Crystal Surface Research Articles

Relationship between temperature gradient and growth rate during CZ silicon crystal growth

Temperature distribution in the growing crystal is the most important parameter that determines the grown-in-defects, growth rate, etc. There is a discussion either higher growth rate leads to larger thermal gradient or smaller thermal gradient. In this study, in order to make clear the reason of this discrepancy, the effects of growth rate on the shape of melt/crystal interface, and temperature distribution in growing crystal were investigated by numerical modeling. Firstly, as increasing the growth rate, the shape of melt/crystal interface becomes more concave. And temperature gradient along center axis on growing crystal increases as increasing the growth rate. On the other hand, temperature gradient along surface of growing crystal decreases as increasing the growth rate. To obtain higher growth rate, heat transfer should be enhanced. Along the center axis, heat transfer in vertical direction by heat conduction is dominant. Then concave interface shape and larger thermal gradient along center axis were obtained. In the periphery of grown crystal near the triple points, because of concave interface shape, heat transfer in radial direction, and radiative heat transfer from growing crystal become more important than heat transfer in vertical direction. Then smaller thermal gradient along the growing crystal surface was obtained. This surface temperature profile agrees well with Abe’s measurement results. It is cleared that higher growth rate leads to the higher heat transfer, and melt/crystal interface shape, and temperature distribution in growing crystal are determined by the balance of growth rate and heat transfer between heat conduction in vertical direction and heat conduction in radial direction combined with radiation heat transfer from crystal surface.

Features of the defect structure of a lithium-gradient nonlinear optical single crystal LiNbO3 and their manifestation in the Raman spectra

LiNbO3 crystal with a lithium composition gradient of Li/Nb = 0.8 wt%/cm (Li0.97..1.01Nb1.03..0.99O3) were obtained. A monotonic change in the edge of the UV absorption edge is observed when scanning the surface of the gradient crystal along the growth direction. Raman spectra from different areas of studied crystal were analyzed in a wide frequency range, which includes the region of fundamental vibrations of the crystal lattice (100–900 cm−1) and the region of overtone processes (900–3000 cm−1). A compositionally homogeneous, congruent LiNbO3 crystal was used as a comparison sample. It was found that in the spectra obtained from different parts of the gradient crystal, there is a significant scatter in the frequency values of the lines corresponding to the fundamental vibrations of the crystal lattice, but at the same time, the number of lines corresponding to the fundamental vibrations of the lattice for the gradient and compositionally homogeneous LiNbO3 crystals is the same. Moreover, in the spectrum of a gradient crystal in the region of overtone processes of fundamental vibrations, significantly more lines (35 lines) are observed than in the spectrum of compositionally homogeneous crystals (15 lines). The data obtained show that the state of the defect structure of compositionally homogeneous crystals and gradient LiNbO3 crystal is significantly different. The discovered differences between the defective structure of a gradient crystal and the defective structure of a compositionally homogeneous crystal may be the reason for compensation (damping) of distortions during nonlinear optical conversion of laser radiation by a gradient crystal due to the uneven temperature distribution along the length of the crystal. In compositionally homogeneous crystals, such temperature distortions significantly limit the efficiency of nonlinear optical conversion.

Recent Progress of Thin Crystal Engineering for Perovskite Solar Cells.

Metal halide perovskite single crystals hold promise for photovoltaics with high efficiency and stability due to their superior optoelectronic properties and weak bulk ion migration. The past several years have witnessed rapid development of single-crystal perovskite solar cells (PSCs) with efficiency rocketed from 6.5% to 24.3%, however, which still lags behind their polycrystalline counterparts. Moreover, the poor device stability under light illumination is contrary to the high ion migration barrier of perovskite single crystals. The key limiting factors should be the low crystalline quality and high surface defect density of solution-grown thin single crystals. Under this circumstance, a review paper summarizing the recent progress and challenges will be instructive for future development of this emerging field. In this manuscript, the crystal engineering used to enhance carrier transport and suppress carrier recombination in vertical single-crystal PSCs will be summarized initially, including crystal growth, component control, surface and interface modification. Subsequently, the application of perovskite single crystals in lateral single-crystal PSCs will be discussed and compared with the conventionally vertical structure. Finally, the challenges and proposed strategies for the development of single-crystal PSCs are provided.

Microwave absorption studies in X-band of magnetized barium hexaferrite

Abstract To enhance the magnetic and microwave absorbing properties, barium hexaferrite, BaFe12O19, was studied in the x-band (7–13 GHz) frequency range. The BaFe12O19 was prepared as non-magnetized and magnetized samples. The crystal structure, surface morphology, magnetic and microwave absorption of BaFe12O19 were studied with X-ray diffraction (XRD), optical microscope, permagraph and vector network analyzer (VNA), respectively. XRD result showed the formation of M-type hexagonal polycrystalline structure. The hysteresis loop results verified the formation of permanent magnet with high saturation magnetization. The VNA results showed that reflection loss and absorption were − 71.07 dB and 67.96% for magnetized barium hexaferrite, respectively.

Relation of V/III ratio of AlN interlayer with the polarity of nitride

Abstract N-polar GaN film was obtained by using a high-temperature AlN buffer layer. It was found that the polarity could be inverted by a thin low-temperature AlN interlayer with the same V/III ratio as that of the high-temperature AlN layer. Continuing to increase the V/III ratio of the low-temperature AlN interlayer, the Ga-polarity of GaN film was inverted to N-polarity again but the crystal quality and surface roughness of GaN film greatly deteriorated. Finally, we analyzed the chemical environment of the AlN layer by x-ray photoelectron spectroscopy (XPS), which provides a new direction for the control of GaN polarity.

Designing of a High Performance NiMgPO4/CNT Electrode Material for a Battery-Supercapacitor Hybrid Device

Improved pseudo-capacitance performance can be obtained by phosphates and transition-metal oxides by achieving oxidation states that boost redox (reduction-oxidation) processes. In this work, the nickel magnesium phosphate (NiMgPO4) is synthesized using the hydrothermal method, Additional, carbon nanotubes (CNTs) are blended with NiMgPO4. To build the supercapattery device (NiMgPO4@CNT//AC) and evaluate its electrochemical characteristics, we used NiMgPO4@CNT as the anode & activated carbon as cathode. We also used X-ray diffraction, scanning electron micrscopy, Brunauer–Emmett–Teller, and X-ray photoelectron spectroscopy techniques to analyze the crystal structure, surface area, and elemental composition. The nanocomposite NiMgPO4@CNT demonstrated a high specific capacity of 1243 C g−1 or 2071.66 F g−1 in a three-electrode system, which was much more than that of the separate reference materials. The supercapattery device shows a specific capacity of 251 C g−1, energy density of 44.5 Wh kg−1 and power density of 1030 W kg−1 is observed. The hybrid electrode exhibited a capacity retention of 85% after 5000 cycles and a columbic efficiency of 91% during the stability measurement. These findings emphasize NiMgPO4@CNT’s potential as an electrode composite material that holds promise for high-performance supercapattery device building.

Reprecipitation-mediated regulation on the surface architecture of uniform spray dried lactose microspheres

Lactose microspheres (LMs) are commonly used in the pharmaceutical field. Although the surface architecture of LMs directly correlates with the performance of the final products, surface manipulation remains challenging. In this study, uniform LMs were fabricated using template-assisted spray drying with polyethylene glycol 200 as the template. The influence of the solvent composition (methanol, ethanol, 1-butanol, and acetone, with and without added water) and post-treatment parameters (time and temperature) on the moisture content, particle morphology, surface architecture, and crystal polymorphism were investigated. The sample surfaces post-treated using methanol were covered with particulate crystals with a crystallinity of ∼88.3 %, whereas those treated using acetone were covered by coral-like crystals with a crystallinity of ∼80.6 %. This is attributed to the higher solubility of lactose in methanol than in acetone. Adding a small amount of water to the post-treatment solvent facilitated amorphous lactose reprecipitation, achieving a block-like crystal stacking surface with a more stable Lα∙H2O content (∼40.4 % w/w). Lα∙H2O enriched on the LM surfaces prevents water absorption during storage, thus maintaining their high dispersity, uniformity, and surface architecture. This study provides a promising strategy for tailoring the surface architecture of spherical crystalline lactose microspheres.

Exploring the mechanisms of benzanilide crystal growth and morphology: Crystal surface structure, solvent diffusion and solvent-interface interactions

Flaky crystals are fragile, rendering them unsuitable for various applications including use, processing, storage and transportation. This work investigates the growth and morphology regulation mechanisms of flaky crystals using benzanilide as a model material. Initially, block-like crystals are prepared by solvent screening and cooling crystallization with its morphology greatly improved. Subsequently, growth kinetics of (111), (1–10) and (020) faces are established with crystal growth experiments. The crystal growth of (001) face is also determined to follow a two-dimensional nucleation model with the microscopic surface analysis using atomic force microscopy. The changes of the surface integration resistance and the growth step height are regarded as kinetic mechanisms of the growth behavior and crystal morphology modulation by solvent and supersaturation. Finally, the molecular mechanism of the modulation of the solvent in crystal morphology is revealed base on crystal surface structure analysis and molecular dynamics simulations. The weak solvent-interface polar interactions facilitate the incorporation of benzanilide molecules into the weak polarity (001) face, leading to the surface roughening and increased crystal thickness when employing strongly polar solvents such as acetonitrile. Unlike the former, the relatively weak hydrogen bonding interactions between solvents and strong polarity (020) face, and the higher diffusion ability of molecules promote the rapid growth and disappearance of (020) face in ethanol and acetonitrile with strong hydrogen bond formation ability. This study can contribute to a deeper understanding of the solvent effect on crystal morphology and provide guidance for optimizing crystallization conditions to obtain shape-tailored crystal products.

Surface science studies on electron-induced reactions of NH3 and their perspectives for enhancing nanofabrication processes

Ammonia (NH3) dissociates efficiently when it interacts with an electron beam. This applies not only to single electron-NH3 collisions in the gas phase but also to electron irradiation of NH3 adsorbed on surfaces. The dissociation products include atomic hydrogen which can act as a reducing agent or NH2 radicals that can bind to suitable surfaces or to adsorbed molecules. This chemistry can be exploited in nanofabrication processes that use electron beams for deposition, etching, or modification of materials. This review describes the current state of insight regarding electron-induced reactions of NH3 adsorbed on surfaces and outlines approaches to the use of these reactions for enhancing electron beam induced nanofabrication processes. First, an overview of surface science studies on electron-induced reactions of NH3 adsorbed on single crystal surfaces is given. This is followed by a summary of studies on the use of NH3 for improving the purity of deposits prepared by electron beam induced deposition (EBID) and on the prospects of NH3 to suppress unwanted thermal surface chemistry during EBID. Finally, we discuss electron-induced reactions of NH3 that are fundamental to the modification of carbonaceous nanomaterials as well as potential application scenarios such as the functionalization of self-assembled monolayers and humidity sensing.

Mechanisms of dissolution and crystallization of amorphous glibenclamide

Amorphous solid dispersions enhance the dissolution and oral bioavailability of poorly water-soluble drugs. However, the link between polymer properties and formulation performance has not been fully clarified yet. We studied the effect of hydroxypropyl cellulose (HPC) polymers molecular weight (Mw) on the storage stability, dissolution kinetics and supersaturation stability of spray-dried amorphous glibenclamide (GLB) formulations. The solid-state stability of amorphous GLB during storage was significantly enhanced by both the 40 kDa (HPC-SSL) and 84 kDa (HPC-L) polymers, regardless of Mw differences. In contrast, HPC-SSL maintained significantly higher aqueous drug concentrations during dissolution, compared to HPC-L (its higher Mw analogue). Dedicated dissolution experiments, in situ optical microscopy and solid-state characterization revealed that aqueous drug concentrations were determined by the interplay between crystallization inhibition, drug ionization, wetting and solubilization effects: (1) HPC prevents surface nucleation, hence inhibiting crystallization, (2) intestinal colloids (bile salts and phospholipids) increase supersaturated drug concentrations via wetting and solubilization effects and (3) pH and drug ionization severely impact the degree of supersaturation. The better performance of the lower Mw HPC-SSL was due to its superior inhibition of surface crystallization. These insights into the molecular mechanisms of dissolution and crystallization of amorphous solids provide foundation for rational formulation development.

Use of magnetic fields to impact glass-transition and crystallization during manufacturing of ZBLAN optical fibers

ZBLAN (ZrF4-BaF2-LaF3-AlF3-NaF) is the most stable glass among the Heavy Metal Fluoride (HMF) family and has a wide range of applications in medical industry, telecommunication, IR transmission, among others. But, due to crystal formation while manufacturing of ZBLAN fiber its theoretical minimum loss has not been achieved yet. Some techniques such as high cooling rate and microgravity conditions have been utilized to reduce the crystal formation but are challenging to implement during manufacturing of these fibers. Alternatively, magnetic field (MF), also a body force like gravity, is expected to influence the crystal formation mechanism and glass kinetics. In this work, ZBLAN glass is processed under magnetic fields of various intensities while simulating fiber drawing manufacturing process conditions. Then, the processed ZBLAN is analyzed using Differential Scanning Calorimetry (DSC) at varying scanning rates. Various glass kinetics parameters such as activation energy, fragility, and preferred crystallization mechanism in terms of Avrami parameter (n) have been analyzed. The glass transition temperature (Tg) increases for a given sample as scanning rate (β) increases. Samples processed under varying magnetic fields, at the same scanning rate, displayed higher glass transition temperatures. Also, when the magnetic field increases, the activation energy required for glass transition decreases, and the fragility index (m) decreases. There is also a preference for surface crystallization over volume crystallization. These results encourage application of magnetic fields for reducing crystal formation while processing ZBLAN glass.

Investigation of the microscopic damage mechanisms in cotton fibers induced by mechanical friction

For the problem of friction damage in cotton fiber processing, a multi-scale combination of investigation methods is proposed. The surface of damaged cotton fiber is detected by relevant test means with damage features such as dislocations, defects and cracks. The internal pyranose ring and glycosidic bond fail, the crystallinity decreases, and the number of hydrogen bonds decreases. Anisotropy exists in the frictional properties of the microscopic surface of the cotton fiber. The results of molecular dynamics simulation showed that the cellulose main chain failed mainly at the glycosidic bond, and the side chain failed mainly at the hydroxymethyl functional group. Its interchain hydrogen bond O3H…O5 was the least damaged. The cellulose crystal (200) surfaces had poor abrasion resistance, and the frictional properties of each crystal surface were anisotropic. The results of the study provide a theoretical basis for improving friction and wear problems in cotton fiber processing.

Exploring the Effect of Ionic Liquid Conformation on the Selective CO2 Capture of Supported Ionic Liquid-Phase Adsorbents Based on ZIFs.

The CO2 adsorption capacity and the CO2/N2 selectivity of a series of Supported Ionic Liquid-Phase adsorbents (SILPs), including the novel inversely structured SILP "Inverse SILPs", are thoroughly investigated. ZIF-8, ZIF-69 and ZIF-70 were involved as the solid matrix, while ILs, having tricyanomethanide (TCM) as an anion and alkyl-methylimidazolium of different alkyl chain lengths (C2, C6, C8) as a cation, were used as the liquid constituents of the SILPs. The ultimate target of the work was to ratify a few recently reported cases of enhanced CO2 absorptivity in ILs due to their incorporation in ZIFs and to corroborate phenomena of CO2/N2 selectivity improvements in ZIFs, due to the presence of ILs. This ambiguity originates from the vague assumption that the pores of the ZIF are filled with the IL phase, and the free pore volume of a SILP is almost zero. Yet, through the integration of theoretical predictions with N2 porosimetry analysis of an actual sample, it is suggested that a thin layer of IL covered the exterior surface of a ZIF crystal. This layer could act as an impermeable barrier for N2, inhibiting the gas molecules from reaching the empty cavities laying underneath the liquid film during porosimetry analysis. This consideration is based on the fact that the solubility of N2 in the IL is very low, and the diffusivity at 77 K is negligible. In this context, the observed result reflects an averaged adsorptivity of both the IL phase and the empty pores of the ZIF. Therefore, it is incorrect to attribute the adsorption capacity of the SILP solely to the mass of the IL that 'hypothetically' nests inside the pore cavities. In fact, the CO2 adsorption capacity of SILPs is always less than the average adsorptivity of an ideal ZIF/IL mixture, where the two phases do not interact. This reduction occurs because some ZIF pores may become inaccessible, particularly when the IL forms a layer on the pore walls, leaving only a small empty core accessible to CO2 molecules. Additionally, the IL layer masks the active sites on the ZIF's pore walls. It should also be noted that the CO2/N2 selectivity increases only when the ZIF's pores are completely filled with the IL phase. This is because ILs have a higher CO2/N2 selectivity compared to the bare ZIF.

Study on the formation process of methane hydrates on the surface of wax crystals with pour point depressant

Molecular dynamics simulations were applied to clarify the kinetic pathways and mechanism in the process of methane hydrate formation on the wax crystal surface with ethylene–vinyl acetate copolymer (EVA). The simulation results showed that methane molecules near the surfaces would adsorb on the surfaces of wax-EVA eutectic, while hydrates formed in the bulk of the solution away from the surfaces. The VA side chains on the wax crystal surface inhibit/promote the growth of hydrates by influencing the growth and re-dissolution process of methane nano-bubbles on eutectic surface. When a small amount of VA side chains was introduced on the wax crystal surface, as the simulation proceeded, the generated hydrates would gradually decompose. However, when more VA side chains distribute on the surface of wax crystals, the growth rate of hydrates would increase. In addition, hydrates and wax crystals could connect through a semi-cage structure, in which the VA side chain served as the guest of this semi-cage, making the eutectic and hydrates form a whole and increasing the risk of co-deposition of wax crystals and hydrates.

Effects of off-axis angles of 4H-SiC substrates on properties of β-Ga2O3 films grown by low-pressure chemical vapor deposition

In this work, β-Ga2O3 films with (−201) preferred orientation were heteroepitaxially grown on SiC substrates with off-axis angles of 0°, 4° and 8° by low-pressure chemical vapor deposition (LPCVD). It is found that the crystal quality, surface morphology, electrical properties of the β-Ga2O3 films of the film are significantly sensitive to the off-axis angle of SiC substrates. The crystal quality and surface morphology of the film were significantly improved when the 4° off-axis substrate was used, of which the FWHM (Full width at half maximum) was as low as 0.169° and the Ra (Roughness Average) of the smooth surface was 1.98 nm. Due to the improvement of crystal quality, the Hall mobility of the films deposited on 4° off-axis substrates was increased to 50.88 cm2/V·s. The photoluminescence peak intensity of the film increases first and then decreases with the increase of the off-axis angle of the substrate. However, the use of the off-axis substrate has no obvious effect on the oxygen vacancy ratio of the films. The results of this study demonstrate the significance for the preparation of high quality heteroepitaxial β-Ga2O3 films on SiC substrate for the promising applications in power electronic and optoelectronic devices.

Controlling of Crystal Facets by Dysprosium-Modified WO3/Carbon Nanofibers Enhance the Flexible Supercapacitor Performance.

Dysprosium-modified tungsten oxide/carbon nanofibers (Dy-WO3/PCNFs) are fabricated via electrospinning combined with high-temperature calcination to synthesize a flexible, self-supporting electrode material that does not require a conductive agent or binder. XRD and TEM analyses showed that introducing dysprosium promoted the preferential growth of WO3 crystals along the preponderance crystal planes involved in the electrochemical reaction, enhancing the exposure of the (002) and (200) crystal planes. Furthermore, DFT calculations demonstrated that the incorporation of Dy resulted in enhanced adsorption of Dy-WO3 by PCNFs, with an adsorption energy of -1.21eV. The Bader charge results indicate a transfer of 1.70 |e| from PCNFs to Dy-WO3. DFT calculations demonstrate that strong adsorption facilitates charge adsorption/desorption, which contributes to charge transfer and enhances storage capacity. The prepared Dy-WO3/PCNFs exhibited a high specific capacitance (557.28Fg-1 at 0.5Ag-1). Supercapacitors assembled with Dy-WO3/PCNFs as the positive electrode and CNFs as the negative electrode have high energy density (29.8Whkg-1 at a power density of 363.48Wkg-1). This study demonstrates the successful synthesis of Dy-WO3/PCNFs with exceptional electrochemical properties and offers significant insights into the design and application of flexible electrodes by incorporating dysprosium to modulate the crystal surface of WO3.

Preferred crystal surface exposure and near-crystal surface desolvation construct efficient Zn plating/stripping reversibility

The Zn/electrolyte interface stability is related to HER, passivation, dendrites, corrosion and Zn2+ deposition orientation. Reducing the occupation of H2O dipoles in the inner layer of electrical double layer (EDL) is conducive to the inhibition of interfacial side reactions and directing the deposition of Zn2+ along the (002) crystalline surface, which are beneficial to the reduction of dendrites and the improvement of plating/stripping reversibility. A mechanism is elucidated by which Acetyl-L-carnitine Hydrochloride (A-L-CN) reconfigures the EDL structure and guides the selective deposition of Zn2+ in this paper. Theoretical calculations show that A-L-CN can cover the high-energy active sites on the Zn (101) crystal plane and control the specific crystal orientation of the deposits along the (002) crystal plane to produce faceted epitaxial growth. The electrochemical test results show that the Zn anode has excellent plating/stripping reversibility as well as good cumulative capacity (10 mA cm−2, 1 mA h cm−2, ACE of 99.80 %, CPC of 7,753 mA h cm−2). The assembled Zn2+ hybrid supercapacitor (ZHS) and Zn//PANI full cell show excellent performance (ZHS up to 60,000 cycles; the capacity retention ratio of Zn//PANI full cell is 76.7 % after 1,000 cycles). The work offers the possibility of achieving stabilized Zn/electrolyte interface performance.

Stepwise Crystallization and Mass Transport Limitations in Annealed SPEEK Thin Films

Pt-supported SPEEK (sulfonated poly ether ether ketone) thin films, mimicking the ionomer-electrode interface in polymer electrolyte fuel cells (PEFCs), were synthesized with thicknesses from 12 to 105 nm. Their glass transition temperature (Tg) was analyzed via in-situ thermal ellipsometry, revealing a thickness-dependent Tg decrease, indicative of confinement effects. Particularly, a 30 nm film, typical of practical ionomer films, exhibited surface crystallization preceding that at the buried interface, a phenomenon linked to higher mobility at the free surface, as con-firmed by grazing incidence wide-angle X-ray scattering (GI-WAXS) at both sub-critical (0.09º) and supercritical (0.14º) angles. This study elucidates the dynamic interplay between the high-mobility free surface and the interaction-intensive buried interface in confined SPEEK thin films. It was observed that below 30 nm thickness, interfacial interactions become the primary factor influencing transition temperature. Additionally, spatially heterogeneous crystallization, more pronounced in the out-of-plane direction, correlates with reduced proton conduction.

Capturing Different Intermediate Phases during Zeolite Synthesis.

Despite extensive efforts over the past several decades, the current mechanistic understanding of zeolite crystallization is still far from satisfactory, thus precluding the synthesis of designer zeolites. Here we show that the nucleation and in situ transformation pathways during the synthesis of medium-pore zeolite TNU-9 can be altered by controlling the extent of cooperative structure direction between Na+ and Cs+ ions in the presence of 1,4-bis(N-methylpyrrolidinium)butane cations as an organic structure-directing agent. The intermediate phase selectivity was found to change from bikitaite to analcime to layered MCM-22 precursor when the gel Na/Cs ratio was adjusted to 7, 15, and 20, respectively. We also show that the transformation of bikitaite into TNU-9 begins at the surface of intermediate crystals, unlike that of analcime and MCM-22 precursor by a dissolution-recrystallization process. The force field simulation results suggest that the nucleation of different intermediate phases is not thermodynamically but kinetically controlled. This study provides a new basis for advancing the fundamental understanding of zeolite crystallization pathways.

Growth of broken crystals tracked in 4D using X-ray computed tomography and its influence on impurity incorporation

Crystallization is a commonly used unit operation for separation and purification. During processing, crystals may break due to mechanical stress, e.g., intentionally by milling or unintentionally through collision with stirrers. This study investigates the growth of broken crystals in three dimensions using X-ray micro-computed tomography. The results show that damaged regions of crystals grow faster than faceted regions, and crystals become faceted through growth. Initially, this happens on a microscale, producing faceted but concave regions on the crystal surface. Eventually, crystals become convex. Shape-healing through growth incorporates inclusions in the crystals. These findings have important implications for designing and optimizing crystallization processes in the pharmaceutical, food, and chemical industries, as purity is often a critical quality criterion adversely affected by inclusions. In addition, the kinetics in crystallization processes are likely to be strongly affected by the growth of non-faceted and concave crystals.