Flat Silicon Substrates Research Articles

In silico monitoring of non-reactive gas blistering on crystalline substrates

Blistering from gas aggregation occurs very rarely on solid substrates; however, it is commonly observed under high-pressure gas or plasma environments. This is due to the repeated aggregation process of gas molecules penetrating beneath the surface, but it has been difficult to find cases that demonstrate the dynamic mechanism on the atomic level. In this study, the dynamics of physical bombardment of argon atoms on the flat monocrystalline silicon substrate are simulated to propose an initiation principle for gas-aggregate formation. Simulations of extremely large numbers of argon atoms bombarding a limited area of single crystal silicon revealed inhomogeneous aggregation properties consistent with the experimental observations. Particularly, the results suggest that momentum transfer formed by collisions between argon trapped in the surface grooves and the argon used for bombardment is the governing factor for the aggregation behavior. The aggregated argon clusters grow in the in-plane direction while generating stress propagation in the thickness direction, ultimately causing an expansion pressure that lifts the adjacent silicon surface upwards. Our work provides a deterministic understanding of the initiation process of blister formation, which rarely occurs in physical sputtering on defect-free substrates.

Bottom-Illuminated Photothermal Nanoscale Chemical Imaging with a Flat Silicon ATR in Air and Liquid.

We demonstrate a novel approach for bottom-illuminated atomic force microscopy and infrared spectroscopy (AFM-IR). Bottom-illuminated AFM-IR for measurements in liquids makes use of an attenuated total reflection setup where the developing evanescent wave is responsible for photothermal excitation of the sample of interest. Conventional bottom-illuminated measurements are conducted using high-refractive-index prisms. We showcase the advancement of instrumentation through the introduction of flat silicon substrates as replacements for prisms. We illustrate the feasibility of this technique for bottom-illuminated AFM-IR in both air and liquid. We also show how modern rapid prototyping technologies enable commercial AFM-IR instrumentation to accept these new substrates. This new approach paves the way for a wide range of experiments since virtually any established protocol for Si surface functionalization can be applied to this sample carrier. Furthermore, the low unit cost enables the rapid iteration of experiments.

Oxidation resistance and mechanical properties of AlTiZrHfTa(-N) high entropy films deposited by reactive magnetron sputtering

(AlTiZrHfTa)1−xNx refractory high entropy films (RHEFs) were deposited by direct current magnetron sputtering in various nitrogen ratios (RN2 = N2/(Ar+N2)) on flat glass, silicon and sapphire substrates. The nitrogen-free film is amorphous while the nitrides are single-phased solid solutions with Face-Centered Cubic (FCC) structures. The hardness increases from 6.4 GPa for the nitrogen-free film to 25.3 GPa for the film obtained at RN2 = 20%. A preferred orientation from (111) to (200) occurs when RN2 increases from 5% to 50%. H/E and H3/H2 reports show high values for the film deposited at RN2 = 20% compared to that at 10%. However, this latter has the best compromise in terms of mechanical properties related to a lower residual stress value. The nitrides films obtained with RN2 ≥ 5%, are thermally stable at 800 °C for 3 h under vacuum. Compared to the metallic film they show an improved oxidation resistance. In fact, the Kp constant of the nitride (RN2=20%) is lower (1.22 10−7 g2 cm−4 h−1) than that of the nitrogen-free film (1.77 10−6 g2 cm−4 h−1). The corresponding activation energies (Ea) are respectively calculated at 94.8 KJ. mol−1 and 45.5 KJ.mol−1. After oxidation process, TEM analysis reveal the formation of homogeneous mixed oxide.

Competitive Adsorption of a Monoclonal Antibody and Nonionic Surfactant at the PDMS/Water Interface.

Interfacial adsorption of monoclonal antibodies (mAbs) can cause structural deformation and induce undesired aggregation and precipitation. Nonionic surfactants are often added to reduce interfacial adsorption of mAbs which may occur during manufacturing, storage, and/or administration. As mAbs are commonly manufactured into ready-to-use syringes coated with silicone oil to improve lubrication, it is important to understand how an mAb, nonionic surfactant, and silicone oil interact at the oil/water interface. In this work, we have coated a polydimethylsiloxane (PDMS) nanofilm onto an optically flat silicon substrate to facilitate the measurements of adsorption of a model mAb, COE-3, and a commercial nonionic surfactant, polysorbate 80 (PS-80), at the siliconized PDMS/water interface using spectroscopic ellipsometry and neutron reflection. Compared to the uncoated SiO2 surface (mimicking glass), COE-3 adsorption to the PDMS surface was substantially reduced, and the adsorbed layer was characterized by the dense but thin inner layer of 16 Å and an outer diffuse layer of 20 Å, indicating structural deformation. When PS-80 was exposed to the pre-adsorbed COE-3 surface, it removed 60 wt % of COE-3 and formed a co-adsorbed layer with a similar total thickness of 36 Å. When PS-80 was injected first or as a mixture with COE-3, it completely prevented COE-3 adsorption. These findings reveal the hydrophobic nature of the PDMS surface and confirm the inhibitory role of the nonionic surfactant in preventing COE-3 adsorption at the PDMS/water interface.

Photoelectrochemical properties of Cu2O/PANI/Si-based photocathodes for CO2 conversion

The present study was aimed at converting carbon dioxide (CO2) into value-added products such as methanol, which can provide not only a potential solution for controlling the carbon dioxide concentration level in the atmosphere but also can offer an alternative approach for the production of renewable energy sources. From this perspective, various hybrid photoelectrocatalysts were synthesized, characterized and used as photocathodes for photoelectrochemical (PEC) reduction of carbon dioxide to methanol in an aqueous medium under visible light irradiation. Flat silicon (Si) and pyramidal textured silicon (SiPY) substrates, covered with polyaniline (PANI) with or without sensitization with copper (I) oxide (Cu2O) particles, were investigated. It was observed that the combination of PANI and copper (I) oxide greatly increased PEC carbon dioxide reduction to methanol owing to the enhancement in the carbon dioxide chemisorption capacity by the photocathode surface and at the same time facilitated the separation of photogenerated electron–hole (e−/h+) pairs. The PEC results demonstrated that the applied potential impacts the photocurrent stability. Sensitization with copper (I) oxide effectively separated the photogenerated e−/h+ pairs and, therefore, enhanced the PEC carbon dioxide reduction activity of the hybrid photocatalyst. The best faradaic efficiency for methanol formation reached 57.66%, which was recorded when the copper (I) oxide/PANI/SiPY heterostructure was used as a photocathode at an applied potential of −1.2 V against the saturated calomel electrode.

Vertical nanowires enhanced X-ray radiation damage of cells

Cell behavior is affected by nanostructured surface, but it remains unknown how ionizing radiation affects cells on nanostructured surface. This paper reports an experimental investigation of X-ray radiation induced damage of cells placed on an array of vertically aligned silicon nanowires. X-ray photoelectrons and secondary electrons produced from nanowire array are measured and compared to those from flat silicon substrate. The cell functions including morphology, viability, adhesion and proliferation have been examined and found to be drastically affected when cells are exposed to X-ray radiation, compared to those sitting on flat substrate and those only exposed to X-ray. The enhanced cell damage on nanowires upon X-ray exposure is attributed to nanowire enhanced production of photoelectrons including Auger electrons and secondary electrons, which have high escaping probability from sharp tips of nanowires. The escaped photoelectrons ionize water molecules and generate hydroxyl free radicals that can damage DNAs of cells. An inference of this work is that the contrast in scanning electron microscopy is useful in assessing the effects of nanomaterials for enhanced X-ray radiation therapy.

Composite Norland Optical Adhesive (NOA)/silicon flow focusing devices for colloidal particle manipulation and synthesis

Microfluidic flow focusing devices are widely used to generate steep chemical concentration gradients at the interface between miscible or partially miscible streams. In this study, first we present an optimised protocol for the manufacturing of composite flow focusing devices, consisting of a micropatterned layer of Norland Optical Adhesive (NOA) glue bound to flat or microgrooved silicon substrates. Then, three different applications of these devices are demonstrated, namely (i) particle spreading and focusing in continuous flows past flat substrates, (ii) particle accumulation within the dead-end cavities of microgrooved substrates and (iii) synthesis of nano-sized liposomes. Colloidal particle spreading, focusing and accumulation were achieved through diffusiophoresis transport induced by salt concentration gradients at the interface between electrolyte streams. Epi-fluorescence microscopy was adopted to characterise the spatio-temporal distribution of silica and polystyrene nanoparticles in the devices with flat or microgrooved surfaces. The effects of particle zeta potential and groove thickness on particle dynamics were investigated. 1,2-di-(9Z-octadecenoyl)-sn-glycero-3-phosphocholine (DOPC) liposomes were generated by hydrodynamic focusing and characterised via dynamic light scattering. Liposome populations with controlled narrow size distributions could be achieved by adjusting the flow rate conditions in the devices. This work demonstrates that composite NOA/silicon flow junction devices offer a competitive alternative to conventional PDMS chips and can support a wide range of microfluidic applications, including nanoparticle synthesis, characterisation and filtration, drug encapsulation and biochemical analysis.

Study on total reflection performance of films grown by atomic layer deposition relevant to X-ray reflective optics.

For X-ray reflective optics that work based on the concept of total external reflection, coating the reflector surface with high-density film is a common idea to enhance performance. Atomic layer deposition (ALD) has been proven to be a promising way to coat the reflector surface with a large curvature, even the inner surface of an X-ray capillary. In this paper, HfO2 and iridium films were prepared on flat silicon and glass substrates via ALD, and X-ray reflectivity (XRR) was used as a main tool to investigate the effect of film properties on the total reflection performance.

Atomic layer deposition of titanium phosphate onto reinforcing fibers using titanium tetrachloride, water, and tris(trimethylsilyl) phosphate as precursors

A thermal atomic layer deposition process with precursors tris(trimethylsilyl) phosphate (TTMSP), titanium tetrachloride (TiCl4), and water was used with various pulse sequences in order to deposit titanium phosphate onto bundles of carbon fibers (diameter of one filament = 7 μm, 6000 filaments per bundle) and flat silicon substrates. Pulse sequence 1, TTMSP/N2/TiCl4/N2, which comprises no water, yields no significant deposition. Pulse sequence 2, TTMSP/N2/H2O/N2/TiCl4/N2, which comprises a water pulse, yields a mixed phosphate/oxide coating and shows a self-limiting character at 200 °C with a growth per cycle of 0.22 nm cycle−1. Wet chemical analysis of the coating revealed a ratio of Ti:P between 3:1 and 2:1 in reasonable agreement with the composition Ti2.4P1O7 obtained from X-ray photoelectron spectroscopy. Thus, the deposited material can approximately be described as a mixture of Ti¾PO4 and TiO2 in a molar ratio of 1:1.5. The coating shifts the temperature of the onset of oxidation—3% weight loss in thermogravimetry—of the carbon fibers from 630 °C (uncoated C-fiber) to 750 °C (with the titanium phosphate coating).

Low-Field Electron Emission Capability of Thin Films on Flat Silicon Substrates: Experiments with Mo and General Model for Refractory Metals and Carbon.

Herein, we describe a study of the phenomenon of field-induced electron emission from thin films deposited on flat Si substrates. Films of Mo with an effective thickness of 6–10 nm showed room-temperature low-field emissivity; a 100 nA current was extracted at macroscopic field magnitudes as low as 1.4–3.7 V/μm. This result was achieved after formation treatment of the samples by combined action of elevated temperatures (100–600 °C) and the electric field. Morphology of the films was assessed by AFM, SEM, and STM/STS methods before and after the emission tests. The images showed that forming treatment and emission experiments resulted in the appearance of numerous defects at the initially continuous and smooth films; in some regions, the Mo layer was found to consist of separate nanosized islets. Film structure reconstruction (dewetting) was apparently induced by emission-related factors, such as local heating and/or ion irradiation. These results were compared with our previous data obtained in experiments with carbon islet films of similar average thickness deposited onto identical substrates. On this basis, we suggest a novel model of emission mechanism that might be common for thin films of carbon and refractory metals. The model combines elements of the well-known patch field, multiple barriers, and thermoelectric models of low-macroscopic-field electron emission from electrically nanostructured heterogeneous materials.

Covalently formation of insulation and barrier layers in high aspect ratio TSVs

Polymers have been widely explored as the alternative material for silicon oxide in through-silicon vias (TSVs). However, an acceptable adhesion between polymers and metallic diffusion barriers is often challenging, especially when it comes to ultrathin films with extremely low roughness. This paper proposes a cost-effective and highly reliable wet deposition path to successively fabricate polyacrylic acid (PAA) insulation films and nickel diffusion barriers on the silicon substrate. PAA films were firstly pretreated to form diazo functional groups through aryldiazonium chemistry. With an electrochemical reduction, catalytic palladium nanoparticles and palladium chelates were introduced to the pretreated substrate by robust Pd-C covalent bonds and electrostatic interaction, respectively. After being immersed into the plating solution, a continuous and uniform nickel layer on the PAA substrate with high adhesion strength can be obtained. Therefore, a stable interface between polymer insulation layers and nickel diffusion barrier can be provided by the proposed covalent fabrication approach. This wet polymer metallization approach on the flat silicon substrate was further extended in TSVs (3 μm × 30 μm) for practical deployment.

Creating Quantum Emitters in Hexagonal Boron Nitride Deterministically on Chip-Compatible Substrates

Two-dimensional hexagonal boron nitride (hBN) that hosts room-temperature single-photon emitters (SPEs) is promising for quantum information applications. An important step toward the practical application of hBN is the on-demand, position-controlled generation of SPEs. Strategies reported for deterministic creation of hBN SPEs either rely on substrate nanopatterning that is not compatible with integrated photonics or utilize radiation sources that might introduce unpredictable damage or contamination to hBN. Here, we report a radiation- and lithography-free route to deterministically activate hBN SPEs by nanoindentation with atomic force microscopy (AFM). The method applies to hBN flakes on flat silicon dioxide-silicon substrates that can be readily integrated into on-chip photonic devices. The achieved SPE yields are above 30% for multiple indent sizes, and a maximum yield of 36% is demonstrated for indents around 400 nm. Our results mark an important step toward the deterministic creation and integration of hBN SPEs with photonic and plasmonic devices.

Fluorescence Signal Enhancement in Antibody Microarrays Using Lightguiding Nanowires.

Fluorescence-based detection assays play an essential role in the life sciences and medicine. To offer better detection sensitivity and lower limits of detection (LOD), there is a growing need for novel platforms with an improved readout capacity. In this context, substrates containing semiconductor nanowires may offer significant advantages, due to their proven light-emission enhancing, waveguiding properties, and increased surface area. To demonstrate and evaluate the potential of such nanowires in the context of diagnostic assays, we have in this work adopted a well-established single-chain fragment antibody-based assay, based on a protocol previously designed for biomarker detection using planar microarrays, to freestanding, SiO2-coated gallium phosphide nanowires. The assay was used for the detection of protein biomarkers in highly complex human serum at high dilution. The signal quality was quantified and compared with results obtained on conventional flat silicon and plastic substrates used in the established microarray applications. Our results show that using the nanowire-sensor platform in combination with conventional readout methods, improves the signal intensity, contrast, and signal-to-noise by more than one order of magnitude compared to flat surfaces. The results confirm the potential of lightguiding nanowires for signal enhancement and their capacity to improve the LOD of standard diagnostic assays.

Influence of PLGA nanoparticles on the deposition of model water-soluble biocompatible polymers by dip coating

This work relies on the use of dip-coating at various withdrawal speeds to form nanocomposite films, with a detailed analysis of the influence of the mode of deposition on the nanoparticle (NP) concentration in the dried film. While the deposition of polymer solutions on the one hand and colloidal suspensions of NPs on the other hand have been separately studied by dip coating, their combination is far being a simple superposition of the two separate behaviors. The formation of nanocomposite thin films composed of model water-soluble biocompatible polymers (polyvinyl alcohol - PVA and polyvinylpyrrolidone - PVP) loaded with poly(lactic-co-glycolic acid) (PLGA) nanoparticles (NPs) was studied through a dip coating process. Flat silicon substrates were removed at a controlled withdrawal speed from an aqueous colloidal suspension. Thin films of PLGA NPs with concentrations ranging from 1 to 10 % wt./wt. in PVA or PVP matrices were prepared. The presence of nanoparticles on the well-established process of thin film deposition was examined, as well as the influence of the deposition regime on the nanoparticle concentration in the deposited coating. We demonstrate that the presence of colloidal dispersion of PLGA nanoparticles in water solution of PVA and PVP does not modify the process of film deposition by dip coating. A typical “V” shaped curve was observed, with two well-known deposition regimes: capillary and draining modes respectively obtained at low and high withdrawal speeds. Due to crystallization at low withdrawal speed (favored by slow evaporation of the solvent) it was not possible to identify individual PLGA nanoparticles by AFM in the case of the PVA matrice. Amorphous PVP nanocomposite films were successfully prepared by dip coating, and allowed us to identify individual PLGA nanoparticles with AFM. Because of the prevalence of an evaporation-driven phenomenon at low withdrawal speed, incorporation of NPs was observed over the whole range of withdrawal speeds, showing original behavior compared to recent studies relying on a pure Landau-Levich regime (i.e. non-evaporative systems). Our results indicate that the nanoparticles were not equally retrieved from the solution in the capillary and the draining regimes. This suggests that the balance between the viscous drag and the interfacial effects depends on the deposition mode and calls for a more detailed analysis of the physical processes involved in both regimes.

Impact of Silanization Parameters and Antibody Immobilization Strategy on Binding Capacity of Photonic Ring Resonators.

Ring resonator-based biosensors have found widespread application as the transducing principle in “lab-on-a-chip” platforms due to their sensitivity, small size and support for multiplexed sensing. Their sensitivity is, however, not inherently selective towards biomarkers, and surface functionalization of the sensors is key in transforming the sensitivity to be specific for a particular biomarker. There is currently no consensus on process parameters for optimized functionalization of these sensors. Moreover, the procedures are typically optimized on flat silicon oxide substrates as test systems prior to applying the procedure to the actual sensor. Here we present what is, to our knowledge, the first comparison of optimization of silanization on flat silicon oxide substrates to results of protein capture on sensors where all parameters of two conjugation protocols are tested on both platforms. The conjugation protocols differed in the chosen silanization solvents and protein immobilization strategy. The data show that selection of acetic acid as the solvent in the silanization step generally yields a higher protein binding capacity for C-reactive protein (CRP) onto anti-CRP functionalized ring resonator sensors than using ethanol as the solvent. Furthermore, using the BS3 linker resulted in more consistent protein binding capacity across the silanization parameters tested. Overall, the data indicate that selection of parameters in the silanization and immobilization protocols harbor potential for improved biosensor binding capacity and should therefore be included as an essential part of the biosensor development process.

Fabrication of Silver-Silicon Gratings for Surface Plasmon Excitation Using Nanosecond Laser Interference Lithography

We introduce a new two-step method to fabricate silver-silicon gratings that can excite surface plasmons efficiently. The grating structure was firstly created on a flat silicon substrate by single-pulse nanosecond laser interference lithography. Next, a silver layer of 50 nm was evaporated on the silicon substrate. With proper laser energy, a silver-silicon grating with a period of 1120 nm and depth of 18 nm was successfully fabricated. This grating can produce high-quality surface plasmon resonance (SPR) peaks at various incident angles. Moreover, a SPR sensor was experimentally demonstrated based on the silver-silicon grating, which had high sensitivity of 961.5 nm/RIU and figure of merit of 60. Our method is an efficient way to fabricate periodically nanostructured metals at high speed and low cost.

How does substrate hydrophobicity affect the morphological features of reconstituted wax films and their interactions with nonionic surfactant and pesticide?

HypothesisSurfactants are widely used in agri-sprays to improve pesticide efficiency, but the mechanism underlying their interactions with the surface wax film on plants remains poorly understood. To facilitate physical characterisations, we have reconstituted wheat cuticular wax films onto an optically flat silicon substrate with and without octadecyltrimethoxysilane modification to control surface hydrophobicity. ExperimentsImaging techniques including scanning electron microscopy (SEM) unravelled morphological features of the reconstituted wax films similar to those on leaves, showing little impact from the different substrates used. Neutron reflection (NR) established that reconstituted wax films were comprised of an underlying wax film decorated with top surface wax protrusions, a common feature irrespective of substrate hydrophobicity and highly consistent with what was observed from natural wax films. NR measurements, with the help of isotopic H/D substitutions to modify the scattering contributions of the wax and solvent, revealed different wax regimes within the wax films, illustrating the impact of surface hydrophilicity on the nanostructures within the wax films. FindingsIt was observed from both spectroscopic ellipsometry and NR measurements that wax films formed on the hydrophobic substrate were more robust and durable against attack by nonionic surfactant C12E6 solubilised with pesticide Cyprodinil (CP) than films coated on the bare hydrophilic silica. Thus, the former could be a more feasible model for studying the wax-surfactant-pesticide interactions.

In Situ Study of Layer-by-Layer Polyelectrolyte Deposition in Nanopores of Anodic Aluminum Oxide by Reflectometric Interference Spectroscopy

The modification of cylindrical anodic aluminum oxide (AAO) nanopores by alternating layer-by-layer (LBL) deposition of poly(sodium-4-styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) was studied in situ by reflectometric interference spectroscopy (RIfS). In particular, the kinetics of polyelectrolyte deposition inside the pores with a diameter of 37 ± 3 nm and a length of 3.7 ± 0.3 μm were unraveled, and potential differences in the LBL multilayer growth compared to flat silicon substrates as well as the effect of different ionic strengths and different types of ions were investigated. RIfS measures the effective optical thicknesses, which is-for a constant pore length-proportional to the effective refractive index of the AAO sample, from which, in turn, the deposited mass of the polymer or the corresponding layer thickness can be estimated. Compared to the multilayer growth by the LBL deposition on the flat aminosilane-primed silicon wafers, which was assessed by spectroscopic ellipsometry, the thickness increment per deposited bilayer, as well as the dependence of this increment on the ionic strength (0.01-0.15) and the counterion type (Na+ vs Ca2+) inside the aminosilane-primed nanopores, was for the first bilayers to within the experimental error identical. For thicker multilayers, the pore diameter became smaller, which led to reduced thickness increments and eventually virtually completely filled the pores. The observed kinetics is consistent with the mass-transport-limited adsorption of the polyelectrolyte to the charged surface according to a Langmuir isotherm with a negligible desorption rate. In addition to fundamental insights into the buildup of polyelectrolyte multilayers inside the AAO nanopores, our results highlight the sensitivity of RIfS and its use as an analytical tool for probing processes inside the nanopores and for the development of biosensors.

Development of super-smooth flat silicon mirror substrates using bowl-feed chemical-mechanical polishing

Silicon is one of the important optical substrate materials used for making high reflectivity, high damage threshold mirrors for high power/energy IR lasers and grazing incidence synchrotron X-ray mirrors. These applications require ultra-low roughness or super-smooth substrates that ensure extremely low scattering losses. The present work is an attempt to fabricate super-smooth, flat silicon substrates using the conventional Chemical-Mechanical Polishing (CMP) method with bowl-feed technique. The roughness parameters of the ultra-smooth flat silicon surfaces fabricated using bowl-feed CMP have been measured in Atomic Force Microscope (AFM) and by hard X-Ray Reflectivity (XRR) and are found to be of the order of 5 Å. The surface morphologies of the polished silicon surfaces were also investigated using a Scanning Electron Microscope (SEM). We briefly discuss the bowl-feed CMP process of producing super-smooth, flat silicon substrates and presented the results of surface roughness measurements using various techniques.

Control of tip nanostructure on superhydrophobic shape memory arrays toward reversibly adjusting water adhesion

In this paper, a fresh strategy for superhydrophobic surface adhesion control was advanced, which was demonstrated through tuning the pillar tip nanostructure on a shape memory polymer (SMP) substrate. The micro-/nanostructured pillars show low-adhesive superhydrophobicity. The nanostructure on pillar tips disappears after pressing by a flat silicon substrate and the surface becomes high-adhesive superhydrophobicity. The nanostructure reappears and the surface returns to the initial low-adhesive state with a further heating process. Invertible low/high adhesion switching can be realized by simply controlling the nanostructure on pillar tips, and the smart controllability can be explained by the polymer’s shape memory effect (SME), based on which, different surface microstructure shapes and corresponding different solid/liquid contact states can be obtained. The work reports smart surface adhesion control through dynamically tuning the surface structure in the nanoscale on SMP. The results can provide a novel method for design of smart superhydrophobic surfaces and further improved the insight into the action of nanostructure on surface wetting/adhesion.