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Results for “acceptor doping”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

The role of deep acceptor centers in the oxidation of acceptor-doped wide-band-gap perovskites ABO{sub 3}

The impact of deep acceptor centers on defect thermodynamics and oxidation of wide-band-gap acceptor-doped perovskites without mixed-valence cations is studied. These deep centers are formed by the acceptor-bound small hole polarons whose stabilization energy can be high enough (significantly higher than the hole-acceptor Coulomb interaction energy). It is shown that the oxidation enthalpy ΔH{sub ox} of oxide is determined by the energy ε{sub A} of acceptor-bound states along with the formation energy E{sub V} of oxygen vacancies. The oxidation reaction is demonstrated to be either endothermic or exothermic, and the regions of ε{sub A} and E{sub V} values corresponding to the positive or negative ΔH{sub ox} are determined. The contribution of acceptor-bound holes to the defect thermodynamics strongly depends on the acceptor states depth ε{sub A}: it becomes negligible at ε{sub A} less than a certain value (at which the acceptor levels are still deep). With increasing ε{sub A}, the concentration of acceptor-bound small hole polarons can reach the values comparable to the dopant content. The results are illustrated with the acceptor-doped BaZrO{sub 3} as an example. It is shown that the experimental data on the bulk hole conductivity of barium zirconate can be described both in the band transport model and in the model of hopping small polarons localized on oxygen ions away from the acceptor centers. Depending on the ε{sub A} magnitude, the oxidation reaction can be either endothermic or exothermic for both mobility mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

The Influence of Local Distortions on Proton Mobility in Acceptor Doped Perovskites

Optimizing proton conduction in solids remains the most promising solution for achieving intermediate temperature (~750–1000 K) solid oxide fuel cell devices, and enabling selective membranes for H 2 separation. Proton conduction, a thermally activated process, exhibits its highest rates in yttrium (Y) acceptor doped BaZrO 3 at an optimal doping level of 20% Y. The presence of extended defects such as grain boundaries has typically generated a wide variability in reported conductivity values. This has hindered a fundamental mechanistic understanding of how (acceptor) doping levels correlate with the activation energy of protons to produce an optimal doping level for fast proton transport. While isolated dopants have been suggested as the primary source of proton trapping, our results indicate that it is the local dopant-density that matters. Here in this work, we show that increasing the local dopant density promotes localized lattice distortions in the presence of point defects such as oxygen-vacancies or proton interstitials. An increasing distortion amplitude traps the point defects more strongly in the form of polarons, forming defect-clusters at higher concentrations. This leads to a monotonic increase in the activation energy (and hence a decrease in proton mobility) as observed in our measurements. The optimum doping level can now be explained as a competition between increasing proton concentration with doping levels and increasing activation energy due to defect-clusters formed by defect-polarons. Based on our findings, we demonstrate how to improve proton conductivity in doped BaZrO 3 , by inhibiting this dopant-lattice polaronic interaction. Finally, this approach should be generally applicable for ionic conduction in perovskite oxides such as oxygen-ion conduction in solid-oxide fuel cells and alkali-ion conduction in solid-state batteries where carriers might get trapped as defect-polarons.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Increasing Saturated Electron-Drift Velocity in Donor–Acceptor Doped pHEMT Heterostructures

Field dependences of the electron-drift velocity in typical pseudomorphic high-electron-mobility transistor (pHEMT) heteroepitaxial structures (HESs) and in those with donor–acceptor doped (DApHEMT) heterostructures with quantum-well (QW) depth increased by 0.8–0.9 eV with the aid of acceptor layers have been studied by a pulsed technique. It is established that the saturated electron-drift velocity in DA-pHEMT-HESs is 1.2–1.3 times greater than that in the usual pHEMT-HESs. The electroluminescence (EL) spectra of DA-pHEMT-HESs do not contain emission bands related to the recombination in widebandgap layers (QW barriers). The EL intensity in these HESs is not saturated with increasing electric field. This is indicative of a suppressed real-space transfer of hot electrons from QW to barrier layers, which accounts for the observed increase in the saturated electron-drift velocity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2016

Improvement in synthesis of (K 0.5 Na 0.5 )NbO 3 powders by Ge 4+ acceptor doping

In this study, the effects of doping with GeO 2 on the synthesis temperature, phase structure and morphology of (K 0.5 Na 0.5 )NbO 3 (KNN) ceramic powders were studied using XRD and SEM. The results show that KNN powders with good crystallinity and compositional homogeneity can be obtained after calcination at up to 900°C for 2 h. Introducing 0.5 mol.% GeO 2 into the starting mixture improved the synthesis of the KNN powders and allowed the calcination temperature to be decreased to 800°C, which can be ascribed to the formation of the liquid phase during the synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Acceptor doping in the proton conductor SrZrO 3

Perovskite zirconates such as SrZrO 3 exhibit improved proton solubility and conductivity when doped with trivalent cations substituting at the Zr site. In this work, we present a detailed study of Sc and Y dopants in SrZrO 3 based on first-principles, hybrid density-functional calculations. When substituting at the Zr site (ScZr, YZr), both dopants give rise to a single, deep acceptor level, where the neutral impurity forms a localized hole polaron state. The ε(0/-) charge transition levels are 0.60 eV and 0.58 eV above the valence-band maximum for ScZr and YZr, respectively. Under certain growth conditions, Sc and Y will form self-compensating donor species by substituting at the Sr site (ScSr, YSr), and this is detrimental to proton conductivity. Due to its larger ionic radius, Y exhibits a greater tendency than Sc to self-compensate at the Sr site. We also investigated the proton–dopant association. The binding energy of a proton to a negatively charged acceptor impurity is 0.41 eV for Sc and 0.31 eV for Y, indicating that proton transport is limited by trapping at impurity sites.

Weston, Leigh↗
DOE OSTI2018

On the structural stability of crystalline ceria phases in undoped and acceptor-doped ceria materials under in situ reduction conditions

The reduction of pure and Sm-doped ceria in hydrogen has been studied by synchrotron-based in situ X-ray diffraction to eventually prove or disprove the presence of crystalline cerium hydride (CeH x ) phases and the succession of potential structural phase (trans)formations of reduced cerium oxide phases during heating-cooling cycles up to 1273 K. Despite a recent report on the existence of bulk and surface CeH x phases during reductive treatment of pure CeO 2 in H 2 , structural analysis by Rietveld refinement as well as additional 1 H-NMR spectroscopy did not reveal the presence of any crystalline CeH x phase. Rather, a sequence of phase transformations during the re-cooling process in H 2 has been observed. In both samples, the reduced/defective fluorite lattice undergoes at first a transformation into a bixbyite-type lattice with a formal stoichiometry Ce 0.58 3+ Ce 0.42 4+ O 1.71 and Sm 0.15 3+ Ce 0.39 3+ Ce 0.46 4+ O 1.73 , before a transformation into rhombohedral Ce 7 O 12 takes place in pure CeO 2 . This phase is clearly absent for the Sm-doped material. Finally, a triclinic Ce 11 O 20 phase appears for both materials, which can be recovered to room temperature, and on which a phase mixture of bixbyite Ce 0.66 3+ Ce 0.34 4+ O 1.67 , rh-Ce 0.60 3+ Ce 0.40 4+ O 1.70 and tri-Ce 0.48 3+ Ce 0.52 4+ O 1.76 (for pure CeO 2 ) or bixbyite Sm 0.15 3+ Ce 0.47 3+ Ce 0.38 4+ O 1.69 and tri-Sm 0.15 3+ Ce 0.31 3+ Ce 0.54 4+ O 1.77 (for Sm-doped CeO 2 ) prevails. The absence of the rhombohedral phase indicates that Sm doping leads to the stabilization of the bixbyite phase over the rhombohedral one at this particular oxygen vacancy concentration. It is worth noting that recent work proves that hydrogen is indeed incorporated within the structures during the heat treatments, but under the chosen experimental conditions it has apparently no effect on the salient structural principles during reduction.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Precipitation of dopants on acceptor-doped LaMnO3±δ revealed by defect chemistry from first principles

Perovskite oxides degrade at elevated temperatures while precipitating dopant-rich particles on the surface. A knowledge-based improvement of surface stability requires a fundamental and quantitative understanding of the dopant precipitation mechanism on these materials. We propose that dopant precipitation is a consequence of the variation of dopant solubility between calcination and operating conditions in solid oxide fuel cells (SOFCs) and electrolyzer cells (SOECs). To study dopant precipitation, we use 20% (D = Ca, Sr, Ba)-doped LaMnO3+δ (LDM20) as a model system. We employ a defect model taking input from density functional theory calculations. The defect model considers the equilibration of LDM20 with a reservoir consisting of dopant oxide (DO), peroxide (DO2), and O2 in the gas phase. The equilibrated non-stoichiometry of the A-site and B-site as a function of temperature, T, and oxygen partial pressure, p(O2), reveals three regimes for LDM20: A-site deficient (oxidizing conditions), A-site rich (atmospheric conditions), and near-stoichiometric (reducing conditions). Assuming an initial A/B non-stoichiometry, we compute the dopant precipitation boundaries in a p–T phase diagram. Our model predicts precipitation both under reducing (DO) and under highly oxidizing conditions (DO2). We found precipitation under anodic, SOEC conditions to be promoted by large dopant size, while under cathodic, SOFC conditions precipitation is promoted by initial A-site excess. The main driving forces for precipitation are oxygen uptake by the condensed phase under oxidizing conditions and oxygen release assisted by B-site vacancies under reducing conditions. Possible strategies for mitigating dopant precipitation under in electrolytic and fuel cell conditions are discussed.

Hess, Franziska (ORCID:000000024460643X)↗
DOE OSTI2021

AlCl 3 -Dosed Si(100)-2 × 1: Adsorbates, Chlorinated Al Chains, and Incorporated Al

The adsorption of AlCl 3 on Si(100) and the effect of annealing the AlCl 3 -dosed substrate were studied to reveal key surface processes for the development of atomic-precision, acceptor-doping techniques. This investigation was performed via scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. At room temperature, AlCl 3 readily adsorbed to the Si substrate dimers and dissociated to form a variety of species. Annealing the AlCl 3 -dosed substrate at temperatures below 450 °C produced unique chlorinated aluminum chains (CACs) elongated along the Si(100) dimer row direction. An atomic model for the chains is proposed with supporting DFT calculations. Al was incorporated into the Si substrate upon annealing at 450 °C and above, and Cl desorption was observed for temperatures beyond 450 °C. Al-incorporated samples were encapsulated in Si and characterized by secondary ion mass spectrometry (SIMS) depth profiling to quantify the Al atom concentration, which was found to be in excess of 10 20 cm –3 across a ~2.7 nm-thick δ-doped region. Here, the Al concentration achieved here and the processing parameters utilized promote AlCl 3 as a viable gaseous precursor for novel acceptor-doped Si materials and devices for quantum computing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Solution–Doped Donor–Acceptor Copolymers Based on Diketopyrrolopyrrole and 3, 3'–Bis (2–(2–(2–Methoxyethoxy) Ethoxy) ethoxy)–2, 2'–Bithiophene Exhibiting Outstanding Thermoelectric Power Factors with p –Dopants

The design of polymeric semiconductors exhibiting high electrical conductivity (σ) and thermoelectric power factor (PF) will be vital for flexible large-area electronics. In this work, four polymers based on diketopyrrolopyrrole (DPP), 2,3-dihydrothieno[3,4-b][1,4]dioxine (EDOT), thieno[3,2-b]thiophene (TT), and 3, 3'-bis (2-(2-(2-methoxyethoxy) ethoxy) ethoxy)-2, 2'-bithiophene (MEET) are investigated as side-chains, with the MEET polymers newly synthesized for this study. These polymers are systematically doped with tetrafluorotetracyanoquinodimethane ( F 4 TCNQ), CF3SO3H, and the synthesized dopant Cp(CN) 3 -(COOMe) 3 , differing in geometry and electron affinity. The DPP-EDOT-based polymer containing MEET as side-chains exhibits the highest conductivity (σ) ≈700 S cm–1 in this series with the acidic dopant (CF 3 SO 3 H). This polymer also shows the lowest oxidation potential by cyclic voltammetry (CV), the strongest intermolecular interactions evidenced by differential scanning calorimetry (DSC), and has the most oxygen-based functionality for possible hydrogen bonding and ionic screening. Other polymers exhibit high σ ≈300–500 S cm–1 and power factor up to 300 µW m –1 K –2 . The mechanism of conductivity is predominantly electronic, as validated by time-dependent conductance studies and transient thermo voltage monitoring over time, including for those doped with the acid. Furthermore, these materials maintain significant thermal stability and air stability over ≈6 weeks. Density functional theory calculations reveal molecular geometries and inform about frontier energy levels. Raman spectroscopy, in conjunction with scanning electron microscopy (SEM-EDS) and x-ray diffraction, provides insight into the solid-state microstructure and degree of phase separation of the doped polymer films. Infrared spectroscopy enables this study to further quantify the degree of charge transfer from polymer to dopant.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Mechanism of the Generation of Donor–Acceptor Pairs in Heavily Doped n-ZrNiSn with the Ga Acceptor Impurity

The nature of the mechanism of the simultaneous generation of donor–acceptor pairs under heavy doping of n-ZrNiSn intermetallic semiconductor with the Ga acceptor impurity is established. Such spatial arrangement in the crystal lattice of ZrNiSn{sub 1–x}Ga{sub x} is found when the rate of movement of the Fermi level εF found from calculations of the density distribution of electron states coincides with that experimentally established from dependences lnρ(1/T). It is shown that when the Ga impurity atom (4s{sup 2}4p{sup 1}) occupies the 4b sites of Sn atoms (5s{sup 2}5p{sup 2}), structural defects of both acceptor nature and donor nature in the form of vacancies in the 4b site are simultaneously generated. The results are discussed in the scope of the Shklovskii–Efros model of a heavily doped and compensated semiconductor.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Melt-grown semi-insulating Mn:β-Ga 2 O 3 single crystals exhibiting unique visible absorptions and luminescence

In this study, several acceptor dopants have been explored in β-Ga 2 O 3 to produce semi-insulating substrates and epitaxial films. Fe and Mg make up the majority of research thus far; however, other transition metals provide potential alternatives for optimized performance. β-Ga 2 O 3 bulk single crystals were grown by the Czochralski and vertical gradient freeze methods with a nominal dopant concentration of 0.25 at. % Mn. Ultraviolet-visible-near infrared spectroscopy and photoluminescence revealed polarization- and orientation-dependent optical absorptions (pleochroism) coupled with an orange luminescence. All samples were electrically insulating, on the order of 10 9 –10 11 ohm cm at room temperature, indicative of acceptor doping. Actual dopant concentrations of the intentionally doped transition metal and background impurities were determined via glow discharge mass spectrometry, indicating the macroscale segregation behavior. High-temperature resistivity measurements indicated an experimental acceptor level of 1.7 ± 0.2 eV. Hydrogenation of samples resulted in an increase in the orange luminescence and O–H stretching modes observable in the infrared spectrum. Density functional theory calculations were performed to determine the likely site-occupancy and acceptor level of Mn in the bandgap.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Doping properties of cadmium-rich arsenic-doped CdTe single crystals: Evidence of metastable AX behavior

Cd-rich composition and group-V element doping are of interest for simultaneously maximizing the hole concentration and minority carrier lifetime in CdTe, but the critical details concerning point defects are not yet fully established. Herein, we report on the properties of arsenic doped CdTe single crystals grown from Cd solvent by the travelling heater method. The photoluminescence spectra and activation energy of 74 +/- 2 meV derived from the temperature-dependent Hall effect are consistent with AsTe as the dominant acceptor. Doping in the 10^16 to 10^17/cm^3 range is achieved for measured As concentrations between 10^16 and 10^20/cm^3 with the highest doping efficiency of 40% occurring near 10^17 As/cm^3. We observe persistent photoconductivity, a hallmark of light-induced metastable configuration changes consistent with AX behavior. Additionally, quenching experiments reveal at least two mechanisms of increased p-type doping in the dark, one decaying over 2-3 weeks and the other persisting for at least 2 months. These results provide essential insights for the application of As-doped CdTe in thin film solar cells.

14 SOLAR ENERGY↗
DOE OSTI2019

Efficient Blue Phosphorescent OLEDs with Improved Stability and Color Purity through Judicious Triplet Exciton Management

Abstract Highly efficient and stable blue phosphorescent organic light‐emitting diodes are achieved by employing a step‐wise graded doping of platinum(II) 9‐(pyridin‐2‐yl)‐2‐(9‐(pyridin‐2‐yl)‐9 H ‐carbazol‐2‐yloxy)‐9 H ‐carbazole (PtNON) in a device setting. A device employing PtNON demonstrates a high peak external quantum efficiency (EQE) of 17.4% with an estimated LT 70 lifetime of over 1330 h at a brightness of 1000 cd m −2 . PtNON is then investigated as a “triplet sensitizer” in an alternating donor–acceptor doped emissive layer to further improve the device emission color purity by carefully managing an efficient Förster resonant energy transfer from PtNON to 2,5,8,11‐tetra‐ tert ‐butylperylene as a selected acceptor material. Thus, such OLED devices demonstrate an EQE of 16.9% with color coordinates of (0.16, 0.25) and an estimated luminance (LT 70 ) lifetime of 628 h at a high brightness of 1000 cd m −2 .

Klimes, Kody↗
DOE OSTI2024

Thermal stability and coalescence dynamics of exsolved metal nanoparticles at charged perovskite surfaces

Exsolution reactions enable the synthesis of oxide-supported metal nanoparticles, which are desirable as catalysts in green energy conversion technologies. It is crucial to precisely tailor the nanoparticle characteristics to optimize the catalysts’ functionality, and to maintain the catalytic performance under operation conditions. We use chemical (co)-doping to modify the defect chemistry of exsolution-active perovskite oxides and examine its influence on the mass transfer kinetics of Ni dopants towards the oxide surface and on the subsequent coalescence behavior of the exsolved nanoparticles during a continuous thermal reduction treatment. Nanoparticles that exsolve at the surface of the acceptor-type fast-oxygen-ion-conductor SrTi 0.95 Ni 0.05 O 3–δ (STNi) show a high surface mobility leading to a very low thermal stability compared to nanoparticles that exsolve at the surface of donor-type SrTi 0.9 Nb 0.05 Ni 0.05 O 3–δ (STNNi). Our analysis indicates that the low thermal stability of exsolved nanoparticles at the acceptor-doped perovskite surface is linked to a high oxygen vacancy concentration at the nanoparticle-oxide interface. For catalysts that require fast oxygen exchange kinetics, exsolution synthesis routes in dry hydrogen conditions may hence lead to accelerated degradation, while humid reaction conditions may mitigate this failure mechanism.

25 ENERGY STORAGE↗
DOE OSTI2016

Design of p-type cladding layers for tunnel-injected UV-A light emitting diodes

Here, we discuss the engineering of p-AlGaN cladding layers for achieving efficient tunnel-injected III-Nitride ultraviolet light emitting diodes (UV LEDs) in the UV-A spectral range. We show that the capacitance-voltage measurements can be used to estimate the compensation and doping in the p-AlGaN layers located between the multi-quantum well region and the tunnel junction layer. By increasing the p-type doping concentration to overcome the background compensation, on-wafer external quantum efficiency and wall-plug efficiency of 3.37% and 1.62%, respectively, were achieved for the tunnel-injected UV LEDs emitting at 325 nm. We also show that interband tunneling hole injection can be used to realize UV LEDs without any acceptor doping. The work discussed here provides new understanding of hole doping and transport in AlGaN-based UV LEDs and demonstrates the excellent performance of tunnel-injected LEDs for the UV-A wavelength range.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Localization of Upper-Valley Electrons in a Narrow-Bandgap Channel: a Possible Additional Mechanism of Current Increase in DA–DpHEMT

The influence of the localization of upper-valley electrons in a narrow-bandgap channel on the drift velocity burst in Al{sub x}Ga{sub 1 –x}As–GaAs transistor heterostructures with double-sided doping has been theoretically estimated. It is established that the fraction of electrons passing in this case from the narrow-bandgap channel to wide-bandgap material is smaller than in the usual structures, which can lead in some cases to an increase in the electron drift velocity by up to 15%. This phenomenon can provide an additional mechanism of current increase in transistors based on heterostructures with donor–acceptor doping.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Precipitation Hardening in Ferroelectric Ceramics

Domain wall motion in ferroics, similar to dislocation motion in metals, can be tuned by well-concepted microstructural elements. In demanding high-power applications of piezoelectric materials, the domain wall motion is considered as a lossy hysteretic mechanism that should be restricted. Current applications for so-called hard piezoelectrics are abundant and hinge on the use of an acceptor-doping scheme. However, this mechanism features severe limitations due to enhanced mobility of oxygen vacancies at moderate temperatures. By analogy with metal technology, the authors present here a new solution for electroceramics, where precipitates are utilized to pin domain walls and improve piezoelectric properties. Through a sequence of sintering, nucleation, and precipitate growth, intragranular precipitates leading to a fine domain structure are developed as shown by transmission electron microscopy, piezoresponse force microscopy, and phase-field simulation. This structure impedes the domain wall motion as elucidated by electromechanical characterization. As a result, the mechanical quality factor is increased by ≈50% and the hysteresis in electrostrain is suppressed considerably. This is even achieved with slightly increased piezoelectric coefficient and electromechanical coupling factor. This novel process can be smoothly implemented in industrial production processes and is accessible to simple laboratory experimentation for microstructure optimization and implementation in various ferroelectric systems.

36 MATERIALS SCIENCE↗