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.     

In situ observations of the real-time stress-evolution and delamination of thin Ta films on Si(100)

Polycrystalline sputtered Ta coatings on Si(100) substrates were thermally tested for 1 h at 585 °C, while their stress evolution and eventual delamination were observed in situ and in real-time using a recently developed synchrotron X-ray white beam technique. Films deposited at ‘low’ (0.26-0.67 Pa), ‘intermediate’ (0.80-0.93 Pa), and ‘high’ (1.06-2.00 Pa) Ar pressures exhibited severe, moderate, and no blistering, respectively. These results were explained by the attendant stress data, which indicated the development of high, moderate, and low maximum compressive stress in the low, intermediate, and high-pressure coatings, respectively. Additionally, the structure of the films was probed before and after thermal testing using X-ray diffraction in both grazing incidence and θ−2θ scanning geometries. It was determined that all coatings made a complete conversion to orthorhombic Ta₂O₅ after the 1 h thermal test, regardless of their deposition pressure.     

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.     

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.     

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.     

Transmission electron microscope analysis of epitaxial growth processes in the sputtered β-FeSi2/Si(001) films

The crystallographic orientation relationships and the formation process of β-FeSi₂/Si(001) films were investigated by transmission electron microscopy. A film produced by sputtering pure iron onto a silicon substrate at 600 °C consists of α- and β-FeSi₂ particles. The crystallographic relationships obtained are: (112)_α‖(111)_Si and (101)_β‖(111)_Si or (110)_β‖(111)_Si. The grains of α- and β-FeSi₂ grown inside the substrate adopt the epitaxy to Si(111), irrespective of the surface orientation of the substrate. At 500 °C, on the contrary, there are few α-FeSi₂ grains and some grains of β-FeSi₂ with (100)_β‖(001)_Si [010]_β‖[110]_Si. These results demonstrate that the lower temperature and the higher Fe concentration suppress the formation of α-FeSi₂ and promote the formation of β-FeSi₂ on/below the substrate surface.     

Charge trapping during constant current stress in Hf-doped Ta2O5 films sputtered on nitrided Si

Metal-insulator-silicon structures containing Hf-doped Ta₂O₅ dielectric films sputtered on rapid thermally nitrided Si are shown to have very good reliability properties. Stress-induced leakage currents are low, both at low and at high-fields. It is found that charge trapping during the stress is the dominant wear-out mode for very long stress times of 500 s even for injected current densities J_s as high as 100 mA/cm². Stress curves approach saturation at long stress time, indicating that the trap generation rate is very low, even compared to the observed reduced trapping at pre-existing traps.Applying a trapping kinetics model, two trapping sites with characteristic trapping times τ₁ = 3.2 s and τ₂ = 49 s were determined and attributed to pre-existing defects in the bulk Hf:Ta₂O₅ layer and not in the interfacial SiO_xN_y layer. It was found that both τ₁ and τ₂ do not depend on J_s, which may be explained by the presence of a mechanism of charging the active sites through field activated emission of charge from them.     

Optical emission from LiNbO3(:Fe)/porous Si structures

Using pulsed laser deposition, a layer of LiNbO₃(:Fe) film with a thickness of 180 nm was coated onto porous Si (PS) stored in air for 1 year. A photoluminescence (PL) band enhanced about three times was observed at ∼625 nm with a same peak position as that of the stored PS. It is revealed that a new PL excitation band occurs at ∼363 nm, which is nearly equal to the fundamental optical absorption edge position of LiNbO₃. The X-ray diffraction results disclose that the enhancement of the PL intensity is closely related to formation of a textured LiNbO₃ film. Based on spectral analysis, we attribute the enhanced PL to optical transition in the E′ defect centers localized at the surfaces of PS nanocrystals, whereas the photoexcited carriers mainly come from the coated LiNbO₃ film. This kind of LiNbO₃(:Fe)/PS structures is expected to have important applications in modern ferroelectric optoelectronics.     

Cu(In,Ga)Se2 thin films and devices sputtered from a single target without additional selenization

Typically, Cu(In,Ga)Se₂ (CIGS) thin films for photovoltaic devices are deposited by co-evaporation or, alternately, by deposition of the metals with or followed by treatment in a selenium environment. In this article, we describe CIGS films that are instead deposited by RF magnetron sputtering from a single quaternary target without any additional selenization. Devices built with these films exhibit efficiencies as high as 8.9%. We demonstrate that deposition power can be varied in order to change the film morphology and improve device performance.     

Sputtering deposited ternary Zn1−xCdxO crystal films on Si(111) substrates

Using the d.c. reactive magnetron sputtering method we have successfully deposited completely (002)-oriented ternary Zn_1−xCd_xO (0≤x≤0.6) alloy crystal films without Cd segregation on Si(111) substrates. X-Ray photoelectron spectroscopy measurements show that Cd/Zn ratios in the films are nearly consistent with those in the targets. The Zn and Cd exist only in oxidized states, no evidence of metallic Zn or Cd was observed. The O/(Cd+Zn) atomic ratios of the films are in the range of 0.89-0.98. Transmission electron microscopy measurements show that for the (002)-oriented films the grains are columnar structures with the c-axis perpendicular to the Si substrate. By post-annealing treatments in O₂ ambient, the crystal quality of the Zn_1−xCd_xO films can be improved. For the sample of x=0.2, the optimal annealing temperature is 500 °C.     

Na effect on flexible Cu(In,Ga)Se2 photovoltaic cell depending on diffusion barriers (SiOx, i-ZnO) on stainless steel

Cu(In,Ga)Se₂ (CIGS) based-photovoltaic (PV) cells with different diffusion barriers of SiOx and i-ZnO were fabricated on stainless steel (STS) substrate and their electrical characteristics were investigated by measuring J–V curves under illuminated and dark conditions. The physical properties of the CIGS film depending on type of diffusion barrier were also analyzed using X-ray diffraction and secondary ion mass spectroscopy. The efficiency of the CIGS-PV cell with i-ZnO barrier was approximately 2% higher than that with the SiOx barrier. Through the analysis of dark J–V curves, we discovered that distinctive defects were formed in the band gap of CIGS based on which diffusion barrier contacted the STS. The diffraction pattern showed a slightly different tendency of the peak intensity ratio of (220/204)/(112) in the PV cell with the i-ZnO barrier, which was slightly higher than that in the PV cell with SiOx barrier. In elemental depth profile, a deficient Ga profile was observed near the surface of the CIGS film with the SiOx barrier, and an abundant Na profile within the CIGS film with the i-ZnO barrier was detected. This is attributed to a difference in thermal conduction through the diffusion barriers during CIGS film growth, originating from the larger thermal conductivity of ZnO compared with SiOx.     

Cu diffusion kinetics in (Cu, Ni)3Sn intermetallic compound nanolayers investigated by an Energy-Dispersive-X-ray-based permeation test

The Energy-Dispersive-X-ray-based permeation and oxidation test has been further developed by an improved theoretical analysis, in which chemical potential gradients rather than concentration gradients are employed. The developed test is able to characterize diffusion kinetics in diffusion barriers at the nanometer scale. The Cu flux coefficient in (Cu, Ni)₃Sn intermetallic compound nanolayers was determined from the test to be 8.48 × 10^− 15 mol·(m·s·J/mol)^–1 exp(− 52.3 kJ·mol^− 1/RT) in a temperature range of 250 °C–400 °C.     

Thin film interaction between low-k dielectric hydrogen silsesquioxane (HSQ) and Ti barrier layer

The interaction between low-k dielectric hydrogen silsesquioxane (HSQ) and Ti barrier layer has been studied using four-point-probe sheet resistance measurement, X-ray diffraction, conventional Rutherford backscattering spectrometry (RBS), nuclear resonance analysis (NRA), elastic recoil detection (ERD), secondary ion mass spectrometry (SIMS), Auger electron spectroscopy (AES) and thermal desorption spectroscopy (TDS). The conventional intermetal dielectrics SiO₂ and plasma-enhanced tetraethylorthosilicate (PETEOS) have been studied also for the purpose of comparison with HSQ. In the low temperature regime (300–550°C), a considerable amount of oxygen atoms, from various sources, diffuses into Ti film to form a Ti(O) solid solution, raising the resistivity of Ti significantly and causing the expansion of the Ti lattice. A good correlation between the oxygen composition in the Ti film, the sheet resistance variation of Ti and the change of Ti lattice parameter C₀ have been observed. At the same temperature, there are more oxygen atoms incorporated into the Ti film in Ti/HSQ than those for Ti/PETEOS, suggesting that additional HSQ-related oxygen sources, such as the moisture uptake and the conversion reaction of HSQ, may be attributed to this. In the high temperature regime (550–700°C), HSQ reacts with Ti to form a final TiO/Ti₅Si₃/HSQ stack structure. It is assumed that a few competing reactions occur in this regime. At 550–650°C, HSQ reacts directly with Ti; in the meantime, part of HSQ undergoes conversion reactions, with the reaction products SiO₂ and SiH₄ reacting with Ti to form Ti silicide. At 650–700°C, HSQ is almost completely converted into SiO₂, so the dominant mechanism is Ti reaction with SiO₂. Before HSQ is completely turned into SiO₂, the Ti/HSQ system is more reactive than both Ti/PETEOS and Ti/SiO₂. The initiating temperature for the Ti/HSQ reaction exhibits no obvious Ti thickness dependence.     

Electroless Ni-B plating on SiO2 with 3-aminopropyl-triethoxysilane as a barrier layer against Cu diffusion for through-Si via interconnections in a 3-dimensional multi-chip package

Electroless Ni-B was plated on SiO₂ as a barrier layer against Cu diffusion for through-Si via (TSV) interconnections in a 3-dimensional multi-chip package. The electroless Ni-B was deposited on the entire area of the SiO₂ side wall of a deep via with vapor phase pre-deposition of 3-aminopropyl-triethoxysilane on the SiO₂. The carrier lifetimes in the Si substrates plated with Ni-B/Cu did not decrease with an increase in annealing temperature up to 400 °C. The absence of degradation of carrier lifetimes indicates that Cu atoms did not diffuse into the Si through the Ni-B. The advantages of electroless Ni-B (good conformal deposition and forming an effective diffusion barrier against Cu) make it useful as a barrier layer for TSV interconnections in a 3-dimensional multi-chip package.     

Rod-like β-FeSi2 phase grown on Si (111) substrate

Pure Fe with coverage of 0.5-2.0 nm was deposited on Si (111) 7×7 surfaces by reactive deposition epitaxy (RDE) in an integrated ultrahigh vacuum (UHV) system. Transmission electron microscopy (TEM) confirmed that the as-deposited epitaxial phase exhibits rod-like and equilateral triangular morphology. The as-deposited phase was identified as c-FeSi₂ by electron diffraction and high-resolution transmission electron microscopy. It was found that there exists lattice distortion in epitaxial c-FeSi₂ phase. Upon annealing at 1073 K, the metastable c-FeSi₂ transforms into equilibrium β-FeSi₂ phase, the latter inherits completely the morphology of c-FeSi₂ phase. Based on RDE and subsequent annealing, a new fabrication technique to grow rod-like semiconducting β-FeSi₂ on a Si substrate has been proposed in the present work.     

Structure and electrical properties of Mo back contact for Cu(In, Ga)Se2 solar cells

Mo layers were deposited on soda lime glass via DC magnetron sputtering of a Mo target in a pure Ar atmosphere. The structure and electrical resistivity of Mo thin films, which may be varied by controlling the sputtering pressure, were investigated. The films showed (110) preferred orientation regardless of the working pressure. Films sputtered at low working pressure had low resistivity but adhered poorly to glass. A study of the deposition of a Mo bilayer was conducted. Optimum properties of the Mo bilayer were obtained when the bottom layer was deposited at 10 mtorr and the top layer was deposited at 2.5 mtorr. The extremely low resistivity of 6.57 μΩ-cm was obtained, which is better than other literatures. A Cu(In, Ga)Se₂ cell fabricated on a Mo film sputtered under optimized conditions showed 10.40% efficiency.     

Electrical properties of LiNbO3 (electrolyte)/Cu (anode) bi-layers

In this work specific film structures of Li-Nb-O/Li/Li-Nb-O are investigated by AC Impedance Spectroscopy measurements at different temperatures. This gives the opportunity to investigate properties of the material itself and, at the same time, to consider the influence of the grain boundaries on the ionic behavior of the polycrystalline Lithium Niobate. On the other hand, LiNbO₃/Li/Cu multi-layers are studied as electrolyte/anode bi-layers and potential parts of “Li-free” microbatteries. The Li deficiency in the as deposited Li-Nb-O films is cured by forming a “sandwich” of Li-Nb-O/Li/Li-Nb-O, which after annealing becomes ionic conductor. The electrical behavior of an annealed film depends on two sources. The first is due to properties of the material itself and the second is based on the network of the grain boundaries. The average size of the grains is strongly influenced by the structure of the ohmic-contact/substrate. The electrical behavior of the electrolyte/anode interface of the “Li-free” structure LiNbO₃/Li/Cu/Au is very similar to the impedance measurements of the single LiNbO₃ single films. The whole multilayer structure, though, presents a third relaxation time which is consistent of a small resistance. This resistance is independent of temperature and it seems that is due to the metallic interface Li/Cu/Au.     

SiO2/Si(111)表面Ge量子点的生长研究

Si衬底用化学方法清洗后,表面大约残余1.0 nm厚SiO2薄膜.利用原子力显微镜(AFM)和反射高能电子衍射(RHEED)来研究温度和Ge蒸发厚度对在SiO2薄膜表面生长的Ge量子点的影响.实验结果表明,当衬底温度超过500 ℃时,SiO2开始与Ge原子发生化学反应,并形成与Si(111)表面直接外延的Ge量子点.在650 ℃时,只有Ge的厚度达到0.5nm时,Ge量子点才开始形成.     

Structure and magnetic properties of sputtered (Fe1 − xCrx)0.09Cu0.91 solid solution films

The surface morphology of the (Fe_1 − xCr_x)_0.09Cu_0.91 films does not change significantly as x increases. No Fe or Cr granules form in the films because of the low deposition temperature and the non-equilibrium deposition procedure, suggesting that Fe and Cr atoms disperse in the Cu matrix. With increasing x, the lattice constant c and single cell volume decrease, but the lattice constants (a, b) first increase and latterly decrease. The films show spin-glass-like manner that looks like superparamagnetism at high temperatures and are ferromagnetic at low temperatures. The peak temperature of the zero-field-cooling curves decreases from 37 to 23 K as x increases from 0 to 0.25. Below the peak temperatures, the field-cooled magnetization decreases with decreasing temperature due to the antiferromagnetically coupling of the disordered spin-glass-like moments. The coercivity increases greatly below 50 K because of the pinning effect of the frozen spin-glass-like moments at low temperatures.