Ultrathin Mo/MoN bilayer nanostructure for diffusion barrier application of advanced Cu metallization

Ultrathin Mo (5 nm)/MoN (5 nm) bilayer nanostructure has been studied as a diffusion barrier for Cu metallization. The Mo/MoN bilayer was prepared by magnetron sputtering and the thermal stability of this barrier is investigated after annealing the Cu/barrier/Si film stack at different temperatures in vacuum for 10 min. The failure of barrier structure is indicated by the abrupt increase in sheet resistance and the formation of Cu₃Si phase proved by X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS). High resolution transmission electron microscopy (HRTEM) examination suggested that the ultrathin Mo/MoN barrier is stable and can prevent the diffusion of Cu at least up to 600 °C.     

Low temperature deposited Zr-B film applicable to extremely thin barrier for copper interconnect

We have prepared thin Zr-B films at low temperatures as a new material applicable to an extremely thin barrier against Cu diffusion in Si-ULSI metallization. The obtained Zr-B films mainly consist of the ZrB₂ phase with a nanocrystalline texture on SiO₂ and a fiber texture on Cu. The resistivity of the Zr-B films depends on the substrate of SiO₂ or Cu. The constituent ratio of B/Zr is almost 2, though the contaminants of oxygen, nitrogen, and carbon are incorporated in the film. The nanocrystalline structure of the Zr-B film on SiO₂ is stable due to annealing at temperatures up to 500 °C for 30 min. We applied the 3-nm thick Zr-B film to a diffusion barrier between Cu and SiO₂, and the stable barrier properties were confirmed. We can demonstrate that the thin Zr-B film is a promising candidate for thin film application to a metallization material in Si-ULSIs.     

Ultrathin amorphous Ti–Al film used as a diffusion barrier for copper metallization

The viability of ultrathin amorphous Ti–Al film (～4 nm) as a diffusion barrier layer between Cu and Si for the application in Si-based ultra-large scale integration (ULSI) has been investigated. The Cu/Ti–Al/Si heterostructures are annealed in a high vacuum at various temperatures. There is no impurity peaks in the X-ray diffraction patterns for the samples up to annealing temperature of 800 ^°C, although the island-like grains were observed on the surface of the 800 ^°C annealed sample due to dewetting and agglomeration of the Cu film. No inter-reactions can be found from the images of transmission electron microscopy and Ti–Al is still amorphous after high-temperature annealing. These results indicate that Ti–Al film can effectively separate Cu from Si at high temperatures, and that the amorphous ultrathin Ti–Al film can be a very good barrier layer for Cu metallization.     

Copper diffusion in Ti-Si-N layers formed by inductively coupled plasma implantation

Ternary Ti-Si-N refractory barrier films of 15 nm thick was prepared by low frequency, high density, inductively coupled plasma implantation of N into Ti_xSi_y substrate. This leads to the formation of Ti-N and Si-N compounds in the ternary film. Diffusion of copper in the barrier layer after annealing treatment at various temperatures was investigated using time-of-flight secondary ion mass spectrometer (ToF-SIMS) depth profiling, X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) and sheet resistance measurement. The current study found that barrier failure did not occur until 650 °C annealing for 30 min. The failure occurs by the diffusion of copper into the Ti-Si-N film to form Cu-Ti and Cu-N compounds. FESEM surface morphology and EDX show that copper compounds were formed on the ridge areas of the Ti-Si-N film. The sheet resistance verifies the diffusion of Cu into the Ti-Si-N film; there is a sudden drop in the resistance with Cu compound formation. This finding provides a simple and effective method of monitoring Cu diffusion in TiN-based diffusion barriers.     

Atom beam sputtered Mo2C films as a diffusion barrier for copper metallization

The saddle field fast atom beam sputtered (ABS) 50 nm thick molybdenum carbide (Mo₂C) films as a diffusion barrier for copper metallization were investigated. To study the diffusion barrier properties of Mo₂C films, the as-deposited and annealed samples were characterized using four probes, X-ray diffraction, field enhanced scanning electron microscopy, energy dispersive X-ray analysis, atomic force microscopy and Rutherford back scattering techniques. The amorphous structure of the barrier films along with presence of carbon atoms at the molybdenum carbide-silicon interface is understood to reduce effective grain boundaries and responsible for increased thermal stability of Cu/Mo₂C/Si structure. The lowest resistivity of the as-deposited molybdenum carbide barrier films was ∼29 μΩ cm. The low carbon containing molybdenum carbide was found thermally stable up to 700 °C, therefore can potentially be used as a diffusion barrier for copper metallization.     

Phosphorous doped Ru film for advanced Cu diffusion barriers

Copper diffusion barrier properties of phosphorous doped Ru film are studied. Phosphorous out-diffusion to Ru from underneath phosphosilicate glass (PSG) layer results in P doped Ru film. The doped Ru film improves copper barrier properties and has excellent thermal stability. XRD graph indicates that there is no copper silicide and ruthenium silicide formations after annealing at 550 °C for 30 min in vacuum. This result is consistant with AES depth profiles which show no Cu, Ru, O and Si inter-diffusion. The phosphorous doped Ru barrier also blocks oxygen's diffusion to copper from the PSG layer. The phosphorous doped Ru film could be an alternative Cu diffusion barrier for advanced Cu interconnects.     

The film thickness dependent thermal stability of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>:Ag thin films as high-temperature solar selective absorbers

The monolayer Al₂O₃:Ag thin films were prepared by magnetron sputtering. The microstructure and optical properties of thin film after annealing at 700 °C in air were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and spectrophotometer. It revealed that the particle shape, size, and distribution across the film were greatly changed before and after annealing. The surface plasmon resonance absorption and thermal stability of the film were found to be strongly dependent on the film thickness, which was believed to be associated with the evolution process of particle diffusion, agglomeration, and evaporation during annealing at high temperature. When the film thickness was smaller than 90 nm, the film SPR absorption can be attenuated until extinct with increasing annealing time due to the evaporation of Ag particles. While the film thickness was larger than 120 nm, the absorption can keep constant even after annealing for 64 h due to the agglomeration of Ag particles. On the base of film thickness results, the multilayer Al₂O₃:Ag solar selective thin films were prepared and the thermal stability test illustrated that the solar selectivity of multilayer films with absorbing layer thickness larger than 120 nm did not degrade after annealing at 500 °C for 70 h in air. It can be concluded that film thickness is an important factor to control the thermal stability of Al₂O₃:Ag thin films as high-temperature solar selective absorbers.     

A new TiW seed layer for SmCo5 films with perpendicular magnetic anisotropy

A new seed layer TiW is proposed for SmCo₅ films with perpendicular magnetic anisotropy. The influence of a TiW seed layer on the microstructure and the surface morphology of Cu underlayer are studied. The grain size and surface roughness dependence of Cu underlayer on the thickness and the annealing of the TiW seed layer are also investigated. The improvement in the perpendicular magnetic properties of SmCo₅ film from the TiW seed layer is approved. The results show that a 5 nm Ti₃W₇ seed layer improves the microstructure and surface morphology of Cu underlayer, and significantly improves the perpendicular magnetic properties of SmCo₅ film. The diffusion barrier and a high melting point of the TiW seed layer are regarded as the physical mechanism of the improvement for SmCo₅ film with perpendicular magnetic anisotropy.     

Evaluation of the barrier capability of Zr-Si films with different substrate temperature for Cu metallization

Barrier capability of Zr-Si diffusion barriers in Cu metallization has been investigated. Amorphous Zr-Si diffusion barriers were deposited on the Si substrates by RF reactive magnetron sputtering under various substrate temperatures. An increase in substrate temperature results in a slightly decreased deposition rate together with an increase in mass density. An increase in substrate temperature also results in grain growth as deduced from field emission scanning electron microscopy (FE-SEM) micrographs. X-ray diffraction (XRD) spectra and Auger electron spectroscopy (AES) depth profiles for Cu/Zr-Si(RT)/Si and Cu/Zr-Si(300 °C)/Si samples subjected to anneal at various temperatures show that the thermal stability was strongly correlated with the deposition temperature (consequently different density and chemical composition etc.) of the Zr-Si barrier layers. ZrSi(300 °C) with higher mass density make the Cu/Zr-Si(300 °C)/Si sample more stable. The appearance of Cu₃Si in the Cu/Zr-Si/Si sample is attributed to the failure mechanism which may be associated with the diffusion of Cu and Si via the grain boundaries of the Zr-Si barriers.     

Diffusion barrier performance of TiVCr alloy film in Cu metallization

In this study, 15 nm-thick sputter-deposited TiVCr alloy thin films were developed as diffusion barrier layers for Cu interconnects. The TiVCr alloy film tends to form a solid solution and a simple crystal structure from the constituted elements. Under TEM, the 15 nm-thick as-deposited TiVCr alloy film was observed to have a dense semi-amorphous or nanocrystalline structure. In conjunction with X-ray diffraction, transmission electron microscopy, and energy-dispersive spectroscopy analyses, the Si/TiVCr/Cu film stack remained stable at a high temperature of 700 °C for 30 min. The electrical resistance of Si/TiVCr/Cu film stack remained as low as the as-deposited value. These indicated that the mixed TiVCr refractory elements’ alloy barrier layer is very beneficial to prevent Cu diffusion.     

Thermal stability of thin amorphous Ta-Si-N films used in Au/GaN metallization

Ta-Si-N ternary barrier films were obtained by reactive rf magnetron sputtering of a Ta₅Si₃ target in an Ar-N₂ gas discharge. The films were tested as diffusion barriers between Au and GaN layers. The efficiency of these films as diffusion-suppressing barriers is determined by transmission electron microscopy, secondary-ion mass spectroscopy, and X-ray diffraction analysis. It is shown that the diffusion barrier with optimized properties (Ta₃₄Si₂₅N₄₁) in an Au/GaN metallization system can be used to advantage at temperatures above 800°C. A correlation between the composition, microstructure, resistivity, thermal stability, and diffusion-suppressing properties of the films is discussed.     

Influence of oxygen on diffusion in the Cu/Mo/Au system

The annealing behaviour of the Cu/Mo/Au metallization system is investigated. Backscattering spectrometry reveals a rapid diffusion of Cu and Au across the Mo film and the formation of AuCu after annealing at 600°C for 30 min in vacuum, but only when no impurity is detected in the as-deposited polycrystalline Mo layer. The Au-Cu interaction is impeded when 5.5 at% of oxygen is introduced in the as-deposited Mo layer. The thin film microstructures are analyzed using X-ray diffraction and transmission electron microscopy. The thermal stability difference between the samples with a pure Mo layer and a contaminated Mo layer is discussed in terms of fast diffusion process inhibited by a grain boundary decoration with oxygen atoms.     

Highly stable carbon-doped Cu films on barrierless Si

Electrical resistivities and thermal stabilities of carbon-doped Cu films on silicon have been investigated. The films were prepared by magnetron sputtering using a Cu-C alloy target. After annealing at 400 °C for 1 h, the resistivity maintains a low level at 2.7 μΩ-cm and no Cu-Si reaction is detected in the film by X-ray diffraction (XRD) and transmission electron microscopy (TEM) observations. According to the secondary ion mass spectroscopy (SIMS) results, carbon is enriched near the interfacial region of Cu(C)/Si, and is considered responsible for the growth of an amorphous Cu(C)/Si interlayer that inhibits the Cu-Si inter-diffusion. Fine Cu grains, less than 100 nm, were present in the Cu(C) films after long-term and high-temperature annealings. The effect of C shows a combination of forming a self-passivated interface barrier layer and maintaining a fine-grained structure of Cu. A low current leakage measured on this Cu(C) film also provides further evidence for the carbon-induced diffusion barrier interlayer performance.     

Properties of reactively sputtered W–B–N thin film as a diffusion barrier for Cu metallization on Si

Thin films of W–B–N (10 nm) have been evaluated as diffusion barriers for Cu interconnects. The amorphous W–B–N thin films were prepared at room temperature via reactive magnetron sputtering using a W₂B target at various N₂/(Ar + N₂) flow ratios. Cu diffusion tests were performed after in-situ deposition of 200 nm Cu. Thermal annealing of the barrier stacks was carried out in vacuum at elevated temperatures for one hour. X-ray diffraction patterns, sheet resistance measurement, cross-section transmission electron microscopy images, and energy-dispersive spectrometer scans on the samples annealed at 500°C revealed no Cu diffusion through the barrier. The results indicate that amorphous W–B–N is a promising low resistivity diffusion barrier material for copper interconnects.     

High performance of thin nano-crystalline ZrN diffusion barriers in Cu/Si contact systems

A thermally stable thin diffusion barrier in Cu/Si contacts was developed using a thin nano-crystalline ZrN film. The Cu/ZrN/Si contact system using a reactively sputtered ZrN barrier with 20 nm in thickness consisting of several to 10 nm grains tolerated annealing at 600 °C for 1 h without any Cu penetration through the barrier. This was interpreted that the scarce structural change in the prepared nano-crystalline ZrN film due to annealing was favorite for the thermal stability of thin barrier application.     

Effect of tin-doped indium oxide film as capping layer on the agglomeration of copper film and the appearance of copper silicide

In this work, the effect of tin-doped indium oxide (ITO) film as capping layer on the agglomeration of copper film and the appearance of copper silicide was studied. Both samples of Cu 100 nm/ITO 10 nm/Si and ITO 20 nm/Cu 100 nm/ITO 10 nm/Si were prepared by sputtering deposition. After annealing in a rapid thermal annealing (RTA) furnace at various temperatures for 5 min in vacuum, the samples were characterized by four probe measurement for sheet resistance, X-ray diffraction (XRD) analysis for phase identification, scanning electron microscopy (SEM) for surface morphology and transmission electron microscopy (TEM) for microstructure.The results show that the sample with ITO capping layer is a good diffusion barrier between copper and silicon at least up to 750 °C, which is 100 °C higher than that of the sample without ITO capping layer. The failure temperature of the sample with ITO capping layer is about 800 °C, which is 100 °C higher than that of the sample without ITO capping layer. The ITO capping layer on Cu/ITO/Si can obstacle the agglomeration of copper film and the appearance of Cu₃Si phase.     

Ti薄膜与AlN陶瓷的界面反应

用X射线衍射分析、二次离子质谱、卢瑟福背散射谱、俄歇电子能谱等表面分析技术，研究了Ti膜与AlN陶瓷衬底的界面固相反应-在高真空中用电子束蒸发的方法在抛光的200℃ AlN陶瓷衬底上淀积200nm的Ti膜，并在真空恒温炉中退火-实验表明，退火中Ti膜与AlN界面发生了扩散与反应-650℃，1h退火已观测到明显的界面反应-界面反应产物主要是钛铝化物及Ti-N化合物-铝化物是Ti-Al二元化合物和Ti-Al-N三元化合物，850℃，4h退火后则主要由Ti₂AlN组成- 关键词：     

Fabrication of quantum wires by selective intermixing induced in GaAs/AlGaAs quantum well heterostructures by SiO2 capping and subsequent annealing

Results are presented demonstrating that selective intermixing of GaAs/AlGaAs quantum well heterostructures by SiO₂ capping and subsequent annealing can be spatially localized with a length scale compatible with the observation of lateral quantum confinement effects. Patterning of a 400 nm-thick SiO₂ encapsulation layer deposited by rapid thermal chemical vapor deposition into arrays of wires was performed using high resolution electron beam lithography and subsequent reactive ion etching. After high temperature (850°C) annealing, photoluminescence experiments indicate the creation of double barrier quantum wires when small trenches (< 100 nm) are etched in the SiO₂ film at a period greater than 800 nm. Signatures of the formation of one-dimensional subbands are observed both in photoluminescence excitation spectroscopy and linear polarization anisotropy analysis. A mechanism involving the ability of the stress field generated during annealing at the SiO₂ film edges to pilot the diffusion of the excess gallium vacancies which are responsible for the enhanced interdiffusion under SiO₂ is suggested to account for the high lateral selectivity achievable with this novel process.     

Influence of alkali metallization (Li, Na and K) on photoluminescence properties of porous silicon

We present results for alkali metallization effects on photoluminescence (PL) properties of porous silicon (PS). The metallization of PS was realized by immersion plating in solutions containing 3 mM LiNO₃, KNO₃ and NaNO₃ metal salts. The surface bond configuration of PS was monitored by Fourier transmission infrared spectroscopy (FTIR) and it was found that the PS surface was oxidized after metallization. Surface properties of PS were investigated by field emission scanning electron microscopy (FE-SEM) and it was found that the PS surface was covered by alkali metals for short immersion times. The PL intensity increased for critical immersion times and PL spectrum shifted to high energy region with the metallization. The experimental results suggest a possibility that the metallization provides a relatively easy way to achieve an increase in the PL intensity and oxidation of the PS surface.     

Thermal stability of W2B and W2B5 contacts on ZnO

Rectifying contact formation on n-type bulk single crystal ZnO using novel W₂B or W₂B₅ metallization schemes was studied using current-voltage, scanning electron microscopy and Auger electron spectroscopy (AES) measurements. When a single Au overlayer was used to reduce the metal sheet resistance, the contacts were ohmic for all annealing conditions due to outdiffusion of Zn through the metal. By sharp contrast, when a bilayer of Pt/Au was used on top of the boride layers, rectifying contacts with barrier heights of ∼0.4 eV for W₂B were obtained. The highest barrier height of 0.66 eV was achieved for W₂B₅ annealed at 600 °C, although at this condition the contact showed a reacted appearance and AES showed almost complete intermixing of the metallization.