Surface morphology and surface chemical states of epitaxial Pb(Zr0.95Ti0.05)O3 thin films grown on SrTiO3(100) by sputter deposition

0.95 Ti_0.05)O₃ thin films of an orthorhombic perovskite structure were obtained on SrTiO₃(100) substrates by radio frequency sputter deposition. The surface morphology of the films was investigated with atomic force microscopy, scanning electron microscopy, and reflection electron microscopy. It is shown that the film surfaces are rather bumpy. There are undulations of about 400 nm in length in an in-plane direction. The mean roughness perpendicular to the surface is 39.6 nm, for the film thickness of 0.45 μm. The surface roughening was probably caused by island-shaped nucleation and growth during the film growth. It has also been found that some gorges and a number of small pits remain at the film surfaces. The surface chemical states of the films were characterized by using X-ray photoelectron spectroscopy. A Pb enrichment layer and a large amount of adsorbed oxygen have been found at the surfaces of the films. Near the film surface Pb and Zr exist mainly in the forms of, besides Pb(Zr,Ti)0₃, metal Pb, metal Zr, oxygen-chemisorbed Pb, and various lead oxides. In addition, a small amount of lead, whose binding energy of Pb 4f_7/2 is much lower than that of metal Pb, was observed at the film surfaces, but its chemical state is unknown up to now. Received: 2 June 1997/Accepted: 22 September 1997     

Microstructures and dielectric properties of compositionally graded (Ba1-xSrx) TiO3 thin films prepared by pulsed laser deposition

Compositionally graded (Ba_1-xSr_x)TiO₃ (BST) (x:0.0∼0.25) thin films were grown on Pt (111)/TiO₂/SiO₂/Si (100) substrates using layer-by-layer pulsed laser deposition in the temperature range 550–650 °C. Both downgraded (Ba/Sr ratio varying from 100/0 at the bottom surface to 75/25 at the top surface) and upgraded (Ba/Sr ratio varying from 75/25 at the bottom surface to 100/0 at the top surface) BST films were prepared. Their microstructures were systematically studied by X-ray diffractometry and scanning electron microscopy. A grain morphology transition from large ‘rosettes’ (>0.30 μm) to small compact grains (70–110 nm) was observed in the downgraded BST films as the deposition temperature was increased from 550 to 650 °C. No such grain morphology transition was detected in the upgraded BST films. Dielectric measurements with metal electrodes revealed an enhanced dielectric behavior in the downgraded films. This enhancement is mainly attributed to the large compressive stress field built up near the interface between the downgraded film and substrate. Furthermore, the BaTiO₃ layer in the downgraded BST films not only serves as a bottom layer but also as an excellent seeding layer for enhancing the crystallization of the subsequent film layers in the downgraded films. Received: 10 December 2001 / Accepted: 12 March 2002 / Published online: 19 July 2002 RID="*" ID="*"Corresponding author. Fax: 86-25/359-5535, E-mail: xhzhu@public1.ptt.js.cn     

Nucleation and initial growth of diamond by biased hot filament chemical vapour deposition

6 cm^-2 for non-scratched silicon. The maximum value of the nucleation density was over 10¹¹ cm^-2 on mirror-polished Si(100) at -300 V. The transportation process of the ion flux from the filament to the substrate is discussed in detail for biased substrates. The nucleation enhancement by the positive bias is believed to be a result of the increased impingement of the electrons emitted from the filament to the substrate surface. The studies have shown that electron emission from diamond plays a key role in negative-bias-enhanced nucleation by accelerating the dissociation of molecular hydrogen and hydrocarbon species into various free radicals and causing a plasma to be ignited near the substrate surface. The negative bias pretreatment is also a critical step in growing heteroepitaxial diamond films: the enlargement of the area of diamond clusters in contact with the substrate enhances the orientated growth of the films. Received: 18 October 1996/Accepted: 4 February 1997     

Structural and dielectric properties of Bi4Ti3O12 thin films prepared by metalorganic solution deposition

Ferroelectric Bi₄Ti₃O₁₂ thin films with single phase and nanosized microstructure were prepared on Pt/Ti/SiO₂/Si(111) substrate by metalorganic solution deposition using titanium butoxide and bismuth nitrate at relatively low annealing temperatures. The internal strain in Bi₄Ti₃O₁₂ thin films was calculated from the peak shifts and broadening of XRD patterns. With increase in annealing temperature, the uniform strain decreased from positive to zero and then to negative, and the non-uniform strain decreased and was negative. The total strain was negative and in the range of -0.2%–-1.0%, from which the stress of the films was calculated to be about -1.4×10⁹ N/m². The mode values of strain decreased with increase in annealing temperature and increased with increase in film thickness. The dielectric constant increased with increase in annealing temperature and film thickness. The dielectric properties were interpreted by considering the influence of strain, grain size, and grain boundaries. The strain lowered the polarization and increased the dielectric constant. The larger the grain size and the thinner the grain boundary, the greater the dielectric constant. The influence of grain size and grain boundary was stronger than that of the strain. Received: 23 September 1998 / Accepted: 6 January 1999 / Published online: 24 March 1999     

Low-temperature fabrication of silicon nitride films by ArF excimer laser irradiation

The low-temperature fabrication of silicon nitride films by ArF excimer laser irradiation has been studied. Two fabrication methods are presented. One is photoenhanced direct nitridation of a silicon surface with NH₃ for very thin gate insulators, and the other is photo-enhanced deposition of silicon nitride films with Si₂H₆ and NH₃ gases for stable passivation films. The ArF excimer laser irradiation dissociates the NH3 gas producing NH and NH₂ radicals which proved effective in instigating the nitridation reaction. The quality of both films has been much improved and the growth temperature has been lowered by using laser irradiation. These photo-enhanced processes seem to be promising ULSI techniques because they do not depend on high temperatures and are free from possible reactor contamination.     

Preparation and crystallization of Pb(Zr0.95Ti0.05)O3 thin films deposited by radio-frequency magnetron sputtering with a stoichiometric ceramic target

0.95 Ti_0.05)O₃ (PZT 95/5) thin films of perovskite structure were prepared on various substrates by the radio-frequency magnetron sputtering with a stoichiometric ceramic target. The crystal structure of the films showed a strong dependency on the crystal structure of the substrates. After conventional-furnace annealing at 750 °C, crack-free and transparent epitaxial PZT 95/5 films were successfully obtained on SrTiO₃(100) substrates, and highly oriented films on LaAlO₃(012). The films on r-sapphire exhibit slightly preferred orientation along both the (040) and (122) axes of the orthorhombic PZT 95/5 phase. The films on YSZ(100) consist principally of the perovskite PZT 95/5 phase with random orientation with a small portion of unknown phase. However, the formation of the perovskite PZT 95/5 phase was not observed in the films on Si(110) or (111)Pt-coated Si substrates. The crystallization of the perovskite PZT 95/5 on these substrates could be improved by rapid thermal annealing (RTA). Single perovskite phase was obtained in the films on (111)Pt/Si which had RTA at 750 °C for 1 min. No tangible loss of Pb from the films occurred during either the sputtering or annealing. Received: 17 April 1997/Accepted: 18 November 1997     

Structural, optical and electrical properties of ZnO and ZnO-Al2O3 films prepared by dc magnetron sputtering

ZnO and ZnO-Al₂O₃ thin films were prepared by dc magnetron sputtering and their structural, optical and electrical properties were studied comparatively. It is discovered that the ZnO-Al₂O₃ thin films remain transparent in a shorter wavelength range than the ZnO films, resulting from the increase of their band gap. Their resistivity decreases by seven orders of magnitude, which is caused by doping of Al to ZnO grains in the film. Preferential orientation of ZnO grains in the ZnO-Al₂O₃ thin films deteriorates because of the existence of Al₂O₃ impurity phase in the film. Received: 5 January 1999 / Accepted: 11 October 1999 / Published online: 8 March 2000     

Ferroelectricity of lanthanum-modified lead titanate thin films obtained by a diol-based sol-gel method

Lanthanum-modified lead titanate thin films have been prepared by a diol-based sol-gel method from precursor solutions with a growing excess of PbO. The films were crystallized with thermal treatments at 650 °C and heating rates of 10 °C  min^-1 and higher than 500 °C min^-1 by direct insertion in a pre-heated furnace. The structure, microstructure, and composition of the films were studied by grazing-incidence X-ray diffraction, electron microscopies, and energy-dispersive X-ray spectroscopy. A 20 mole % excess of PbO must be included in the precursor solution in order to compensate PbO volatilization occurring during the thermal treatment and, thus, obtain single-phase perovskite-type structure films. Non-textured porous films were obtained when a 10 °C min^-1 rate is used, whereas [001]/[100] oriented films without porosity were obtained when rapid heating was used. Dielectric permittivity, ac current density, hysteresis loops, and switching curves were measured in the films. Values of remanent polarization and coercive field are comparable to those reported for similar films. The effects on the ferroelectric properties of an electrical and a post-crystallization thermal treatments were characterised. Received: 5 January 1998 / Accepted: 20 November 1998 / Published online: 17 March 1999     

AFM studies of surface morphologies of sputtered SrTiO3 films and annealed MgO substrates

3 films on single-crystal MgO(100) substrates. Meanwhile, surface morphologies of as-polished and post-annealed MgO(100) substrates are investigated as well. Effects of the miscut (or misorientation) of the substrate surface on morphologies and growth mechanisms are discussed. For comparison, a typical surface morphology and growth mechanism of the spiral island structure in sputtered PrBa₂Cu₃O_7-δ films on MgO(100) substrates are presented. Received: 27 March 1998     

Orientation selective growth of MgO films on Si (100) by pulsed laser deposition

Selective growth of single-oriented (110), (100) and (111) MgO films on Si (100) substrates without buffer layers was obtained via a two-step method by pulsed laser deposition. It was found that the orientation of the films was determined at the initial deposition stage by the substrate temperature only. The ambient pressure during deposition, the laser fluence and the etching of the Si substrates have no apparent effect on the orientation of the films, but affect their crystalline quality. Under the present deposition conditions, the surfaces of all three different single-oriented films were very smooth and devoid of any particulates. Received: 23 January 2001 / Accepted: 6 June 2001 / Published online: 2 October 2001     

Preparation and characterisation of compositionally graded BaxSr1-xTiO3 thin films

Ba_xSr_1-xTiO₃ thin films with a compositional gradient of x=0.3 to 1 (in 0.1 mole fraction increments) were fabricated on Pt/Ti/SiO₂/Si substrates using a modified sol–gel technique. The graded film crystallised in a perovskite structure and consists of a uniform microstructure with comparatively larger grains. The room-temperature relative dielectric constant (ε_r) and dielectric loss (cosδ) at 100 kHz were found to be 305 and 0.03 respectively. Dielectric peaks were not observed in the temperature range from -20 °C to 120 °C. The dielectric constant and dielectric loss were almost independent of temperature. Polarisation–electric field measurements at room temperature revealed a saturated but slim hysteresis loop with a remanent polarisation (P_r) of 0.6 μC/cm² and a coercive field (E_c) of 2.4 kV/mm. The graded film behaves as a stack of Ba_xSr_1-xTiO₃ capacitors connected in series and hence the dielectric Curie peaks are removed. Received: 4 October 2001 / Accepted: 17 October 2001 / Published online: 23 January 2002     

Growth and characterization of silicon nitride films on various underlying materials

Characteristics of silicon nitride (SiN_x:H) films, grown by plasma enhanced chemical vapor deposition (PECVD) on various metals such as Ta, IrMn, NiFe, Cu, and CoFe at various temperatures down to 100 °C, were studied using measurements of BHF etch rate, surface roughness and Auger electron spectroscopy (AES). The results were compared with those obtained for SiN_x:H films on Si. The deposition rate of SiN_x:H films increased slightly as deposition temperature decreased, and showed a weak dependence on the underlying materials. The surface of the nitride films deposited on all underlying materials at lower temperatures (below 150 °C) became rougher. In particular, a bubble-like surface was observed on the nitride film deposited on NiFe at 100 °C. At higher deposition temperatures (above 200 °C), SiN_x:H films on all the above metals had small RMS values, except for films on Cu which cracked at 250 °C. BHF (10:1) etch rate increased dramatically for nitride films deposited below 150 °C. For different underlying films, the BHF etch rate was quite different, but exhibited the same trend with decrease in deposition temperature. AES measurements showed that Si and N concentrations in the SiN_x:H films were only slightly different for the various deposition temperatures and underlying materials. AES depth profile of nitride films indicated that both surface O content and the depth of oxygen penetrating into SiN_x:H increased for low temperature-deposited films. However, there was no observed oxygen signal from within the films, even for films deposited at 100 °C, and both Si and N concentrations were uniform throughout the film. Received: 26 October 2001 / Accepted: 2 March 2001 / Published online: 20 June 2001     

Optical properties of residual shallow donors in GaN epitaxial layers grown by horizontal LP-MOCVD

Received: 1 May 1998/Accepted: 23 June 1998     

Synthesis and microstructure of metal oxide thin films containing metal nanoparticles by liquid phase deposition (LPD) method

Au nanoparticles dispersed SiO₂-TiO₂ composite films have been prepared by a novel wet process, Liquid Phase Deposition (LPD) method. The composite films were characterized by XRD, XPS, TEM, ICP, SEM and UV-VIS absorption spectroscopy. The results showed that the SiO₂-TiO₂ composite films containing Au^III and Au^I ionic species were co-deposited from a mixed solution of ammonium silicofluoride, ammonium hexafluorotitanate, boric acid and tetrachloroauric acid. The heat treatment induced the reduction of Au ions and formation of Au nanoparticles in the film. TEM observation revealed that the Au nanoparticles with 5-10 nm in diameter were found to be dispersed uniformly in the SiO₂-TiO₂ matrix. The optical absorption band due to the surface plasmon resonance of dispersed Au particles were observed at the wavelength of 550 nm and shifted toward longer wavelength with increasing heat treatment temperature. Received 28 November 2000     

The orientation-selective growth of LaNiO3 films on Si(100) by pulsed laser deposition using a MgO buffer

Highly (100)-oriented, (110)-oriented and polycrystalline LaNiO₃ (LNO) films were successfully prepared on Si(100) using an oriented MgO film as a buffer. It was somewhat surprising to find that that the orientation relation between the LNO film and the corresponding MgO buffer was: LNO(100)\MgO(110), LNO(110)\MgO(111) and LNO(polycrystalline)\MgO(100). The crystalline quality of the LNO films was shown to be sensitive to the preparation conditions of the MgO buffer. The film surface was very smooth, without micrometer-sized droplets being observed. All LNO films were of metallic conductivity, with a room-temperature resistivities of approximately 250, 280 and 420 μΩ cm for the (110)-oriented, (100)-oriented and polycrystalline LNO, respectively. Received: 2 April 2001 / Accepted: 23 October 2001 / Published online: 3 June 2002     

X-ray evidence for the absence of 90°-domains in polycrystalline PbTiO3 thin films with grains below a critical size

3 thin films is systematically studied by using X-ray diffraction (XRD). The PbTiO₃ thin films with different average grain sizes were prepared on various substrates by a sol-gel process. The films on NaCl and fused glass are randomly grain-oriented, while those on (111)Pt/Ti/SiO₂/Si are highly {100} cubic index grain-oriented . It is found from the XRD patterns of the films on NaCl that with decreasing average grain size from 230 to 80 nm, the intensities of high h index (h>l) peaks (hkl), such as (100), (110), (200), (201), (210), (211), etc., decrease rapidly and ultimately disappear, whereas another set of peaks (lkh), including (001), (002), (102), (112), etc., are still intense. This interesting result suggests that at grain size below a certain critical size an increasing number of grains no longer show 90°-domains, which is confirmed by TEM observations. Meanwhile, X-ray evidence of such a grain-size-related absence of 90°-domains is also found for PbTiO₃ films on Pt(111) and fused-glass substrates. The volume fractions of single-domain grains (without 90°-domains) in the films are estimated from their XRD patterns. By combining SEM and TEM investigations, the critical grain size for the formation of 90°-domains is further determined to be near 200 nm. Received: 19 December 1996/Accepted: 24 March 1997     

Structure and spectroscopic characterization of polycrystalline vanadyl phthalocyanine (VOPc) films fabricated by vacuum deposition

Received: 24 March 1997/Accepted: 8 September 1997     

Structure, refractive-index dispersion and the optical absorption edge of chemically deposited ZnxCd(1-x)S thin films

Zinc cadmium sulfide, Zn_xCd_(1-x)S, thin films have been deposited by a simple and inexpensive chemical bath deposition method from an aqueous medium using thiourea as a sulfide-ion source. The structure of the deposited films has been characterized by X-ray diffraction and transmission electron microscopy. It was observed from X-ray diffraction that the as-deposited films were amorphous in nature. However Zn_xCd_(1-x)S films annealed at 423 K for 1.5 h show a crystalline structure with a small scattering volume. The obtained results were confirmed throughout the transmission electron microscopy and the corresponding electron-diffraction patterns. The optical constants of Zn_xCd_(1-x)S films annealed at 423 K for 1.5 h in the compositional range 0≤x≤1 were estimated using transmission and reflection spectra in the wavelength range 300–2500 nm. The band gap varies non-linearly with the value of x. The dependence of the refractive index on the wavelength obeys the single-oscillation model, from which the dispersion parameters and the high-frequency dielectric constant were determined. A graphical representation of the surface and volume energy-loss functions was also given. Received: 23 February 2001 / Accepted: 26 February 2001 / Published online: 27 June 2001     

Epitaxial growth of CeO2 on (100) InP using reactive r.f. magnetron sputtering

The epitaxial growth of CeO₂ thin films has been realized on (100) InP substrates using reactive r.f. magnetron sputtering. Oxide films were nucleated in the presence of molecular hydrogen (4% H₂/Ar sputtering gas) in order to reduce the native oxide formation on the InP surface, which interferes with CeO₂ epitaxy. A metal cerium target was used as the cation source, with water vapor serving as the oxidizing species. Epitaxial films were sputter-deposited at a substrate temperature of 550 °C in a H₂O vapor pressure of approximately 10^-3 Torr. Crystallinity of the oxide films was examined using θ–2θ X-ray diffraction, ω-rocking curves, and in-plane φ-scans. The best results were obtained when the initial nucleation layer was deposited with P(H₂O)<10^-5 Torr, followed by deposition at P(H₂O)=10^-3 Torr. The epitaxial growth of CeO₂ on InP could prove enabling in efforts to integrate functional oxides with InP-based optoelectronic and microwave technologies. Received: 20 February 20002 / Accepted: 21 February 2002 / Published online: 19 July 2002     

Al2O3 thin films by plasma-enhanced chemical vapour deposition using trimethyl-amine alane (TMAA) as the Al precursor

2 O₃ thin films by plasma-enhanced chemical vapour deposition (PECVD) using trimethyl-amine alane (TMAA) as the Al precursor. The thin films were deposited on both Si and quartz silica (SiO₂) substrates. Deposition rates were typically 60 Å min^-1 keeping the TMAA temperature constant at 45 °C. The deposited Al₂O₃ thin films were stoichiometric alumina with low carbon contamination (0.7–1.3 At%). The refractive index ranged from 1.54 to 1.62 depending on the deposition conditions. The deposition rate was studied as a function of both the RF power and the substrate temperature. The structure and the surface of the deposited Al₂O₃ thin films were studied using X-ray diffraction, atomic force microscopy (AFM) and scanning electron microscopy (SEM). Received: 20 May 1997/Accepted: 12 June 1997