Volmer-Weber Growth Research Articles

Electrical transport properties of topographically demorphed films of La1-xBaxMnO3 grown on (00l)-oriented LaAlO3 substrate via spin-coating method

Herein, the crystal structure, valence, and electrical transport properties of La1-xBaxMnO3 films were examined by preparing La1-xBaxMnO3 films with varying Ba content (x = 0.22, 0.24, 0.26, 0.28) on LaAlO3 substrates using the sol-gel spin coating technique. The La1-xBaxMnO3 films prepared in the study exhibit topographically demorphed and non-dense characteristics in the microstructure, which is mainly caused by the Volmer-Weber growth mode of the films and the volatilization of organic matter during the sol-gel sintering process for films preparation. The increase of Ba doping leads to MnO6 deformation, decrease in grain boundary scattering, increase in Mn4+ ion content, and enhancement of both the double exchange mechanism and the Jahn-Teller effect. The four-probe results showed that the peak resistivity of the films decreased significantly with the increase in Ba2+ doping, and the metal-insulator transition temperature (Tp) shifted to higher temperatures. Peak temperature coefficient of resistivity (TCR) corresponding temperature (Tk) increased from 283.05 K (x = 0.22) to 309.31 K (x = 0.28), which was consistent with the trend of Tp; the peak value of TCR decreased with the increase of Ba doping. When x = 0.24, the Tk of the La1-xBaxMnO3 films reach room temperature (294.25 K) with TCR = 9.01 % K−1. In conclusion, the electrical properties of La1-xBaxMnO3 can be optimized by varying the amount of Ba doping to obtain La1-xBaxMnO3 films with room-temperature Tk and higher TCR values, providing reasonable data support and theoretical explanation for the Ba doping mechanism.

Deposition pressure-controlled phase tailoring and stability of β-W for spintronic applications

Understanding the nucleation and growth of tungsten (W) is technologically important in spin-to-charge interconversion for realizing energy-efficient spintronic devices. Here, we have systematically investigated the effect of Ar deposition pressure (PAr) on the nucleation and growth of W. The observed surface topography as a function of PAr reveals a microstructural transition from zone T to zone 1 in the structure zone model. The physical origin for the increasing roughness as a function of PAr correlates with the surface diffusion of adatoms and growth kinetics in the Volmer–Weber growth mechanism. Grazing incidence x-ray diffraction (GIXRD) results show that W exhibits a structural phase transition from a mixed phase of (α+β)-W to a single phase of β-W as a function of PAr. The analysis of the electron diffraction patterns obtained from the films grown on amorphous-SiNx windows also supports these observations. The observed transition is fundamentally correlated with the growth kinetics in zone T and zone I. Thickness-dependent GIXRD results qualitatively prove that the film grown in zone T exhibits compressive strain, whereas that grown in zone I exhibits only tensile strain. The critical thickness for the phase transition is strongly attributed to the strain during nucleation and growth. The increasing resistivity as a function of PAr corroborates the change in structural phases. Thickness-dependent resistivity measurements correlate with the degree of crystallinity via relative intensity observed from the GIXRD results. Our results strongly suggest that W structural phases can be deterministically controlled via PAr for developing low-power spintronic devices.

Engineering the Blackbody Absorption of the Au-Branch-on-Au-Plate Heterostructures.

Utilizing the strong ligand control effects of l-cysteine (l-Cys), the growth of Au on Au triangular nanoplate (AuTN) seeds was continuously tuned from layer-by-layer (the Frank-van der Merwe) to layer-plus-island (the Stranski-Krastanov), and island (the Volmer-Weber) growth modes, leading to the formation of a series of Au-on-AuTN heterostructures. Within the window of VW growth mode (featured by the growth of Au spikes and branches on AuTNs), the effective localized surface plasmon resonance (LSPR) coupling led to the selective strengthening of the "valley" absorptions, leading to smooth and flat absorption curves. Interestingly, through engineering the number/density, size, and branching degree of the Au branches, except for the black color, full spectrum absorption within 400-1300 nm wavelength was achieved on Au-branch-on-AuTN structures. Mechanistic studies revealed that the blackbody absorption property of the Au-branch-on-AuTN originates from the well-balanced intraparticle LSPR couplings among the neighboring Au branches. The tunable blackness and the full spectrum absorption property made the Au-branch-on-AuTN heterostructure a suitable candidate for various plasmonic-related applications, such as a wide spectrum light absorber, photoacoustic imaging contrast agent, and photothermal therapy medium. In addition, our strong ligand control in Au-branch-on-AuTN heterostructures could be extended to other hybrid systems with diverse material combinations, so long as to find the proper strong ligand.

Multiscale Simulation of CVD Diamond Growth on (1 0 0)‐, (1 1 1)‐, and (1 1 0)‐Oriented Faces

The growth of chemical vapor deposition diamond in microwave plasma ignited in H2/CH4 gas mixture is investigated using a multiscale approach. The plasma composition and temperatures are determined as a function of the growth conditions using an axial one‐dimensional simulator. The growth process is then studied at the atomic scale using a kinetic Monte‐Carlo simulator developed for (1 0 0), (1 1 1), and (1 1 0) orientations. The calculated growth rates are then injected in a geometric model that predicts the final morphology of the crystal. The simulation of the growth on an etch pit shows that the time necessary to entirely fill the pit is around half an hour. The study of the growth on the three orientations reveals that the surface temperature and methane concentration influence the number, shape, and size of the islands when they appear. On the (1 0 0) surface, the formation of islands may be related to Stranski–Krastanov growth mode, whereas the (1 1 1) surface conducts to Frank–van der Merwe growth mode, and the (1 1 0) surface is governed by Volmer–Weber growth mode.

Structural Defects on Graphene Generated by Deposition of CoO: Effect of Electronic Coupling of Graphene.

Understanding the interactions in hybrid systems based on graphene and functional oxides is crucial to the applicability of graphene in real devices. Here, we present a study of the structural defects occurring on graphene during the early stages of the growth of CoO, tailored by the electronic coupling between graphene and the substrate in which it is supported: as received pristine graphene on polycrystalline copper (coupled), cleaned in ultra-high vacuum conditions to remove oxygen contamination, and graphene transferred to SiO2/Si substrates (decoupled). The CoO growth was performed at room temperature by thermal evaporation of metallic Co under a molecular oxygen atmosphere, and the early stages of the growth were investigated. On the decoupled G/SiO2/Si samples, with an initial low crystalline quality of graphene, the formation of a CoO wetting layer is observed, identifying the Stranski-Krastanov growth mode. In contrast, on coupled G/Cu samples, the Volmer-Weber growth mechanism is observed. In both sets of samples, the oxidation of graphene is low during the early stages of growth, increasing for the larger coverages. Furthermore, structural defects are developed in the graphene lattice on both substrates during the growth of CoO, which is significantly higher on decoupled G/SiO2/Si samples mainly for higher CoO coverages. When approaching the full coverage on both substrates, the CoO islands coalesce to form a continuous CoO layer with strip-like structures with diameters ranging between 70 and 150 nm.

Internal strain identification of seed-layered ZrO2, aluminum-, and yttrium-doped ZrO2 thin films via grazing incidence x-ray diffraction

Grazing incidence x-ray diffraction reveals that conventional post-deposition-annealed ZrO2 and in situ crystallized (by local epitaxy) ZrO2 thin films (<15 nm) have different internal strain states. A comparison between single- and two-step grown films enables the diverse strain components to be discretely identified. In particular, thickness-dependent intrinsic growth strain is unevenly distributed within the film according to the Volmer–Weber growth. Furthermore, extrinsic thermal strain, locally present in the annealed seed layer, does not spread over the in situ crystallized upper main layer of the two-step film. Post-deposition annealing of the two-step film renders the strain state identical to the single-step films by imposing thermal strain on the in situ crystallized main layer. Local strains created by diffused aluminum and yttrium dopants are also examined. Since each stress factor plays a vital role in the phase formation and electrical behaviors of ZrO2 and other fluorite-structure films, this method will pave the way for understanding the film's internal strain distribution and accompanying performance engineering.

Change in Growth Mode of BGaN Layers Grown on GaN

A change in the growth mode from Stranski–Krastanov one, which is characteristic of MOCVD grown GaN, to the laterally grown BGaN in the Volmer–Weber growth mode is described. This change in growth is evidenced by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images of BGaN grown on GaN at high temperatures. It is postulated on the basis of SIMS and XRD results that this change in growth is initiated by the transfer of boron atoms from gallium substitutional to interstitial. The proposed mechanism for the observed growth change is related to the generation of nitrogen interstitials and subsequent reactions with boron interstitials, which result in the formation of a BN layer at the growth front. The observed large change in the growth mode is due to a lattice mismatch between the grown BGaN and the atomic layer of BN and stays behind the change to the Volmer–Weber growth mode. The consequence of the Volmer–Weber growth mode is the textural layer of BGaN. The textural character of this material is associated with large voids between grown BGaN “plates”. These large voids are responsible for the termination of threading dislocations propagating in the c-direction. It is also postulated that the blocked threading dislocations from the GaN underlayer and laterally grown BGaN layers along the a-directions are responsible for the decrease in defect concentration within these layers.

A Stranski–Krastanov to Volmer–Weber transition in the growth mode of self-assembled quantum dots

We present recent experiments for tensile-strained Ge QDs on InAlAs(111)A where we observe that growth proceeds via the Stranski–Krastanov (SK) growth mode at lower temperatures and transitions to the Volmer–Weber (VW) growth mode at higher temperatures. We discuss atomistic kinetic Monte Carlo simulations that show how the SK to VW growth mode transition is affected by model parameters. We find that systems are more likely to transition from a SK to a VW mode when the bond energy between substrate atoms is weaker than the bond energy between atoms of the deposited material. We also show how entropic effects due to intermixing can stabilize a layer-by-layer growth mode in certain parameter regimes.

Steering the Selective Production of Glycolic Acid by Electrocatalytic Oxidation of Ethylene Glycol with Nanoengineered PdBi-Based Heterodimers.

Heterodimers of metal nanocrystals (NCs) with tailored elemental distribution have emerged as promising candidates in the field of electrocatalysis, owing to their unique structures featuring heterogeneous interfaces with distinct components. Despite this, the rational synthesis of heterodimer NCs with similar elemental composition remains a formidable challenge, and their impact on electrocatalysis has remained largely elusive. In this study, Pd@Bi-PdBi heterodimer NCs are synthesized through an underpotential deposition (UPD)-directed growth pathway. In this pathway, the UPD of Bi promotes a Volmer-Weber growth mode, allowing for judicious modulation of core-satellite to heterodimer structures through careful control of supersaturation and growth kinetics. Significantly, the heterodimer NCs are employed in the electrocatalytic process of ethylene glycol (EG) with high activity and selectivity. Compared with pristine Pd octahedra and common PdBi alloy NC, the unique heterodimer structure of the Pd@Bi-PdBi heterodimer NCs endows them with the highest electrocatalytic performance of EG and the best selectivity (≈93%) in oxidizing EG to glycolic acid (GA). Taken together, this work not only heralds a new strategy for UPD-directed synthesis of bimetallic NCs, but also provides a new design paradigm for steering the selectivity of electrocatalysts.

Microstructure and physical properties of black-aluminum antireflective films.

The microstructure and physical properties of reflective and black aluminum were compared for layers of different thicknesses deposited by magnetron sputtering on fused silica substrates. Reflective Al layers followed the Volmer-Weber growth mechanism classically observed for polycrystalline metal films. On the contrary, the extra nitrogen gas used to deposit the black aluminum layers modified the growth mechanism and changed the film morphologies. Nitrogen cumulated in the grain boundaries, favoring the pinning effect and stopping crystallite growth. High defect concentration, especially vacancies, led to strong columnar growth. Properties reported for black aluminum tend to be promising for sensors and emissivity applications.

Flexible Transparent Conductive Electrodes: Unveiling Growth Mechanisms, Material Dimensions, Fabrication Methods, and Design Strategies.

Flexible transparent conductive electrodes (FTCEs) constitute an indispensable component in state-of-the-art electronic devices, such as wearable flexible sensors, flexible displays, artificial skin, and biomedical devices, etc. This review paper offers a comprehensive overview of the fabrication techniques, growth modes, material dimensions, design, and their impacts on FTCEs fabrication. The growth modes, such as the "Stranski-Krastanov growth," "Frank-van der Merwe growth," and "Volmer-Weber growth" modes provide flexibility in fabricating FTCEs. Application of different materials including 0D, 1D, 2D, polymer composites, conductive oxides, and hybrid materials in FTCE fabrication, emphasizing their suitability in flexible devices are discussed. This review also delves into the design strategies of FTCEs, including microgrids, nanotroughs, nanomesh, nanowires network, and "kirigami"-inspired patterns, etc. The pros and cons associated with these materials and designs are also addressed appropriately. Considerations such as trade-offs between electrical conductivity and optical transparency or "figure of merit (FoM)," "strain engineering," "work function," and "haze" are also discussed briefly. Finally, this review outlines the challenges and opportunities in the current and future development of FTCEs for flexible electronics, including the improved trade-offs between optoelectronic parameters, novel materials development, mechanical stability, reproducibility, scalability, and durability enhancement, safety, biocompatibility, etc.

Morphology of ultrathin gold and copper coatings thermally evaporated on polydimethylsiloxane elastomers: From isolated nanoparticles to continuous coatings

This article presents a morphological study of ultrathin gold and copper coatings (between 1 nm and 20 nm equivalent metal thickness) thermally evaporated on polydimethylsiloxane (PDMS). Results are discussed on the basis of transmission electron microscopy and atomic force microscopy. Gold is demonstrated to grow in the form of isolated particles following a Volmer-Weber growth mode, whereas copper more likely grows in the form of a continuous film, following a Stranski–Krastanov growth mode. Our results demonstrate a negligible role of the PDMS elastic modulus (between 0.5 and 2.5 MPa) in the gold and copper coatings morphology respectively. However, significant morphological changes are observed when the metals are thermally evaporated on a PDMS substrate of extremely higher surface elastic modulus obtained after O2 plasma exposure.

Flexible Transparent Electrodes Formed from Template-Patterned Thin-Film Silver.

Template-patterned, flexible transparent electrodes (TEs) formed from an ultrathin silver film on top of a commercial optical adhesive - Norland Optical Adhesive 63 (NOA63) -are reported. NOA63 is shown to be an effective base-layer for ultrathin silver films that advantageously prevents coalescence of vapor-deposited silver atoms into large, isolated islands (Volmer-Weber growth), and so aids the formation of ultrasmooth continuous films. 12 nm silver films on top of free-standing NOA63 combine high, haze-free visible-light transparency (T ≈ 60% at 550nm) with low sheet-resistance ( ≈ 16 Ω sq-1), and exhibit excellent resilience to bending, making them attractive candidates for flexible TEs. Etching the NOA63 base-layer with an oxygen plasma before silver deposition causes the silver to laterally segregate into isolated pillars, resulting in a much higher sheet resistance ( > 8 × 106 Ω sq-1) than silver grown on pristine NOA63 . Hence, by selectively etching NOA63 before metal deposition, insulating regions may be defined within an otherwise conducting silver film, resulting in a differentially conductive film that can serve as a patterned TE for flexible devices. Transmittance may be increased (to 79% at 550nm) by depositing an antireflective layer of Al2O3 on the Ag layer at the cost of reduced flexibility.

On the Microcrystal Structure of Sputtered Cu Films Deposited on Si(100) Surfaces: Experiment and Integrated Multiscale Simulation.

Sputtered Cu/Si thin films were experimentally prepared at different sputtering pressures and characterized using X-ray diffraction (XRD) and an atomic force microscope (AFM). Simultaneously, an application-oriented simulation approach for magnetron sputtering deposition was proposed in this work. In this integrated multiscale simulation, the sputtered atom transport was modeled using the Monte Carlo (MC) and molecular dynamics (MD) coupling method, and the deposition of sputtered atoms was simulated using the MD method. This application-oriented simulation approach was used to simulate the growth of Cu/Si(100) thin films at different sputtering pressures. The experimental results unveiled that, as the sputtering pressure decreased from 2 to 0.15 Pa, the surface roughness of Cu thin films gradually decreased; (111)-oriented grains were dominant in Cu thin films and the crystal quality of the Cu thin film was gradually improved. The simulation results were consistent with the experimental characterization results. The simulation results revealed that the transformation of the film growth mode from the Volmer-Weber growth mode to the two-dimensional layered growth mode resulted in a decrease in the surface roughness of Cu thin films; the increase in the amorphous compound CuSix and the hcp copper silicide with the decrease in the sputtering pressure was responsible for the improvement of the crystal quality of the Cu thin film. This work proposed a more realistic, integrated simulation scheme for magnetron sputtering deposition, providing theoretical guidance for the efficient preparation of high-quality sputtered films.

Nucleation and quantum confinement of nano-platelet Bi2–Bi2Se3

The nucleation, nano-platelet growth, and optical properties under quantum confinement are investigated in the topological semimetal superlattice Bi2–Bi2Se3 as a function of thickness and Ar + ion pressure in sputtered growths. Quantum confinement and evolution of the band structure with a series of reduced dimensionality and surface terminations are studied by density functional theory corroborating the observed optical properties. An initial Volmer–Weber growth mode of nano-platelets is observed until a pressure-dependent critical thickness, where a transition to Frank–van der Merwe growth occurs. Nucleation statistics characterized using atomic force microscopy find the nearest-neighbor ordering of nano-platelets. Optical properties using ultraviolet to visible light spectroscopy measurements in transmission mode reveal a marked increase in optical bandgap below a nano-platelet critical volume reaching a maximum of 2.21 eV. Raman vibrational spectroscopy is performed, revealing softening of vibrational modes as the nano-platelet volume decreases.

Critical behavior in the epitaxial growth of two-dimensional tellurium films on SrTiO3 (001) substrates

Materials’ properties may differ in the thin-film form, especially for epitaxial ultra-thin films, where the substrates play an important role in their deviation from the bulk quality. Here by molecular beam epitaxy (MBE) and scanning tunneling microscopy/spectroscopy, we investigate the growth kinetics of ultra-thin tellurium (Te) films on SrTiO3 (STO) (001). The MBE growth of Te films usually exhibits Volmer–Weber (VW) island growth mode and no a-few-monolayer film with full coverage has been reported. The absence of wetting-layer formation in the VW growth mode of Te on STO (001) is resulted from its low diffusion barriers as well as its relatively higher surface energy compared with those of the substrate and the interface. Here we circumvent these limiting factors and achieve the growth of ultra-thin β-Te films with near-complete coverages by driving the growth kinetics to the extreme condition. There is a critical thickness (3 monolayer) above which the two-dimensional Te films can form on the STO (001) substrate. In addition, the scanning tunneling spectra on the ultra-thin Te film grown on STO exhibits an enormously large forbidden gap compared with that grown on the graphene substrate. Our work establishes the necessary conditions for the growth of ultra-thin materials with similar kinetics and thermodynamics.

Critical behavior in the epitaxial growth of two-dimensional tellurium films on SrTiO3 (001) substrates

Materials’ properties may differ in the thin-film form, especially for epitaxial ultra-thin films, where the substrates play an important role in their deviation from the bulk quality. Here by molecular beam epitaxy (MBE) and scanning tunneling microscopy/spectroscopy, we investigate the growth kinetics of ultra-thin tellurium (Te) films on SrTiO3 (STO) (001). The MBE growth of Te films usually exhibits Volmer–Weber (VW) island growth mode and no a-few-monolayer film with full coverage has been reported. The absence of wetting-layer formation in the VW growth mode of Te on STO (001) is resulted from its low diffusion barriers as well as its relatively higher surface energy compared with those of the substrate and the interface. Here we circumvent these limiting factors and achieve the growth of ultra-thin β-Te films with near-complete coverages by driving the growth kinetics to the extreme condition. There is a critical thickness (3 monolayer) above which the two-dimensional Te films can form on the STO (001) substrate. In addition, the scanning tunneling spectra on the ultra-thin Te film grown on STO exhibits an enormously large forbidden gap compared with that grown on the graphene substrate. Our work establishes the necessary conditions for the growth of ultra-thin materials with similar kinetics and thermodynamics.

New insights into thermal processes of metal deposits on h-BN/Rh(1 1 1): A comparison of Au and Rh

In this paper the thermal properties of Au and Rh deposits are compared on hexagonal boron nitride (h-BN) “nanomesh” prepared on Rh(111), applying STM, XPS, low energy ion scattering (LEIS), LEED, and DFT. At room temperature, both metals essentially follow Volmer-Weber (3D) growth. Upon subsequent annealing, agglomeration (sintering), intercalation, and desorption are competing surface processes for both metals. For the more reactive Rh, we suggest an additional encapsulation mechanism: between 600 K and 750 K, fragments of decomposed h-BN diffuse locally from the bottom onto the metal clusters covering them partially. STM data indicates that agglomeration of gold nanoparticles proceeds faster compared to rhodium. At higher temperatures (∼1050 K–1100 K), all non-desorbing gold atoms diffuse below h-BN, even for large initial coverages. On the other hand, for larger Rh deposits (≥5 ML), the outermost layer always contains Rh. Accumulation of gold at the interface between h-BN and Rh(111) significantly enhances the thermal stability of h-BN, attributed to the lower reactivity of Au in the decomposition of h-BN compared to Rh(111). At elevated substrate temperatures, intercalation of individual adatoms takes place during deposition, which requires higher temperatures for rhodium due to its slower diffusion and higher probability of nucleation.

Hot Spot Engineering in Hierarchical Plasmonic Nanostructures

The controllable nanogap structures offer an effective way to obtain strong and tunable localized surface plasmon resonance (LSPR). A novel hierarchical plasmonic nanostructure (HPN) is created by incorporating a rotating coordinate system into colloidal lithography. In this nanostructure, the hot spot density is increased drastically by the long-range ordered morphology with discrete metal islands filled in the structural units. Based on the Volmer-Weber growth theory, the precise HPN growth model is established, which guides the hot spot engineering for improved LSPR tunability and strong field enhancement. The hot spot engineering strategy is examined by the application of HPNs as the surface-enhanced Raman spectroscopy (SERS) substrate. It is universally suitable for various SERS characterization excited at different wavelengths. Based on the HPN and hot spot engineering strategy, single-molecule level detection and long-range mapping can be realized simultaneously. In that sense, it offers a great platform and guides the future design for various LSPR applications like surface-enhanced spectra, biosensing, and photocatalysis.

Single-crystalline PbTe film growth through reorientation

Heteroepitaxy enables the engineering of novel properties, which do not exist in a single material. Two principal growth modes are identified for material combinations with a large lattice mismatch, Volmer-Weber, and Stranski-Krastanov. Both lead to the formation of three-dimensional islands, hampering the growth of flat defect-free thin films. This limits the number of viable material combinations. Here, we report a distinct growth mode found in molecular beam epitaxy of PbTe on InP initiated by pregrowth surface treatments. Early nucleation forms islands analogous to the Volmer-Weber growth mode, but film closure exhibits a flat surface with atomic terracing. Remarkably, despite multiple distinct crystal orientations found in the initial islands, the final film is single crystalline. This is possible due to a reorientation process occurring during island coalescence, facilitating high quality heteroepitaxy despite the large lattice mismatch, difference in crystal structures, and diverging thermal expansion coefficients of PbTe and InP. This growth mode offers a new strategy for the heteroepitaxy of dissimilar materials and expands the realm of possible material combinations.