Investigations of failure mechanisms at Ta and TaO diffusion barriers by secondary neutral mass spectrometry

One of the most important processes in Cu metallization for highly integrated circuits is to fabricate reliable diffusion barriers. Recently, thin films made of refractory metals and their compounds have been widely used in solid-state electronics as barriers because of their good electric properties, favourable thermal properties and chemical stability. Thermal stability of Tantalum (Ta) and Tantalum-oxide (TaO_x) layers as a diffusion barrier in Si/Ta/Cu, Si/TaO_x/Cu and Si/Ta-TaO_x/Cu systems have been investigated. Si/Ta (10 nm)/Cu (25 nm)/W (10 nm), Si/TaO_x (10 nm)/Cu (25 nm)/W (10 nm) and Si/Ta (5 nm)TaO_x (5 nm)/Cu (25 nm)/W (10 nm) thin layers were prepared by DC magnetron sputtering. A tungsten cap layer was applied to prevent the oxidation of the samples during the annealing process. The samples were annealed at various temperatures (473 K-973 K) in vacuum. Transmission Electron Microscopy, X-ray diffraction, X-Ray Photoelectron Spectroscopy and Secondary Neutral Mass Spectrometry were used to characterize the microstructure and diffusion properties of the thin films. Our results show that at the beginning phase of the degradation of the Si/Ta/Cu system Ta atoms migrate through the copper film to the W/Cu interface. In the Si/TaO_x/Cu system the crystallization of TaO and the diffusion of Si through the barrier determine the thermal stability. The Ta-TaO bilayer proved to be an excellent barrier layer between the Si and Cu films up to 1023 K. The observed outstanding performance of the combined film is explained by the continuous oxidation of Ta film in the TaO_x-Ta bilayer.     

Modification of AZO thin-film properties by annealing and ion etching

Effects of annealing and ion etching on the structural, electrical and optical properties of sputtered ZnO:Al (AZO) thin films were investigated. The post-deposition annealing at temperatures T_A = 200-400 °C in the forming gas (80% N₂/20% H₂) for 1 h and ion RF-sputter etching after annealing were used. Ion-sputter etching rate was 7 nm/min. The surface topography changed noticeably after ion-sputter etching: the surface of the sample was rougher (R_a = 33 nm) in comparison with annealed sample only (R_a = 9 nm). After the post-deposition annealing temperature T_A = 400 °C and ion-sputter etching thin films have higher integral transmittance (in the range of λ = 400-1000 nm) than non-etched samples. The figure of merit (F) became higher with increase of annealing temperature and the maximum value was F = 8%/Ω at T_A = 400 °C (R_s = 10 Ω, T_int = 86%).     

Effects of hydrogen annealing on the microstructure and optical properties of single-phased Ag2O film deposited using direct-current reactive magnetron sputtering

Single-phased and (111)-oriented Ag₂O film deposited using direct-current reactive magnetron sputtering is annealed using different annealing temperatures (T_a) for 1 h in Ar and H₂ mixture. After hydrogen annealing, a very weak but clear Ag(200) diffraction peak begins to appear, and the Ag₂O diffraction peak weakens at T_a = 175 °C. However, the Ag diffraction peak becomes discernable at T_a = 190 °C. No Ag₂O diffraction peaks but rather Ag diffraction peaks are discerned at T_a = 200 °C. The hydrogen reduction effect can reduce the film's critical thermal decomposition temperature to 175 °C. After hydrogen annealing, the surface of the film evolutes from compact and uniform to osteoporosis, and then to a porous structure. Moreover, the optical properties of the film obviously change at T_a over 190 °C, indicating that the hydrogen reduction can significantly enhance the decomposition of Ag₂O due to H₂ dissociation on the surface followed by gaseous H₂O molecule formation and desorption.     

Ag transport in CrN-Ag nanocomposite coatings

2-μm-thick CrN-Ag composite coatings containing 22 at.% Ag were deposited on Si(001) by reactive co-sputtering at T_s = 300, 400, and 500 °C. Subsequent vacuum annealing at T_a = 425, 525, and 625 °C causes Ag transport to the surface. Auger electron spectroscopy and plan-view microscopy are used to quantify the Ag transport to the surface, which increases strongly with increasing ΔT = T_a − T_s. Compositional depth profiles and cross-sectional microscopy show that annealing causes a negligible Ag gradient through the composite layer, suggesting that the Ag transport is detachment-limited as opposed to diffusion-limited. Statistical analyses of Ag aggregate size-distributions within the matrix show that large aggregates (≥ 50 nm) are unaffected by annealing, while the Ag in a large fraction of small aggregates (< 50 nm) moves to the surface, leaving behind 10-50 nm wide voids in the annealed composite. This indicates that the Ag from the smaller grains, with a higher chemical potential and thus a higher detachment rate, is transferred to the large grains on the surface which are 200-1000 nm wide.     

Influence of magnetic annealing on high-frequency magnetic properties of FeCoNd films

FeCoNd thin film with thickness of 166 nm has been fabricated on silicon (1 1 1) substrates by magnetron co-sputtering and annealed for one hour under magnetic field at different temperatures (T_a) from 200 °C to 700 °C. The As-deposited and annealed FeCoNd film samples at T_a ≤ 500 °C were amorphous while the ones obtained at T_a ≥ 600 °C were crystallized. We found that the perpendicular anisotropy field gradually decreases as the annealing temperature increases from room temperature to 300 °C. A well induced in-plane uniaxial anisotropy is achieved at the annealing temperature between 400 and 600 °C. The variation of the dynamic magnetic properties of annealed FeCoNd films can be well explained by the Landau-Lifshitz equation with the variation of the anisotropy field re-distribution and the damping constant upon magnetic annealing. The magnetic annealing might be a powerful post treatment method for high frequency application of magnetic thin films.     

Oscillatory behavior of the magnetic properties of Nd–Fe–B films with Mo and Mo–Cu additions

A series of Ta/NdFeB/Ta thin films with Mo and Mo–Cu additions embedded by alloying and by stratification have been prepared by r.f. sputtering. The influence of additions, their embedding mode, and annealing temperature on the structural and magnetic behavior of Ta/NdFeB/Ta thin films is presented. The use of additions of Mo and Mo–Cu leads to refined grain structure and improvement in the hard magnetic characteristics of Ta/NdFeB/Ta thin films. The Ta/[NdFeBMo(540 nm)/Ta films and Ta/[NdFeB(180 nm)/MoCu(dnm)] × n/Ta multilayer films present enhanced coercivities and M_r/M_s ratios in comparison with the Ta/NdFeB(540 nm)/Ta films. The stratification of Ta/NdFeB/Ta thin films with Mo–Cu interlayers leads to an oscillatory behavior of hard magnetic characteristics of the Ta/[NdFeB(180 nm)/MoCu(dnm)] × n/Ta multilayer films, when the thickness, d, of Mo–Cu interlayers varies by increments of 1 nm. When the thickness of Mo–Cu interlayers varies by increments of 2 nm the oscillatory behavior of the magnetic characteristics is not revealed. For a thickness of the Mo–Cu interlayer of 3 nm in the Ta/[NdFeB(180 nm)/MoCu(3 nm)] × 3/Ta thin films annealed at 650 °C, the c-axis of part of the hard magnetic Nd₂Fe₁₄B grains is oriented out-of-plane.     

Investigations of diffusion kinetics in Si/Ta/Cu/W and Si/Co/Ta systems by secondary neutral mass spectrometry

Proper understanding of the degradation mechanisms and diffusion kinetics of copper and cobalt interconnections for advanced microelectronics is important from the point of view of fundamental research and technology as well. In this paper Si(substrate)/Ta(10 nm)/Cu(25 nm)/W(10 nm) and Si(substrate)/Co(150 nm)/Ta(10 nm) samples, prepared by DC magnetron sputtering, were in investigated. The samples were annealed at several temperatures ranging from 423 K to 823 K for various times. The composition distributions were detected by means of Secondary Neutral Mass Spectrometry (SNMS). Microstructural characterization of samples was carried out by means of Transmission Electron Microscopy (TEM). It is shown that the changes in the composition profiles were mainly caused by grain boundary, GB, diffusion and the effective GB diffusion coefficients of Ta in Cu were determined both by the “first appearance” and “centre-gradient” methods. The activation energy is 100 kJ/mol. The importance of the Ta penetration into the Cu and its accumulation at the Cu/W interface can lead to an increase of the Ta content in the copper film. This can be an important factor in the change/degradation of the physical parameters (e.g. the electrical resistance) of interconnects. Furthermore a Ta segregation factor in Cu was evaluated. Preliminary results in the Si(substrate)/Co(150 nm)/Ta(10 nm) indicate fast (GB) diffusion of the Si into the Co layer, formation of a cobalt silicide layer at the Co/Si interface and Si accumulation first at the Ta/Co interface and later a retarded accumulation at the free Ta surface.     

Investigations of diffusion kinetics in Si/Ta/Cu/W and Si/Co/Ta systems by secondary neutral mass spectrometry

Proper understanding of the degradation mechanisms and diffusion kinetics of copper and cobalt interconnections for advanced microelectronics is important from the point of view of fundamental research and technology as well. In this paper Si(substrate)/Ta(10 nm)/Cu(25 nm)/W(10 nm) and Si(substrate)/Co(150 nm)/Ta(10 nm) samples, prepared by DC magnetron sputtering, were in investigated. The samples were annealed at several temperatures ranging from 423 K to 823 K for various times. The composition distributions were detected by means of Secondary Neutral Mass Spectrometry (SNMS). Microstructural characterization of samples was carried out by means of Transmission Electron Microscopy (TEM). It is shown that the changes in the composition profiles were mainly caused by grain boundary, GB, diffusion and the effective GB diffusion coefficients of Ta in Cu were determined both by the “first appearance” and “centre-gradient” methods. The activation energy is 100 kJ/mol. The importance of the Ta penetration into the Cu and its accumulation at the Cu/W interface can lead to an increase of the Ta content in the copper film. This can be an important factor in the change/degradation of the physical parameters (e.g. the electrical resistance) of interconnects. Furthermore a Ta segregation factor in Cu was evaluated. Preliminary results in the Si(substrate)/Co(150 nm)/Ta(10 nm) indicate fast (GB) diffusion of the Si into the Co layer, formation of a cobalt silicide layer at the Co/Si interface and Si accumulation first at the Ta/Co interface and later a retarded accumulation at the free Ta surface.     

Grazing incidence X-ray study of Ge-nanoparticle formation in (Ge:SiO2)/SiO2 multilayers

We present the study of formation of Ge-nanoparticles (Ge-NP) in germanosilicate (Ge:SiO₂) multilayer (ML) films under thermal treatment. In anticipation of controllable formation of Ge-NP, ML films were prepared by magnetron deposition at room temperature as 20 bi-layer stacks, each bi-layer comprised of a 7 nm thick layer of (Ge + SiO₂) (molar ratio: 60:40) succeeded by a 7 nm thick layer of pure SiO₂, and then annealed for 1 h, up to T_a = 900 °C. Formation and morphology of Ge-NP were analyzed by combining the information obtained from the grazing incidence small angle X-ray scattering and X-ray diffraction. It was found that precipitation of Ge-NP starts at T_a = 600 °C, while high degree of in-plane confinement and lateral ordering of rather uniform precipitated particles is achieved at T_a =  700-800 °C range. At still higher annealing temperature T_a > 800 °C, volume fraction of precipitated Ge-NP in SiO₂ matrix diminishes due to the out-diffusion of Ge atoms from the film, while Ge-NP are no more well confined to (Ge + SiO₂) layers.     

Magnetoresistance enhancement of amorphous CoNbZr-buffered magnetoresistive multilayers

Amorphous CoNbZr alloys are thermally stable and thus have been intensively studied as soft layers of a pseudo-spin-valve (PSV). By depositing a wedge-shaped Co inset layer (IL) between the CoNbZr and Cu layer, we were able to simultaneously fabricate CoNbZr(t_CNZ)/Co(0-3 nm)/Cu/Co PSVs with various CoNbZr and Co IL thicknesses. We have investigated the dependence of magnetic properties, giant magnetoresistance (GMR) effect, and microstructure on the thickness of the amorphous CoNbZr buffer layer. The GMR enhancement behaviour of the PSVs with different CoNbZr thickness was also studied along the inset Co wedge. By optimizing the thickness of CoNbZr and Co IL, a maximum GMR ratio of 7% was obtained in the stack of CoNbZr(4 nm)/Co(1.2 nm)/Cu(2.2 nm)/Co(4 nm).