Silicon Structures Research Articles

Mitigation of Volumetric Expansion in Silicon Anodes via Engineered Porosity: Electrochemical Performances and Stress Distribution Implication

To overcome the significant volume expansion issue encountered by traditional silicon anodes in lithium‐ion batteries, this study employs chemical etching techniques to treat aluminum–silicon alloys of various ratios, successfully preparing three types of porous silicon electrode materials with different pore structures. Through a series of electrochemical tests, this article investigates the role of porous silicon structures in improving electrode performance. The results demonstrate that the porous silicon anodes exhibit superior cycle stability and rate capability compared to traditional solid silicon anodes. This confirms the effectiveness of the porous structure in mitigating the significant volume expansion during the charge and discharge process of silicon materials and in preventing premature electrode failure, thereby significantly enhancing the electrode's cycle life. Remarkably, the porous silicon with a high porosity rate shows exceptionally outstanding performance. Additionally, using computer simulations, this study also models the impact of changes in pore size within the porous silicon material at different states of charge and discharge on the stress distribution at the particle center and surface. These experimental and simulation results jointly provide strong empirical evidence for applying porous silicon materials as high‐performance anode materials for lithium‐ion batteries and offer essential guidance for future stress analysis and electrode design of porous silicon electrode materials.

A deformation mismatch strategy enables over 120% stretchability of encapsulated serpentine silicon strips for stretchable electronics

AbstractIt is significant to develop stretchable electronics based on silicon materials for practical applications. Although various stretchable silicon structures have been reported, electronic systems based on them exhibit limited stretchability due to the constraints between them and polymer substrates. Here, an innovative strategy of deformation mismatch is proposed to break the constraints between silicon structures and polymers and effectively reduce the strain concentration in silicon structures. As a result, encapsulated serpentine silicon strips (S‐Si strips) achieve unprecedented stretchability, exceeding 120%. The encapsulated S‐Si strip also exhibits remarkable mechanical stability and durability, enduring 100 000 cycles of 100% stretch without fracture. The effect of key parameters, including the central angle, thickness, and width of the S‐Si strip, on the deformation mismatch is revealed through combing experiments and theoretical analysis, which will guide the rational implementation of the deformation mismatch strategy. Electrical testing showcases the strain‐insensitive nature and good electrical stability of encapsulated S‐Si strips, benefiting practical applications. This work provides a new paradigm of silicon materials with excellent stretchability and will facilitate the development of stretchable electronics.

Unlocking and optimizing the thermodynamic potential of tetragonal Si and Ge: Strategies and insights from a tight-binding simulation framework for material engineering

This study theoretically explores the effects of external fields and doping on the electronic and thermoelectric properties of tetragonal silicon (T-Si) and tetragonal germanium (T-Ge) structures using a tight-binding model, Green’s function formalism, and the Kubo formula. External parameters modify the positions and intensities of the density of states (DOS) peaks, influencing charge carrier excitation and conductivity trends. Applying bias voltage introduces zero-intensity regions in thermal conductivity due to band gap opening, reducing thermal properties. In contrast, chemical potential and magnetic field significantly enhance thermal properties by increasing intensity and shifting the peak position. T-Ge exhibits higher thermal properties than T-Si across the selected parameter ranges. The findings highlight the potential for optimizing and enhancing the thermoelectric properties of tetragonal structures through external controllable parameters.

On how Doping with Atoms of Gadolinium and Scandium affects the Surface Structure of Silicon

The experimental team has developed a technology of step-by-step low-temperature diffusion doping of gadolinium and scandium into silicon that allows the clusters of impurity atoms to be uniformly distributed throughout the entire bulk of the silicon material. It was shown that, unlike the samples obtained under the high-temperature diffusion doping technology, in the samples obtained under the novel technology the team had detected any surface erosion or formation of alloys and silicide in the near-surface region. The authors have revealed increased thermostability and radiation resistance of silicon samples dotted with clusters of impurity atoms of gadolinium and scandium. The authors have conducted comprehensive studies by using the techniques of tagged atoms, autoradiography, measurement of conductivity and Hall effect, isothermal relaxation of capacitance and current of diffusion, solubility, and electrophysical properties of scandium in silicon under various doping conditions and for a wide temperature range (1100 ÷ 1250 0С). Diffusion parameters, solubility and acceptor nature of scandium in silicon as well as thermal stability of silicon doped with gadolinium and scandium impurity atoms have been established.

Upright Pyramid Surface Textures for Light Trapping and MoOx Layer in Ultrathin Crystalline Silicon Solar Cells

In this work, ray tracing is used to investigate the optical characteristics of various surface structures in ultrathin crystalline silicon (c-Si) for solar cells. Ultrathin c-Si with a thickness of 20 μm is used as the substrate. The light trapping includes front upright pyramids with a molybdenum oxides (MoOx) anti-reflection (AR) layer. Planar ultrathin c-Si (without a MoOx AR layer and upright pyramids) is used as a reference. The wafer ray tracer was developed by a photovoltaic (PV) lighthouse to model the MoOx AR layer to reduce the front surface reflectance and impacts of the AR layer on ultrathin Si solar cells. The optical properties are calculated on the AM1.5 global solar energy spectrum across the 200–1200 nm wavelength region. From the absorbance profile, the photogenerated current density (Jph) in the substrate is also calculated with various surface structures. The front upright pyramids with the MoOx layer result in the largest absorbance enhancement due to the enhanced light scattering by the pyramids and MoOx AR layer. The Jph of 37.41 mA/cm2 is improved when compared to the planar ultrathin c-Si reference. This study is significant as it illustrates the potential of ultrathin c-Si as a promising PV module technology in the future.

Seed-guided high-repetition-rate femtosecond laser oxidation for functional three-dimensional silicon structure fabrication

Laser oxidation provides a flexible maskless functional three-dimensional silicon structure fabrication strategy. Here, oxide layers are fabricated on silicon substrates by high-repetition-rate femtosecond laser irradiation. Formation mechanisms of the femtosecond laser oxidation are analyzed to tune the oxide layer morphology. When the laser fluence is high, the oxidation process is accompanied by laser ablation, so the oxide layer is always on top of laser ablated groove. To obtain the flat oxide layer, defect is firstly generated on silicon substrate by the laser irradiation at a high laser fluence of 126 mJ/cm2, function as a high optical absorption. It is called seed as it can assist to achieve lower fluence laser oxidation at 38 mJ/cm2 and result in a flat oxide layer. Full width at half-maximum of the oxide layer is also reduced. The laser fabricated oxide layers are used as etching masks. Three-dimensional silicon gratings are fabricated by deep reactive ion etching, which demonstrate desirable beam diffraction properties.

Scalable Nanoimprint Manufacturing of Functional Multilayer Metasurface Devices

AbstractOptical metasurfaces, consisting of subwavelength‐scale meta‐atom arrays, hold great promise of overcoming the fundamental limitations of conventional optics. Due to their structural complexity, metasurfaces usually require high‐resolution yet slow and expensive fabrication processes. Here, using a metasurface polarimetric imaging device as an example, the photonic structures and the Nanoimprint lithography (NIL) processes are designed, creating two separate NIL molds over a patterning area of > 20 mm2 with designed Moiré alignment markers by electron‐beam writing, and further subsequently integrate silicon and aluminum metasurface structures on a chip. Uniquely, the silicon and aluminum metasurfaces are fabricated by using the nanolithography and 3D pattern‐transfer capabilities of NIL, respectively, achieving nanometer‐scale linewidth uniformity, sub‐200 nm translational overlay accuracy, and <0.017 rotational alignment error while significantly reducing fabrication complexity and surface roughness. The micro‐sized multilayer metasurfaces have high circular polarization extinction ratios as large as ≈20 and ≈80 in blue and red wavelengths. Further, the metasurface chip‐integrated CMOS imager demonstrates high accuracy in broad‐band, full Stokes parameter analysis in the visible wavelength ranges and single‐shot polarimetric imaging. This novel, NIL‐based, multilayered nanomanufacturing approach is applicable to the scalable production of large‐area functional structures for ultra‐compact optic, electronic, and quantum devices.

Fabrication of humidity monitoring sensor using porous silicon nitride structures for alkaline conditions

Porous silicon nitride structures were fabricated for a humidity sensor. The porous silicon structures were fabricated by the metal-assisted chemical etching process, and the conformal silicon nitride thin film was deposited by the atomic layer deposition process. The optimized porous sensor with the 10 nm-thick silicon nitride thin film had a hydrophilic surface and compared to other sensors, had an excellent humidity sensing response. Especially, it showed a superior humidity sensing response at 1 kHz with fast response and recovery times of 13.3 s and 12.4 s, respectively, were observed. Based on the electrochemical impedance spectroscopy results, the equivalent circuits and humidity sensing mechanism were discussed. The chemical stability of the silicon nitride was characterized using Tafel analysis in alkaline electrolytes. Additionally, the sensor's humidity sensing capabilities were tested under cement-embedded conditions.

Biophysical features of using a recombination sensor to detect lactate dehydrogenase: sensitivity mechanisms analysis

Background. Most pathologies of the human body (in particular, malignant neoplasms, myocardial hypoxia, liver diseases, etc.) are accompanied by a violation of the integrity of cells in target tissues and the release of intracellular macromolecules into the extracellular environment. Thus, an important diagnostic and prognostic indicator is the level of activity of certain enzymes in blood serum, which are normally intracellular. One of the most promising areas of modern medical electronics and biophysics is the development and optimization of enzyme screening methods in biological fluids. In this study, we aimed to investigate the biophysical characteristics of using a recombination sensor for determining LDH activity in biological fluids. Materials and Methods. Experiments were performed on preparations of standard human blood serum. The reference determination of lactate dehydrogenase activity was carried out photometrically based on the change (decrease) in the concentration of the reduced form of the NADH coenzyme. The passage of the lactate dehydrogenase reaction was experimentally recorded by measuring the photocurrent of a silicon structure with a buried barrier under light irradiation from the region of strong absorption (λ = 532 nm). Results. The biophysical features of the device were studied. The detection of lactate dehydrogenase becomes possible due to the transfer of a hydrogen ion from nicotinamide adenine dinucleotide (NADH) to pyruvate, as a result of which lactate and NAD+ are formed. The effect is explained by the local electrostatic influence on the parameters of the recombination centers in the near-surface bending zone near the silicon surface, which leads to a change in the surface recombination rate. Conclusions. Our approach can be considered as a promising way to develop a highly sensitive method for the detection of lactate dehydrogenase. It has been experi­mentally shown that effective detection is possible in two changes at the surface ben­ding of the deep barrier silicon substrate zone.

Exploring re-entrant auxetic silicone structures to design bra pads

Auxetic materials, known for their negative Poisson's ratio and unique form-fitting deformation, are proposed in this study for designing bra pads to accommodate different bra cup sizes. The deformation elasticity behaviour of re-entrant auxetic structures with a bow-tie shape, made of silicone elastomer, is systematically analysed for size accommodation and shape conformity, and compared with traditional polyurethane foam and spacer fabric used in bra pads. The results indicate that the auxetic structures exhibit desirable mechanical properties, including superior elasticity and stable deformation under tensile loading. Additionally, these structures facilitate 3D shape conformity to breast shapes, thereby improving overall bra fit. Amongst the 4 different unit cell dimensions studied, the auxetic elastomer with a cell size of 9.14 mm is the most promising candidate, which has superior elasticity, linear expansion, and excellent shape conformity. This auxetic elastomer enables increases in area from an A to D cup thus offering the potential to realize a one-size-fits-more concept. The findings provide the grounds for future research endeavours that aim to develop support in different areas of bras and optimize the arrangement of unit cells to enhance the functional aspects of bras.

Continuously Geometrical Tuning to Boost Circular Dichroism in 3D Chiral Metamaterials

AbstractChiral metamaterials possess unique optical chiral responses, and the attainment of remarkable intrinsic chirality typically necessitates the disruption of their mirror symmetry to facilitate cross‐coupling between electric and magnetic dipoles. However, achieving such symmetry breaking in a flexible and controllable manner remains challenging due to the limited range of applications afforded by available methodologies. Here, a method is proposed for fabricating robust three‐dimensional (3D) chiral metamaterials by projecting arbitrary planar chiral metasurfaces onto on‐demand height‐tunable 3D silicon structures, thereby effectively modulating their optical chiral responses through continuously tuning the degree of cross‐coupling between dipoles. Experimental and simulation results demonstrate this approach's ability to precisely control circular dichroism (CD) from a non‐chiral state to various activated and enhanced chirality. Enhancing CD with high precision and continuous control manners can naturally provide an advanced opportunity and platform for the future design and actual applications of chiral optical systems.

Multimessenger measurements of the static structure of shock-compressed liquid silicon at 100 GPa

The ionic structure of high-pressure, high-temperature fluids is a challenging theoretical problem with applications to planetary interiors and fusion capsules. Here we report a multimessenger platform using velocimetry and angularly and spectrally resolved x-ray scattering to measure the thermodynamic conditions and ion structure factor of materials at extreme pressures. We document the pressure, density, and temperature of shocked silicon near 100GPa with uncertainties of 6%, 2%, and 20%, respectively. The measurements are sufficient to distinguish between and rule out some ion screening models. Published by the American Physical Society 2024

Generating quantum correlated photon pairs in a hybrid silicon–BTO platform

Here, we show photon pair generation from ring resonator and waveguide structures in a hybrid silicon–BTO on an insulator platform with a pulsed pump. Our analysis of single photon and coincidence generation rates show that spontaneous four-wave mixing is comparable to that expected from SOI devices with similar characteristics and find γeff of (14.7 ± 1.3) and (2.0 ± 0.3) MHz/mW2 for ring resonator and waveguide structures, respectively.

Free-standing ultrathin silicon wafers and solar cells through edges reinforcement

Crystalline silicon solar cells with regular rigidity characteristics dominate the photovoltaic market, while lightweight and flexible thin crystalline silicon solar cells with significant market potential have not yet been widely developed. This is mainly caused by the brittleness of silicon wafers and the lack of a solution that can well address the high breakage rate during thin solar cells fabrication. Here, we present a thin silicon with reinforced ring (TSRR) structure, which is successfully used to prepare free-standing 4.7-μm 4-inch silicon wafers. Experiments and simulations of mechanical properties for both TSRR and conventional thin silicon structures confirm the supporting role of reinforced ring, which can share stress throughout the solar cell preparation and thus suppressing breakage rate. Furthermore, with the help of TSRR structure, an efficiency of 20.33% (certified 20.05%) is achieved on 28-μm silicon solar cell with a breakage rate of ~0%. Combining the simulations of optoelectrical properties for TSRR solar cell, the results indicate high efficiency can be realized by TSRR structure with a suitable width of the ring. Finally, we prepare 50 ~ 60-μm textured 182 × 182 mm2 TSRR wafers and perform key manufacturing processes, confirming the industrial compatibility of the TSRR method.

Scutellarin-loaded pH/H2O2 dual-responsive polymer cyclodextrin mesoporous silicon framework nanocarriers for enhanced cancer therapy

Stimulus-responsive nanomaterials, particularly with targeting capabilities, have garnered significant attention in the cancer therapy. However, the biological safety of these innovative materials in vivo remains unknown, posing a hurdle to their clinical application. Here, a pH/H2O2 dual-responsive and targeting nano carrier system (NCS) was developed using core shell structure of Fe3O4 mesoporous silicon (MSN@Fe3O4) as main body, scutellarin (SCU) as antitumor drug and polymer cyclodextrin (PCD) as molecular switch (denoted as PCD@SCU@MSN@Fe3O4, abbreviated as NCS). The NCS, with an average particle size of 100 nm, displayed exceptional SCU loading capacity, a result of its uniform radial channel structure. The in vitro investigation under condition of pH and H2O2 indicated that NCS performed excellent pH/H2O2-triggered SCU release behavior. The NCS displayed a higher cytotoxicity against tumor cells (Huh7 and HCT116) due to its pH/H2O2 dual-triggered responsiveness, while the PCD@MSN@Fe3O4 demonstrated lower cytotoxicity for both Huh7 and HCT116 cells. In vivo therapeutic evaluation of NCS indicates significant inhibition of tumor growth in mouse subcutaneous tumor models, with no apparent side-effects detected. The NCS not only enhances the bioavailability of SCU, but also utilizes magnetic targeting technology to deliver SCU accurately to tumor sites. These findings underscore the substantial clinical application potential of NCS.

Novel Fast Cure Silicone Inks for Single‐Step, Support‐Free 3D Printing of Tall, Overhanging, and High Aspect Ratio Structures

AbstractSilicone elastomers have a broad variety of applications, such as soft robotics, biomedical devices, and structural metamaterials. The extrusion‐based method known as direct ink write (DIW) has enabled the production of additively manufactured silicone structures. However, this method is limited to manufacturing mostly planar or pseudo‐3D structures. Due to the low self‐supporting capabilities of extruded strands for traditional silicone‐based “inks,” obtaining tall or overhanging structures, or structures comprised by thin walls is not feasible. Here, a novel Fast Cure silicone‐based ink is demonstrated that enables manufacturing of complex 3D structures. The Fast Cure ink is a two‐part mixture and silicone structures are produced by inline mixing and coextrusion of a part containing a catalyst (part A) and a part containing a crosslinker (part B). By the virtue of crosslinking, the extruded strands rapidly rigidize, increasing their self‐supportive capacity. Hence, structures can be obtained with superior shape retention and previously unobtainable parts are realized that are tall, with aspect ratios higher than 3, and have overhanging features, achieving inclination angles smaller than 35° with respect to the printing plane. These minimal sag parts are achieved without requiring extra curing or mechanisms, support structures, or suspension baths.

Ordered silicon nanocone fabrication by using pseudo-Bosch process and maskless etching

Nanocone arrays are widely employed for applications such as antireflection structures and field emission devices. Silicon nanocones are typically obtained by an etching process, but the profile is hard to attain because anisotropic dry etching generally gives vertical or only slightly tapered sidewall profiles, and isotropic dry plasma etching gives curved sidewalls. In this work, we report the fabrication of cone structures by using masked etching followed by maskless etching techniques. The silicon structure is first etched using fluorine-based plasma under the protection of a hard metal mask, with a tapered or vertical sidewall profile. The mask is then removed, and maskless etching with an optimized nonswitching pseudo-Bosch recipe is applied to achieve the cone structure with a sharp apex. The gas flow ratio of C4F8 and SF6 is significantly increased from 38:22 (which creates a vertical profile) to 56:4, creating a taper angle of approximately 80°. After subsequent maskless etching, the sidewall taper angle is decreased to 74°, and the structure is sharpened to give a pointed apex. The effect of an oxygen cleaning step is also studied. With the introduction of periodic oxygen plasma cleaning steps, both the etch rate and surface smoothness are greatly improved. Lastly, it was found that the aspect ratio-dependent etching effect becomes prominent for dense patterns of cone arrays, with a greatly reduced etch depth at a 600 nm pitch array compared to a 1200 nm pitch array.

Molecular dynamics study of surface alkalization reaction in high calcium systems

Alkali-activated materials (AAMs) offer significant benefits in the field of civil engineering, thanks to their energy-efficient and environmentally-friendly properties, as well as their exceptional strength and durability. However, the fundamental chemical reaction underlying the use of AAMs has not yet been fully understood. The process of the silicate depolymerization of the supplementary gelling materials is determined by their nano characteristics, which have certain restrictions by using experimental techniques. In this study, we utilized reactive molecular dynamics (MD) simulations to elucidate the chemical events occurring during alkali-activation in different AAMs. The sodium hydroxide (NaOH) solution selectively dissolves the silicon chains, while the aluminum chains remain intact. Furthermore, the laminar structures of silicon and aluminum in metakaolin (MK) crystal are entirely disturbed. However, the disintegration of silicon chains is negligible, and the Slag minerals maintain their layered structure. Calcium ions are crucial in stabilizing the chemical process of alkali activation. Furthermore, this study evaluates the fluctuations in their activity. Gaining insight into the minute details of this reaction provides essential theoretical foundations for developing eco-friendly and high-performing alkali-activated concrete materials.

Observation of high-pressure polymorphs in bulk silicon formed at relativistic laser intensities

Silicon polymorphs with exotic electronic and optical properties have recently attracted significant attention due to their wide range of useful band gap characteristics. They are typically formed by static high-pressure techniques, which limits the crystal structures that can be made. This constitutes a major obstacle to study these polymorphs and their incorporation into existing technology. Approaches have attempted to address this shortcoming through using dynamic conditions and chemical precursor materials. Here, we report on an approach to create unusual crystal structures deep in the bulk of a silicon crystal by irradiating it with a laser pulse at ultrarelativistic intensity of up to 7.5×1019 W/cm2. Laser-generated electrons with MeV energy swiftly penetrate the target with speed close to the speed of light and deposit their energy into a large volume across the whole thickness of the sample. The relativistic electron current creates, via branching propagation and ionization, high-energy-density conditions for thermodynamically nonequilibrium phase transformation paths into new crystal polymorphs. X-ray microdiffraction and synchrotron x-ray diffraction analyses indicate, along with conventional dc-Si, the presence of exotic silicon structures in the bulk of the laser intact target volume. These structures are identified as body-centered bc8-Si, rhombohedral r8-Si, hexagonal-diamond hd-Si, and the tetragonal Si-VIII, all phases of Si that have previously been made through static techniques. Additionally, simple-tetragonal st12-Si and body-centered tetragonal bt8-Si were observed along with signatures of not yet identified diffraction spots. Both st12-Si and bt8-Si have only been observed in ultrafast laser microexplosion conditions at much lower laser intensity ∼1014 W/cm2 and within a micron-thin surface layer. The findings here are supported by direct observation of nanoparticles with high-resolution transmission electron microscopy and corresponding fast Fourier transform analysis of their interatomic distances. The presented analyses of absorbed laser energy, generation of the MeV electron current, and deposition of energy across the whole target thickness provide a solid basis for drawing the conclusion that the observed silicon polymorphs were produced because of laser-generated high-energy electrons fast-penetrating deeply into the bulk of silicon. In contrast to solid-solid transformations, the plasma-solid transitions offer a paradigm for the creation of exotic, high-energy density materials inside the bulk of the sample by using laser pulses at relativistic intensities. Published by the American Physical Society 2024

Characterization of Silicon from Rice Husk Doped with Cobalt: Analysis of Structure and Magnetoelectric Properties

The development of Si-based materials has attracted increasing attention, particularly for application in semiconductors, batteries, sensors, and optical technology. Silicon has abundant availability, high energy storage capacity, and low work potential. However, it faces compatibility challenges due to its low electrical conductivity and extremely small magnetic susceptibility. This research aimed to investigate the influence of Co dopants on the structure, morphology, electrical conductivity, and magnetic susceptibility of silicon. Silicon was synthesized using the magnesiothermic reduction method, and silicon was modified with Co metal dopants at 0.1% and 0.5% concentrations through the impregnation method. XRD analysis results showed that Si, 0.1% Co/Si, and 0.5% Co/Si exhibit silicon diffraction patterns at 2θ = 28.42º; 47.28º; 56.11º; 69.13º; and 76.36º. The morphology of Si and Co/Si revealed a rough, uneven, and porous surface with particles appearing spherical. Electrical conductivity increases with Co concentration: Si = 1223 µS/cm, 0.1% Co/Si= 1376 µS/cm, and 0.5% Co/Si= 1529 µS/cm. Magnetic susceptibility measurements indicated that Si, 0.1% Co/Si, and 0.5% Co/Si are paramagnetic at a range of 1.18 x10-6 to 1.25 x10-5 SI. These characterization results confirmed that the modification with Co dopants can enhance the magnetoelectric properties of silicon.