Stimuli-responsive nanostructured surfaces

The coupling of stimuli-responsive macromolecules to nanostructured surfaces opens the perspective for the fabrication and integration of "smart" micro- and nano-electro-mechanical systems (MEMS&NEMS) in which the smallest motile unit is the polymeric chain. The goal of this work was to develop thermoresponsive, durable nanoporous surfaces as a first step toward the fabrication of functional nanocontainers and nanovalves. The proposed strategy involves in a first step the design and implementation of a clean-room compatible, reproducible and up-scalable method for defining organized nanoporous arrays in MEMS compatible surfaces, such as silicon, silicon oxide and silicon nitride. The main objective of the second step was the covalent immobilization of responsive macromolecules on the obtained structures, as to provide the later with a "smart" behavior. The nanostructuring step was realized by block-copolymer assisted lithography. This newly developed technique enables the definition of nanoscale features on semiconductor substrates over large surface areas and in a cost effective manner. A novel method for patterning thin metal films by a lift-off approach, using spin coated block-copolymer micelles monolayers as a template, was investigated. The obtained nanoporous mask was used as resist for the structuring of hard substrates in plasma-assisted processes and structures with aspect ratios as high as 1:10 were be obtained. By using different block-copolymer micelles and spin-coating conditions, the proposed approach enables the variation of the nanopores' diameter from 40 to 80 nm and a surface coverage between 11.7% and 25.5 % in an independent manner. This technique was successfully integrated in a standard microfabrication process for the batch production of thin nanoporous silicon nitride membranes. The 100 nm thick membranes span over thousands of square micrometers and present porosities higher than 109 pores/cm2. They are thus competitive in terms of porosity with the commercially available polymeric membranes. In addition they are two orders of magnitude thinner than polymeric membranes, this making them extremely interesting for applications where permeation rate or response time is important. The rapid flow of water soluble small molecular species through the nanopores was demonstrated in a qualitative manner in this work. Another series of investigations targeted the functionalization of the available nanoporous surfaces with responsive molecules. Poly(N-isopropyl acrylamide) (PNIPAAM) was chosen as a model system. Its coupling to silicon surfaces by a "grafting-to" approach from melt, using an epoxy-functionalized silane as anchoring layer was studied. The analysis of the yielded grafting density showed results superior to those obtained by classic grafting-to approaches. The relation between the polymer's weight and its responsiveness was investigated in liquid media by atomic force microscopy and by dynamic force spectroscopy. Polymers with more than 500 monomers in the back bone were shown to exhibit enhanced responsiveness. Additionally, two bioengineered polymers from the class of elastin-like polymers (ELPs) were investigated as possible candidates for the fabrication of stimuli responsive nanovalves. The molecules were synthesized in collaboration with the Bioforge group (Universidad de Valladolid, Spain) and details of the bioproduction process are presented. A method for the covalent photoattachment of macromolecules using a benzophenone-functionalized silane, was tested in this work. First the capacity of the benzophenone silane to graft synthetic thermo-responsive polymers such as PNIPAAM was demonstrated. The temperature-induced morphology change of the photografted PNIPAAM was not affected by this anchoring strategy and was monitored by tapping AFM in liquid media. The investigations were then extended to the photo-immobilization of ELPs on nanoporous silicon surfaces and the XPS measurements revealed the success of this step. However no conformation modification of the proteins could be evidenced by tapping-mode AFM in liquid media under different ionic strengths.

On the Powder Formation in the Plasma Enhanced Chemical Vapor Deposition Process for the Deposition of SiOx Barrier Coatings

Marina Ricci

Nowadays thin films play an important role in everyday life and in industries. Thin film technology has been developed primarily for the growing demand for development of smaller and smaller devices that require advanced materials and new processing techniques suitable for micro and nano technology. One of the methods of producing thin films is by means of plasma technology. This is a technique by which plasma, also known as 'the fourth state of matter', is used to generate ions, electrons and radicals which deposit at a surface where they will form a thin film. The source of these depositing species could be either gaseous, liquid or solid in origin. Most of the time a plasma is generated by means of an electrical discharge. Plasma technologies are used for various applications. One of these is Plasma Enhanced Chemical Vapor Deposition (PECVD). PECVD systems have widespread applications in the electronic sector, because of their exibility in depositing different films such as silicon oxide thin films (SiOx). These films, currently deposited by organosilicon compounds, such as hexamethyldisiloxane (HMDSO), have dielectric and good barrier properties. The aim of the work at CRPP consists in optimizing PECVD processes for the deposition of these films on polymers. In this study, the species in gaseous phase and the powder produced in oxygen-diluted HMDSO plasmas were experimentally characterized in a radiofrequency (RF) capacitively-coupled reactor at 13.56 MHz. The gaseous phase of these plasmas and the particle formation were studied by in-situ infrared absorption spectroscopy and optical emission spectroscopy. The study of the powder formation is important because the particle deposition imposes an upper limit on the deposition rate. Particle formation was firstly studied as a function of HMDSO/O2 ratio. Analysis of the time evolution of the infrared absorption spectra gives the development of the size, the number density, the structure and the particle composition. At high oxygen dilution the formation of large particles is observed. The analysis of HMDSO/O2 plasma at low O2 content suggests that at the beginning of the process very small particles are formed by polymerization; the same particles do not grow much and keep sizes around 50 nm. The admixture of inert or non-reactant gases, such as Ar or N2, into the plasma promotes polymerization of the monomer; a high value of one of these inert or non-reactant gases leads to small powder particle size, since only polymerization takes place in this case. Particle size around 50 nm is also found in this case. At the same time we see a decrease of the carbon content and a weak reduction of the stoichiometry in SiOx indicated by the shift of the SiOSi asymmetric stretching vibration. This reduction also influences the deposited layers, less oxidized and, thus, quite far from a stoichiometric character. Hexamethyldisilazane (HMDSN) and tetramethylsilane (TMS) are other reagents that have been identified as alternatives to HMDSO. The in-situ infrared absorption spectra show that HMDSO/O2 and HMDSN/O2 plasmas are quite similar, but in the second case a lower SiOSi stretching peak intensity, due to NH and SiN peaks, is seen. TMS/O2 and HMDSN/O2 plasma spectra show a low SiOSi bending and stretching peak intensity, due also to the oxygen atom absence in their chemical structure. Two separate chapters are respectively devoted to the silicon nitride thin films (SiNx) and plasma crystal formation. SiNx layers are deposited by three different organosilicon compounds, such as HMDSN, TMS and bis(dimethylamino)dimethylsilane (BDMADMS). No powder formation is visualized in this contest. The ex-situ infrared absorption spectra show the difficulty to produce stable SiNx films; they present a low SiN peak intensity and are quite hygroscopic. Furthermore, in HMDSO/O2 plasmas at high oxygen dilution and high pressure, later in time into the discharge, accretion leads to larger and larger particles which can finish up in particles forming a plasma crystal. The study of RF harmonics shows the presence of instabilities, clear indications of the passage from small particulate to plasma crystal structure.

EPFL2011

Design and fabrication of suspended-gate MOSFETs for MEMS resonator, switch and memory applications

Nicolas Abelé

Wireless communication systems and handset devices are showing a rapid growth in consumer and military applications. Applications using wireless communication standards such as personal connectivity devices (Bluetooth), mobile systems (GSM, UMTS, WCDMA) and wireless sensor network are the opportunities and challenges for the semi-conductor industry. The trend towards size and weight reduction, low power consumption and increased functionalities induces major technological issues. Today, the wireless circuit size is limited by the use of lots of external or "off-chip" components. Among them, quartz crystal, used as the time reference in any wireless systems, is the bottleneck of the miniaturization. Microelectromechanical systems (MEMS) is an emerging technology which has the capability of replacing the quartz. Based on similar technology than the Integrated Circuit (IC), MEMS are referred as electrostatically, thermally or piezoelectrically actuated mechanical structures. In this thesis, a new MEMS device based on the hybridization of a mechanical vibrating structure and a solid-sate MOS transistor has been developed. The Resonant Suspended-Gate MOSFET (RSG-MOSFET) device combines both advantages of a high mechanical quality factor and the transistor intrinsic gain. The physical mechanisms behind the actuation and the behavior of this device were deeply investigated and a quasi-static model was developed and validated, based on measured characteristics. Furthermore, the dynamic model of the RSG-MOSFET was created, taking into account the non-linear mechanical vibrations of the gate and the EKV model, used for MOSFET modeling. Two fabrication processes were successfully developed to demonstrate the proof of concept of such a device and to optimize the performances respectively. Aluminum-silicon (Al-Si1%) and pure silicon-based RSG-MOSFETs were successfully fabricated. DC and AC characterizations on both devices enabled to understand, extract and evaluate the mechanical and MOSFET effects. A specifically developed RF characterization methodology was used to measure the linear and non-linear behaviors of the resonator and to evaluate the influence of each polarization voltages on the signal response. RSG-MOSFET with resonant frequencies ranging from 5MHz to 90MHz and quality factor up to 1200 were measured. Since MEMS resonator quality factor is strongly degraded by air damping, a 0-level thin film vacuum packaging (10-7 mBar) process was developed, compatible with both AlSi-based and silicon-based RSG-MOSFET. The technology has the unique advantage of being done on already released structure and the room temperature process makes it suitable for above-IC integration. In parallel, a front-end compatible process was defined and major build blocks were developed in industrial environment at STMicroelectronics. This technology is based on the Silicon-On-Nothing technology, originally developed for advanced transistor, and therefore making the MEMS resonator process compatible with CMOS co-integration. DC characterizations of SG-MOSFET had shown interesting performances of this device for current switch and memory applications. Mechanical contact of the gate with the MOSFET channel induces a current switching slope greater than 0.8mV/decade, much better than the theoretical MOSFET limit of 60mV/decade. Maximum switch isolations of -37dB at 2 GHz and -27dB at 10GHz were measured on these devices. A novel MEMS-memory has been demonstrated, based on the direct charge injection to the storage media by the mechanical contact of the metal gate. Charge injection and retention mechanisms were investigated based on measured devices. Cycling study of up to 105 cycles were performed without noticing major degradations of the electrical behavior neither mechanical fatigue of the suspended gate. The measured retention time places this memory in between the DRAM and the FLASH memories. A scaling study has shown integration and compatibilities capabilities with existing CMOS.

EPFL2007

Fabrication of Functional Silicon Surfaces using Metallic Nanostructures Produced by Block Copolymer Self-Assembly

Li Wang

Self-assembly is the autonomous organization of components into patterns or structures without human intervention. At the molecular level, self-assembly usually involves non-covalent interactions of various natures, such as van der Waals, electrostatic and hydrophobic interactions, hydrogen and coordination bonds. Thus, this process provides one solution to the fabrication of ordered aggregates from components with typical sizes in the submicron scale, which is a key to applications in nanotechnology. The work presented in this thesis aims at producing hybrid and functional nanostructured silicon surfaces using self-assembled metallic nanostructures. As self-assembling tool, we use polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) copolymers, which are amphiphilic molecules able to form well-defined nanostructures and to guide the positioning of metallic components into periodic arrangements. Various approaches were explored to reach this goal. First, self-assembled monolayers of PS-b-P2VP copolymer micelles were used as nanoreactors for the chemical synthesis of metal nanostructures of tunable dimensions and morphologies. This was achieved via a post-loading method, where the micelle cores are impregnated with metal salts after their deposition on silicon surfaces. Gold, silver and iron oxide nanoparticle (NP) arrays of controlled sizes and periodicities were produced. We also exploited the responsive properties of PS-b-P2VP micelles to create ordered arrays of gold nanorings having feature sizes below 100 nm. Surface plasmon resonance properties were studied and showed a significant change of optical properties between the gold particle and nanoring morphologies. Then, we focused our efforts on the controlled positioning of preformed gold NPs using PS-b-P2VP micelles as guiding templates. Two methods were developed. In the first, hierarchical positioning of NPs was achieved in one step during the spontaneous micelle phase inversion into nanoring structures. In the second, we used block copolymer-assisted lithography for producing periodic amino-silane nanopatterns, which then acted as electrostatic traps for the selective immobilization of gold NPs in aqueous solution. For both approaches, we showed the formation of ordered arrangements of individual gold NPs or clusters on silicon surfaces, whose morphologies, densities and periodicities could be tuned by simply varying the initial block copolymer molecular weights or deposition conditions. In a last part, we demonstrated the fabrication of functional silicon surfaces with high aspect ratio and controlled morphologies using self-assembled metallic patterns. Using a simple and efficient process called metal-assisted chemical etching (MAC-Etch), both highly porous silicon surfaces and ultra long silicon nanowires were produced. In particular, we reported for the first time the possible fabrication of free-standing nanoporous silicon membranes by this method and demonstrated the effective transport of molecules across the pores. Finally, the catalytic properties of self-assembled gold NPs were evaluated to grow vertically aligned silicon nanowires in a Low Pressure Chemical Vapor Deposition (LPCVD) reactor via a Vapor-Liquid-Solid (VLS) growth mechanism.

EPFL2011

On the Powder Formation in the Plasma Enhanced Chemical Vapor Deposition Process for the Deposition of SiOx Barrier Coatings

Marina Ricci

EPFL2011

Fabrication of Functional Silicon Surfaces using Metallic Nanostructures Produced by Block Copolymer Self-Assembly

Li Wang

EPFL2011

Design and fabrication of suspended-gate MOSFETs for MEMS resonator, switch and memory applications

Nicolas Abelé

EPFL2007