Effect of Ag-alloying addition on the stress-temperature behavior of electroplated copper thin films

The effect of Ag-alloying on the microstructural and thermo-mechanical properties of electrochemically deposited Cu thin films was investigated using the focused ion beam technique, scanning electron microscopy and the electron back scatter diffraction (EBSD) technique as well as the substrate curvature method to study their stress-temperature and stress relaxation behavior. The results show that the linear elastic behavior of 1 μm thick Cu films is significantly improved by alloying. Additionally, after annealing such films have an excellent low electrical resistivity of 1.9-2.0 μΩ cm, which meets the requirements of the roadmap ITRS [International Technology Roadmap for Semiconductors, Edition 2003, part: interconnect, available at http://public.itrs.net/].     

Carbon precipitation and diffusion in SiGeC alloys under silicon self-interstitial injection

In this work we investigate the diffusion and precipitation of supersaturated substitutional carbon in 200-nm-thick SiGeC layers buried under a silicon cap layer of 40 nm. The samples were annealed in either inert (N₂) or oxidizing (O₂) ambient at 850 °C for times ranging from 2 to 10 h. The silicon self-interstitial (I) flux coming from the surface under oxidation enhances the C diffusion with respect to the N₂-annealed samples. In the early stages of the oxidation process, the loss of C from the SiGeC layer by diffusion across the layer/cap interface dominates. This phenomenon saturates after an initial period (2–4 h), which depends on the C concentration. This saturation is due to the formation and growth of C-containing precipitates that are promoted by the I injection and act as a sink for mobile C atoms. The influence of carbon concentration on the competition between precipitation and diffusion is discussed. Received: 19 October 2001 / Accepted: 19 December 2001 / Published online: 20 March 2002 / Published online: 20 March 2002     

Base doping and dopant profile control of SiGe npn and pnp HBTs

Incorporation of high doping concentrations and the creation and maintaining of steep doping profiles during processing are key enabler for high level RF performance of heterojunction bipolar transistors (HBTs). In this paper, we discuss results of base doping and dopant profile control for npn and pnp SiGe HBTs fabricated within 0.25 μm BiCMOS technologies. High level of electrically active B and P doping concentrations (up to 10²⁰ cm⁻³) have been incorporated into SiGe. By adding C to SiGe steep doping profiles have been maintained due to the prevention of dopant diffusion during device processing. It is shown that broadening of P doping profiles caused by segregation could be reduced by lowering the deposition temperature for the SiGe cap. B and P atomic layer doping is shown to be suitable for the creation of steep and narrow doping profiles. This result is demonstrating the capability of the atomic layer processing approach for future devices with critical requirements of dopant dose and location control.     

X-ray photoelectron spectroscopy study of NiSi formation on shallow junctions

The influence of boron (B)/arsenic (As) on X-ray photoelectron spectroscopy (XPS) study of NiSi formation on shallow junctions is investigated in this paper. The Ni-silicide film was formed after 30 s soak anneal at 450 °C on ultra shallow p+/n or n+/p junctions. The atomic ratio of Ni/Si profile in depth was probed by XPS and the results show that a uniform NiSi layer forms on B-doped p+/n junction while a non-uniform, Ni-rich silicide layer forms on As-doped n+/p junction. It does not agree with the results of other independent phase identification methods such as X-ray diffraction, Rutherford backscattering spectroscopy, and Raman scattering spectroscopy, which all demonstrate the formation of NiSi on both n+/p and p+/n junctions. Comparing the raw binding energy spectra of Ni and Si for each silicide film, the similar spectra for Ni signals are revealed. But the Si signals with an obviously smaller intensity is found to be responsible for the apparent Ni rich silicide formation on As-doped n+/p junction. It indicates that As atoms in the silicide film can affect the sputtering yield of Ni and Si, while no noticeable effect is observed for B atoms. More As atoms than B atoms segregation into the silicide layer is indeed verified by secondary ion mass spectroscopy. And micro-Raman scattering spectroscopy further confirms that the degree of crystallinity for NiSi on n+/p junction is inferior to that on p+/n junction.     

Effect of organic additives on characterization of electrodeposited Co-W thin films

Co-W thin films were electrodeposited from aqueous bath with different organic additives. Electrochemical analysis showed that the transient state was limited and polarization behaviors were more evident during Co-W electrodeposition in the presence of organic additives. SEM measurement indicated that the surface morphology was affected by the nature of the organic additives to a large extent. Homogeneous Co-W thin films were obtained from the solutions containing ethyl methacrylate. Moreover, it was obvious that the presence of organic additives, in the electroplating bath, modified the structure and magnetic properties of the Co-W thin films according to the XRD and VSM measurements.     

Structure and composition of the segregated Cu in V2O5/Cu system

We have investigated segregation of copper at the surface of V₂O₅ films deposited onto Cu substrate by employing surface analysis techniques. X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) confirmed that the Cu is segregated at the surface and its chemical state is Cu₂O. According to secondary ion mass spectroscopy (SIMS) and glow discharge spectroscopy (GDS), the Cu concentration inside the deposited V₂O₅ layer is low. Ultraviolet photoelectron spectroscopy (UPS) and scanning tunneling spectroscopy (STS) revealed the segregation alters the surface local density of states. Surface analysis of deposited samples in ultra high vacuum (UHV) condition verified that the segregation occurs during the deposition. We have extended kinetic tight binding Ising model (KTBIM) to explain the surface segregation during the deposition. Simulation data approve the possibility of surface segregation during room temperature deposition. These results point out that on pure Cu substrate, oxidation occurs during the segregation and low surface energy of Cu₂O is the original cause of the segregation.     

On the migration of defects and impurities in microelectromechanical systems subject to a large number of light pulses

The migration of defects in light-irradiated microelectromechanical systems (MEMS) is treated theoretically. The effects of temperature gradients on atomic demixing are considered. It is found that, when the migration energy of defects and impurities is less than about 0.5 eV, their migration has to be introduced in the modelling of ageing of MEMS. Received: 17 July 2000 / Accepted: 31 March 2000 / Published online: 27 June 2001     

Electrodeposition of n-type Bi2Te3−ySey thermoelectric thin films on stainless steel and gold substrates

Thermoelectric films of n-Bi₂Te_3−ySe_y were prepared by potentiostatic electrodeposition technique onto stainless steel and gold substrates at room temperature. These films were used for morphological, compositional and structural analysis by environment scanning electron microscope (ESEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The effect of different substrates on the structure and morphology of Bi₂Te_3−ySe_y films and relation between Se content in the electrodepositing solutions and in the films were also investigated. These studies revealed that Bi, Te and Se could be co-deposited to form Bi₂Te_3−ySe_y semiconductor compound in the solution containing Bi³⁺, HTeO₂⁺ and H₂SeO₃. The morphology and structure of the films are sensitive to the substrate material. The doped content of Se element in the Bi₂Te_3−ySe_y compound can be controlled by adjusting the Se⁴⁺ concentration in the electrodepositing solution. X-ray diffraction analysis indicates that the films prepared at −40 mV versus saturated calomel electrode (SCE) exhibit strong (1 1 0) orientation with rhombohedral structure.     

Surfactant-mediated growth of Si1-xSnx layers by molecular-beam epitaxy

1-x Sn_x (0.01≤x≤0.04) layers on Si(001) and relaxed Si-Ge substrates. The Si_1-xSn_x layers were investigated using Rutherford backscattering spectrometry, atomic force microscopy, transmission electron microscopy and preferential-etching experiments. The investigation of surfactant-mediated growth of epitaxial Si_1-xSn_x was motivated by a possible use of relatively higher growth temperatures without relaxation by surface precipitation. It is demonstrated that higher growth temperatures are attainable when Bi is used as surfactant if the surface-segregated Sn layer is relatively small, equivalent to Si_1-xSn_x layers of low strain. The increase in growth temperature leads to a significant improvement in the crystalline quality of these Si_1-xSn_x layers. Received: 4 December 1998/Accepted: 9 December 1998     

Study of nickel silicide formation on Si(1 1 0) substrate

Nickel silicide formation on Si(1 1 0) and Si(1 0 0) substrate was investigated in this paper. It is confirmed that nickel monosilicide (NiSi) starts to form after 450 °C annealing for Si(1 0 0) substrate, but a higher annealing temperature is required for NiSi formation on Si(1 1 0) substrate, which is demonstrated by X-ray diffraction (XRD) and Raman scattering spectroscopy. The higher formation temperature of NiSi is attributed to the larger Ni₂Si grain size formed on Si(1 1 0) substrate. Ni silicided Schottky contacts on both Si(1 0 0) and Si(1 1 0) substrates were also fabricated for electrical characteristics evaluation. It clearly reveals that the rectifying characteristics of NiSi/n-Si(1 1 0) Schottky contacts is inferior to that of NiSi/n-Si(1 0 0) Schottky contacts, which is attributed to a lower Schottky barrier height and a rougher contact interface. The formation kinetics for nickel silicide on Si(1 1 0) substrate is also discussed in this paper.     

Effect of Pretreatment of TaN Substrates on Atomic Layer Deposition Growth of Ru Thin Films

The polycrystalline ruthenium films are grown on TaN substrates by atomic layer deposition （ALD） using bis（cyclopentadienyl） ruthenium [RuCp2] and oxygen as ruthenium precursor and reactant respectively at a deposition temperature of 330℃. The low-energy Ar ion bombardment and Ru pre-deposition are performed to the underlying TaN substrates before ALD process in order to improve the Ru nucleation. X-ray diffraction, x-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy are carried out to characterize the properties of ALD Ru films. The results show that the nucleation density of Ru films with Ar^＋ bombardment to the underlying TaN substrates is much higher than that of the ones without any pretreatment. The possible reasons are discussed.     

Structure and properties of electrodeposited Fe-Ni-W alloys with different levels of tungsten content: A comparative study

Fe-Ni-W alloys with 18 wt%, 35 wt% and 55 wt% tungsten have been obtained by electrodeposition from an ammoniacal citrate bath. The deposits are smooth, of nice appearance, and adhere well to iron and steel. The morphology and structure of Fe-Ni-W alloys were studied by SEM and XRD, respectively. The structure of the as-plated deposits changed from crystalline to amorphous with increasing tungsten content. The amorphous structure crystallized under heat treatment condition. The wear and corrosion resistance of the deposits were tested by MPX-2000 wear-tear equipment and neutral salt spray test (NSS), respectively. The alloys with 55 wt% tungsten, after heat treatment at proper temperatures, appear to have good wear resistance and hardness. The alloys with 18 wt% tungsten are very corrosion-resistant.     

Influence of complexing agent on the electrodeposited Co-Pt-W magnetic thin films

Complexing agents are often used to improve the quality of electrodeposited alloys. Influence of different complexing agents with hydroxycarboxylic acid group on the electrodeposited Co-Pt-W thin films has been investigated. Cathodic polarization curves show that the polarization behaviors of electroplating bath with different complexing agents are very different. Surface morphology, phase composition and magnetic properties are observed by means of FESEM, XRD and vibrating sample magnetometer (VSM), respectively. It has been found out that, if citrate was used as complexing agent, the Co-Pt-W thin films were homogeneous and the granular crystals with the average grain size of 2 μm have been observed. Co-Pt-W thin films exhibited hexagonal close packed (hcp) lattice and strong perpendicular anisotropic magnetic behavior (H_c⊥ = 215.5 kA/m; H_c∥ = 55.4 kA/m). In the presence of gluconate, needle-like deposits were obtained and a strong face centered cubic (fcc(1 1 1)) texture was measured. The Co-Pt-W thin films showed isotropic magnetic behavior. In the case of tartate and malate, the coexistence of needle-like deposits and cellular deposits appeared. The XRD patterns showed that the mixed fcc and hcp phase formed. Perpendicular anisotropic magnetic behaviors of thin films, from malate or tartate baths, were not obvious.     

Effects of NaN3 Added in Fe-C System on Inclusion and Impurity of Diamond Synthesized at High Pressure and High Temperature

Effects of NaN3 added in Fe-C system to synthesize nitric diamond at high pressure and high temperature are investigated. Diamond crystals with high nitrogen concentration are synthesized by the system of Fe-C and NaN3 additive at pressure 5.8 GPa and at temperatures 1750-1780 K for 15 min. The synthetic diamond crystals have a cubo-octahedral or octahedral shape with yellowish green or green colour. Some disfigurements are observed on the surfaces of most diamond crystals. The composition and content of inclusions formed by iron in diamond are changed and iron nitride is detected in diamond crystals synthesized with Fe-C-NaN3 additive. As the amount of NaN3 additive increases, Fe3C decreases and iron nitride increases with α-Fe being nearly constant. Moreover, the nitrogen concentrations in diamond crystals synthesized with 1.5 wt% NaN3 additive is up to 2250ppm in substitutional form.     

Non-equilibrium grain boundary cosegregation of Mo and P

The segregation of P at grain boundaries is believed to be an important cause of temper embrittlement in steels. As an alloy element, Mo may reduce the embrittlement. However, the concentration measured by Auger electron spectroscopy at the grain boundary in 2.25Cr1MoV and 12Cr1MoV showed that the concentration of P increased with that of Mo, which indicates that Mo and P cosegregated to the grain boundary in Cr-Mo steels.     

Property changes of electroplated Cu/Co alloys and multilayers by organic additives

We investigated the change of magnetic properties of the electroplated Cu/Co alloys and multilayers caused by organic additives and high temperature annealing. When plated with a pure Cu/Co electrolyte, the alloy contained ∼25% of Cu and ∼75% of Co. The alloy was made of hcp-Co, fcc-Co and Cu(1 1 1) and was super-paramagnetic at room temperature. As we add a few organic additives in the plating electrolyte, the hcp-Co of the films disappeared. The organic additives contained in the electrolytes changed paramagnetic Cu/Co multilayers to ferromagnets. High-temperature thermal annealing increased coercivity due to the growth of the Co grains.     

Formation of Mixture of A and C Centres in Diamond Synthesized with Fe90Ni10-C-High-Content Additive NaN3 by HPHT

Very rich nitrogen concentration with the dominant C centres and some A centres are found in diamonds grown from a Fe90Ni10-C-high-content NaN3 additive system. The concentrations of C centres rapidly increase with increasing content of NaN3 additive, while the concentrations of A centres increase slowly. The total nitrogen concentration tends to increase rapidly with increasing content of NaN3 additive when the content of NaN3 is below 0.7 wt%. However, the total concentration of nitrogen in the diamonds increases slowly when the content of NaN3 is further increased up to 1.0 wt%, and the total nitrogen average concentration are calculated to be around 2230ppm for most of the analysed synthetic diamonds. Eurthermore, the nitrogen impurities in different crystal sectors of the diamonds are inhomogeneously distributed. The nitrogen impurities in the diamonds in [111] zones are incorporated more easily than that in [100].     

Ab initio study of formation, migration and binding properties of helium-vacancy clusters in aluminum

Ab initio calculations based on density functional theory have been performed to study the dissolution and migration of helium, and the stability of small helium-vacancy clusters He_nV_m (n, m=0-4) in aluminum. The results indicate that the octahedral configuration is more stable than the tetrahedral. Interstitial helium atoms are predicted to have attractive interactions and jump between two octahedral sites via an intermediate tetrahedral site with low migration energy. The binding energies of an interstitial He atom and an isolated vacancy to a He_nV_m cluster are also obtained from the calculated formation energies of the clusters. We find that the di- and tri-vacancy clusters are not stable, but He atoms can increase the stability of vacancy clusters.     

Investigation into defects occurring on the polymer surface during the photolithography process

With a view to improving the realisation of polymer optical waveguide some features relevant to the photolithography process are analysed. This paper focuses on defects that occur on the surface of polymer layers involved in the process. For example, depending on the heat treatment or the deposited material, some worm-like defects appear on the polymer surface. When they occur, the waveguide surface roughness becomes too high (about one hundred nm and more). This means that the optical performance of the waveguides is too poor. In this document, we show the changes in temperature on polymer film surfaces which are coated with a thin inorganic layer and the occurrence of these defects is observed. This work confirms that the defect occurrence is clearly linked to the glass transition temperature. The paper reports that, in some cases, the adjustment of thermal properties by annealing can advantageously shift the glass transition, without changing the target optical properties.     

Comparison of profile tailing in SIMS analyses of various impurities in silicon using nitrogen,oxygen, and neon ion beams at near-normal incidence

We have performed a systematic SIMS study into the effect of (i) the chemical nature and (ii) the energy of the primary ions on the decay length which characterizes the exponential fall-off of impurity sputter profiles. The samples consisted of low resistivity, p-type Si covered with thin metallic overlayers. Bombardment was carried out at 2° off normal. Aspect (i) was investigated for tracers of Cu and Ga using N ₂ ⁺ , O ₂ ⁺ , and Ne⁺ primary ions at an energy of 5 keV/atom. The effect of the beam energy, aspect (ii), was studied for eight different tracer species and N ₂ ⁺ primary ions at energies between 2 and 5 keV/atom. In the case of Ga, was found to be shorter with N ₂ ⁺ or O ₂ ⁺ primary ions (=7.0 and 7.5 nm, respectively) than with Ne⁺ (=12 nm). This effect is attributed to beam induced formation of Si₃N₄ or SiO₂ layers, whereby the effective width of the internal distribution of intermixed Ga impurities in the Si subsystem is reduced significantly. In contrast to Ga, the decay length for Cu is smallest under bombardment with Ne⁺ (=16 nm), quite large with N ₂ ⁺ (26 nm) and extremely large with O ₂ ⁺ (2.2 m). Segregation of Cu atoms at the Si₃N₄/Si and the SiO₂/Si interface, respectively, is responsible for this depressed impurity removal rate. Within experimental accuracy the observed variation of the decay length with N ₂ ⁺ energy E [keV/atom] can be written in the form =kE ^p, where k and p are element specific parameters which range from k=1.2 nm for Pb to 10 nm for Cu and from p=0.6 for Cu and Ag to 1.0 for Pb. The results are discussed with reference to conceivable shapes of the distribution of intermixed impurity atoms.On leave from NTT Applied Electronics Laboratories, 3-9-11, Midori-cho, Musashino-shi, Tokyo 180, Japan