Molecular Beam Epitaxy Conditions Research Articles

Real-time observation of liquid-gallium ordering on epitaxially-grown GaN(0001) by X-ray scattering measurements

X-ray crystal truncation rod (CTR) measurements are commonly used to analyze surface or interfacial atomic structures quantitatively. However, it is difficult to expand the measurement range to determine three-dimensional atomic structures in real time. We developed a method for CTR measurements that involves the simultaneous intensity measurements of X-rays and electron diffraction under molecular beam epitaxial conditions. Using the proposed method, we observed the formation of liquid gallium ordering on the GaN(0001) surface and determined the ordered structure within each layer.

Multiscale Kinetic Monte Carlo Simulation of Self-Organized Growth of GaN/AlN Quantum Dots.

A three-dimensional kinetic Monte Carlo methodology is developed to study the strained epitaxial growth of wurtzite GaN/AlN quantum dots. It describes the kinetics of effective GaN adatoms on an hexagonal lattice. The elastic strain energy is evaluated by a purposely devised procedure: first, we take advantage of the fact that the deformation in a lattice-mismatched heterostructure is equivalent to that obtained by assuming that one of the regions of the system is subjected to a properly chosen uniform stress (Eshelby inclusion concept), and then the strain is obtained by applying the Green’s function method. The standard Monte Carlo method has been modified to implement a multiscale algorithm that allows the isolated adatoms to perform long diffusion jumps. With these state-of-the art modifications, it is possible to perform efficiently simulations over large areas and long elapsed times. We have taylored the model to the conditions of molecular beam epitaxy under N-rich conditions. The corresponding simulations reproduce the different stages of the Stranski–Krastanov transition, showing quantitative agreement with the experimental findings concerning the critical deposition, and island size and density. The influence of growth parameters, such as the relative fluxes of Ga and N and the substrate temperature, is also studied and found to be consistent with the experimental observations. In addition, the growth of stacked layers of quantum dots is also simulated and the conditions for their vertical alignment and homogenization are illustrated. In summary, the developed methodology allows one to reproduce the main features of the self-organized quantum dot growth and to understand the microscopic mechanisms at play.

Determination of the flow and activation energy of phosphorus desorption during annealing of an InP(001) substrate in an arsenic flux under molecular beam epitaxy conditions

We report experimental study of phosphorus desorption from epi-ready InP(001) substrates during high-temperature annealing in an arsenic flux. InPAs solid solution and InAs islands are formed on the surface in the process of annealing. The original method is proposed to determine the amount of phosphorus atoms desorbing from the surface by determining the amount of arsenic atoms in the solid solution of InPAs and InAs islands. The flux of phosphorus desorbing from the surface increases from 1·10-4 monolayer · cm-2·s-1 at 500oC annealing temperature to 7.3·10-4 monolayer · cm-2· s-1at 540oC. The activation energy of the phosphorus desorption process is 2.7±0.2 eV. Keywords: InP, annealing, desorption, activation energy.

In Ukrainian

By the method of density functional theory (B3LYP, 6-31G **) three types of displacements are calculated, namely oscillations as a whole, rotation and diffusion of dimers > Ge = Ge <, > Ge = Si < and > Si = Si <, which are formed on the crystalline surface of Si (001) (4×2) during the deposition of germanium atoms under conditions of molecular beam epitaxy. Calculations of angles of buckling of addimers are carried out. It is shown that when the addimers as a whole oscillate around the equilibrium position, the energy barriers are quite low, the highest of them occurs for a mixed addimer > Si = Ge <. Pure adders > Ge = Ge < and > Si = Si < oscillate between two degenerate states with an energy barrier of 0.042 and 0.014 eV, respectively. The structures of the transition state and the intermediate when the addimer > Ge = Ge < is moved between adjacent cells in the approximation of the constant bond length > Ge = Ge < are obtained. As calculations have shown, all transformations of surface dimers occur with relatively small activation energies, the numerical values of which agree satisfactorily with the results of STM experiments available in the literature.

(Invited) Ga2O3 Phase Control and Heterojunctions Using Plasma-Enhanced Atomic Layer Epitaxy

Ga2O3 has emerged as a promising material for next generation power electronics. While β-Ga2O3 (monoclinic) is the most stable and studied of six Ga2O3 polymorphs, the slightly less energetically favorable α-, ε-, and κ-Ga2O3 phases have unique characteristics that can be exploited such as larger bandgaps, alloying for dopant control, or polarization beneficial to the formation of two-dimensional electron gas (2DEG) channels. Specifically, α-Ga2O3 (rhombohedral, corundum) has the largest bandgap of ~5.3 eV and can be alloyed with α-Al2O3 (8.8 eV) and α-In2O3 (3.7 eV) for bandgap engineering. Both ε-Ga2O3 (hexagonal, P63mc) and κ-Ga2O3 (orthorhombic, Pna21 ) phases are polar, with a predicted spontaneous polarization strength up to 10 times larger than GaN and 3 times larger than AlN. Like the III-N system, polarization induced charges can lead to higher charge densities and mobilities in 2DEGs formed at heterojunctions, which would improve the viability of Ga2O3 electronic devices. Plasma-enhanced atomic layer deposition (PEALD) is a popular, conformal, energy-enhanced synthesis method for thin films due to its many advantages, including: deposition at reduced growth temperatures, access to metastable phases, improved crystallinity, and increased growth rates. In this work, we use PEALD to produce high-quality heteroepitaxial Ga2O3 and (AlxGa1-x)2O3 (AlGO) films and investigate materials properties such as phase selectivity, ternary solubility limits, and electrical and optical performance.All Ga2O3 films were deposited in a Veeco Fiji G2 reactor equipped with a load lock and turbo pump using trimethygallium, trimethylaluminum, and O2 plasma. Initial studies on c-plane sapphire substrates at 350°C and 8 mTorr show the phase could be altered from β to α by a varying the pure O2 flow during plasma pulse from 5-40 sccm [1]. Optical emission spectroscopy indicate that the changes in the relative concentration of atomic oxygen is crucial for phase selectivity while the high ion flux to the surface can contribute to the crystallinity at low Tg [2]. To grow ε(κ)-Ga2O3 on c-plane sapphire required going to a much higher temperature (500°C), pressure (100’s mTorr), and O2 flow (100sccm) [1]. Without modifications to the current ALD system, pure ε(κ)-Ga2O3 on sapphire was not achieved under any conditions. Using optimum growth conditions for the three phases on sapphire, films were deposited on GaN and diamond to determine the effect of substrate structure. Transmission electron microscopy was conducted to determine the specific phases (β, ε, and κ) present in each case, and showed the amount of each phase varied with PEALD parameters. While films on diamond resulted in mixed β/ε(κ) phases, pure ε(κ)-phase films were attained on GaN and the strain varied with pressure and Tg. Vertical breakdown measurements were taken for both β- and ε(κ)-Ga2O3/n+ GaN substrates. Breakdown fields varied between 3.8-7.0 MV/cm dependent on the phase and strained state of the Ga2O3 films. β-Ga2O3 films showed less variability in breakdown field from device to device than ε(κ)-Ga2O3 films, but neither showed a dependence on device size.While PEALD is beneficial for depositing thin films of metastable phases, practical devices often require much thicker barrier and active layers. For this reason, we investigated integrating PEALD metastable Ga2O3 films with traditional semiconductor deposition techniques, such as molecular beam epitaxy (MBE), capable of extending these layers beyond 100 nm in thickness. The same MBE conditions were used to deposit Ga2O3 films on GaN substrates with and without PEALD ε(κ)-Ga2O3 nucleation layers. Those deposited without the PEALD metastable nucleation layer resulted in stable β-phase films, while those with nucleation layers resulted in pure ε(κ)-phase films. This shows importance of PEALD for realizing practical device structures using metastable phases.Finally, to investigate heterojunctions for 2DEG formation, AlxGa1-xO films were developed. While the full stoichiometric range could be reached using a PEALD digital alloying method, crystallinity was lost above x = 0.2 for the β phase, x = 0.35 for the ε(κ) phase, and x=0.6 for the α phase. Initial device structures will be shown in order to establish the feasibility of these films in device applications.[1] Wheeler, et al. Chem. Mater. 2020, 32, 1140-1152[2] Boris, et al. JVST A 2019, 37(6), 060909 Figure 1

Experimental verification of the origin of positive linear magnetoresistance in CoFe(V1−xMnx)Si Heusler alloys

The origin of the positive linear magnetoresistance (PLMR) effect at low temperatures in $\mathrm{CoFe}({\mathrm{V}}_{1\ensuremath{-}x}{\mathrm{Mn}}_{x})\mathrm{Si}$ Heusler alloys is discussed. From anomalous dispersion x-ray diffraction measurements, we can clarify that the crystal structure of the epitaxial CoFeVSi films grown by molecular beam epitaxy (MBE) is $L{2}_{1}\mathrm{B}$ type. By employing the substitution of Mn for V in the CoFeVSi film in MBE conditions, we experimentally demonstrate homogeneous $\mathrm{CoFe}({\mathrm{V}}_{1\ensuremath{-}x}{\mathrm{Mn}}_{x})\mathrm{Si}$ films and systematic control of the magnetic moments. The PLMR effect gradually decreases with increasing Mn contents but it can be seen even for $\mathrm{CoFe}({\mathrm{V}}_{0.5}{\mathrm{Mn}}_{0.5})\mathrm{Si}$. We note that the PLMR effect disappears for $\mathrm{CoFe}({\mathrm{V}}_{0.25}{\mathrm{Mn}}_{0.75})\mathrm{Si}$. According to theoretical calculations of the electronic band structures of $\mathrm{CoFe}({\mathrm{V}}_{1\ensuremath{-}x}{\mathrm{Mn}}_{x})\mathrm{Si}$, the gaplesslike electronic band structure due to the V-$d$ state in the minority spins of CoFeVSi is varied to the band gap by increasing the substitution of Mn. This means that the electronic band structure near the Fermi level in $\mathrm{CoFe}({\mathrm{V}}_{1\ensuremath{-}x}{\mathrm{Mn}}_{x})\mathrm{Si}$ can be experimentally controlled by substituting Mn for V. From these considerations, we can conclude that the PLMR effect in $\mathrm{CoFe}({\mathrm{V}}_{1\ensuremath{-}x}{\mathrm{Mn}}_{x})\mathrm{Si}$ is caused by the presence of the V state-induced gaplesslike structure in the minority spin electronic band near the Fermi level.

Great Differences between Low-Temperature Grown Co2FeSi and Co2MnSi Films on Single-Crystalline Oxides

Using extremely low synthesis temperatures in molecular beam epitaxy (MBE) conditions on MgO(001), SrTiO3(001), and MgAl2O4(001), we find great differences in the crystallinity and magnetic properties between Co-based full-Heusler-alloy Co2FeSi and Co2MnSi films. For example, while L21-ordered Co2FeSi films can be demonstrated on all the oxides even at less than 80 °C, only the B2-ordered and amorphous Co2MnSi films can be obtained. Considering the experimental results and the findings obtained from theoretical calculations, we can conclude that the stability of the Heusler/oxide interfaces and the alloying energy of the disordered Heusler alloys are two of the most important factors for the low-temperature growth of epitaxial Co2FeSi and Co2MnSi films on these oxides. We suggest that Co2FeSi is more suitable for low-temperature formed spintronic devices than Co2MnSi.

Bandgap, electrical and structural properties of thick InN (0001) films grown under optimal conditions

The improvement potential for the structural, electrical and opto-electronic properties of heteroepitaxial InN-on-GaN (0001) films by using optimal conditions (substrate temperature, In and N fluxes) of plasma-assisted molecular beam epitaxy and increasing the epilayer thickness to few micrometres has been investigated. The increase of InN thickness to 3.7 μm resulted to a-type component threading dislocation density of 6x109 cm−2 and directly measured electron mobility of 2330 cm2/Vs and concentration of 4.5x1017 cm−3. The optical bandgap of this film at 300K was 0.637 eV. However, a degradation in the integrity of the interfacial InN/GaN region was observed in films thicker than 1 μm, with the formation of voids and the nucleation of microcracks, which may be related to strain relaxation or thermal decomposition.

Microscopy and spectroscopy study of nanostructural phase transformation from β-MoO3 to Mo under UHV – MBE conditions

We report a simple reduction of molybdenum oxide (β-MoO3) grown on reconstructed Si(100) by thermal annealing in ultra-high vacuum (UHV) using molecular beam epitaxy (MBE). By increasing the substrate temperature during deposition or the annealing temperature after growth, the morphologies of as-deposited structures were found to vary from nanoribbons (NRs) of β-MoO3 to nanoparticles (NPs) of Mo. The change in morphologies have been associated with a structural transition from β-MoO3 to MoO2 at 400 °C and MoO2 to Mo at 750 °C. The in-situ X-ray photoelectron spectroscopy (XPS) measurements revealed a shift of the Mo 3d peaks towards lower binding energies, representing the reduction in Mo oxidation states until a pure Mo 3d peak at 750 °C was observed. The ex-situ KPFM measurements showed a decrease in the local work function (Φ) (from ≈ 5.27 ± 0.05 eV to ≈ 4.83 ± 0.05 eV) with increasing substrate temperature. A gradual reduction of the band gap from ≈ 3.32 eV for β-MoO3 NRs to zero band gap for Mo NPs is also observed during the annealing up to 750 °C.

Growth and characterisation of MnSb(0 0 0 1)/InGaAs(1 1 1)A epitaxial films

MnSb layers have been grown on InxGa1-xAs(1 1 1) A virtual substrates using molecular beam epitaxy (MBE). The effects of both substrate temperature (Tsub) and Sb/Mn beam flux ratio (JSb/Mn) were investigated. The surface morphology, layer and interface structural quality, and magnetic properties have been studied for a 3 × 3 grid of Tsub and JSb/Mn values. Compared to known optimal MBE conditions for MnSb/GaAs(1 1 1) [Tsub = 415°C,JSb/Mn = 6.5], a lower substrate temperature is required for sharp interface formation when growing MnSb on In0.48Ga0.52As(1 1 1) A [Tsub = 350°C,JSb/Mn = 6.5]. At high flux ratio (JSb/Mn = 9.5) elemental Sb is readily incorporated into MnSb films. At higher substrate temperatures and lower flux ratios, (In,Ga) Sb inclusions in the MnSb are formed, as well as MnAs inclusions within the substrate. The Sb and (In,Ga) Sb inclusions are epitaxial, while MnAs inclusions are endotaxial, i.e. all have a crytallographic relationship to the substrate and epilayer. MBE optimisation towards different device structures is discussed along with results from a two-stage growth scheme.

Ab-initio study of boron incorporation and compositional limits at GaN and AlN (0001) surfaces

Density functional theory calculations are employed to investigate B incorporation at the GaN(0001) and AlN(0001) surfaces. It is found that under typical metal-organic chemical vapor deposition (MOCVD) and metal rich molecular beam epitaxy (MBE) conditions, the maximum B contents at the surfaces are in the order of 3% for GaN and 15% for AlN. Under MBE N-rich growth conditions the calculations reveal a rehybridization enhanced solubility mechanism that dominates at the surface. This mechanism offers a promising route to kinetically stabilize B contents above the bulk solubility limit and as high as 25%.

Anti-reflection behavior of a surface Ga-doped ZnO nanoneedle structure and the controlling factors

The anti-reflection functions of a surface nanostructure–including transparent conductive Ga-doped ZnO (GaZnO) nanoneedles (NNs), a GaZnO thin film, and buried Ag nanoparticles (NPs), on GaN and Si templates through the combination of the effects of gradient effective refractive index, index matching, and the surface plasmon (SP) resonances in the visible and infrared range–are studied by measuring its reflection, transmission, and scattering behaviors. The NNs are grown under different molecular beam epitaxy conditions with the low-temperature vapor-liquid-solid mode by using Ag NPs as growth catalyst. Based on the crystal structure study, it is found that the c-axis of a GaZnO NN is controlled by the local Ag (111) orientation of the un-melted portion of an Ag NP, which is influenced by the crystal structure of the growth template. On c-plane GaN, by using small and separate Ag NPs as catalysts, the alignment of GaN (002), Ag (111), and ZnO (002) leads to the growth of mostly vertical NNs for producing a strong anti-reflection effect. On Si (100), no crystal matching condition can be used such that the grown NNs are randomly oriented, leading to a relatively weaker anti-reflection effect. The GaZnO thin film and buried Ag NPs also make contributions to the anti-reflection function through the effects of index matching and SP resonance.

Effects of cationic growth conditions of molecular beam epitaxy on ferromagnetic properties of Mn-doped ZnSnAs2 thin films

The effects of cationic growth parameters of molecular beam epitaxy on the crystalline and magnetic properties of Mn-doped ZnSnAs2, (Zn,Sn,Mn)As2, thin films were investigated in order to control ferromagnetism at room temperature. The combination of cationic beam equivalent pressures of Zn, Sn, and Mn atoms was varied at an optimal substrate temperature of 320 °C. Clear hysteresis loops were observed for the samples at 300 K, indicating ferromagnetism at room temperature. We found that the change in Zn flux does not significantly affect the composition of (Zn,Sn,Mn)As2 thin films and ferromagnetic properties and that ferromagnetic properties definitely depend on the amounts of Mn and Sn fluxes. X-ray photoelectron spectroscopy analysis revealed that the sum of the amounts of Mn2+ and Mn4+, which may contribute to the ferromagnetism in (Zn,Sn,Mn)As2 thin films, was approximately 60–70% of the total Mn amount with respect to ferromagnetic (Zn,Sn,Mn)As2 samples. This result indicates that the ferromagnetic properties could be controlled in multilayered (Zn,Sn,Mn)As2 by changing the combination of Zn, Sn, and Mn fluxes.

Growth rate dependence of boron incorporation into BxGa1−xAs layers

This work provides a comprehensive study of the incorporation behavior of B in growing GaAs under molecular beam epitaxy conditions. Structural characterization of superlattices revealed a strong dependence of the BAs growth rate on the GaAs growth rate used. In general, higher GaAs growth rates lead to a higher apparent BAs growth rate, although lower B cell temperatures showed saturation behavior. Each B cell temperature requires a minimum GaAs growth rate for producing smooth films. The B incorporation into single thick layers was found to be reduced to 75–80% compared to superlattice structures. The p-type carrier densities in 1000nm thick layers were found to be indirectly proportional to the B content. Furthermore, 500nm thick BxGa1−xAs layers showed significantly lower carrier concentrations, indicating B segregation on the surface during growth of thicker layers.

Review Article: Molecular beam epitaxy of lattice-matched InAlAs and InGaAs layers on InP (111)A, (111)B, and (110)

For more than 50 years, research into III–V compound semiconductors has focused almost exclusively on materials grown on (001)-oriented substrates. In part, this is due to the relative ease with which III–Vs can be grown on (001) surfaces. However, in recent years, a number of key technologies have emerged that could be realized, or vastly improved, by the ability to also grow high-quality III–Vs on (111)- or (110)-oriented substrates These applications include: next-generation field-effect transistors, novel quantum dots, entangled photon emitters, spintronics, topological insulators, and transition metal dichalcogenides. The first purpose of this paper is to present a comprehensive review of the literature concerning growth by molecular beam epitaxy (MBE) of III–Vs on (111) and (110) substrates. The second is to describe our recent experimental findings on the growth, morphology, electrical, and optical properties of layers grown on non-(001) InP wafers. Taking InP(111)A, InP(111)B, and InP(110) substrates in turn, the authors systematically discuss growth of both In0.52Al0.48As and In0.53Ga0.47As on these surfaces. For each material system, the authors identify the main challenges for growth, and the key growth parameter–property relationships, trends, and interdependencies. The authors conclude with a section summarizing the MBE conditions needed to optimize the structural, optical and electrical properties of GaAs, InAlAs and InGaAs grown with (111) and (110) orientations. In most cases, the MBE growth parameters the authors recommend will enable the reader to grow high-quality material on these increasingly important non-(001) surfaces, paving the way for exciting technological advances.

Initiation strategies for simultaneous control of antiphase domains and stacking faults in GaAs solar cells on Ge

Incorporating a Ge junction into a lattice-matched GaInP/GaAs/GaInNAsSb triple-junction cell grown by molecular beam epitaxy (MBE) could enable concentrated efficiencies of ∼50%. Epitaxial integration allows lift-off and wafer bonding steps to be avoided, but growth of III–Vs on Ge by MBE can lead to antiphase domains (APD) and stacking fault pyramids (SFP), both of which diminish solar cell performance. Initiating growth by migration-enhanced epitaxy (MEE) is typically cited as necessary to obtain high-quality III–Vs on Ge. In this work, the authors show that typical MEE growth conditions force a compromise between APD height (hAPD) and SFP density (ρSFP). As APDs can readily self-terminate while SFPs cannot, a two-step initiation strategy was employed, where MEE is performed under conditions that minimize ρSFP followed by low-temperature MBE conditions that encourage APD termination. By doing so, the authors obtained ρSFP < 104 cm−2 with hAPD ≤ 57 nm. The authors also demonstrated that high-quality GaAs on Ge can be grown without MEE initiation using conventional MBE conditions, though with taller APDs. Both the two-step initiation and conventional MBE initiation yield GaAs cells with high open-circuit voltage and internal quantum efficiency, demonstrating promising paths toward epitaxial integration of high-efficiency solar cells on Ge.

The c(4 × 4)–a(1 × 3) surface reconstruction transition on InSb(0 0 1): Static versus dynamic conditions

The transition between the a(1×3) and c(4×4) surface reconstructions of InSb(001) has been carefully monitored by reflection high energy electron diffraction as a function of temperature and Sb2 flux, without incident In flux. Arrhenius-like behaviour is observed across the whole range of Sb2 fluxes and temperatures, allowing accurate internal calibration of substrate temperature. This behaviour is in contrast to aggregated data obtained under dynamic molecular beam epitaxy conditions, which show two regimes rather than a single Arrhenius-like phase boundary. The results are explained qualitatively by the atomistic kinetics in static versus dynamic conditions.

Infrared transmission spectroscopy of charge carriers in self-assembled InAs quantum dots under surface electric fields

We present a study on the intersublevel spacings of electrons and holes in a single layer of InAs self-assembled quantum dots. We use Fourier transform infrared transmission spectroscopy via a density chopping scheme for direct experimental observation of the intersublevel spacings of electrons without any external magnetic field. Epitaxial, complementary-doped and semi-transparent electrostatic gates are grown within the ultra high vacuum conditions of molecular beam epitaxy to voltage-tune the device, while a two dimensional electron gas (2DEG) serves as a back contact. Spacings of the hole sublevels are indirectly calculated from the photoluminescence spectrum by using a simple model given by Warburton et al []. Additionally, we observe that the intersubband resonances of the 2DEG are enhanced due to the quantum dot layer on top of the device.

Investigation of the peculiarities of Ge island growth on Si (100) under MBE conditions

The results of investigating the features of Ge-island formation on Si (100) under conditions of molecular-beam epitaxy is presented. Nanosized structures at heteroboundaries (islets and quantum dots) are attracting great interest due to new useful properties and broad prospects of their application.

Compositional dependence of the absorption edge and dark currents in Ge1−x−ySixSny/Ge(100) photodetectors grown via ultra-low-temperature epitaxy of Ge4H10, Si4H10, and SnD4

Lattice-matched Ge1−x−ySixSny (x ≤ 0.2, y ≤ 0.05) alloys were deposited defect-free on Ge(001) substrates via low-temperature (330–290 °C) reactions of Ge4H10, Si4H10 and SnD4 hydrides, and used to fabricate pin photodetectors. The growth is carried out under gas-source molecular beam epitaxy conditions in a specially designed single-wafer reactor. Optical responsivity measurements reveal absorption edges between 0.88 eV and 0.98 eV, which are used to determine the compositional dependence of the direct band gap. A study of the I-V characteristics of the diodes shows that the dark current is very weakly correlated with the number of Si-Sn bonds in the alloy.