Preparation of Pt-PtOx thin films as electrode for memory capacitors

Pt-PtO_x thin films were prepared on Si(100) substrates at temperatures from 30 to 700°C by reactive r.f. magnetron sputtering with platinum target. Deposition atmosphere was varied with O₂/Ar flow ratio. The deposited films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. Resistively of the deposited films was measured by d.c. four probe method. The films mainly consisted of amorphous PtO and Pt₃O₄ (or Pt₂O₃) below 400°C, and amorphous Pt was increased in the film as a deposition temperature increased to 600°C. When deposition temperature was thoroughly increased, (111) oriented pure Pt films were formed at 700°C. Compounds included in the films strongly depended on substrate temperature rather than O₂/Ar flow ratio. Electrical resistivity of Pt-PtO_x films was measured to be from the order of 10⁻¹ Ω cm to 10⁻⁵ Ω cm, which was related to the amount of Pt phase included in the deposited films.     

The evolution of a-GaAs1−xNx/c-GaAs interface states as a function of Ar-NH3 plasma

This work concerns investigations on electrical properties of amorphous GaAs_1−xN_x thin films grown on GaAs substrates. Film deposition was carried out by RF sputtering of a GaAs target by adding a nitrogen carrier gas (NH₃) to an Ar plasma. Chemical etching of substrates followed by different plasma treatments (like reverse bias and/or NH₃ glow discharge) prior to film deposition have been studied. The effects of substrate and growth temperature and of total pressure in the reactor have been analysed. Electrical characteristics (C–V and C–V(T)) have enabled us to put in evidence the evolution of interface states of the a-GaAs_1−xN_x/c-GaAs junctions. The amorphous GaAs_1−xN_x thin films are potentially interesting to be considered for GaAs-based MIS structures, due to their relatively high resistivity values, or as passivating layers on GaAs devices.     

Diffusion barrier properties of sputtered TaNx between Cu and Si using TaN as the target

TaN_x films sputtered from a TaN target were used as diffusion barriers between Cu thin films and Si substrates. Material characteristics of TaN_x films and metallurgical reactions of Cu/TaN_x/Si systems annealed in the temperature range 400–900 °C for 60 min were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, cross-sectional transmission electron microscopy, and sheet resistance measurements. We found that the deposition rate decreased with increasing bias. TaN, β-Ta, and Ta₂N phases appeared and/or coexisted in the films at specific biases. A step change in N/Ta ratio was observed whenever a bias was applied to the substrate. After depositing a copper overlayer, we observed that the variation percentage of sheet resistance for Cu (70 nm)/TaN_x (25 nm, x=0.37 and 0.81)/Si systems stayed at a constant value after annealing up to 700 °C for 60 min; however, the sheet resistance increased dramatically after annealing above 700 and 800 °C for Cu/TaN_0.37/Si and Cu/TaN_0.81/Si systems, respectively. At that point, the interface was seriously deteriorated and formation of Cu₃Si was also observed.     

Analysis of interface states and series resistance at MIS structure irradiated under Co γ-rays

In this research, we investigated the effect of ⁶⁰Co γ-ray exposure on the electrical properties of Au/SnO₂/n-Si (MIS) structures using current–voltage (I–V) measurements. The fabricated devices were exposed to γ-ray doses ranging from 0 to 300 kGy at a dose rate of 2.12 kGy h⁻¹ in water at room temperature. The density of interface states N_ss as a function of E_c–E_ss is deduced from the forward bias I–V data for each dose by taking into account the bias dependence effective barrier height and series resistance of device at room temperature. Experimental results show that the γ-irradiation gives rise to an increase in the zero bias barrier height Φ_BO, as the ideality factor n and N_ss decrease with increasing radiation dose. In addition, the values of series resistance were determined using Cheung's method. The R_s increases with increasing radiation dose. The results show that the main effect of the radiation is the generation of interface states with energy level within the forbidden band gap at the insulator/semiconductor interface.     

Investigations of diffusion kinetics in Si/Ta/Cu/W and Si/Co/Ta systems by secondary neutral mass spectrometry

Proper understanding of the degradation mechanisms and diffusion kinetics of copper and cobalt interconnections for advanced microelectronics is important from the point of view of fundamental research and technology as well. In this paper Si(substrate)/Ta(10 nm)/Cu(25 nm)/W(10 nm) and Si(substrate)/Co(150 nm)/Ta(10 nm) samples, prepared by DC magnetron sputtering, were in investigated. The samples were annealed at several temperatures ranging from 423 K to 823 K for various times. The composition distributions were detected by means of Secondary Neutral Mass Spectrometry (SNMS). Microstructural characterization of samples was carried out by means of Transmission Electron Microscopy (TEM). It is shown that the changes in the composition profiles were mainly caused by grain boundary, GB, diffusion and the effective GB diffusion coefficients of Ta in Cu were determined both by the “first appearance” and “centre-gradient” methods. The activation energy is 100 kJ/mol. The importance of the Ta penetration into the Cu and its accumulation at the Cu/W interface can lead to an increase of the Ta content in the copper film. This can be an important factor in the change/degradation of the physical parameters (e.g. the electrical resistance) of interconnects. Furthermore a Ta segregation factor in Cu was evaluated. Preliminary results in the Si(substrate)/Co(150 nm)/Ta(10 nm) indicate fast (GB) diffusion of the Si into the Co layer, formation of a cobalt silicide layer at the Co/Si interface and Si accumulation first at the Ta/Co interface and later a retarded accumulation at the free Ta surface.     

Investigations of diffusion kinetics in Si/Ta/Cu/W and Si/Co/Ta systems by secondary neutral mass spectrometry

Proper understanding of the degradation mechanisms and diffusion kinetics of copper and cobalt interconnections for advanced microelectronics is important from the point of view of fundamental research and technology as well. In this paper Si(substrate)/Ta(10 nm)/Cu(25 nm)/W(10 nm) and Si(substrate)/Co(150 nm)/Ta(10 nm) samples, prepared by DC magnetron sputtering, were in investigated. The samples were annealed at several temperatures ranging from 423 K to 823 K for various times. The composition distributions were detected by means of Secondary Neutral Mass Spectrometry (SNMS). Microstructural characterization of samples was carried out by means of Transmission Electron Microscopy (TEM). It is shown that the changes in the composition profiles were mainly caused by grain boundary, GB, diffusion and the effective GB diffusion coefficients of Ta in Cu were determined both by the “first appearance” and “centre-gradient” methods. The activation energy is 100 kJ/mol. The importance of the Ta penetration into the Cu and its accumulation at the Cu/W interface can lead to an increase of the Ta content in the copper film. This can be an important factor in the change/degradation of the physical parameters (e.g. the electrical resistance) of interconnects. Furthermore a Ta segregation factor in Cu was evaluated. Preliminary results in the Si(substrate)/Co(150 nm)/Ta(10 nm) indicate fast (GB) diffusion of the Si into the Co layer, formation of a cobalt silicide layer at the Co/Si interface and Si accumulation first at the Ta/Co interface and later a retarded accumulation at the free Ta surface.     

(Fe,Ti) 16N2 films with high saturation magnetization prepared by facing target sputtering

(Fe,Ti)-N films with a Ti concentration of 10 at.% were prepared on Si(100) and NaCl substrates by facing targets sputtering. The effects of the nitrogen pressure (P_N) and the substrate temperature (T_s) on the formation of various (Fe,Ti)-N phases and their microstructures were investigated in detail. X-ray diffractometer and transmission electron microscope provided complete identification of the phases present in the films and the characterization of their microstructures. Films deposited at a lower P_N = 1 3 × 10⁻² Pa or a lower T_s = RT consist of mainly -phase. Films deposited at a higher P_N = 1.3 2 × 10⁻¹ Pa or a higher T_s = 200 °C contain a great many γ' and Fe₂N phases with a higher nitrogen content. When P_N = 4 7 × 10⁻² Pa and T_s = 100 150 °C, it is advantageous to the formation of ′' phase. These films exhibit a high saturation magnetization (M_s) up to the range of 2.3 2.5 T, which is larger than that of pure iron.     

Investigations of failure mechanisms at Ta and TaO diffusion barriers by secondary neutral mass spectrometry

One of the most important processes in Cu metallization for highly integrated circuits is to fabricate reliable diffusion barriers. Recently, thin films made of refractory metals and their compounds have been widely used in solid-state electronics as barriers because of their good electric properties, favourable thermal properties and chemical stability. Thermal stability of Tantalum (Ta) and Tantalum-oxide (TaO_x) layers as a diffusion barrier in Si/Ta/Cu, Si/TaO_x/Cu and Si/Ta-TaO_x/Cu systems have been investigated. Si/Ta (10 nm)/Cu (25 nm)/W (10 nm), Si/TaO_x (10 nm)/Cu (25 nm)/W (10 nm) and Si/Ta (5 nm)TaO_x (5 nm)/Cu (25 nm)/W (10 nm) thin layers were prepared by DC magnetron sputtering. A tungsten cap layer was applied to prevent the oxidation of the samples during the annealing process. The samples were annealed at various temperatures (473 K-973 K) in vacuum. Transmission Electron Microscopy, X-ray diffraction, X-Ray Photoelectron Spectroscopy and Secondary Neutral Mass Spectrometry were used to characterize the microstructure and diffusion properties of the thin films. Our results show that at the beginning phase of the degradation of the Si/Ta/Cu system Ta atoms migrate through the copper film to the W/Cu interface. In the Si/TaO_x/Cu system the crystallization of TaO and the diffusion of Si through the barrier determine the thermal stability. The Ta-TaO bilayer proved to be an excellent barrier layer between the Si and Cu films up to 1023 K. The observed outstanding performance of the combined film is explained by the continuous oxidation of Ta film in the TaO_x-Ta bilayer.     

Atomic-layer doping in Si by alternately supplied PH3 and SiH4

Atomic-layer doping of P in Si epitaxial growth by alternately supplied PH₃ and SiH₄ was investigated using ultraclean low-pressure chemical vapor deposition. Three atomic layers of P adsorbed on Si(100) are formed by PH₃ exposure at a partial pressure of 0.26 Pa at 450°C. By subsequent SiH₄ exposure at 220 Pa at 450°C, Si is epitaxially grown on the P-adsorbed surface. Furthermore, by 12-cycles of exposure to PH₃ at 300–450°C and SiH₄ at 450°C followed by 20-nm thick capping Si deposition, the multi-layer P-doped epitaxial Si films of average P concentrations of 10²¹ cm⁻³ are formed. The resistivity of the film is as low as 2.4×10⁻⁴ Ω cm. By annealing the sample at 550°C and above, it is found that the resistivity increases and the surface may become rough, which may be due to formation of SiP precipitates at 550°C and above. These results suggest that the epitaxial growth of very low-resistive Si is achieved only at a very low-temperature such as 450°C.     

Structural, chemical, and electrical characterisation of reactively sputtered WSx thin films

WS_x films were sputter-deposited on Si, SiO₂/Si, and glass substrates from a WS₂ target in an Ar/H₂S atmosphere. Their structure, morphology, chemical composition, and electrical properties were investigated as a function of deposition parameters such as working pressure and H₂S fraction. Films could be grown in the composition range WS_0.3−WS_3.5. Crystallisation was achieved at substrate temperatures T_s > 70 °C and compositions 0.7 ≤ x ≤ 1.95. While the first 5–50 nm near the interface exhibited a basal orientation (c), further growth resulted in the formation of edge-oriented platelets (c) giving rise to a porous, lamellar microstructure. The crystalline structure was mainly turbostratic, while some degree of ordered stacking was present in samples grown at high substrate temperature (600 °C). Resistivity measurements showed a semiconductor-type temperature dependence characterised by activation energies up to 95 meV. Sheet resistance was found to be nearly independent of film thickness, suggesting that the main carrier transport takes place in an interfacial layer of about 20 nm in thickness.     

Low-temperature epitaxial growth of conductive LaNiO3 thin films by RF magnetron sputtering

Epitaxial growth of LaNiO₃ (LNO) thin films was successful on CeO₂/YSZ/Si(100), MgO(100) and SrTiO₃ (STO)(100) substrates by RF magnetron sputtering at 300 °C, although pulsed laser deposition requires 600 °C to prepare epitaxial LNO films according to the literature. Epitaxial LNO films deposited on CeO₂/YSZ/Si(100) and STO(100) had single orientation of LNO[100]//CeO₂[110]//YSZ[110]//Si[110]) and LNO[100]//STO[100], respectively. On the other hand, epitaxial LNO films deposited on MgO(100) had mixed orientations of LNO[100]//MgO[100] and LNO[100]//MgO[110]. The lattice parameter, composition and resistivity of the LNO thin films were strongly dependent on the substrate temperature. The minimum resistivity of LNO films was approximately 5×10⁻⁶ Ω m, which value almost agrees with the resistivity in the literature. It was found that the temperature to achieve minimum resistivity was 200 °C, irrespective of the type of substrate. The surface of the LNO films was smooth and flat.     

Synthesis of AlN by reactive sputtering

We present a systematic study of the sub-band gap optical absorption coefficients (hν) in the range 1.2–6 eV vs. deposition-temperature (T_s from 27 to 450°C) films deposited on silica by 13.6 MHz magnetron sputtering of an Al target with 53 and 72% N₂ in the reactive mixture. X-ray diffraction, infrared absorption and Raman diffusion are also presented, mainly on films deposited on Si in the same run to help in the characterisation of the films. All signals are specific of AlN polycrystalline films, which are of better quality when deposited with 72% N₂. The lowest sub-band gap optical absorption around 5×10² cm⁻¹ is obtained for deposition on silica at T_s=300°C with 72% N₂ and is close to that of heteroepitaxial films deposited on sapphire.     

Thermally stable Pd/Sn and Pd/Sn/Au ohmic contacts to n-type GaAs

Thermal stability of novel Pd/Sn and Pd/Sn/Au Ohmic contacts to n-GaAs has been investigated and compared to the non-alloyed Pd/Ge and alloyed Au–Ge/Ni metallizations. Metallization samples are furnace annealed at various temperatures and systematically characterized utilizing Scanning Electron Microscopy (SEM) and current–voltage (I–V) measurements. Contact resistivities, ρ_c, of the proposed metallization are measured using a conventional Transmission Line Model (cTLM) method. The Pd/Sn Ohmic contacts display superior thermal stability at 410°C when compared to the Pd/Ge contacts. After annealing at 410°C for 4 h, ρ_c of the Pd(50 nm)/Sn(125 nm) metallization remains in the low 10⁻⁵ Ω cm² range, whereas ρ_c values increase to 10⁻⁴ Ω cm² for the Pd(50 nm)/Ge(126 nm) contacts. At 410°C, the Pd/Sn/Au metallizations also display better thermal stability than that of non-alloyed Pd/Ge and alloyed Au–Ge/Ni metallizations. The long-term stability at 300°C of the Pd/Sn and Pd/Sn/Au Ohmic contacts is also reported.     

Effect of Si target sputtering power on diffusion barrier properties of Ta–Si–N thin films

Abstract

Ta–Si–N thin films and Cu/Ta–Si–N thin films were deposited on p type Si(111) substrates by magnetron reactive sputtering. Then the films were characterised by four point probe sheet resistance measurement, AFM, SEM and XRD respectively. According to the XRD results, the authors found that the crystallisation of Ta nitrides in Ta–Si–N/Si thin films is suppressed effectively when fabricated by a high Si target sputtering power. As the Si target power varies, the failure temperature of Cu/Ta–Si–N/Si is changed. The sample fabricated by the Si target power of 200 W fails after 800°C rapid thermal annealing and it has the highest failure temperature. The investigation of failure mechanism shows that Cu atoms diffuse through grain boundaries or amorphous structure of the Ta–Si–N barrier, and react with Si to form Cu–Si phase. And it causes the failure of the barrier.     

Stresses in sputtered RUOx thin films

RuO_x thin films have been deposited by reactive sputtering in an O₂/Ar atmosphere. The films were characterized for their stress and resistivity as a function of deposition temperature (room temperature, 300°C) and the O₂ content (25–100%) in the sputtering gas. Additionally, the stresses in these films were determined as a function of annealing temperature (up to 600°C) using an in-situ curvature measurement technique. The as-deposited films were found to be under a state of compressive stress for all deposition conditions. The compressive stresses sharply increased with increasing deposition temperature from a value of around 200 MPa at 200°C to 1400 MPa at 300°C. This dramatic increase has been attributed to differences in microstructure at these deposition temperatures. The microstructural differences also led to the widely differing stress-temperature behavior during annealing of these films. For films deposited at temperatures lower than 200°C, the annealing process resulted in a decrease in the compressive stress and resistivity of the films. However, films deposited at a temperature of 300°C did not show any changes in the compressive stress or resistivity after annealing. The results of this study can be used to deposit RuO_x thin films with low resistivity and minimal stresses.     

用于Cu互连的Ta/Ti-Al集成薄膜的结构和阻挡性能

应用射频磁控溅射法在(001)Si衬底上制备了Cu(120nm)/Ta(5nm)/Ti-Al(5nm)/Si异质结,借助原子力显微镜(AFM)、X射线衍射(XRD)和四探针测试仪(FPP)等方法研究了Ta(5nm)/Ti-Al(5nm)集成薄膜用作Cu和Si之间阻挡层的结构和性能。研究发现,Cu/Ta/Ti-Al/Si异质结即使经受850℃高温退火后,样品的XRD图中也没有出现杂峰,表明样品各层之间没有发生明显的化学反应。相对于800℃退火的样品,850℃退火样品的表面均方根粗糙度急剧增大,同时方块电阻也增加了一个数量级,表明Ta(5nm)/Ti-Al(5nm)集成薄膜在850℃时,阻挡性能完全失效。由于Ta和Cu之间存在良好粘附性以及Ti-Al强的化学稳定性,Ta(5nm)/Ti-Al(5nm)集成薄膜在800℃以下具有良好的阻挡性能。     

Structural investigations of homoepitaxial Si films grown at low temperature by pulsed magnetron sputtering on Si(111) substrates

Using pulsed magnetron sputtering at low substrate temperature (T_s = 580 °C) the homoepitaxial growth on Si(111) was studied. The films were comprehensively characterized by cross-section transmission electron microscopy and various diffraction methods. Up to a film thickness of 1240 nm no breakdown of the epitaxial growth was observed. The surface microstructure, characterized by electron backscatter diffraction, exhibits exclusively crystalline structure with (111) orientation. Careful analysis of selected area electron diffraction patterns and high-resolution X-ray diffraction data clearly proves the existence of twinning/stacking faults in the {111} planes. Besides these defects – which are typical for low-temperature epitaxy – no additional significant defects related to the energetic particle bombardment by the sputter deposition method are observed.     

Phase formation at rapid thermal annealing of Al/Ti/Ni ohmic contacts on 4H-SiC

Ohmic contacts to the top p-type layers of 4H-SiC p⁺–n–n⁺ epitaxial structures having an acceptor concentration lower than 1×10¹⁹ cm⁻³ were fabricated by the rapid thermal anneal of multilayer Al/Ti/Pt/Ni metal composition. The rapid thermal anneal of multilayer A1/Ti/Pt/Ni metal composition led to the formation of duplex cermet composition containing Ni₂Si and TiC phases. The decomposition of the SiC under the contact was found to be down to a depth of about 100 nm. The contacts exhibited a contact resistivity R_c of 9×10⁻⁵ Ω cm⁻² at 21°C, decreasing to 3.1×10⁻⁵ Ω cm⁻² at 186°C. It was found that thermionic emission through the barrier having a height of 0.097 eV is the predominant current transport mechanism in the fabricated contacts.     

Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.     

Preparation of (Ti1−xAlx)N films from mixed alkoxide solutions by plasma CVD

(Ti_1−xAl_x)N films were prepared on a Si wafer at 700°C from toluene solution of alkoxides (titanium tetraetoxide and aluminum tri-butoxide) in an Ar/N₂/H₂ plasma by the thermal plasma chemical vapor deposition (CVD) method. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, electrical resistivity, and Vickers micro-hardness. Single phase TiN formed at an Al atomic fraction of 0–0.2, with a mixed TiN and AlN phase occurring up to 0.6 and single phase AlN forming above 0.8. The films had relatively sooth surfaces, 0.4 μm thick at an Al atomic fraction of 0.2, and thickened with increasing Al fraction. The atomic concentration of Ti, Al, N, O, and C determined from their respective XPS areas showed that the Ti and Al contents of the films changes with the solution composition in a complementary way. The impurities were about 10 at.% oxygen and carbon. The electrical resistivity was almost unchanged from the value of 10³ μΩ cm at 0–0.6 Al but then suddenly increased to 10⁴ μΩ cm at higher Al contents. The hardness showed a synergic maximum of about 20 GPa at an Al fraction of 0.6–0.8.