Dissociation of PtSi,NiSi and PdGe in presence of Pt,Ni and Pd films,respectively

⁴He⁺ ions backscattering spectrometry and x-ray diffractometry were used to study interactions between PtSi and Pt, NiSi and Ni, PdGe and Pd. Due to the dissociation of the compound the formation of a phase richer in metal was observed to grow at the original compound/metal interface in the temperature range considered, 280–325°C for Pt₂Si, 325°C for Ni₂Si and 180–260°C for Pd₂Ge. The growth kinetics of these new phases (Pt₂Si and Pd₂Ge) follow a parabolic relation between thickness and annealing time. At a given temperature the growth rate of Pt₂Si and Pd₂Ge in compound-metal structure is a factor higher than in the usual semiconductor-metal structure. Partially supported by Consiglio nazionale delle Ricerche (Italy) and by Commission of the European Communities.     

Palladium-vacancy pairs in p-type and n-type germanium

Time differential perturbed angular correlation spectroscopy was performed for n-type and p-type germanium samples that had been recoil-implanted with the probe ¹⁰⁰Pd/¹⁰⁰Rh. Two different measurements with the detectors aligned along <100> and <110> crystallographic directions of germanium confirm that the palladium probe pairs with the nearest neighbour vacancy and not a dopant. The pairs interact with a coupling constant of υ _Q = 10.7(2) MHz and this agrees with what has been observed in undoped Ge. This further suggests that the palladium pairs with a vacancy in germanium, doped or un-doped. It was also observed that there are more Pd-V pairs in Ga-doped than there are in Sb-doped Ge. DFT calculations of the binding energies of the Pd-defect complexes support the experimental observations.     

Evidence of palladium-defect pairing in intrinsic germanium

Time Differential Perturbed Angular Correlation measurements were performed in intrinsic germanium with the ¹⁰⁰Pd/¹⁰⁰Rh probe. The probe was produced via ⁹²Zr(¹²C, 4n)¹⁰⁰Pd and recoil-implanted into samples. Parallel measurements with the ¹¹¹In/¹¹¹Cd probe confirmed the quality of the germanium studied. The measurements with the ¹⁰⁰Pd/¹⁰⁰Rh probe show a modulation pattern in the ratio function with a quadrupole interaction frequency of 8.3(2) Mrad/s. The pattern depends on sample orientation and it is most pronounced after annealing at 500°C. After annealing at 700°C the effect vanishes due to strong damping of the ratio function. The pattern may be caused, similar to what has been observed for highly doped n-type silicon, by the pairing of the Pd-atom with a vacancy located in the < 111 > direction. The disappearance of the pattern would indicate the dissociation of this pair. Pair formation and dissociation may be relevant to palladium-induced-crystallization processing of germanium.     

A leed-aes study of thin Pd films on Si(111) and (100) substrates

A system Pd (deposit)-Si (substrate) has been studied by LEED and AES. Pd₂Si formed on Si(111) became epitaxial after a short time of annealing at a temperature between 300 and 700°C, while the Pd₂Si formed on Si(100) did not, in both cases the surfaces of the Pd₂Si being covered with a very thin Si layer. A sequence of superstructures (3√3 × 3√3), (1 × 1), and (2√3 × 2√3) was observed successively in Pd/Si(111) as the annealing temperature was increased. A (√3 × √3) structure was obtained by sputtering the 3√3 surface slightly. It was found that the √3 structure corresponds to Pd²Si(0001)-(1 × 1) grown epitaxially on Si(111), and that the 3√3 structure comes from the thin Si layer accumulated over the silicide surface, while the 2√3 and 1 structures arise from a submonolayer of Pd adsorbed on Si(111). Superstructures observed on a Pd/Si(100) system are also studied.     

Failure behavior of ITO diffusion barrier between electroplating Cu and Si substrate annealed in a low vacuum

A structure of Cu/ITO(10 nm)/Si was first formed and then annealed at various temperatures for 5 min in a rapid thermal annealing furnace under 10⁻² Torr pressure. In Cu/ITO(10 nm)/Si structure, the ITO(10 nm) film was coated on Si substrate by sputtering process and the Cu film was deposited on ITO film by electroplating technique. The various Cu/ITO(10 nm)/Si samples were characterized by a four-point probe, a scanning electron microscope, an X-ray diffractometer, and a transmission electron microscope. The results showed that when the annealing temperature increases near 600 °C the interface between Cu and ITO becomes unstable, and the Cu₃Si particles begin to form; and when the annealing temperature increases to 650 °C, a good many of Cu₃Si particles about 1 μm in size form and the sheet resistance of Cu/ITO(10 nm)/Si structure largely increases.     

Effects of germanium incorporation on optical performances of silicon germanium passive devices for group-IV photonic integrated circuits

Optical interconnect in integrated optoelectronic circuits is one of the promising next-generation technologies for replacing metalized interconnect. Efforts have been made to use silicon (Si)-compatible materials such as germanium (Ge) and Ge-buffered III–V compound semiconductors, along with Si, as optical sources for Si and group-IV integrated optoelectronic systems. This opens the possibility that higher fraction of Ge with its high refractive index (n) can be incorporated in Si waveguide for optical interconnect and the graftability between Si and group-IV or III–V materials would be improved in silicon photonics. In this work, advantageous features of nano-structured silicon germanium (Si_1−xGe_x) optical waveguide with different Ge fraction (x) were evaluated by both optical simulations and theoretical calculations, which are mainly found in the enhanced optical confinement and better interfacing capability. Along with the SiGe waveguide, performance of Si_1−xGe_x microring resonator under material loss in the effect of extinction coefficient (k) has been investigated to suggest the necessity of optimizing the Ge content in Si_1−xGe_x passive devices. While carrying out the establish design criteria, n and k have been modelled in closed-form functions of Ge fraction at 1550 nm. Furthermore, by examining high-resolution transmission electron microscopy (HR-TEM) images, process compatibility of Ge with either group-IV alloys or III–V compound semiconductors is confirmed for the monolithically integrated photonic circuits.     

Formation of Ge nanocrystals and evolution of the oxide matrix in as-deposited and annealed LPCVD SiGeO films

SiGeO films were deposited by LPCVD using Si₂H₆, GeH₄ and O₂ as reactive gases and furnace annealed to segregate the possible excess of Si and Ge in the form of nanocrystals embedded in an oxide matrix. For low GeH₄:Si₂H₆ flow ratios and deposition temperatures of 450 ^°C or lower, the deposited film consists of a SiO₂ matrix incorporating Ge. No Ge oxides and no nanocrystals are detected. After annealing of the samples with SiO₂ matrices at temperatures of 600 ^°C or higher, quasi-spherical isolated Ge nanocrystals with diameters ranging from 4.5 to 9 nm and homogeneously distributed throughout the whole film thickness are formed. In the samples deposited with low GeH₄:Si₂H₆ flow ratios, the original SiO₂ matrix holds its composition.     

XPS study of annealing induced effects on surface and interface electronic properties of Si/Ge nanostructures

The present study is focused on the influence of vacuum thermal treatment on surface/interface electronic properties of Si/Ge multilayer structures (MLS) characterized using X-ray photoelectron spectroscopy (XPS) technique. Desired [Si(5 nm)/Ge(5 nm)]_×10 MLS were prepared using electron beam evaporation technique under ultra high vacuum (UHV) conditions. The core-level XPS spectra of as-deposited as well as multilayer samples annealed at different temperatures such as 100 °C, 150 °C and 200 °C for 1 h show substantial reduction in Ge 2p peak integrated intensity, whereas peak intensity of Si 2p remains almost constant. The complete interdiffusion took place after annealing the sample at 200 °C for 5 h as confirmed from depth profiling of annealed MLS. The asymmetric behaviour in intensity patterns of Si and Ge with annealing was attributed to faster interdiffusion of Si into Ge layer. However, another set of experiments on these MLS annealed at 500 °C suggests that interdiffusion can also be studied by annealing the system at higher temperature for relatively shorter time duration.     

Energetics of Ge nucleation on SiO2 and implications for selective epitaxial growth

We have measured the time evolution of Ge nucleation density on SiO₂ over a temperature range of 673–973 K and deposition rates from 5.1 × 10¹³ atoms/cm² s (5 ML/min) to 6.9 × 10¹⁴ atoms/cm² s (65 ML/min) during molecular beam epitaxy. The governing equations from mean-field theory that describe surface energetics and saturation nucleation density are used to determine the size and binding energy of the critical Ge nucleus and the activation energy for Ge surface diffusion on SiO₂. The critical nucleus size is found to be a single Ge atom over substrate temperatures from 673 to 773 K, whereas a three-atom nucleus is found to be the critical size over substrate temperatures from 773 to 973 K. We have previously reported 0.44 ± 0.03 eV for the Ge desorption activation energy from SiO₂. This value, in conjunction with the saturation nucleation density as a function of substrate temperature, is used to determine that the activation energy for surface diffusion is 0.24 ± 0.05 eV, and the binding energy of the three-atom nucleus is 3.7 ± 0.1 eV. The values of the activation energy for desorption and surface diffusion are in good agreement with previous experiments of metals and semiconductors on insulating substrates. The small desorption and surface diffusion activation barriers predict that selective growth occurring on window-patterned samples is by direct impingement of Ge onto Si and ready desorption of Ge from SiO₂. This prediction is confirmed by the small integral condensation coefficient for Ge on SiO₂ and two key observations of nucleation behavior on the window-patterned samples. The first observation is the lack of nucleation exclusion zones around the windows, and second is the independence of the random Ge nucleation density on patterned versus unpatterned oxide surfaces. We also present the Ge nucleation density as a function of substrate temperature and deposition rate to demarcate selective growth conditions for Ge on Si with a window-patterned SiO₂ mask.     

Solid phase epitaxy of Ge films on CaF2/Si(1 1 1)

At room temperature deposited Ge films (thickness < 3 nm) homogeneously wet CaF₂/Si(1 1 1). The films are crystalline but exhibit granular structure. The grain size decreases with increasing film thickness. The quality of the homogeneous films is improved by annealing up to 200 °C. Ge films break up into islands if higher annealing temperatures are used as demonstrated combining spot profile analysis low energy electron diffraction (SPA-LEED) with auger electron spectroscopy (AES). Annealing up to 600 °C reduces the lateral size of the Ge islands while the surface fraction covered by Ge islands is constant. The CaF₂ film is decomposed if higher annealing temperatures are used. This effect is probably due to the formation of GeF_x complexes which desorb at these temperatures.     

Comparative AES and RHEED study of the formation of Pd silicide on clean and oxide covered Si(100) and (111) surfaces

The formation and epitaxial orientation of Pd silicide on clean and native oxide covered Si(100) and (111) surfaces was studied by Auger electron spectroscopy (AES) and reflection high energy electron diffraction (RHEED). Pd was vapor deposited in UHV on to the substrates up to thicknesses of about 6 nm. On clean Si substrates, ultra-thin Pd deposits reacted to form Pd₂Si already at room temperature, as detected by a characteristic splitting of the Si LVV Auger peak. However, a polycrystalline structure with very small crystallite sizes was indicated by diffuse ring patterns in RHEED. When the initial thickness of the Pd deposit exceeded about 3 nm, the diffraction ring pattern of unreacted metal developed. During annealing of room temperature deposits of Pd, the (100) and (111) substrates behaved differently. Larger crystallites formed on Si(100), but the films remained polycrystalline, though textured. On Si(111), virtually perfect epitaxial re-orientation of the silicide was found. When the substrates were initially covered with native oxide of about 2 nm thickness, silicide formation started at about 200°C, resulting in polycrystalline, but strongly textured Pd₂Si. Upon further annealing at temperatures up to 600°C, an additional phase of epitaxially oriented Pd₂Si developed on Si(111), similar to that on clean Si(100). In all experiments, extended annealing at temperatures above 250°C caused segregation of Si to the surface. This was accompanied by the development of an additional peak in the Auger electron spectra at about 313 eV, which we assign to a plasmon loss of δE = 17 eV in the Si overlayer, being excited by Pd Auger electrons of energy 330 eV.     

Size-dependent oxidation of Pdn (n 13) on alumina/NiAl(110): Correlation with Pd core level binding energies

Small Pd clusters Pd_n (n = 1, 4, 7, 10, 13) deposited on alumina/NiAl(110) at room temperature were examined by X-ray photoelectron spectroscopy (XPS), as-deposited and after exposure to O₂ at temperatures ranging from 100 to 500 K. After O₂ exposure at 100 K, the Pd clusters showed XPS shifts indicative of oxidation. The exception was Pd₄, which did not oxidize under any conditions. The inertness of Pd₄/alumina/NiAl(110) appears to be correlated with a significantly higher-than-expected Pd 3d binding energy, which we attribute to a particularly stable valence shell. None of the clusters examined oxidized during O₂ exposures at 300 K or above, but He⁺ scattering showed that oxygen was bound on the cluster surfaces. Upon heating, all the oxygen associated with these small clusters appeared to spill over and react with the alumina/NiAl(110) support.     

Enhancement of magnetic properties of Co/Pd multilayered perpendicular magnetic recording media by using Pd/Si dual seedlayer

Effects of the introduction of a Pd/Si dual seedlayer on the microcrystalline structure and magnetic properties of [Co/Pd]_n multilayered perpendicular magnetic recording media were investigated. The Pd/Si dual seedlayer was composed of a Pd upper seedlayer and a Si under seedlayer. The Pd upper seedlayer with a thickness of up to 10 nm markedly increased the coercivity of [Co/Pd]_n multilayered media in the direction perpendicular to the film surface. The highest coercivity of 7.8 kOe was obtained for the [Co/Pd]₁₀ medium with a Pd (10 nm)/Si (100 nm) dual seedlayer. The Pd upper seedlayer not only facilitated the formation of regular interfaces between the Co and Pd layers, but also reduced the thickness of the deteriorated initial layer in the [Co/Pd]_n multilayer, resulting in enhancement of the magnetic anisotropy field. The [Co/Pd]_n multilayered medium with the Pd/Si dual seedlayer exhibited weak intergranular exchange coupling between [Co/Pd]_n grains, which led to excellent read–write characteristics.     

Ion dose and anneal temperature dependent studies of silicon implanted AlxGa1−xN

Electrical and optical activation studies of Al_xGa_1−xN (x = 0.11 and 0.21) implanted with silicon were made as a function of ion dose and anneal temperature. Silicon ions were implanted at 200 keV with doses ranging from 1 × 10¹⁴ to 1 × 10¹⁵ cm⁻² at room temperature. The implanted samples were subsequently annealed from 1100 to 1300 °C for 20 min in a nitrogen environment. A maximum electrical activation efficiency of 91% was obtained for the Al_0.11Ga_0.89N implanted with the highest dose of 1 × 10¹⁵ cm⁻² even after annealing at 1150 °C. 100% activation efficiencies were successfully obtained for the Al_0.21Ga_0.79N samples after annealing at 1300 °C for both doses of 5 × 10¹⁴ and 1 × 10¹⁵ cm⁻². The mobility of the Si-implanted Al_xGa_1−xN increases with annealing temperature, and the highest mobilities are 109 and 98 cm²/V·s for Al_0.11Ga_0.89N and Al_0.21Ga_0.79N, respectively. The cathodoluminescence (CL) spectra for all the samples exhibited a sharp neutral-donor-bound exciton peak, and the CL intensity increases with annealing temperature, indicating successive improved implantation damage recovery as the annealing temperature is increased. These results provide the optimum annealing conditions for activation of implanted Si ions in Al_xGa_1−xN.     

Ion implantation damage and crystalline-amorphous transition in Ge

Experimental studies on the damage produced in (100) Ge substrates by implantation of Ge⁺ ions at different energies (from 25 to 600 keV), fluences (from 2×10¹³ to 4×10¹⁴ cm⁻²) and temperature (room temperature, RT, or liquid-nitrogen temperature, LN₂T) have been performed by using the Rutherford backscattering spectrometry technique. We demonstrated that the higher damage rate of Ge with respect to Si is due to both the high stopping power of germanium atoms and the low mobility of point defects within the collision cascades. The amorphization of Ge has been modeled by employing the critical damage energy density model in a large range of implantation energies and fluences both at RT and LN₂T. The experimental results for implantation at LN₂T were fitted using a critical damage energy density of ∼1 eV/atom. A fictitious value of ∼5 eV/atom was obtained for the samples implanted at RT, essentially because at RT the damage annihilation plays a non-negligible role against the crystalline–amorphous transition phase. The critical damage energy density model was found to stand also for other ions implanted in crystalline Ge (Ar⁺ and Ga⁺).     

Pd-Si薄膜固相反应的透射电子显微镜研究

本工作利用透射电子显微术研究了Pd-Si薄膜固相反应的初始生成相及生成相Pd₂Si与(111)取向Si衬底的取向关系随Pd膜厚度、退火温度等因素的变化规律。实验结果表明:在衬底保持室温的条件下,Pd沉积到Si(111)上时也能够生成一层外延的Pd₂Si,其厚度足以在常规的选区电子衍射中产生明显的信号。在170℃退火时,Pd-Si反应即可持续到生成200nm厚的外延的Pd₂Si。在Pd膜厚度为400nm的条件下,Pd₂Si与Si(111)衬底的取向关系为[0001]_(Pd2Si)轴织构。 关键词：     

Incorporation of the transition metal Hf into GaN

The perturbed angular correlation (PAC) technique was applied to study the incorporation of the transition metal Hf into GaN after implantation. To this end the PAC probe ¹⁸¹Hf(¹⁸¹Ta) was implanted into epitaxial Wurtzite GaN layers (1.3 μm on sapphire) with an energy of 160 keV and doses of 7× 10¹² at/cm². PAC spectra were recorded during an isochronal annealing programme, using rapid thermal annealing (RTA) and furnace annealing, in the 300–1000oC temperature range. After implantation the spectra show a damped oscillation corresponding to a quadrupole interaction frequency (QIF) of ν_Q= 340 MHz for 30% of the probe nuclei. Annealing up to 600oC reduces the damping of this frequency without an increase of the probe atom fraction f_s in these sites. Above 600oC f_s grows rapidly until after the 900oC RTA step more than 80% of the Hf probes experience a well defined QIF due to the incorporation of Hf on undisturbed sites of the hexagonal GaN wurtzite lattice. An interaction frequency of ν_Q= 340 MHz is derived. RTA and furnace annealing yield similar results for annealing up to 800oC, where the undisturbed fraction reaches about 60%. Then RTA at higher temperatures increases this fraction, while furnace annealing leads to a decrease down to 22% after annealing at 1000oC. To our knowledge this is the first time that a transition metal probe like Hf is incorporated to such a large extent into a semiconductor lattice. This revised version was published online in August 2006 with corrections to the Cover Date.     

Spin-diffusion lengths in dilute Cu(Ge) and Ag(Sn) alloys

We used current-perpendicular-to-plane (CPP) exchange-biased spin valves to directly measure spin-diffusion lengths ?_sf^N for N=Cu(2.1 at% Ge) and Ag(3.6 at% Sn) alloys. We found ?_sf^{Cu(2% Ge)}=117₋₆⁺¹⁰ nm and ?_sf^{Ag(4% Sn)}=39±3 nm. The good agreement of this ?_sf^{Cu(2% Ge)} with the value ?_sf^{Cu(2% Ge)}=121±10 nm derived from an independent spin-orbit cross-sectional measurement for Ge in Cu quantitatively validates the use of Valet-Fert theory for CPP-MR data analysis to layer thicknesses several times larger than had been done before. From the value of ?_sf^{Ag(4% Sn)}, we predicted the ESR spin-orbit cross-section for Sn impurities in Ag.     

Structural and optical properties of Ge nanocrystals obtained by hot ion implantation into SiO2 and further ion irradiation

In this work, SiO₂ layers containing Ge nanocrystals (NCs) obtained by the hot implantation approach were submitted to an ion irradiation process with different 2 MeV Si⁺ ion fluences. We have investigated the photoluminescence (PL) behavior and structural properties of the irradiated samples as well as the features of the PL and structural recovery after an additional thermal treatment. We have shown that even with the highest ion bombardment fluence employed (2×10¹⁵ Si/cm²) there is a residual PL emission (12% from the original) and survival of some Ge NCs is still observed by transmission electron microscopy analysis. Even though the final PL and mean diameter of the nanoparticles under ion irradiation are independent of the implantation temperature or annealing time, the PL and structural recovery of the ion-bombarded samples have a memory effect. We have also observed that the lower the ion bombardment fluence, the less efficient is the PL recovery. We have explained such behavior based on current literature data.     

First-principles study of small palladium clusters on NiAl(1 1 0) alloy surface

Theoretical calculations focused on the geometry, stability, electronic and magnetic properties of small palladium clusters Pd_n (n=1–5) adsorbed on the NiAl(1 1 0) alloy surface were carried out within the framework of density functional theory (DFT). In agreement with the experimental observations, both Ni-bridge and Al-bridge sites are preferential for the adsorption of single palladium atom, with an adsorption energy difference of 0.04 eV. Among the possible structures considered for Pd_n (n=1–5) clusters adsorbed on NiAl(1 1 0) surface, Pd atoms tend to form one-dimensional (1D) chain structure at low coverage (from Pd₁ to Pd₃) and two-dimensional (2D) structures are more stable than three-dimensional (3D) structures for Pd₄ and Pd₅. Furthermore, metal-substrate bonding prevails over metal–metal bonding for Pd cluster adsorbed on NiAl(1 1 0) surface. The density of states for Pd atoms of Pd/NiAl(1 1 0) system are strongly affected by their chemical environment. The magnetic feature emerged upon the adsorption of Pd clusters on NiAl(1 1 0) surface was due to the charge transfer between Pd atoms and the substrate. These findings may shade light on the understanding of the growth of Pd metal clusters on alloy surface and the construction of nanoscale devices.