Characterization of TiN/TiSi2 bilayer for application to ULSI

The properties of TiN/TiSi₂ bilayer formed by rapid thermal annealing (RTA) in an NH₃ ambient after the titanium film is deposited on the silicon substrate is investigated. It is found that the formation of TiN/TiSi₂ bilayer depends on the RTA temperature and a competitive reaction for the TiN/TiSi₂ bilayer occurs at 600°C. Both the TiN and TiSi₂ layers represent titanium-rich films at 600°C anneal. The TiN layer has a stable structure at 700°C anneal while the TiSi₂ layer has C₄₉ and C₅₄ phase. Both the TiN and TiSi₂ layers have stable structures and stoichiometries at 800°C anneal. When the TiN/TiSi₂ bilayer is formed, the redistribution of boron atoms within the TiSi₂ layer gets active as the anneal temperature is increased. According to secondary ion mass spectroscopy analysis, boron atoms pile up within the TiN layer and at the TiSi₂−Si interface. The electrical properties for n⁺ and p⁺ contacts are investigated. The n⁺ contact resistance increases slightly with increasing annealing temperature but the p⁺ contact resistance decreases. The leakage current indicates degradation of the contact at high annealing temperature for both n⁺ and p⁺ junctions.     

Stress Analysis and Output Power Measurement of an n-Mg2Si Thermoelectric Power Generator with an Unconventional Structure

We examine the mechanical stability of an unconventional Mg₂Si thermoelectric generator (TEG) structure. In this structure, the angle θ between the thermoelectric (TE) chips and the heat sink is less than 90°. We examined the tolerance to an external force of various Mg₂Si TEG structures using a finite-element method (FEM) with the ANSYS code. The output power of the TEGs was also measured. First, for the FEM analysis, the mechanical properties of sintered Mg₂Si TE chips, such as the bending strength and Young’s modulus, were measured. Then, two-dimensional (2D) TEG models with various values of θ (90°, 75°, 60°, 45°, 30°, 15°, and 0°) were constructed in ANSYS. The x and y axes were defined as being in the horizontal and vertical directions of the substrate, respectively. In the analysis, the maximum tensile stress in the chip when a constant load was applied to the TEG model in the x direction was determined. Based on the analytical results, an appropriate structure was selected and a module fabricated. For the TEG fabrication, eight TE chips, each with dimensions of 3 mm × 3 mm × 10 mm and consisting of Sb-doped n-Mg₂Si prepared by a plasma-activated sintering process, were assembled such that two chips were connected in parallel, and four pairs of these were connected in series on a footprint of 46 mm × 12 mm. The measured power generation characteristics and temperature distribution with temperature differences between 873 K and 373 K are discussed.     

An Investigation of Electrical Contacts for Higher Manganese Silicide

Five metals with large work functions including Co, Ni, Cr, Ti, and Mo and two silicides including MnSi and TiSi₂ were examined to determine the best contact material for the thermoelectric material higher manganese silicide (HMS). Three-layer structures of HMS/contact/HMS were prepared in a sintering process. The contact resistance was measured versus temperature. The structures were subjected to x-ray diffraction and energy-dispersive x-ray spectroscopy examination. Thermal stability of the structures was determined by heating the samples to 700°C for different time intervals. The pure metals failed to make reliable contacts due to poor mechanical and chemical stability at high temperatures. In contrast, the metal silicides (MnSi and TiSi₂) showed superior chemical and mechanical stability after the thermal stability test. The observed contact resistance of MnSi and TiSi₂ was within the range of practical interest (10^?5????cm² to 10^?4????cm²) over the entire range of investigated temperatures (20°C to 700°C). The best properties were found for the nanograined MnSi, for which the resistance of the contact was as low as 10^?6????cm².     

Oxidation of titanium disilicide on polycrystalline silicon

Oxidation mechanisms of titanium disilicide on polycrystalline silicon was investigated. Poly-Si was deposited on the oxidized Si wafer by CVD method, Ti was then deposited on the poly-Si by the electron beam gun and thus TiSi₂ was formed by thermal annealing in vacuum. During the wet oxidation, Rutherford backscattering spectroscopy (RBS) results show a two-step oxidation process, namely, TiSi₂ first dissociates and forms TiO_x and SiO₂, while after the formation of TiO_x reaches the saturation level, the poly-Si rapidly diffuses through the TiSi₂ to form SiO₂. The calculated activation energy of reaction is 2.06 eV, and that of diffusion is 1.51 eV. Sheet resistances were measured and found to be consistent with the two-step oxidation model. Radioactive³¹Si was used as a marker to study the kinetics of the oxidation and found that during the diffusion process of oxidation, the poly-Si atoms transported through TiSi₂ by grain boundary and/or interstitial diffusion. Department of Physics.     

Characterization of a rapid thermal anneal TiNxOy/TiSi2 contact barrier

In this paper, the physical and electrical properties of a TiN_xO_y/TiSi₂ dual layer contact barrier are reported. The TiN_xO_y/TiSi₂ barrier was formed by rapidly annealing a Ti thin film on Si in an N₂ ambient. During this process, the Ti film surface reacts with N₂ to form a TiN_xO_y skin layer and the bulk of the Ti film reacts with Si to form an underlying TiSi₂ layer. The influences of rapid thermal anneal (RTA) conditions on the TiN_xO_y layer were investigated by varying the RTA temperature from 600 to 1100° C and cycle duration from 30 to 100 s. It is found that the resulting TiN_xO_y and TiSi₂ layer thicknesses are dependent on RTA temperature and the starting Ti thickness. For a starting Ti thickness of 500Å, 150Å thick TiN_xO_y and 800Å thick TiSi₂ are obtained after an RTA at 900° C for 30 s. The TiN_xO_y thickness is limited by a fast diffusion of Si into Ti to form TiSi₂. When a Ti film is deposited on SiO₂, Ti starts to react with SiO₂ from 600° C and a significant reduction of the SiO₂ thickness is observed after an RTA at 900° C. The resulting layer is composed of a surface TiN_xO_y layer followed by a complex layer of titanium oxide and titanium suicide. In addition, when Ti is depos-ited on TiSi₂, thicker TiN_xO_y and TiSi₂ layers are obtained after RTA. This is because the TiSi₂ layer retards the diffusion of Si from the underlying substrate into the Ti layer. NMOSFETs were fabricated using the TiN_xO_y/TiSi₂ as a contact barrier formed by RTA at 900° C for 30 s and a significant reduction of contact resistance was obtained. In addition, electromigration test at a high current density indicated that a significant improvement in mean time to failure (MTF) has been obtained with the barrier.     

Interface Microstructure and Performance of Sb Contacts in Bismuth Telluride-Based Thermoelectric Elements

A thermoelectric joint composed of p-type Bi_0.5Sb_1.5Te₃ (BiSbTe) material and an antimony (Sb) interlayer was fabricated by spark plasma sintering. The reliability of the thermoelectric joints was investigated using electron probe microanalysis for samples with different accelerated isothermal aging time. After aging for 30 days at 300°C in vacuum, the thickness of the diffusion layer at the BiSbTe/Sb interface was about 30 μm, and Sb₂Te₃ was identified to be the major interfacial compound by element analysis. The contact resistivity was 3 × 10^?6 ohm cm² before aging and increased to 8.5 × 10^?6 ohm cm² after aging for 30 days at 300°C, an increase associated with the thickness of the interfacial compound. This contact resistivity is very small compared with that of samples with solder alloys as the interlayer. In addition, we have also investigated the interface behavior of Sb layers integrated with n-type Bi₂Se_0.3Te_2.7 (BiSeTe) material, and obtained similar results as for the p-type semiconductor. The present study suggests that Sb may be useful as a new interlayer material for bismuth telluride-based power generation devices.     

Effect of rapid thermally nitrided titanium films contacting silicided and nonsilicided junctions

The effect of rapid thermally nitrided titanium films contacting silicided (titanium disilicided) and nonsilicided junctions has been studied in the temperature range of 800 to 900°C. The rapid thermal nitridation of titanium films used as diffusion barriers between aluminum and silicon, has a major impact on shallow junction complementary metal oxide semiconductor technologies. During the process of rapid thermal nitridation, the dopants in the junctions undergo a redistribution and affect the electrical properties of shallow junction structures. This work focuses on using novel contact resistance structures to measure the variation in electrical parameters for rapid thermally nitrided titanium films annealed at different temperatures. The self-aligned silicide (salicide) junctions in this study were formed using rapid thermally annealed titanium films. Electrical contact resistance testers were used to measure the interface contact resistance between the salicide and silicon, as well as between the metal and the salicide. The results show that the interface contact resistance to the p⁻ diffused salicided junctions increases with rapid thermal nitridation of the additional titanium film, whereas the interface contact resistance to the n⁻ diffused salicided junction shows a decrease. Further, as a function of the rapid thermal annealing temperature (for fixed titanium thickness), the nonsalicided diffusions show an increase in the interface contact resistance. The boron profiles at the TiSi₂/Si interface obtained using secondary ion mass spectroscopy show an excellent qualitative agreement with the electrical results for each of the conditions discussed. The films were also characterized using Rutherford back-scattering spectrometry and transmission electron microscopy and the results show good agreement with the measured variation in electrical parameters. These results also show that as the anneal temperature is increased, the TiN thickness increases, further the change in the silicide/silicon interface position with the nitridation of the additional titanium layer was verified. This work was carried out when the author was working at AT&T Bell Labs     

Heat-Pipe-Associated Localized Thermoelectric Power Generation System

The present study focused on how to improve the maximum power output of a thermoelectric generator (TEG) system and move heat to any suitable space using a TEG associated with a loop thermosyphon (loop-type heat pipe). An experimental study was carried out to investigate the power output, the temperature difference of the thermoelectric module (TEM), and the heat transfer performance associated with the characteristic of the researched heat pipe. Currently, internal combustion engines lose more than 35% of their fuel energy as recyclable heat in the exhaust gas, but it is not easy to recycle waste heat using TEGs because of the limited space in vehicles. There are various advantages to use of TEGs over other power sources, such as the absence of moving parts, a long lifetime, and a compact system configuration. The present study presents a novel TEG concept to transfer heat from the heat source to the sink. This technology can transfer waste heat to any location. This simple and novel design for a TEG can be applied to future hybrid cars. The present TEG system with a heat pipe can transfer heat and generate power of around 1.8 V with T _TEM = 58°C. The heat transfer performance of a loop-type heat pipe with various working fluids was investigated, with water at high heat flux (90 W) and 0.05% TiO₂ nanofluid at low heat flux (30 W to 70 W) showing the best performance in terms of power generation. The heat pipe can transfer the heat to any location where the TEM is installed.     

Diffusion Soldering of Pb-Doped GeTe Thermoelectric Modules with Cu Electrodes Using a Thin-Film Sn Interlayer

Directly coating a GeTe(Pb) thermoelectric device with a Ni barrier layer and an Ag reaction layer and then diffusion soldering with a Cu electrode coated with Ag and Sn leads to breakage at the GeTe(Pb)/Ni interface and low bonding strengths of about 6 MPa. An improved process, precoating with 1 μm Sn film and heating at 250°C for 3 min before electroplating with Ni and Ag layers, results in satisfactory bonding strengths ranging from 12.6 MPa to 19.1 MPa. The precoated Sn film leads to the formation of a (Ni,Ge)₃Sn₄ layer between the GeTe(Pb) thermoelectric material and Ni barrier layer, reducing the thermal stress at the GeTe(Pb)/Ni interface.     

Top-Down Silicon Nanowire-Based Thermoelectric Generator: Design and Characterization

A silicon nanowire (SiNW) array-based thermoelectric generator (TEG) was assembled and characterized. The SiNW array had pitch of 400?nm, and SiNW diameter and height of <100?nm and ~1???m, respectively. The SiNW array was formed using a top-down approach: deep-ultraviolet (UV) lithography and dry reactive-ion etching. Specific groups of SiNWs were doped n- and p-type using ion implantation, and air gaps between the SiNWs were filled with silicon dioxide (SiO₂). The bottom and top electrodes were formed using a nickel silicidation process and aluminum metallization, respectively. Temperature difference across the TEG was generated with a heater and a commercial Peltier cooler. A maximum open-circuit voltage of 2.7?mV was measured for a temperature difference of 95?K across the whole experimental setup, corresponding to power output of 4.6?nW. For further improvement, we proposed the use of polyimide as a filler material to replace SiO₂. Polyimide, with a rated thermal conductivity value one order of magnitude lower than that of SiO₂, resulted in a larger measured thermal resistance when used as a filler material in a SiNW array. This advantage may be instrumental in future performance improvement of SiNW TEGs.     

Microwave Resistivity of Thermally Oxidized High Resistivity Silicon Wafers

We used a microwave dielectric resonator to study how the process of thermal oxidation of high resistivity silicon wafers reduces the wafer microwave resistivity. Measurements were performed before surface thermal oxidation, after the oxidation, and after wet oxide removal. We show that the process of oxide growth decreases the microwave resistivity of the wafer from approximately 20 kΩ cm to as low as 400 Ω cm (typically to 1–2 kΩ cm), depending on the dielectric layer thickness and the growth process conditions. After the wet removal of SiO₂, the resistivity of the wafers increased, but it did not reach the initial value.     

Stacked Micro Heat Exchange System for Optimized Thermal Coupling of MicroTEGs

This study presents modeling and experimental results of micro thermoelectric generators (μTEGs) integrated into a multilayer micro heat exchange system. The multilayer configuration benefits from low heat transfer resistances at small fluid flow rates and at the same time from low required pumping powers. The compact stacked power device allows for high net output power per volume, and therefore a reduction in size, weight, and cost compared with conventional large-scale heat exchangers. The influence of the boundary conditions and the system design parameters on the net output power of the micro heat exchange system was investigated by simulation. The theoretical results showed a major impact of the microchannel dimensions and the μTEG thickness on the overall output performance of the system. By adapting the applied fluid flow rate, the system’s net power output can be maximized for varying operating temperatures. Experimental measurements of the cross-flow micro heat exchange system were in good agreement with the performed simulations. A net μTEG output power of 62.9 mW/cm² was measured for a double-layer system at an applied water inlet temperature difference of 60 K with a Bi₂Te₃ μTEG (ZT of 0.12), resulting in a net volumetric efficiency factor of 37.2 W/m³/K².     

Fabrication of High-Temperature-Stable Thermoelectric Generator Modules Based on Nanocrystalline Silicon

High-temperature-stable thermoelectric generator modules (TGMs) based on nanocrystalline silicon have been fabricated, characterized by the Harman technique, and measured in a generator test facility at the German Aerospace Center. Starting with highly doped p- and n-type silicon nanoparticles from a scalable gas-phase process, nanocrystalline bulk silicon was obtained using a current-activated sintering technique. Electrochemical plating methods were employed to metalize the nanocrystalline silicon. The specific electrical contact resistance ρ _c of the semiconductor–metal interface was characterized by a transfer length method. Values as low as ρ _c < 1 × 10^?6 Ω cm² were measured. The device figure of merit of a TGM with 64 legs was approximately ZT = 0.13 at 600°C as measured by the Harman technique. Using a generator test facility, the maximum electrical power output of a TGM with 100 legs was measured to be roughly 1 W at hot-side temperature of 600°C and cold-side temperature of 300°C.     

Model for Increasing the Power Obtained from a Thermoelectric Generator Module

We have developed a model for finding the most efficient way of increasing the power obtained from a thermoelectric generator (TEG) module with a variety of operating conditions and limitations. The model is based on both thermoelectric principles and thermal resistance circuits, because a TEG converts heat into electricity consistent with these two theories. It is essential to take into account thermal contact resistance when estimating power generation. Thermal contact resistance causes overestimation of the measured temperature difference between the hot and cold sides of a TEG in calculation of the theoretical power generated, i.e. the theoretical power is larger than the experimental power. The ratio of the experimental open-loop voltage to the measured temperature difference, the effective Seebeck coefficient, can be used to estimate the thermal contact resistance in the model. The ratio of the effective Seebeck coefficient to the theoretical Seebeck coefficient, the Seebeck coefficient ratio, represents the contact conditions. From this ratio, a relationship between performance and different variables can be developed. The measured power generated by a TEG module (TMH400302055; Wise Life Technology, Taiwan) is consistent with the result obtained by use of the model; the relative deviation is 10%. Use of this model to evaluate the most efficient means of increasing the generated power reveals that the TEG module generates 0.14 W when the temperature difference is 25°C and the Seebeck coefficient ratio is 0.4. Several methods can be used triple the amount of power generated. For example, increasing the temperature difference to 43°C generates 0.41 W power; improving the Seebeck coefficient ratio to 0.65 increases the power to 0.39 W; simultaneously increasing the temperature difference to 34°C and improving the Seebeck coefficient ratio to 0.5 increases the power to 0.41 W. Choice of the appropriate method depends on the limitations of system, the cost, and the environment.     

A Thermoelectric Generator Concept Using a p–n Junction: Experimental Proof of Principle

Conventional thermoelectric generators (TEGs) use single p- and n-doped legs for thermoelectric energy harvesting. We explore a concept using thermoelectric p–n junctions made from densified silicon nanoparticles. The nanoparticle powder was synthesized in a microwave plasma reactor using silane, diborane, and phosphine as precursors. To achieve a bulk sample with a p–n junction, a layer of boron-doped nanoparticle powder was stacked on a layer of phosphorus-doped powder and compacted by current-activated pressure- assisted densification. To use the p–n structure as a TEG, a temperature gradient was applied along the p–n junction. It is expected that this temperature gradient leads to electron–hole pair generation and separation in the junction, and diffusion of the charge carriers. A reference method was used to characterize the open-circuit voltage of the p–n junction TEG.     

Design,Modeling, Fabrication,and Evaluation of Thermoelectric Generators with Hot-Wire Chemical Vapor Deposited Polysilicon as Thermoelement Material

This paper presents the design, modeling, fabrication, and evaluation of thermoelectric generators (TEGs) with p-type polysilicon deposited by hot-wire chemical vapor deposition (HWCVD) as thermoelement material. A thermal model is developed based on energy balance and heat transfer equations using lumped thermal conductances. Several test structures were fabricated to allow characterization of the boron-doped polysilicon material deposited by HWCVD. The film was found to be electrically active without any post-deposition annealing. Based on the tests performed on the test structures, it is determined that the Seebeck coefficient, thermal conductivity, and electrical resistivity of the HWCVD polysilicon are 113 μV/K, 126 W/mK, and 3.58 × 10^?5 Ω m, respectively. Results from laser tests performed on the fabricated TEG are in good agreement with the thermal model. The temperature values derived from the thermal model are within 2.8% of the measured temperature values. For a 1-W laser input, an open-circuit voltage and output power of 247 mV and 347 nW, respectively, were generated. This translates to a temperature difference of 63°C across the thermoelements. This paper demonstrates that HWCVD, which is a cost-effective way of producing solar cells, can also be applied in the production of TEGs. By establishing that HWCVD polysilicon can be an effective thermoelectric material, further work on developing photovoltaic-thermoelectric (PV-TE) hybrid microsystems that are cost-effective and better performing can be explored.     

Laser-induced titanium disilicide formation for submicron technologies

Currently, a two-step anneal is employed for the formation of titanium selfaligned silicide (Salicide). The first rapid thermal anneal (RTA) step is to achieve the C49 TiSi₂ phase, and the second step is to form the low resistivity C54 phase. However, as the width of the polysilicon line decreases, conversion of C49 to C54 TiSi₂ becomes increasingly difficult. This is because the C49 to C54 phase transformation nucleates only at locations where three C49 grains intersect and the number of such intersection points is reduced as the gate length decreases. In this paper; we have investigated the effect of replacing the first RTA step by a laser anneal step on the formation of C54 TiSi₂, with all other steps remaining unchanged. Our results show that the laser annealing process can form a fine-grained metastable C49 TiSi₂ precursor layer. Upon subjecting this precursor layer to a second RTA step, C54 titanium disilicide can be obtained.     

Selective deposition of TiSi2 on oxide patterned wafers using low pressure chemical vapor deposition

The selective deposition of titanium disilicide was investigated using a cold-wall, low pressure chemical vapor deposition (LPCVD) technique with silane and titanium tetrachloride as the silicon and titanium sources, respectively. In-situ hydrogen plasma effectively cleaned the silicon wafer surface for deposition of C54 TiSi₂ at 760‡ C with full selectivity. A new method using a plasma only at the beginning of the deposition of the silicide further decreased the temperature to 680‡ C without losing selectivity. The result was a fine grained film probably due to the enhanced nucleation rate of the silicide. Cross-sectional TEM studies showed that the silicide grew into the silicon substrate, suggesting significant silicon consumption. The silicon substrate, consequently, seems to play a major role in the silicide formation. Silane, on the other hand, plays a minor role as a silicon source but does act as a scavenger of HC1 in the gas or on the silicide surface.     

Thermoelectric Properties of High-Doped Silicon from Room Temperature to 900 K

Silicon is investigated as a low-cost, Earth-abundant thermoelectric material for high-temperature applications up to 900 K. For the calculation of module design the Seebeck coefficient and the electrical as well as thermal properties of silicon in the high-temperature range are of great importance. In this study, we evaluate the thermoelectric properties of low-, medium-, and high-doped silicon from room temperature to 900 K. In so doing, the Seebeck coefficient, the electrical and thermal conductivities, as well as the resulting figure of merit ZT of silicon are determined.     

Studies on Effective Utilization of SOFC Exhaust Heat Using Thermoelectric Power Generation Technology

Solid oxide fuel cells (SOFCs) are being researched around the world. In Japan, a compact SOFC system with rated alternative current (AC) power of 700 W has become available on the market, since the base load electricity demand for a standard home is said to be less than 700 W AC. To improve the generating efficiency of SOFC systems in the 700-W class, we focused on thermoelectric generation (TEG) technology, since there are a lot of temperature gradients in the system. Analysis based on simulations indicated the possibility of introducing thermoelectric generation at the air preheater, steam generator, and exhaust outlet. Among these options, incorporating a TEG heat exchanger comprising multiple CoSb₃/SiGe-based TEG modules into the air preheater had potential to produce additional output of 37.5 W and an improvement in generating efficiency from 46% to 48.5%. Furthermore, by introducing thermoelectric generation at the other two locations, an increase in maximum output of more than 50 W and generating efficiency of 50% can be anticipated.