Realization of a viable nonvolatile ferroelectric thin film memory technology hinges on the successful solution of the reliability problems associated with the ferroelectric capacitor concurrent with the integration of these materials with the appropriate Si-CMOS based drive electronics. This integration process introduces a variety of structural, chemical, ionic and electronic interfaces in the memory elements. In this paper, the influence of some of the interfaces on the ferroelectric properties and on the process integration is discussed.

(PbBa)(ZrTiNb)03 thin films and powders have been prepared using the sol-gel technique. Solutions were synthesized in 2-methoxyethanol based upon our previous PZT solution preparation. Three different approaches were used for incorporating barium into PZT alkoxide solutions. Thermal analysis and x-ray diffraction results indicated that barium methoxypropoxide gave the best results. PBZTN (71% Pb and 71% Zr) was deposited onto sapphire substrates as well as oxidized silicon substrates. Optical transmission measurements showed greater than 80% transmission for wavelengths longer than 400 nm. Films with thickness of 3000 Å on sapphire exhibited a refractive index of 2.19 at λ=633 nm.

Metalorganic precursor solutions of composition Zr : Ti = 0.53 : 0.47 were used to spin-cast PZT layers on sputtered Pt films. After annealing at temperatures of 550 °C - 800 °C, the PZT films of tetragonal perovskite structure reproducibly showed different textures and surface morphologies, depending on whether or not a Ti layer was used as an adhesion layer for the Pt film. The texture differences were found to be independent of annealing treatment. It is argued that the observed texture differences are caused by a change in Pt-PZT interface composition, resulting from the diffusion of Ti into the Pt film during annealing; X-ray diffraction of an annealed Pt/Ti/SiO2/Si film combination provided evidence for a compound Pt3Ti. Annealing at 850 °C caused severe diffusion of Ti from the metal layer into the PZT film, leading to a tetragonal PZT layer with lattice constants corresponding to a Zr : Ti ratio of 30 : 70.

We have studied BaxSr1-xTiO3 (BST) thin films (x=0.5) grown on Si (100) with and without a Pt/Ta barrier layer using 90° off-axis RF sputtering. The growth conditions were optimized according to film crystallinity, stoichiometry, and dielectric properties. Polycrystalline BST films with strong (100) texture were obtained via growth on Si (100). The measured dielectric constant from these films was low, presumably because of the parasitic effect of native oxide at BST/Si interface as revealed by TEM. On the other hand, BST films grown on Si with Pt/Ta barrier layers have crystallinity inferior to that on bare Si as determined by X-ray diffraction. Nevertheless, the best BST films on Pt/Ta layers still have good dielectric properties with dielectric constant exceeding 330, leakage current density < 1×10−6 A/cm2 (±1 V), and loss tangent 0.05 at 1 MHz.

Pulsed laser ablation has been used to deposit thin films of SrFeO25+x (x = 0 to ≈0.5). Previous work has shown that the orientation of the films, determined by powder x-ray diffraction depended strongly upon the deposition temperature. Films grown below 770 K showed little or no orientation. A growth temperature of 900 K resulted in films oriented (200). Growth temperatures of > 1000 K produced films oriented predominantly (110). At 673 K in an oxygen atmosphere, oriented films readily converted from the oxygen deficient brownmillerite form (x=0) to the oxygen rich cubic (or distorted cubic) perovskite form (x≈0.3). Films which exhibited no initial orientation did not react with oxygen under these conditions. Cycling non-oriented films between 230 and 800 ppm of oxygen in 101.3 kPa of nitrogen at 673 K resulted in weak (110) orientation. Once oriented, the films reacted readily with oxygen and exhibited measurable resistance changes. The conversion from oxygen deficient to oxygen rich form was monitored by x-ray diffraction and the DC resistance of the films.

A PbTiO3 thin film prepared on silicon substrate by sol-gel technique has been studied by micro-Raman spectroscopy. The spectra, in comparison to the single crystal work, show high background in the low frequency region and Raman lines are broader, thus revealing the polycrystalline nature of the film. The frequencies of the Raman bands in the film are clearly shifted to lower frequencies compared to the corresponding ones in the single crystal or powder forms. This phenomenon is similar to the hydrostatic pressure effect on the Raman lines of PbTiO3 single crystal. The film, therefore, has grains under stress. This stress is caused by non-equilibrium defects and diffusion at the interface. Measurements at different film positions showed variation in the frequency and width of the Raman bands which are associated with the stress and grain size inhomogeneities. The measured shift in the Raman frequencies suggest grain sizes ≤l μm. XRD indicates grain size around 22 nm.

Bi4Ti3O12 thin films have been grown on indium tin oxide coated glass by pulsed laser deposition. The films are rapidly thermal annealed at 650 °C in various kinds of ambients. X-ray diffraction and scanning electron microscopy are used to investigate crystallization and microstructures, respectively. Using Auger electron microscopy, chemical compositions and depth profiles are examined. Optical and current-voltage characteristics measurements of the films show that their transmittance and leakage current behaviors are strongly dependent upon the microstructures. O2 partial pressure in the rapid thermal annealing process is found to be an important parameter which determines crystallization, microstructures, and leakage current behaviors of the Bi4Ti3O12 thin films.

The mechanical properties of zirconia are known to be a function of phase composition. We show here that a nanolaminate geometry can be used to control the phase composition of zirconia films. The experiment consisted of growth of nanoscale multilayer films (nanolaminates) of polycrystalline zirconia and amorphous alumina by reactive sputter deposition on Si (111) and fused silica substrates. The films were characterized using x-ray diffraction and high resolution electron microscopy. The results show that both monoclinic (m) and tetragonal (t) zirconia polymorphs were formed in the zirconia layers. Most crystallites are oriented with either close-packed {111}-t or {111}-m planes parallel to the substrate. The volume fraction of tetragonal zirconia, the desired phase for transformation-toughening behavior, increases with decreasing zirconia layer thickness. Nanolaminates with a volume fraction of tetragonal zirconia exceeding 0.8 were produced without the addition of a stabilizing dopant, and independent of the kinetic factors that limit tetragonal zirconia growth in pure zirconia films.

Oxide films, 0.2-2.0 μm in thickness on Zr-2.5Nb and 11 μm thick on Zr-20Nb alloys, formed in steam at 673 K, have been examined using TEM, XRD and Raman spectroscopy. Columnar grains of mostly monoclinic Zr02 in oxide films on Zr-2.5Nb exhibit a dual texture: a fibre mode with an axis close to the 102m pole and a [001]m growth mode with an orientation relationship [100]m // [4510]α and (010)m // (0001)α with the α-Zr metal. In both modes, “tetragonal” (and/or cubic) ZrO2 was present. Raman spectroscopy differentiated two non-cubic “tetragonal” forms of ZrOz within the [001]m growth texture. In thin oxides (0.5 μm or less), this corresponds to the tetragonal ZrO2 observed in ceramic zirconia and is characterised by a Raman band near 260 cm−1. The 278 and related 438 cm−1 Raman bands observed here in some oxide films (and in other Zr corrosion oxides) are attributed to a separate, non-cubic phase structurally related to the tetragonal ZrO2. The intensities of the 278 and 438 cm−1 bands are dependent not only on the amount of this modified-tetragonal phase but also on the oxide texture (related to the metal texture) and the beam orientation. The lack of Raman response from the “tetragonal” ZrO2 within the fibre mode of texture indicates either a low volume fraction or a cubic-like structure. For oxide on Zr-20Nb, XRD and Raman spectroscopy show a mixture of monoclinic and “tetragonal” ZrO2; the Raman results indicate the “tetragonal” ZrO2 has a high crystal symmetry or nearly cubic structure.

Lead zirconate titanite (PZT) thin films have been prepared on Pt/Ti/SiO2/Si and Pt/Ta/Si2/Si substrates by electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR PECVD) at low temperatures using metal-organic (MO) sources. One of the advantages of this method is the easy control of the cation concentrations in the PZT films through the adjustment of the flow rates of each MO sources. The film compositional ratio Ti/Zr was found to be linearly proportional to the flow rate ratio of the input Ti and Zr MO sources. The Pb/(Zr+Ti) ratio was not so much affected by the Ti source flow rate but was inversely proportional to the Zr source flow rate. Pb concentration in the deposited PZT films increased with increasing Ti source flow rate and with decreasing substrate temperature. Perovskite single phase PZT films were successfully fabricated at low temperatures below 500 °C. The perovskite structure was obtained when the Pb/(Zr+Ti) ratio in the deposited film was close to 1.

Highly preferentially oriented lead lathanum zirconate titanate(PLZT) thin films were fabricated on various substrates using the spin coating of metal organic solutions having the composition of (9/50/50) and (10/0/100). The substrates used in this study were SrTiO3(100), MgO(100), r-plane sapphire, PLT-coated glass, and Pt/Ti/MgO substrates. The films were heat-treated at 600°C and 700°C using the direct insertion method. The phases and the orientation of the PLZT thin films were examined using X-ray diffraction(XRD). Pole figure and X-ray rocking curves were measured to study the film orientation. The films were grown with (100), (110), and (001) plane being parallel to the surfaces of SrTiO3, sapphire, and Pt/Ti/MgO, respectively. The dielectric and optical properties of both the oriented films and the noncrystalline films were measured and discussed.

We present a novel oxidation method to improve the surface roughness at the poly-oxide/poly-Si interface. Instead of directly oxidizing the poly-Si to the desired thickness of the SiO2, a thin oxide layer is thermally grown on the poly-Si layer and then an a-Si layer is deposited on the top of the oxide layer. The a-Si layer is used as a silicon-source during next step of oxidation. The a-Si layer is fully oxidized until the poly-oxide/poly-Si interface advances below the initial interface. For comparison, the poly-oxide/poly-Si interface is also obtained by the conventional oxidation method. The surface roughness at the interface is investigated using transmission electron microscopy (TEM) and atomic force microscopy (AFM). For the novel oxidation method with the 50 Å thick intermediate oxide, the rms surface roughness at the poly-oxide/poly-Si interface is 30 Å, whereas that is 120 Å for the conventional method.

Ruthenium dioxide (RuO2) thin films are evaluated as bottom electrode for dielectric SrTiO3. It was found that a RuO2 (50nm) / Ru (20nm) barrier layer on a Si substrate is effective as an oxygen barrier layer and as a metal diffusion barrier layer for sputter deposited SrTiO3 films at substrate temperature of 450°C. To test suitability for high temperature processes, RuO2/Ru electrodes were annealed in air at 600°C. 100nm-thiick RuO2 was sufficient to prevent oxygen diffusion. After annealing in the same condition, the leakage current of sputter deposited SrTiO3 (150nm) on RuO2(50nm) / Ru(50nm) was 7.6 × 10 −9 (A/cm2) at 2V.

Pulsed-laser deposition has been used to grow thin films of the rock-salt and spinel structured oxides NiO, CoO and C03O4 on single-crystal substrates of α-Al2O3, MgO and C-Z1O2. The resultant microstructures were characterized in plan-view by transmission electron microscopy and by low-voltage scanning electron microscopy. In all the depositions, the parameters could be controlled to grow predominantly single-crystal films. In the NiO/(0001)α-Al2O3 and CoO/(100)c-ZrO2 systems, {111}-oriented films were observed which were found to be twinned close to 60° and 90° about <111> respectively. Growth of cobalt oxide films on (100) MgO at 800°C and 15 mTorr of oxygen produced {100}-oriented domains of C03O4 meeting at antiphase boundaries. These observations and other recent studies re-emphasize the role of substrate crystallography in governing the orientation relationships in the overlayer.

Depositions of high quality SiO2 and SnO2 films from the reaction of homoleptic amido precursors M(NMe2)4 (M = Si, Sn) and oxygen were carried out in an atmospheric pressure chemical vapor deposition reactor. The films were deposited on silicon, glass and quartz substrates at temperatures of 250 to 450 °C. The silicon dioxide films are stoichiometric (O/Si = 2.0) with less than 0.2 atom % C and 0.3 atom % N and have hydrogen contents of 9 ± 5 atom °. They are deposited with growth rates from 380 to 900 Å/min. The refractive indexes of the SiO2 films are 1.46, and infrared spectra show a possible Si-OH peak at 950 cm−1. X-Ray diffraction studies reveal that the SiO2 film deposited at 350°C is amorphous. The tin oxide films are stoichiometric (O/Sn = 2.0) and contain less than 0.8 atom % carbon, and 0.3 atom % N. No hydrogen was detected by elastic recoil spectroscopy. The band gap for the SnO2 films, as estimated from transmission spectra, is 3.9 eV. The resistivities of the tin oxide films are in the range 10−2 to 10−3 Ω cm and do not vary significantly with deposition temperature. The tin oxide film deposited at 350°C is crystalline cassitterite with some (101) orientation.

The evolution of microstructure of thin oxide films during growth has been quantitatively analysed by atomic force microscopy (AFM). The oxide films were formed in pure oxygen atmosphere at temperatures ranging from 873 to 1173 K on polycrystalline nickel substrates. The substrates were both pure and superficially modified by nanometer-sized dispersions of CeO2. The incorporation of reactive element into the oxide inhibits the growth kinetics and affects the microscopic surface morphology. The extent of this effect depends essentially on the substrate surface microstructure prior to modification and the size of CeO2 particles. A correlation was found between the surface topography and the reduction of oxide growth rate caused by the reactive element.

CeO2 ceramics were manufactured in the form of surface coatings deposited onto various substrates by sol-gel technology. The size of the CeO2 crystallites, dried at room temperature, was about 5 nm and did not change significantly after heating, up to 680 K. Further increase of the temperature resulted in a rapid growth of crystallites. The process of growth depends also on the film thickness and nature of substrate. The results obtained using thermogravimetric analysis (TGA) and infrared spectroscopy (IR) demonstrated that the thermal decomposition of gel was completed at about 750 K. There was no evident texture in both the as-deposited state and after heat-treatment. X-ray diffraction (XRD), the atomic force microscopy (AFM), and transmission electron microscopy (TEM) were used to characterize the structure of coatings. The examples of application of CeO2 ceramics as coatings for high temperature corrosion protection are presented. The role of size of CeO2 particles in modification of grain boundary transport is discussed.

Polyxylylene thin films grown by the chemical vapor deposition (CVD) process have long been utilized to achieve uniform, pinhole-free conformal coatings. They have recently been cited as possible low dielectric constant films for intermetal layers in high-speed ICs. Homopolymer films are highly crystalline and have a glass transition temperature around room temperature. We have demonstrated that room temperature copolymerization with previously untested comonomers can be achieved during the CVD process. Copolymerizing chloro-p-xylylene with perfluorooctyl methacrylate results in the dielectric constant at optical frequencies being lowered from 2.68 to 2.19. Copolymerizing p-xylylene with vinylbiphenyl resulted in films which increase the temperature at which oxidative scission occurs from 320 to 450C. Copolymerizing p-xylylene with 9-vinylanthracene resulted in a brittle, yellow film.

The hardnesses and elastic moduli of sputter-deposited Fe/Pt and Fe/Cr multilayers grown on MgO(001) are evaluated as a function of composition wavelength, Λ. Structural determination by x-ray diffraction showed these films to be oriented in the plane as well as out of the plane. The mechanical behavior of these films was evaluated by nanoindentation. The combination of nanoindentation and x-ray diffraction is an attempt to determine the structural underpinnings of the mechanical behavior of these metal multilayer systems. For both systems there is no observed enhancement in the elastic modulus (the so-called supermodulus effect) across a wide range of bilayer spacings. Nanoindentation results show that for Fe/Pt multilayers, the hardness is enhanced over that expected from a simple rule of mixtures by a factor of approximately 2.5, with a maximum enhancement of 2.8 times this value at a wavelength of 25 Å. This enhancement in hardness occurs for bilayer spacings from 20 Å to 100 Å and is not a strong function of Λ over this range. Results for Fe/Cr multilayers show a hardness enhancement over a similar wavelength range of approximately two times the rule of mixtures value, with a maximum enhancement of 2.2 times this value at a wavelength of 40 Å. The larger hardness enhancement in the Fe/Pt system may be due to the structural barrier (FCC/BCC) to dislocation motion between the two materials. The dominant mechanism responsible for the hardness enhancement in Fe/Pt and Fe/Cr multilayers is not yet known, however three models for dislocation interactions which could account for the hardness enhancement in these multilayers are discussed.

Several characteristics of compositionally-modulated Au-Ni thin films have been observed to vary with composition wavelength for wavelengths between 0.9 and 4.0 nm. The average lattice parameter normal to the film plane displays a maximum, the elastic stiffness shows a minimum and the substrate interaction stress in the film goes through a compressive peak in this regime. These variations are all consistent with a model in which deviations from bulk behavior are confined to the interfaces in the material. In this paper, we present the results of microstructural analyses of these films. Symmetric and asymmetric θ–2θ x-ray diffraction scans were conducted with scattering vectors oriented at a variety of angles to the film normal. Rocking curve analyses were also conducted. Features arising from the composition modulation in symmetric scans are quite sharp. However, asymmetric scans and rocking curves indicate that these films have a relatively poor {111} texture. Data from all scans provide clear evidence that Au intermixes preferentially into Ni. These results are supported by computer simulations of the diffraction spectra and the results of electron-image and -diffraction analyses. These measurements provide a consistent explanation for the mechanical properties of these films.