Tomi Laurila

Reactive sputter deposition and properties of Ta x N thin films

The aim of this work was to evaluate tantalum nitride thin films fabricated using reactive sputtering with adjusted deposition parameters. Thin TaxN films were deposited reactively on Si wafers using reactive RF magnetron sputtering at various N2/Ar gas ratios. The films were investigated by four-point probe sheet resistance measurement, profilometry, X-ray diffraction, scanning electron microscope, 2 MeV 4He+ backscattering spectroscopy, and atomic force microscopy. As the amount of nitrogen was increased, the phases in the as-deposited films were identified as β-Ta, Ta2N (5% N2-flow), hexagonal TaN (10% N2-flow) and f.c.c.-TaN (15% N2-flow) with resistivities of 166 µΩ cm, 234 µΩ cm, 505 µΩ cm and 531 µΩ cm, respectively. Only the phase obtained at 5% N2-flow showed a reasonable uniformity over the wafer suggesting suitability as thin film resistors. The value of temperature coefficient of resistance (TCR) determined for the Ta2N thin film resistor was - 103 ppm/°C.

Thermodynamics, diffusion and the Kirkendall effect in solids

Thermodynamics, phases and phase diagrams.- Structure of Materials.- Ficks laws of diffusion.- Development of interdiffusion zone in different systems.- Atomic mechanism of diffusion.- Interdiffusion and the Kirkendall effect in binary systems.- Growth of phases with narrow homogeneity range and line compounds by interdiffusion.- Microstructural evolution of the diffusion zone.- Interdiffusion in multicomponent systems.- Short circuit diffusion.- Reactive phase formation in thin film systems.

Phase formation between lead-free Sn-Ag-Cu solder and Ni(P)/Au finishes

The interfacial reactions of near-eutectic Sn–Ag–Cu solder with Ni(P)∕Au metal finishes on printed wiring boards as well as in component under bump metallizations have been investigated in this work. With the help of the scanning electron microscopy and transmission electron microscopy it was discovered that the first phase to form was the metastable nanocrystalline ternary NiSnP layer that provided the substrate for the subsequent formation of (Cu,Ni)6Sn5. During cooling or in the subsequent reflows the metastable NiSnP layer partially transformed into the columnar Ni3P. In this transformation Sn atoms and impurities, which do not dissolve into the Ni3P, diffuse towards the remaining NiSnP layer. When the specimens are further annealed in solid state at 170°C the Ni3P phase transforms into Ni5P2 implying that some more Ni has diffused towards the solder. However, when Ni(P)∕Au finishes with a higher P content were used, only the ternary NiSnP layer was observed. Based on the mass balance and available th...

Piezoelectric coefficients and spontaneous polarization of ScAlN

We present a computational study of spontaneous polarization and piezoelectricity in Sc(x)Al(1-x)N alloys in the compositional range from x = 0 to x = 0.5, obtained in the context of density functional theory and the Berry-phase theory of electric polarization using large periodic supercells. We report composition-dependent values of piezoelectric coefficients e(ij), piezoelectric moduli d(ij) and elastic constants C(ij). The theoretical findings are complemented with experimental measurement of e33 for a series of sputtered ScAlN films carried out with a piezoelectric resonator. The rapid increase with Sc content of the piezoelectric response reported in previous studies is confirmed for the available data. A detailed description of the full methodology required to calculate the piezoelectric properties of ScAlN, with application to other complex alloys, is presented. In particular, we find that the large amount of internal strain present in ScAlN and its intricate relation with electric polarization make configurational sampling and the use of large supercells at different compositions necessary in order to accurately derive the piezoelectric response of the material.

Diamond-like carbon (DLC) thin film bioelectrodes: effect of thermal post-treatments and the use of Ti adhesion layer.

The effect of thermal post-treatments and the use of Ti adhesion layer on the performance of thin film diamond like carbon bioelectrodes (DLC) have been investigated in this work. The following results were obtained: (i) The microstructure of the DLC layer after the deposition was amorphous and thermal annealing had no marked effect on the structure, (ii) formation of oxygen containing SiOx and Ti[O,C] layers were detected at the Si/Ti and Ti/DLC interfaces with the help of transmission electron microscope (TEM), (iii) thermal post-treatments increased the polar fraction of the surface energy, (iv) cyclic voltammetry (CV) measurements showed that the DLC films had wide water windows and were stable in contact with dilute sulphuric acid and phosphate buffered saline (PBS) solutions, (v) use of Ti interlayer between Pt(Ir) microwire and DLC layer was crucial for the electrodes to survive the electrochemical measurements without the loss of adhesion of the DLC layer, (vi) DLC electrodes with small exposed Pt areas were an order of magnitude more sensitive towards dopamine than Pt electrodes and (vii) thermal post-treatments did not markedly change the electrochemical behavior of the electrodes despite the significant increase in the polar nature of the surfaces. It can be concluded that thin DLC bioelectrodes are stable under physiological conditions and can detect dopamine in micro molar range, but their sensitivity must be further improved.

Combined Thermodynamic-Kinetic Analysis of the Interfacial Reactions between Ni Metallization and Various Lead-Free Solders

In this paper we will demonstrate how a thermodynamic-kinetic method can be utilized to rationalize a wide range of interfacial phenomena between Sn-based lead-free solders and Ni metallizations. First, the effect of P on the interfacial reactions, and thus on the reliability, between Sn-based solders and electroless Ni/immersion Au (ENIG) metallizations, will be discussed. Next, the effect of small amounts of Cu in Sn-based solders on the intermetallic compound (IMC), which forms first on top of Ni metallization, will be covered. With the help of thermodynamic arguments a so called critical Cu concentration for the formation of (Cu,Ni)6Sn5 can be determined as a function of temperature. Then the important phenomenon of redeposition of (Au,Ni)Sn4 layer on top of Ni3Sn4 IMC will be discussed in detail. The reasons leading to this behaviour will be rationalized with the help of thermodynamic information and an explanation of why this phenomenon does not occur when an appropriate amount of Cu is present in the soldering system will be given. Finally, interfacial reaction issues related to low temperature Sn-Zn and Sn-Bi based solders and Ni metallization will be discussed.

Integrated Carbon Nanostructures for Detection of Neurotransmitters

Carbon-based materials, such as diamond-like carbon (DLC), carbon nanofibers (CNFs), and carbon nanotubes (CNTs), are inherently interesting for neurotransmitter detection due to their good biocompatibility, low cost and relatively simple synthesis. In this paper, we report on new carbon-hybrid materials, where either CNTs or CNFs are directly grown on top of tetrahedral amorphous carbon (ta-C). We show that these hybrid materials have electrochemical properties that not only combine the best characteristics of the individual “building blocks” but their synergy makes the electrode performance superior compared to conventional carbon based electrodes. By combining ta-C with CNTs, we were able to realize electrode materials that show wide and stable water window, almost reversible electron transfer properties and high sensitivity and selectivity for detecting dopamine in the presence of ascorbic acid. Furthermore, the sensitivity of ta-C + CNF hybrids towards dopamine as well as glutamate has been found excellent paving the road for actual in vivo measurements. The wide and stable water window of these sensors enables detection of other neurotransmitters besides DA as well as capability of withstanding higher potentials without suffering from oxygen and hydrogen evolution.

Effect of Ni content on the diffusion-controlled growth of the product phases in the Cu(Ni)-Sn system

Abstract A strong influence of Ni content on the diffusion-controlled growth of the (Cu,Ni)3Sn and (Cu,Ni)6Sn5 phases by coupling different Cu(Ni) alloys with Sn in the solid state is reported. The continuous increase in the thickness ratio of (Cu,Ni)6Sn5 to (Cu,Ni)3Sn with the Ni content is explained by combined kinetic and thermodynamic arguments as follows: (i) The integrated interdiffusion coefficient does not change for the (Cu,Ni)3Sn phase up to 2.5 at.% Ni and decreases drastically for 5 at.% Ni. On the other hand, there is a continuous increase in the integrated interdiffusion coefficient for (Cu,Ni)6Sn5 as a function of increasing Ni content. (ii) With the increase in Ni content, driving forces for the diffusion of components increase for both components in both phases but at different rates. However, the magnitude of these changes alone is not large enough to explain the high difference in the observed growth rate of the product phases because of Ni addition. (iv) Kirkendall marker experiments indicate that the Cu6Sn5 phase grows by diffusion of both Cu and Sn in the binary case. However, when Ni is added, the growth is by diffusion of Sn only. (v) Also, the observed grain refinement in the Cu6Sn5 phase with the addition of Ni suggests that the grain boundary diffusion of Sn may have an important role in the observed changes in the growth rate.

Glutamate detection by amino functionalized tetrahedral amorphous carbon surfaces.

In this paper, a novel amperometric glutamate biosensor with glutamate oxidase (GlOx) immobilized directly on NH2 functionalized, platinum doped tetrahedral amorphous carbon (ta-C) film, has been successfully developed. First, we demonstrate that direct GlOx immobilization is more effective on amino-groups than on carboxyl- or hydroxyl-groups. Second, we show that anodizing and plasma treatments increase the amount of nitrogen and the proportion of protonated amino groups relative to amino groups on the aminosilane coating, which subsequently results in an increased amount of active GlOx on the surface. This effect, however, is found to be unstable due to unstable electrostatic interactions between GlOx and NH3(+). We demonstrate the detection of glutamate in the concentration range of 10µM-1mM using the NH2 functionalized Pt doped ta-C surface. The biosensor showed high sensitivity (2.9nA μM(-1)cm(-2)), low detection limit (10μM) and good storage stability. The electrode response to glutamate was linear in the concentrations ranging from 10µM to 500µM. In conclusion, the study shows that GlOx immobilization is most effective on aminosilane treated ta-C surface without any pre-treatments and the fabricated sensor structure is able to detect glutamate in the micromolar range.

Energy band alignment and electronic states of amorphous carbon surfaces in vacuo and in aqueous environment

In this paper, we obtain the energy band positions of amorphous carbon (a–C) surfaces in vacuum and in aqueous environment. The calculations are performed using a combination of (i) classical molecular dynamics (MD), (ii) Kohn-Sham density functional theory with the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional, and (iii) the screened-exchange hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE). PBE allows an accurate generation of a-C and the evaluation of the local electrostatic potential in the a-C/water system, HSE yields an improved description of energetic positions which is critical in this case, and classical MD enables a computationally affordable description of water. Our explicit calculation shows that, both in vacuo and in aqueous environment, the a-C electronic states available in the region comprised between the H2/H2O and O2/H2O levels of water correspond to both occupied and unoccupied states within the a-C pseudogap region. These are localized states associated to sp2 ...