Study of the Formation Mechanism of Cu/Ge/Pd Ohmic Contact to <Emphasis Type="Italic">n</Emphasis>-Type InGaAs

This study investigates electrical characteristics and the formation mechanism of the Cu/Ge/Pd Ohmic contact to n-type InGaAs. After annealing the contact at 250°C for 20 min, Cu₃Ge and Pd₁₂Ga₅As₂ compounds formed and Ge diffused into the InGaAs layer, achieving a heavily doped InGaAs layer with a low contact resistivity of 1 × 10⁻⁶ Ω cm². Thermal stability tests were performed on the Cu/Ge/Pd Ohmic contact to InGaAs after Ohmic contact formation, showing no obvious degradation after a 72 h reliability test at 250°C. The results indicate excellent electrical characteristics and thermal stability using Cu/Ge/Pd as an Ohmic contact metal to an n-InGaAs layer.     

Pd-Ge contact to n-GaAs with the TiW diffusion barrier

Pd-Ge based ohmic contact to n-GaAs with a TiW diffusion barrier was investigated. Electrical analysis as well as Auger electron spectroscopy and the scanning electron microscopy were used to study the contact after it was subjected to different furnace and rapid thermal annealing and different aging steps. All analyses show that TiW can act as a good barrier metal for the Au/Ge/Pd/n-GaAs contact system. A value of 1.45 × 10⁻⁶ Ω-cm² for the specific contact resistance was obtained for the Au/TiW/Ge/Pd/n-GaAs contact after it was rapid thermally annealed at 425°C for 90 s. It can withstand a thermal aging at 350°C for 40 h with its ρ_c increasing to 2.94 × 10⁻⁶Ω-cm² and for an aging at 410°C for 40 h with its ρ_c increasing to 1.38 × 10⁻⁵ Ω-cm².     

Fabrication of Source/Drain Electrodes for a-Si:H Thin-Film Transistors Using a Single Cu Alloy Target

A Cu alloy/Cu alloy oxide bilayer structure was formed on an n ⁺-a-Si:H substrate using a single Cu alloy target. It was employed for the source/drain electrodes in the fabrication of a-Si:H thin-film transistors with good electrical performance, high thermal stability, and good adhesion. Transmission electron microscopy and electron energy-loss spectroscopy analyses revealed that the initial sputtering of the Cu alloy in O₂/Ar allowed for preferential oxidation of Si and the formation of a SiO _x /Cu-supersaturated a-Si:H bilayer at the copper oxide–a-Si:H interface. This bilayer turned into an SiO _x /Cu₃Si bilayer after annealing at 300°C. It provided a stable contact structure with low contact resistance.     

Thermally stable Ge/Cu/Ti ohmic contacts to n-type GaN

The performance of a novel Ge/Cu/Ti metallization scheme on n-type GaN has been investigated for obtaining thermally and electrically stable low-resistance ohmic contacts. Isochronal (2 min.) anneals in the 600–740°C temperature range and isothermal (690°C) anneals for 2–10 min. duration were performed in inert atmosphere. For the 690°C isothermal schedule, ohmic behavior was observed after annealing for 3 min. or longer with a lowest contact resistivity of 9.1 × 10⁻⁵ Ωcm² after the 10 min. anneal for a net donor doping concentration of 9.2 × 10¹⁷ cm^−Ω3. Mean roughness (R_a) for anneals at 690°C was almost constant at around 5 nm, up to an annealing duration of 10 min., which indicates a good thermal stability of the contact scheme.     

Sputtered copper films with insoluble Mo for Cu metallization: A thermal annealing study

The thermal annealing behavior of Cu films containing insoluble 2.0 at. % Mo magnetron co-sputtered on Si substrates is discussed in the present study. The Cu-Mo films were vacuum annealed at temperatures ranging from 200°C to 800°C. X-ray diffraction (XRD) and scanning electron microscopy (SEM) observations have shown that Cu₄Si was formed at 530°C, whereas pure Cu film exhibited Cu₄Si growth at 400°C. Twins are observed in focused ion beam (FIB) images of as-deposited and 400°C annealed, pure Cu film, and these twins result from the intrinsically low stacking-fault energy. Twins appearing in pure Cu film may offer an extra diffusion channel during annealing for copper silicide formation. In Cu-Mo films, the shallow diffusion profiles for Cu into Si were observed through secondary ion mass spectroscopy (SIMS) analysis. Higher activation energy obtained through differential scanning calorimetry (DSC) analysis for the formation of copper silicide further confirms the beneficial effect of Mo on the thermal stability of Cu film.     

Pd/Ge contacts to n-type GaAs

Sintered metal-semiconductor contacts, formed by thin, evaporated layers of Pd and Ge on n-type GaAs, were studied using Auger electron spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, secondary ion mass spectroscopy, current-voltage measurements, and capacitance-voltage measurements. Prior to sintering, the as-deposited Pd/Ge/GaAs contacts were rectifying and exhibited a reproducible Schottky barrier energy φ_Bn of 0.67±0.02 eV. Auger analysis indicated the initial behavior of the contact structure, upon sintering, to be an interdiffusion and reaction of Pd and Ge on a non-reacting GaAs substrate. Two germanide phases, Pd₂Ge and PdGe, were identified using X-ray diffraction and Auger analysis. The intervening Ge layer prevented the reaction of Pd with the GaAs substrate at low temperatures. Because of the PdGe reaction, φ_Bn increased to approximately 0.85 eV. Sintering at higher temperatures (i.e. between 300 and 400°C) produced additional reactions between Pd and the GaAs substrate. The electrical properties of the contact remained rectifying and φ_Bn exhibited little change from the value of 0.85 eV with the interdiffusion of Pd, Ga, and As. Sintering above 400°C resulted in the formation of ohmic contacts. The diffusion of Ge to the GaAs interface was found to correlate with the onset of ohmic behavior. Current conduction in the contact was best described by thermionic-field emission theory, and a specific contact resistance of 3.5 × 10^?4Ω-cm² was obtained after sintering above 550°C, independent of the initial impurity concentration in the substrate. Over the entire range of sintering temperatures (i.e. at or below 600°C), the interaction between the thin-film layers appeared to be governed by diffusion-controlled, solid-phase processes with no evidence of the formation of a liquid phase. As a result, the surface of the contact structure remained smooth and uniform during sintering.     

Ir Diffusion Barriers in Ni/Au Ohmic Contacts to <Emphasis Type="Italic">p</Emphasis>-Type CuCrO<Subscript>2</Subscript>

The use of Ir diffusion barriers in Ni/Au-based Ohmic contacts to p-type CuCrO₂ layers was investigated. A specific contact resistance of ~5 × 10⁻⁴ Ω cm² was achieved after annealing at 500°C for the Ir-containing contacts, and the contacts were rectifying for lower anneal temperatures. In this case, the contact resistance was basically independent of the measurement temperature, indicating that tunneling is the dominant transport mechanism in the contacts. The morphology for the Ir-containing contacts was still smooth at 500°C although Auger electron spectroscopy depth profiling showed that some of the nickel had diffused to the surface and had oxidized. Contacts annealed at 800°C showed that some copper and most of the nickel had diffused to the surface and oxidized. The presence of the Ir diffusion barrier does increase the thermal stability of the contacts by ∼200°C compared to conventional Ni/Au contacts. By contrast, the use of other materials such as TaN, ZrN, and W₂B₅ as the diffusion barrier led to poorer thermal stability, with the contact resistance increasing sharply above 400°C.     

Ohmic contact formation in palladium-based metallizations to n-Type InP

Two Pd-based metallizations have been systematically studied, i.e., Au/Ge/Pd and Pd/Ge contacts to n-type InP, in an attempt to better understand the role of the metallization constituents in forming ohmic contacts. Ohmic contacts were obtained with minimum specific resistances of 2.5 × 10⁻⁶ Ω-cm² and 4.2 × 10⁻⁶ Ω-cm² for the Au/Ge/Pd and the Pd/Ge contacts, respectively. The annealing regime for ohmic contact formation is 300-375°C for the Au/Ge/Pd/InP system and 350-450°C for the Pd/GelnP system. Palladium, in both cases, reacts with InP to form an amorphous layer and then an epitaxial layer at low temperatures, providing good metallization adhesion to InP substrates and improved contact morphology. Ohmic contact formation in both contacts is attributed to Ge doping, based on the solid state reaction-driven decomposition of an epitaxial layer at the metallization/InP interface, producing a very thin, heavily doped InP layer. Gold appears to be responsible for the difference in contact resistance in the two systems. It is postulated that Au reacts strongly with In to form Au-In compounds, creating additional In site vacancies in the InP surface region (relative to the Au-free metallization), thereby enhancing Ge doping of the InP surface and lowering the contact resistance. Both contacts degrade and ultimately become Schottky barriers again if over annealed, due to consumption of additional InP, which destroys the heavily doped InP layer.     

Diffusion behavior of Cu in Cu/electroless Ni and Cu/electroless Ni/Sn-37Pb solder joints in flip chip technology

For Cu pads used as under bump metallization (UBM) in flip chip technology, the diffusion behavior of Cu in the metallization layer is an important issue. In this study, isothermal interdiffusion experiments were performed at 240°C for different times with solid-solid and liquid-solid diffusion couples assembled in Cu/electroless-Ni (Ni-10 wt.% P) and Cu/electroless Ni (Ni-10 wt.% P)/ Sn-37Pb joints. The diffusion structure and concentration profiles were examined by scanning electron microscopy and electron microprobe analysis. The interdiffusion fluxes of Cu, Ni and P were calculated from the concentration profiles with the aid of Matano plane evaluation. The values of J_Cu, J_Ni, and J_P decreased with increasing annealing time. The average effective interdiffusion coefficients on the order of 10⁻¹⁴ cm²/s were also evaluated within the diffusion zone. The amounts of Cu dissolved in the intermetallic compounds (IMCs) Ni₃Sn₄ and Ni₃P that precipitate after annealing the Cu/electroless Ni/Sn-37Pb joints were about 0.25 at.% and 0.5 at.%, respectively. For the short period of annealing, it appears that the presence of electroless Ni (EN) with the Sn-Pb soldering reaction assisted the diffusion of Cu through the EN layer.     

Ohmic contacts to n-type GaN using Pd/Al metallization

Ohmic contacts to n-type GaN grown by metalorganic chemical vapor deposition were formed using a Pd/Al-based metallization. Ohmic contact resistances and specific contact resistances were investigated as a function of rapid thermal annealing temperature, Pd interlayer thickness, and annealing time. As-deposited Pd/AI was found to produce rectifying contacts while the metallization exhibited ohmic characteristics after annealing at temperatures as low as 400°C. A minimum contact resistance of 0.9 ohm-mm (specific contact resistance = 1.2 × 10⁻⁵ ohm-cm²) was obtained upon annealing at 650°C for 30 s. For comparison, Al and Ti/Al contacts were also investigated. Auger electron spectroscopy, secondary ion mass spectrometry, and x-ray diffraction were used to investigate metallurgical reactions.     

An electrical method to characterize thermal reactions of Pd/GaAs and Ni/GaAs contacts

Capacitance-voltage (C-V) and current-voltage (I-V) measurements were used to study the thermal reaction of Pd/GaAs contacts and Ni/GaAs contacts. The thickness of GaAs consumed by the metal/GaAs reaction during annealing was calculated from C-V analyses and I-V analyses. For annealing temperatures below 350°C, the Schottky characteristics of the diodes were good but the electrical junction moves into the GaAs after annealing. The amount of junction movement was calculated directly from our measurements. The diffusion coefficients of Pd and Ni in GaAs at 300°C were estimated both to be around 1.2 × 10¹⁴ cm₂/s.     

Low resistance bilayer Nd/Al ohmic contacts on n-type GaN

A bilayer Nd/Al metallization structure has been deposited onto low pressure organometallic vapor phase epitaxy grown n-type GaN ( 1 × 10¹⁸ cm⁻³) by electron-beam evaporation. Ohmic metal contacts were patterned photolithographically for standard transmission line measurement, and then thermally annealed at temperatures ranging from 200 to 350°C and from 500 to 650°C using conventional thermal annealing (CTA) and rapid thermal annealing (RTA), respectively. The lowest values for the specify contact resistivity of 9.8 × 10⁻⁶ Ω−cm² and 8 × 10⁻⁶ Ω−cm² were obtained using Nd/Al metallization with CTA of 250°C for 5 min and RTA of 600°C for 30 s. Examination of the surface morphology using atomic force microscopy as a function of annealing temperature revealed that the surface roughness was strongly influenced by conventional thermal annealing, it was smooth in the temperature range from 550 to 650°C for rapid thermal annealing. Auger electron spectroscopy depth profiling was employed to investigate the metallurgy and interdiffusion of contact formation.     

Cu3Ge ohmic contacts to n-type GaAs

We show that Cu-Ge alloys prepared by depositing sequentially Cu and Ge layers onto GaAs substrates at room temperature followed by annealing at 400°C form a low-resistance ohmic contact to n-type GaAs over a wide range of Ge concentration that extends from 20 to 40 at.%. A contact resistivity of (4-6) x 10^-7 Ω cm² is obtained on n-type GaAs with doping concentrations of～ 1 x 10¹⁷ cm^-3. The contact resistivity is affected only slightly by varying the Ge concentration in the range studied and is not influenced by the deposition sequence of the Cu and Ge layers. In addition, the contacts are electrically stable during annealing at 450°C after contact formation. Structure and properties of Cu-Ge contact layers having lower and higher Ge concentrations from the stoichiometric Cu₃Ge composition are compared. High-resolution transmission electron microscopy and x-ray diffractometry have been used to study the ordering in the ε₁-Cu₃Ge (average lattice parameters: a₀= 5.30Å, b₀= 4.20Å, c₀= 4.56Å) which is responsible for orthorhombic distortion of the parent hexagonal ζ-phase. The results suggest that the formation of theξ and ε-Cu₃Ge phases creates a highly doped n⁺-GaAs surface layer which leads to the low contact resistivity.     

Thermal Stability of Nitride-Based Diffusion Barriers for Ohmic Contacts to <Emphasis Type="Italic">n</Emphasis>-GaN

The use of TaN, TiN, and ZrN diffusion barriers for Ti/Al-based contacts on n-GaN (n ∼ 3 × 10¹⁷ cm⁻³) is reported. The annealing temperature (600–1,000°C) dependence of the Ohmic contact characteristics using a Ti/Al/X/Ti/Au metallization scheme, where X is TaN, TiN, or ZrN, deposited by sputtering was investigated by contact resistance measurements and Auger electron spectroscopy (AES). The as-deposited contacts were rectifying and transitioned to Ohmic behavior for annealing at ≥600°C. A minimum specific contact resistivity of ∼6 × 10⁻⁵ Ω-cm⁻² was obtained after annealing over a broad range of temperatures (600–900°C for 60 s), comparable to that achieved using a conventional Ti/Al/Pt/Au scheme on the same samples. The contact morphology became considerably rougher at the high end of the annealing range. The long-term reliability of the contacts at 350°C was examined; each contact structure showed an increase in contact resistance by a factor of three to four over 24 days at 350°C in air. AES profiling showed that the aging had little effect on the contact structure of the nitride stacks.     

Effects of post-annealing by the rapid thermal process on the characteristics of MOCVD-Cu/TiN/Si structures

Effects of rapid thermal annealing on the characteristics of Cu films deposited from the (hfac)Cu(VTMS) precursor and on the barrier properties of TiN layers were studied. By the post-annealing, the electrical characteristics of Cu/TiN and the microstructures of Cu films were significantly changed. The properties of Cu films were more sensitive to the annealing temperature than the annealing time. Sheet resistances were decreased in 400–450°C ranges, and abrupt increases were observed above 750°C. It was also found that the copper films showed pronounced grain growth with the (111) preferred orientation. The grain growth and condensation of copper were observed below 500°C without formation of the CuO and Cu₂O phase resulting in surface degradation. Above 500°C, the oxide compound of copper was partially formed on the surface and the inter-reaction on the Cu-TiN interface was started. The inter-reaction of Cu-Ti and Cu-Si interface vigorously occurred and the surface roughness was continuously deteriorated above 650°C. It revealed that the optimum annealing conditions for MOCVD-Cu/PVD-TiN structures to enhance the electrical characteristics without degradation of TiN barriers were in the range of 400°C.     

Diffusion barrier performance of Zr–N/Zr bilayered film in Cu/Si contact system

Zr–N/Zr bilayered film as a diffusion barrier between Cu and Si is evaluated. The thermal stability of the diffusion barrier is investigated by annealing the Cu/Zr–N/Zr/Si samples in N₂ for an hour. XRD, SEM and AES results for the above contact systems after annealing at 700 °C show that Cu film has preferential (1 1 1) crystal orientation and no diffraction peaks of Cu₃Si and a Cu–Zr–Si ternary compound are observed for all Cu/Zr–N/Zr/Si contact systems. In addition, the atomic distribution of Zr and Si is evident and grows with increasing temperature up to 700 °C, which corresponds to the Zr–Si phase having low contact resistivity. Low contact resistivity and high thermal stability diffusion barrier can be expected by the application of the Zr–N/Zr bilayered film as a diffusion barrier between Cu and Si.     

A Study on the Thermal Reliability of Cu/SnAg Double-Bump Flip-Chip Assemblies on Organic Substrates

The Cu/SnAg double-bump structure is a promising candidate for fine-pitch flip-chip applications. In this study, the interfacial reactions of Cu (60 μm)/SnAg (20 μm) double-bump flip chip assemblies with a 100 μm pitch were investigated. Two types of thermal treatments, multiple reflows and thermal aging, were performed to evaluate the thermal reliability of Cu/SnAg flip-chip assemblies on organic printed circuit boards (PCBs). After these thermal treatments, the resulting intermetallic compounds (IMCs) were identified with scanning electron microscopy (SEM), and the contact resistance was measured using a daisy-chain and a four-point Kelvin structure. Several types of intermetallic compounds form at the Cu column/SnAg solder interface and the SnAg solder/Ni pad interface. In the case of flip-chip samples reflowed at 250°C and 280°C, Cu₆Sn₅ and (Cu, Ni)₆Sn₅ IMCs were found at the Cu/SnAg and SnAg/Ni interfaces, respectively. In addition, an abnormal Ag₃Sn phase was detected inside the SnAg solder. However, no changes were found in the electrical contact resistance in spite of severe IMC formation in the SnAg solder after five reflows. In thermally aged flip-chip samples, Cu₆Sn₅ and Cu₃Sn IMCs were found at the Cu/SnAg interface, and (Cu, Ni)₆Sn₅ IMCs were found at the SnAg/Ni interface. However, Ag₃Sn IMCs were not observed, even for longer aging times and higher temperatures. The growth of Cu₃Sn IMCs at the Cu/SnAg interface was found to lead to the formation of Kirkendall voids inside the Cu₃Sn IMCs and linked voids within the Cu₃Sn/Cu column interfaces. These voids became more evident when the aging time and temperature increased. The contact resistance was found to be nearly unchanged after 2000 h at 125°C, but increases slightly at 150°C, and a number of Cu/SnAg joints failed after 2000 h. This failure was caused by a reduction in the contact area due to the formation of Kirkendall and linked voids at the Cu column/Cu₃Sn IMC interface.     

Thermal Stability Study of Cu(MoN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>) Seed Layer on Barrierless Si

This study reports the good thermal stability of a sputtered Cu(MoN _x ) seed layer on a barrierless Si substrate. A Cu film with a small amount of MoN _x was deposited by reactive co-sputtering of Cu and Mo in an Ar/N₂ gas mixture. After annealing at 560°C for 1 h, no copper silicide formation was observed at the interface of Cu and Si. Leakage current and resistivity evaluations reveal the good thermal reliability of Cu with a dilute amount of MoN _x at temperatures up to 560°C, suggesting its potential application in advanced barrierless metallization. The thermal performance of Cu(MoN _x ) as a seed layer was evaluated when pure Cu is deposited on top. X-ray diffraction, focused ion beam microscopy, and transmission electron microscopy results confirm the presence of an ∼10-nm-thick reaction layer formed at the seed layer/Si interface after annealing at 630°C for 1 h. Although the exact composition and structure of this reaction layer could not be unambiguously identified due to trace amounts of Mo and N, this reaction layer protects Cu from a detrimental reaction with Si. The Cu(MoN _x ) seed layer is thus considered to act as a diffusion buffer with stability up to 630°C for the barrierless Si scheme. An electrical resistivity of 2.5 μΩ cm was obtained for the Cu/Cu(MoN _x ) scheme after annealing at 630°C.     

Interdiffusion of the p-InP with Au−Zn,Ti/Au,Pd/Au,Ti/Pd/Au at interface and their electrical properties

 In this report,the interdiffusion between the p-InP with Au-Zn,Ti/Au,Pd/Au and Ti/Pd/Au at interface have been investigated by Auger electron spectroscopy and electron spectroscopy for chemical analysis.The surface morphology for the heat treatment are observed with scanning electron microscopy. It is found that the indiffusion of Au is easier than that of Pd and Ti and the outdiffusion of In is easier than that of P.The combination state of In and Au is formed during the heat treatment of p-InP/Au-Zn. The effects of the alloying temperature and time on the specific contacts resistance of p-InP/Au-Zn system are studided.The low specific contact resistance,p_c=2.4-2.7×10~(-4)Ω-cm~2,is obtained when alloying at 450℃ for 2 min or at 350℃ for 30 min. These results indicate that the specific contact resistance strongly depend on the“interdiffusion degree”.The Zn in Au-Zn ahoy distributes onto the most surface layer of p-InP/Au-Zn system during evaporation process and heat treatment.It may be one of the reasons for the higher specific contacts resistance.     

Pd/Zn/Pd/Au ohmic contacts to ρ-Type InP

Low resistance ohmic contacts (ρ_c = 7 x 10^-5 Ω-cm ² ) have been fabricated to Zn-doped p-type InP using an annealed Pd/Zn/Pd/Au metallization. Palladium reacts with InP at low temperatures to form a Pd₂InP ternary phase, which is initially amorphous but crystallizes and grows epitaxially on InP. Zinc reacts with some of the overlying Pd to form PdZn (≅250° C), which decomposes at 400-425° C to form PdP₂, freeing up Zn to diffuse into Au as well as InP. The contact resistance reaches a minimum as the decomposition reaction takes place. The resultant ohmic contact is laterally uniform and consists of epitaxial Pd₂InP adjacent to InP, followed by a thin layer of PdP₂ and then the outer Au layer. Further annealing leads to a breakdown of the contact structure,i.e. decomposition of Pd₂InP, and an increase in contact resistance.