Effects of electric field annealing on the interface diffusion of Cu/Ta/Si stacks

In the present paper, the effects of electric field annealing on interface diffusion of Cu/Ta/Si stacks were studied by means of XRD, XPS and TEM. The barrier property of Ta films was evaluated based on the diffusion of Cu atoms. It was found that the external electric field accelerates the diffusion of Cu atoms through Cu/Ta/Si interfaces during annealing. With the increment of annealing temperature, the effect of the electric field upon the atomic diffusion becomes more significant. The mechanism of accelerated interface diffusion is suggested and the failure of Ta barrier layer is discussed based on the mobility of vacancies and Cu atoms inside Cu/Ta/Si stacks caused by the electric field.     

In situ TEM study of stability of TaRhx diffusion barriers using a novel sample preparation method

The atomic diffusion mechanisms associated with metallurgical failure of TaRh_x diffusion barriers for Cu metallizations were studied by in situ transmission electron microscopy (TEM). The issues related to in situ heating of focused ion beam (FIB) prepared cross-sectional TEM samples that contain Cu thin films are discussed. The Cu layer in Si/(13 nm)TaRh_x/Cu stacks showed grain growth and formation of voids at temperatures exceeding 550 °C. For Si/(43 nm)TaRh_x/Cu stacks, grain growth of Cu was delayed to higher temperatures, i.e., 700 °C, and void formation was not observed. Extensive surface diffusion of Cu, however, preceded bulk diffusion. Therefore, a 10 nm film of electron beam evaporated C was deposited on both sides of the TEM lamellae to limit surface diffusion. This processing technique allowed for direct observation of atomic diffusion and reaction mechanisms across the TaRh_x interface. Failure occurred by nucleation of orthorhombic RhSi particles at the Si/TaRh_x interface. Subsequently, the barrier at areas adjacent to RhSi particles was depleted in Rh. This created lower density areas in the barrier, which facilitated diffusion of Cu to the Si substrate to form Cu₃Si. The morphology of an in situ annealed lamella was compared with an ex situ bulk annealed sample, which showed similar reaction morphology. The sample preparation method developed in this study successfully prevented surface diffusion/delamination of the Cu layer and can be employed to understand the metallurgical failure of other potential diffusion barriers.     

Thickness‐dependent electroforming behavior of ultra‐thin Ta2O5 resistance switching layer

Electroforming behaviours of Ta₂O₅ resistance switching memory cell with a diameter of 28 nm and different thickness (0.5–2.0 nm) of Ta₂O₅ layer have been examined. The devices showed a constant forming electric field of 0.54 V/nm regardless of Ta₂O₅ thickness. The electroforming with negative bias to top TiN electrode was ascribed to electric field‐ driven migration of oxygen vacancies, originally residing near the bottom interface, toward the top electrode interface and formation of conducting filaments. The estimated electroforming energy (0.094–0.14 eV) was favourably compared with the hopping energy of electrons from the V_O site to a nearby Ta site. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Diffusion of gallium into cadmium sulphide

Measurements of the Ga diffusion into CdS, in the presence of exces Ga metal, using optical and mixroprobe analyser techniques are reported. A reaction layer of CdGa₂S₄ forms on the CdS crystals below 1240±20 K. Above this temperature the reaction layer is liquid. The Ga diffusion is concentration dependent and also orientation dependent with the faster diffusion perpendicular to the hexagonal c-axis of CdS. The anisotropy of the activation energy was calculated to be 0.20±0.06 eV. In the temperature range 940–1240K the linearly concentration dependent diffusion yielded activation energy values for defect motion of 2.39±0.13 eV perpendicular to the c-direction and 2.21 ±0.13 eV parallel to the c-direction.     

Atomic diffusion in annealed Cu/SiO2/Si（100） system prepared by magnetron sputtering

Cu thin films are deposited on p-type Si (100) substrates by magnetron sputtering at room temperature. The inter-face reaction and atomic diffusion of Cu/SiO2/Si (100) systems are studied by x-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS). Some significant results can be obtained. The onset temperature of interdiffusion for Cu/SiO2/Si(100) is 350 C. With the annealing temperature increasing, the interdiffusion becomes more apparent. The calculated diffusion activation energy is about 0.91 eV. For the Cu/SiO2/Si (100) systems copper silicides are not formed below an annealing temperature of 350 C. The formation of the copper silicides phase is observed when the annealing temperature arrives at 450 C.     

Study of the component distribution in Si/GexSi1−x /Si heterostructures grown by molecular beam epitaxy

This paper reports on a study of the depth profile of components in GeSi heterostructures grown on low-temperature silicon (LTSi: T _gr ～ 350–400° C) and porous silicon by molecular-beam epitaxy. An excess Ge concentration was found by Auger electron spectroscopy depth profiling at the Ge_xSi_1?x /LTSi interface, which decreased in all samples subjected to annealing. The Ge diffusion activation energy was calculated to be E _a ≈ 1.6 eV in this case. An enhanced Ge concentration was also detected by x-ray photoelectron spectroscopy at the Si cap surface. Possible reasons for the surface enrichment of the silicon layer and of the Ge_xSi_1?x film interface by germanium are considered, and the relation between the component distribution and the structural features of plastically strain-relieved layers are discussed.     

Atom beam sputtered Mo2C films as a diffusion barrier for copper metallization

The saddle field fast atom beam sputtered (ABS) 50 nm thick molybdenum carbide (Mo₂C) films as a diffusion barrier for copper metallization were investigated. To study the diffusion barrier properties of Mo₂C films, the as-deposited and annealed samples were characterized using four probes, X-ray diffraction, field enhanced scanning electron microscopy, energy dispersive X-ray analysis, atomic force microscopy and Rutherford back scattering techniques. The amorphous structure of the barrier films along with presence of carbon atoms at the molybdenum carbide-silicon interface is understood to reduce effective grain boundaries and responsible for increased thermal stability of Cu/Mo₂C/Si structure. The lowest resistivity of the as-deposited molybdenum carbide barrier films was ∼29 μΩ cm. The low carbon containing molybdenum carbide was found thermally stable up to 700 °C, therefore can potentially be used as a diffusion barrier for copper metallization.     

Kinetics of induced magnetic directional order in a Fe40Ni40P14B6 amorphous alloy

The amorphous Fe₄₀Ni₄₀P₁₄B₆ alloy (Metglas 2826) has been annealed under magnetic field at several temperatures. The kinetics of induced magnetic anisotropy exhibits a broad spectrum (β = 4) of time constants; it obeys exactly an Arrhenius law with an activation energy of 1.74 ± 0.04 eV. These values are identical to those determined by resistivity measurements. This suggests the formation of short range directional order.     

Surface diffusion of lead on tungsten

Field electron microscopy is used to study the surface diffusion of lead on tungsten. A simple method to measure rough values of the diffusion coefficient and its dependence on sub-monolayer coverage is described and tested. In the region around (001) the displacement energy found is about 1.30 eV/atom up to 10¹⁵ atoms/cm² where it decreases to 0.78 eV/atom. In the residual region except (110) this energy at 1.5×10¹⁴ atoms/cm² is 1.22 eV/atom, it decreases at 4 × 10¹⁴ atoms/cm² to 0.61 eV/atom and increases at 10¹⁵ atoms/cm² to 0.78 eV/atom. Corresponding values of the diffusion coefficient D and of the preexponential D₀ are given. The dependence of D on submonolayer coverage is discussed.     

Lattice structures and electronic properties of MO/MoSe2 interface from first-principles calculations

Using first-principles plane-wave calculations within density functional theory, we theoretically studied the atomic structure, bonding energy and electronic properties of the perfect Mo (110)/MoSe₂ (100) interface with a lattice mismatch less than 4.2%. Compared with the perfect structure, the interface is somewhat relaxed, and its atomic positions and bond lengths change slightly. The calculated interface bonding energy is about −1.2 J/m², indicating that this interface is very stable. The MoSe₂ layer on the interface has some interface states near the Fermi level, the interface states are mainly caused by Mo 4d orbitals, while the Se atom almost have no contribution. On the interface, Mo-5s and Se-4p orbitals hybridize at about −6.5 to −5.0 eV, and Mo-4d and Se-4p orbitals hybridize at about −5.0 to −1.0 eV. These hybridizations greatly improve the bonding ability of Mo and Se atom in the interface. By Bader charge analysis, we find electron redistribution near the interface which promotes the bonding of the Mo and MoSe₂ layer.     

Mechanism and kinetics of Cu2O oxidation in chemical looping with oxygen uncoupling

In chemical looping with oxygen uncoupling, oxygen carrier (OC) circulates between the fuel and air reactors to release and absorb O₂ repeatedly. In order to assess the re-oxidation characteristic of Cu-based OC in the air reactor from the microscopic mechanism and macroscopic kinetics perspective, DFT calculations and isothermal oxidation experiments were conducted. In DFT calculations, Cu₂O(111) surface was chosen as the objective surface to explore the oxygen uptake as well as the atomic transportation pathways, and to determine the rate-limiting steps basing on the energy barrier analyses. It was found that the energy barrier of the surface reaction step (0.96?eV) is smaller than that of the ions diffusion step (1.61?eV). Moreover, the Cu cations outward diffusion occurs more easily than O anions inward diffusion, which confirmed the epitaxial growth characteristic of Cu₂O oxidation. The isothermal oxidation experiments were conducted in a thermogravimetric analyzer (TGA), and about 3.5?mg CuO@TiO₂-Al₂O₃ particles within the diameter range of 75–110?µm were tested between 540 and 600 °C, where the internal and external gas diffusion effects were eliminated. Mixtures of 5.2-21.0?vol.% O₂ in N₂ were adopted as the gas agent for oxidation. Based on the understandings obtained from DFT calculations, a simple mathematical model with unknown parameters of the surface reaction process (mainly the activation energy, E_k) and ions diffusion process (mainly the activation energy, E_D) was established to describe the overall oxidation process in TGA experiments. Eventually, these unknown parameters were determined as E_k=?50.5?kJ/mol and E_k=?79.2?kJ/mol via global optimization. With the attained parameters, simulations reproduced the experimental results very well, which demonstrated that this simplification model, where grain is converted almost layer by layer but different from the feature of the shrinking core model is able to accurately describe the overall oxidation process of Cu₂O.     

Suppression of interlayer segregation in spin-valve NiFe/Cu/NiFe/FeMn multilayers

Experimental results show that Cu atoms can float out to or segregate to the NiFe/FeMn interface for Ta/NiFe/Cu/NiFe/FeMn/Ta spin-valve multilayers, which results in a drop of the exchange-coupling field (H_ex) of NiFe/FeMn in the spin-valve multilayers. However, when a small amount of Bi atoms is deposited between the Cu and the pinned NiFe layers, Cu segregation to the NiFe/FeMn interface can be suppressed. At the same time, H_ex of NiFe/FeMn in the spin-valve multilayers with a Bi interfacial layer can be effectively increased. PACS 75.70.Cn; 82.80.Pv     

Energetics of atomic hydrogen diffusion on Si(100)

We present first principles calculations of the potential energy surface for the diffusion of a single hydrogen atom on Si(100)2 × 1. Surface relaxation is found to be very important for the energetics of diffusion. A strong anisotropy is predicted for hydrogen motion: H should diffuse mainly along dimer rows, where activation energies are ~ 1.3 eV, while the barrier for row-to-row hopping is ~ 0.5 eV higher. Our results indicate that diffusion can be considered a fast process compared to H₂ recombinative desorption.     

Diffusion of rhodium layers on the stepped surface of a tungsten micro-crystal

We have investigated the spreading of rhodium at coverages of 0.25, 0.5, 1, 2 and 3 ML over the curved surface of a field emitter tip using field electron microscopy. We have found that the activation energy of spreading as well as the prefactor for the diffusivity depend strongly on the thickness of the layer diffusing, due to a change in interactions in the adsorbate-substrate system. The derived average activation energy for spreading first decreases from E_dif = 1.32 eV/atom at Θ = 0.25 ML to E_dif = 0.71 eV at Θ ≈ 2 ML and than rises again to E_dif = 1.20 eV at Θ ≈ 3 ML. The prefactor for the diffusivity D₀ also decreases with increasing coverage from 0.5 to 1 ML, and stays almost constant for multilayer diffusion in a range of few orders of magnitude lower than for single atom diffusion. We register typical spreading behavior with a sharp moving boundary in the (0 1 1)-(0 0 1) zone of the tip and an unusual picture of diffusion in the (0 1 1)-(1 1 2) region of the tip. In the second region diffusion proceeds without a sharp boundary, independent of the thickness of the moving layer. We think that such an unusual picture can be caused by the change in composition of the second and next layers of adsorbing material due to the early stage of faceting observed in this region of the tip at higher temperature. The results are compared with data for diffusion of individual Rh atoms and small clusters; to understand the observed diffusion we propose taking account of the atomic surface structure of the substrate, modified by strong interactions of the Rh adsorbate with the W micro-crystal surface.     

Quantum size effect in electron transmission through Cu and Ag films on W(110)

The transmission coefficient of very low energy electrons ( ? 10 eV) normally incident on (111) epitaxial films of Cu and Ag on W(110) is modulated by interference between scattering from the vacuum/metal and metal/metal interfaces. Comparison with calculations of free-electron scattering from a one-dimensional potential model, in which grading of the metal/metal interface is represented by a smoothing of the potential step, indicates that this interface is abrupt within approximately one layer spacing. We obtain a value of 11.0 (8.0) ± 1.0 eV for the inner potential of Cu (Ag) and mean free path lengths of $\text{39 ± 8}\text{A}\text{?}$ at an energy of 7.0 eV relative to the Fermi energy and $\text{29 ± 11}\text{A}\text{?}$ at 9.0 eV for Cu, and $\text{25 ± 10}\text{A}\text{?}$ at 7.5 eV for Ag. Work function values are obtained by the field emission retarding potential technique. We investigate the effects of the surface potential barrier, inelastic scattering and surface roughness, and evaluate the validity of the one-dimensional model presented.     

Ta/Ni/Ta multilayered ohmic contacts on n-type SiC

The interface formation, electrical properties and the surface morphology of multilayered Ta/Ni/Ta/SiC contacts were reported in this study. It was found that the conducting behavior of the contacts so fabricated is much dependent on the metal layer thickness and the subsequent annealing temperature. Auger electron spectroscopy (AES) and X-ray diffraction analyses revealed that Ni₂Si and TaC formed as a result of the annealing. The Ni atoms diffused downward to metal/SiC interface and converted into Ni₂Si layer in adjacent to the SiC substrate. The released carbon atoms reacted with Ta atoms to form TaC layer. Ohmic contacts with specific contact resistivity as low as 3 × 10⁻⁴ Ω cm² have been achieved after thermal annealing. The formation of carbon vacancies at the Ni₂Si/SiC interface, probably created by dissociation of SiC and formation of TaC during thermal annealing, should be responsible for the ohmic formation of the annealed Ta/Ni/Ta contacts. The addition of Ta into the Ni metallization scheme to n-SiC restricted the accumulation of carbon atoms left behind during Ni₂Si formation, improving the electrical and microstructure properties.     

Effects of controlling Cu spacer inter-diffusion by diffusion barriers on the magnetic and electrical stability of GMR spin-valve devices

An ultra-thin Co or CoFe diffusion barrier inserted at the NiFe/Cu interfaces was revealed to effectively control the electrical and magnetic stability of NiFe/Cu/NiFe-based giant magnetoresistance (GMR) spin-valve spintronics devices (SVSDs) operating at high current density. It was found that the activation energy, E_a, related to the electromigration (EM)-induced inter-diffusion process for the patterned NiFe(3)/Cu(2)/NiFe(3 nm) magnetic multi-layered devices (MMLD) was remarkably increased from 0.52±0.2 eV to 1.17±0.16 eV after the insertion of an ultra-thin Co diffusion barrier at the NiFe/Cu interfaces. The dramatically reduced “current shunting paths” from the Cu spacer to the NiFe thin films and the development of “self-healing process” resulted from the effectively restrained Cu inter-diffusion (intermixing with Ni atoms) due to the diffusion barriers were found to be primarily responsible for the improvement of electrical and magnetic stability. The further investigation on the effects of controlling Cu spacer inter-diffusion by diffusion barriers on the EM and thermomigration (TM)-induced magnetic degradation was carried out for the NiFe/(Co or Co₉₀Fe₁₀)/Cu/(Co or Co₉₀Fe₁₀)/NiFe/FeMn top exchange-biased GMR (EBGMR) SVSDs electrically stressed under the applied DC current density of J=2.5×10⁷ A/cm² (I=16.5∼17.25 mA). It was clearly confirmed that the Co and the CoFe diffusion barriers effectively control the Cu spacer inter-diffusion resulting in a smaller reduction in both GMR ratio and exchange bias field of the EBGMR SVSDs. Furthermore, it was obviously observed that the effects of CoFe diffusion barrier on controlling the Cu spacer inter-diffusion are more significant than that of Co. The effectively reduced Mn atomic inter-diffusion at the NiFe/FeMn interface and the well-maintained interfacial spin-dependent scattering resulted from the control of EM and TM-induced Cu spacer inter-diffusion were the main physical reasons for the significant improvement of magnetic and electrical degradation of top EBGMR SVSDs.     

Photoemission from Ni0.84Cu0.16(111): Observation of surface energy band dispersion

Angle-resolved photoemission spectra have been obtained for annealed Ni_0.84Cu_0.16(111) single crystals. Emission peaks 1.8–4.0 eV below the Fermi energy are attributed to electronic states of the Cu-rich surface layer. The measured dispersion of these peaks is in close correspondence with the calculated energy bands of a free Cu (111) monolayer. Ni-derived bulk transitions are also identified.     

Specific features of the temperature characteristics of electrical conductivity and photoconductivity of polymer composites containing Cu(II)/Cr(III) heterometallic complexes

The temperature characteristics of the electric current and the photocurrent in films of composites based on electrically neutral poly(vinyl butyral) with additions of Cu(II)/Cr(III) heterometallic cation-anion complexes are investigated. The electrical conductivity and photoconductivity of the polymer composite films in the visible optical range increase with a decrease in the distance between the metal centers in the complexes and upon introduction of acceptor additions of the C₆₀ fullerene into the composition of the polymer binder and increase exponentially with increasing temperature. The activation energy of electrical conduction and photoconduction exceeds 1 eV and depends weakly on the strength of the external electric field. The temperature characteristics of the electrical conductivity and photoconductivity of the materials under investigation are explained by the specific features of trapping of charge carriers at the interface between particles of the heterometallic complex and the polymer binder.     

Atomic Diffusion in Cu/Si （111） and Cu/SiO2/Si （111） Systems by Neutral Cluster Beam Deposition

The Cu films are deposited on two kinds of p-type Si （111） substrates by ionized duster beam （ICB） technique. The interface reaction and atomic diffusion of Cu/Si （111） and Cu/SiO2/Si （111） systems are studied at different annealing temperatures by x-ray diffraction （XRD） and Rutherford backscattering spectrometry （RBS）. Some significant results are obtained： For the Cu/Si （111） samples prepared by neutral dusters, the interdiffusion of Cu and Si atoms occurs when annealed at 230℃. The diffusion coefficients of the samples annealed at 230℃ and 500℃ are 8.5 ×10^-15 cm^2.s^-1 and 3.0 ×10^-14 cm^2.s^-1, respectively. The formation of the copper-silicide phase is observed by XRD, and its intensity becomes stronger with the increase of annealing temperature. For the Cu/SiO2//Si （111） samples prepared by neutral dusters, the interdiffusion of Cu and Si atoms occurs and copper silicides are formed when annealed at 450℃. The diffusion coefficients of Cu in Si are calculated to be 6.0 ×10^-16 cm^2.s^-1 at 450℃, due to the fact that the existence of the SiO2 layer suppresses the interdiffusion of Cu and Si.