Thomas Defforge

Plasma-deposited fluoropolymer film mask for local porous silicon formation

The study of an innovative fluoropolymer masking layer for silicon anodization is proposed. Due to its high chemical resistance to hydrofluoric acid even under anodic bias, this thin film deposited by plasma has allowed the formation of deep porous silicon regions patterned on the silicon wafer. Unlike most of other masks, fluoropolymer removal after electrochemical etching is rapid and does not alter the porous layer. Local porous regions were thus fabricated both in p+-type and low-doped n-type silicon substrates.

Enhanced quantum yield of photoluminescent porous silicon prepared by supercritical drying

The effect of supercritical drying (SCD) on the preparation of porous silicon (pSi) powders has been investigated in terms of photoluminescence (PL) efficiency. Since the pSi contains closely spaced and possibly interconnected Si nanocrystals (<5 nm), pore collapse and morphological changes within the nanocrystalline structure after common drying processes can affect PL efficiency. We report the highly beneficial effects of using SCD for preparation of photoluminescent pSi powders. Significantly higher surface areas and pore volumes have been realized by utilizing SCD (with CO2 solvent) instead of air-drying. Correspondingly, the pSi powders better retain the porous structure and the nano-sized silicon grains, thus minimizing the formation of non-radiative defects during liquid evaporation (air drying). The SCD process also minimizes capillary-stress induced contact of neighboring nanocrystals, resulting in lower exciton migration levels within the network. A significant enhancement of the PL quantum yiel...

In situ investigation of mesoporous silicon oxidation kinetics using infrared emittance spectroscopy.

In this paper, we study the thermal oxidation kinetics of mesoporous silicon layers, synthesized by electrochemical anodization, from 260 °C up to 1100 °C. A specific apparatus is employed to heat the mesoporous samples in air and to record at the same time their infrared emittance. Based on Bruggeman effective medium approximation, an optical model is set up to realistically approximate the dielectric function of the porous material with an emphasis on the surface chemistry and oxide content. A transition temperature of 600 °C is evidenced from data processing which gives evidence of two oxidation mechanisms with distinct kinetics. Between 260-600 °C, the oxidation is surface-limited with kinetics dependent on the hydrogen desorption rate. However, above 600 °C, the oxide growth is limited by oxygen diffusion through the existing oxide layer. A parabolic law is employed to fit the oxidation rate and to extract the high-temperature activation energy (EA = 1.5 eV). A precise control of the oxide growth can thus be achieved.

Investigation of direct current electrical properties of electrochemically etched mesoporous silicon carbide

In this study, we show I-V characterizations of various metal/porous silicon carbide (pSiC)/silicon carbide (SiC) structures. SiC wafers were electrochemically etched from the Si and C faces in the dark or under UV lighting leading to different pSiC morphologies. In the case of low porosity pSiC etched in the dark, the I-V characteristics were found to be almost linear and the extracted resistivities of pSiC were around 1.5 × 104 Ω cm at 30 °C for the Si face. This is around 6 orders of magnitude higher than the resistivity of doped SiC wafers. In the range of 20-200 °C, the activation energy was around 50 meV. pSiC obtained from the C face was less porous and the measured average resistivity was 10 Ω cm. In the case high porosity pSiC etched under UV illumination, the resistivity was found to be much higher, around 1014 Ω cm at room temperature. In this case, the extracted activation energy was estimated to be 290 meV.

Copper-selective electrochemical filling of macropore arrays for through-silicon via applications

In this article, the physico-chemical and electrochemical conditions of through-silicon via formation were studied. First, macropore arrays were etched through a low doped n-type silicon wafer by anodization under illumination into a hydrofluoric acid-based electrolyte. After electrochemical etching, ‘almost’ through-silicon macropores were locally opened by a backside photolithographic process followed by anisotropic etching. The 450 × 450-μm² opened areas were then selectively filled with copper by a potentiostatic electrochemical deposition. Using this process, high density conductive via (4.5 × 105 cm−²) was carried out. The conductive paths were then electrically characterized, and a resistance equal to 32 mΩ/copper-filled macropore was determined.

In-depth porosity control of mesoporous silicon layers by an anodization current adjustment

The formation of thick mesoporous silicon layers in P+-type substrates leads to an increase in the porosity from the surface to the interface with silicon. The adjustment of the current density during the electrochemical etching of porous silicon is an intuitive way to control the layer in-depth porosity. The duration and the current density during the anodization were varied to empirically model porosity variations with layer thickness and build a database. Current density profiles were extracted from the model in order to etch layer with in-depth control porosity. As a proof of principle, an 80 μm-thick porous silicon multilayer was synthetized with decreasing porosities from 55% to 35%. The results show that the assessment of the in-depth porosity could be significantly enhanced by taking into account the pure chemical etching of the layer in the hydrofluoric acid-based electrolyte.

Porous silicon formation by hole injection from a back side p+/n junction for electrical insulation applications

In this paper, we propose to study the formation of porous silicon (PS) in low doped (1 × 1014 cm−3) n-type silicon through hole injection from a back side p+/n junction in the dark. This technique is investigated within the framework of electrical insulation. Three different types of junctions are investigated. The first one is an epitaxial n-type layer grown on p+ doped silicon wafer. The two other junctions are carried out by boron diffusion leading to p+ regions with junction depths of 20 and 115 μm. The resulting PS morphology is a double layer with a nucleation layer (NL) and macropores fully filled with mesoporous material. This result is unusual for low doped n-type silicon. Morphology variations are described depending on the junction formation process, the electrolyte composition, the anodization current density and duration. In order to validate the more interesting industrial potentialities of the p+/n injection technique, a comparison is achieved with back side illumination in terms of resulting morphology and experiments confirm comparable results. Electrical characterizations of the double layer, including NL and fully filled macropores, are then performed. To our knowledge, this is the first electrical investigation in low doped n type silicon with this morphology. Compared to the bulk silicon, the measured electrical resistivities are 6–7 orders of magnitude higher at 373 K.

Optimized plasma-polymerized fluoropolymer mask for local porous silicon formation

Mass production of hybrid silicon/porous silicon substrates requires a simple, low-cost, and reliable patterning process to locally form porous regions on silicon wafers. An innovative masking technology based on plasma-polymerized fluoropolymer (PPFP) has been proposed as a promising candidate. However, the use of PPFP film on silicon substrate requires an adhesion promoter which may cause several side effects, including film peeling-off and pinhole formation. This work aims to improve the adhesion strength without using the adhesion promoter. The present study shows that, by adopting a hydrogen-terminated surface and an optimized gas precursor composition of 25/25 sccm CHF3/C2H4, good adhesion of PPFP to silicon is obtained before and during porous silicon formation. PPFP mask deposited at high pressure shows well-defined borders after anodization. Finally, an optimized PPFP-based patterning process is proposed.

Shape-controlled electrochemical synthesis of mesoporous Si/Fe nanocomposites with tailored ferromagnetic properties

This study reports on an original and efficient way to synthesize iron nanowires and cubic-shaped nanoparticles by electrochemical deposition on a mesoporous silicon host and its impact on magnetic properties. The selective growth of iron nanostructures inside the pores can be achieved, thanks to the presence of a native oxide layer on the pore walls, suggesting a surface-state assisted electrochemical process. Because of hydrogen coevolution, the pH of the solution controls the shape of the iron nanostructures (particles or wires) while the electrodeposition current density can be adjusted to suppress the parasitic deposition on top of the structure. Under optimal conditions, nanowires with lengths up to 2 μm are synthesized after 15 seconds of deposition. Magnetic characterization of the ferromagnetic nanowire composite exhibits an easy axis of magnetization in the pore direction due to shape anisotropy with a remanence ratio of 0.6. The shape anisotropy of the nanoparticle composite is weaker than for the nanowire composite because of the homogeneous dispersion of the particles. The versatility of the mesoporous silicon framework is thus a considerable asset to tune the nanocomposite’s magnetic properties.

Elaboration of high aspect ratio monocrystalline silicon suspended nanobridges by low temperature alkaline treatment of dry etched trenches

This paper describes the elaboration of high aspect ratio (250), high linear density (500 cm−1) suspended silicon nanobridges into low concentrated alkaline solutions. Trenches were first etched into silicon using the deep reactive ion etching STiGer process. These structures were immersed into low concentrated potassium hydroxide (KOH) or tetramethylammonium hydroxide (TMAH) solutions. The behaviors of KOH and TMAH as silicon trenches etching agents (kinetic and quality of etching) were studied to optimize the silicon nanowires (SiNWs) formation and the elaboration of the suspended structures. The limits of the SiNWs thickness in these conditions were also discussed.