Copper-Silver Alloy for Advanced Barrierless Metallization

In this study we observed significantly improved properties, over a pure copper (Cu) film, for a copper-silver alloy film made with a pure copper film co-sputtered with a minute amount of either Ag_0.3N_0.4 or Ag_1.2N_0.7 on a barrierless Si substrate. In either case, no noticeable interaction between the film␣and the Si substrate was found after annealing at 600°C for 1 h. The Cu(Ag_0.3,N_0.4) film was thermally stable after annealing at 400°C for 240 h. The film’s resistivity was ∼2.2 μΩ cm after annealing at 600°C, while its leakage current was found to be lower than that of a pure Cu film by three orders of magnitude. The adhesion of the Cu(Ag_1.2,N_0.7) film to the Si substrate was approximately seven times that of a pure Cu film to a silicon substrate. Hence, a Cu film doped with Ag and N seems to be a better candidate for both barrierless metallization and the making of superior interconnects.     

Structural and Passivative Behaviors of Cu(In) Thin Film

This investigation prepares a low-resistivity and self-passivated Cu(In) thin film. The dissociation behaviors of dilute Cu-alloy thin films, containing 1.5–5at.%In, were prepared on glass substrates by a cosputter deposition, and were subsequently annealed in the temperature range of 200–600 °C for 10–30 min. Thus, self-passivated Cu thin films in the form In₂O₃/Cu/SiO₂ were obtained by annealing Cu(In) alloy films at an elevated temperature. Structural analysis indicated that only strong copper diffraction peaks were detected from the as-deposited film, and an In₂O₃ phase was formed on the surface of the film by annealing the film at an elevated temperature under oxygen ambient. The formation of In₂O₃/Cu/SiO₂ improved the resistivity, adhesion to SiO₂, and passivative capability of the studied film. A dramatic reduction in the resistivity of the film occurred at 500 °C, and was considered to be associated with preferential indium segregation during annealing, yielding a low resistivity below 2.92 μΩcm. The results of this study can be potentially exploited in the application of thin-film transistor–liquid crystal display gate electrodes and copper metallization in integrated circuits.     

Effect of Annealing Ambient on the Self-Formation Mechanism of Diffusion Barrier Layers Used in Cu(Ti) Interconnects

Copper (titanium) [Cu(Ti)] films with low titanium (Ti) concentration were found to form thin Ti-rich barrier layers at the film/substrate interfaces after annealing, which is referred to as self-formation of the barrier layers. This Cu(Ti) alloy was one of the best candidates for interconnect materials used in next-generation ultra-large-scale integrated (ULSI) devices that require both very thin barrier layers and low-resistance interconnects. In the present paper, in order to investigate the influences of annealing ambient on resistivity and microstructure of the Cu alloys, the Cu(7.3at.%Ti) films were prepared on the SiO₂ substrates and annealed at 500°C in ultra-high vacuum (UHV) or argon (Ar) with a small amount of impurity oxygen. After annealing the film at 500°C in UHV, the resistivity was not reduced below 16 μΩ-cm. Intermetallic compounds of Cu₄Ti were observed to form in the films and believed to cause the high resistivity. However, after subsequently annealing in Ar, these compounds were found to decompose to form surface TiO _x and interfacial barrier layers, and the resistivity was reduced to 3.0 μΩ-cm. The present experiment suggested that oxygen reactive to titanium during annealing played an important role for both self-formation of the interfacial barrier layers and reduction of the interconnect resistivity.     

Electroless Cu deposition process on TiN for ULSI interconnect fabrication via Pd/Sn colloid activation

In this study, (100)-orientation silicon wafer coated with TiN barrier is catalyzed by a Pd/Sn colloid, which serves as an activator for electroless copper deposition. After activation, electroless deposition of Cu occurs on the catalytic surface. The coverage of the Cu deposit reaches 100% and the adsorptive amount of Pd is greatly increased by the conditioning process. The correlation between deposition rate, resistivity, morphology, crystal structure, and composition of the deposit when varying the temperature of the plating bath is discussed. The deposition rate of Cu is monitored by both the electrochemical method and the profilometer (α-step), while the other properties of the deposit are measured by four-point probe, scanning electron microscopy (SEM), x-ray diffraction (XRD), and Auger electron microscopy (AES). Deposition at 70°C is favorable due to the higher deposition rate, lower resistivity, less impurities, and more preferred orientation in the crystal structure than that at lower temperature. Problems regarding adhesion and high resistivity can be greatly mitigated via 400°C thermal annealing. The resistivity of Cu can be reduced to 2.2 μΩcm. Moreover, trenches of 1 μm and 0.25 μm on patterned wafer have been successfully filled by electroless deposition of Cu with the aid of surfactant C12.     

Thermal performance of sputtered insoluble Cu(W) films for advanced barrierless metallization

The thermal performance of sputtered Cu films with dilute insoluble W (1.3 at.%) on barrierless Si substrates has been studied, using the analyses of focused ion beam, x-ray diffraction, and electrical resistivity measurement. The role of the Cu(W) film as a seed layer has been confirmed based on the thermal performance evaluations in both thermal cycling and isothermal annealing at various temperatures. The electrical resistivity of ∼1.8 μΩ-cm for Cu/Cu(W) film is obtained after thermal annealing at 400°C. Because of the good thermal stability, the Cu(W) seed layer is also considered to act as a diffusion buffer and is stable up to 490°C for the barrierless Si scheme. The results indicate that the Cu/Cu(W) scheme has potential in advanced barrierless metallization applications.     

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.     

Neutralization of electrically active aluminum in recrystallized silicon-on-sapphire films

We report the effect of steam oxidation at 875° C on the electrical resistivity, crystalline quality (measured by ion channeling), and Al concentration (measured by secondary ion mass spectrometry) in 0.25 μm thick, Si-implanted and recrystallized, Si-on-sapphire films. After a deep Si implantation (180 keV, 1.4×l0¹⁵ Si/cm²) at room temperature, and solid-phase epitaxial regrowth from the non-amorphized, 0.03 μm thick surface region, the initially undoped SOS films become doped p-type, and their resistivity decreases from (1−5)xl0¹⁴ ficm to 0.5 Ωcm. The doping is due to electrically active Al, released from the A1₂O₃ by the Si implantation, and present in the recrystallized films at a concentration of ≃2×l0¹⁶ Al/cm³ . After a 75 min steam oxidation at 875 °C, which consumes 0.06 Μm of Si, the resistivity of the recrystallized films increases to over 40 Ωcm, but the Al concentration is unchanged. The oxidation also uncovers higher quality material below the non-recrystallized surface layer. A semi-quantitative model is proposed to explain the electrical data, based on the diffusion of oxygen from the Si/SiO₂ interface into the SOS film during oxidation, and the formation of Al-O-Si neutral complexes. Data on the stability of the high-resistivity films against high-temperature annealing or re-amorphization and annealing is given.     

Comparative study of electrically conductive thick films with and without glass

An air-fireable, glass-free, electrically conductive thick-film material (96.6% Ag, 1.38% Cu, 0.28% Al, 0.35% Ti, and 1.39% Sn by weight) and a conventional glass-containing, electrically conductive thick-film materials (96.6% Ag and 3.4% glass frit by weight), both on alumina substrates, were studied by electrical, mechanical, thermal, and microscopic methods. The volume electrical resistivity of the glass-free thick film (2.5×10⁻⁶ Ω·cm, 30-μm thick) is lower than that of the glass-containing thick film (3.9×10⁻⁶ Ω·cm, 19-μm thick), with each film processed at its optimum firing temperature. The optimum firing temperature is 930°C and 850°C for glass-free and glass-containing thick films, respectively, as indicated by the criteria of low resistivity and high scratch resistance. The glass-free thick film has a higher scratch resistance than the glass-containing thick film, both fired at their respective optimum temperatures, suggesting that the former has higher bond strength to the alumina substrate. The formation process of the glass-free and glass-containing thick films is similar. The process involves solid-state diffusion of silver, which results in a silver network and grain boundaries. However, the sintering of silver particulates in the glass-containing thick film is enhanced by the viscous flow of glass.     

Electrically Nonconductive Thermal Pastes with Carbon as the Thermally Conductive Component

Electrically nonconductive thermal pastes have been attained using carbon (carbon black or graphite) as the conductive component and ceramic (fumed alumina or exfoliated clay) as the nonconductive component. For graphite particles (5 μm), both clay and alumina are effective in breaking up the electrical connectivity, resulting in pastes with electrical resistivity up to 10¹³Ω·cm and thermal contact conductance (between copper surfaces of roughness 15 μm) up to 9 × 10⁴ W/m²·°C. For carbon black (30 nm), clay is more effective than alumina, providing a paste with resistivity 10¹¹ Ω·cm and thermal contact conductance 7 × 10⁴ W/m²·°C. Carbon black increases the thermal stability, whereas either graphite or alumina decreases the thermal stability. The antioxidation effect of carbon black is further increased by the presence of clay up to 1.5 vol.%. The addition of clay (up to 0.6 vol.%) or alumina (up to 2.5 vol.%) to graphite paste enhances the thermal stability.     

Time-dependent characteristics of titanium-silicide contacts to 6H-silicon carbide

The processing conditions necessary to achieve low resistivity of the C54-TiSi₂ phase in contact with 6H-SiC are explored. This study demonstrates that an interlayer of Si between a Ti layer and the 6H-SiC substrate suppresses the formation of TiC, and that a metallization consisting of either Ti-rich or Si-rich silicide phases may be chosen. When the Ti-to-Si layer thickness ratio is 1:3, the C54-TiSi₂ and TiSi phases are observed following a 600°C/30 min and an 850°C/30 min annealing cycle. When the Ti-to-Si layer thickness ratio is 1:1, Ti₅Si₃ and TiSi phases are observed following the same annealing cycle. Time-dependent, in-situ resistance measurements are rationalized in terms of these microstructural developments. The Ti₅Si₃/TiSi structure is demonstrated to have a resistivity of 239 μΩ·cm, whereas the TiSi₂/TiSi structure has a resistivity of only 23 μΩ·cm. Explanations for different microstructures observed are presented.     

The effects of boron in the Cu(B)/Ti/SiO<Subscript>2</Subscript> system on the Cu-Ti reaction,resistivity, and diffusion barrier properties

The behavior of boron in Cu(4.8at.%B)/Ti/SiO₂ was investigated as a function of temperature, and its influences on the Cu-Ti interaction, resistivity, and diffusion barrier properties were also studied. The results showed the formation of a titanium boride layer at the Cu-Ti interface, after heating the Cu(B)/Ti/SiO₂ at 400°C and higher, effectively served as a barrier for the Cu and Ti diffusion, and significantly enhanced the Cu (111) texture. The resistivity dropped from 16.3 to 2.33 μΩ-cm after heating at 600°C, and continued to decrease up to 800°C. As a result, the Cu, in the form of B(O)_x/Cu/TiB₂/Ti(O)_x/SiO₂ multilayers, obtained by heating the Cu(B)/Ti/SiO₂, showed high thermal stability with low resistivity and, thus, can be used as interconnections in advanced integrated circuits. Since the Cu, in the form of B(O)_x/Cu/TiB₂/Ti(O)_x/SiO₂ multilayers, obtained by heating the Cu(B)/Ti/SiO₂, showed high thermal stability with low resistivity, it can be used as interconnections in advanced integrated circuits.     

Novel Cu/Cr/Ge/Pd Ohmic Contacts on Highly Doped n-GaAs

The thermal stability of the Cu/Cr/Ge/Pd/n⁺-GaAs contact structure was evaluated. In this structure, a thin 40 nm layer of chromium was deposited as a diffusion barrier to block copper diffusion into GaAs. After thermal annealing at 350°C, the specific contact resistance of the copper-based ohmic contact Cu/Cr/Ge/Pd was measured to be (5.1 ± 0.6) × 10⁻⁷ Ω cm². Diffusion behaviors of these films at different annealing temperatures were characterized by metal sheet resistance, X-ray diffraction data, Auger electron spectroscopy, and transmission electron microscopy. The Cu/Cr/Ge/Pd contact structure was very stable after 350°C annealing. However, after 400°C annealing, the reaction of copper with the underlying layers started to occur and formed Cu₃Ga, Cu₃As, Cu₉Ga₄, and Ge₃Cu phases due to interfacial instability and copper diffusion.     

Amorphous chromium silicide formation in hydrogenated amorphous silicon

The interaction between thin films of hydrogenated amorphous silicon and sputter-deposited chromium has been studied. Following deposition of the chromium films at room temperature, the films were annealed over a range of times and temperatures below 350°C. It was found that an amorphous silicide was formed only a few nanometers thick with the square of thickness proportional to the annealing time. The activation energy for the process was 0.55±0.05 eV. The formation process of the silicide was very reproducible with the value of density derived from the thickness and Cr surface density being close to the value for crystalline CrSi₂ for all films formed at temperatures ≤300°C. The specific resistivity of the amorphous CrSi₂ was ≈600 μΩ·cm and independent of annealing temperature.     

Effect of growth temperature on properties of transparent conducting gallium-doped ZnO films

Transparent conducting gallium-doped ZnO films are deposited on glass substrates by magnetron sputtering of conducting ceramic targets. The dependences of structural, electric, and optical characteristics of ZnO:Ga films on the substrate temperature are investigated during the deposition. Stability of resistivity of films is considered during annealing in air. It is found that the films deposited at the substrate temperature of 250°C have the lowest resistivity of 3.8 × 10⁻⁴ Ω cm, while those deposited at 200°C have the highest thermal stability.     

Low-temperature metal-organic chemical vapor deposition (LTMOCVD) of device-quality copper films for microelectronic applications

Copper films for potential use in multilevel metallization in ULSIC’s were produced by low temperature (250–350° C) metal-organic chemical vapor deposition (LTMOCVD) in atmospheres of pure H₂ or mixture Ar/H₂ from the β-diketonate precursor bis(1,1,1,5,5,5-hexafluoroacetylacetonato) copper(ll), Cu(hfa)₂. The films were analyzed by x-ray diffraction (XRD), Rutherford backscattering (RBS), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), and energy-dispersive x-ray spectroscopy (EDXS). The results of these studies showed that the films were uniform, continuous, adherent and highly pure—oxygen and carbon contents were below the detection limits of AES. Four point resistivity measurements showed that the copper films had very low resistivity, as low as 1.9 μΩcm for the films deposited in pure hydrogen atmosphere. Our preliminary results seem to indicate that LTMOCVD is a very attractive technique for copper multilevel metallizations.     

Low-Temperature Synthesis of High-Adhesion Cu(Mg) Alloy Films on Glass Substrates

Cu(0.5 at.%Mg) alloy films were deposited on glass substrates, and annealed at 200–400 °C in vacuum. The resistivity of the Cu(Mg) films was reduced to about 3.0 μΩcm after annealing at 200 °C for 30 min, and the tensile strength of adhesion of the Cu(Mg) films to the glass substrates was increased to 30–40 and 35–55 MPa after annealing at 250 and 300 °C, respectively. The reduction in resistivity can be explained as reduced impurity scattering and grain-boundary scattering, since Mg segregation to the film surface and Cu(Mg)/glass interface, and consequent Cu grain growth, were observed. Increased adhesion of the Cu(Mg) films to glass substrates after annealing was also explained by the strong segregation of Mg atoms, and the formation of a reaction layer at the interface. Mg atoms were observed to have reacted with the glass substrates and formed a thin crystalline MgO layer at the interface in the samples annealed at 300 °C, while Mg atoms were highly concentrated above the Cu(Mg)/glass interface without oxide formation at the interface in the samples annealed at 250 °C. Thus, the process temperature and time to obtain low-resistivity and high-adhesion Cu alloy films on glass substrates could be reduced to 250 °C and 30 min using Cu(Mg) films.     

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.     

Microstructure and properties of multilayer-derived tungsten silicide

In metallization, peeling and oxidation of tungsten silicide are the most serious problems of tungsten rich silicide. In this study, multilayer-derived silicon rich tungsten silicide with the silicon film on the outermost surface is investigated to avoid these problems. The dependence of sheet resistance on the annealing conditions is studied. X-ray diffraction results indicate that silicide formation is nearly completed after 30 min annealing at 750° C. Microstructures of silicide and polycides are investigated by electron microscopy. Silicide deposited on SiO₂ has smaller grains that deposited on poly-Si. A resistivity of 60 μΩ-cm is obtained for multilayer-derived WSi_2.3.     

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.     

Thermal stability of Cu(W) and Cu(Mo) films for advanced barrierless Cu metallization: Effects of annealing time

The current study investigates the effects of insoluble substances (W and Mo) in pure Cu films on the thermal stability, microstructure, and electrical properties of the films. The results can be used to assess the feasibility of the barrierless Cu film in the metallization process. The films investigated were deposited using magnetron sputtering onto the barrierless Si (100) substrate and then annealed between 400°C and 450°C in vacuum for long periods of time. After annealing, the film properties were examined by x-ray diffraction (XRD), the four-point probe method, leakage current measurements, and focused ion beam (FIB) analysis. The results indicate that no detectable copper silicide is formed after 48-h annealing of Cu(W) films at 400°C. In contrast, for the Cu(Mo) film, copper silicide is formed after 18-h annealing at the same temperature and hence electrical properties are poor. This evidence suggests that the Cu(W) film has better thermal stability during long periods of annealing and is suitable for an advanced barrierless metallization process.