In situ control of oxygen vacancies in TiO2 by atomic layer deposition for resistive switching devices.

Oxygen vacancies (V(O)) have profound effects on the physical and chemical performance of devices based on oxide materials. This is particularly true in the case of oxide-based resistive random access memories, in which memory switching operation under an external electrical stimulus is closely associated with the migration and ordering of the oxygen vacancies in the oxide material. In this paper, we report on a reliable approach to in situ control of the oxygen vacancies in TiOx films. Our strategy for tight control of the oxygen vacancy is based on the utilization of plasma-enhanced atomic layer deposition of titanium oxide under precisely regulated decomposition of the precursor molecules (titanium (IV) tetraisopropoxide, Ti[OCH(CH3)2]4) by plasma-activated reactant mixture (N2+O2). From the various spectroscopic and microstructural analyses by using Rutherford backscattering spectrometry, x-ray photoelectron spectroscopy, high-resolution transmission electron microscopy, confocal Raman spectroscopy, and spectroscopic ellipsometry, we found that the precursor decomposition power (R(F)) of plasma-activated reactant mixture determines not only the oxygen vacancy concentration but also the crystallinity of the resulting TiO(x) film: nanocrystalline anatase TiO(x) with fewer oxygen vacancies under high R(F), while amorphous TiOx with more oxygen vacancies under low RF. Enabled by our controlling capability over the oxygen vacancy concentration, we were able to thoroughly elucidate the effect of oxygen vacancies on the resistive switching behavior of TiO(x)-based memory capacitors (Pt/TiO(x)/Pt). The electrical conduction behavior at the high resistance state could be explained within the framework of the trap-controlled space-charge-limited conduction with two characteristic transition voltages. One is the voltage (V(SCL)) for the transition from Ohmic conduction to space-charge-limited conduction, and the other is the voltage (V(TFL)) for transition from space-charge-limited conduction to trap-filled-limited conduction. In this work, we have disclosed for the first time the dependence of these two characteristic transition voltages (i.e., V(SCL) and V(TFL)) on the oxygen vacancy concentration.

In situ determination of the pore opening point during wet-chemical etching of the barrier layer of porous anodic aluminum oxide: nonuniform impurity distribution in anodic oxide.

Wet-chemical etching of the barrier oxide layer of anodic aluminum oxide (AAO) was systematically investigated by using scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS), and a newly devised experimental setup that allows accurate in situ determination of the pore opening point during chemical etching of the barrier oxide layer. We found that opening of the barrier oxide layer by wet-chemical etching can be significantly influenced by anodization time (tanodi). According to secondary ion mass spectrometry (SIMS) analysis, porous anodic aluminum oxide (AAO) samples formed by long-term anodization contained a lower level of anionic impurity in the barrier oxide layer compared to the short-term anodized one and consequently exhibited retarded opening of the barrier oxide layer during the wet-chemical etching. The observed compositional dependence on the anodization time (tanodi) in the barrier oxide layer is attributed to the progressive decrease of the electrolyte concentration upon anodization. The etching rate of the outer pore wall at the bottom part is lower than that of the one at the top part due to the lower level of impurity content in that region. This indicates that a concentration gradient of anionic impurity in the outer pore wall oxide may be established along both the vertical and radial directions of cylindrical pores. Apart from the effect of electrolyte concentration on the chemical composition of the barrier oxide layer, significantly decreased current density arising from the lowered concentration of electrolyte during the long-term anodization (~120 h) was found to cause disordering of pores. The results of the present work are expected to provide viable information not only for practical applications of nanoporous AAO in nanotechnology but also for thorough understanding of the self-organized formation of oxide nanopores during anodization.

In-situ synchrotron X-ray scattering study of thin film growth by atomic layer deposition.

We report an atomic layer deposition chamber for in-situ synchrotron X-ray scattering study of thin film growth. The chamber was designed for combined synchrotron X-ray reflectivity and two-dimensional grazing-incidence X-ray diffraction measurement to do a in-situ monitoring of ALD growth. We demonstrate ruthenium thermal ALD growth for the performance of the chamber. 10, 20, 30, 50, 70, 100, 150 and 250-cycled states are measured by X-ray scattering methods during ALD growth process. Growth rate is calculated from thickness values and the surface roughness of each state is estimated by X-ray reflectivity analysis. The crystal structure of initial growth state is observed by Grazing-incidence X-ray diffraction. These results indicate that in-situ X-ray scattering method is a promising analysis technique to investigate the initial physical morphology of ALD films.

Nanoscale bit formation in highly (111)-oriented ferroelectric thin films deposited on glass substrates for high-density storage media.

PbTiO(3) (PTO) ferroelectric films on Pt(111) bottom electrode layers covering Ta/glass were prepared using pulsed laser deposition. X-ray diffraction patterns revealed that the PTO films were preferentially (111)-oriented. The films were highly crystalline and had a smooth surface with root mean square (RMS) roughness of 1.5 nm. Ferroelectric properties of the PTO films were characterized using piezoresponse force microscopy (PFM). PFM techniques achieved ferroelectric polarization bits with a minimum width of 22 nm, which corresponds to a potential recording density of 1.3 Tbit/in(2) in ferroelectric storage devices.

Ultrahigh density array of epitaxial ferroelectric nanoislands on conducting substrates.

An ultrahigh density array of epitaxial PbTiO(3) (PTO) nanoislands with uniform size was fabricated on a single-crystalline Nb-doped SrTiO(3) (100) substrate over a large area (cm(2) scale) by simple but robust method utilizing polystyrene-block-poly(4-vinylpridine) copolymer micelles. Each nanoisland has an average volume of 2.6 x 10(3) nm(3) (a height of 7 nm and a diameter of 22 nm). Because of uniform nanoislands over a large area, a synchrotron X-ray diffraction experiment was successfully employed to analyze the domain structures of PTO nanoislands. They showed well-defined epitaxy on the substrate, which was also confirmed by high-resolution transmission electron microscopy. All of the nanoislands existing in the entire area showed distinct piezoresponse that confirms the existence of ferroelectricity at this size. The results indicate that the critical size of ferroelectrics could be scaled-down further, thereby much increasing the density of ferroelectric devices.

Non-Kolmogorov-Avrami-Ishibashi switching dynamics in nanoscale ferroelectric capacitors.

Switching dynamics of nanoscale ferroelectric capacitors with a radius of 35 nm were investigated using piezoresponse force microscopy. Polarization switching starts with only one nucleation event occurring only at the predetermined places. The switching dynamics of nanoscale capacitors did not follow the classical Kolmogorov-Avrami-Ishibashi model. On the basis of the consideration of two separate (nucleation and growth) steps within a nonstatistical finite system, we have proposed a model which is in good agreement with the experimental results.

Wafer-scale arrays of epitaxial ferroelectric nanodiscs and nanorings.

Wafer-scale arrays of well-ordered Pb(Zr(0.2)Ti(0.8))O3 nanodiscs and nanorings were fabricated on the entire area (10 mm x 10 mm) of the SrRuO3 bottom electrode on an SrTiO3 single-crystal substrate using the laser interference lithography (LIL) process combined with pulsed laser deposition. The shape and size of the nanostructures were controlled by the amount of PZT deposited through the patterned holes and the temperature of the post-crystallization steps. X-ray diffraction and transmission electron microscopy confirmed that (001)-oriented PZT nanostructures were grown epitaxially on the SrRuO3(001) bottom electrode layer covering the (001)-oriented single-crystal substrate. The domain structures of PZT nano-islands were characterized by reciprocal space mapping using synchrotron x-ray radiation. Ferroelectric properties of each PZT nanostructure were characterized by scanning force microscopy in the piezoresponse mode.

Individually addressable epitaxial ferroelectric nanocapacitor arrays with near Tb inch-2 density.

Ferroelectric materials have emerged in recent years as an alternative to magnetic and dielectric materials for nonvolatile data-storage applications. Lithography is widely used to reduce the size of data-storage elements in ultrahigh-density memory devices. However, ferroelectric materials tend to be oxides with complex structures that are easily damaged by existing lithographic techniques, so an alternative approach is needed to fabricate ultrahigh-density ferroelectric memories. Here we report a high-temperature deposition process that can fabricate arrays of individually addressable metal/ferroelectric/metal nanocapacitors with a density of 176 Gb inch(-2). The use of an ultrathin anodic alumina membrane as a lift-off mask makes it possible to deposit the memory elements at temperatures as high as 650 degrees C, which results in excellent ferroelectric properties.

Stability of ferroic phases in the highly piezoelectric Pb(ZrxTi1-x)O3 ceramics.

The morphotropic phase boundary in the phase diagram of the technologically important Pb(ZrxTi1-x)O3 (PZT) ceramics has been traditionally believed to separate ferroelectric tetragonal and rhombohedral phase regions. This old picture has come under close scrutiny during the last eight years following the discovery of new monoclinic phases in the Cm and Cc space groups. This article presents a brief overview of these discoveries in which the use of multiple diffraction probes (X-ray, electron, neutron diffraction) in conjunction with physical property measurements has played a crucial role. A new phase diagram of PZT showing the stability fields of these structures below room temperature is also presented.

Surfactant-free hydrothermal synthesis of highly tetragonal barium titanate nanowires: a structural investigation.

Barium titanate nanowires synthesized with a surfactant-free hydrothermal method have been characterized by various techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), synchrotron X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The TEM and SEM analyses show the uniform cylindrical nanowires. The Rietveld refinement with synchrotron X-ray powder diffraction showed that the lattice parameters of cubic and tetragonal phases were a (= b = c) = 4.0134 A and a (= b) = 3.9998 A, c = 4.0303 A, respectively. The final weighted R-factor, R(wp), was 6.75% and the goodness of fit indicator was 1.30. The mass fraction of tetragonal and cubic phases based on the refined scale factor for the two phases were 98.4% and 1.6%, respectively, which clearly show the nanowires are tetragonal. The XPS analysis has shown that as-obtained BaTiO3 nanowires were phase pure. The Raman spectra confirm the tetragonal phase of the BaTiO3 nanowires. The dielectric constant measurement shows the shift in the transition temperature (Tc = 105 degrees C) compared to the bulk transition temperature (Tc = 132 degrees C). The dielectric constant at Tc was 174 measured at 1 kHz frequency.

Fabrication of 3-dimensional PbZr(1-x)Ti(x)O3 nanoscale thin film capacitors for high density ferroelectric random access memory devices.

PbZr(x)Ti(1-x)O3 (PZT) thin films were deposited on 3-dimensional (3D) nano-scale trench structures for use in giga-bit density ferroelectric random access memories. PZT thin films were deposited by liquid delivery metalorganic chemical vapor deposition using Pb(thd)2, Zr(MMP)4, and Ti(MMP)4 precursors dissolved in ethyl cyclohexane. Iridium thin films were deposited by atomic layer deposition, and they exhibited excellent properties for capacitor electrodes even at a thickness of 20 nm. The trench capacitor was composed of three layers, viz. Ir/PZT/lr (20/60/20 nm), and had a diameter of 250 nm and a height of 400 nm. Almost 100% step coverage was obtained at a deposition temperature of 530 degrees C. The PZT thin film capacitors with a thickness of 60 nm on a planar structure exhibited a remnant polarization (Pr) of 28 microC/cm2, but the Pr value of the 3D PZT capacitors decreased slightly with decreasing 3D trench pattern size. The transmission electron microscope analysis indicated that the PZT thin films had compositional uniformity in the 3D trench region. Both columnar and granular grains were formed on the sidewalls of the trench capacitors, and their relative proportion exhibited strong size dependence. The trench capacitors with more columnar PZT grains showed good switching behavior under an external bias of 2.1 V and had a remnant polarization of 19-24 microC/cm2.