Frank-van Der Merwe Mode Research Articles

Growth Behavior of Ni on Hydrogen-Etched WS2 Surface.

Transition metal dichalcogenides (TMDs) are 2D materials in which the layers are stacked together by van der Waals forces. Although TMDs are expected to be promising for electronic applications, forming a uniform electrode on them is challenging because of the low adhesion forces between metals and TMDs. This study focuses on improving the quality of metal electrodes by introducing atomic H to create surface defects, using Ni on WS2 as an example. The detailed effects of H etching and subsequent Ni growth were investigated using scanning tunneling microscopy (STM) and synchrotron-based X-ray photoemission (XPS) techniques. Our studies reveal that introducing point defects of ∼3.05 × 1011 cm-2 on the WS2 surface, results in a significant shift in Ni growth from the Volmer-Weber to a near Frank-van der Merwe mode. The origin of the change is the bond formation between the Ni and W atoms, which is expected to realize ohmic contact. The optimization of metal-TMD interfaces offers valuable insights for advanced applications.

Three-dimensional nanoframes with dual rims as nanoprobes for biosensing

Three-dimensional (3D) nanoframe structures are very appealing because their inner voids and ridges interact efficiently with light and analytes, allowing for effective optical-based sensing. However, the realization of complex nanoframe architecture with high yield is challenging because the systematic design of such a complicated nanostructure lacks an appropriate synthesis protocol. Here, we show the synthesis method for complex 3D nanoframes wherein two-dimensional (2D) dual-rim nanostructures are engraved on each facet of octahedral nanoframes. The synthetic scheme proceeds through multiple executable on-demand steps. With Au octahedral nanoparticles as a sacrificial template, sequential processes of edge-selective Pt deposition and inner Au etching lead to Pt octahedral mono-rim nanoframes. Then, adlayers of Au are grown on Pt skeletons via the Frank-van der Merwe mode, forming sharp and well-developed edges. Next, Pt selective deposition on both the inner and outer boundaries leads to tunable geometric patterning on Au. Finally, after the selective etching of Au, Pt octahedral dual-rim nanoframes with highly homogeneous size and shape are achieved. In order to endow plasmonic features, Au is coated around Pt frames while retaining their geometric shape. The resultant plasmonic dual-rim engraved nanoframes possess strong light entrapping capability verified by single-particle surface-enhanced Raman scattering (SERS) and show the potential of nanoprobes for biosensing through SERS-based immunoassay.

Heteroepitaxial Growth of Colloidal Crystals: Dependence of the Growth Mode on the Interparticle Interactions and Lattice Spacing.

Epitaxial growth is one of the most important techniques for the control of crystal growth, especially for growing thin-film semiconductor crystals. Similarly, colloidal epitaxy, a template-assisted self-assembly method, is a powerful technique for controlling the structure of colloidal crystals. In this study, heteroepitaxial growth, which differs from homoepitaxial growth of conventional colloidal epitaxy, using foreign colloidal crystals as a substrate, was used to grow single-component colloidal crystal films. The Frank-van der Merwe (FM), Stranski-Krastanov (SK), and Volmer-Weber (VW) modes were observed, and the mode varied with the lattice-misfit ratio and interparticle interactions between the substrate and epitaxial phase. The transition of the growth mode (from SK to VW) and the coexistence of different growth modes (FM and VW) were observed, and their processes were revealed by in situ observation. Colloidal heteroepitaxy was confirmed to be useful for controlling structure, which will enable exploration of novel colloidal self-assembly structures.

Strain-Modulated Seeded Growth of Highly Branched Black Au Superparticles for Efficient Photothermal Conversion.

Creating highly branched plasmonic superparticles can effectively induce broadband light absorption and convert light to heat regardless of the light wavelength, angle, and polarization. However, their direct synthesis in a controllable manner remains a significant challenge. In this work, we propose a strain modulation strategy to produce branched Au nanostructures that promotes the growth of Au on Au seeds in the Volmer-Weber (island) mode instead of the typical Frank-van der Merwe (layer-by-layer) mode. The key to this strategy is to continuously deposit polydopamine formed in situ on the growing surface of the seeds to increase the chemical potential of the subsequent deposition of Au, thus achieving continuous heterogeneous nucleation and growth. The branched Au superparticles exhibit a photothermal conversion efficiency of 91.0% thanks to their small scattering cross-section and direction-independent absorption. Even at a low light power of 0.5 W/cm2 and a low dosage of 25 ppm, these particles show an excellent efficacy in photothermal cancer therapy. This work provides the fundamental basis for designing branched plasmonic nanostructures and expands the application scope of the plasmonic photothermal effect.

Frank-van der Merwe growth in bilayer graphene

Frank-van der Merwe growth in bilayer graphene

Molecular dynamics study on the deposition of Ni/graphene composite film

The Ni/graphene composite films deposited on Fe (001) substrate were studied by molecular dynamics simulation. The effects of incident energy and graphene nanoplatelet (GNP) size on the growth of the films were studied. The surface roughness, growth mode, crystal structure and orientation of the films under different deposition conditions were compared and analyzed. The simulation results show that when the incident energy is low, the Stranski-Krastanov growth mode is dominant; when the incident energy reaches a certain value, the film begins to grow in the Frank-Vander Merwe mode. The surface roughness decreases with the increase of incident energy due to the enhancement of surface diffusion. With the addition of GNPs, the surface roughness of the films increased significantly. The crystal structure and orientation of the deposited films were studied based on the adaptive common neighbor analysis and centrosymmetric parameters. The incident energy affects the crystal structure and orientation of the films. GNPs affect the growth mode of Ni grains, which makes Ni grains grow along (111) direction on it.

Asymmetrical Molecular Decoration of Gold Nanorods for Engineering of Shape-Controlled AuNR@Ag Core-Shell Nanostructures.

Gold-silver (Au@Ag) core-shell nanostructures have a stronger surface plasma response, wider absorption and scattering in the UV-vis-NIR region, and distinctive optical properties, which are widely explored in biosensors, information processing, photothermal therapy, and catalysis. Core-shell nanostructures are usually formed by the deposition of the second metal atoms onto the first core metal particles via the chemical wet method. The conventional approaches for the manipulation of the shape usually were done by homogeneous growth or etching of isotropic nanoparticles. Through in situ modification of the first metal core at the different locations, the different growth model of the second metal can be regulated to control the shapes of core-shell structures. Herein, we modified the gold nanorods (AuNRs) asymmetrically at the end and side parts using thiolated molecules to regulate the morphology of gold nanorod@silver (AuNR@Ag) core-shell nanoparticles. Interestingly, the obvious eccentric nanostructures of AuNR@Ag core-shell nanoparticles were obtained with the increase of the molecular weight of macromolecules modified at the end of AuNRs. Therefore the growth mode was adjusted from Frank-van der Merwe mode to Stranski-Krastanow mode. By changing the length of the hydrocarbon chain and functional groups of the small mercaptan molecules at the side of AuNRs, the silver shell exhibits selective growth at the side of the AuNRs, resulting in heterogeneous core-shell nanoparticles and various shapes of the AuNR@Ag core-shell. Our method opens up a new avenue toward preparing core-shell nanostructures with controlled shapes, and the obtained structures are promising in various applications.

Role of RF power on physical properties of RF magnetron sputtered GaN/p-Si(1 0 0) thin film

Abstract GaN thin films were deposited on p-Si(1 0 0) substrates using RF magnetron sputtering at various RF powers. Influence of RF power on morphological, optical and structural properties of GaN thin films were investigated and presented in detail. XRD results proved that the films were polycrystalline in structure with (1 0 0) and (1 1 0) planes of hexagonal GaN. It was found that increasing RF power led to deterioration of crystal structure of the films due to increased decomposition of GaN. Stress in GaN thin films was calculated from XRD measurements and the reasons for this stress were discussed. Furthermore, it was analyzed and interpreted whether the experimental measurement results support each other. E2 (high) optical phonon mode of hexagonal GaN was obtained from the analysis of Raman results. UV-Vis spectroscopy results showed that optical band gap of the films varied by changing RF power. The reasons of this variation were discussed. AFM study of the surfaces of the GaN thin films showed that some of them were grown in Stranski-Krastanov mode and others were grown in Frank-Van der Merwe mode. AFM measurements revealed almost homogeneous, nanostructured, low-roughness surface of the GaN thin films. SEM analysis evidenced agglomerations in some regions of surface of the films and their possible causes have been discussed. It has been inferred that morphological, optical, structural properties of GaN thin film can be changed by controlling RF power, making them a potential candidate for LED, solar cell, diode applications.

Detailed Structural and Morphological Characterization of InGaN Thin Films Grown by RF Magnetron Sputtering with Various Substrate Temperature

Indium Gallium Nitride thin film was successfully grown on the substrate using an RF magnetron sputter under condition of different substrate temperatures. Various experimental measurements were taken to understand effect of substrate temperature on the structure of thin film and results were analyzed. Grazing mode of XRD results confirmed that thin film has a hexagonal structure with plane for and substrate temperature. It was seen that structural parameters of thin film show a change with substrate temperature change. Reasons were discussed. Strain and stress values in thin film were calculated from experimental results and it was found that all thin film has compressive stress. Morphological parameters of thin film were measured by AFM and it was understood that these properties are varied by changing substrate temperature. Also, growth mode of some thin film was found to be layer-plus-island mode (Stranski-Krastanov growth mode), others was found to be layer by layer growth mode (Frank van der Merwe mode). SEM analysis gives that increasing substrate temperature worsened the surface structure of thin film; it is compatible with and supports XRD results. Compositional values in thin film were found from XPS analysis. In addition to our material, carbon and oxygen have also been obtained from XPS results, as expected. Detailed structural and morphological properties of thin film have been seen to change by changing substrate temperature and we believe this may play an important role in the production of based optoelectronic devices.

Layer, island and dendrite crystallizations of amorphous films as analogs of Frank-van der Merwe, Volmer-Weber and Stranski-Krastanov growth modes

Layer, island and dendrite crystallizations of amorphous films as analogs of Frank-van der Merwe, Volmer-Weber and Stranski-Krastanov growth modes

Physical properties of RF magnetron sputtered GaN/n-Si thin film: impacts of RF power

GaN thin film was successfully produced on $$n{\text{-}}Si\left({100} \right)$$ substrate by RF magnetron sputter under different RF power. Experimental measurement techniques such as UV/Vis spectroscopy, field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), and Micro-Raman Spectroscopy were used to research effects of Radio Frequency power on physical properties of produced thin film. It has been found that produced thin film was polycrystalline structure with (100) and (110) planes of hexagonal $$GaN$$ from X-ray diffraction measurement result. It also proved that increasing RF power gives rise to deterioration in crystal quality of $$GaN$$ thin film. Reason of this deterioration was discussed. It has been achieved that increasing RF power has resulted in decreasing optical band gap energy of $$GaN$$ thin film. Reasons for these changes in optical band gap energy were explained. It was seen that some thin films were grown as layer-plus-island mode (Stranski–Krastanov growth mode) and others were grown as layer-by-layer growth mode (Frank van der Merwe mode) from AFM analysis. It has been found that increasing RF power has resulted in improvement of surface morphology of thin film from field emission scanning electron microscopy analysis. However, reaching RF power to 125 W leads to start to deteriorate of surface of $$GaN$$ thin film. The reasons for this have been discussed. $$E_{1} \left( {TO} \right)$$ transverse optical phonon mode of hexagonal $$GaN$$ with different intensity was detected from Micro-Raman Spectroscopy measurement. The reasons for this difference have been discussed. It was concluded that RF power has played a significant role in growing high quality $$GaN$$ thin film. Morphological, structural, and optical properties of $$GaN$$ thin film were enhanced by controlling RF power, making them a potential candidate for LED, solar cell, diode application.

Modes and kinetics of crystals growth in amorphous films of oxides

The morphology and kinetics of crystals growth in amorphous films of Cr2O3, ZrO2, and HfO2 have been studied by the methods of transmission electron microscopy (“in situ”) with video registration of structural changes. Based on the frame-by-frame analysis of the video the kinetic curves of the phase transformations have been constructed, which reveal typical features of the main crystallization modes: layer (Cr2O3), island (ZrO2), and dendrite (HfO2) polymorphous crystallization. For each mode the numerical values of the relative crystallization lengths (2036 for Cr2O3, 77 for ZrO2 and 4180 for HfO2) are determined. The crystal growth modes at electron-beam heating of amorphous films are compared with crystal growth modes on substrates at vapor condensation in vacuum (Frank-van der Merwe, Volmer-Weber and Stranski-Krastanov growth modes).

Physical mechanism of surface roughening on the radial core-shell nanowire heterostructure with alloy shell

We proposed a quantitative thermodynamic theory to address the physical process of surface roughening during the epitaxial growth of core-shell NW with alloy layer. The surface roughening origins from the transformation of the Frank-van der Merwe (FM) mode to the Stranski-Krastanow (SK) mode. In addition to the radius of NW core, the composition and thickness of alloy shell could determine the growth behaviors due to their modulation to the strain. The established theoretical model not only explains the surface roughening caused by the alloy shell layer, but also provides a new way to control the growth of core-shell NW.

Ultra-hard amorphous AlMgB14 films RF sputtered onto curved substrates

Recently, hard AlMgB14 (BAM) coatings were deposited for the first time by RF magnetron sputtering using a single stoichiometric ceramic target. High target sputtering power and sufficiently short target-to-substrate distance were found to be critical processing conditions. They enabled fabrication of stoichiometric in-depth compositionally homogeneous films with the peak values of nanohardness 88 GPa and Young’s modulus 517 GPa at the penetration depth of 26 nm and, respectively, 35 GPa and 275 GPa at 200 nm depth in 2 µm thick film (Grishin et al 2014 JETP Lett. 100 680). The narrow range of sufficiently short target-to-substrate distance makes impossible to coat non flat specimens. To achieve ultimate BAM films’ characteristics onto curved surfaces we developed two-step sputtering process. The first thin layer is deposited as a template at low RF power that facilitates a layered Frank van der Merwe mode growth of smooth film occurs. The next layer is grown at high RF target sputtering power. The affinity of subsequent flow of sputtered atoms to already evenly condensed template fosters the development of smooth film surface. As an example, we made BAM coating onto hemispherical 5 mm in diameter ball made from a hard tool steel and used as a head of a special gauge. Very smooth (6.6 nm RMS surface roughness) and hard AlMgB14 films fabricated onto commercial ball-shaped items enhance hardness of tool steel specimens by a factor of four.

Ge epitaxial films on GaAs (100), (110), and (111) substrates for applications of CMOS heterostructural integrations

Epitaxial Ge films were grown on GaAs (100), (110), and (111) substrates by using ultra-high vacuum chemical vapor deposition and studied with various methods. The incubation times and growth rates were quite different for these three GaAs substrates because the surface arsenic coverage on GaAs and hydrogen desorption energy on Ge are different for each orientation. High-resolution x-ray diffraction measurements, direct band-gap emission of photoluminescence measurements, and cross-sectional transmission electron microscopy showed that the Ge films had high crystal quality, low defect density, and sharp Ge/GaAs interfaces. In this study, atomic force microscopy analysis found that the Ge films grow on GaAs (100) and (111) via the Frank van der Merwe mode, while the Ge film grows on GaAs (110) via the Volmer-Weber mode at the initial growth stage, which can be explained by the thermodynamic theory of capillarity. Interestingly, when the thickness of the Ge film on the GaAs (110) substrate increases to ∼220 nm, the 3D Ge islands merge and form a smooth surface (rms roughness of 0.3 nm), which is useful for devices. The authors also fabricated Ge metal-oxide-semiconductor capacitors (MOSCAPs) on GaAs (100) and (110) substrates. Both Ge/GaAs (100) and Ge/GaAs (110) MOSCAPs exhibit good capacitance–voltage responses with strong inversion behaviors, which means the grown material has reached device quality. The Ge/GaAs (110) structure especially offers optimal integration of Ge pMOSFETs on GaAs substrates because Ge (110) has a high hole mobility compared with Ge (100) and (111).

Physical Mechanism of Surface Roughening of the Radial Ge-Core/Si-Shell Nanowire Heterostructure and Thermodynamic Prediction of Surface Stability of the InAs-Core/GaAs-Shell Nanowire Structure

As a promising and typical semiconductor heterostructure at the nanoscale, the radial Ge/Si NW heterostructure, that is, the Ge-core/Si-shell NW structure, has been widely investigated and used in various nanodevices such as solar cells, lasers, and sensors because of the strong changes in the band structure and increased charge carrier mobility. Therefore, to attain high quality radial semiconductor NW heterostructures, controllable and stable epitaxial growth of core-shell NW structures has become a major challenge for both experimental and theoretical evaluation. Surface roughening is usually undesirable for the epitaxial growth of high quality radial semiconductor NW heterostructures, because it would destroy the core-shell NW structures. For example, the surface of the Ge-core/Si-shell NWs always exhibits a periodic modulation with island-like morphologies, that is, surface roughening, during epitaxial growth. Therefore, the physical understanding of the surface roughening behavior during the epitaxial growth of core-shell NW structures is essential and urgent for theoretical design and experimentally controlling the growth of high quality radial semiconductor NW heterostructures. Here, we proposed a quantitative thermodynamic theory to address the physical process of epitaxial growth of core-shell NW structures and surface roughening. We showed that the transformation from the Frank-van der Merwe mode to the Stranski-Krastanow mode during the epitaxial growth of radial semiconductor NW heterostructures is the physical origin of surface roughening. We deduced the thermodynamic criterion for the formation of the surface roughening and the phase diagram of growth and showed that the radius of the NWs and the thickness of the shell layer can not only determine the formation of the surface roughening in a core-shell NW structure, but also control the periodicity and amplitude of the surface roughness. The agreement between the theoretical results and the experimental data of the Ge-core/Si-shell NW structure implied that the established approach could be applicable to the understanding and design of various semiconductor core-shell NW structures. Consequentially, we used the established theoretical model to study the epitaxial growth of the InAs-core/GaAs-shell NW structure and predict the surface roughening formation, as well as the periodicity and amplitude of the surface roughness, which provided useful information to theoretically design and experimentally control the epitaxial growth of the radial InAs-core/GaAs-shell NW structure.

Growth of Al on a W(110) surface

Using low energy electron diffraction and low energy ion scattering spectroscopy, we investigated the growth mode of Al on a W(110) surface at room temperature and at 1000K. We found that Al grew on the W(110) surface in the Frank–van der Merwe mode when the W substrate was kept at room temperature during Al deposition. It was found that at a coverage higher than 2monolayer (ML) in Al grown at room temperature, Al atoms had a well-ordered face centered cubic (fcc) (111) surface. The [11¯0] direction of the Al grown at room temperature on the (111) surface was parallel to the [001] direction of the W(110) substrate surface. When the temperature of the W substrate was kept at 1000K, the adsorbed Al atoms grew in the Volmer–Weber mode. The 1.5ML Al/W(110) surface prepared at 1000K shows two domains of the fcc Al(111) surfaces along with a W(110) surface. We also found that the early stage of Al film growth shows W(110) structure. However as the film becomes thicker (above 3.5–4 layers) the Al face is turned into fcc (111) face.

Molecular beam epitaxy and characterization of thin Bi2Se3 films on Al2O3 (110)

The structural and electronic properties of thin Bi2Se3 films grown on Al2O3 (110) by molecular beam epitaxy are investigated. The epitaxial films grow in the Frank-van der Merwe mode and are c-axis oriented. They exhibit the highest crystallinity, the lowest carrier concentration, and optimal stoichiometry at a substrate temperature of 200 °C determined by the balance between surface kinetics and desorption of Se. The crystallinity of the films improves with increasing Se/Bi flux ratio. Our results enable studies of thin topological insulator films on inert, non-conducting substrates that allow optical access to both film surfaces.

Growth of Sn on Mo(110) studied by AES and STM

Scanning tunneling microscopy (STM) and Auger electron spectroscopy (AES) have been used to investigate the growth behavior of ultra-thin Sn films on a Mo(110) surface at room temperature. An analysis of STM and AES measurements indicates that layer-by-layer growth (Frank-van der Merwe mode) for the first two layers of Sn is observed. For submonolayer coverage, tin prefers to nucleate randomly and creates one atom high islands on Mo terraces. In the completed first and second layer, no ordered regions were observed. As the sample is post-annealed to 800K, the rearrangement of an existing film suggests a Sn–Mo surface alloy formation.

Crossover from layering to island formation in Langmuir-Blodgett growth: Role of long-range intermolecular forces

Combined studies by atomic force microscopy, x-ray reflectivity, and Fourier transform infrared spectroscopy on transition-metal stearate (M-St, M = Mn, Co, Zn, and Cd) Langmuir-Blodgett films clearly indicate association of bidentate coordination of the metal-carboxylate head group to layer-by-layer growth as observed in MnSt and CoSt and partially in ZnSt. Crossover to islandlike growth, as observed in CdSt and ZnSt, is associated with the presence of unidentate coordination in the head group. Morphological evolutions as obtained from one, three, and nine monolayers (MLs) of M-St films are consistent with Frank van der Merwe, Stranski-Krastanov, and Volmer Weber growth modes for M=Mn/Co, Zn, and Cd, respectively, as previously assigned, and are found to vary with number (n) of metal atoms per head group, viz. n=1 (Mn/Co), n=0.75 (Zn), and n=0.5 (Cd). The parameter n is found to decide head-group coordination such that n=1.0 corresponds to bidentate and n=0.5 corresponds to unidentate coordination; the intermediate value in Zn corresponds to a mixture of both. The dependence of the growth mode on head-group structure is explained by the fact that in bidentate head groups, with the in-plane dipole moment being zero, intermolecular forces between adjacent molecules are absent and hence growth proceeds via layering. On the other hand, in unidentate head groups, the existence of a nonzero in-plane dipole moment results in the development of weak in-plane intermolecular forces between adjacent molecules causing in-plane clustering leading to islandlike growth.