A Bondable Metallization Stack That Prevents Diffusion of Oxygen and Gold into Monolithically Integrated Circuits Operating Above 500°C

We investigate use of tantalum silicide (TaSi₂, 400 nm)/platinum (Pt, 200 nm)/iridium (Ir, 200 nm)/platinum (Pt, 200 nm) as both a bond metal and a diffusion barrier to prevent oxygen (from air) and gold (from the wire bond) from infiltrating silicon carbide (SiC) monolithically integrated circuits operating above 500°C for over 1000 h in air. The TaSi₂/Pt/Ir/Pt metallization is easily bonded for electrical connection to off-chip circuitry and does not require extra anneals or masking steps. It can be used directly on ohmic contact metals, dielectric insulating layers, or interconnect metal, because it adheres to silicon dioxide (SiO₂), silicon nitride (Si₃N₄), and titanium (Ti). In this study, we investigate use of the new metallization of TaSi₂/Pt/Ir/Pt (in deposition order) with TaSi₂ resting on top of a Ti-SiC contact annealed at 600°C for 30 min in nitrogen, which allows the TaSi₂ layer to react with the bottom platinum layer to form the Pt₂Si diffusion barrier at the Pt-Ir interface. Since the iridium layer does not readily form a silicide, it prevents the silicon from migrating into the topmost platinum layer during further annealing or high-temperature integrated circuit operation. This leaves a pure platinum layer at the surface, ideal for gold wire bonding. We discuss the characteristics of the TaSi₂/Pt/Ir/Pt metallization at 500°C after 10 h, 100 h, and 1000 h in air ambient and N₂ ambient. Auger electron spectroscopy (AES) depth profiles of the metallization and field-emission scanning electron microscopy-focused ion beam (FESEM-FIB) cross-sections are also discussed.     

Investigation of Thermal Stability and Degradation Mechanisms in Ni-Based Ohmic Contacts to <Emphasis Type="Italic">n</Emphasis>-Type SiC for High-Temperature Gas Sensors

We investigated the thermal stability of Pt/TaSi _x /Ni/SiC ohmic contacts, which have been implemented in SiC-based gas sensors developed for applications in diesel engines and power plants. The contacts remained ohmic on lightly doped n-type (~1 × 10¹⁶ cm⁻³) 4H-SiC for over 1000 h in air at 300°C. Although a gradual increase in specific contact resistance from 3.4 × 10⁻⁴ Ω cm² to 2.80 × 10⁻³ Ω cm² was observed, the values appeared to stabilize after ~800 h of heating in air at 300°C. The contacts heated at 500°C and 600°C, however, showed larger increases in specific contact resistance followed by nonohmic behavior after 240 h and 36 h, respectively. Concentration profiles from Auger electron spectroscopy and electron energy-loss spectroscopy show that loss of ohmic behavior occurs when the entire tantalum silicide layer has oxidized.     

Improved Thermal Stability Observed in Ni-Based Ohmic Contacts to <Emphasis Type="Italic">n</Emphasis>-Type SiC for High-Temperature Applications

The high-temperature stability of a Pt/TaSi₂/Ni/SiC ohmic contact metallization scheme was characterized using a combination of current–voltage measurements, Auger electron spectroscopy, and transmission electron microscopy imaging and associated analytical techniques. Increasing the thicknesses of the Pt and TaSi₂ layers promoted electrical stability of the contacts, which remained ohmic at 600°C in air for the extent of heat treatment; the specific contact resistance showed only a gradual increase from an initial value of 5.2 × 10⁻⁵ Ω cm². We observed a continuous silicon oxide layer in the thinner contact structures, which failed after 36 h of heating. Meanwhile, thicker contacts with enhanced stability contained a much lower oxygen concentration that was distributed across the contact layers, precluding the formation of an electrically insulating contact structure.     

Electrical properties of inhomogeneous SiC MIS structures

Current-voltage characteristics of metal contacts on 6H-SiC with a thin (5–20Å) oxide layer have been measured in the temperature range 300 to 1000K. The contacts were investigated in both H₂ and O₂-atmospheres. As the SiC surface was nonideal due to pin holes and other defects generated during the growth process, it was necessary to treat the Schottky contacts as inhomogeneous contacts. The inhomogeneity explains the nonideal current-voltage behavior of the contacts such as ideality factors much larger than unity and voltage dependent ideality factors. It was found that some metals gave Schottky contacts in the entire temperature range, while other metals were ohmic at higher temperatures. Several different contact metals were investigated: Al, Ti, TaSi_x, and Pd were found to be ohmic at high temperatures, while Pt, Pt+Cr, Ni, Cr and another TaSi_x contact were found to behave like Schottky contacts in the entire temperature range. This is a preliminary investigation of the electrical characteristics of different metals that could be useful for high temperature gas sensor purposes.     

Microstructural analysis of a Au/Pt/Pd/Zn ohmic contact to an AlGaAs/GaAs heterojunction bipolar transistor

Gold-based ohmic contacts, incorporating Pt, Pd, and Zn layers, to AIGaAs/GaAs heterojunction bipolar transistors (HBTs) have been characterized using transmission electron microscopy (TEM). The metallization was deposited onto a 30 nm graded emitter layer of n-type Al_xGa_1−xAs, which was on a 30 nm emitter layer of n-type Al_0.3Ga_0.7As, with the aim of contacting the underlying 80 nm thick graded base layer of p-type Al_xGa_1−xAs. Metal layers were deposited sequentially using electron beam evaporation and the resultant metallizations were annealed at temperatures ranging from 250-500°C for up to several minutes. A minimum contact resistance of ≈8.5 × 10⁻⁷ Ω-cm² was achieved, which corresponded to the decomposition of ternary phases at the metallization/semiconductor interface, to binary phases, i.e., PdGa and PtAs₂. Long term stability tests were done on the optimum contacts. Anneals at 270°C for up to four weeks in duration produced virtually no change in microstructure, with the exception of some outward diffusion of Ga and As.     

Au and non-Au based rare earth metal-silicide ohmic contacts to p-InGaAs

The aim of this study is to improve the electrical properties of ohmic contacts that plays crucial role on the performance of optoelectronic devices such as laser diodes (LDs), light emitting diodes (LEDs) and photodetectors (PDs). The conventional (Pd/Ir/Au, Ti/Pt/Au and Pt/Ti/Pt/Au), Au and non-Au based rare earth metal-silicide ohmic contacts (Gd/Si/Ti/Au, Gd/Si/Pt/Au and Gd/Si/Pt) to p-InGaAs were investigated and compared each other. To calculate the specific contact resistivities the Transmission Line Model (TLM) was used. Minimum specific contact resistivity of the conventional contacts was found as 0.111 × 10⁻⁶ Ω cm² for Pt/Ti/Pt/Au contact at 400 °C annealing temperature. For the rare earth metal-silicide ohmic contacts, the non-Au based Gd/Si/Pt has the minimum value of 4.410 × 10⁻⁶ Ω cm² at 300 °C annealing temperature. As a result, non-Au based Gd/Si/Pt contact shows the best ohmic contact behavior at a relatively low annealing temperature among the rare earth metal-silicide ohmic contacts. Although the Au based conventional ohmic contacts are thermally stable and have lower noise in electronic circuits, by using the non-Au based rare earth metal-silicide ohmic contacts may overcome the problems of Au-based ohmic contacts such as higher cost, poorer reliability, weaker thermal stability, and the device degradation due to relatively higher alloying temperatures. To the best of our knowledge, the Au and non-Au based rare earth metal-silicide (GdSi_x) ohmic contacts to p-InGaAs have been proposed for the first time.     

Ohmic contacts to n-type GaN

Ohmic contacts to n-GaN using Ag, Au, TiN, Au/Ti, Au/Mo/Ti, and Au/Si/Ti have been studied. The Fermi level of GaN appears to be unpinned, and metals and compounds with work functions less than the electron affinity resulted in ohmic contacts. Reactively sputter deposited TiN was ohmic as deposited. However, Au/Ti, Au/Mo/Ti, and Au/Si/Ti required heat treatments to form ohmic contacts, with the best being an RTA at 900°C. Ag and Au were shown to diffuse across the GaN surface at T>500°C; therefore, they are unstable, poor ohmic contact metallizations as single metals. The other contact schemes were thermally stable up to 500°C for times of 30 min.     

Low resistance, thermally stable Au/Pt/Ti/WSiN ohmic contacts on n+-InGaAs/n-GaAs layer systems

The electrical properties of the ohmic contact systems Au/Pt/Ti/WSiN and Au/Pt/Ti to n⁺-InGaAs/GaAs layers grown by metalorganic vapor phase epitaxy were investigated and compared to each other. The thermal stability properties of these contact systems were characterized by accelerated stress tests at elevated temperatures and by complementary thin film x-ray diffraction analysis to evaluate the microstructural properties of degraded and nondegraded structures. The goal of these efforts was to develop stable, homogeneous emitter contacts for power heterojunction bipolar transistors. It was found that for both contact systems the best (specific) contact resistance R_c (ρ _c) is about 0.05 Ωmm (2 × 10⁻⁷ Ωcm²) in the as-deposited state. Au/Pt/Ti/WSiN contacts show no degradation after aging at 400°C for more than 20 h. This is in contrast to standard Au/Pt/Ti contacts which significantly degrade even after short time annealing at 400°C. The good long-time stability of the Au/Pt/Ti/WSiN system is related to the advantageous properties of the reactively sputtered WSiN barrier layer.     

Simultaneous Formation of Ni/Al Ohmic Contacts to Both n- and p-Type 4H-SiC

The fabrication procedure for silicon carbide power metal oxide semiconductor field-effect transistors can be improved through simultaneous formation (i.e., using the same contact materials and a one-step annealing process) of ohmic contacts on both the n-source and p-well regions. We have succeeded in the simultaneous formation of Ni/Al ohmic contacts to n- and p-type SiC after annealing at 1000°C for 5 min in an ultrahigh vacuum. Ohmic contacts to n-type SiC were found when the Al-layer thickness was less than about 6 nm, while ohmic contacts to p-type SiC were observed for an Al-layer thickness greater than about 5 nm. Only the contacts with an Al-layer thickness in the range of 5 nm to 6 nm exhibited ohmic behavior to both n- and p-type SiC, with a specific contact resistance of 1.8 × 10⁻⁴ Ω cm² and 1.2 × 10⁻² Ω cm² for n- and p-type SiC, respectively. An about 100-nm-thick contact layer was uniformly formed on the SiC substrate, and polycrystalline δ-Ni₂Si(Al) grains were formed at the contact/SiC interface. In the samples that exhibited ohmic behavior to both n- and p-type SiC, the distribution of the Al/Ni ratios in the δ-Ni₂Si(Al) grains was larger than that observed for any of the samples that showed ohmic behavior to either n- or p-type SiC. Furthermore, the grain size of the δ-Ni₂Si(Al) grains in the samples showing ohmic behavior to both n- and p-type SiC was smaller than the grains in any of the samples that showed ohmic behavior to either n- or p-type SiC. Thus, the large distribution in the Al/Ni ratios and a fine microstructure were found to be characteristic of the ohmic contacts to both n- and p-type SiC. Grains with a low Al concentration correspond to ohmic contacts to n-type SiC, while grains with a high Al concentration correspond to ohmic contacts to p-type SiC.     

Microstructural analysis of NiInGe ohmic contacts for n-type GaAs

NiInGe ohmic contact materials, which are attractive to use in future GaAs devices, were previously developed in our laboratories. Although the NiInGe contacts provided low contact resistances of about 0.3 Ω-mm and excellent thermal stability, further reduction of the contact resistance (R_C) of the NiInGe contacts was mandatory to use these contacts in submicron devices. In this paper, the microstructural parameters, which influence the R_C values, were investigated by correlating the R_C values with the microstructure at the interface between the contact materials and the GaAs substrate. The R_C values of the NiInGe contacts were found to depend strongly on the volume fraction and the In concentration (x) of the In_xGa_1−xAs compound semiconductor layers, which were formed at the metal/GaAs interface. Both the volume fraction and the In concentration of the In_xGa_1−xAs layers were found to depend on the thickness of the In layer used in the NiInGe contact and the annealing temperature to form the ohmic contact. A R_C value of 0.18 Ω-mm was obtained for the Ni (18 nm)/In (13 nm)/Ge (30 nm) contact (where a slash “/” indicates the deposition sequence) after annealing at temperature of 650°C for 5 sec.     

A DRAM compatible Cu contact using self-aligned Ta-silicide and Ta-barrier

As an alternative to W contacts currently used in MOSFETs for DRAM, Cu contacts using self-aligned Ta-silicide and Ta-based barrier were studied experimentally. The silicidation of PVD Ta layers was studied first on 300 mm blanket Si wafers. The developed method was applied to patterned wafers in the contacts, that land on poly gate and active areas of NMOS, with a sequence including the PVD of Ta, a silicidation annealing, a Ta-based Cu diffusion barrier and a Cu seed for plating the Cu plug. X-ray diffraction (XRD), X-ray reflection (XRR) and sheet resistance tests of the blanket wafers show that a Ta layer of about 10 nm reacts with Si substrate and forms TaSi₂ at 650 °C in a reducing ambient. Cross-sectional SEM observation reveals that the selected processing flow fills the 90 nm contacts. Top-view SEM observation on the samples after 420 °C sintering demonstrates that the Cu diffusion barrier is effective. I_on-I_off curves of the devices show a performance for NMOS comparable to the reference samples which use Ni(Pt)Si and the same barrier and Cu contacts, indicating that the stack of the barrier/TaSi₂/p-type Si has a contact resistance comparable to the barrier/Ni(Pt)Si/p-type Si.     

Effect of Cryogenic Temperature Deposition of Various Metal Contacts on Bulk Single-Crystal <Emphasis Type="Italic">n</Emphasis>-Type ZnO

The effect of cryogenic temperatures during metal deposition on the contact properties of Pd, Pt, Ti, and Ni on bulk single-crystal n-type ZnO has been investigated. Deposition at both room and low temperature produced contacts with Ohmic characteristics for Ti and Ni metallizations. By sharp contrast, both Pd and Pt contacts showed rectifying characteristics after deposition with barrier heights between 0.37 eV and 0.69 eV. Changes in contact behavior were measured on Pd to anneal temperatures of ∼300 °C, showing an increase in barrier height along with a decrease in ideality factor with increasing annealing temperature. This difference with annealing temperature is in sharp contrast to previous results for Au contacts to ZnO. There were no differences in near-surface stoichiometry for the different deposition temperatures; however, low temperature contacts demonstrated some peeling/cracking for Pt and Pd.     

Study of contact resistivity, mechanical integrity, and thermal stability of Ti/Al and Ta/Al ohmic contacts to n-type GaN

The annealing conditions and contact resistivities of Ta/Al ohmic contacts to n-type GaN are reported for the first time. The high temperature stability and mechanical integrity of Ti/Al and Ta/Al contacts have been investigated. Ta/Al (35 nm/115 nm) contacts to n-type GaN became ohmic after annealing for 3 min at 500°C or for 15 s at 600°C. A minimum contact resistivity of 5×10⁻⁶Ω cm² was measured after contacts were repatterned with an Al layer to reduce the effect of a high metal sheet resistance. Ti/Al and Ta/Al contacts encapsulated under vacuum in quartz tubes showed a significant increase in contact resistivity after aging for five days at 600°C. Cross section transmission electron microscopy micrographs and electrical measurements of aged samples indicate that the increased contact resistivity is primarily the result of degradation of the metal layers. Minimal reactions at the metal/GaN interface of aged samples were observed.     

20.7% efficient ion‐implanted large area n‐type front junction silicon solar cells with rear point contacts formed by laser opening and physical vapor deposition

In this work, we report on ion‐implanted, high‐efficiency n‐type silicon solar cells fabricated on large area pseudosquare Czochralski wafers. The sputtering of aluminum (Al) via physical vapor deposition (PVD) in combination with a laser‐patterned dielectric stack was used on the rear side to produce front junction cells with an implanted boron emitter and a phosphorus back surface field. Front and back surface passivation was achieved by thin thermally grown oxide during the implant anneal. Both front and back oxides were capped with SiN_x, followed by screen‐printed metal grid formation on the front side. An ultraviolet laser was used to selectively ablate the SiO₂/SiN_x passivation stack on the back to form the pattern for metal–Si contact. The laser pulse energy had to be optimized to fully open the SiO₂/SiN_x passivation layers, without inducing appreciable damage or defects on the surface of the n⁺ back surface field layer. It was also found that a low temperature annealing for less than 3 min after PVD Al provided an excellent charge collecting contact on the back. In order to obtain high fill factor of ~80%, an in situ plasma etching in an inert ambient prior to PVD was found to be essential for etching the native oxide formed in the rear vias during the front contact firing. Finally, through optimization of the size and pitch of the rear point contacts, an efficiency of 20.7% was achieved for the large area n‐type passivated emitter, rear totally diffused cell. Copyright © 2014 John Wiley & Sons, Ltd.     

Study on ta diffusion barrier in Al/Si system

The property of Ta as a diffusion barrier is studied for Al/Ta/Si structure. Interfacial reactions of Al(180 nm)/Ta(130 nm)/Si and Al(180 nm)/Ta(24 nm)/Si, in the temperature range 450∼600°C for 30 min, have been investigated. In Al/Ta(130 nm)/Si system, which is Ta-excess case, Al₃Ta is formed at 500°C. At 575°C, TaSi₂ is formed at the interface of Ta Si. At 600°C, after Al₃Ta decomposes at the interface of Al₃Ta TaSi₂, free Ta is bonded to TaSi₂ with the supply of Si from Si substrate and free Al diffuses through TaSi₂, resulting in Al spiking. In Al/Ta(24 nm)/Si system, which is Al-excess case, Al₃Ta is formed at 500°C. At the same temperature of 500°C, after Al₃Ta decomposes at the interface of Al₃Ta/Si, free Ta reacts with Si to form TaSi₂ and free Al diffuses to Si substrate, resulting in Al spiking. The results of interfacial reactions can be understood from the calculated Al-Si-Ta ternary phase diagram. It can be concluded that the reaction at Al/Ta should be suppressed to improve the performance of Ta diffusion barrier in Al/Si system.     

Vanadium-based ohmic contacts to n-type Al<Subscript>0.6</Subscript>Ga<Subscript>0.4</Subscript>N

Four vanadium-based contacts to n-type Al_0.6Ga_0.4N were compared in this work. Both V/Al/Pd/Au and V/Al/V/Au contacts with optimized layer thicknesses provided lower specific-contact resistances than did the previously reported V/Al/Pt/Au ohmic contact. Specific contact resistances of the V/Al/Pd/Au (15 nm/85 nm/20 nm/95 nm) and V/Al/V/Au (15 nm/85 nm/20 nm/95 nm) contacts were 3×10⁻⁶ Ω·cm² and 4×10⁻⁶ Ω·cm², respectively. On the other hand, an analogous V/Al/Mo/Au contact never became ohmic, even after it was annealed at 900°C for 30 sec. Compared to the V/Al/Pd/Au contact, the V/Al/V/Au contact required a less severe annealing condition (30 sec at 700°C instead of 850°C). The V/Al/V/Au contact also provided a smoother surface, with a root-mean-square (RMS) roughness of 39 nm.     

Simultaneous formation of p- and n-type ohmic contacts to 4H-SiC using the ternary Ni/Ti/Al system

Fabrication procedures for silicon carbide power metal oxide semiconductor field effect transistors (MOSFETs) can be improved through simultaneous formation (i.e., same contact materials and one step annealing) of ohmic contacts on both the p-well and n-source regions. We have succeeded with the simultaneous formation of the ohmic contacts for p- and n-type SiC semiconductors by examining ternary Ni/Ti/Al materials with various compositions, where a slash symbol “/” indicates the deposition sequence starting with Ni. The Ni(20 nm)/Ti(50 nm)/Al(50 nm) combination provided specific contact resistances of 2 × 10⁻³ Ω-cm² and 2 × 10⁻⁴ Ω-cm² for p- and n-type SiC, respectively, after annealing at 800°C for 30 min, where the doping level of Al in the SiC substrate was 4.5 × 10¹⁸ cm⁻³ and the level of N was 1.0 × 10¹⁹ cm⁻³.     

Electromigration of Cu/low dielectric constant interconnects

Electromigration in damascene Cu/low dielectric constant interconnects with overlayers of CoWP, Ta/TaN, SiN_x or SiC_xN_yH_z and Cu(Ti) interconnects capped with SiN_x was studied. The results showed that the migration fast path in the bamboo-like lines primarily occurred at the interface. Cu lines fabricated with various forms of TaN/Ta liner including PVD TaN, ALD TaN, and PVD body centered cubic α- or tetragonal β-Ta liners were also investigated. Both thin surface layers of CoWP or Ta/TaN and the addition of Ti in the Cu lines significantly reduced the Cu/cap interface diffusivity and remarkably improved the electromigration lifetime when compared with Cu lines capped with SiN_x or SiC_xN_yH_z. Activation energies for electromigration were found to be 1.9–2.4 eV, 1.4 eV, 0.85–1.1 eV, and 1.3 eV for the bamboo-like Cu lines capped with CoWP, Ta/TaN, and SiN_x or SiC_xN_yH_z, and Cu(Ti) bamboo lines capped with SiN_x, respectively. The structural phase of the Ta was found to have an insignificant effect on the Cu mass flow rate. A large via size, thicker liner and/or stable connected exposed liner can provide a longer lifetime and tighter lifetime distribution, at the expense of chip density or effective Cu line conductivity.     

Control of the Ti diffusion in Pt/Ti bottom electrodes for the fabrication of PZT thin film transducers

For the achievement of microactuators based on piezoelectric thin films, a Pt/Ti/Si bottom electrode is widely used. This study presents the experimental results for Ti out-diffusion in Pt and Si for both sputtered Pt/Ti and Pt/TiO_x electrodes. These results have been compared before and after a rapid thermal annealing (RTA). The diffusion has been characterized by secondary ion mass spectroscopy (SIMS) analysis using Cs⁺ as a primary ion source. The Pt orientation has been observed by XRD measurements. Ti thin films (20 nm) have been sputtered in pure Ar whereas TiO_x films have been obtained by reactive sputtering in a mixture of Ar/O₂ (90/10). Finally, the Pt (100 nm) has been sputtered without vacuum breaking. After RTA (400°C, 30 s, in N₂), the Pt film exhibited a (1 1 1) orientation for both Ti and TiO_x adhesion films. The roughness of the Pt film measured by AFM with TiO_x underlayer was 80% less than that of the Pt/Ti bi-layer. The TiO_x film, as shown by SIMS analysis, has drastically reduced the diffusion of Ti in both Pt and Si. This phenomenon is accompanied by a very low Pt roughness. These results are analyzed in terms of diffusion and regrowth mechanisms inside the Pt film.     

Approach for Al2O3 rear surface passivation of industrial p‐type Si PERC above 19%

Atomic layer deposition (ALD) of thin Al₂O₃ (≤10 nm) films is used to improve the rear surface passivation of large‐area screen‐printed p‐type Si passivated emitter and rear cells (PERC). A blister‐free stack of Al₂O₃/SiO_x/SiN_x is developed, leading to an improved back reflection and a rear recombination current (J_0,rear) of 92 ± 6 fA/cm². The Al₂O₃/SiO_x/SiN_x stack is blister‐free if a 700°C anneal in N₂ is performed after the Al₂O₃ deposition and prior to the SiO_x/SiN_x capping. A clear relationship between blistering density and lower open‐circuit voltage (V_OC) due to increased rear contacting area is shown. In case of the blister‐free Al₂O₃/SiO_x/SiN_x rear surface passivation stack, an average cell efficiency of 19.0% is reached and independently confirmed by FhG‐ISE CalLab. Compared with SiO_x/SiN_x‐passivated PERC, there is an obvious gain in V_OC and short‐circuit current (J_SC) of 5 mV and 0.2 mA/cm², respectively, thanks to improved rear surface passivation and rear internal reflection. Copyright © 2012 John Wiley & Sons, Ltd.