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.     

Investigation of stress behaviors and mechanism of void formation in sputtered TiSix films

We have investigated the stress behaviors and a mechanism of void formation in TiSi_x films during annealing. TiSi_x thin films were prepared by DC magnetron sputtering using a TiSi_2.1 target in the substrate temperature range of 200–500 °C. The as-deposited TiSi_x films at low substrate temperature (<300 °C) have an amorphous structure with low stress of 1×10⁸ dynes/cm². When the substrate temperature increases to 500 °C, the as-deposited TiSi_x film has a mixture of C49 and C54 TiSi₂ phase with stress of 8×10⁹ dynes/cm². No void was observed in the as-deposited TiSi_x film. Amorphous TiSi_x film transforms to C54 TiSi₂ phase with a random orientation of (311) and (040) after annealing at 750 °C. The C49 and C54 TiSi₂ mixture phase transforms to (040) preferred C54 TiSi₂ phase after annealing over 650 °C. By increasing substrate temperature, the transformation temperature for C54 TiSi₂ can be reduced, resulting in relieved stress of TiSi₂ film. The easy nucleation of the C54 phase was attributed to an avoidance of amorphous TiSi_x phase. We found that amorphous TiSi_x→C54 TiSi₂ transformation caused higher tensile stress of 2×10¹⁰ dynes/cm², resulting in more voids in the films, than C49→C54 transformation. It was observed that void formation was increased with thermal treatment. The high tensile stress caused by volume decreases in the silicide must be relieved to retard voids and cracks during C54 TiSi₂ formation.     

Morphological changes induced by thermal anneals in NiFe/Ag multilayers; their relation to the resistive and magnetoresistive properties

(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.     

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.     

Effects of deposition parameters on the crystallinity of CeO2 thin films deposited on Si(100) substrates by r.f.-magnetron sputtering

Deposition temperature, r.f.-power and seed layer deposition time were important parameters effecting the crystallinity of CeO₂ thin films deposited by r.f.-magnetron sputtering on Si(100) substrates. The CeO₂ (200) peak was notable for a deposition temperature above 600°C. With decreased r.f.-power and thus lower deposition rate, the intensity of the CeO₂(200) peak increased. When the seed layer deposition time was less than 20 s, the CeO₂(200) peak dominated. Transmission electron microscopy (TEM) diffraction revealed that the deposited CeO₂ thin film had a polycrystalline structure. Annealing at 950°C in O₂ atmosphere for 30 min increased and sharpened the CeO₂(200) peak.     

Atmospheric plasma discharge chemical vapor deposition of SnOx thin films using various tin precursors

A series of 0.2–0.6 μm thick SnO_x films were deposited onto borosilicate and sodalime silica glass substrates by atmospheric plasma discharge chemical vapor deposition at 80 °C. SnO_x films deposited from monobutyltin trichloride contained a large percentage of SnCl₂:2H₂O, and therefore were partially soluble in water. SnO_x coatings deposited from tetrabutyltin were not soluble in water or organic solvents, had good adhesion even at growth rates as high as 2.3 nm/s, had high transparency of  90% and electrical resistivity of 10⁷ Ω cm. As-grown tin oxide coatings were amorphous with a small concentration of SnO₂, SnO and Sn crystalline phases as determined by grazing angle X-ray diffraction and X-ray photoelectron spectroscopy measurements. Upon annealing in air at 600 °C the resistivity of SnO_x films decreased to 5–7 Ω cm. Furthermore, optical and X-ray measurements indicated that SnO_x was converted into SnO₂ (cassiterite) with a direct band gap of 3.66 eV. Annealing of as-grown SnO_x films in vacuum at 340 °C led to formation of the p-type conductor SnO/SnO_x. The indirect band gap of SnO was calculated from the optical spectra to be 0.3 eV.     

Microstructure modification of amorphous titanium oxide thin films during annealing treatment

Thin films of titanium oxide have been deposited on (100) silicon wafers and on quartz substrates by reactive r.f. magnetron sputtering from a 99.6% pure Titanium target. Amorphous and overoxidised coatings (TiO_2.2) have been obtained from this technique. The influence of the post-deposition annealing between 300 °C and 1100 °C on the structural and optical properties and on the surface morphology has been investigated. The results of X-ray diffraction showed that films annealed from 300 to 500 °C have an anatase crystalline structure whereas those annealed at 1100 °C have a rutile crystalline structure. Optical analyses showed that UV-Vis transmission spectra are strongly modified by the annealing temperature and refractive index of TiO_x layers also changes. Atomic force microscopy measurements corroborate optical and structural analyses and showed that the surface of the coatings can have various appearances and morphologies for the annealing temperatures investigated.     

Formation of low-resistivity poly-Si and SiNx films by Cat-CVD for ULSI application

In this paper, bulk-Si metal–oxide–semiconductor field effect transistors (MOSFETs) are fabricated using the catalytic chemical vapor deposition (Cat-CVD) method as an alternative technology to the conventional high-temperature thermal chemical vapor deposition. Particularly, formation of low-resistivity phosphorus (P)-doped poly-Si films is attempted by using Cat-CVD-deposited amorphous silicon (a-Si) films and successive rapid thermal annealing (RTA) of them. Even after RTA processes, neither peeling nor bubbling are observed, since hydrogen contents in Cat-CVD a-Si films can be as low as 1.1%. Both the crystallization and low resistivity of 0.004 Ω·cm are realized by RTA at 1000 °C for only 5 s. It is also revealed that Cat-CVD SiN_x films prepared at 250 °C show excellent oxidation resistance, when the thickness of films is larger than approximately 10 nm for wet O₂ oxidation at 1100 °C. It is found that the thickness required to stop oxygen penetration is equivalent to that for thermal CVD SiN_x prepared at 750 °C. Finally, complementary MOSFETs (CMOSs) of single-crystalline Si were fabricated by using Cat-CVD poly-Si for gate electrodes and SiN_x films for masks of local oxidation of silicon (LOCOS). At 3.3 V operation, less than 1.0 pA μm⁻¹ of OFF leakage current and ON/OFF ratio of 10⁷–10⁸ are realized, i.e. the devices can operate similarly to conventional thermal CVD process.     

Epitaxial growth of strained Si1−yCy films by the hot-wire cell method and its application to metal oxide semiconductor devices

We succeeded in obtaining strained Si_1−yC_y films at a substrate temperature of 200 °C by the hot-wire cell method. The substitutional carbon concentration in films annealed at 700 °C was 0.9%, while it was limited to 0.13% for a sample grown by gas-source molecular beam epitaxy (MBE) at a substrate temperature of 700 °C. We investigated the thermal stability of strained Si_1−yC_y films for device application. Annealing at over 900 °C caused the formation of 3C-SiC and relaxation of the strain occurred. From this result, we found that the process temperature should be lower than 800 °C. A low-temperature MOSFET process, in which all process temperatures after deposition of Si_1−yC_y were lower than 800 °C, was developed and a strained Si_1−yC_y MOSFET was fabricated.     

Characterization of cobalt annealed on silicon-germanium epilayers

Cobalt-coated single-crystal Si-Ge layers grown epitaxially by ultrahigh vacuum chemical vapor deposition on silicon substrates were annealed by rapid thermal annealing in the temperature range from 450 °C to 800 °C for periods ranging from 1 to 3 min. The measured sheet resistivities of the films exhibit strong dependence on the annealing conditions. The Co-SiGe film annealed at 700 °C for 3 min had the lowest sheet resistivity (3Ω/p). Structural studies using cross-sectional transmission electron microscopy showed that the cobalt films reacted with the SiGe layer and the thickness of the resulting film increases with increasing annealing temperature or time. Electron diffraction and X-ray microanalysis using energy-dispersive spectrometry showed that CoSi₂ was formed during initial annealing. The detection of germanium in the reacted layer and the deviation of the reacted layer's lattice constant from that of CoSi₂ indicated that germanium diffused into the CoSi₂ and formed ternary compounds (Co_xSi_yGe_z) during further annealing.     

Structure and conducting properties of La0.5Sr0.5CoO3−δ films on YSZ

La_0.5Sr_0.5CoO_3−δ (LSCO) thin films were deposited on yttria stabilized zirconia (YSZ) substrates by pulsed laser deposition (PLD) for application to thin film solid oxide fuel cell electrodes. During the deposition, the substrate temperature was varied from 450 to 750°C, and the oxygen pressure in the chamber was varied from 80 to 310 mTorr. Films deposited at 650°C and an oxygen background pressure of 150 mTorr were mostly (100) oriented. Deposition at higher temperatures or under lower oxygen pressures lead to mostly (110) oriented films. Films with low electrical resistivity of 10⁻³ Ω·cm were obtained.     

Inductively coupled plasma — plasma enhanced chemical vapor deposition silicon nitride for passivation of InP based high electron mobility transistors (HEMTs)

Silicon nitride thin films have been deposited on InP-based structures at both room and high temperatures in an RF-inductively coupled plasma enhanced chemical vapor deposition (ICP-PECVD) equipment. Metal insulating semiconductor (MIS) diodes have been widely investigated using either SiH₄+NH₃ or SiH₄+N₂ gas phase. I–V measurements conducted on these diodes reveal high resistivity and breakdown electric field even at low deposition temperature (50°C). Double channel (DC) High electron mobility transistors (HEMTs) have been passivated by SiN_x films deposited at room temperature using SiH₄+NH₃ precursors. Passivated devices exhibit a very low drift over a 45 h period of stress under high gate-drain electric field.     

Effect of deposition temperature on the structural and thermoelectric properties of bismuth telluride thin films grown by co-sputtering

Thermoelectric bismuth telluride thin films were prepared on SiO₂/Si substrates by radio-frequency (RF) magnetron sputtering. Co-sputtering method with Bi and Te targets was adopted to control films' composition. Bi_xTe_y thin films were elaborated at various deposition temperatures with fixed RF powers, which yielded the stoichiometric Bi₂Te₃ film deposition without intentional substrate heating. The effects of deposition temperature on surface morphology, crystallinity and electrical transport properties were investigated. Hexagonal crystallites were clearly visible at the surface of films deposited above 290 °C. Change of dominant phase from rhombohedral Bi₂Te₃ to hexagonal BiTe was confirmed with X-ray diffraction analyses. Seebeck coefficients of all samples have negative value, indicating the prepared Bi_xTe_y films are n-type conduction. Optimum of Seebeck coefficient and power factor were obtained at the deposition temperature of 225 °C (about − 55 μV/K and 3 × 10^− 4 W/K²·m, respectively). Deterioration of thermoelectric properties at higher temperature could be explained with Te deficiency and resultant BiTe phase evolution due to the evaporation of Te elements from the film surface.     

Effect of precursor solution on the formation of perovskite phase of Pb(Mg1/3Nb2/3)O3 thin films

Precursor solutions for Pb(Mg_1/3Nb_2/3)O₃ (PMN) synthesis were obtained by Pechini's method. The influence of the concentration of organic materials on the phase formation has been studied. For this purpose, PMN solutions were prepared with different precursors and were characterized by thermogravimetric and differential thermal analysis. The obtained solutions were deposited onto a Si (100) substrate by dip coating and pre-treated in a hot plate at 300 °C for 1 h. The films were annealed at 600, 700, 800 and 900 °C for 1 h and characterized by X-ray diffraction. The perovskite phase was formed after annealing at 600 and 700 °C when the solution of PMN was prepared with a lower amount of organic material and starting with niobium oxide. By increasing the temperature to 800 or 900 °C, only the formation of pyrochlore phase was observed. With the solution prepared from niobium ethoxide, only the presence of pyrochlore phase was observed independently of the annealing temperature.     

Relaxation of extrinsic and intrinsic stresses in germanium substrates with silicon films

Si films were deposited on Ge substrates at 400°C by two different Physical Vapor Deposition techniques: (A) ion beam sputtering and (B) magnetron sputtering. The intrinsic stresses in the as-deposited films were measured to be compressive and much greater in samples (A), about −1500 to −2000 MPa than in samples (B), about −300 to −500 MPa. The substrates were subsequently exposed to thermal treatments for varying times at 800°C. In the lower stressed (B) samples, the films had relaxed and reduced the overall curvature of the structure whereas in the high stresses (A) samples, an irreversible large increase in the substrate curvature was found to occur. This indicated that plastic deformation in the Ge substrates itself had occurred.     

The effect of rapid thermal annealing on structural and electrical properties of TiB2 thin films

This work reports on the effect of post-deposition rapid thermal annealing on the structural and electrical properties of deposited TiB₂ thin films. The TiB₂ thin films, thicknesses from 9 to 450 nm, were deposited by e-beam evaporation on high resistivity and thermally oxidized silicon wafers. The resistivity of as-deposited films varied from 1820 μΩ cm for the thinnest film to 267 μΩ cm for thicknesses greater than 100 nm. In the thickness range from 100 to 450 nm, the resistivity of TiB₂ films has a constant value of 267 μΩ cm.

A rapid thermal annealing (RTA) technique has been used to reduce the resistivity of deposited films. During vacuum annealing at 7 × 10⁻³ Pa, the film resistivity decreases from 267 μΩ cm at 200 °C to 16 μΩ cm at 1200 °C. Heating cycles during RTA were a sequence of 10 s. According to scanning tunneling microscopy analysis, the decrease in resistivity may be attributed to a grain growth through polycrystalline recrystallization, as well as to an increase in film density.

The grain size and mean surface roughness of annealed films increase with annealing temperature. At the same time, the conductivity of the annealed samples increases linearly with grain size. The obtained results show that RTA technique has a great potential for low resistivity TiB₂ formation.     

Transparent conducting F-doped SnO2 thin films grown by pulsed laser deposition

Transparent conducting fluorine-doped tin oxide (SnO₂:F) films have been deposited on glass substrates by pulsed laser deposition. The structural, electrical and optical properties of the SnO₂:F films have been investigated as a function of F-doping level and substrate deposition temperature. The optimum target composition for high conductivity was found to be 10 wt.% SnF₂ + 90 wt.% SnO₂. Under optimized deposition conditions (T_s = 300 °C, and 7.33 Pa of O₂), electrical resistivity of 5 × 10^− 4 Ω-cm, sheet resistance of 12.5 Ω/□, average optical transmittance of 87% in the visible range, and optical band-gap of 4.25 eV were obtained for 400 nm thick SnO₂:F films. Atomic force microscopy measurements for these SnO₂:F films indicated that their root-mean-square surface roughness ( 6 Å) was superior to that of commercially available chemical vapor deposited SnO₂:F films ( 85 Å).     

The mechanical properties and resistivity of Au/NiCr/Ta multi-layered films on Si-(111) substrate

Au/NiCr/Ta multi-layered metallic films were deposited on Si substrate by magnetron sputtering at different substrate temperatures. The residual stress, hardness and resistivity were investigated as a function of substrate temperature by laser polarization phase shift technique, nanoindentation technique and four point probe method, respectively. The residual stress in as-deposited films at different substrate temperatures was tension with 385 MPa-606 MPa. Nanoindentation tests at shallow indentation depths (h ≤ t/4) where the hardness is reliable for metal films on hard substrate. Au film at deposition temperature 200 °C has the highest hardness 4.2 GPa. The resistivity in the deposited films reached the lowest value 3.1 μΩ.cm at substrate temperature 200 °C. The most interesting facts are that the hardness decreases with increasing residual stress and resistivity increases with increasing residual stress. The relationship of residual stress and resistivity may hint that there is a definite correlation between the mechanical properties and electrical properties in the metallic films.     

Cat-CVD-prepared oxygen-rich μc-Si:H for wide-bandgap material

Microcrystalline phase-involved oxygen-rich a-Si:H (hydrogenated amorphous silicon) films have been obtained using catalytic chemical vapor deposition (Cat-CVD) process. Pure SiH₄ (silane), H₂ (hydrogen), and O₂ (oxygen) gases were introduced in the chamber by maintaining a pressure of 0.1 Torr. A tungsten catalyzer was fixed at temperatures of 1750 and 1950 °C for film deposition on glass and crystalline silicon substrates at 200 °C. As revealed from X-ray diffraction spectra, the microcrystalline phase appears for oxygen-rich a-Si:H samples deposited at a catalyzer temperature of 1950 °C. However, this microcrystalline phase tends to disappear for further oxygen incorporation. The oxygen content in the deposited films was corroborated by FTIR analysis revealing SiOSi bonds and typical SiH bonding structures. The optical bandgap of the sample increases from 2.0 to 2.7 eV with oxygen gas flow and oxygen incorporation to the deposited films. In the present thin film deposition conditions, no strong tungsten filament degradation was observed after a number of sample preparations.     

Photoluminescence properties of the Yb:Er co-doped Al2O3 thin film fabricated by microwave ECR plasma source enhanced RF magnetron sputtering

The Yb:Er co-doped Al₂O₃ thin film was deposited on oxidized silicon wafers by microwave ECR plasma source enhanced RF magnetron sputtering, and annealed from 800 °C to 1000 °C. The photoluminescence at 1.53 μm of thin film was obtained under room temperature. The mixture phase structure of γ and θ is observed by XRD, and the compositions of the thin film are investigated by EPMA. The maximum PL intensity was achieved with O₂:Ar at 1:1, annealing temperature at 900 °C, and experimental ratio of Yb:Er at 1:3.6. The energy transfer mechanism between Er and Yb ions is supported by theoretical analysis and experiment results.