Casamento, Joseph; Baksa, Steven M.; Behrendt, Drew; Calderon, Sebastian; Goodling, Devin; Hayden, John; He, Fan; Jacques, Leonard; Lee, Seung H.; Smith, Walter; Suceava, Albert; Tran, Quyen; Zheng, Xiaojun; Zu, Rui; Beechem, Thomas; Dabo, Ismaila; Dickey, Elizabeth C.; Esteves, Giovanni; Gopalan, Venkatraman; Henry, Michael D.; Ihlefeld, Jon F.; Jackson, Thomas N.; Kalinin, Sergei V.; Kelley, Kyle P.; Liu, Yongtao; Rappe, Andrew M.; Redwing, Joan; Trolier-Mckinstry, Susan; Maria, Jon P.
Wurtzite ferroelectrics are an emerging material class that expands the functionality and application space of wide bandgap semiconductors. Promising physical properties of binary wurtzite semiconductors include a large, reorientable spontaneous polarization, direct band gaps that span from the infrared to ultraviolet, large thermal conductivities and acoustic wave velocities, high mobility electron and hole channels, and low optical losses. The ability to reverse the polarization in ternary wurtzite semiconductors at room temperature enables memory and analog type functionality and quasi-phase matching in optical devices and boosts the ecosystem of wurtzite semiconductors, provided the appropriate combination of properties can be achieved for any given application. In this article, advances in the design, synthesis, and characterization of wurtzite ferroelectric materials and devices are discussed. Highlights include: the direct and quantitative observation of polarization reversal of ∼135 μC/cm2 charge in Al1−xBxN via electron microscopy, Al1−xBxN ferroelectric domain patterns poled down to 400 nm in width via scanning probe microscopy, and full polarization retention after over 1000 h of 200 °C baking and a 2× enhancement relative to ZnO in the nonlinear optical response of Zn1−xMgxO. The main tradeoffs, challenges, and opportunities in thin film deposition, heterostructure design and characterization, and device fabrication are overviewed.
As ferroelectric hafnium zirconium oxide (HZO) becomes more widely utilized in ferroelectric microelectronics, integration impacts of intentional and nonintentional dielectric interfaces and their effects upon the ferroelectric film wake-up (WU) and circuit parameters become important to understand. In this work, the effect of the addition of a linear dielectric aluminum oxide, Al2O3, below a ferroelectric Hf0.58Zr0.42O2 film in a capacitor structure for FeRAM applications with niobium nitride (NbN) electrodes was measured. Depolarization fields resulting from the linear dielectric is observed to induce a reduction of the remanent polarization of the ferroelectric. Addition of the aluminum oxide also impacts the WU of the HZO with respect to the cycling voltage applied. Intricately linked to the design of a FeRAM 1C/1T cell, the metal-ferroelectric-insulator-metal (MFIM) devices are observed to significantly shift charge related to the read states based on aluminum oxide thickness and WU cycling voltage. A 33% reduction in the separation of read states are measured, which complicates how a memory cell is designed and illustrates the importance of clean interfaces in devices.
This work demonstrated both NbN and Nb make good electrodes for stabilizing orthorhombic phase of Hf0.6Zr0.4O2 ferroelectric films. Wake up are < 100 cycles. Pr can be as high as 30 µC/cm2 - respectively 14 and 18 µC/cm2 here. Further, capacitance suggests an orthorhombic phase can be stabilized. Addition of a linear dielectric under modest thickness can tune the Pr and reduce leakage.
Ferroelectric phase stability in hafnium oxide is reported to be influenced by factors that include composition, biaxial stress, crystallite size, and oxygen vacancies. In the present work, the ferroelectric performance of atomic layer deposited Hf0.5Zr0.5O2 (HZO) prepared between TaN electrodes that are processed under conditions to induce variable biaxial stresses is evaluated. The post-processing stress states of the HZO films reveal no dependence on the as-deposited stress of the adjacent TaN electrodes. All HZO films maintain tensile biaxial stress following processing, the magnitude of which is not observed to strongly influence the polarization response. Subsequent composition measurements of stress-varied TaN electrodes reveal changes in stoichiometry related to the different preparation conditions. HZO films in contact with Ta-rich TaN electrodes exhibit higher remanent polarizations and increased ferroelectric phase fractions compared to those in contact with N-rich TaN electrodes. HZO films in contact with Ta-rich TaN electrodes also have higher oxygen vacancy concentrations, indicating that a chemical interaction between the TaN and HZO layers ultimately impacts the ferroelectric orthorhombic phase stability and polarization performance. The results of this work demonstrate a necessity to carefully consider the role of electrode processing and chemistry on performance of ferroelectric hafnia films.
Fields, Shelby S.; Olson, David H.; Jaszewski, Samantha T.; Fancher, Chris M.; Smith, Sean W.; Dickie, Diane A.; Esteves, Giovanni; Henry, Michael D.; Davids, Paul; Hopkins, Patrick E.; Ihlefeld, Jon F.
The elastic moduli of amorphous and crystalline atomic layer-deposited Hf1-xZrxO2 (HZO, x = 0, 0.31, 0.46, 0.79, 1) films prepared with TaN electrodes on silicon substrates were investigated using picosecond acoustic measurements. The moduli of the amorphous films were observed to increase between 211 ± 6 GPa for pure HfO2 and 302 ± 9 GPa for pure ZrO2. In the crystalline films, it was found that the moduli increased upon increasing the zirconium composition from 248 ± 6 GPa for monoclinic HfO2 to 267 ± 9 GPa for tetragonal ZrO2. Positive deviations from this increase were observed for the Hf0.69Zr0.31O2 and Hf0.54Zr0.46O2 compositions, which were measured to have moduli of 264 ± 8 GPa and 274 ± 8 GPa, respectively. These two compositions contained the largest fractions of the ferroelectric orthorhombic phase, as assessed from polarization and diffraction data. The biaxial stress states of the crystalline films were characterized through sin2(ψ) x-ray diffraction analysis. The in-plane stresses were all found to be tensile and observed to increase with the increasing zirconium composition, between 2.54 ± 0.6 GPa for pure HfO2 and 5.22 ± 0.5 GPa for pure ZrO2. The stresses are consistent with large thermal expansion mismatches between the HZO films and silicon substrates. These results demonstrate a device-scale means to quantify biaxial stress for investigation on its effect on the ferroelectric properties of hafnia-based materials.
Rummel, Brian D.; Miroshnik, Leonid; Patriotis, Marios; Li, Andrew; Sinno, Talid R.; Henry, Michael D.; Balakrishnan, Ganesh; Han, Sang M.
Surface acoustic wave devices have been fabricated on a GaAs 100 substrate to demonstrate the capability of 2D Raman microscopy as an imaging technique for acoustic waves on the surface of a piezoelectric substrate. Surface acoustic waves are generated using a two-port interdigitated transducer platform, which is modified to produce surface standing waves. We have derived an analytical model to relate Raman peak broadening to the near-surface strain field of the GaAs surface produced by the surface acoustic waves. Atomic force microscopy is used to confirm the presence of a standing acoustic wave, resolving a total vertical displacement of 3 nm at the antinode of the standing wave. Stress calculations are performed for both imaging techniques and are in good agreement, demonstrating the potential of this Raman analysis.
Computing uses energy. At the bare minimum, erasing information in a computer increases the entropy. Landauer has calculated %7E kBT log(2) Joules is dissipated per bit of energy erased. While the success of Moores law has allowed increasing computing power and efficiency for many years, these improvements are coming to an end. This project asks if there is a way to continue those gains by circumventing Landauer through reversible computing. We explore a new reversible computing paradigm, asynchronous ballistic reversible computing or ABRC. The ballistic nature of data in ABRC matches well with superconductivity which provides a low-loss environment and a quantized bit encoding the fluxon. We discuss both these and our development of a superconducting fabrication process at Sandia. We describe a fully reversible 1-bit memory cell based on fluxon dynamics. Building on this model, we propose several other gates which may also offer reversible operation.
Ihlefeld, Jon F.; Luk, Ting S.; Smith, Sean; Fields, Shelby S.; Jaszewski, Samantha T.; Hirt, Daniel M.; Riffe, Will T.; Bender, Scott; Constantin, Costel; Ayyasamy, Mukil V.; Balachandran, Prasanna V.; Lu, Ping; Henry, Michael D.; Davids, Paul
Composition dependence of second harmonic generation, refractive index, extinction coefficient, and optical bandgap in 20 nm thick crystalline Hf1-xZrxO2 (0 ≤ x ≤ 1) thin films is reported. The refractive index exhibits a general increase with increasing ZrO2 content with all values within the range of 1.98-2.14 from 880 nm to 400 nm wavelengths. A composition dependence of the indirect optical bandgap is observed, decreasing from 5.81 eV for HfO2 to 5.17 eV for Hf0.4Zr0.6O2. The bandgap increases for compositions with x > 0.6, reaching 5.31 eV for Hf0.1Zr0.9O2. Second harmonic signals are measured for 880 nm incident light. The magnitude of the second harmonic signal scales with the magnitude of the remanant polarization in the composition series. Film compositions that display near zero remanent polarizations exhibit minimal second harmonic generation while those with maximum remanent polarization also display the largest second harmonic signal. The results are discussed in the context of ferroelectric phase assemblage in the hafnium zirconium oxide films and demonstrate a path toward a silicon-compatible integrated nonlinear optical material.
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.
In this study we examine a split-foundry multilevel application specific integrated circuit (ASIC) Si-interposer and die bonded using the direct bond interface (DBI) process, in addition to shortloop vehicles. The designs have been subject to relaxed pattern density rules, and exhibit chemical mechanical planarization (CMP) systematic process issues of varying degrees. We find that the interconnect formation is robust against moderate dielectric thickness variation, as well as a moderate degree of copper corrosion. We discuss and demonstrate various CMP methods which have a clear and repeatable impact. Pattern density effects and defectivity on the bond quality are examined using focused ion beam scanning electron microscope (FIB-SEM) images at the feature scale (sub 100 um) and intra-die scale (few mm). Impact to the CMP performance, including plug recess, and defectivity are discussed.
We report on the fabrication and characterization of Nb/Ta-N/Nb Josephson junctions grown by room temperature magnetron sputtering on 150-mm diameter Si wafers. Junction characteristics depend upon the Ta-N barrier composition, which was varied by adjusting the N2 flow during film deposition. Higher N2 flow rates raise the barrier resistance and increase the junction critical current. This work demonstrates the viability of Ta-N as an alternative barrier to aluminum oxide, with the potential for large scale integration.
We measure the frequency dependence of a niobium microstrip resonator as a function of temperature from 1.4 to 8.4 K. In a 2-micrometer-wide half-wave resonator, we find the frequency of resonance changes by a factor of 7 over this temperature range. From the resonant frequencies, we extract inductance per unit length, characteristic impedance, and propagation velocity (group velocity). We discuss how these results relate to superconducting electronics. Over the 2 K to 6 K temperature range where superconducting electronic circuits operate, inductance shows a 19% change and both impedance and propagation velocity show an 11% change.
In a previous paper, we described a new abstract circuit model for reversible computation called asynchronous ballistic reversible computing (ABRC), in which localized information-bearing pulses propagate ballistically along signal paths between stateful abstract devices and elastically scatter off those devices serially, while updating the device state in a logically-reversible and deterministic fashion. The ABRC model has been shown to be capable of universal computation. In the research reported here, we begin exploring how the ABRC model might be realized in practice using single flux quantum solitons (fluxons) in superconducting Josephson junction (JJ) circuits. One natural family of realizations could utilize fluxon polarity to represent binary data in individual pulses propagating near-ballistically, along discrete or continuous long Josephson junctions or microstrip passive transmission lines, and utilize the flux charge (-1, 0, +1) of a JJ-containing superconducting loop with Φ0 < IcL < 2Φ0 to encode a ternary state variable internal to a device. A natural question then arises as to which of the definable abstract ABRC device functionalities using this data representation might be implementable using a JJ circuit that dissipates only a small fraction of the input fluxon energy. We discuss conservation rules and symmetries considered as constraints to be obeyed in these circuits, and begin the process of classifying the possible ABRC devices in this family having up to three bidirectional I/O terminals, and up to three internal states.
In an ongoing project at Sandia National Laboratories, we are attempting to develop a novel style of superconducting digital processing, based on a new model of reversible computation called Asynchronous Ballistic Reversible Computing (ABRC). We envision an approach in which polarized flux-ons scatter elastically from near-lossless functional components, reversibly updating the local digital state of the circuit, while dissipating only a small fraction of the input fluxon energy. This approach to superconducting digital computation is sufficiently unconventional that an appropriate methodology for hand-design of such circuits is not immediately obvious. To gain insight into the design principles that are applicable in this new domain, we are creating a software tool to automatically enumerate possible topologies of reactive, undamped Josephson junction circuits, and sweep the parameter space of each circuit searching for designs exhibiting desired dynamical behaviors. But first, we identified by hand a circuit implementing the simplest possible nontrivial ABRC functional behavior with bits encoded as conserved polarized fluxons, namely, a one-bit reversible memory cell with one bidirectional I/O port. We expect the tool to be useful for designing more complex circuits.
We report transport measurements of electrons on helium in a microchannel device where the channels are 200 nm deep and 3μm wide. The channels are fabricated above amorphous metallic Ta 40 W 40 Si 20 , which has surface roughness below 1 nm and minimal variations in work function across the surface due to the absence of polycrystalline grains. We are able to set the electron density in the channels using a ground plane. We estimate a mobility of 300cm2/Vs and electron densities as high as 2.56×109cm-2. We demonstrate control of the transport using a barrier which enables pinch-off at a central microchannel connecting two reservoirs. The conductance through the central microchannel is measured to be 10 nS for an electron density of 1.58×109cm-2. Our work extends transport measurements of surface electrons to thin helium films in microchannel devices above metallic substrates.
Direct bond interconnect (DBI) processes enable chip to chip, low resistivity electrical connections for 2.5-D scaling of electrical circuits and heterogenous integration. This work describes SiO2/Cu DBI technology with Cu interconnect performance investigated over a range of inter-die Cu gap heights and post-bond annealing temperatures. Chemical mechanical polishing (CMP) generates wafers with a controlled Cu recess relative to the SiO2 surface, yielding die pairs with inter-die Cu gap heights ranging between 9 and 47 nm. Bonded die with different gap heights show similar per-connection resistance after annealing at 400 degrees Celsius but annealing at lower temperatures between 250 and 350 degrees Celsius results in failing or high-resistance interconnects with intermediate gaps showing lowest resistance. Cross-section scanning electron microscope (SEM) image analysis shows that the microstructure is largely independent of post-bond annealing temperature, suggesting that the temperature behavior is due to nanoscale scale interfacial effects not observable by SEM. The bond strength is affirmed by successful step-wise mechanical and chemical removal of the handle silicon layer to reveal metal from both die. This work demonstrates a 2.5-D integration method using a 3 micron Cu DBI process on a 7.5 micron pitch with electrical contacts ranging between 3.8 and 4.8 Ohms per contact plug.
In a previous study, we described a new abstract circuit model for reversible computation called Asynchronous Ballistic Reversible Computing (ABRC), in which localized information bearing pulses propagate ballistically along signal paths between stateful abstract devices, and elastically scatter off those devices serially, while updating the device state in a logically-reversible and deterministic fashion. The ABRC model has been shown to be capable of universal computation. In the research reported here, we begin exploring how the ABRC model might be realized in practice using single flux quantum (SFQ) solitons (fluxons) in superconducting Josephson junction (JJ) circuits. One natural family of realizations could utilize fluxon polarity to represent binary data in individual pulses propagating near-ballistically along discrete or continuous long Josephson junctions (LJJs) or microstrip passive transmission lines (PTLs), and utilize the flux charge (-1, 0, +1) of a JJ-containing superconducting loop with Φ0 < IcL < 2Φ0 to encode a ternary state variable internal to a device. A natural question then arises as to which of the definable abstract ABRC device functionalities using this data representation might be implementable using a JJ circuit that dissipates only a small fraction of the input fluxon energy. We discuss conservation rules and symmetries considered as constraints to be obeyed in these circuits, and begin the process of classifying the possible ABRC devices in this family having up to 3 bidirectional I/O terminals, and up to 3 internal states.
Ferroelectricity in doped and alloyed hafnia thin films has been demonstrated using several different electrodes, with TiN and TaN being most prominent. In this work, we demonstrate ferroelectric Hf0.58Zr0.42O2 thin films with superconducting NbN electrodes at cryogenic temperatures. Demonstration of polarization - electric field [P(E)] response at liquid helium cryogenic temperatures, 4 K, suggests that the polarization is switchable over a wide temperature range after an initial 600 °C anneal. Further, room temperature P(E) and capacitance measurements demonstrate an expected polarization response with wake-up required to reach the steady state. Wake-up cycling at 4 K is observed to have no effect upon the ferroelectric phase suggesting an oxygen vacancy mobility freeze out whereas wake-up cycling at 294 K demonstrates close to a 3× increase in remanent polarization. This integration of a ferroelectric Hf0.58Zr0.42O2 thin film with NbN demonstrates the suitability of a highly scalable ferroelectric in applications for cryogenic technologies.
Scott, Ethan A.; Smith, Sean; Henry, Michael D.; Rost, Christina M.; Giri, Ashutosh; Gaskins, John T.; Fields, Shelby S.; Jaszewski, Samantha T.; Ihlefeld, Jon F.; Hopkins, Patrick E.
We report on the thermal resistances of thin films (20 nm) of hafnium zirconium oxide (Hf1-xZrxO2) with compositions ranging from 0 ≤ x ≤ 1. Measurements were made via time-domain thermoreflectance and analyzed to determine the effective thermal resistance of the films in addition to their associated thermal boundary resistances. We find effective thermal resistances ranging from 28.79 to 24.72 m2 K GW-1 for amorphous films, which decreased to 15.81 m2 K GW-1 upon crystallization. Furthermore, we analyze the heat capacity for two compositions, x = 0.5 and x = 0.7, of Hf1-xZrxO2 and find them to be 2.18 ± 0.56 and 2.64 ± 0.53 MJ m-3K-1, respectively.
In this study, the scaling of polarization and pyroelectric response across a thickness series (5–20 nm) of Hf0.58Zr0.42O2 films with TaN electrodes was characterized. Reduction in thickness from 20 nm to 5 nm resulted in a decreased remanent polarization from 17 to 2.8 μC cm-2. Accompanying the decreased remanent polarization was an increased absolute pyroelectric coefficient, from 30 to 58 μC m-2 K-1. The pyroelectric response of the 5 nm film was unstable and decreased logarithmically with time, while that of 10 nm and thicker films was stable over a time scale of >300 h at room temperature. Finally, the sign of the pyroelectric response was irreversible with differing polarity of poling bias for the 5 nm thick film, indicating that the enhanced pyroelectric response was of electret origins, whereas the pyroelectric response in thicker films was consistent with a crystallographic origin.
We report on the fabrication and characterization of nanocrystalline ZnO films for use as a random laser physical unclonable function (PUF). Correlation between processing conditions and film microstructure will be made to optimize the lasing properties and random response. We will specifically examine the repeatability and security of PUFs demonstrated in this novel system. This demonstration has promise to impact many of Sandia's core missions including counterfeit detection.
Substitution of Al by Sc has been predicted and demonstrated to improve the piezoelectric response in AlN for commercial market applications in radio frequency filter technologies. Although cosputtering with multiple targets have achieved Sc incorporation in excess of 40%, industrial processes requiring stable single target sputtering are currently limited. A major concern with sputter deposition of ScAl is the control over the presence of non-c-axis oriented crystal growth, referred to as inclusions here, while simultaneously controlling film stress for suspended microelectromechanical systems (MEMS) structures. In this paper, we describe 12.5% ScAl single target reactive sputter deposition process and establishes a direct relationship between the inclusion occurrences and compressive film stress allowing for the suppression of the c-axis instability on silicon (100) and Ti/TiN/AlCu seeding layers. An initial high film stress, for suppressing inclusions, is then balanced with a lower film stress deposition to control total film stress to prevent Euler buckling of suspended MEMS devices. Contour mode resonators fabricated using these films demonstrate effective coupling coefficients up to 2.7% with figures of merit of 42. Finally, this work provides a method to establish inclusion free films in ScAlN piezoelectric films for good quality factor devices.