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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Unconventional Error Cancellation Explains the Success of Hartree–Fock Density Functional Theory for Barrier Heights

Energy barriers, which control the rates of chemical reactions, are seriously underestimated by computationally efficient semilocal approximations for the exchange-correlation energy. The accuracy of a semilocal density functional approximation is strongly boosted for reaction barrier heights by evaluating that approximation non-self-consistently on Hartree–Fock electron densities, which has been known for ~30 years. Here, the conventional explanation is that the Hartree–Fock theory yields the more accurate density. This work presents a benchmark Kohn–Sham inversion of accurate coupled-cluster densities for the reaction H 2 + F → HHF → H + HF and finds a strong, understandable cancellation between positive (excessively overcorrected) density-driven and large negative functional-driven errors (expected from stretched radical bonds in the transition state) within this Hartree–Fock density functional theory. This confirms earlier conclusions (Kaplan, A. D., et al. J. Chem. Theory Comput. 2023, 19, 532–543) based on 76 barrier heights and three less reliable, but less expensive, fully nonlocal density functional proxies for the exact density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Reducing the Barrier Height in Organic Transistors

Abstract Reducing the Schottky barrier height and Fermi level de‐pinning in metal‐organic semiconductor contacts are crucial for enhancing the performance of organic transistors. The reduction of the Schottky barrier height in bottom‐contact top‐gate organic transistors is demonstrated by adding 1 nm thick atomic layer deposited Al 2 O 3 on the source and drain contacts. By using two different donor‐acceptor copolymers, both p‐ and n‐ type transistors are investigated. Temperature‐dependent current–voltage measurements from non‐treated, self‐assembled monolayer treated, and Al 2 O 3 treated Au source‐drain contact field‐effect transistors with varying channel lengths are carried out. The drain current versus drain voltage near zero gate voltage, which may be described by the thermionic emission model at temperatures above 150 K, allows the estimation of the Schottky barrier height ( φ B ). The Al 2 O 3 contact‐treated transistors show more than 40% lower φ B compared with the non‐treated contacts in the p ‐type transistor. Similarly, an isoindigo‐based transistor, with n ‐type transport, shows a reduction in φ B with Al 2 O 3 treated contacts suggesting that such ultrathin oxide layers provide a universal method for reducing the barrier height.

Ghobadi, Arash↗
NASA NTRS1987

Extended active space CASSCF/MRSD CI calculations of the barrier height for the reaction O + H2 yields OH + H

The convergence of the barrier height for the O + H2 yields OH + H reaction is studied as a function of the size of the active space in the CASSCF calculation and the size of the basis set. The basis set employed in this study is described. The sources of the differences between the POL-CI and MRSD-CI calculations for barrier height are examined. It is observed that the barrier height is rapidly convergent with respect to the expansion of the active space. The effects of adding active orbitals on the barrier height are investigated. The barrier height estimated from corrected MRSD-CI data is 12.4 kcal/mol.

Walch, Stephen P.↗
NASA NTRS1988

Barrier height enhancement of InP-based n-Ga(0.47)In(0.53)As Schottky-barrier diodes grown by molecular beam epitaxy

Barrier height enhancement of an InP-based p(+)n-Ga(0.47)In(0.53)As Schottky diode grown by MBE has been demonstrated for infra-red photodetector applications. A barrier height of 0.35 eV for n-Ga(0.47)In(0.53)As Schottky barrier diodes, was increased to the effective barrier height of 0.55 eV, with a p(+)-Ga(0.47)In(0.53)As surface layer of 30 nm thick. The results show a reverse leakage current density of 0.0015 A/sq cm and a junction capacitance of 0.3 pF, which are comparable to those of p-Ga(0.47)In(0.53)As Schottky-barrier diodes at a reverse bias voltage of 5 V.

Kim, J. H.↗
NASA NTRS1993

Computed barrier heights for H + CH2O yields CH3O yields CH2OH

The barrier heights (including zero-point effects) for H + CH2O yields CH3O and CH3O yields CH2OH have been computed using complete active space self consistent field (CASSCF)/gradient calculations to define the stationary point geometries and harmonic frequencies and internally contracted configuration-interaction (CCI) to refine the energetics. The computed barrier heights are 5.6 kcal/mol and 30.1 kcal/mol, respectively. The former barrier height compares favorably to an experimental activation energy of 5.2 kcal/mol.

Walch, Stephen P.↗
NASA NTRS1993

Computed barrier heights for H + CH2O yields CH3O yields CH2OH

The barrier heights (including zero-point effects) for H + CH2O yields CH3O and CH3O yields CH2OH have been computed using complete active space self consistent field (CASSCF)/gradient calculations to define the stationary point geometries and harmonic frequencies and internally contracted configuration-interaction (CCI) to refine the energetics. The computed barrier heights are 5.6 kcal/mol and 30.1 kcal/mol, respectively. The former barrier height compares favorably to an experimental activation energy of 5.2 kcal/mol.

Walch, Stephen P.↗
NASA NTRS1986

Extended active space CASSCF/MRSD CI calculations of the barrier height for the reaction: O + H2 yields OH + H

The convergence of the barrier height for the O + H2 yields OH + H reaction was studied as a function of the size of the active space and basis set completeness. The barrier height is rapidly convergent with respect to expansion of the active space. Addition of 2p yields 2p' correlation terms to the active space lowers the barrier to the O + H2 reaction by about 2.0 kcal/mole, but addition of 3d and other terms has little additional effect. Multireference singles and doubles contracted CI plus Davidson's correction calculations using a (5s5p3d2f1g/4s3p2d1f) basis set with a 5 sigma 2 pi active space lead to a barrier height of 12.7 kcal/mole. Including an estimate of the CI contraction error and basis set superposition error leads to 12.4 kcal/mole as the best estimate of the barrier height.

Walch, Stephen P.↗
DOE OSTI2023

Investigating the effect of aluminum oxide fixed charge on Schottky barrier height in molybdenum oxide-based selective contacts

A tunneling atomic layer deposited (ALD) AlO x layer was inserted in a Si|SiO x |AlO x |MoO x |metal tunnel diode structure to investigate the impact of fixed interface charge on Schottky barrier height. ALD AlO x provides a synthesis-tunable fixed charge and can provide excellent field effect passivation at the SiO x |AlO x interface. A large (>1 × 10 12 q.cm –2 ) negative fixed charge density was expected to decrease Schottky barrier height on p-type silicon and increase Schottky barrier height on n-type silicon by up to 0.4 eV based on an electrostatic model. Fixed charge density and interface trap state density were measured using a thick layer of AlO x in metal oxide semiconductor capacitor structures (MOSCAPs); Schottky barrier height and specific contact resistivity were measured using a tunneling-active layer of AlO x in contacted structures with MoO x . In some samples, HfO x interface layers were inserted between AlO x and silicon to quench the fixed negative charge. The Schottky barrier height was found to vary with processing conditions but did not have a strong correlation with expected fixed charge density. Here, while fixed charge may play a role in determining the Schottky barrier height, other parameters also have significant affect. Further work is needed to minimize contact resistivity and elucidate other factors impacting the Schottky barrier height.

14 SOLAR ENERGY↗
DOE OSTI2024

The rise and fall of stretched bond errors: Extending the analysis of Perdew–Zunger self-interaction corrections of reaction barrier heights beyond the LSDA

Incorporating self-interaction corrections (SIC) significantly improves chemical reaction barrier height predictions made using density functional theory methods. We present a detailed orbital-by-orbital analysis of these corrections for three semi-local density functional approximations (DFAs) situated on the three lowest rungs of Jacob’s ladder of approximations. The analysis is based on Fermi–Löwdin Orbital Self-Interaction Correction (FLOSIC) calculations performed at several steps along the reaction pathway from the reactants (R) to the transition state (TS) to the products (P) for four representative reactions selected from the BH76 benchmark set. For all three functionals, the major contribution to self-interaction corrections of the barrier heights can be traced to stretched bond orbitals that develop near the TS configuration. The magnitude of the ratio of the self-exchange–correlation energy to the self-Hartree energy (XC/H) for a given orbital is introduced as an indicator of one-electron self-interaction error. XC/H = 1.0 implies that an orbital’s self-exchange–correlation energy exactly cancels its self-Hartree energy and that the orbital, therefore, makes no contribution to the SIC in the FLOSIC scheme. For the practical DFAs studied here, XC/H spans a range of values. Here, the largest values are obtained for stretched or strongly lobed orbitals. We show that significant differences in XC/H for corresponding orbitals in the R, TS, and P configurations can be used to identify the major contributors to the SIC of barrier heights and reaction energies. Based on such comparisons, we suggest that barrier height predictions made using the strongly constrained and appropriately normed meta-generalized gradient approximation may have attained the best accuracy possible for a semi-local functional using the Perdew–Zunger SIC approach.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Exploiting Fixed Charge to Control Schottky Barrier Height in Si|Al 2 O 3 |MoO x – based Tunnel Diodes

The insertion of a tunneling atomic layer deposited (ALD) Al 2 O 3 film between MoO x and p-type Si has been studied to investigate Schottky barrier height tunability with varied negative fixed charge density. This work seeks to increase the hole-selectivity of MoO x -based contacts through manipulation of interface fixed charge. Fixed charge density and interface trap state densities are determined as a function of alumina processing conditions in metal-oxide-semiconductor capacitors (MOSCAPs). Schottky barrier heights were determined from Mott-Schottky analysis of tunnel diodes. An alumina deposition temperature of 80°C and post-deposition annealing at 425°C yielded the highest magnitude of negative fixed charge density (-3.5 × 10 12 q . cm –2 ). High deposition temperature and/or post-deposition annealing produced the lowest interface trap state density (1 × 10 12 eV -1 . cm –2 ). On p-type silicon, Schottky barrier height minimization was not clearly correlated with increasing fixed charge density. However, on n-type silicon, a significant increase in Schottky barrier height was evident (~0.8 eV to > 1 eV) and is attributed to the large negative fixed charge. Here, the findings from this work indicate that Schottky barrier height in carrier selective contacts can be tuned by electrostatic engineering of the SiO x |Al 2 O 3 interface.

aluminum oxide↗
NASA NTRS1983

An XPS study of silicon/noble metal interfaces - Bonding trends and correlations with the Schottky barrier heights

This X-ray photoemission (XPS) study demonstrates a correlation of intrinsic TM-Si chemical bond formation with Schottky barrier heights for the near-noble transition metals (TM = Ni, Pd, Pt) and their corresponding silicides (TM2Si and TMSi) on Si(100). It is found that the barrier height correlates with the strength of the TM-Si orbital interaction as well as with the charge density around the Si atom. These observations suggest a dominant role for intrinsic chemical interactions in establishing the Schottky barrier heights in these TM-Si systems.

Grunthaner, P. J.↗
DOE OSTI2021

Voltage-Dependent Barrier Height of Electron Transport through Iron Porphyrin Molecular Junctions

Electron transport through iron porphyrin (FeP) molecules self-assembled on a gold (Au) substrate was investigated using conductive atomic force microscopy (AFM) to measure current–voltage (I–V) characteristics. In the direct tunneling region (|V| ≤ 0.1 V), the Simmons model was used to characterize the electron transport. Furthermore, the energy barrier between the Fermi energy level of Au and the highest occupied molecular orbital (HOMO) level of the FeP molecule was determined to be between 0.3 and 0.6 eV; the range of the electron attenuation coefficient was 0.6–0.8 Å–1. Instead of a constant barrier height, a voltage-dependent barrier height was adapted to simulate the experimental I–V curves over the entire voltage range (|V| ≤ 2 V) using the Simmons model for the intermediate case. The voltage-dependent barrier height is supported by a previously predicted response of molecular-projected self-consistent Hamiltonian orbitals. The dependence showed that the HOMO level relative to the Fermi energy level of the Au electrode decreased as the bias voltage increased. To verify the deposition of the FeP on the Au substrate, Raman spectroscopy and AFM analysis were performed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Study of self-interaction-errors in barrier heights using locally scaled and Perdew-Zunger self-interaction methods

We study the effect of self-interaction errors on the barrier heights of chemical reactions. For this purpose we use the well-known Perdew-Zunger [J. P. Perdew and A. Zunger, Phys. Rev. B,23, 5048 (1981)] self-interaction-correction(PZSIC), as well two variations of the recently developed, locally scaled self-interaction correction (LSIC) [Zope et al.,J. Chem. Phys.151, 214108 (2019)] to study the barrier heights of the BH76 benchmark dataset. Our results show that both PZSIC and especially the LSIC methods improve the barrier heights relative to the local density approximation(LDA). The version of LSIC that uses the iso-orbital indicator z as a scaling factor gives a more consistent improvement than an alternative version that uses an orbital-dependent factor based on the ratio of orbital densities to the total electron density. We show that LDA energies evaluated using the self-consistent and self-interaction-free PZSIC densities can be used to assess density-driven errors. Furthermore, the LDA reaction barrier errors for the BH76 set are found to contain significant density-driven errors for all types of reactions contained in the set, but the corrections due to adding SIC to the functional are much larger than those stemming from the density for the hydrogen transfer reactions and of roughy equal size for the non-hydrogen transfer reactions.

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

Interfacial Chemistry-Induced Modulation of Schottky Barrier Heights: In Situ Measurements of the Pt–Amorphous Indium Gallium Zinc Oxide Interface Using X-ray Photoelectron Spectroscopy

A method to modulate the Schottky barrier heights for platinum and amorphous indium gallium zinc oxide (a-IGZO) interfaces is demonstrated through thermal processing and background ambient pressure control. The interfacial chemistries that modulate barrier heights for the Pt/a-IGZO system were investigated using in-situ X-ray photoelectron spectroscopy. A significant reduction of indium, from In 3+ to In 0 , occurs during deposition of Pt on to the a-IGZO surface in ultra-high vacuum. Post-annealing and controlling the background ambient O 2 pressure allows tuning the degree of indium reduction and the corresponding Schottky barrier height between 0.17 to 0.77 eV. Understanding the detailed interfacial chemistries at Pt/a-IGZO interfaces may allow for improved electronic device performance, including Schottky diodes, memristors, and metalsemiconductor field-effect transistors.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2019

The Most Reliable and Precise Model to Determine Schottky Barrier Height and Photoelectron Yield Spectroscopy

Schottky barrier height (SBH), φ, plays a crucial role in the design of electronic and photo-electronic devices. In order to reckon SBH via internal photoemission (IPE), the technique is through extrapolating square root of IPE yield-and cube root of IPE yield-photon energy plots to zero before this work, this work was motivated by the most reliable and precise model to determine the SBH via IPE. A phenomenological model for connection IPE quantum yield and photon energy has been successfully established based on Fermi–Dirac distribution. The results of experimental observations fitted via the model indicate that the modeled quantum yield agrees well with experimental data. This model emphasizes the threshold of photon energy for calculating SBH, and the SBH of InN/GaN, p-type GaP/p-type Si, Pt/GaP, Au/GaAs, Si/SiO{sub 2} and Cu/SiO{sub 2} were obtained with high reliability after the method had been applied.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Barrier Heights for Diels–Alder Transition States Leading to Pentacyclic Adducts: A Benchmark Study of Crowded, Strained Transition States of Large Molecules

Theoretical characterization of reactions of complex molecules depends on providing consistent accuracy for the relative energies of intermediates and transition states. Here we employ the DLPNO-CCSD(T) method with core–valence correlation, large basis sets, and extrapolation to the CBS limit to provide benchmark values for Diels–Alder transition states leading to competitive strained pentacyclic adducts. We then used those benchmarks to test a diverse set of wave function and density functional methods for the absolute and relative barrier heights of these transition states. Our results show that only a few of the tested density functionals can predict the absolute barrier heights satisfactorily, although relative barrier heights are more accurate. The most accurate functionals tested are ωB97M-V, M11plus, ωB97X-V, PBE-D3(0), M11, and MN15 with MUDs from best estimates less than 3.0 kcal. Furthermore, these findings can guide selection of density functionals for future studies of crowded, strained transition states of large molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1984

Effect of barrier height on friction behavior of the semiconductors silicon and gallium arsenide in contact with pure metals

Friction experiments were conducted for the semiconductors silicon and gallium arsenide in contact with pure metals. Polycrystalline titanium, tantalum, nickel, palladium, and platinum were made to contact a single crystal silicon (111) surface. Indium, nickel, copper, and silver were made to contact a single crystal gallium arsenide (100) surface. Sliding was conducted both in room air and in a vacuum of 10 to the minus 9th power torr. The friction of semiconductors in contact with metals depended on a Schottky barrier height formed at the metal semiconductor interface. Metals with a higher barrier height on semiconductors gave lower friction. The effect of the barrier height on friction behavior for argon sputtered cleaned surfaces in vacuum was more specific than that for the surfaces containing films in room air. With a silicon surface sliding on titanium, many silicon particles back transferred. In contrast, a large quantity of indium transferred to the gallium arsenide surface.

Mishina, H.↗