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Material interaction during integration of tungsten gate stack for 1 Gb DRAM was investigated by Transition Electron Microscopy (TEM), X-ray Diffraction analysis (XRD) and Auger Electron Spectroscopy (AES). During selective side-wall oxidation tungsten gate conductor undergoes a structural transformation. The transformation results in the reduction of tungsten crystal lattice spacing, re-crystallization of tungsten and/or growth of grains. During a highly selective oxidation process, a relatively small but noticeable amount of oxygen was incorporated into the tungsten layer. The incorporation of oxygen is attributed to the formation of a stable WO x (x<2) composite.
We demonstrate the use of a synchrotron radiation source for in situ x-ray diffraction analysis during rapid thermal annealing (RTA) of 0.35 μm Salicide (self-aligned silicide) and 0.4 μm Polycide (silicided polysilicon) TiSi2 Complementary Metal Oxide Semiconductor (CMOS) gate structures. It is shown that the transformation from the C49 to C54 phase of TiSi2 occurs at higher temperatures in submicron gate structures than in unpatterned blanket films. In addition, the C54 that forms in submicron structures is (040) oriented, while the C54 that forms in unpatterned Salicide films is randomly oriented. Although the preferred oreintation of the initial C49 phase was different in the Salicide and Polycide gate structures, the final orientation of the C54 phase formed was the same. An incomplete conversion of C49 into C54-TiSi2 during the RTA of Polycide gate structures was observed and is attributed to the retarding effects of phosphorus on the transition.
Crystallization, precipitation, and phase transformation phenomena were observed in titanium suicide thin film samples during in situ heating experiments in a transmission electron microscope. The as-deposited TixSiy films were 110 nm in thickness with a composition of 1 Ti to 2.33 Si. Crystallization of the C49 phase was followed isothermally near the sputter deposition temperature. The movement of individual grain boundaries was recorded so that a “velocity of crystallization” could be calculated. The precipitation of excess silicon from the C49 phase was first observed in the 650°C to 750°C temperature range. The precipitates were predominantly of the incoherent type, with a smaller number existing at the grain boundaries. Ostwald ripening then occurred up to the C49 to C54 phase transformation which was accompanied by a dramatic increase in grain size. Grain boundary movement during the phase transformation was such that large precipitates, which were originally at C49-C49 boundaries, ended up within resulting C54 crystals. Many of these larger precipitates were found to exist as epitaxial “islands” at the TiSi2/Si substrate interface.
Measurement of resistance in-situ during rapid thermal annealing is a powerful technique for process characterization and optimization. A major advantage of in-situ resistance measurements is the very rapid process learning. With silicides, in-situ resistance measurements can quickly determine an appropriate thermal process in which a low resistance silicide phase is formed without the agglomeration or inversion of silicide/polycrystalline silicon structures. One example is an optimized two step anneal for CoSi2 formation which was developed in less than one clay. Examples of process characterization include determining the phase formation kinetics of TiSi2 (C49 and C54), Co2Si, and CoSi2 using in-situ ramped resistance measurements. The stability of TiSi2 or CoSi2/poly-Si structures has also been characterized by isothermal measurements. Resistance measurements have been made at heating rates from 1 to 100°C/s and temperatures up to 1000°C. The sample temperature was calibrated by melting Ag, Al, or Au/Si eutectics.
Titanium silicides are used as source, gate and drain contacts and local interconnections in CMOS integrated circuits. In these applications, it is important that the titanium silicide phase have a low resistivity (< 20μΩ-cm) and not agglomerate during high temperature processing. The Ti/Si system has two silicide phases that are useful for electronic applications, high resistivity C49-TiSi2 (60-70 μΩ-cm) which forms at 600 - 700°C and low resistivity (15-20 μΩ-cm) C54-TiSi2 which forms from 700 to 850°C. This paper will review how the size of the thermal annealing process window for forming low resistivity C54-TiSi2 from high resistivity C49-TiSi2 without having the silicide agglomerate varies with annealing treatments, electronic dopants, and contact size. In addition, processing methods to improve the size of the process window will be discussed.
We describe an approach for rapid evaluation of thin film interfacial reactions using a combination of temperature-ramped in situ measurements of sheet resistance, calorimetry and stress. Electrical, mechanical and thermal measurements at elevated temperatures provide detailed reaction information which is unavailable in room temperature measurements. Kinetic data is particularly useful in making comparisons with mechanistic models. The following examples are discussed:
1. Effects of interfacial oxygen on Ta as a diffusion barrier between Cu and Si,
2. Effects of interfacial oxygen on the Cu/Mg reaction to form CuMg2 and Cu2Mg,
3. Effects of the density of internal interfaces (grain boundaries) on Al2Cu dissolution and precipitation in Al-Cu alloys.
Stresses which build up in thin films, such as tantalum, during thermal processing, can cause major reliability problems in x-ray optics and electronic applications. We have demonstrated that 50 nm to 200 nm thick sputtered beta tantalum thin films undergo repeated compressive stress increases when thermally cycled from room temperature to 400°C (at 10°C/min) and back in a purified He ambient because of low levels of oxygen gettered by the tantalum. The oxygen contamination is a result of the poor quality of the quartz annealing chamber atmospheric seal. As-deposited stress in the sputter deposited tantalum films ranges from -1 to -4 GPa. The compressive stress build up was monitored in situ and was shown to increase -0.5 GPa on average after each thermal cycle for a final value of -6 to -7 GPa after seven cycles. After being cycled thermally seven times any perturbation of the film such as a four point probe resistivity measurement can cause the film to instantaneously crack in a serpentine pattern relieving the large compressive stress. Auger electron spectroscopy depth profiling analysis indicated that the as-deposited films contained one atomic percent oxygen which increased to eight to twelve percent after seven thermal cycles accompanied by an approximate doubling in resistivity. In conclusion, the increase in oxygen concentration in tantalum thin films which occurs upon thermal cycling leads to a repetitive increase in compressive stress which could be detrimental when the films are used in x-ray or electronic applications.
We analyze the formation of VSi2 at the amorphous-vanadium-silicide/amorphous-Si interface by linear-heating and isothermal calorimetry, and cross-sectional transmission electron microscopy. We show evidence that indicates sporadic VSi2 nucleation with a steady-state nucleation rate after a transient period. The results are contrasted with those obtained for Al2Ni nucleating at the polycrystalline-Al/polycrystalline-Ni interface, where the kinetics appears to be controlled by growth of a fixed number of nuclei at quickly consumed preferred nucleation sites.
The growth of an amorphous Ti-Si phase and subsequent formation of crystalline silicides during solid-state reactions in Ti/a-Si multilayer films have been studied using power-compensated differential scanning calorimetry, cross-sectional transmission electron microscopy, and thin-film x-ray diffraction. By analyzing calorimetric data we have determined the activation energies for the formation of the various silicides (amorphous Ti-silicide, TiSi, C49-TiSi2, Ti5Si3) as well as their heats of formation. An amorphous silicide is the first phase to form during heating and we have measured the composition profile of this amorphous layer using scanning transimission electron microscopy. Metastable phase equilibria in the Ti-Si system are discussed in light of the thermodynamic and compositional information obtained in our experiments.
The effect of deposition pressure and controlled oxygen dosing on the diffusion barrier performance of thin film Ta to Cu penetration was investigated. In-situ resistivity, Auger compositional profiling, scanning electron microscopy and cross-sectional transmission electron microscopy were used to determine the electrical, chemical and structural changes that occur in Cu/Ta bilayers on Si upon heating. A 20 nm Ta barrier allowed the penetration of Cu at temperatures ranging from 320 to 630°C depending on processing conditions. Barrier failure temperature is dependent upon the deposition pressure and oxygen contamination at the Ta/Cu interface. This indicates the importance of understanding how deposition conditions affect diffusion barrier performance.
This study provides information regarding how an intermetallic phase nucleates and grows at an interface between elemental components during solid-state reactions. The reaction of Al/Ni multilayer films was chosen as a model case. The main experimental technique employed was differential scanning calorimetry (DSC), with assistance of other analytical tools such as crosssectional transmission electron microscopy/microanalysis (XTEM/STEM) and thin-film x-ray diffraction. Al/Ni multilayer films were prepared by electron-beam evaporation in high and ultrahigh vacuum systems. We show evidence that interdiffusion of Al and Ni precedes the formation of Al3Ni, forming metastable solid solutions. Using isothermal calorimetry and modeling, we find that Al3Ni subsequently nucleates in the interdiffused region at preferred sites, and that the nucleation sites are quickly consumed in the early stages of Al3Ni formation. The nucleation site density strongly depends on the grain sizes of the deposited films, suggesting that only certain types of intergranular defects can serve as nucleation sites. After coalescence into a continuous layer, Al3Ni thickens through a diffusion-limited process. A kinetic model is applied which yields calculated calorimetric traces in good agreement with experimental data. The results are discussed in light of the the calculated free energy-composition diagram for the Al-Ni system. The implications of our results to the phase selection during thin-film reactions are discussed.
We report a quantitative investigation of silicidation in Ti/amorphous-Si thin-films using Differential Scanning Calorimetry (DSC), thin-film X-ray diffraction and Cross-sectional Transmission Electron Microscopy (XTEM). Multilayered thin films were used to facilitate calorimetric observation of the heat released or absorbed at many reacting interfaces. It is shown that calorimetric analysis, combined with structural analysis using X-ray diffraction and XTEM, is effective in providing both kinetic and thermodynamic information about interdiffusion reactions in thin films. The present paper describes experimental results for multilayers with an atomic concentration ratio of 1 Ti to 2 Si and modulation periods ranging from 10 to 60 nm. A thin amorphous titanium suicide layer was found to exist between the as-deposited Ti and a-Si layers. Heating the multilayer film caused the amorphous Ti-silicide to grow over a broad temperature range by an exothermic reaction. An endothermic relaxation occurs during the late stage of amorphous suicide growth. Heating to temperatures over 800K causes C49-TiSi2 to form at the a-si1icide/a-Si interface. Temperatures at which all the above structural transitions occur vary with modulation period. Analysis of the DSC data indicates an activation energy of 3.1 eV for the formation of C49-TiSio, which is attributed to both the nucleation and the early growth of the suicide. The heat of formation for C49-TiSi2 from a reaction of a-silicide and a-Si was found to be -30±5KJ/mol. Nucleation appears to be the controlling step in C49-TiSi2 formation.
Cross-sectional transmission and scanning transmission electron microscopy and thermodynamic and kinetic analysis have been used to characterize amorphous and crystalline nickel silicide formation in nickel/amorphous-silicon multilayer thin films. An amorphous-nickelsilicide layer was formed between the nickel and amorphous-silicon layers during deposition. Heating caused crystalline Ni2Si to form at the nickel/amorphous-nickel-silicide interface. The composition of the amorphous-siicide was determined to be approximately 1 Ni atom to 1 Si atom. Thermodynamic analysis indicates that amorphous-nickel-silicide could be in equilibrium with nickel and amorphous-silicon if there were kinetic barriers to the formation of the crystalline silicides. Kinetic analysis indicates that the “nucleation surface energies” of the crystalline silicides, other than Ni3Si, must be 1.6 to 3.0 times larger than that of amorphous-nickel-silicide.
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