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1.
Nano Lett ; 24(19): 5737-5745, 2024 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-38686670

RESUMO

Tungsten oxide (WO3) doped indium oxide (IWO) field-effect transistors (FET), synthesized using atomic layer deposition (ALD) for three-dimensional integration and back-end-of-line (BEOL) compatibility, are demonstrated. Low-concentration (1∼4 W atom %) WO3-doping in In2O3 films is achieved by adjusting cycle ratios of the indium and tungsten precursors with the oxidant coreactant. Such doping suppresses oxygen deficiency from In2O2.5 to In2O3 stoichiometry with only 1 atom % W, allowing devices to turn off stably and enhancing threshold voltage stability. The ALD IWO FETs exhibit superior performance, including a low subthreshold slope of 67 mV/decade and negligible hysteresis. Strong tunability of the threshold voltage (Vth) is achieved through W concentration tuning, with 2 atom % IWO FETs showing an optimized Vth for enhancement-mode and a high drain current. ALD IWO FETs have remarkable stability under bias stress and nearly ideal performance extending to sub-100 nm channel lengths, making them promising candidates for high-performance monolithic 3D integrated devices.

2.
J Am Chem Soc ; 142(1): 134-145, 2020 Jan 08.
Artigo em Inglês | MEDLINE | ID: mdl-31779305

RESUMO

Silicon germanium (SiGe) is a multifunctional material considered for quantum computing, neuromorphic devices, and CMOS transistors. However, implementation of SiGe in nanoscale electronic devices necessitates suppression of surface states dominating the electronic properties. The absence of a stable and passive surface oxide for SiGe results in the formation of charge traps at the SiGe-oxide interface induced by GeOx. In an ideal ALD process in which oxide is grown layer by layer, the GeOx formation should be prevented with selective surface oxidation (i.e., formation of an SiOx interface) by controlling the oxidant dose in the first few ALD cycles of the oxide deposition on SiGe. However, in a real ALD process, the interface evolves during the entire ALD oxide deposition due to diffusion of reactant species through the gate oxide. In this work, this diffusion process in nonideal ALD is investigated and exploited: the diffusion through the oxide during ALD is utilized to passivate the interfacial defects by employing ozone as a secondary oxidant. Periodic ozone exposure during gate oxide ALD on SiGe is shown to reduce the integrated trap density (Dit) across the band gap by nearly 1 order of magnitude in Al2O3 (<6 × 1010 cm-2) and in HfO2 (<3.9 × 1011 cm-2) by forming a SiOx-rich interface on SiGe. Depletion of Ge from the interfacial layer (IL) by enhancement of volatile GeOx formation and consequent desorption from the SiGe with ozone insertion during the ALD growth process is confirmed by electron energy loss spectroscopy (STEM-EELS) and hypothesized to be the mechanism for reduction of the interfacial defects. In this work, the nanoscale mechanism for defect suppression at the SiGe-oxide interface is demonstrated, which is engineering of diffusion species in the ALD process due to facile diffusion of reactant species in nonideal ALD.

3.
Nanotechnology ; 31(33): 335703, 2020 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-32344388

RESUMO

We investigate in-situ laser reflectometry for measuring the axial growth rate in chemical vapor deposition of assemblies of well-aligned vertical germanium nanowires grown epitaxially on single crystal substrates. Finite difference frequency domain optical simulations were performed in order to facilitate quantitative analysis and interpretation of the measured reflectivity data. The results show an insensitivity of the reflected intensity oscillation period to nanowire diameter and density within the range of experimental conditions investigated. Compared to previous quantitative in-situ measurements performed on III-V nanowire arrays, which showed two distinct rate regimes, we observe a constant, steady-state nanowire growth rate. Furthermore, we show that the measured reflectivity decay can be used to determine the germanium nanowire nucleation time with good precision. This technique provides an avenue to monitor growth of nanowires in a variety of materials systems and growth conditions.

4.
J Hepatol ; 71(4): 699-706, 2019 10.
Artigo em Inglês | MEDLINE | ID: mdl-31226388

RESUMO

BACKGROUND & AIMS: Liver function tests (LFTs) are frequently requested blood tests which may indicate liver disease. LFTs are commonly abnormal, the causes of which can be complex and are frequently under investigated. This can lead to missed opportunities to diagnose and treat liver disease at an early stage. We developed an automated investigation algorithm, intelligent liver function testing (iLFT), with the aim of increasing the early diagnosis of liver disease in a cost-effective manner. METHODS: We developed an automated system that further investigated abnormal LFTs on initial testing samples to generate a probable diagnosis and management plan. We integrated this automated investigation algorithm into the laboratory management system, based on minimal diagnostic criteria, liver fibrosis estimation, and reflex testing for causes of liver disease. This algorithm then generated a diagnosis and/or management plan. A stepped-wedged trial design was utilised to compare LFT outcomes in general practices in the 6 months before and after introduction of the iLFT system. Diagnostic outcomes were collated and compared. RESULTS: Of eligible patients with abnormal LFTs, 490 were recruited to the control group and 64 were recruited to the intervention group. The primary diagnostic outcome was based on the general practitioner diagnosis, which agreed with the iLFT diagnosis in 67% of cases. In the iLFT group, the diagnosis of liver disease was increased by 43%. Additionally, there were significant increases in the rates of GP visits after diagnosis and the number of referrals to secondary care in the iLFT group. iLFT was cost-effective with a low initial incremental cost-effectiveness ratio of £284 per correct diagnosis, and a saving to the NHS of £3,216 per patient lifetime. CONCLUSIONS: iLFT increases liver disease diagnoses, improves quality of care, and is highly cost-effective. This can be achieved with minor changes to working practices and exploitation of functionality existing within modern laboratory diagnostics systems. LAY SUMMARY: There is a growing epidemic of advanced liver disease, this could be offset by early detection and management. Checking liver blood tests (LFTs) should be an opportunity to diagnose liver problems, but abnormal results are often incompletely investigated. In this study we were able to substantially increase the diagnostic yield of the abnormal LFTs using the automated intelligent LFT system. With the addition of referral recommendations and management plans, this strategy provides optimum investigation and management of LFTs and is cost saving to the NHS.


Assuntos
Automação Laboratorial/métodos , Hepatopatias/diagnóstico , Testes de Função Hepática/métodos , Atenção Primária à Saúde , Algoritmos , Desenho Assistido por Computador , Análise Custo-Benefício , Diagnóstico Precoce , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Avaliação de Resultados em Cuidados de Saúde , Atenção Primária à Saúde/economia , Atenção Primária à Saúde/métodos , Índice de Gravidade de Doença , Reino Unido
5.
CMAJ ; 195(16): E591, 2023 04 24.
Artigo em Inglês | MEDLINE | ID: mdl-37094874
6.
Nano Lett ; 17(7): 4390-4399, 2017 07 12.
Artigo em Inglês | MEDLINE | ID: mdl-28604007

RESUMO

Resistance switching in TiO2 and many other transition metal oxide resistive random access memory materials is believed to involve the assembly and breaking of interacting oxygen vacancy filaments via the combined effects of field-driven ion migration and local electronic conduction leading to Joule heating. These complex processes are very difficult to study directly in part because the filaments form between metallic electrode layers that block their observation by most characterization techniques. By replacing the top electrode layer in a metal-insulator-metal memory structure with easily removable liquid electrolytes, either an ionic liquid (IL) with high resistance contact or a conductive aqueous electrolyte, we probe field-driven oxygen vacancy redistribution in TiO2 thin films under conditions that either suppress or promote Joule heating. Oxygen isotope exchange experiments indicate that exchange of oxygen ions between TiO2 and the IL is facile at room temperature. Oxygen loss significantly increases the conductivity of the TiO2 films; however, filament formation is not observed after IL gating alone. Replacing the IL with a more conductive aqueous electrolyte contact and biasing does produce electroformed conductive filaments, consistent with a requirement for Joule heating to enhance the vacancy concentration and mobility at specific locations in the film.

7.
Nat Mater ; 15(1): 99-105, 2016 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-26480231

RESUMO

Metal oxide protection layers for photoanodes may enable the development of large-scale solar fuel and solar chemical synthesis, but the poor photovoltages often reported so far will severely limit their performance. Here we report a novel observation of photovoltage loss associated with a charge extraction barrier imposed by the protection layer, and, by eliminating it, achieve photovoltages as high as 630 mV, the maximum reported so far for water-splitting silicon photoanodes. The loss mechanism is systematically probed in metal-insulator-semiconductor Schottky junction cells compared to buried junction p(+)n cells, revealing the need to maintain a characteristic hole density at the semiconductor/insulator interface. A leaky-capacitor model related to the dielectric properties of the protective oxide explains this loss, achieving excellent agreement with the data. From these findings, we formulate design principles for simultaneous optimization of built-in field, interface quality, and hole extraction to maximize the photovoltage of oxide-protected water-splitting anodes.

8.
Nanotechnology ; 28(41): 415704, 2017 Oct 13.
Artigo em Inglês | MEDLINE | ID: mdl-28776501

RESUMO

The performance of nanostructured semiconductors is frequently limited by interface defects that trap electronic carriers. In particular, high aspect ratio geometries dramatically increase the difficulty of using typical solid-state electrical measurements (multifrequency capacitance- and conductance-voltage testing) to quantify interface trap densities (D it). We report on electrochemical impedance spectroscopy (EIS) to characterize the energy distribution of interface traps at metal oxide/semiconductor interfaces. This method takes advantage of liquid electrolytes, which provide conformal electrical contacts. Planar Al2O3/p-Si and Al2O3/p-Si0.55Ge0.45 interfaces are used to benchmark the EIS data against results obtained from standard electrical testing methods. We find that the solid state and EIS data agree very well, leading to the extraction of consistent D it energy distributions. Measurements carried out on pyramid-nanostructured p-Si obtained by KOH etching followed by deposition of a 10 nm ALD-Al2O3 demonstrate the application of EIS to trap characterization of a nanostructured dielectric/semiconductor interface. These results show the promise of this methodology to measure interface state densities for a broad range of semiconductor nanostructures such as nanowires, nanofins, and porous structures.

9.
J Chem Phys ; 146(5): 052820, 2017 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-28178835

RESUMO

Atomic layer deposition of a silicon rich SiNx layer on Si0.7Ge0.3(001), Si0.5Ge0.5(001), and Si0.5Ge0.5(110) surfaces has been achieved by sequential pulsing of Si2Cl6 and N2H4 precursors at a substrate temperature of 285 °C. XPS spectra show a higher binding energy shoulder peak on Si 2p indicative of SiOxNyClz bonding while Ge 2p and Ge 3d peaks show only a small amount of higher binding energy components consistent with only interfacial bonds, indicating the growth of SiOxNy on the SiGe surface with negligible subsurface reactions. Scanning tunneling spectroscopy measurements confirm that the SiNx interfacial layer forms an electrically passive surface on p-type Si0.70Ge0.30(001), Si0.50Ge0.50(110), and Si0.50Ge0.50(001) substrates as the surface Fermi level is unpinned and the electronic structure is free of states in the band gap. DFT calculations show that a Si rich a-SiO0.4N0,4 interlayer can produce lower interfacial defect density than stoichiometric a-SiO0.8N0.8, substoichiometric a-Si3N2, or stoichiometric a-Si3N4 interlayers by minimizing strain and bond breaking in the SiGe by the interlayer. Metal-oxide-semiconductor capacitors devices were fabricated on p-type Si0.7Ge0.3(001) and Si0.5Ge0.5(001) substrates with and without the insertion of an ALD SiOxNy interfacial layer, and the SiOxNy layer resulted in a decrease in interface state density near midgap with a comparable Cmax value.

10.
Nano Lett ; 16(3): 1713-8, 2016 Mar 09.
Artigo em Inglês | MEDLINE | ID: mdl-26837774

RESUMO

Kinking, a common anomaly in nanowire (NW) vapor-liquid-solid (VLS) growth, represents a sudden change of the wire's axial growth orientation. This study focuses on defect-free kinking during germanium NW VLS growth, after nucleation on a Ge (111) single crystal substrate, using Au-Ge catalyst liquid droplets of defined size. Statistical analysis of the fraction of kinked NWs reveals the dependence of kinking probability on the wire diameter and the growth temperature. The morphologies of kinked Ge NWs studied by electron microscopy show two distinct, defect-free, kinking modes, whose underlying mechanisms are explained with the help of 3D multiphase field simulations. Type I kinking, in which the growth axis changes from vertical [111] to ⟨110⟩, was observed in Ge NWs with a nominal diameter of ∼ 20 nm. This size coincides with a critical diameter at which a spontaneous transition from ⟨111⟩ to ⟨110⟩ growth occurs in the phase field simulations. Larger diameter NWs only exhibit Type II kinking, in which the growth axis changes from vertical [111] directly to an inclined ⟨111⟩ axis during the initial stages of wire growth. This is caused by an error in sidewall facet development, which produces a shrinkage in the area of the (111) growth facet with increasing NW length, causing an instability of the Au-Ge liquid droplet at the tip of the NW.

11.
Nano Lett ; 16(1): 637-43, 2016 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-26686394

RESUMO

III-V nanowires are candidate building blocks for next generation electronic and optoelectronic platforms. Low bandgap semiconductors such as InAs and InSb are interesting because of their high electron mobility. Fine control of the structure, morphology, and composition are key to the control of their physical properties. In this work, we present how to grow catalyst-free InAs1-xSbx nanowires, which are stacking fault and twin defect-free over several hundreds of nanometers. We evaluate the impact of their crystal phase purity by probing their electrical properties in a transistor-like configuration and by measuring the phonon-plasmon interaction by Raman spectroscopy. We also highlight the importance of high-quality dielectric coating for the reduction of hysteresis in the electrical characteristics of the nanowire transistors. High channel carrier mobilities and reduced hysteresis open the path for high-frequency devices fabricated using InAs1-xSbx nanowires.


Assuntos
Arsenicais/química , Índio/química , Nanoestruturas/química , Nanotecnologia , Nanofios/química , Catálise , Elétrons , Semicondutores , Propriedades de Superfície
12.
Nano Lett ; 16(12): 7521-7529, 2016 12 14.
Artigo em Inglês | MEDLINE | ID: mdl-27802056

RESUMO

Germanium-tin alloy nanowires hold promise as silicon-compatible optoelectronic elements with the potential to achieve a direct band gap transition required for efficient light emission. In contrast to Ge1-xSnx epitaxial thin films, free-standing nanowires deposited on misfitting germanium or silicon substrates can avoid compressive, elastic strains that inhibit formation of a direct gap. We demonstrate strong room temperature photoluminescence, consistent with band edge emission from both Ge core nanowires, elastically strained in tension, and the almost unstrained Ge1-xSnx shells grown around them. Low-temperature chemical vapor deposition of these core-shell structures was achieved using standard precursors, resulting in Sn incorporation that significantly exceeds the bulk solubility limit in germanium.

13.
J Chem Phys ; 143(16): 164711, 2015 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-26520547

RESUMO

Current logic devices rely on 3D architectures, such as the tri-gate field effect transistor (finFET), which utilize the (001) and (110) crystal faces simultaneously thus requiring passivation methods for the (110) face in order to ensure a pristine 3D surface prior to further processing. Scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), and correlated electrical measurement on MOSCAPs were utilized to compare the effects of a previously developed in situ pre-atomic layer deposition (ALD) surface clean on the InGaAs (001) and (110) surfaces. Ex situ wet cleans are very effective on the (001) surface but not the (110) surface. Capacitance voltage indicated the (001) surface with no buffered oxide etch had a higher C(max) hypothesized to be a result of poor nucleation of HfO2 on the native oxide. An in situ pre-ALD surface clean employing both atomic H and trimethylaluminum (TMA) pre-pulsing, developed by Chobpattana et al. and Carter et al. for the (001) surface, was demonstrated to be effective on the (110) surface for producing low D(it) high C(ox) MOSCAPs. Including TMA in the pre-ALD surface clean resulted in reduction of the magnitude of the interface state capacitance. The XPS studies show the role of atomic H pre-pulsing is to remove both carbon and oxygen while STM shows the role of TMA pre-pulsing is to eliminate H induced etching. Devices fabricated at 120 °C and 300 °C were compared.

14.
Nano Lett ; 14(6): 3427-31, 2014 Jun 11.
Artigo em Inglês | MEDLINE | ID: mdl-24797453

RESUMO

Carrier and phonon dynamics in dense arrays of aligned, single-crystal Ge nanowires (NWs) of controlled diameter are investigated by ultrafast optical pump-probe measurements, effective medium calculations, and elasticity analysis. Both a pronounced induced absorption and the amplitude and spectral range of Fabry-Perot oscillations observed in the probe signal are predicted for the NW array/air metamaterial by effective medium calculations. Detected temporal oscillations of reflectivity are consistent with excitation of radial breathing mode acoustic phonons by the intense pump pulse.

15.
Rural Remote Health ; 15(2): 3134, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-26103433

RESUMO

INTRODUCTION: Palliative care has been both more available and more heavily researched in urban than in rural areas. This research studies factors associated with palliative care program (PCP) enrollment and place of death across the urban/rural continuum. Importantly, rather than simply comparing urban and rural areas, this article examines how the effects of demographic, geographic, and socioeconomic factors differ across service delivery settings within the Canadian province of Nova Scotia. METHODS: This study linked PCP patient enrollment files from three districts to Nova Scotia vital statistics death certificate data. Postal codes of the decedents were mapped to 2006 Canadian dissemination area census data. The study examined 23 860 adult residents of three district health authorities, who died from 2003 to 2009 with a terminal illness, organ failure, or frailty and who were not nursing home residents. Demographic, geographic, and socioeconomic predictors of PCP enrollment and place of death were investigated using logistic regression across the entire study area, and stratified by district of residence. Univariate and multivariate (adjusted) odds ratios (OR) and their 95% confidence intervals (CI) are reported. RESULTS: Overall, 40.3% of the study subjects were enrolled in a PCP, and 73.4% died in hospital. Odds of PCP enrollment were highest for females (OR: 1.30; 95%CI: 1.22, 1.39), persons aged 50-64 years (OR: 1.50; 95%CI: 1.35, 1.67), and persons with a terminal disease such as cancer. While in overall multivariate analysis residents of census metropolitan areas and agglomerations had higher odds of enrollment (OR: 1.51; 95%CI: 1.29, 1.77), and those at greater distance from a PCP had lower odds (OR: 0.33; 95%CI: 0.27, 0.40), stratified analysis revealed a more nuanced picture. Within each district, travel time to PCP remained a significant predictor of enrollment but the magnitude of its effect differed markedly. There was no consistent relationship with urban/rural residence, social deprivation, or economic deprivation. Enrollment in a PCP was associated with lower adjusted odds of dying in hospital (OR: 0.78; 95%CI: 0.72, 0.84), and those living at greater distance from a PCP had higher odds of hospitalization (OR: 1.52; 95%CI: 1.28, 1.81), but there was no consistent relationship for urban/rural residence or across districts. CONCLUSIONS: Geographic patterns of PCP enrollment and place of death differed by district, as did the impact of economic and social deprivation. Analysis and reporting of population-based indicators of access should be grounded in an understanding of the characteristics of geographic areas and local context of health services. Although more research is needed, these findings show promise that disparities in access between urban and rural settings are not unavoidable, and positive aspects of rural and remote communities may be leveraged to improve care at end of life.


Assuntos
Cuidados Paliativos/estatística & dados numéricos , Características de Residência/estatística & dados numéricos , População Rural/estatística & dados numéricos , População Urbana/estatística & dados numéricos , Idoso , Idoso de 80 Anos ou mais , Censos , Atestado de Óbito , Feminino , Hospitalização/estatística & dados numéricos , Humanos , Armazenamento e Recuperação da Informação , Masculino , Pessoa de Meia-Idade , Análise Multivariada , Nova Escócia/epidemiologia , Avaliação de Resultados em Cuidados de Saúde/estatística & dados numéricos , Cuidados Paliativos/tendências , Vigilância da População , Serviços Postais , Avaliação de Programas e Projetos de Saúde , Carência Psicossocial , Qualidade de Vida , Estudos Retrospectivos , Fatores Socioeconômicos
16.
BMC Palliat Care ; 13: 25, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24855451

RESUMO

BACKGROUND: Improving end-of-life care is an important international issue. Recently Nova Scotia researchers conducted a mortality follow-back survey to provide a population-based description of care provided to adults during their last 30 days of life as perceived by knowledgeable bereaved family members. Here we describe the relationship between the location where the decedent received the majority of care during their last 30 days and the informant's perception of the extent of unmet need, as defined by multiple domains of patient-focused, family-centred care. METHOD: Death certificate identified informants (next-of-kin) of eligible adults who died between June 2009 and May 2011, in Nova Scotia, Canada were invited to participate in a telephone interview based on the After-Death Bereaved Family Member Interview. Whether or not the informant expressed unmet need or concerns for six patient-focused, family-centred care domains were assessed in relation to the location where the majority of care occurred during the decedent's last 30 days. RESULTS: 1358 informants took part (25% response rate). Results of 1316 eligible interviews indicated home (39%) was the most common location of care, followed by long-term care (29%), hospital (23%) and hospital-based palliative-care units (9%). Unmet need ranged from 5.6% for dyspnea help to 66% for the emotional and spiritual needs of the family. Although the mean score for overall satisfaction was high (mean = 8.7 in 1-10 scale; SD 1.8), 57% were not completely satisfied. Compared to home, adjusted results indicated greater dissatisfaction with overall care and greater communication concerns in the hospital. Greater unmet need occurred at home for dyspnea. Less overall dissatisfaction and unmet need were expressed about care provided in long-term care facilities and hospital-based palliative-care units. CONCLUSION: Bereaved informants were generally highly satisfied with the decedent's care during their last 30 days but variations were evident. Overall, no one location stood out as exceptionally different in terms of perceived unmet need within each of the patient-focused, family-centred care domains. Communication in various forms and family emotional and spiritual support were consistently viewed as lacking in all locations and identified as targeted areas for impacting quality care at end of life.

17.
ACS Nano ; 18(27): 17600-17610, 2024 Jul 09.
Artigo em Inglês | MEDLINE | ID: mdl-38916257

RESUMO

Hafnia-based ferroelectric (FE) thin films are promising candidates for semiconductor memories. However, a fundamental challenge that persists is the lack of understanding regarding dimensional scaling, including thickness scaling and area scaling, of the functional properties and their heterogeneity in these films. In this work, excellent ferroelectricity and switching endurance are demonstrated in 4 nm-thick Hf0.5Zr0.5O2 (HZO) capacitors with molybdenum electrodes in capacitors as small as 65 nm × 45 nm in size. The HZO layer in these capacitors can be crystallized into the ferroelectric orthorhombic phase at the low temperature of 400 °C, making them compatible for back-end-of-line (BEOL) FE memories. With the benefits of thickness scaling, low operation voltage (1.2 V) is achieved with high endurance (>1010 cycles); however, a significant fatigue regime is noted. We observed that the bottom electrode, rather than the top electrode, plays a dominant role in the thickness scaling of HZO ferroelectric behavior. Furthermore, ultrahigh switched polarization (remanent polarization 2Pr ∼ 108 µC cm-2) is observed in some nanoscale devices. This study advances the understanding of dimensional scaling effects in HZO capacitors for high-performance FE memories.

18.
Nano Lett ; 12(3): 1385-91, 2012 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-22364183

RESUMO

Epitaxial growth of a highly strained, coherent SiGe alloy shell around a Ge nanowire core is investigated as a method to achieve surface passivation and carrier confinement, important in realizing nanowire devices. The high photoluminescence intensity observed from the core-shell nanowires with spectral features similar to that of bulk Ge indicates effective surface passivation. Thermal stability of these core-shell heterostructures has been systematically investigated, with a method demonstrated to avoid misfit strain relaxation during postgrowth annealing.


Assuntos
Cristalização/métodos , Germânio/química , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Silício/química , Substâncias Macromoleculares/química , Teste de Materiais , Conformação Molecular , Tamanho da Partícula , Propriedades de Superfície , Temperatura
19.
ACS Appl Mater Interfaces ; 15(43): 50246-50253, 2023 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-37856882

RESUMO

Ferroelectric materials have been widely researched for applications in memory and energy storage. Among these materials and benefiting from their excellent chemical compatibility with complementary metal-oxide-semiconductor (CMOS) devices, hafnia-based ferroelectric thin films hold great promise for highly scaled semiconductor memories, including nonvolatile ferroelectric capacitors and transistors. However, variation in the switched polarization of this material during field cycling and a limited understanding of the responsible mechanisms have impeded their implementation in technology. Here, we show that ferroelectric Hf0.5Zr0.5O2 (HZO) capacitors that are nearly free of polarization "wake-up"─a gradual increase in switched polarization as a function of the number of switching cycles─can be achieved by introducing ultrathin HfO2 buffer layers at the HZO/electrodes interface. High-resolution transmission electron microscopy (HRTEM) reveals crystallite sizes substantially greater than the film thickness for the buffer layer capacitors, indicating that the presence of the buffer layers influences the crystallization of the film (e.g., a lower ratio of nucleation rate to growth rate) during postdeposition annealing. This evidently promotes the formation of a polar orthorhombic (O) phase in the as-fabricated buffer layer samples. Synchrotron X-ray diffraction (XRD) reveals the conversion of the nonpolar tetragonal (T) phase to the polar orthorhombic (O) phase during electric field cycling in the control (no buffer) devices, consistent with the polarization wake-up observed for these capacitors. The extent of T-O transformation in the nonbuffer samples is directly dependent on the duration over which the field is applied. These results provide insight into the role of the HZO/electrodes interface in the performance of hafnia-based ferroelectrics and the mechanisms driving the polarization wake-up effect.

20.
Nat Mater ; 10(7): 539-44, 2011 Jun 19.
Artigo em Inglês | MEDLINE | ID: mdl-21685904

RESUMO

A leading approach for large-scale electrochemical energy production with minimal global-warming gas emission is to use a renewable source of electricity, such as solar energy, to oxidize water, providing the abundant source of electrons needed in fuel synthesis. We report corrosion-resistant, nanocomposite anodes for the oxidation of water required to produce renewable fuels. Silicon, an earth-abundant element and an efficient photovoltaic material, is protected by atomic layer deposition (ALD) of a highly uniform, 2 nm thick layer of titanium dioxide (TiO(2)) and then coated with an optically transmitting layer of a known catalyst (3 nm iridium). Photoelectrochemical water oxidation was observed to occur below the reversible potential whereas dark electrochemical water oxidation was found to have low-to-moderate overpotentials at all pH values, resulting in an inferred photovoltage of ~550 mV. Water oxidation is sustained at these anodes for many hours in harsh pH and oxidative environments whereas comparable silicon anodes without the TiO(2) coating quickly fail. The desirable electrochemical efficiency and corrosion resistance of these anodes is made possible by the low electron-tunnelling resistance (<0.006 Ω cm(2) for p(+)-Si) and uniform thickness of atomic-layer deposited TiO(2).

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