Effect of substrate temperature on the thermal stability of Cu/Zr-N/Si contact system

The effect of substrate temperature on the thermal stability of Cu/Zr-N/Si contact systems was investigated. Zr-N films were deposited on the Si substrates by RF reactive magnetron sputtering under various substrate temperatures. Cu films were in-situ sputtered onto the Zr-N films subsequently. The contact systems were characterized using four-point probe sheet resistance measurements (Rs), X-ray diffraction (XRD), and scanning electron microscopy (SEM) respectively. It was found that the sheet resistances of Cu/Zr-N (350 °C)/Si contact system were lower than those of Cu/Zr-N (150 °C)/Si specimens after annealing at 650 °C. Cu/Zr-N (350 °C)/Si contact systems showed better thermal stability so that the Cu₃Si phase could not be detected. It is indicated from the comparison analysis results that the Zr-N film showed better diffusion barrier performance deposited under higher substrate temperature.     

Comparative study of copper films prepared by ionized metal plasma sputtering and chemical vapor deposition in the Cu/TaN/SiO2/Si multilayer structure

This work investigated the properties of ionized metal plasma (IMP) deposited copper (Cu) and chemical vapor deposited (CVD) Cu on IMP-TaN (tantalum nitride) diffusion barrier in the Cu(200 nm)/TaN(30 nm)/SiO₂(250 nm)/Si multi-layer structure. The IMP-Cu film deposited on IMP-TaN had a preferred orientation (220) with a grain size of around 30 nm and roughness (RMS) of 1.391 nm, while the CVD-Cu had a (111) preferred orientation with a grain size around 170 nm and roughness (RMS) of 15.416 nm as determined by atomic force microscopy (AFM) and x-ray diffraction (XRD) analyses. Thermal stability study of the structures was also performed by sheet resistance measurements, scanning electron microscopy (SEM), XRD and Rutherford backscattering spectroscopy (RBS). These results revealed that IMP-Cu on IMP-TaN has higher thermal stability, less intermixing and/or agglomeration than CVD-Cu on IMP-TaN at the same annealing temperatures. The higher thermal stability of IMP-Cu than CVD-Cu can be accounted by their difference in microstructure. The failure mechanisms of IMP-Cu and CVD-Cu in multiplayer structure were also discussed.     

Effect of NiO and/or TiO2 mullite formation and microstructure from gels

Polymeric and colloidal gels with a constant molar ratio of (Al+Ni and/or Ti)/Si=3/1 and various (Al/Ni and/or Ti) ratios (up to 21.42 mol% NiO+TiO2) were prepared and used to study the effect of the precursor chemical homogeneity on mullite formation processes and the resulting microstructure. Both kinds of gel precursors were preheated at 750°C for 3 h in order to obtain appropriate gel-derived glasses for further thermal processing. After annealing for several time periods at temperatures between 750 and 1500°C, differences in crystallization pathways were observed. Polymeric gels crystallized Al–Si and NiAl2O4 spinels from the amorphous form at temperatures in the range between 900 and 1000°C, depending on the amount of aluminium substitution. Mullite formation was initiated at temperatures between 1100 and 1200°C, except for the higher substituted 3:2 mullite in which it was produced at 1000°C. In constrast, -Al2O3 and NiAl2O4 spinel were the first crystalline phases identified at 750°C in specimens from colloidal gels, whereas mullite was formed at temperatures higher than 1200°C. In specimens with high substitution, mullite was observed at lower temperatures. Although the sequences of reaction from either kind of gel were rather different, mainly at low temperatures (as could be inferred from the chemical homogeneity attained in both gel-derived glasses), the final set of crystalline phases after long annealing at 1400°C was quite similar. Differences in the microstructure of specimens from either type of gel precursor after annealing at 1400°C concerned the size of mullite particles and the presence of secondary phases in specimens derived from colloidal precursors. © 1998 Kluwer Academic Publishers     

Effect of thin Mo2C layer on thermal stability of Si/SiO2/Ti/Cu system

The effect of introducing a thin Mo₂C (30 nm) layer between Ti and Cu on the thermal stability of Si/SiO₂/Ti/Cu system was studied using four-point probe (FPP), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDAX) and X-ray diffraction (XRD) techniques. The measured value of the sheet resistance in the bi-layered diffusion barrier structure does not show any change up to an annealing temperature of 750??C. The sheet resistance when measured after annealing at 800??C marginally increases but less than twice its value at room temperature. The XRD analysis indicated no copper diffusion and the formation of Cu₃Si phase up to 800??C. The bi-layered barrier structure annealed at elevated temperature shows copper-depleted and agglomerated regions. The sheet resistance measurement, study of surface morphology and the XRD analysis confirm that the insertion of thin Mo₂C layer increases the thermal stability of the system from 400??C to 750??C. The increased thermal stability of the system is ascribed to longer diffusion path length in the bi-layered system probably because of grain boundaries mismatch at Ti-Mo₂C interface.     

Effect of annealing on the characteristics of Au/Cr bilayer films grown on glass

Au layers with thickness of about 110 nm were sputter-deposited on unheated glass substrates coated with a Cr layer about 20 nm thick. The chamber was evacuated to a pressure of 2 Pa and then sputtering was carried out at Ar pressure of 4 Pa. The Au/Cr bilayer films were annealed in a vacuum of 5×10⁻⁴ Pa at 170°C, 180°C, 200°C and 250°C for from 5 to 120 min, respectively. Atomic force microscopy was used to observe the structural characteristic of the bilayer films. Auger electron spectroscopy was used to analyze the composition inside the Au layers. The sheet resistance of the films was measured using the four-point probe technique. The grain size of the bilayer film gradually increases with an increase in annealing temperature while its average surface roughness ranging from 4.5 to 6.8 nm does not show any systematic change with annealing temperature and time. No impurities such as carbon, nitrogen and oxygen are detected inside all of the Au layers. When the annealing temperature reaches 200°C and the annealing time exceeds 30 min, chromium atoms markedly diffuse into the Au layer. Furthermore, for the bilayer films annealed at 250°C, chromium atoms have markedly diffused into the Au layer even for annealing time of 5 min. Regardless of the increase in grain size of the Au layer, the diffusion of chromium atoms into the Au layer causes an increase in the resistivity of the bilayer film.     

Self-forming AlOx layer as Cu diffusion barrier on porous low-k film

The copper diffusion barrier properties of an ultrathin self-forming AlO_x layer on a porous low-k film have been investigated. Cu-3 at.% Al alloy films were directly deposited onto porous low-k films by co-sputtering, followed by annealing at various temperatures. Transmission electron microscopy micrographs showed that a ∼ 5 nm layer self-formed at the interface after annealing. X-ray photoelectron spectroscopy analysis showed that this self-formed layer was Al₂O₃. Sharp declines of the Cu and Si concentrations at the interface indicated a lack of interdiffusion between Cu and the porous low-k film for annealing up to 600 °C for 30 min. The leakage currents from Cu(Al)/porous low-k/Si structures were similar to as-deposited films even after a 700 °C, 5 min anneal while a Cu sample without Al doping failed at lower temperatures. Adding small amounts of Al to bulk Cu is an effective way to self-form copper diffusion layer for advanced copper interconnects.     

Interaction of TiW film with GaAs

The interactions of co-evaporated Ti_0.3W_0.7 films with GaAs have been studied after annealing at temperatures in the range of 650 to 900° C for 15 min employing Rutherford backscattering, transmission and scanning electron microscopy. X-ray diffraction and energy-dispersive X-ray analysis techniques. Reaction has been found to take place at 650° C as evidenced by the presence of an AsTi compound in the region near the interface of TiW film and GaAs. Gallium diffuses out to the surface at temperatures above 750° C and causes surface morphological degradation, which can be related to the instability of the TiW Schottky barrier height at higher temperatures 750° C as reported in the literature.     

A Study of Ta-Si-N/Ti Bilayer Diffusion Barrier for Copper/Silicon Contact Systems

Ta-Si-N (10 nm)/Ti (20 nm) bilayer film has been designed with the purpose of using as diffusion barrier in copper interconnection. Ta-Si-N/Ti bilayer diffusion barriers were deposited on the substrate of n-type (100) silicon wafer using radio-frequency (RF) magnetron sputtering, followed by in situ deposition of copper. To investigate the thermal stability of the Ta-Si-N/Ti diffusion barriers, annealing was subsequently conducted in N₂ gas for 60 min and annealing temperatures were chosen at 600°C, 650°C, 700°C, 750°C, and 800°C. X-ray diffraction (XRD) revealed that Ta-Si-N layer grown on the Ti layer exhibited an amorphous phase. The results indicated that Ta-Si-N/Ti film can prevent copper diffusion at 750°C. After annealing at 750°C, the production of Ti-Si layer can effectively decrease contact resistance between barrier and silicon.     

Epitaxial growth of rhenium with sputtering

We have grown epitaxial Rhenium (Re) (0001) films on α-Al₂O₃ (0001) substrates using sputter deposition in an ultra high vacuum system. We find that better epitaxy is achieved with DC rather than with RF sputtering. With DC sputtering, epitaxy is obtained with the substrate temperatures above 700 °C and deposition rates below 0.1 nm/s. The epitaxial Re films are typically composed of terraced hexagonal islands with screw dislocations, and island size gets larger with high temperature post-deposition annealing. The growth starts in a three dimensional mode but transforms into two dimensional mode as the film gets thicker. With a thin (∼2 nm) seed layer deposited at room temperature and annealed at a high temperature, the initial three dimensional growth can be suppressed. This results in larger islands when a thick film is grown at 850 °C on the seed layer. We also find that when a room temperature deposited Re film is annealed to higher temperatures, epitaxial features start to show up above ∼600 °C, but the film tends to be disordered.     

Microstructural study of SnO2 thin layers deposited on sapphire by sol-gel dip-coating

Tin oxide (SnO₂) films have been grown onto (006) sapphire substrates by sol-gel dip-coating using tin alkoxide solutions. It is shown, using grazing-incidence X-ray diffraction, reciprocal space mapping and atomic force microscopy, that thermal annealing at 500 °C induces the crystallization of SnO₂ in the rutile-type phase. Further annealing treatments at temperatures lower than 1100 °C give rise to slow grain growth controlled by surface diffusion, whereas rapid grain growth (controlled by an evaporation-condensation mechanism) takes place at temperatures higher than 1100 °C. Concomitantly, the film splits into isolated islands and a fibre texture occurs at higher temperatures.     

Inkjet-printing of indium tin oxide (ITO) films for transparent conducting electrodes

Indium-tin-oxide (ITO) films have been prepared by inkjet-printing using ITO nanoparticle inks. The electrical and optical properties of the ITO films were investigated in order to understand the effects of annealing temperatures under microwave. The decrease in the sheet resistance and resistivity of the inkjet-printed ITO films was observed as the annealing temperature increases. The film annealed at 400 °C showed the sheet resistance of 517 Ω/sq with the film thickness of ∼580 nm. The optical transmittance of the films remained constant regardless of their annealing temperatures. In order to further reduce the sheet resistance of the films, Ag-grid was printed in between two layers of inkjet-printed ITO. With 3 mm Ag-grid line-to-line pitch, the Ag-grid inserted ITO film has the sheet resistance of 3.4 Ω/sq and the transmittance of 84% after annealing at 200 °C under microwave.     

Structural properties of indium tin oxide thin films prepared for application in solar cells

Indium tin oxide (ITO) thin films prepared by rf sputtering were annealed in several temperatures. The electrical, optical and structural properties of these films are systematically investigated. The post annealing of the samples lead to considerably higher electrical conductivity, better optical transparency and larger grain size for the films. In an optimum annealing temperature of 400 °C, we have found that a maximized conductivity of films is achieved without a remarkable loss in their transparency. The sheet resistance of 2.3 Ω/□ and average grain size of 30 nm, are the results of the optimized post processing of films. The investigation for microstructure of films investigated by X-ray diffraction measurement (XRD) shows that a preferential crystal growth toward the (2 2 2) orientation takes place when the annealing temperature increases to 400 °C.     

The effect of sputtering gas pressure on structure and photocatalytic properties of nanostructured titanium oxide self-cleaning thin film

Titanium oxide thin films were deposited by DC reactive magnetron sputtering on ZnO (80 nm thickness)/soda-lime glass and SiO₂ substrates at different gas pressures. The post annealing on the deposited films was performed at 400 °C in air atmosphere. The results of X-ray diffraction (XRD) showed that the films had anatase phase after annealing at 400 °C. The structure and morphology of deposited layers were evaluated by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The surface grain size and roughness of TiO₂ thin films after annealing were around 10-15 nm and 2-8 nm, respectively. The optical transmittance of the films was measured using ultraviolet-visible light (UV-vis) spectrophotometer and photocatalytic activities of the samples were evaluated by the degradation of Methylene Blue (MB) dye. Using ZnO thin film as buffer layer, the photocatalytic properties of TiO₂ films were improved.     

Thickness effect on grain growth and precipitate coarsening of a copper-silver thin film in an advanced metallization process

Annealing of Cu(Ag)/SiO₂/Si films was carried out to investigate the relationship between grain growth and precipitate coarsening. Ag in copper was selected as an immiscible dopant for diffusion and precipitation. Annealing effects were characterized in terms of resistivity, morphology, preferred orientation, grain growth, precipitation, and diffusional characteristics. The lowest observed resistivity was 2.06 cm in a 900 nm thick film annealed at 500 °C. The resistivity decrease was attributed to Ag precipitation and grain growth. A transition thickness exists at below 220 nm in the grain growth and the precipitate coarsening of the Cu(Ag) films. A relationship was established between grain growth and precipitate coarsening above the transition thickness that fits well to the experimental data. The grain size in the Cu(Ag) film can thus be predicted from the Ag precipitate size by using this relationship.     

Deposition of WNxCy thin films for diffusion barrier application using the dimethylhydrazido (2) tungsten complex (CH3CN)Cl4W(NNMe2)

Tungsten nitride carbide (WN_xC_y) thin films were deposited by chemical vapor deposition using the dimethylhydrazido (2⁻) tungsten complex (CH₃CN)Cl₄W(NNMe₂) (1) in benzonitrile with H₂ as a co-reactant in the temperature range 300 to 700 °C. Films were characterized using X-ray diffraction (XRD), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy and four-point probe to determine film crystallinity, composition, atomic bonding, and electrical resistivity, respectively. The lowest temperature at which growth was observed from 1 was 300 °C. For deposition between 300 and 650 °C, AES measurements indicated the presence of W, C, N, and O in the deposited film. The films deposited below 550 °C were amorphous, while those deposited at and above 550 °C were nano-crystalline (average grain size < 70 Å). The films exhibited their lowest resistivity of 840 µΩ-cm for deposition at 300 °C. WN_xC_y films were tested for diffusion barrier quality by sputter coating the film with Cu, annealing the Cu/WN_xC_y/Si stack in vacuum, and performing AES depth profile and XRD measurement to detect evidence of copper diffusion. Films deposited at 350 and 400 °C (50 and 60 nm thickness, respectively) were able to prevent bulk Cu transport after vacuum annealing at 500 °C for 30 min.     

Thermal stability of atomic layer deposited Ru layer on Si and TaN/Si for barrier application of Cu interconnection

The thermal stability of thin Ru single layer and Ru/TaN bilayers grown on bare Si by plasma enhanced atomic layer deposition (PEALD) have been studied with Cu/Ru, Cu/Ru/TaN structures as a function of annealing temperature. To investigate the characteristics as a copper diffusion barrier, a 50 nm thick Cu film was sputtered on Ru and Ru/TaN layers and each samples subjected to thermal annealing under N2 ambient with varied temperature 300, 400, and 500 degrees C, respectively. It was found that the single 5 nm thick ALD Ru layer acted as an effective Cu diffusion barrier up to 400 degrees C. On the other hand ALD Ru (5 nm)/TaN (3.2 nm) showed the improved diffusion barrier characteristics even though the annealing temperature increased up to 500 degrees C. Based on the experimental results, the failure mechanism of diffusion barrier would be related to the crystallization of amorphous Ru thin film as temperature raised which implies the crystallized Ru grain boundary served as the diffusion path of Cu atoms. The combination of ALD Ru incorporated with TaN layer would be a promising barrier structure in Cu metallization.     

Effect of thermal annealing on transparent conductive LaNiO3 thin film prepared by an aqueous method

Dense, crack-free and uniform lanthanum nickel oxide (LNO) thin films were prepared by an aqueous method on various substrates, such as single crystal silicon, microcrystalline glass ceramic (GC) and amorphous glass. The effects of various thermal annealing temperatures on the microstructure, interface and electrical properties of the LNO films were investigated by XRD and SEM with the EDX and a four-probe method, respectively. It was found that with the increase in thermal annealing temperature, the LNO film on Si substrates displayed a structure change from pseudocubic to rhombohedral and was accompanied by the appearance of a NiO impure phase, while the LNO film on a GC substrate diffused into the substrate. In these cases, the film resistivity was increased. As a result, a LNO thin film with a resistivity of 2–3 × 10^–5 · m was achieved by thermally annealing at 750–800°C for 1 hour in air. The measurement of the surface resistance under different temperatures shows that the LNO film possesses better high temperature stability. Its transmittance spectrum was also observed.     

Effect of phosphorus on the copper diffusion barrier properties of electroless CoWP films

The properties of electroless CoWP barrier films with different phosphorus contents in Cu/CoWP/Si stacked samples were explored. The Cu/CoWP/Si stacked samples with 30 nm CoWP films, contained about 5.7, 8.2 and 10.8 at.% P, were prepared by electroless deposition, and then annealed in a rapid thermal annealer at a temperature between 300 and 700 °C. The effect of phosphorus content in CoWP film on the barrier properties in preventing copper diffusion and the failure of the Cu/CoWP/Si stacked samples after thermal annealing were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectrometer (EDS), Auger electron spectroscopy (AES), and sheet resistance measurement. Increasing the phosphorus content in the electroless CoWP film markedly improves the barrier properties. The failure temperature of Cu/CoWP/Si increased from 500 to 600 °C with the phosphorus content in CoWP film increasing from 5.7 to 10.8 at.%, and the failure of the Cu/CoWP/Si has mainly arisen from the interdiffusion of copper and cobalt during thermal annealing.     

Thermal stability of Ti/Mo and Ti/MoN nanostructures for barrier applications in Cu interconnects

This work focuses on the barrier capabilities of sputter deposited Ti/Mo and Ti/MoN nanofilms against diffusion of Cu into Si substrates. The thermal stability of the corresponding bi-layer barrier structures is investigated after annealing Cu/barrier layer/Si samples at different temperatures in N(2) for 5?min. The drastic increase in sheet resistance of Cu and the probing of Cu(3)Si with x-ray diffraction after high temperature annealing indicate the failure of these barrier structures. The formation of Cu(3)Si at the barrier breakdown temperature is also confirmed by scanning electron microscopy and energy dispersive x-ray spectroscopy. Cu?diffusion barrier performance analyses show that a Ti(5?nm)/MoN(5?nm) bi-layer nanostructure fails only after annealing at 800?°C; on the other hand, a Ti(5?nm)/Mo(5?nm) barrier stack is found to break down at 700?°C.     

Effects of substrate temperature and post-deposition anneal on properties of evaporated cadmium telluride films

The effects of substrate temperature and post-deposition heat treatment steps on the morphology, structural, optical and electrical properties of thin film CdTe layers grown by vacuum evaporation were investigated. Scanning electron microscopy and X-ray diffraction (XRD) techniques were employed to study the structural changes. It was observed that the grain sizes and morphologies of as-deposited layers were similar for substrate temperatures of − 173 °C and − 73 °C. However, CdTe films produced at a substrate temperature of 27 °C had substantially larger grain size and clearly facetted morphology. Annealing at 200-400 °C in air did not cause any appreciable grain growth in any of the films irrespective of their growth temperature. However, annealing at 400 °C reduced faceting in all cases and initiated fusing between grains. XRD studies showed that this behavior after annealing at 400 °C coincided with an onset of a degree of randomization in the originally strong (111) texture of the as-grown layers. Optical band gap measurements showed sharpening of the band-edge upon annealing at 400 °C and a band gap value in the range of 1.46-1.49 eV. Resistivity measurements indicated that annealing at 400 °C in air forms a highly resistive compensated CdTe film. All results point to 400 °C to be a critical annealing temperature at which optical, structural and electrical properties of CdTe layers start to change.