Quartz clock

Summary

Quartz clocks and quartz watches are timepieces that use an electronic oscillator regulated by a quartz crystal to keep time. This crystal oscillator creates a signal with very precise frequency, so that quartz clocks and watches are at least an order of magnitude more accurate than mechanical clocks. Generally, some form of digital logic counts the cycles of this signal and provides a numerical time display, usually in units of hours, minutes, and seconds. Since the 1980s, when the advent of solid-state digital electronics allowed them to be made compact and inexpensive, quartz timekeepers have become the world's most widely used timekeeping technology, used in most clocks and watches as well as computers and other appliances that keep time. Explanation Chemically, quartz is a specific form of a compound called silicon dioxide. Many materials can be formed into plates that will resonate. However, quartz is also a piezoelectric material: that is, when a quartz crystal

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In UV-curable printing technology, an ink or a varnish is exposed to the UV-light source within a fraction of a second. Subsequent polymerization therefore proceeds in the dark, referred to as dark curing. Because dark curing can be critical and contributes to a large part of the overall conversion and to the final properties of the printed ink, the aim of this work was to get a better understanding of the dark curing process. Because an ink is a complex mixture of components, simpler systems representative of free radical and cationic chemistry were studied. Special attention was given to free radical polymerization with a detailed kinetic modeling. For cationic systems, the study was more application oriented. Attenuated-Total-Reflection Fourier-Transform Infrared (ATR-FTIR) spectroscopy was found to be the method of choice to follow in real-time the progress of the reaction under UV irradiation and in the dark. This technique allowed the study of curing conditions close to those encountered in industry. Dark curing of free radical was examined in systems consisting of a monomer (multifunctional acrylate) and a photoinitiator. The reactivities of different monomers were investigated and it was found that the chemistry of the spacer between the acrylate functional groups had an influence on the extent of dark curing. For example, TPGDA (tripropylene glycol diacrylate) led to higher overall conversion than HDDA (hexanediol diacrylate) although both are diacrylate monomers. Several explanations were put forward, such as the effect of dissolved oxygen, primary cyclization and initiation efficiency. The efficiency of photoinitiators (PIs) was examined and different behaviours were highlighted. For example, it was observed that DMPA (dimethoxyphenyl acetophenone) has a better quantum yield for α-cleavage compared to HCPK (1-hydroxycyclohexylphenyl ketone), whereas HCPK is more efficient in initiating the reaction, resulting in a better overall conversion in the dark. It is suggested that the two primary radicals resulting from the cleavage of the PI behave differently for DMPA and HCPK. One radical effectively initiates the reaction and the second is mainly involved in the termination process. These two different behaviours were observed under specific experimental conditions: (i) by covering the sample with a quartz plate and taking into account dissolved molecular oxygen and (ii) by curing under inert conditions with nitrogen. Photo-crosslinking polymerization reactions are strongly influenced by diffusion effects due to the formation of an infinite network. Therefore, it was proposed that a redistribution of reactivity within the system occurs, such as the diffusion of unreacted photoinitiators towards concentrations of unreacted monomers. This diffusion process has two positive effects: (i) for the same UV dose, but different intensities, a higher extent of conversion was reached with longer irradiation times under the condition investigated; (ii) multiple exposures led to a higher overall conversion than for a single exposure, for a fixed overall UV dose. Other parameters were explored, such as temperature and diffusing oxygen from air. With temperature, different trends were observed depending on the photoinitiator and the start of dark curing, either starting before the maximum rate of polymerization (Rp,max), or after Rp,max. The development of a kinetic model to describe dark curing of free radical polymerization was proposed. Existing models based on physical parameters, such as those incorporating diffusion-controlled phenomena and free-volume are relatively complex and require extensive information on the system studied. Therefore, a semi empirical approach was chosen in order to study the variation of fitting parameters when changing curing parameters, such as the photoinitiator concentration and type, the irradiation time, the UV light intensity and the temperature. The model was derived from kinetic data and it was assumed that rate coefficients are time-dependent and that termination, which was considered to be a first-order process, is propagation dependent. The kinetic equation has the form of a stretched exponential function and incorporates four fitting parameters. The model was evaluated for a large number of experimental data and very good fits were obtained with a random distribution of residuals. The exponent β was found to be sensitive to the termination process and reflected different reactivities in the dark as in the case of DMPA and HCPK. Dark curing of cationic systems continues until complete monomer conversion but at a slower rate. Thus systems with high reaction rates, both during UV irradiation and during the first seconds of the dark period, are of most importance for UV-curable printing technology. The most widely used diepoxide monomer in cationic ink formulation is 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (DECC). In order to improve its reactivity during the first seconds of dark curing, the influence of several parameters was examined, such as the addition of an oxetane co-monomer (TMPO), the influence of relative humidity, UV dose, light intensity, temperature, and film thickness. The enhanced reactivity of DECC with TMPO was confirmed. During the cationic curing process, two reaction mechanisms compete; an activated chain end (ACE) mechanism and an activated monomer (AM) mechanism. It was observed that these two processes depend on the presence of hydroxyl containing compounds such as TMPO monomer, polyol compounds, and, most important, water. When the concentration of these components is increased the AM mechanism is enhanced, leading to higher conversion but at a slower curing rate, and a degradation of the mechanical properties. The presence of water is unavoidable and its concentration in the ink varies in presence of hydrophilic compounds, such as polyol. Furthermore, the water content increases with increasing relative humidity in air. It was shown that the reactivity of the system decreased as the percent of relative humidity increased. Moreover, although a higher overall conversion is achieved, the crosslink density of the film was severely reduced. This lower crosslink density was the result of the predominance of chain transfer reactions, leading to more pendant and short chains which were hydroxyl terminated. Moreover, the extent of conversion was thickness dependent since less water diffuses into the deeper layers occurred in thicker films.

EPFL2007

Resonators for time and frequency reference applications are essential elements found in most electronic devices surrounding us. The continuous minimization and ubiquitous distribution of such electronic devices and circuits demands for resonators of smaller size, lower cost, and reduced power consumption. Micro-electro-mechanical (MEM) resonators have the potential to replace the widely used quartz resonators, which are relative large and difficult to integrate with electronic circuits. The MEM resonators can be CMOS compatible, smaller in size, and therefore cheaper than quartz resonators, while providing similar performance characteristics. The required hermitic encapsulation of the MEM resonator at a low pressure and in a clean environment, has been the dominant bottle-neck on their path to successful commercialisation. In this work, the development, fabrication, and characterization of an encapsulated low frequency MEM resonator, based on the vibrating body field effect transistor (VB-FET), is presented. This in-plane flexural mode resonator was designed for a resonance frequency of 262 kHz, and fabricated on a silicon-on-insulator (SOI) wafer. The VB-FET provides a higher signal gain and lower motional resistance compared to other electro-mechanical transducers. A thin film encapsulation process was developed for the wafer level packaging of the resonators. In two fabrication runs the VB-FET resonators were fabricated with 150 nm to 400 nm wide trenches at the gate and drive electrodes using ebeam lithography. Two ion implantations realized the n-type channel enhancement FET on the vibrating structure, and the p-type gate on the non-vibrating structures. A quality factor for up to 12,000 was measured with resonance frequencies around 210 kHz, and a temperature dependency of the frequency of -850 ppm/K. Losses at the anchor points, intrinsic stress in the resonator's body, and stress induced by the thermal gate oxide are explanations for this low performance. With the gate bias voltage a tuning of the resonance frequency of up to 5.2 kHz/V was possible. A motional resistance down to 1 kΩ was measured. Pressure dependent measurement showed that significant air damping occurs at 1 Pa for this resonator. A thin film encapsulation process was developed for the VB-FET MEM resonator based on sacrificial polysilicon and a silicon oxide cap. In numerous tests, individual encapsulation process steps were optimized. Arrays of submicron trenches in the encapsulation cap were used for release etching the sacrificial polysilicon. A sputtered silicon oxide layer closed these release etch trenches with minimal contamination inside the cavity. Cavities spanning 45 μm in width and more than 70 μm in length were successful fabricated. Although, the final encapsulation of the MEM resonators showed a breaking of the silicon oxide cap and a contamination by the sealing polysilicon. No functional encapsulated resonators could be measured. The novelty of this work is the fabrication of a VB-FET MEM resonator with a resonance frequency lower than 300 kHz, which held certain fabrication challenges. Also, the thin film encapsulation process using submicron etch release trenches and sacrificial polysilicon has not been report before. Based on the documented measurement results, further investigations and optimizations regarding the resonator design could result in a considerable improvement of the resonator's performance. The developed thin film encapsulation process requires assumingly only a small modification to produce a functional encapsulation. Provided a sufficient pressure level can be achieved inside the cavity, this encapsulation process could be applied to other resonators and MEMS structures, which have a silicon oxide surface layer.

EPFL2013

Nanogap MEM resonators on SOI

Nicoleta-Diana Ciressan

Today's consumer electronics based on a large variety of time-keeping and frequency reference applications is based on quartz-crystal oscillators, because of their excellent performances in terms of quality factor, thermal and frequency stability. However, macroscopic size and CMOS incompatibility of quartz-crystal resonators draw a major limit on the miniaturization of wireless communication applications. For this reason, silicon microelectromechanical (MEM) resonators are considered promising candidates to replace quartz-oscillators in VLSI communication systems, due to their compactness, design flexibility and CMOS process compatibility. This work reports on the design, fabrication and characterization of MEM bulk lateral resonators with resonance frequencies in the order of tens of MHz. The need of stable, low cost and high yield processes for fabricating devices with extremely narrow (sub 100 nm) transduction gaps is a main research driver, together with the requirements of improved designs which include high quality factors and appropriate power handling. We are investigating two major designs: (1) longitudinal beam resonators and (2) novel fragmented-membrane resonators that respond to both high quality factor (Q) and low motional resistance (Rm) requirements. We propose several design optimizations for solving some of the issues which currently affect the MEM resonator performance, like the frequency stability and Q enhancement through energy loss minimization. An original fabrication process is presented, which enables the manufacturing of SOI-based, fully monocrystalline devices with 100 nm transduction gaps and aspect ratios as high as [60:1], without the need of advanced lithography techniques. We successfully validate the fabrication process on two different SOI substrates, with silicon film thicknesses of 1.5 µm and 6.25 µm. This thickness range combined to the doping level corresponds to partially depleted SOI, which can be a substrate of choice for the fabrication of future integrated hybrid MEMS-CMOS integrated circuits for communication applications. The fabricated structures are successfully characterized, demonstrating excellent resonator performance at room temperature. Q's as high as 235'000 and Rm's as low as 59 kΩ have been extracted in vacuum. Atmospheric pressure frequency response measurements of the fragmented membrane resonators show Q's of 3'600. This value is among the best reported to date, opening the possibility for atmospheric pressure applications such as mass-detection for gas sensing applications with detection done without a special package, just by direct exposure of the resonator to the environment. A novel study on temperature dependence (between 80 K and 320 K) of the fragmented membrane resonators is presented and discussed. Significant Q increase and Rm reduction are experimentally observed at cryogenic temperatures. The bulk mode resonators developed and discussed in this thesis can successfully be integrated in oscillator circuits, as we demonstrate by simulating a Pierce topology based on the calibrated equivalent circuit model of a 24.48 MHz fragmented membrane BLR. Our oscillator shows very good phase-noise performance of -142 dBc/Hz at 1 kHz offset from the carrier and the noise floor at -144 dBc/Hz, which nearly meets the GSM specifications.

EPFL2009

EPFL2013

EPFL2007

Nanogap MEM resonators on SOI

Nicoleta-Diana Ciressan

EPFL2009