Progress in the understanding of Ni silicide formation for advanced MOS structures

Metallic silicides have been used as contact materials on source/drain and gate in metal-oxide semiconductor (MOS) structure for 40 years. Since the 65 nm technology node, NiSi is the preferred material for contact in microelectronic due to low resistivity, low thermal budget, and low Si consumption. Ni(Pt)Si with 10 at.% Pt is currently employed in recent technologies since Pt allows to stabilize NiSi at high temperature. The presence of Pt and the very low thickness (<10 nm) needed for the device contacts bring new concerns for actual devices. In this work, in situ techniques [X-ray diffraction (XRD), X-ray reflectivity (XRR), sheet resistance, differential scanning calorimetry (DSC)] were combined with atom probe tomography (APT) to study the formation mechanisms as well as the redistribution of dopants and alloy elements (Pt, Pd.) during the silicide formation. Phenomena like nucleation, lateral growth, interfacial reaction, diffusion, precipitation, and transient phase formation are investigated. The effect of alloy elements (Pt, Pd.) and dopants (As, B.) as well as stress and defects induced by the confinement in devices on the silicide formation mechanism and alloying element redistribution is examined. In particular APT has been performed for the three-dimensional (3D) analysis of MOSFET at the atomic scale. The advances in the understanding of the mechanisms of formation and redistribution are discussed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pt redistribution in N-MOS transistors during Ni salicide process

Atom probe tomography was used to study the redistribution of platinum during Ni(10 at.%Pt) silicidation of n-doped polycrystalline Si. These measurements were performed after the two annealing steps of standard salicide process both on a field-effect transistor and on unpatterned region submitted to the same process. Very similar results are obtained in unpatterned region and in transistor gate contact. The first phase to form is not the expected δ-Ni2Si but the non stoichiometric θ-Ni2Si. Pt redistribution is strongly influenced by this phase and the final distribution is different from what is reported in literature. © 2013 Elsevier B.V. All rights reserved.

Ni(Pt)-silicide contacts on CMOS devices: Impact of substrate nature and Pt concentration on the phase formation

Ni silicides used as contacts in source/drain and gate of advanced CMOS devices were analyzed by atom probe tomography (APT) at atomic scale. These measurements were performed on 45 nm nMOS after standard self-aligned silicide (salicide) process using Ni(5 at.% Pt) alloy. After the first annealing (RTA1), δ-Ni2Si was the only phase formed on gate and source/drain while, after the second annealing (RTA2), two different Ni silicides have been formed: NiSi on the gate and δ-Ni2Si on the source and drain. This difference between source/drain and gate regions in nMOS devices has been related to the Si substrate nature (poly or mono-crystalline) and to the size of the contact. In fact, NiSi seems to have difficulties to nucleate in the narrow source/drain contact on mono-crystalline Si. The results have been compared to analysis performed on 28 nm nMOS where the Pt concentration is higher (10 at.% Pt). In this case, θ-Ni2Si is the first phase to form after RTA1 and NiSi is then formed at the same time on source (or drain) and gate after RTA2. The absence of the formation of NiSi from δ-Ni 2Si/Si(1 0 0) interface compared to θ-Ni2Si/Si(1 0 0) interface could be related to the difference of the interface energies. The redistributions of As and Pt in different silicides and interfaces were measured and discussed. In particular, it has been evidenced that Pt redistributions obtained on both 45 and 28 nm MOS transistors correspond to respective Pt distributions measured on blanket wafers. © 2013 Elsevier B.V. All rights reserved.

Direct epitaxial growth of θ-Ni2Si by reaction of a thin Ni(10 at.% Pt) film with Si(1 0 0) substrate

The reaction between an 11 nm Ni(10 at.% Pt) film on a Si substrate has been examined by in situ X-ray diffraction (XRD), atom probe tomography (APT) and transmission electron microscopy (TEM). In situ XRD experiments show the unusual formation of a phase without an XRD peak through consumption of the metal. According to APT, this phase has an Si concentration gradient in accordance with the θ-Ni2Si metastable phase. TEM analysis confirms the direct formation of θ-Ni2Si in epitaxy on Si(1 0 0) with two variants of the epitaxial relationship. © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Characterization of nano-scale particles in hot-rolled, high strength low alloy steels (HSLA)

The contribution of nano-scale particles observed using Atom Probe Tomography in an increase of yield strength of conventional and advanced HSLA steels was studied. The advanced HSLA steel showed higher yield strength than conventional HSLA steel. There were two types of carbides, which primarily contribute to an increase in yield strength of conventional HSLA steel: (i) coarse TiC with average size of 25±5nm and (ii) fine TiC with average radius of 3±1.2nm. The presence of two types of carbides was found in the microstructure of advanced HSLA steel: (i)
nano-scale Ti0.98Mo0.02C0.6 carbides with average radius of 2.2±0.5nm, and (ii) C19Cr7Mo24 particles with an average radius of 1.5±0.3nm. The contribution of precipitation hardening in the yield strength of advanced HSLA steel due to the nano-scale particles was 174MPa, while this value in the conventional HSLA steel was 128MPa.

A study of the strengthening mechanism in the thermomechanically processed TRIP/TWIP steel

The strengthening mechanism responsible for the unique combination of ultimate tensile strength and elongation in a multiphase Fe-0.2C-1.5Mn-1.2Si-0.3Mo-0.6Al-0.02Nb (wt%) steel was studied. The microstructures with different volume fraction of polygonal fenite, bainite and retained austenite were simulated by controlled thermomechanical processing. The interupted tensile test was used to study the bainitic ferrite, retained austenite and polygonal ferrite behavior as a function of plastic strain. X-ray analysis was used to characterize the volume fraction and carbon content of retained austenite. TEM and heat-tinting were utilized to analyze the effect of bainitic fenite morphology on the strain induced transformation of retained austenite and retained austenite twinning as a function of strain in the bulk material. The study has shown that the austenite twinning mechanism is more preferable than the transformation induced plasticity mechanism during the early stages of deformation for a microstructure containing I5% polygonal ferrite, while the transformation induced plasticity effect is the main mechanism in when there is 50% of polygonal ferrite in the microstructure. The baillitic fenite morphology affects the deformation mode of retained austenite during straining. The polygonal fenite behavior during straining depends on dislocation substructure tonned due to the deformation and the additional mobile dislocations caused by the TRIP effect. TRIP and TWIP effects depend not only on the chemical and mechanical stability of retained austenite, but also on the interaction of the phases during straining.

Microstructure and mechanical properties of thermomechanically processed TRIP steel

The strengthening mechanism responsible for the unique combination of ultimate tensile strength and elongation in a multiphase Fe-0.2C-1.5Mn-1.2Si-0.3Mo-0.6Al-0.02Nb (wt%) steel was studied. The microstructures with different volume fractions of polygonal ferrite, bainite and retained austenite were simulated by controlled thermomechanical processing. The interrupted tensile test was used to study the bainitic ferrite, retained austenite and polygonal ferrite behaviour as a function of plastic strain. X-ray analysis was used to characterise the volume fraction and carbon content of retained austenite. Transmission electron microscopy was utilised to analyse the effect of bainitic ferrite morphology on the strain induced transformation of retained austenite and retained austenite twinning as a function of strain in the bulk material. The study has shown that the austenite twinning mechanism is more preferable than the transformation induced plasticity (TRIP) mechanism during the early stages of deformation for a microstructure containing 15% polygonal ferrite, while the transformation induced plasticity effect is the main mechanism when there is 50% of polygonal ferrite in the microstructure. The bainitic ferrite morphology affects the deformation mode of retained austenite during straining. The polygonal ferrite behaviour during straining depends on dislocation substructure formed due to the deformation and the additional mobile dislocations caused by the TRIP effect. Operation of TRIP or twinning mechanisms depends not only on the chemical and mechanical stability of retained austenite, but also on the interaction of the phases during straining.

Effect of bake-hardening on the structure-property relationship of multiphase steels for the automotive industry

The effect of a bake-hardening (BH) treatment on the microstructure and mechanical properties has been studied in C-Mn-Si TRansformation Induced Plasticity (TRIP) and Dual Phase (DP) steels after: (i) thermomechanical processing (TMP) and (ii) intercritical annealing (IA). The steels were characterized using X-ray diffraction, transmission electron microscopy (TEM) and three-dimensional atom probe tomography (APT). All steels showed high BH response. however, the DP and trip steels after IA/BH showed the appearance of upper and lower yield points, while the stress-strain behavior of the trip steel after TMP/BH was still continuous. This was due to the higher volume fraction of bainite and more stable retained austenite in the TMP/BH steel, the formation of plastic deformation zones with high dislocation density around the "as-quenched” martensite and “TRIP” martensite in the IA/BH DP steel and IA/BH TRIP steel, respectively.

Characterization of the bake-hardening behavior of transformation induced plasticity and dual-phase steels using advanced analytical techniques

The bake-hardening (BH) behavior of TRansformation Induced Plasticity (TRIP) and Dual-Phase (DP) steels after intercritical annealing (IA) has been studied using transmission electron microscopy, X-ray diffraction and three dimensional atom probe tomography. It was found for the DP steel that carbon can segregate to dislocations in the ferrite plastic deformation zones where there is a high dislocation density around the "asquenched" martensite. The carbon pinning of these dislocations, in turn, increases the yield strength after aging. It was shown that bake-hardening also leads to rearrangement of carbon in the martensite leading to the formation of rod-like low temperature carbides in the DP steel. Segregation of carbon to microtwins in retained austenite of the TRIP steel was also evident. These factors, in combination with the dislocation rearrangement in ferrite through the formation of cells and microbands in the TRIP steel after pre-straining, lead to the different bake-hardening responses of the two steels.

Nano-scale analysis of nano-bainite formed in advanced high strength steels

The effect of composition and processing schedule on the microstructure of C-Mn-Si-Mo-(Al)-(Nb) steels containing nano-bainite was studied using transmission electron microscopy (TEM) and atom probe tomography (APT). The major phase formed in all steels was nano-bainite. However, the steels with lower carbon and alloying addition content subjected to TMP had better mechanical properties than high alloyed steel after isothermal treatment. The presence of ferrite in the microstructure can improve not only ductility but lead to the formation of retained austenite with optimum chemical stability.

Application of advanced analytical techniques to study structure-property relationship of hot rolled high strength low alloy steel

The microstructure-property relationship in conventional high strength low alloy (HSLA) steel was evaluated using data obtained from transmission electron microscopy (TEM) and atom probe tomography (APT). Atom probe tomography allowed the characterisation of fine TiC particles with average radius of 3±1·2 nm that were not observed by TEM. The increase in the yield strength of steel due to the presence of fine precipitates was calculated to be 128 MPa.

Solute segregation and texture modification in an extruded magnesium alloy containing gadolinium

The alloy Mg-1.5Gd has been extruded at different temperatures to produce two significantly different textures. At lower extrusion temperatures there was significant solute clustering in the matrix, coupled with segregation of solute to the grain boundaries. At higher temperatures these two phenomena were both less pronounced. It is suggested here that segregation of solute to the grain boundaries plays a significant role in the texture modification effect that rare earth elements have in magnesium alloys.

Understanding of the bainite transformation in a nano-structured bainitic steel

A 0.79C-1.5Si-1.98Mn-0.98Cr-0.24Mo-1.06Al-1.58Co (wt%) steel was isothermally heat treated at 200°C for 10 days to form a nano-scale bainitic microstructure consisting of nanobainitic ferrite laths with high dislocation density and retained austenite films. The crystallographic analysis using TEM and EBSD revealed that the bainitic ferrite laths are close to the Nishiyama-Wassermann orientation relationship with the parent austenite. There was only one type of packet identified in a given transformed austenite grain. Each packet consisted of two different blocks having variants with the same habit plane, but different crystallographic orientations. The presence of fine C-rich clusters and Fe-C carbides with a wide range of compositions in bainitic ferrite was revealed by Three-dimensional Atom Probe Tomography (APT). The high carbon content of bainitic ferrite compared to the para-equilibrium level of carbon in ferrite, absence of segregation of carbon to the austenite/bainitic ferrite interface and absence of partitioning of substitutional elements between the retained austenite and bainitic ferrite were also found using APT.