skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Impact of high-power impulse magnetron sputtering pulse width on the nucleation, crystallization, microstructure, and ferroelectric properties of hafnium oxide thin films
The impact of the high-power impulse magnetron sputtering (HiPIMS) pulse width on the crystallization, microstructure, and ferroelectric properties of undoped HfO2 films is investigated. HfO2 films were sputtered from a hafnium metal target in an Ar/O2 atmosphere, varying the instantaneous power density by changing the HiPIMS pulse width with fixed time-averaged power and pulse frequency. The pulse width is shown to affect the ion-to-neutral ratio in the depositing species with the shortest pulse durations leading to the highest ion fraction. In situ x-ray diffraction measurements during crystallization demonstrate that the HiPIMS pulse width impacts nucleation and phase formation, with an intermediate pulse width of 110 μs stabilizing the ferroelectric phase over the widest temperature range. Although the pulse width impacts the grain size with the lowest pulse width resulting in the largest grain size, the grain size does not strongly correlate with the phase content or ferroelectric behavior in these films. These results suggest that precise control over the energetics of the depositing species may be beneficial for forming the ferroelectric phase in this material.  more » « less
Award ID(s):
2004326
PAR ID:
10527143
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
American Vacuum Society
Date Published:
Journal Name:
Journal of Vacuum Science & Technology A
Volume:
42
Issue:
2
ISSN:
0734-2101
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Colloidal semiconductor nanoparticles (NPs) have long been used as a reliable method for depositing thin films of semiconductor materials for applications, such as photovoltaics via solution-processed means. Traditional methods for synthesizing colloidal NPs often utilize heavy, long-chain organic species to serve as surface ligands, which, during the fabrication of selenized chalcogenide films, leaves behind an undesirable carbonaceous residue in the film. In an effort to minimize these residues, this work looks at using N-methyl-2-pyrrolidone (NMP) as an alternative to the traditional species used as surface ligands. In addition to serving as a primary ligand, NMP also serves as the reaction medium and coating solvent for fabricating CuInS2 (CIS) NPs and thin-film solar cells. Through the use of the NMP-based synthesis, a substantial reduction in the number of carbonaceous residues was observed in selenized films. Additionally, the resulting fine-grain layer at the bottom of the film was observed to exhibit a larger average grain size and increased chalcopyrite character over those of traditionally prepared films, presumably as a result of the reduced carbon content. As a result, a gallium-free CuIn(S,Se)2 device was shown to achieve power-conversion efficiencies of over 11% as well as possessing exceptional carrier generation capabilities with a short-circuit current density (JSC) of 41.6 mA/cm2, which is among the highest for the CIGSSe family of devices fabricated from solution-processed methods. 
    more » « less
  2. In this work, we investigate the device-to-device variations in the remanent polarization of metal–ferroelectric–insulator–metal stacks based on ferroelectric hafnium–zirconium–oxide (HZO). Our study employs a 3D dynamic multi-grain phase-field model to consider the effects of the polycrystalline nature of HZO in conjunction with the multi-domain polarization switching. We explore the dependence of variations on various design factors, such as the ferroelectric thickness and voltage stimuli (set voltage, pulse amplitude, and width), and correlate the trends to the underlying polarization switching mechanisms. Our analysis reveals a non-monotonic dependence of variations on the set voltage due to the coupled effect of the underlying polycrystalline structure variations and the voltage dependence of polarization switching mechanisms. We further report that collapsing of oppositely polarized domains at higher set voltages can lead to an increase in variations, while ferroelectric thickness scaling lowers the overall device-to-device variations. Considering the dynamics of polarization switching, we highlight the key role of voltage and temporal dependence of domain nucleation in dictating the trends in variations. Finally, we show that using a lower amplitude pulse for longer duration to reach a target mean polarization state results in lower variations compared to using a higher amplitude pulse for shorter duration. 
    more » « less
  3. Abstract The presence of the top electrode on hafnium oxide‐based thin films during processing has been shown to drive an increase in the amount of metastable ferroelectric orthorhombic phase and polarization performance. This “Clamping Effect,” also referred to as the Capping or Confinement Effect, is attributed to the mechanical stress and confinement from the top electrode layer. However, other contributions to orthorhombic phase stabilization have been experimentally reported, which may also be affected by the presence of a top electrode. In this study, it is shown that the presence of the top electrode during thermal processing results in larger tensile biaxial stress magnitudes and concomitant increases in ferroelectric phase fraction and polarization response, whereas film chemistry, microstructure, and crystallization temperature are not affected. Through etching experiments and measurement of stress evolution for each processing step, it is shown that the top electrode locally inhibits out‐of‐plane expansion in the HZO during crystallization, which prevents equilibrium monoclinic phase formation and stabilizes the orthorhombic phase. This study provides a mechanistic understanding of the clamping effect and orthorhombic phase formation in ferroelectric hafnium oxide‐based thin films, which informs the future design of these materials to maximize ferroelectric phase purity and corresponding polarization behavior. 
    more » « less
  4. Many biological lab-on-a-chip applications require electrical and optical manipulation as well as detection of cells and biomolecules. This provides an intriguing challenge to design robust microdevices that resist adverse electrochemical side reactions yet achieve optical transparency. Physical isolation of biological samples from microelectrodes can prevent contamination, electrode fouling, and electrochemical byproducts; thus this manuscript explores hafnium oxide (HfO2) films - originating from traditional transistor applications – for suitability in electrokinetic microfluidic devices for biological applications. HfO2 films with deposition times of 6.5, 13, and 20 min were sputter deposited onto silicon and glass substrates. The structural, optical, and electrical properties of the HfO2 films were investigated using atomic force microscopy (AFM), X-ray diffraction, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, ellipsometry, and capacitance voltage. Electric potential simulations of the HfO2 films and a biocompatibility study provided additional insights. Film grain size after corrosive Piranha treatment was observed via AFM. The crystalline structure investigated via X-ray diffraction revealed all films exhibited the (111) characteristic peak with thicker films exhibiting multiple peaks indicative of anisotropic structures. Energy dispersive X-ray spectroscopy via field emission scanning electron microscopy and Fourier transform infrared spectroscopy both corroborated the atomic ratio of the films as HfO2. Ellipsometry data from Si yielded thicknesses of 58, 127, and 239 nm and confirmed refractive index and extinction coefficients within the normal range for HfO2; glass data yielded unreliable thickness verifications due to film and substrate transparency. Capacitance-voltage results produced an average dielectric constant of 20.32, and the simulations showed that HfO2 dielectric characteristics were sufficient to electrically passivate planar microelectrodes. HfO2 biocompatibility was determined with human red blood cells by quantifying the hemolytic potential of the HfO2 films. Overall results support hafnium oxide as a viable passivation material for biological lab-on-a-chip applications. 
    more » « less
  5. Material properties of Ga–Sb binary alloy thin films deposited under ultra-high vacuum conditions were studied for analog phase change memory (PCM) applications. Crystallization of this alloy was shown to occur in the temperature range of 180–264 °C, with activation energy >2.5 eV depending on the composition. X-ray diffraction (XRD) studies showed phase separation upon crystallization into two phases, Ga-doped A7 antimony and cubic zinc-blende GaSb. Synchrotron in situ XRD analysis revealed that crystallization into the A7 phase is accompanied by Ga out-diffusion from the grains. X-ray absorption fine structure studies of the local structure of these alloys demonstrated a bond length decrease with a stable coordination number of 4 upon amorphous-to-crystalline phase transformation. Mushroom cell structures built with Ga–Sb alloys on ø110 nm TiN heater show a phase change material resistance switching behavior with resistance ratio >100 under electrical pulse measurements. TEM and Energy Dispersive Spectroscopy (EDS) studies of the Ga–Sb cells after ∼100 switching cycles revealed that partial SET or intermediate resistance states are attained by the variation of the grain size of the material as well as the Ga content in the A7 phase. A mechanism for a reversible composition control is proposed for analog cell performance. These results indicate that Te-free Ga–Sb binary alloys are potential candidates for analog PCM applications. 
    more » « less