Dimensional Scaling of Perovskite Ferroelectric Thin Films

Open Access
Keech, Ryan Robert
Graduate Program:
Materials Science and Engineering
Doctor of Philosophy
Document Type:
Date of Defense:
July 18, 2016
Committee Members:
  • Susan E Trolier-Mckinstry, Dissertation Advisor
  • Susan E Trolier-Mckinstry, Committee Chair
  • Clive A Randall, Committee Member
  • Thomas R Shrout, Committee Member
  • Mehdi Kiani, Outside Member
  • Glenn Martyna, Special Member
  • Ferroelectric
  • piezoelectric
  • thin films
  • nanotechnology
  • patterning
  • logic device
  • materials science
  • perovskite
  • PMN-PT
  • declamping
  • lead magnesium niobate lead titanate
  • scaling
Dimensional size reduction has been the cornerstone of the exponential improvement in silicon based logic devices for decades. However, fundamental limits in the device physics were reached ~2003, halting further reductions in clock speed without significant penalties in power consumption. This has motivated the research into next generation transistors and switching devices to reinstate the scaling laws for clock speed. This dissertation aims to support the scaling of devices that are based on ferroelectricity and piezoelectricity and to provide a roadmap for the corresponding materials performance. First, a scalable growth process to obtain highly {001}-oriented lead magnesium niobate – lead titanate (PMN-PT) thin films was developed, motivated by the high piezoelectric responses observed in bulk single crystals. It was found that deposition of a 2-3 nm thick PbO buffer layer on {111} Pt thin film bottom electrodes, prior to chemical solution deposition of PMN-PT reduces the driving force for Pb diffusion from the PMN-PT to the bottom electrode, and facilitates nucleation of {001}-oriented perovskite grains. Energy dispersive spectroscopy demonstrated that up to 10% of the Pb from a PMN-PT precursor solution may diffuse into the bottom electrode. PMN-PT grains with a mixed {101}/{111} orientation in a matrix of Pb-deficient pyrochlore phase were then promoted near the interface. When this is prevented, phase pure films with {001} orientation with Lotgering factors of 0.98-1.0, can be achieved. The resulting films of only 300 nm in thickness exhibit longitudinal effective d33,f coefficients of ~90 pm/V and strain values of ~1% prior to breakdown. 300 nm thick epitaxial and polycrystalline lead magnesium niobate – lead titanate (70PMN-30PT) blanket thin films were studied for the relative contributions to property thickness dependence from interfacial and grain boundary low permittivity layers. Epitaxial PMN-PT films were grown on SrRuO3 /(001)SrTiO3, while polycrystalline films with {001}-Lotgering factors >0.96 were grown on Pt/TiO2/SiO2/Si substrates via chemical solution deposition. It was found that both film types exhibited similar, thickness-independent high-field εr of ~300 with highly crystalline electrode/dielectric interfaces. The dielectric data suggest that irreversible domain wall motion is the major contributor to the overall dielectric response and its thickness dependence. In epitaxial films the irreversible Rayleigh coefficients reduced 85% upon decreasing thickness from 350 to 100 nm. Tmax was the only measured small signal quantity which was more thickness dependent in polycrystalline than epitaxial films. This was attributed to the relaxor nature present in the films, potentially stabilized by defect concentrations, and/or chemical inhomogeneity. The effective interfacial layers are found to contribute to the measured thickness dependence in d33,f measured by X-ray diffraction. Finally, high field piezoelectric characterization revealed a field-induced rhombohedral to tetragonal phase transition in epitaxial films. While the mechanisms causing thickness dependence are mostly understood, the functional properties of blanket PMN-PT films remain about an order of magnitude lower than what is achieved in constraint-free bulk single crystals. These property reductions are attributed to substrate clamping, and the process of declamping via lateral subdivision was studied in 300-350 nm thick, {001} oriented 70PMN-30PT films on Si substrates. In the clamped state, the films exhibit relative permittivity near 1500 and loss tangents of approximately 0.01. The films showed slim hysteresis loops with remanent polarizations of about 8 μC/cm2 and breakdown fields over 1500 kV/cm. Using optical and electron beam lithography combined with reactive ion etching, the PMN-PT films were systematically patterned down to lateral feature sizes of 200 nm in spatial scale with nearly vertical sidewalls. Upon lateral scaling, which produced partially declamped films, there was an increase in both small and large signal dielectric properties, including a doubling of the relative permittivity in structures with width-to-thickness aspect ratios of 0.7. In addition, declamping resulted in a counterclockwise rotation of the hysteresis loops, increasing the remanent polarization to 13.5 μC/cm2. Rayleigh analysis, Preisach modeling, and the relative permittivity as a function of temperature also indicated changes in the domain wall motion and intrinsic response of the laterally scaled PMN-PT. The longitudinal piezoelectric coefficient, d33,f, was interrogated as a function of position across the patterned structures by finite element modeling, piezoresponse force microscopy, and nanoprobe synchrotron X-ray diffraction. It was found that d33,f increased from the clamped value of 40-50 pm/V to ~160 pm/V at the free sidewall under 200 kV/cm excitation. The sidewalls partially declamped the piezoelectric response 500-600 nm into the patterned structure, raising the piezoelectric response at the center of features with lateral dimensions less than 1 μm (3:1 width to thickness aspect ratio). The normalized data from all three characterization techniques are in excellent agreement, with quantitative differences providing insight to the field dependence of the piezoelectric coefficient and its declamping behavior.