Ferroelectric hafnium zirconium oxide holds great promise for a broad spectrum of complementary metal–oxide–semiconductor (CMOS) compatible and scaled microelectronic applications, including memory, low-voltage transistors, and infrared sensors, among others. An outstanding challenge hindering the implementation of this material is polarization instability during field cycling. In this study, the nanoscale phenomena contributing to both polarization fatigue and wake-up are reported. Using synchrotron X-ray diffraction, the conversion of non-polar tetragonal and polar orthorhombic phases to a non-polar monoclinic phase while field cycling devices comprising noble metal contacts is observed. This phase exchange accompanies a diminishing ferroelectric remanent polarization and provides device-scale crystallographic evidence of phase exchange leading to ferroelectric fatigue in these structures. A reduction in the full width at half-maximum of the superimposed tetragonal (101) and orthorhombic (111) diffraction reflections is observed to accompany wake-up in structures comprising tantalum nitride and tungsten electrodes. Combined with polarization and relative permittivity measurements, the observed peak narrowing and a shift in position to lower angles is attributed, in part, to a phase exchange of the non-polar tetragonal to the polar orthorhombic phase during wake-up. These results provide insight into the role of electrodes in the performance of hafnium oxide-based ferroelectrics and mechanisms driving wake-up and fatigue, and demonstrate a non-destructive means to characterize the phase changes accompanying polarization instabilities.

We introduce using sputtered aluminum oxide (alumina) as a resilient etch mask for fluorinated silicon reactive ion etches. Achieving selectivity of 5000:1 for cryogenic silicon etching and 68:1 for SF(6)/C(4)F(8) silicon etching, we employ this mask for fabrication of high-aspect-ratio silicon micropillars and nanopillars. Nanopillars with diameters ranging from below 50 nm up to several hundred nanometers are etched to heights greater than 2 microm. Micropillars of 5, 10, 20, and 50 microm diameters are etched to heights of over 150 microm with aspect ratios greater than 25. Processing and characterization of the sputtered alumina is also discussed.

Visible and near-IR photoluminescence (PL) is reported from sub-10 nm silicon nanopillars. Pillars were plasma etched from single crystal Si wafers and thinned by utilizing strain-induced, self-terminating oxidation of cylindrical structures. PL, lifetime, and transmission electron microscopy were performed to measure the dimensions and emission characteristics of the pillars. The peak PL energy was found to blue shift with narrowing pillar diameter in accordance with a quantum confinement effect. The blue shift was quantified using a tight binding method simulation that incorporated the strain induced by the thermal oxidation process. These pillars show promise as possible complementary metal oxide semiconductor compatible silicon devices in the form of light-emitting diode or laser structures.

Pyroelectric coefficients were measured for 20 nm thick crystalline hafnium zirconium oxide (Hf1-xZrxO2) thin films across a composition range of 0 ≤ x ≤ 1. Pyroelectric currents were collected near room temperature under zero applied bias and a sinusoidal oscillating temperature profile to separate the influence of non-pyroelectric currents. The pyroelectric coefficient was observed to correlate with zirconium content, increased orthorhombic/tetragonal phase content, and maximum polarization response. The largest measured absolute value was 48 μCm−2 K−1 for a composition with x = 0.64, while no pyroelectric response was measured for compositions which displayed no remanent polarization (x = 0, 0.91, and 1).

By using a dry etch chemistry which relies on the highly preferential etching of silicon, over that of gallium (Ga), we show resist-free fabrication of precision, high aspect ratio nanostructures and microstructures in silicon using a focused ion beam (FIB) and an inductively coupled plasma reactive ion etcher (ICP-RIE). Silicon etch masks are patterned via Ga(+) ion implantation in a FIB and then anisotropically etched in an ICP-RIE using fluorinated etch chemistries. We determine the critical areal density of the implanted Ga layer in silicon required to achieve a desired etch depth for both a Pseudo Bosch (SF(6)/C(4)F(8)) and cryogenic fluorine (SF(6)/O(2)) silicon etching. High fidelity nanoscale structures down to 30 nm and high aspect ratio structures of 17:1 are demonstrated. Since etch masks may be patterned on uneven surfaces, we utilize this lithography to create multilayer structures in silicon. The linear selectivity versus implanted Ga density enables grayscale lithography. Limits on the ultimate resolution and selectivity of Ga lithography are also discussed.