Direct ion beam deposition of polymeric styrene films and in situ characterization by electron spectroscopy

Polymeric styrene films with thicknesses ranging from about one nm up to a few m have been deposited by means of a direct ion beam deposition (IBD) technique. The deposition energy, which can be chosen independently of the parameters which govern the plasma conditions, has been varied between few eV and 1000 eV. The correlation between the deposition parameters and the resulting film properties in terms of the electronic structure is discussed. The in situ characterization by electron spectroscopy has proved to be a very useful characterization method and ultraviolet photoelectron spectroscopy in particular revealed an extremely high sensitivity to structural differences in the deposited films. The polymeric films have also been characterized by scanning electron microscopy and optical spectroscopy. These techniques have also served to compare films prepared by the direct IBD technique with films obtained by standard rf plasma polymerization (RFPP) in a tubular reactor. Significant differences have been found which are dependent on the deposition parameters; these are discussed in detail.Department of Chemical Engineering, Beijing Institute of Technology, P.O. Box 327 Beijing, 100081 Beijing, P.R. China     

Selective deposition of Au films on GaAs by projection-patterned excimer laser doping combined with electroless plating

Resistless microfabrication of Au thin films on n-type GaAs by projection-patterned laser doping using a KrF excimer laser and a 10% SiH₄-He gas is described. Gold thin films with a linewidth as narrow as 1.57 m are deposited selectively on the doped regions by electroless plating in a commercial Au-24s aqueous solution. The isotropic growth of the deposited films is discussed by comparing the linewidth of the deposited films with that of the doped regions. Furthermore, the dependence of the deposition characteristics of Au thin films on the laser irradiation conditions is investigated.Presented at LASERION '91, June 12–14, 1991, München (Germany)     

Excimer laser projection-patterned deposition of Al via photolytically driven decomposition of trialkylamine alane as adsorbate precursor

Aluminum films have been deposited from trimethylamine alane (CH₃)₃N · AlH₃ and triethylamine alane (C₂H₅)₃N · AlH₃ precursors on Al₂O₃, GaAs and quartz substrates using XeCl (=308 mn) and KrF (=248 nm) excimer lasers. Substrate surface irradiation induces the decomposition of the precursor in the adsorbed phase. The technique allows projection patterned deposition of Al at room temperature. Al deposition proceeds in two steps: surface nucleation, which is a pure photolytic process, and the succesive Al growth, which is photolytically driven but is thermally activated at low laser energy densities (<60 mJ/cm²). The nucleation process strongly depends on the substrate and laser wavelength. Mirror like Al films are deposited at rates up to about one Al monolayer per pulse which corresponds to rates up to 2 m/min when photolyzing at 100 Hz. Al films with good adhesion and resistivities down to 7.5 cm (2.5 times bulk), were deposited. The process has good spatial selectivity. Patterns with 1 m resolution have been generated.     

Formation of hafnium carbide thin films by plasma enhanced chemical vapor deposition from bis(η-cyclopentadienyl)dimethylhafnium as precursor

Thin films of hafnium carbide have been deposited by plasma-enhanced chemical vapor deposition using bis(-cyclopentadienyl)dimethylhafnium, Cp₂ Hf(CH₃)₂, as precursor in 13.56 MHz planar reactor. The influence of the various experimental parameters on film properties has been studied. The carbon content ranged from 11 to 40 weight % and increased with the deposition rate. The film hardness varied between 1300 and 2000 HK. Depending on the carbon content and power delivered in the discharge, the film resistivity and film density ranged from 271 to 10⁵ ·cm and from 3.4 to 10.4 g/cm³, respectively, and the film composition varied from HfC to hafnium containing a-C: H films.     

Evaluation of copper Chemical-Vapor-Deposition films on glass and Si(100) substrates

Thin films of pure copper have been deposited on glass and Si(100) substrates using copper acetylacetonate [Cu(acac)₂] and copper HexaFluoroAcetylacetonate [Cu(HFA)₂] sources. A thermal, cold-wall, reduced pressure (3325–5985 Pa) Metal-Organic Chemical Vapor Deposition (MOCVD) process was employed. The effect of H₂O vapor on the grain size, deposition rate, and resistivity was examined. Electrical resistivities of 2.4 cm for copper films deposited on Si(100) and 3.44 cm for copper films deposited on glass at substrate temperatures of 265° C and a [Cu(acac)₂] source temperature of 147° C with the use of H₂O vapor were measured. When [Cu(HFA)₂] was used, the substrate temperature was 385° C and the source temperature was 85° C. An activation energy for the copper film deposition process was calculated to be 22.2 kJ/mol in the case of the [Cu(acac)₂] source. A deposition rate of 11 nm/min was obtained with Cu(acac)₂ as the source and the rate was 44.4 nm/min with the Cu(HFA)₂ source; both were obtained with the use of H₂O vapor. No selectivity was observed with either source for either substrate. The deposited films were fully characterized using XRD, LVSEM, SAXPS, and RBS.     

Aluminium oxide thin films prepared by plasma-enhanced chemical vapour deposition

Thin films of aluminium oxide have been deposited on glass, quartz, Si(100), steel, nickel, and aluminium by plasma-enhanced chemical vapour deposition (PECVD) using aluminium acetylacetonate (Al(acac)₃) as precursor. The deposits are hard (up to 2370 HK) and show good adherence to the substrates. The influence of various experimental parameters on deposition rate, film composition and hardness has been studied. The bias turned out to be the most effective parameter.On leave from Beijing Solar Energy Research Institute, Beijing, P.R. China     

Influence of thermal treatment of low dielectric constant SiOC(H) films using MTES/O2 deposited by PECVD

Low dielectric constant SiOC(H) films are deposited on p-type Si(100) substrates by plasma enhanced chemical vapor deposition (PECVD) using methyltriethoxysilane (MTES, C₇H₁₈O₃Si) and oxygen gas as precursors. The SiOC(H) films are deposited at room temperature, 100, 200, 300 and 400 °C and then annealed at 100, 200, 300 and 400 °C temperatures for 30 min in vacuum. The influence of deposition temperature and annealing on SiOC(H) films are investigated. Film thickness and refractive index are measured by field emission scanning electron microscopy and ellipsometry, respectively. Chemical bonding characteristics of as-deposited and annealed films are investigated by Fourier transform infrared (FTIR) spectroscopy in the absorbance mode. As more carbon atoms are incorporated into the SiOC(H) films, both film density and refractive index are decreased due to nano pore structure of the film. In the SiOC(H) film, CH₃ group as an end group is introduced into OSiO network, thereby reducing the density to decrease the dielectric constant thereof. The dielectric constant of SiOC(H) film is evaluated by C-V measurements using metal-insulator-semiconductor (MIS), Al/SiOC(H)/p-Si structure and it is found to be as low as 2.2 for annealed samples deposited at 400 °C.     

Influence of radiofrequency power on compositional, structural and optical properties of amorphous silicon carbonitride films

The silicon carbonitride (SiCN) films were deposited on n-type Si (1 0 0) and glass substrates by the radiofrequency (RF) reactive magnetron sputtering of polycrystalline silicon target under mixed reactive gases of acetylene and nitrogen. The films have been characterized by energy dispersive spectrometer (EDS), atomic force microscope (AFM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible spectrophotometer (UVS). The influence of RF power on the compositional, morphological, structural and optical properties of the SiCN films was investigated. The SiCN films deposited at room temperature are amorphous, and the C, Si and O compositions except N in the films are sensitive to the RF power. The surface roughness and optical band gap decrease as the RF power increases. The main bonds in the SiCN films are C-N, N-H_n, C-H_n, C-C, CN, Si-H and Si-C, and the intensities of the CN, Si-H and C-H_n bonds increase with increment of the RF power. The mechanisms of the influence of RF power on the characteristics of the films are discussed in detail.     

Pulsed laser deposition of zirconium silicate thin films as candidate gate dielectrics

Thin films of zirconium silicate Zr_xSi_1-xO₂ (with x=0.69), a material that has been suggested as a possible high-k dielectric, are deposited on silicon wafers by pulsed laser deposition (PLD) under different deposition and post-annealing conditions. The morphology and electrical properties of these films are characterized. It is shown that the films remain amorphous after an ex situ rapid thermal annealing (RTA) at temperatures as high as 800 °C. For the 6 nm thick film deposited at 300 °C in an O₂ ambient with a N₂ ambient post-RTA at 500 °C for 5 min, the equivalent oxide thickness (EOT) is 1.9 nm, as evaluated from capacitance-voltage (C–V) measurements. The samples prepared with the N₂ ambient post-RTA show a slightly higher leakage current than that for samples annealed in the O₂ ambient. For the films deposited in N₂, the smallest EOT of 1.1 nm is obtained, and the films have fair electrical properties in spite of the high interface state density and relatively higher leakage. PACS 77.55.+f; 81.15.Fg; 81.40.Ef     

Barium ferrite (BaFe12O19) thin films prepared by pulsed laser deposition on MgO buffered Si substrates

Barium ferrite (BaFe₁₂O₁₉) thin films have been deposited by pulsed laser deposition (PLD) on Si substrates with MgO underlayers. The films were deposited in oxygen atmosphere by excimer laser (=248 nm, pulse duration=23 ns) in the temperature range 750–900 °C. The experiments showed that the substrate temperature has remarkable effect on the films magnetic and structural properties. The BaFe₁₂O₁₉ films deposited at 900 °C in 200 mTorr oxygen showed some perpendicular orientation, with a perpendicular squareness of 0.5 and an in-plane squareness of 0.3. Such thin BaFe₁₂O₁₉ films have platelet grains with a size of about 300 nm. The perpendicular saturation magnetization and coercivity are 185 emu/cm³ and 1.4 kOe, respectively. PACS 81.15.Fg.; 75.70.Ak; 75.50.Pp; 68.55.j     

Crystallization and surface morphology evolution of erbium fluoride films on different substrates

Erbium fluoride (ErF₃) films were thermally deposited on Ge(1 1 1), Si(0 0 1) and copper mesh grid with different substrate temperature. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the films. The structure of ErF₃ films deposited on germanium and silicon changed from amorphous to crystalline with increasing the substrate temperature, while the crystallization temperature of the films on silicon is higher than that of on germanium. The infrared optical properties of the films change greatly with the evolution of crystal structure. It is also found that the morphology of ErF₃ film on Ge(1 1 1) at 200 °C is modulated by the stress between the substrate and film. The SEM and TEM results confirmed that the ErF₃ films on copper mesh grid were crystalline even at 100 °C. Interestingly, the ErF₃ films show flower-like surface morphology when deposited on copper mesh at 200 °C. The crystallization temperature (T_c) of ErF₃ films on the three substrates has the relation which is which is induced by the wetting angle of ErF₃ films on different substrates.     

Growth and thermal stability of epitaxial BiFeO3 thin films

We have investigated the oxygen pressure and the temperature dependence on BiFeO₃ thin films deposited on SrTiO₃ substrates by pulsed laser deposition. Reflection high energy electron diffraction (RHEED), atomic force microscopy (AFM) and X-ray diffraction measurements indicate that high-quality epitaxial thin films are obtained for and T=650 °C. Outside of this pressure-temperature window, parasitic peaks attributed to β-Bi₂O₃ appear. We find an increase of the out-of-plane lattice parameter with oxygen pressure that we ascribe to Bi-deficiency due to its high volatility at low pressure. Ex-situ anneals have been performed and results show that as-grown single-phase BiFeO₃ thin films degrade after annealing, whereas as-grown BiFeO₃ containing impurity phases evolve toward a single-phase structure. These experiments demonstrate that parasitic phases can stabilize compounds which are usually unstable in air at elevated temperatures.     

The Effect of Substrate Temperature on the Properties of Nanostructured Silicon Carbide Films Deposited by Hypersonic Plasma Particle Deposition

Nanostructured silicon carbide films have been deposited on molybdenum substrates by hypersonic plasma particle deposition. In this process a thermal plasma with injected reactants (SiCl₄ and CH₄) is expanded through a nozzle leading to the nucleation of ultrafine particles. Particles entrained in the supersonic flow are then inertially deposited in vacuum onto a temperature-controlled substrate, leading to the formation of a consolidated film. In the experiments reported, the deposition substrate temperature T_s has ranged from 250°C to 700°C, and the effect of T_s on film morphology, composition, and mechanical properties has been studied. Examination of the films by scanning electron microscopy has shown that the grain sizes in the films did not vary significantly with T_s. Micro-X-ray diffraction analysis of the deposits has shown that amorphous films are deposited at low T_s, while crystalline films are formed at high T_s. Rutherford backscattering spectrometry has indicated that the films are largely stoichiometric silicon carbide with small amounts of chlorine. The chlorine content decreases from 8% to 1.5% when the deposition temperature is raised from 450°C to 700°C. Nanoindentation and microindentation tests have been performed on as-deposited films to measure hardness, Young's modulus and to evaluate adhesion strength. The tests show that film adhesion, hardness and Young's modulus increase with increasing T_s. These results taken together demonstrate that in HPPD, as in vapor deposition processes, the substrate temperature may be used to control film properties, and that better quality films are obtained at higher substrate temperatures, i.e. T_s700°C.     

Dielectric properties of SrZrO3 thin films prepared by pulsed laser deposition

SrZrO₃ (SZO) thin films have been prepared on Pt-coated silicon substrates and directly on Si substrates by pulsed laser deposition (PLD) using a ZrSrO target at a substrate temperature of 400 °C in 20 Pa oxygen ambient. X-ray –2 scans showed that the as-deposited films remain amorphous at a substrate temperature of 400 °C. The dielectric constant of SZO has been determined to be in the range 24–27 for the Pt/SZO/Pt structure. Capacitance–voltage (C–V) characteristics of a metal-oxide-semiconductor (MOS) structure for SZO films deposited in 20 Pa oxygen ambient and 20 Pa nitrogen ambient (SZON) indicated that incorporation of nitrogen during the substrate heating and film deposition can suppress the formation of an interfacial SiO₂ layer, and the SZON films have a lower equivalent oxide thickness (EOT) than that of the SZO films. However, the leakage current of the SZON films is larger than that of the SZO films. The EOT is about 1.2 nm for a 5-nm SZON film deposited at 400 °C. The leakage-current characteristics of as-deposited SZON films and SZON films post-annealed in oxygen ambient by rapid thermal annealing (RTA) have been studied comparatively. The films post-annealed with RTA have a lower leakage current than the as-deposited SZON films. Optical transmittance measurements showed that the band gap of the films is about 5.7 eV. It is proposed that SrZrO₃ films prepared at 400 °C are potential materials for alternative high-k gate-dielectric applications. PACS 77.84.Bw; 77.84.-s; 77.55.+f     

Control of a- and c-plane preferential orientations of ZnO thin films

We report orientation-controllable growth of ZnO thin films and their orientation-dependent electrical characteristics. ZnO thin films were deposited on single-crystalline (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃ substrates using pulsed laser deposition (PLD) at different substrate temperatures (400-800 °C). It was found that the orientation of ZnO films could be controlled by using different substrates of single-crystalline (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃. The a-plane () and c-plane (0 0 0 2) oriented ZnO films are formed on LaAlO₃ and SrTiO₃, respectively. In both cases, the degree orientation increased with increasing deposition temperature T_s. Both the surface free energy and the degree of lattice mismatch are ascribed to play an important role for the orientation-controllable growth. Further characterization show that the grain size of the films with both orientations increases for a substrate temperature increase (i.e. from T_s = 400 °C to T_s = 800 °C), whereas the electrical properties of ZnO thin films depend upon their crystalline orientation, showing lower electrical resistivity values for a-plane oriented ZnO films.     

Y1Ba2Cu3O7-δ thin films from KrF laser ablation with substrate heating and in situ patterning by CO2 laser radiation

Y₁Ba₂Cu₃O_7– thin films were deposited by KrF laser ablation while replacing conventional contact heating by cw CO₂ laser irradiation of the substrate front surface. The HTSC films obtained on (100)ZrO₂ showed T _c(R=0)=90 K, T(90–10%)=0.5 K, j _c=2.5 × 10⁶ A/cm², a sharp transition in the ac susceptibility X(T), and pure c-axis orientation. Micrographs of thin films (< 0.5 m) showed a smooth morphology while thick films (>1 m) contained many crystallites sticking in the bulk material. Furthermore, in situ patterning was achieved during deposition by local laser heating of a selected substrate surface area. The resulting planar films contained amorphous, semiconducting parts only 1 mm or less apart from crystalline material showing the above HTSC quality.Presented at LASERION '91, June 12–14, 1991, München (Germany)     

Texture control and its impact on the properties of SrBi2Ta2O9 thin films prepared by pulsed laser deposition

SrBi₂Ta₂O₉ (SBT) ferroelectric thin films with different preferred orientations were deposited by pulsed laser deposition (PLD). Several methods have been developed to control the preferred orientation of SBT thin films. For SBT films deposited directly on Pt/TiO₂/SiO₂/Si substrates and in situ crystallized at the deposition temperature, the substrate temperature has a significant impact on the orientation and the remnant polarization (Pr) of the films; a higher substrate temperature benefits the formation of (115) texture and larger grain size. The films deposited on Pt/TiO₂/SiO₂/Si substrates at 830 °C are (115)-oriented and exhibit 2Pr of 6 μC/cm². (115)- and (200)-predominant films can be formed by using a La_0.85Sr_0.15CoO₃ (LSCO) buffer layer or by annealing amorphous SBT films deposited on Pt/TiO₂/SiO₂/Si substrates at 450 °C using rapid thermal annealing (RTA). These films exhibit good electric properties; 2Pr of the films are up to 12 μC/cm² and 17 μC/cm², respectively. The much larger 2Pr of the films deposited on the LSCO buffer layer and of the films obtained by RTA than 2Pr of the films deposited on Pt/TiO₂/SiO₂/Si substrates at 830 °C is attributed to a stronger (200) texture. Received: 30 January 2001 / Accepted: 30 May 2001 / Published online: 25 July 2001     

Connection of Residual Losses of a Microwave Energy in Superconducting State of YBa2Cu3O7?δ Films on Sapphire Substrates with Their Resistance in a Normal State

In the work, the results of measurements of temperature dependence of the surface resistance Rs(T) of the YBa₂Cu₃O_– epitaxial films deposited on sapphire substrates have been presented. The films were obtained using the method of impulse laser deposition. The measurements of surface impedance Rs(T) have been carried out at a frequency of 135 GHz. It is shown that Rs(T) agrees with existing model, considering heterogeneity in the YBa₂Cu₃O_7– epitaxial films as the normal spherical domains. Analysis has been carried out for the set of specimens which were obtained at different technological regimes and have different critical parameters and geometry.     

Dependence of glow discharge Si:H:Cl film morphology on diluent gas and SiCl4 partial pressure

TEM, THEED and field-assisted silver ion exchange have been employed to study the glow discharge (GD) SiHCl films deposited from SiH₄-SiCl₄ gas mixtures. The character of the THEED patterns shows that the films are rather amorphous, and that their structure does not alter with the change in the gas mixture. The honeycomb-like morphology of the films is strongly affected by the type of gas in which SiH₄ is diluted (Ar or H₂). An increase in the SiCl₄ partial pressure leads to the uniformity and to the decrease of the island dimension only for the films deposited from SiH₄(H₂)-SiCl₄. A possible correlation between the film morphology and the micropore density is proposed.     

Deposition of copper oxide (Cu2O,CuO) thin films at high temperatures by plasma-enhanced CVD

Copper-oxide films are deposited by plasma-enhanced CVD using copper acetylacetonate as a precursor. The influence of various experimental parameters on deposition rate, film composition and resistivity have been studied. The substrate temperature and the bias are the parameters which affect these properties the most. An increase of the substrate temperature changes the phases of the deposit from Cu₂O-CuO over Cu₂O to Cu. At temperatures 500° C the deposition rates are high but the films consist mainly of metallic Cu. A negative bias enhances the deposition rate only slightly but has a strong effect on the film composition and can completely balance the oxygen deficiency. At a bias of –120 V the films consist of pure CuO even at temperatures 500° C.