Semiconductor Heterointerfaces Research Articles

Measuring Spatially-Resolved Potential Drops at Semiconductor Hetero-Interfaces Using 4D-STEM.

Characterizing long-range electric fields and built-in potentials in functional materials at nano to micrometer scales is of supreme importance for optimizing devices, e.g., the functionality of semiconductor hetero-structures or battery materials is determined by the electric fields established at interfaces which can also vary spatially. In this study, momentum-resolved four-dimensional scanning transmission electron microscopy (4D-STEM) is proposed for the quantification of these potentials and the optimization steps required to reach quantitative agreement with simulations for the GaAs/AlAs hetero-junction model system are shown. Using STEM the differences in the mean inner potentials (∆MIP) of two materials forming an interface and resulting dynamic diffraction effects have to be considered. This study shows that the measurement quality is significantly improved by precession, energy filtering and a off-zone-axis alignment of the specimen. Complementary simulations yielding a ∆MIP of 1.3V confirm that the potential drop due to charge transfer at the intrinsic interface is ≈0.1V, in agreement with experimental and theoretical values found in literture. These results show the feasibility of accurately measuring built-in potentials across hetero-interfaces of real device structures and its promising application for more complex interfaces of other polycrystalline materials on the nanometer scale.

Real-space observation of a two-dimensional electron gas at semiconductor heterointerfaces.

Mobile charge carriers are essential components in high-performance, nano-engineered semiconductor devices. Employing charge carriers confined to heterointerfaces, the so-called two-dimensional electron gas, is essential for improving device performance. The real-space visualization of a two-dimensional electron gas at the nanometre scale is desirable. However, it is challenging to accomplish by means of electron microscopy due to an unavoidable strong diffraction contrast formation at the heterointerfaces. We performed direct, nanoscale electric field imaging across a GaN-based semiconductor heterointerface using differential phase contrast scanning transmission electron microscopy by suppressing diffraction contrasts. For both nearly the lattice-matched GaN/Al0.81In0.19N interface and pseudomorphic GaN/Al0.88In0.12N interface, the extracted quantitative electric field profiles show excellent agreement with profiles predicted using Poisson simulation. Furthermore, we used the electric field profiles to quantify the density and distribution of the two-dimensional electron gas across the heterointerfaces with nanometre precision. This study is expected to guide the real-space characterization of local charge carrier density and distribution in semiconductor devices.

Dynamic Self-Rectifying Liquid Metal-Semiconductor Heterointerfaces: A Platform for Development of Bioinspired Afferent Systems.

The assembly of geometrically complex and dynamically active liquid metal/semiconductor heterointerfaces has drawn extensive attention in multidimensional electronic systems. In this study the chemovoltaic driven reactions have enabled the microfluidity of hydrophobic galinstan into a three-dimensional (3D) semiconductor matrix. A dynamic heterointerface is developed between the atomically thin surface oxide of galinstan and the TiO2-Ni interface. Upon the growth of Ga2O3 film at the Ga2O3-TiO2 heterointerface, the partial reduction of the TiO2 film was confirmed by material characterization techniques. The conductance imaging spectroscopy and electrical measurements are used to investigate the charge transfer at heterointerfaces. Concurrently, the dynamic conductance in artificial synaptic junctions is modulated to mimic the biofunctional communication characteristics of multipolar neurons, including slow and fast inhibitory and excitatory postsynaptic responses. The self-rectifying characteristics, femtojoule energy processing, tunable synaptic events, and notably the coordinated signal recognition are the main characteristics of this multisynaptic device. This novel 3D design of liquid metal-semiconductor structure opens up new opportunities for the development of bioinspired afferent systems. It further facilitates the realization of physical phenomena at liquid metal-semiconductor heterointerfaces.

Room-temperature two-terminal magnetoresistance ratio reaching 0.1% in semiconductor-based lateral devices with L21-ordered Co2MnSi

We report on the highest two-terminal magnetoresistance (MR) ratio at room temperature in semiconductor-based lateral spin-valve devices. From first-principles calculations, we predict energetically stable ferromagnet–semiconductor heterointerfaces consisting of Co2MnSi (CMS) and Ge(111) upon insertion of Fe atomic layers. Using low-temperature molecular beam epitaxy, we demonstrate L21-ordered CMS epilayers at 80 °C on Ge(111), where the CMS layer can be utilized as a spin injector and detector. Two-terminal MR ratios as high as 0.1% are achieved in n-Ge-based lateral spin-valve devices with CMS/Fe/Ge Schottky tunnel contacts annealed at 200 °C. This study will open a path for semiconductor-based spintronic devices with a large MR ratio at room temperature.

Interplay of anomalous strain relaxation and minimization of polarization changes at nitride semiconductor heterointerfaces

We present a methodology to quantify polarization and electron affinity changes at interfaces by combining scanning tunneling spectroscopy, off-axis electron holography in transmission electron microscopy (TEM), and self-consistent calculations of the electrostatic potential and electron phase change. We use a precisely known grown-in doping structure to calibrate the surface potential of the TEM lamella and thereby achieve a quantitative analysis of electron phase changes measured by off-axis electron holography. Using this calibration, we deduce quantitatively polarization and electron affinity changes for ${\mathrm{Al}}_{\text{0.06}}{\mathrm{Ga}}_{\text{0.94}}\mathrm{N}/\mathrm{GaN}$ and ${\mathrm{In}}_{\text{0.05}}{\mathrm{Ga}}_{\text{0.95}}\mathrm{N}/{\mathrm{Al}}_{\text{0.06}}{\mathrm{Ga}}_{\text{0.94}}\mathrm{N}$ interfaces. The latter interface reveals, as expected, biaxial relaxation as well as polarization and electron affinity changes. However, at the ${\mathrm{Al}}_{\text{0.06}}{\mathrm{Ga}}_{\text{0.94}}\mathrm{N}/\mathrm{GaN}$ interface anomalous lattice relaxations and vanishing polarization and electron affinity changes occur, whose underlying physical origin is anticipated to be total energy minimization by the minimization of Coulomb interactions between the polarization-induced interface charges.

Scanning Moiré Fringe Method: A Superior Approach to Perceive Defects, Interfaces, and Distortion in 2D Materials.

Scanning moiré fringe (SMF) is a widely utilized technique for the precise measurement of the strain field in semiconductor transistors and heterointerfaces. With the growing challenges of traditional chip scaling, two-dimensional (2D) materials turn out to be ideal candidates for incorporation into semiconductor devices. Therefore, a method to efficiently locate defects and grain boundaries in 2D materials is highly essential. Here, we present a demonstration of using the SMF method to locate the domain boundaries at the nearly coherent interfaces with sub-angstrom spatial resolution under submicron fields of views. The strain field of small angle grain boundary and lateral heterojunction are instantaneously found and precisely determined by a quick SMF method without any atomic resolution images.

InAs heteroepitaxy on nanopillar-patterned GaAs (111)A

Heteroepitaxy on nanopatterned substrates is a means of defect reduction at semiconductor heterointerfaces by exploiting substrate compliance and enhanced elastic lattice relaxation resulting from reduced dimensions. We explore this possibility in the InAs/GaAs(1 1 1)A system using a combination of nanosphere lithography and reactive ion etching of the GaAs(1 1 1)A substrate for nano-patterning of the substrate, yielding pillars with honeycomb and hexagonal arrangements and varied nearest neighbour distances. Substrate patterning is followed by MBE growth of InAs at temperatures of 150–350 °C and growth rates of 0.011 nm/s and 0.11 nm/s. InAs growth in the form of nano-islands on the pillar tops is achieved by lowering the adatom migration length by choosing a low growth temperature of 150 °C at the growth rate 0.011 nm/s. The choice of a higher growth rate of 0.11 nm/s results in higher InAs island nucleation and the formation of hillocks concentrated at the pillar bases due to reduced adatom migration length. A common feature of the growth morphology for all explored conditions is the formation of hillocks or pyramids with sometimes well-defined facets due to the presence of a concave surface curvature at the pillar bases acting as adatom sinks. This InAs growth at the pillar bases and between pillars is investigated in detail in dependence of MBE growth conditions.

Estimating complete band diagrams of non-ideal heterointerfaces by combining ellipsometry and photoemission spectroscopy

In this work, we show that spectroscopic ellipsometry can be combined with photoemission spectroscopy to obtain complete interface band diagrams of non-ideal semiconductor heterointerfaces, such as interfaces between thin-film polycrystalline materials. The non-destructive ellipsometry measurement probes the near-interface bandgap of the two semiconductors (including the buried semiconductor) after the interface has formed. This is important in the non-ideal case where chemical processes during interface growth modify the electronic properties of the two separated surfaces. Knowledge of near-interface bandgaps improves accuracy in conduction band offset measurements of non-ideal interfaces, and it sheds light on their device physics. Both of those positive outcomes are demonstrated in the Cu2ZnSnS4/CdS interface used here as a case study, where the bandgap of both materials decreases by up to 200 meV from the bulk to the near-interface region. This finding reveals a preferential electron-hole recombination channel near the interface, and it yields corrected values for the interfacial conduction band offset.

Atomic-Resolution Spectrum Imaging of Semiconductor Nanowires.

Over the past decade, III-V heterostructure nanowires have attracted a surge of attention for their application in novel semiconductor devices such as tunneling field-effect transistors (TFETs). The functionality of such devices critically depends on the specific atomic arrangement at the semiconductor heterointerfaces. However, most of the currently available characterization techniques lack sufficient spatial resolution to provide local information on the atomic structure and composition of these interfaces. Atomic-resolution spectrum imaging by means of electron energy-loss spectroscopy (EELS) in the scanning transmission electron microscope (STEM) is a powerful technique with the potential to resolve structure and chemical composition with sub-angstrom spatial resolution and to provide localized information about the physical properties of the material at the atomic scale. Here, we demonstrate the use of atomic-resolution EELS to understand the interface atomic arrangement in three-dimensional heterostructures in semiconductor nanowires. We observed that the radial interfaces of GaSb-InAs heterostructure nanowires are atomically abrupt, while the axial interface in contrast consists of an interfacial region where intermixing of the two compounds occurs over an extended spatial region. The local atomic configuration affects the band alignment at the interface and, hence, the charge transport properties of devices such as GaSb-InAs nanowire TFETs. STEM-EELS thus represents a very promising technique for understanding nanowire physical properties, such as differing electrical behavior across the radial and axial heterointerfaces of GaSb-InAs nanowires for TFET applications.

Spin-orbit interactions in inversion-asymmetric two-dimensional hole systems: A variational analysis

We present an in-depth study of the spin-orbit (SO) interactions occurring in inversion-asymmetric two-dimensional hole gases at semiconductor heterointerfaces. We focus on common semiconductors such as GaAs, InAs, InSb, Ge, and Si. We develop a semi-analytical variational method to quantify SO interactions, accounting for both structure inversion asymmetry (SIA) and bulk inversion asymmetry (BIA). Under certain circumstances, using the Schrieffer-Wolff (SW) transformation, the dispersion of the ground state heavy hole subbands can be written as $E(k) = A k^2 - B k^4 \pm C k^3$ where $A$, $B$, and $C$ are material- and structure-dependent coefficients. We provide a simple method of calculating the parameters $A$, $B$, and $C$, yet demonstrate that the simple SW approximation leading to a SIA (Rashba) spin splitting $\propto k^3$ frequently breaks down. We determine the parameter regimes at which this happens for the materials above and discuss a convenient semi-analytical method to obtain the correct spin splitting, effective masses, Fermi level, and subband occupancy, together with their dependence on the charge density, dopant type, and dopant concentration for both inversion and accumulation layers. Our results are in good agreement with fully numerical calculations as well as with experimental findings. They suggest that a naive application of the simple cubic Rashba model is of limited use in common heterostructures, as well as quantum dots. Finally, we find that for the single heterojunctions studied here the magnitudes of BIA terms are always much smaller than those of SIA terms.

Ab initiodensity functional theory study on the atomic and electronic structure of GaP/Si(001) heterointerfaces

The atomic and electronic band structures of GaP/Si(001) heterointerfaces were investigated by ab initio density functional theory calculations. Relative total energies of abrupt interfaces and mixed interfaces with Si substitutional sites within a few GaP layers were derived. It was found that Si diffusion into GaP layers above the first interface layer is energetically unfavorable. An interface with Si/Ga substitution sites in the first layer above the Si substrate is energetically the most stable one in thermodynamic equilibrium. The electronic band structure of the epitaxial GaP/Si(001) heterostructure terminated by the $(2\ifmmode\times\else\texttimes\fi{}2)$ surface reconstruction consists of surface and interface electronic states in the common band gap of two semiconductors. The dispersion of the states is anisotropic and differs for the abrupt Si-Ga, Si-P, and mixed interfaces. Ga $2p$, P $2p$, and Si $2p$ core-level binding-energy shifts were computed for the abrupt and the lowest-energy heterointerface structures. Negative and positive core-level shifts due to heterovalent bonds at the interface are predicted for the abrupt Si-Ga and Si-P interfaces, respectively. The distinct features in the heterointerface electronic structure and in the core-level shifts open new perspectives in the experimental characterization of buried polar-on-nonpolar semiconductor heterointerfaces.

Coherent phonon spectroscopy characterization of electronic bands at buried semiconductor heterointerfaces

We demonstrate an all-optical approach to probe electronic band structure at buried interfaces involving polar semiconductors. Femtosecond optical pulses excite coherent phonons in epitaxial GaP films grown on Si(001) substrate. We find that the coherent phonon amplitude critically depends on the film growth conditions, specifically in the presence of antiphase domains, which are independently characterized by transmission electron microscopy. We determine the Fermi levels at the buried interface of GaP/Si from the coherent phonon amplitudes and demonstrate that the internal electric fields are created in the nominally undoped GaP films as well as the Si substrates, possibly due to the carrier trapping at the antiphase boundaries and/or at the interface.

半導体異材界面GaAs/XAs(X=Al, In)の第一原理局所応力解析

A first-principles local stress analysis has been applied in order to reveal stress distribution in the vicinity of semiconductor hetero-interfaces of GaAs/XAs (X = Al, As). The weighted Bader integration scheme based on the Yu-Trinkle algorithm is found to be so effective that stress density is accurately integrated to the local stress over the Bader atomic volume. Applying the developed local stress calculation to semiconductor interfaces, we found that interface stress is localized, in the range of a single atom, in the vicinity of the interface. We also found that the nanoscopic stress state reflects the electronic bonding of atoms in the vicinity of the interfaces.

Band alignment of semiconductors from density-functional theory and many-body perturbation theory

The band lineup, or alignment, of semiconductors is investigated via first-principles calculations based on density functional theory (DFT) and many-body perturbation theory (MBPT). Twenty-one semiconductors including C, Si, and Ge in the diamond structure, BN, AlP, AlAs, AlSb, GaP, GaAs, GaSb, InP, InAs, InSb, ZnS, ZnSe, ZnTe, CdS, CdSe, and CdTe in the zinc-blende structure, and GaN and ZnO in the wurtzite structure are considered in view of their fundamental and technological importance. Band alignments are determined using the valence and conduction band offsets from heterointerface calculations, the ionization potential (IP) and electron affinity (EA) from surface calculations, and the valence band maximum and conduction band minimum relative to the branch point energy, or charge neutrality level, from bulk calculations. The performance of various approximations to DFT and MBPT, namely the Perdew-Burke-Ernzerhof (PBE) semilocal functional, the Heyd-Scuseria-Ernzerhof (HSE) hybrid functional, and the $GW$ approximation with and without vertex corrections in the screened Coulomb interaction, is assessed using the $GW{\ensuremath{\Gamma}}^{1}$ approximation as a reference, where first-order vertex corrections are included in the self-energy. The experimental IPs, EAs, and band offsets are well reproduced by $GW{\ensuremath{\Gamma}}^{1}$ for most of the semiconductor surfaces and heterointerfaces considered in this study. The PBE and HSE functionals show sizable errors in the IPs and EAs, in particular for group II-VI semiconductors with wide band gaps, but are much better in the prediction of relative band positions or band offsets due to error cancellation. The performance of the $GW$ approximation is almost on par with $GW{\ensuremath{\Gamma}}^{1}$ as far as relative band positions are concerned. The band alignments based on average interfacial band offsets for all pairs of 17 semiconductors and branch point energies agree with explicitly calculated interfacial band offsets with small mean absolute errors of both $\ensuremath{\sim}0.1\text{eV}$, indicating a good overall transitivity of the band offsets. The alignment based on IPs from selected nonpolar surfaces performs comparably well in the prediction of band offsets at most of the considered interfaces. The maximum errors are, however, as large as 0.3, 0.4, and 0.7 eV for the alignments based on the average band offsets, branch point energies, and IPs, respectively. This margin of error should be taken into account when performing materials screening using these alignments.

Critical Role of Two-Dimensional Island-Mediated Growth on the Formation of Semiconductor Heterointerfaces

We experimentally demonstrate a sigmoidal variation of the composition profile across semiconductor heterointerfaces. The wide range of material systems (III-arsenides, III-antimonides, III-V quaternary compounds, III-nitrides) exhibiting such a profile suggests a universal behavior. We show that sigmoidal profiles emerge from a simple model of cooperative growth mediated by two-dimensional island formation, wherein cooperative effects are described by a specific functional dependence of the sticking coefficient on the surface coverage. Experimental results confirm that, except in the very early stages, island growth prevails over nucleation as the mechanism governing the interface development and ultimately determines the sigmoidal shape of the chemical profile in these two-dimensional-grown layers. In agreement with our experimental findings, the model also predicts a minimum value of the interfacial width, with the minimum attainable value depending on the chemical identity of the species.

Low kV Analysis of the Atomic Structure and Bonding at Complex Oxide - Semiconductor Hetero-interfaces

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 – August 2, 2012.

Time-resolved second harmonic generation study of buried semiconductor heterointerfaces using soliton-induced transparency

The transient second harmonic generation (SHG) and linear optical reflectivity (LOR) signals measured simultaneously in reflection from GaAs/GaSb/InAs and GaAs/GaSb heterostructures revealed a new mechanism for creating self-induced transparency in narrow bandgap semiconductors at low temperatures, which is based on the dual-frequency electro-optic soliton propagation. This allows the ultrafast carrier dynamics at buried semiconductor heterointerfaces to be studied.

Band offsets and band bending at heterovalent semiconductor interfaces

We present a comprehensive study of band offsets and band bending at heterovalent semiconductor heterointerfaces. A perfectly abrupt heterovalent interface is usually thermodynamically unstable, and atomic intermixing of materials with different numbers of valence electrons causes large variations in band offsets and local doping density, depending on the spatial arrangement of atoms at the interface. The studied prototypical II-VI/III-V semiconductor interfaces are $n$-doped ZnSe/GaAs (001) heterostructures with varied composition profiles close to the interface, which were realized by molecular-beam epitaxy with different amounts of Zn or Se predeposited on $n$-GaAs prior to $n$-ZnSe layer growth. The samples are characterized by temperature-dependent electrical transport across the interface, electrochemical capacitance-voltage profiling, Raman spectroscopy, and high-resolution x-ray diffraction. We find that the potential barrier in the conduction band at a Zn-rich $n$-ZnSe/$n$-GaAs interface is as high as 550 meV and it gradually decreases with Se predeposition down to about 70 meV. A large depletion region at the heterointerface, about 50 nm wide, is assigned to significant intermixing of acceptor-type atoms, resulting in an effective electron deficit of $1.5\ifmmode\times\else\texttimes\fi{}{10}^{13}\text{ }{\text{cm}}^{\ensuremath{-}2}$. The depletion width and the acceptor density around the interface are nearly independent from the growth start procedure. Se predeposition, however, partially shifts the depletion region at the heterointerface from GaAs into ZnSe, compared to Zn predeposition. The results are discussed on the basis of a band-bending model accounting for variable band offsets, interface state density and atomic interdiffusion profiles depending on growth start.

(Invited) Carbon Nanotube Exciton Dissociation and Charge Transfer at Semiconductor Heterointerfaces: Driving Forces and Relevance to Photovoltaics

not Available.

Hot-phonon-assisted absorption at semiconductor heterointerfaces monitored by pump-probe second-harmonic generation

We provide the evidence for the hot-LO-phonon-assisted absorption at semiconductor heterointerfaces. The process is demonstrated with $\mathrm{Ga}\mathrm{As}∕\mathrm{Ga}\mathrm{Sb}$ interface when the photon energy is tuned below the band-gap energy for GaAs, but it is in a great excess for GaSb. The excitation of carriers in GaAs in the vicinity of the heterointerface is shown to be assisted by hot LO phonons generated in GaAs and GaSb within the relaxation of hot carriers in GaSb. The effect has been observed in the ultrafast pump-probe experiment through the interfacial-electric-field-induced second-harmonic generation response.