The influence of substrate bias in I-PVD process on the properties of Ti and Al alloy films

The effects of substrate bias power on the microstructure, physical and electrical properties of thin Ti films prepared by ionized physical vapor deposition (I-PVD) process were studied. The influence of Ti underlayer with substrate bias power ranging from 0 to 400 W on the subsequent TiN/AlCu films deposited by conventional PVD process in a multilayer structure was further investigated. Decreasing substrate bias power led: (1) better Ti(002) texture, smoother surface, and lower resistivity in Ti films, and (2) better Al(111) texture, narrower grain size distribution, smoother final surface, better-defined TiN/AlCu interface, and lower residual stress in AlCu alloy films in the corresponding Ti/TiN/AlCu stacks. In both cases, lower substrate bias power resulted in films with desirable microstructures and properties, compared to higher bias powers, for use as Al-based interconnects in IC manufacturing.     

Improvement of the properties and electrical performance on TiCl4-based TiN film using sequential flow chemical vapor deposition process

Sequential flow chemical vapor deposition (SFCVD), utilizing TiCl₄/NH₃ as reactants and immediate NH₃ treatment after film deposition, is applied to produce TiN barrier films in the contact process. Secondary ion mass spectroscopy results indicate that the SFCVD TiN film can effectively block the diffusion of WF₆ into the underlying Ti layer during W deposition. NH₃ treatment immediately after film deposition causes SFCVD TiN films to be less contaminated with carbon than TiN films that are formed by metallic organic compounds chemical vapor deposition (MOCVD) and to contain less chlorine residue than conventional TiCl₄/NH₃ CVD TiN layers even at a low reaction temperature. According to the resistance measurement of Kelvin contacts, the SFCVD process yields a lower resistance and a more uniform distribution than the MOCVD or CVD process. Transmission electron microscopic observations demonstrate that WF₆ can diffuse through the MOCVD TiN to react with the underlying Ti layer, causing a rupture at the Ti/TiN interface and poor W adhesion. The SFCVD TiN can serve as a sufficient diffusion barrier against WF₆ penetration during W CVD deposition.     

TiN薄膜的循环制备和电学性质

用金属有机物化学气相淀积（Metal Organic Chemical Vapor Deposition,MOCVD）制备了TiN薄膜,通过不同循环制备的、厚度相同的平面薄膜电阻率的比较研究了TiN薄膜的电学性质．结果表明,多次循环会引入界面而增大电阻率,与薄膜成分和微结构分析的结果一致．得到了单循环的最优厚度以使样品电阻率最低．通过相同循环、不同厚度样品在真实器件中电学性能的比较,发现介窗（Via）直径越小,TiN薄膜对介窗电阻的影响越大．     

Oxidation of nano-multilayered AlTiSiN thin films between 600 and 1000 degrees C in air

Multilayered AlTiSiN films with a composition of 32.0Al-12.4Ti-4.9Si-50.7N (at.%) were deposited on a steel substrate in a nitrogen atmosphere by cathodic arc plasma deposition. The films consisted of crystalline approximately 8 nm-thick AISiN nanolayers that originated from the Al-Si target and approximately 3 nm-thick TiN nanolayers that originated from the Ti target. Their oxidation characteristics were studied between 600 and 1000 degrees C for up to 20 h in air. They displayed good oxidation resistance due to the formation of a thin, dense Al2O3 surface scale below which an (Al2O3, TiO2, SiO2)-intermixed inner scale existed. They oxidized slower than TiN films because protective Al2O3-rich scales formed on the surface. However, they oxidized faster than CrN films because impure Al2O3 scale formed on the AlTiSiN film. Their oxidation progressed primarily by the outward diffusion of nitrogen and substrate elements, combined with the inward transport of oxygen that gradually reacted with Al, Ti, and Si in the film.     

Diffusion barrier property of TiN and TiN/Al/TiN films deposited with FMCVD for Cu interconnection in ULSI

Flow modulation chemical vapor deposition (FMCVD) with titanium tetrachloride (TiCl₄) and ammonia (NH₃) is effective for depositing titanium nitride (TiN) films with conformal morphology, good step coverage, low electrical resistivity, and low chlorine residual contamination. It means that FMCVD TiN film is a good candidate of diffusion barriers for copper interconnection technology in ULSI. But the diffusion barrier property of FMCVD TiN film against Cu diffusion has not been confirmed. So, firstly, we deposited Cu (100 nm)/FMCVD TiN (25 nm)/Si multilayer films and investigated the thermal stability of Cu/TiN/Si structure. Vacuum annealing was done at 400, 500, 550 and 600 °C. For films annealed for 30 min at 400 °C, Cu diffused through the TiN layer and formed copper silicides on the surface of Si substrates. Therefore, FMCVD films formed under such conditions are unsatisfactory diffusion barriers. To enhance the diffusion barrier property of FMCVD TiN films, we used sequential deposition to introduce a monolayer of Al atoms between two TiN films. Etch-pit tests showed that for TiN films with Al interlayer, Cu diffusion through the barrier occurred at 500 °C and that is 100 °C higher than TiN film without Al interlayer. Al atoms formed AlO_x with oxygen atoms present in the TiN films as impurities, and fill up the grain boundaries of TiN film, thereby blocking the diffusion of Cu atoms.     

X-ray and transmission electron microscopy structural characterization of multifunctional Perovskite thin films

Different multifunctional (PbTiO₃, Sm_0.6Nd_0.4NiO₃, NdMnO₃) thin films were grown by metalorganic chemical vapor deposition (MOCVD) technique on SrTiO₃ and LaAlO₃ substrates. Transmission electron microscopy (TEM) and X-ray diffraction measurements reveal that almost single crystalline thin films can be epitaxially grown on the top of substrates. The relationship between the crystallographic orientation of the films and those of the substrates were determined by reciprocal space mapping and TEM analyses. PbTi03 thin films appear to be under tensile or compressive strain according to the different mismatch of their cell parameter with those of the substrate. Relaxation mechanism as a function of the film thickness arises from coexistence of different type of domains and size and strain effect are analyzed. SmNiO₃ thin films present diffuse scattering strikes and are less well organized when compared to PbTi0₃ thin films. Different domains are observed as well as an additional parasitic phase close to NiO. Its regular distribution can be associated to reduced transport properties. Preliminary observations on NdMnO₃ thin films shows that an amorphous phase is obtained during MOCVD that can be transformed in a single crystalline film by annealing. The films are under tensile or compressive strain according to the different mismatch of their cell parameter with those of the substrate. Magnetic properties are investigated.     

镍基合金基体上离子镀TiN薄膜的制备及性能

在镍基合金Inconel 740H基底上通过多弧离子镀制备Ti N薄膜.控制温度、气体流量、过渡层成分等重要参数,研究其对Ti N薄膜的表面形貌、力学性能以及耐腐蚀性的影响.多弧离子镀沉积过程中,沉积温度分别为200、250、300℃;过渡层成分分别为Al、Cr、Ti;气体流量分别为Ar 5 Sccm∶N240 Sccm,Ar 6 Sccm∶N248 Sccm,Ar 8 Sccm∶N264 Sccm.实验结果表明:在本实验的温度范围内,Ti N薄膜的致密度、结合力以及表面硬度均随着沉积温度的提高而提高;Cr作为过渡层的效果优于Al和Ti,薄膜成分均匀、表面致密,硬度更高,且耐腐蚀性能优异;在Ar、N2流量比一定的情况下,气体流量对Ti N薄膜的表面形貌和力学性能影响不大.本实验的最佳参数是:沉积温度300℃,过渡层成分为Cr,气体流量为Ar 6 Sccm、N248 Sccm.     

Diffusion and adhesion properties of Cu films on polyimide substrates

Copper thin films were prepared on polyimide (PI) substrates by physical vapor deposition (PVD) and chemical vapor deposition (CVD). Titanium nitride (TiN) diffusion barrier layers were deposited between the copper films and the PI substrates by PVD. Auger electron spectroscopy compositional depth profile showed that TiN barrier layer was very effective in preventing copper diffusion into PI substrate even after the Cu/TiN/PI samples were annealed at 300 °C for 5 h. For the as-deposited CVD-Cu/PI, CVD-Cu/TiN/PI, and as-deposited PVD-Cu/PI samples, the residual stress in Cu films was very small. Relatively larger residual stress existed in Cu films for PVD-Cu/TiN/PI samples. For PVD-Cu/TiN/PI samples, annealing can increase the peeling strength to the level observed without a diffusion barrier. The adhesion improvement of Cu films by annealing treatment can be attributed to lowering of the residual tensile stress in Cu films.     

Preparation and properties of thin ZnS:Cu films phosphors

Thin films of ZnS and ZnS:Cu were prepared by an original metalorganic chemical vapour deposition (MOCVD) method under atmospheric pressure onto a glass substrate heated up to 230–250 °C. The film thickness varied from 0.6 to 1 μm. The thin films were doped with Cu and Cl by the thermal treatment during 1 h at 600 °C at atmospheric pressure in the blend composed of a ZnS powder with Cu and Cl compounds. These films were used for fabrication of the thin film electroluminescent (TFEL) devices with a conventional double insulating structure. The structural properties were investigated by use of X-ray diffraction (XRD) techniques and atomic force microscopy (AFM). Electroluminescent (EL) spectra, electrical and EL characteristics were investigated. The EL spectra and characteristics as well as structural parameters depend on the growth conditions and significantly modified after the annealing. Blue color emission with brightness of 10 cd m^− 2 under a sine wave excitation at 60 V and 5 kHz was obtained. The degradation behavior of the TFEL devices with ZnS:[Cu, Cl] films fabricated using an original non-vacuum methods of deposition and annealing is the same as that of commercial thin film phosphor.     

Deposition process,microstructure and mechanical behaviours of RF magnetron sputtered (Ti,Al)N thin films

Abstract

Thin films of (Ti,Al)N with different Al contents were co-deposited using one Ti and one Al targets by radio frequency (RF) pulsed magnetron sputtering. Their composition, microstructure, nanohardness, surface morphology and deposition process were investigated by energy dispersive spectrometer system, X-ray diffraction, nanoindentation, atomic force microscopy and optical emission spectrum. A face cubic centred (fcc) TiN (B1) structure was found in the thin films when Al target power was low. When Al target power was increased, an additional hexagonal AlN (B4) structure appeared. With increasing Al content, the resulting films gradually changed from B1 structure to that of B4, accompanying with decrease of the lattice constant of B1 structure. Simultaneously, the preferred orientation of B4 structural thin films gradually transformed from (111) to (200). The mode of thin films transformed from island to fibre, subsequently to column with increasing Al target power. Optical emission spectrum analysis indicated that Al target surface reached non-metal sputtering mode earlier than that of Ti target under the same deposition parameters, which resulted in a lower sputtering rate of Al target than Ti target and loss of Al content in (Ti,Al)N thin films.     

Effects of annealing temperature on microstructure and electrical properties of Mn-Co-Ni-O thin films

Mn_1.85Co_0.3Ni_0.85O₄ (MCN) thin films were prepared on Al₂O₃ substrates by chemical solution deposition method at different annealing temperature (650, 700, 750 and 800 °C). Effects of annealing temperature on microstructure and electrical properties of MCN thin films were investigated. The MCN thin film annealed at 750 °C is of good crystallization and compact surface. It shows lower resistance (4.8 MΩ) and higher sensitivity (3720.6 K) than those of other prepared films. It also has small aging coefficient (3.7%) after aging at 150 °C for 360 h. The advantages of good properties make MCN thin film very promising for integrated devices.     

Oxidation behavior of (Ti1 − xAlx)N films perpared by r.f. reactive sputtering

(Ti, Al)N films have drawn much attention as alternatives for TiN coatings, which are oxidized easily in air above 500 °C. We have investigated the effect of Al content on the oxidation resistance of (Ti_{1 − x}Al_x)N films prepared by r.f. reactive sputtering.(Ti_{1 − x}Al_xN films (O ≤ x ≤ 0.55) were deposited onto fused quartz substrates by r.f. reactive sputtering. Composite targets with five kinds of Al-to-Ti area ratio were used. The sputtering gas was Ar (purity, 5 N) and N₂ (5 N). The flow rate of Ar and N₂ gas was kept constant at 0.8 and 1.2 sccm, respectively, resulting in a sputtering pressure of 0.4 Pa. The r.f. power was 300 W for all experiments. Substrates were not intentionally heated during deposition. The deposited films (thickness, 300 nm) were annealed in air at 600 900 °C and then subjected to X-ray diffractometer and Auger depth profiling.The as-deposited (Ti_{1 − x}Al_x)N films had the same crystal structure as TiN (NaCl type). Al atoms seemed to substitute for Ti in lattice sites. The preferential orientation of the films changed with the Al content of the film, x. Oxide layers of the films grew during annealing and became thicker as the annealing temperature increased. The thickness of the oxide layer grown on the film surface decreased with increasing Al content in the film. For high Al content films an Al-rich oxide layer was grown on the surface, which seemed to prevent further oxidation. All of the films, however, were oxidized by 900 °C annealing, even if the Al content was increased up to 0.55.     

Synthesis of C-axis-oriented AlN thin films on high-conducting layers: Al, Mo, Ti, TiN, and Ni

Thin piezoelectric polycrystalline films such as AlN, ZnO, etc., are of great interest for the fabrication of thin film bulk/surface acoustic resonators (TFBARs or TFSARs). It is well-known that the degree of c-axis orientation of the thin films correlates directly with the electromechanical coupling. However, the degree of c-axis orientation of the piezoelectric film is, in turn, influenced by other parameters such as the structure of the substrate material, the matter of whether the c-axis is up or down (polarity), and the growth parameters used. The correlation of these three aspects with the electromechanical coupling of the AlN-thin films, is studied here. Thin AlN films, prepared in a magnetron sputtering system, have been deposited onto thin Al, Mo, Ni, Ti, and TiN films. Such thin high-conducting layers are used to form the bottom electrode of TFBAR devices as well as to define a short-circuiting plane in TFSAR devices. In both cases, they serve as a substrate for the growth of the piezoelectric film. It has been found that the degree of orientation and the surface roughness of the bottom metal layer significantly affects the texture of the AlN films, and hence its electroacoustic properties. For this reason, the surface morphology and texture of the metal layers and their influence on the growth of AlN on them has been systematically studied. Finally, FBARs with both Al and Ti electrodes have been fabricated and evaluated electroacoustically.     

Effects of temperature,thickness and atmosphere on mixing in Au-Ti bilayer thin films

The interdiffusion and intermetallic compound formation of Au-Ti bilayer thin films annealed at 125 to 350 °C have been investigated. The bilayer thin films were prepared through electron beam deposition at comparatively low temperature. The interdiffusion of annealed specimens was examined by measuring electrical resistance and the depth-composition profile, and by observation using a transmission electron microscope. Interdiffusion between the thin films was detected at temperature above 175°C in a vacuum of 10^–4 Pa. The starting temperature at which interdiffusion occurred decreases with lowering annealing vacuum. The intermetallic compounds AuTi, Au₄Ti, Au₂Ti and Ti₃Au form during annealing at over 250 °C. The activation energies of Au in Ti and Ti in Au obtained by the penetration depth are approximately 0.45 and 0.41 eV, respectively. These measurements indicate that the diffusion is controlled by a short-circuit mechanism. The diffusion of Ti species in Au depends on the annealing vacuum and Au thickness.     

Improvement of the (1 1 1) texture and microstructures of Cu films by pulsed laser annealing

The improvement of the (1 1 1) texture and microstructure of Cu films on TiN/Si and TiN/SiO₂ substrates by pulsed KrF laser annealing as a function of the laser energy density, the deposition method of Cu films, and the orientation of TiN substrates is studied. Upon annealing at an energy density below 1.0 J cm^–2 the (1 1 1) texture of the evaporated Cu films increases with the energy density, whereas for the sputtered Cu films the (2 0 0) texture is promoted. The higher oxygen concentration in the sputtered Cu films may be responsible for the degradation of the Cu(1 1 1) texture. The enhancement of the Cu(1 1 1) texture is more evident for (1 1 1)-oriented TiN substrates than for (2 0 0)-oriented TiN substrates. The present study shows that pulsed laser annealing is superior to vacuum annealing in improving the (1 1 1) texture and microstructure of Cu films via the melt/solidification process.     

Gap-filling of Cu–Al alloy into nanotrenches by cyclic metalorganic chemical vapor deposition

In this work, Cu–Al alloy thin films with lower values of electrical resistivity than that of an Al-free Cu thin film were produced by cyclic metalorganic chemical vapor deposition (MOCVD), followed by thermal annealing of the Cu/Al multilayer formed, with controlled Cu and Al precursor delivery times. The Ru-coated SiO₂ trench with the opening width of 50 nm and aspect ratio of 1:6.7 could be completely filled by the Cu–Al alloy. The Ru/SiO₂ trench, filled conformally and voidlessly by the Cu–Al (0.7 at.%) alloy, showed no presence of intermetallic compounds.     

In situ annealing of hydroxyapatite thin films

Hydroxyapatite is a bioactive ceramic that mimics the mineral composition of natural bone. Unfortunately, problems with adhesion, poor mechanical integrity, and incomplete bone ingrowth limit the use of many conventional hydroxyapatite surfaces. In this work, we have developed a novel technique to produce crystalline hydroxyapatite thin films involving pulsed laser deposition and postdeposition annealing. Hydroxyapatite films were deposited on Ti–6Al–4V alloy and Si (100) using pulsed laser deposition, and annealed within a high temperature X-ray diffraction system. The transformation from amorphous to crystalline hydroxyapatite was observed at 340 °C. Mechanical and adhesive properties were examined using nanoindentation and scratch adhesion testing, respectively. Nanohardness and Young's modulus values of 3.48 and 91.24 GPa were realized in unannealed hydroxyapatite films. Unannealed and 350 °C annealed hydroxyapatite films exhibited excellent adhesion to Ti–6Al–4V alloy substrates. We anticipate that the adhesion and biological properties of crystalline hydroxyapatite thin films may be enhanced by further consideration of deposition and annealing parameters.     

A study of titanium thin films in transmission laser micro-joining of titanium-coated glass to polyimide

Electron beam evaporation (EB-PVD) and cathodic arc physical vapor deposition (CA-PVD) techniques were used for the preparation of titanium (Ti) thin films onto Pyrex borosilicate 7740 glass wafers and the deposited films were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) techniques. The microstructure and surface morphology of the films were studied as a function of the film deposition techniques. Film properties such as, adherence, microstructure and roughness were interconnected to the laser joint strength between Ti coated glass wafers and polyimide films. Ti thin films on glass had a natural oxide layer on the surface as found from XPS. AFM study showed the formation of a uniform Ti coating consisted of packed crystallites with average size of 35 nm by EB-PVD. The root-mean-square surface roughness of the films was 1-2 nm. Whereas, films prepared by CA-PVD had crystallites with an average size of 120 nm and defects in the form of macro-particles which is a common attribute of this deposition system. The surface roughness of the film was 125 nm. The laser joint strength was found to be influenced by the Ti film quality on the glass substrate.     

Poly-Si films with long carrier lifetime prepared by rapid thermal annealing of Cat-CVD amorphous silicon thin films

Polycrystalline silicon (poly-Si) films thicker than 1.5 μm, consisting of dense small grains called nano-grain poly-Si (ngp-Si), are formed by flash lamp annealing (FLA) of amorphous silicon (a-Si) films prepared by catalytic chemical vapor deposition (Cat-CVD) method. Crystallinity of the ngp-Si films can be controlled by changing lamp irradiance. Secondary ion mass spectroscopy (SIMS) profiles of dopants in the ngp-Si films after FLA shows no serious diffusion. A minority carrier lifetime of over 5 μs is observed from these ngp-Si films after defect termination process using high pressure water vapor annealing (HPWVA), showing possibility of application for high-efficient thin film solar cells.     

Large-area SnO2: F thin films by offline APCVD

In this paper, we reported the successful preparation of fluorine-doped tin oxide (FTO) thin films on large-area glass substrates (1245 mm × 635 mm × 3 mm) by self-designed offline atmospheric pressure chemical vapor deposition (APCVD) process. The FTO thin films were achieved through a combinatorial chemistry approach using tin tetrachloride, water and oxygen as precursors and Freon (F-152, C2H4F2) as dopant. The deposited films were characterized for crystallinity, morphology (roughness) and sheet resistance to aid optimization of materials suitable for solar cells. We got the FTO thin films with sheet resistance 8-11 Ω/□ and direct transmittance more than 83%. X-ray diffraction (XRD) characterization suggested that the as-prepared FTO films were composed of multicrystal, with the average crystal size 200-300 nm and good crystallinity. Further more, the field emission scanning electron microscope (FESEM) images showed that the films were produced with good surface morphology (haze). Selected samples were used for manufacturing tandem amorphous silicon (a-Si:H) thin film solar cells and modules by plasma enhanced chemical vapor deposition (PECVD). Compared with commercially available FTO thin films coated by online chemical vapor deposition, our FTO coatings show excellent performance resulting in a high quantum efficiency yield for a-Si:H solar cells and ideal open voltage and short circuit current for a-Si:H solar modules.