Si Surface Research Articles

Interfacial Si–O coordination for inhibiting the graphite phase enables superior SiC/Nb heterostructure joining by AuNi

The reaction between SiC and Ni-based brazing alloy is extremely intense, where the brittle Ni–Si compound and accompanied dissociate graphite phase as the interfacial reaction product in the joint damage the mechanical properties. In this study, the design of "graphite-controlled" heterogeneous integration component structure on SiC surface is developed to weaken the intense reaction of Ni and SiC. The high-quality surface Si–O coordination was successfully achieved by plasma-enhanced chemical vapor deposition (PECVD) method at relatively low temperature on SiC, which increases the Si bond strength due to that the higher binding energy of Si–O (451 kJ/mol) than that of Si–C (347 kJ/mol). SiO2 films enhance the mechanical properties of the joint through macro-weak side interface interlocking and micro-stress mismatch regulation. The shear strength of SiC/Nb heterostructure joints by AuNi alloy was increased by 44 %, which paves an inspiring way for boosting heterogeneous integration of SiC ceramic components.

Crystal orientation of epitaxial film deposited on silicon surface

Direct growth of oxide film on silicon is usually prevented by extensive diffusion or chemical reaction between silicon (Si) and oxide materials. Thermodynamic stability of binary oxides is comprehensively investigated on Si substrates and shows possibility of chemical reaction of oxide materials on Si surface. However, the thermodynamic stability does not include any crystallographic factors, which is required for epitaxial growth. Adsorption energy evaluated by total energy estimated with the density functional theory predicted the orientation of epitaxial film growth on Si surface. For lower computing cost, the adsorption energy was estimated without any structural optimization (simple total of energy method). Although the adsorption energies were different on simple ToE method, the crystal orientation of epitaxial growth showed the same direction with/without the structural optimization. The results were agreed with previous simulations including structural optimization. Magnesium oxide (MgO), as example of epitaxial film, was experimentally deposited on Si substrates and compared with the results from the adsorption evaluation. X-ray diffraction showed cubic on cubic growth [MgO(100)//Si(100) and MgO(001)//Si(001)] which agreed with the results of the adsorption energy.

Formation of Organic Monolayers on KF-Etched Si Surfaces

Silicon is the most commonly used material in the microelectronics industry, due to its inherent advantages of high natural abundance, low cost, and high purity, coupled with the chemical and electrical stability at the interface with its oxide. For molecular electronics applications, oxide-free Si surfaces are widely used because of the relative ease of removing the oxide (SiOx) by chemical means, yielding a surface which forms strong covalent bonds with a wide range of chemical functional groups; another advantage is that these surfaces remain oxide-free in the absence of oxidising agents. Standard procedures require the use of either HF, NH4F, or a mixture of both as the etching solution; however, these two chemicals are highly corrosive and toxic, posing a significant risk to the experimentalist. Here, we report that for silicon wafers etched by using potassium fluoride, a less toxic chemical, the resulting surface is free of oxides and can be functionalized by self-assembled monolayers of 1,8-nonadiyne. To demonstrate this, Si/SiOx wafers were etched by using either KF or NH4F, followed by hydrosilylation with 1,8-nonadiyne and a click reaction of the terminal alkyne with azidomethylferrocene. The surface coverages and electron transfer kinetics of the ferrocene-terminated KF-etched surfaces are comparable to those formed by acidic fluoride etching procedures. This is the first study comparing the differences between surfaces functionalized by self-assembled monolayers of 1,8-nonadiyne which were etched by KF and NH4F. KF could be used as a replacement chemical for etching silicon wafers when a less corrosive and toxic chemical is required.

Development of Ag@Si composite sinter joining with ultra-high resistance to thermal shock test for SiC power device: Experiment validation and numerical simulation

Owing to its cost-effectiveness and low coefficient of thermal expansion (CTE), micron Si is incorporated into sintered Ag matrix to develop an Ag@Si composite sintering strategy. The Si integration helps reduce cost and alleviate CTE-mismatch of Ag-sintered die attachments. An innovative Ag@Si composite sintering structure is achieved by low-temperature and pressure-less sintering process, where a possibly slight diffusion of native SiO2 on the Si surface toward Ag is indicated by TEM observation, enabling the integration of Ag and Si into one continuous network. Owing to the robust well-bonded composite sintering, the Ag@Si joining strategy provides mechanical/microstructural reliability far beyond the pure Ag sinter joining, demonstrating significant prospects in high-temperature interconnection applications. During the harsh thermal cycling (−50–250 °C), the mitigating effect of the Si addition on CTE mismatch is manifested through the substantial suppression of microstructure deterioration in Ag@Si joint that occurs in pure-Ag-sintered joint, while the shear strength retention rate is doubled. Detailed investigation into the mechanism for elevated performance was conducted by material property and Missies stress analysis. The incorporation of Si helps modify the CTE, elastic properties, and stress distribution of Ag@Si-sintered material, synergistically contributing to the satisfactory joining reliability.

Strain-induced shape transition of VSi2 clusters on Si(111)

We investigated the growth and shape of vanadium silicide clusters on Si(111) using scanning tunneling microscopy, atomic force microscopy and scanning electron microscopy. The deposition of 8 monolayers of vanadium on Si(111) and subsequent annealing at 1200 K leads to the formation of large elongated VSi2 clusters. This is in marked contrast to the deposition of submonolayer amounts of V where the VSi2 islands have a compact shape. The shape transition can be explained by a competition between edge formation and strain relaxation energy terms. The VSi2 clusters, which are aligned along the three high symmetry directions of the Si(111) surface and surrounded by a denuded zone, form a two-dimensional network.

Modification and strengthening mechanism of high strength-toughness as-cast Al–11Si–3Cu alloy modified with minor Sr and Er content

The strength of Al–11Si–3Cu requires improvement to meet the growing demands of manufacturing and expand its application in the automotive market. A new high strength-toughness as-cast Al–11Si–3Cu alloy with the ultimate tensile strength and elongation up to 294 MPa and 3.5 % was developed by using minor Sr and Er modifiers. The TEM and the first principles calculations showed that Sr and Er atoms adsorbed on the eutectic Si surface and prompted the formation of twins that branched in 70.5° and 39° directions, and the synergistic effects of Sr and Er atoms significantly reduced the size of eutectic Si to ∼500 nm. Moreover, the ∼10 nm Al3Er and ∼200 nm Al8Cu4Er particles formed in the alloy, which have positive effects on enhancing the mechanical properties of the alloy. The dislocation lines were stretched when passing through the Al3Er particles and eventually formed dislocation rings, while the motion of the grain boundary was hindered by the Al8Cu4Er particle. Additionally, the modification mechanism of Sr and Er modifiers on the eutectic Si and the strengthening mechanism of the modified alloy were discussed.

Emission of ions and electrons correlated with soft and hard x-rays evolution from thermal plasma

This paper presents a correlation between time evolution of ions and electrons with soft and hard x-rays emitted from argon plasma. The plasma setup comprises of two copper electrodes connected with a dc power supply. Faraday cups were used to monitor time evolution of ions, to extract their energy, temperature, and flux. Double Langmuir probe was employed to determine electron temperature, energy, and density. To explore time-resolved emission of soft x-rays, PIN photodiodes filtered with 24 μm aluminum, 90 μm Mylar, 80 μm copper, and 10 μm silver have been used. To evaluate temporal evolution of hard x-rays, a scintillator–photomultiplier system was utilized. The plasma was generated using argon gas at atmospheric pressure 760 Torr and constant flow rate 5 L/min at 7, 9, and 11 kV. The flux, energy, and temperature of Ar ions increase with the increase in the operating potential. Soft x-ray signals last much longer (3000 ns) than those of electrons' and ions' signals (300 ns). The plasma operated at 11 kV permits highest emission of ions, electrons, and x-rays. The ions, electrons, and hard and soft x-ray irradiation on silicon wafer exhibited the presence of damaged trails. Ion irradiation showed the presence of latent damaged trails. Electron irradiation caused more damage to the Si surface compared to ion irradiation due to higher flux and density. Soft x-rays had a lesser effect as compared to Si exposed to hard x-rays due to higher energy of the hard x-rays. In the case of hard x-rays irradiated Si, erupted volcano-like structure is formed.

Phase transformation mechanism of nominal Si(001) surface driven by hydrogen thermal annealing

Herein, we report the phase transformation mechanism of the nominal Si(001) surface driven by hydrogen thermal annealing. The surface energies of H-terminated Si(001) surface with different phase structures were calculated by density functional theory. The results show that the surface phase with monoatomic steps can transform into the surface phase with diatomic steps under proper ranges of hydrogen chemical potential. Combining thermodynamic and kinetic factors, the phase transformation can’t occur when annealing temperature lower or higher than 800 °C. In addition, surface phases with different types of diatomic steps are alternately transformed through the intermediate phase with monoatomic steps and the imperfection of the transformation process gradually increases with the extension of annealing time. Finally, different experiments have been carried and the experimental results are in good agreement with the phase transformation mechanism. This study provides complete theoretical mechanism and process parameters for controlling the phase structures of the nominal Si(001) surface through hydrogen thermal annealing.

Resilient Si@C architecture fabricated by mechanochemical conjugation and thermal reduction for lithium storage: Simulation on interfacial state evolution

Synchronal comminution via high-energy bead milling not only efficiently pulverizes Si particles and exfoliates graphene oxide (GO) sheets but also facilitates Si surface functionalization and intensify Si-C conjugation. After a thermal reduction, a well-wrapped Si@C anode material can be fabricated for lithium storage. The discharge specific capacities of this Si@C composite sustain at 1110.3 mAh g−1 after 300 cycles at 1 A g−1 and 316.4 mAh g−1 for 800 cycles at 5 A g−1, which are respectively 1.35 and 2.07 times that of its random blended Si/C counterpart. By employing molecular dynamics (MD) simulations with ReaxFF reactive force field to investigate the mechanochemical reactions between Si and GO amidst high-energy milling, an atomic scale portrayal of Si crystal fragmentation and Si-C bonding can be depicted. Analyses focusing on the differential forces exerted on various Si crystal planes, coupled with potential energy (PE) trends, reveal a higher propensity for cleavage in (111) plane, with (311) plane followed. Radial distribution function (RDF) outcomes indicate that ball milling leads to substantial disruption of crystalline order in Si particles, generating a plethora of Si dangling bonds. This disruption stimulates the formation of SiOOC, SiOC and SiC bonds at the Si/C interface, thus enhancing the integration of GO with Si substrate. Subsequent thermal reduction processes not only restore the structural order of Si and GO but also consolidate Si/C bonding.

Spectroscopic and theoretical investigation of Brønsted acid sites in amorphous mixed Zr-Si oxide nanoparticles

Mixed Zr-Si oxide nanoparticles were investigated to disclose the relation between the Brønsted acidity of these materials and the atomic composition of the particles. To this aim, we combined experimental structural characterizations via X-ray absorption and Solid State Nuclear Magnetic Resonance spectroscopies with Reactive Molecular Dynamics simulations and Quantum Chemistry calculations. Despite the materials’ complexity, we identified the surface hydrogens responsible for the Brønsted acidity by estimating the adsorption energy of pyridine on several topologically distinct hydroxyl groups. Among the investigated sites, the hydrogens connected to the oxygen atoms bridging surface Zr and Si atoms (i.e., Zr-O(H)-Si) exhibited the most marked Brønsted acidity. The agreement of all the employed techniques demonstrates how the proposed concerted characterization effectively elucidates these complex amorphous materials’ structure/properties relationships. These new insights allowed us to develop a material with exceptionally high Brønsted acid character that outperformed benchmark silica-alumina and sulfonated zirconia in the dehydrogenation reaction of 1-octanol to produce olefins.

Functionalized interfacial cover design toward pure silicon anode for high power density lithium–ion capacitor

A lithium–ion capacitor, comprising a capacitor–type cathode and battery–type anode, exhibits high power and energy density; however, the integration of different charge storage mechanisms in one cell naturally leads to a kinetic mismatch between the two electrodes, reducing the power density and cycle stability. To solve this problem, high–capacity anode materials with thinner electrodes are required. Silicon, with its high specific capacity, is considered a promising anode material with high energy and power density; however, pure Si anodes undergo rapid capacity fading and exhibit increased internal resistance owing to volume changes during cycling. In this study, both sides of the electrode are covered with functional layers consisting of functionalized herringbone–type carbon nanofibers to protect the Si electrode from degradation. The polar functional groups on the nanofibers weakly interact with the native oxide layer of the Si surface and the carboxyl groups of the binder, ensuring stable contact between electrode materials over repeated cycles. Moreover, the conductive functional cover promotes uniform lithium ion fluxes, aiding the formation of a stable solid electrolyte interphase layer. This study investigates the effects of this strategy on pure Si electrodes by surface morphology analysis, assessment of chemical interactions, and electrochemical testing. This approach has the potential to overcome the degradation of Si electrodes and significantly improve the power and energy density of lithium–ion capacitors.

Crystalline Si Surface Passivation with Nafion for Bulk Defects Detection with Electron Paramagnetic Resonance.

In monocrystalline Si (c-Si) solar cells, identification and mitigation of bulk defects are crucial to achieving a high photoconversion efficiency. To spectroscopically detect defects in the c-Si bulk, it is desirable to passivate the surface defects. Passivation of the c-Si surface with dielectrics such as Al2O3 and SiNx requires deposition at elevated temperatures, which can influence defects in the bulk. Herein, we report on the passivation of different Czochralski (Cz) Si wafer surfaces by an organic copolymer, Nafion. We test the efficacy of the surface passivation at temperatures ranging from 6 to 473 K to detect bulk defects using electron paramagnetic resonance (EPR) spectroscopy. By comparing with state-of-the-art passivation layers, including Al2O3 and liquid HF/HCl, we found that at room temperature, Nafion can provide comparable passivation of n-type Cz Si with an implied open-circuit voltage (iVoc) of 713 mV and a recombination current prefactor J0 of 5 fA/cm2. For p-type Cz Si, we obtained an iVoc of 682 mV with a J0 of 22.4 fA/cm2. Scanning electron microscopy and photoluminescence reveal that Nafion can also be used to passivate the surface of c-Si solar cell fragments scribed from a solar cell module by using a laser. Consistent with previous studies, analysis of the EPR spectroscopy data confirms that the H-terminated surface is necessary, and fixed negative charge in Nafion is responsible for the field-effect passivation. While the surface passivation quality was maintained for almost 24 h, which is sufficient for spectroscopic measurements, the passivation degraded over longer durations, which can be attributed to surface SiOx growth. These results show that Nafion is a promising room-temperature surface passivation technique to study bulk defects in c-Si.

Epitaxial AlN film with improved quality on Si (111) substrates realized by boron pretreatment via MOCVD

This study investigated the growth of AlN epitaxial films on 2-in. Si(111) via metal-organic chemical vapor deposition. By introducing triethylboron (TEB) during trimethylaluminum pretreatment, a nearly crack free AlN epilayer with a thickness of 500 nm was acquired. The x-ray diffraction rocking curves of AlN (002) and (102) exhibited full width at half maximum values of 0.22° and 0.36°, respectively. Atomic force microscopy image analysis showed that after the introduction of TEB, larger grains appeared on the surface of Si(111) substrate, promoting the 3D growth pattern of the subsequent AlN buffer layer. Laytec reflection curves depicted the morphological transition from 3D to 2D growth mode during AlN deposition. At the same time, the curvature value was significantly reduced by 20 km−1, and the Raman spectrum peak of E2(high) shifted from 648.7 to 652.5 cm−1, indicating that the surface tensile stress was greatly reduced, effectively suppressing the crack problem of AlN on Si(111).

The fate of graphene on copper: Intercalation / de-intercalation processes and the role of silicon

Intercalation and de-intercalation processes below graphene (g) grown by chemical vapor deposition (CVD) on Cu foils (g/Cu) were investigated in a combined low-energy electron microscopy and X-ray photoemission electron microscopy study. Exposure of g/Cu to air induces oxygen and water intercalation which can be removed by annealing in vacuum leading to clean and well-ordered graphene on Cu. However, prolonged air exposure leads to intercalation of large amounts of oxygen, most likely inducing the formation of copper oxides. If sufficient intercalated oxygen remains at the interface when exceeding 320 °C, graphene is oxidized and burned off. Cu foils can be loaded with silicon on purpose during foil pre-treatment or accidently during long growth time when applying high temperatures at elevated H2 pressure inducing the reactive removal of Si species from the quartz reactor wall. Due to the dissolution of Si in the Cu bulk, the Si surface concentration remains below detection limit and graphene of equal crystalline quality is grown as if the Cu foil was silicon-free. However, oxygen intercalation underneath graphene on Si-containing Cu foils can induce Si segregation towards the surface and formation of intercalated silica without attacking the covering graphene. Even at high temperatures, segregating Si acts as oxygen scavenger so that graphene resists oxidation. The observed effect explains the usefulness of certain synthesis protocols and paves the way towards large-scale fabrication of electronically decoupled graphene. The effect can be used to immobilize adsorbing oxygen at the interface and image the initial steps of intercalation below graphene in-situ.

Sensitive quantification of the surface Si–OH group in MQ silicone resins by benzoylation and GPC−UV analysis

The content of the Si–OH group markedly affects the physical and chemical properties of MQ silicone resin (MQ) and its secondary processing products. However, current methods for the determination of the Si–OH group are still unsatisfactory due to their insensitivity and inaccuracy. Herein, an accurate analytical method has been developed for the determination of the active Si–OH group in MQ based on benzoylation and GPC–UV analysis. The UV-insensitive Si–OH group in MQ was converted to a UV-sensitive benzoyl group by the benzoylation with p-methoxy benzoyl chloride, which greatly improved its detection sensitivity. The interference of water was also excluded by the introduction of GPC separation. The effect of several derivatization parameters was investigated and optimized, and complete benzoylation of the Si–OH group in MQ was achieved under the optimized experimental parameters. Good linearity was obtained in a range of 0.425–42.5 μg/g for the content of the Si–OH group in MQ, with a correlation coefficient greater than 0.999. Reasonable reproducibility was also obtained, with the intraday RSD (N = 3) of 1.78 % and the interday RSD (3 days) of 3.98 %, respectively. This method has been successfully applied for the determination of the active Si–OH group in several commercial MQs.

Investigating the impact of physical vapour deposition of palladium on electron-irradiated silicon substrates

This study reports on the effect of resistive physical vapour deposition of Pd Schottky contacts on the defects observed in an irradiated n-type Si substrate. Deep-level transient spectroscopy (DLTS) was used in order to investigate the possible defects in Schottky diodes on the n-type Si. In this study the defects present where the diode was deposited first and then irradiated (“post irradiated”) were compared to those present where the substrate was irradiated first, and the Pd deposited after irradiation (“pre-irradiated”). In the post-irradiated material, the familiar radiation-induced defects were observed. However, in the pre-irradiated material, fourteen new defects were observed, with DLTS signatures differing from those of the defects in the post-irradiated diodes. The newly identified defects seemed to be specifically caused by the deposition of Pd contacts after irradiation of the substrate, as these defects were not observed when other metals such as Au, Ni, Al and Ag were deposited after irradiation. In this paper, we will refer to the observed effect that Pd deposition replaced the familiar radiation-induced defects in Si with the new set of defects as the “Pd effect”. Careful experiments ruled out annealing due to inadvertent heating of the sample during deposition as a possible cause. Care was taken to avoid all sources of contamination: The effect was observed for different sources of Pd and crucibles. This effect was inhibited by the presence of a thin intermediate layer of Pd or Au deposited before irradiation. We therefore conclude that the effect is only observed when Pd is deposited directly onto the irradiated Si surface. Out of the fourteen newly observed defects, four defects, with activation energy of 182, 220, 360 and 607 meV, had DLTS signatures corresponding to those of defects previously observed in Pd-containing Si. For the rest of the defects, no defects with similar DLTS signatures were found in literature. We therefore believe that the defects observed are produced by defect enhanced diffusion of Pd. Overall, the study enhances our understanding of defect behaviour in silicon-based devices, particularly under irradiation and metal deposition conditions, and reveals the unique properties and effects of Pd.

Fundamental Origin of Si Surface Defects Caused by Laser Irradiation and Prevention of Suboxide Formation through High Density Ultrathin SiO2

This research investigates surface damage in electronic devices from laser irradiation, particularly focusing on voids, cracks, and vacancies. We discovered that applying a high-density ultrathin SiO2 layer effectively prevents such defects. Atomic Force Microscopy (AFM) analysis showed a significant reduction in surface roughness, with the Rq factor value dropping to 0.158 nm in samples coated with this SiO2 layer. Additionally, X-ray Photoelectron Spectroscopy (XPS) was used to study suboxide formation in the Al2O3/Si structure, revealing insights into defect origins. Electrical tests indicated a substantial decrease in laser-induced damage, evidenced by a leakage current density reduction to 2.4 × 10−6 A/cm2, markedly lower than uncoated samples. Post-metallization annealing (PMA) further improved results, with the interface state density decreasing to 0.63 × 1012 atoms eV−1 cm−2. Our findings highlight the effectiveness of the high-density ultrathin SiO2 layer in mitigating surface defects caused by continuous wave (CW) laser irradiation, promising significant advancements in electronic device manufacturing through potential application in CW laser annealing processes.

Impact of intermittent sputtering on the ordering of triangular surface topography

It is demonstrated that the quality of nanoscale triangular structures on Si (100) surfaces can be improved by applying intermittent ion beam sputtering. This investigation is conducted along the work of Rakhi et al. (2023), which introduces an additional physical parameter space related to intermittent sputtering. Through this approach, we have observed the minimum surface defect density associated with higher-order surface structures, particularly at tT = 8 min. This can have large potential applications in modern cutting-edge technology demands of controlled growth of nanostructures, especially the low dimensional high aspect ratio nanostructures.

Critical behavior of the dimerized Si(001) surface: Continuous order-disorder phase transition in the two-dimensional Ising universality class

Critical behavior of the dimerized Si(001) surface: Continuous order-disorder phase transition in the two-dimensional Ising universality class

Influence of Cerium Oxide Abrasive Particle Morphologies on Polishing Performance

AbstractIn this study, two morphologies of cerium oxide (CeO2) abrasive particles, octahedral and spheroidal, are synthesized by solvothermal method using cerium nitrate hexahydrate (Ce(NO3)3‐6H2O) as raw material. Fourier infrared spectroscopy, X‐ray diffractometer (XRD) and scanning electron microscopy (SEM) are used to characterize the composition and morphology of CeO2 abrasive particles. The synthesized CeO2 is used for chemical mechanical polishing (CMP) of the Si surface of 6H‐SiC wafers, and the surface morphology of the polished wafers are observed using atomic force microscopy (AFM). After polishing with octahedral and spheroidal abrasive particles, the surface roughness of the wafers are 0.327 and 0.287 nm, and the material removal rates (MRR) are 870 and 742 nm h−1, respectively. Calculations comparing the ultraviolet absorption spectra and bandgap energies of the two types of abrasive particles as well as molecular dynamics (MD) simulations reveal that the synthesized octahedral CeO2 particles possessed stronger surface chemical activity and material removal performance.