pressure of the lunar melt inclusions of Hauri et al. (2011).

Diffusion experiments were conducted over a range of fO₂ conditions from IW-2.2 to IW+6.7 and over a range of pH₂/pH₂O from nominally zero to ~10. The water concentrations measured in our quenched experimental glasses by SIMS and FTIR vary from a few ppm to ~430 ppm. Water concentration gradients are well described by models in which the diffusivity of water (D^*_water) is assumed to be constant. The relationship between D^*_water and water concentration is well described by a modified speciation model (Ni et al. 2012) in which both molecular water and hydroxyl are allowed to diffuse. The success of this modified speciation model for describing our results suggests that we have resolved the diffusivity of hydroxyl in basaltic melt for the first time. Best-fit values of D^*_water for our experiments on lunar basalt vary within a factor of ~2 over a range of pH₂/pH₂O from 0.007 to 9.7, a range of fO₂ from IW-2.2 to IW+4.9, and a water concentration range from ~80 ppm to ~280 ppm. The relative insensitivity of our best-fit values of D^*_water to variations in pH₂ suggests that H₂ diffusion was not significant during degassing of the lunar glasses of Saal et al. (2008). D^*_water during dehydration and hydration in H₂/CO₂ gas mixtures are approximately the same, which supports an equilibrium boundary condition for these experiments. However, dehydration experiments into CO₂ and CO/CO₂ gas mixtures leave some scope for the importance of kinetics during dehydration into H-free environments. The value of D^*_water chosen by Saal et al. (2008) for modeling the diffusive degassing of the lunar volcanic glasses is within a factor of three of our measured value in our lunar basaltic melt at 1350 °C.

In Chapter 4 of this thesis, I document significant zonation in major, minor, trace, and volatile elements in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (MgO, FeO, Cr₂O₃, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H₂O, and F, components with a lower concentration in the host olivine than in the melt (Al₂O₃, SiO₂, Na₂O, K₂O, TiO₂, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions concurrent with diffusive propagation of the boundary layer toward the inclusion center.

Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na₂O, K₂O) by coupling to slow diffusing components such as SiO₂ and Al₂O₃. Concentrations of H2O and F decrease towards the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects.

A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150–13,000 °C hr^-1 from the liquidus down to ~1000 °C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1000 °C is 40 s to just over one hour.

Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization.

All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments.

Preparation of tetrahedral amorphous carbon films by filtered cathodic vacuum arc deposition

Tetrahedrally bonded amorphous carbon (ta-C) and nitrogen doped (ta-C:N) films were obtained at room temperature in a filtered cathodic vacuum arc (FCVA) system incorporating an off-plane double bend (S-bend) magnetic filter. The influence of the negative bias voltage applied to substrates (from -20 to -350 V) and the nitrogen background pressure (up to 10-3 Torr) on film properties was studied by scanning electron microscopy (SEM), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-ray photoemission spectroscopy (XPS), secondary ion mass spectroscopy (SIMS) and X-ray reflectivity (XRR). The ta-C films showed sp3 fractions between 84% and 88%, and mass densities around 3.2 g/cm3 in the wide range of bias voltage studied. In contrast, the compressive stress showed a maximum value of 11 GPa for bias voltages around -90 V, whereas for lower and higher bias voltages the stress decreased to 6 GPa. As for the ta-C:N films grown at bias voltages below -200 V and with N contents up to 7%, it has been found that the N atoms were preferentially sp3 bonded to the carbon network with a reduction in stress below 8 GPa. Further increase in bias voltage or N content increased the sp2 fraction, leading to a reduction in film density to 2.7 g/cm3.

Investigation of fluorine three-dimensional redistribution during solid-phase-epitaxial-regrowth of amorphous Si

The fluorine redistribution during partial solid-phase-epitaxial-regrowth at 650°C of a preamorphized Si substrate implanted by F was investigated by atom probe tomography (APT), transmission electron microscopy, and secondary ions mass spectrometry. Three-dimensional spatial distribution of F obtained by APT provides a direct observation of F-rich clusters with a diameter of less than 1.5 nm. Density variation compatible with cavities and F-rich molecular ions in correspondence of clusters are in accordance with cavities filled by SiF 4 molecules. Their presence only in crystalline Si while they are not revealed by statistical analysis in amorphous suggests that they form at the amorphous/crystal interface. © 2012 American Institute of Physics.

Changes in the Mg profile and in dislocations induced by high temperature annealing of blue LEDs

The efficiency of the injection and recombination processes in InGaN/GaN LEDs is governed by the properties of the active region of the devices, which strongly depend on the conditions used for the growth of the epitaxial material. To improve device quality, it is very important to understand how the high temperatures used during the growth process can modify the quality of the epitaxial material. With this paper we present a study of the modifications in the properties of InGaN/GaN LED structures induced by high temperature annealing: thermal stress tests were carried out at 900 °C, in nitrogen atmosphere, on selected samples. The efficiency and the recombination dynamics were evaluated by photoluminescence measurements (both integrated and time-resolved), while the properties of the epitaxial material were studied by Secondary Ion Mass Spectroscopy (SIMS) and Rutherford Backscattering (RBS) channeling measurements. Results indicate that exposure to high temperatures may lead to: (i) a significant increase in the photoluminescence efficiency of the devices; (ii) a decrease in the parasitic emission bands located between 380 nm and 400 nm; (iii) an increase in carrier lifetime, as detected by time-resolved photoluminescence measurements. The increase in device efficiency is tentatively ascribed to an improvement in the crystallographic quality of the samples. © 2013 SPIE.

Growth of crack-free GaN films on Si(111) substrate by using Al-rich AlN buffer layer

GaN epilayers were grown on Si(111) substrate by metalorganic chemical vapor deposition. By using the Al-rich AlN buffer which contains Al beyond stoichiometry, crack-free GaN epilayers with 1 mum thickness were obtained. Through x-ray diffraction (XRD) and secondary ion mass spectroscopy analyses, it was found that a lot of Al atoms have diffused into the under part of the GaN epilayer from the Al-rich AlN buffer, which results in the formation of an AlxGa1-xN layer at least with 300 nm thickness in the 1 mum thick GaN epilayer. The Al fraction x was estimated by XRD to be about 2.5%. X-ray photoelectron spectroscopy depth analysis was also applied to investigate the stoichiometry in the Al-rich buffer before GaN growth. It is suggested that the underlayer AlxGa1-xN originated from Al diffusion probably provides a compressive stress to the upper part of the GaN epilayer, which counterbalances a part of tensile stress in the GaN epilayer during cooling down and consequently reduces the cracks of the film effectively. The method using the Al diffusion effect to form a thick AlGaN layer is really feasible to achieve the crack-free GaN films and obtain a high crystal quality simultaneously. (C) 2004 American Institute of Physics.

Growth of a novel periodic structure of SiC/AlN multilayers by low pressure chemical vapour deposition

A novel 10-period SiC/AlN multilayered structure with a SiC cap layer is prepared by low pressure chemical vapour deposition (LPCVD). The structure with total film thickness of about 1.45 mu m is deposited on a Si (111) substrate and shows good surface morphology with a smaller rms surface roughness of 5.3 nm. According to the secondary ion mass spectroscopy results, good interface of the 10 period SiC/AlN structure and periodic changes of depth profiles of C, Si, Al, N components are obtained by controlling the growth procedure. The structure exhibits the peak reflectivity close to 30% near the wavelength of 322 nm. To the best of our knowledge, this is the first report of growth of the SiC/AlN periodic structure using the home-made LPCVD system.

Study on Mg memory effect in npn type AlGaN/GaN HBT structures grown by MOCVD

AlGaN/GaN npn heterojunction bipolar transistor structures were grown by low-pressure MOCVD. Secondary ion mass spectroscopy (SIMS) measurements were carried out to study the Mg memory effect and redistribution in the emitter-base junction. The results indicated that there is a Mg-rich film formed in the ongrowing layer after the Cp2Mg source is switched off. The Mg-rich film can be confined in the base section by switching off the Cp2Mg source for appropriate time before the end of base growth. Low temperature growth of the undoped GaN spacer suppresses the Mg redistribution from Mg rich film. The delay rate of the Mg profile in sample C with spacer growing in low temperature is about 56 nm/decade, which becomes sharper than 80 nm/decade of the samples A and B without low temperature spacer. (C) 2005 Elsevier Ltd. All rights reserved.

Research on nitrogen implantation energy dependence of the properties of SIMON materials

With different implantation energies, nitrogen ions were implanted into SIMOX wafers in our work. And then the wafers were subsequently annealed to form separated by implantation of oxygen and nitrogen (SIMON) wafers. Secondary ion mass spectroscopy (SIMS) was used to observe the distribution of nitrogen and oxygen in the wafers. The result of electron paramagnetic resonance (EPR) was suggested by the dandling bonds densities in the wafers changed with N ions implantation energies. SIMON-based SIS capacitors were made. The results of the C-V test confirmed that the energy of nitrogen implantation affects the properties of the wafers, and the optimum implantation energy was determined. (c) 2005 Elsevier B.V. All rights reserved.

Influence of high-temperature AIN buffer thickness on the properties of GaN grown on Si(111)

The influences of AlN buffer thickness on the optical and the crystalline properties of metalorganic chemical vapor deposition wurtzite GaN layers on Si(I 11) substrate have been investigated. High-resolution X-ray diffraction and photoluminescence measurement reveal that the thickness of AlN buffer exerts a strong influence on the distribution of dislocation and stress in GaN epilayer. The evidence is further reinforced by atomic force microscopic observation of AlN nucleation process. The optimum thickness of AlN buffer to effectively suppress Si diffusion has been determined by secondary-ion mass spectroscopy to be in the range of 13-20 nm. In addition, it is found that appropriate Si diffusion in AlN buffer helps to compensate the tensile strain in GaN, which subsequently improves the optical quality of GaN on Si(I 1, 1), and reduces the cracks over the GaN surface. (C) 2003 Elsevier B.V. All rights reserved.

Residual donors and compensation in metalorganic chemical vapor deposition as-grown n-GaN

In our recent report, [Xu , Appl. Phys. Lett. 76, 152 (2000)], profile distributions of five elements in the GaN/sapphire system have been obtained using secondary ion-mass spectroscopy. The results suggested that a thin degenerate n(+) layer at the interface is the main source of the n-type conductivity for the whole film. The further studies in this article show that this n(+) conductivity is not only from the contribution of nitride-site oxygen (O-N), but also from the gallium-site silicon (Si-Ga) donors, with activation energies 2 meV (for O-N) and 42 meV (for Si-Ga), respectively. On the other hand, Al incorporated on the Ga sublattice reduces the concentration of compensating Ga-vacancy acceptors. The two-donor two-layer conduction, including Hall carrier concentration and mobility, has been modeled by separating the GaN film into a thin interface layer and a main bulk layer of the GaN film. The bulk layer conductivity is to be found mainly from a near-surface thin layer and is temperature dependent. Si-Ga and O-N should also be shallow donors and V-Ga-O or V-Ga-Al should be compensation sites in the bulk layer. The best fits for the Hall mobility and the Hall concentration in the bulk layer were obtained by taking the acceptor concentration N-A=1.8x10(17) cm(-3), the second donor concentration N-D2=1.0x10(18) cm(-3), and the compensation ratio C=N-A/N-D1=0.6, which is consistent with Rode's theory. Saturation of carriers and the low value of carrier mobility at low temperature can also be well explained. (C) 2001 American Institute of Physics.

Growth of SiGe heterojunction bipolar transistor using Si2H6 gas and Ge solid sources molecular beam epitaxy

N-p-n Si/SiGe/Si heterostructure has been grown by a disilane (Si2H6) gas and Ge solid sources molecular beam epitaxy system using phosphine (PH3) and diborane (B2H6) as n- and p-type in situ doping sources, respectively. X-ray diffraction (XRD) and secondary ion mass spectroscopy (SIMS) measurements show that the grown heterostructure has a good quality, the boron doping is confined to the SiGe base layer, and the Ge has a trapezoidal profile. Postgrowth P implantation was performed to prepare a good ohmic contact to the emitter. Heterojunction bipolar transistor (HBT) has been fabricated using the grown heterostructure and a common-emitter current gain of 75 and a cut-off frequency of 20 GHz at 300 K have been obtained. (C) 2001 Elsevier Science B.V. All rights reserved.