Porous silicon technology for integrated microsystems

With the development of micro systems, there is an increasing demand for integrable porous materials. In addition to those conventional applications, such as filtration, wicking, and insulating, many new micro devices, including micro reactors, sensors, actuators, and optical components, can benefit from porous materials. Conventional porous materials, such as ceramics and polymers, however, cannot meet the challenges posed by micro systems, due to their incompatibility with standard micro-fabrication processes. In an effort to produce porous materials that can be used in micro systems, porous silicon (PS) generated by anodization of single crystalline silicon has been investigated. In this work, the PS formation process has been extensively studied and characterized as a function of substrate type, crystal orientation, doping concentration, current density and surfactant concentration and type. Anodization conditions have been optimized for producing very thick porous silicon layers with uniform pore size, and for obtaining ideal pore morphologies. Three different types of porous silicon materials: meso porous silicon, macro porous silicon with straight pores, and macro porous silicon with tortuous pores, have been successfully produced. Regular pore arrays with controllable pore size in the range of 2µm to 6µm have been demonstrated as well. Localized PS formation has been achieved by using oxide/nitride/polysilicon stack as masking materials, which can withstand anodization in hydrofluoric acid up to twenty hours. A special etching cell with electrolytic liquid backside contact along with two process flows has been developed to enable the fabrication of thick macro porous silicon membranes with though wafer pores. For device assembly, Si-Au and In-Au bonding technologies have been developed. Very low bonding temperature (~200 degrees C) and thick/soft bonding layers (~6µm) have been achieved by In-Au bondi ng technology, which is able to compensate the potentially rough surface on the porous silicon sample without introducing significant thermal stress. The application of the porous silicon material in micro systems has been demonstrated in a micro gas chromatograph system by two indispensable components: an integrated vapor source and an inlet filter, wherein porous silicon performs the basic functions of porous media: wicking and filtration. By utilizing a macro porous silicon wick, the calibration vapor source was able to produce a uniform and repeatable vapor generation for n-decane with less than a 0.1% variation in 9 hours, and less than a 0.5% variation in rate over 7 days. With engineered porous silicon membranes the inlet filter was able to show a depth filtration with nearly 100% collection efficiency for particles larger than 0.3µm in diameter, a low pressure-drop of 523Pa at 20sccm flow rate, and a filter capacity of 500µg/cm2.

Numerical modeling of the failure mechanisms in Si thin film anode for Li-ion batteries

In recent times, the demand for the storage of electrical energy has grown rapidly for both static applications and the portable electronics enforcing the substantial improvement in battery systems, and Li-ion batteries have been proven to have maximum energy storage density in all rechargeable batteries. However, major breakthroughs are required to consummate the requirement of higher energy density with lower cost to penetrate new markets. Graphite anode having limited capacity has become a bottle neck in the process of developing next generation batteries and can be replaced by higher capacity metals such as Silicon. In the present study we are focusing on the mechanical behavior of the Si-thin film anode under various operating conditions. A numerical model is developed to simulate the intercalation induced stress and the failure mechanism of the complex anode structure. Effect of the various physical phenomena such as diffusion induced stress, plasticity and the crack propagation are investigated to predict better performance parameters for improved design.

Improvement of γ-ray energy resolution of LaBr3:Ce3+ scintillation detectors by Sr2+ and Ca2+ co-doping

Commercially available LaBr3:5% Ce3+ scintillators show with photomultiplier tube readout about 2.7% energy resolution for the detection of 662 keV γ-rays. Here we will show that by co-doping LaBr3:Ce3+ with Sr2+ or Ca2+ the resolution is improved to 2.0%. Such an improvement is attributed to a strong reduction of the scintillation light losses that are due to radiationless recombination of free electrons and holes during the earliest stages (1–10 ps) inside the high free charge carrier density parts of the ionization track.

Improvement of LaBr3:5%Ce scintillation properties by Li+, Na+, Mg2+, Ca2+, Sr2+, and Ba2+ co-doping

This paper reports on the effects of Li+, Na+, Mg2+, Ca2+, Sr2+, and Ba2+ co-doping on the scintillation properties of LaBr3:5%Ce3+. Pulse-height spectra of various gamma and X-ray sources with energies from 8 keV to 1.33 MeV were measured from which the values of light yield and energy resolution were derived. Sr2+ and Ca2+ co-doped crystals showed excellent energy resolution as compared to standard LaBr3:Ce. The proportionality of the scintillation response to gamma and X-rays of Ca2+, Sr2+, and Ba2+ co-doped samples also considerably improves. The effects of the co-dopants on emission spectra, decay time, and temperature stability of the light yield were studied. Multiple thermoluminescence glow peaks, decrease of the light yield at temperatures below 295 K, and additional long scintillation decay components were observed and related to charge carrier traps appearing in LaBr3:Ce3+ with Ca2+, Sr2+, and Ba2+ co-doping.

Hyalotekite, (Ba,Pb,K)(4)(Ca,Y)(2)Si-8(B,Be)(2)(Si,B)(2)O28F, a Tectosilicate Related to Scapolite: New Structure Refinement, Phase Transitions and a Short-Range Ordered 3B Superstructure

Hyalotekite, a framework silicate of composition (Ba,Pb,K)(4)(Ca,Y)(2)Si-8(B,Be)(2) (Si,B)(2)O28F, is found in relatively high-temperature(greater than or equal to 500 degrees C) Mn skarns at Langban, Sweden, and peralkaline pegmatites at Dara-i-Pioz, Tajikistan. A new paragenesis at Dara-i-Pioz is pegmatite consisting of the Ba borosilicates leucosphenite and tienshanite, as well as caesium kupletskite, aegirine, pyrochlore, microcline and quartz. Hyalotekite has been partially replaced by barylite and danburite. This hyalotekite contains 1.29-1.78 wt.% Y2O3, equivalent to 0.172-0.238 Y pfu or 8-11% Y on the Ca site; its Pb/(Pb+Ba) ratio ranges 0.36-0.44. Electron microprobe F contents of Langban and Dara-i-Pioz hyalotekite range 1.04-1.45 wt.%, consistent with full occupancy of the F site. A new refinement of the structure factor data used in the original structural determination of a Langban hyalotekite resulted in a structural formula, (Pb1.96Ba1.86K0.18)Ca-2(B1.76Be0.24)(Si1.56B0.44)Si8O28F, consistent with chemical data and all cations with positive-definite thermal parameters, although with a slight excess of positive charge (+57.14 as opposed to the ideal +57.00). An unusual feature of the hyalotekite framework is that 4 of 28 oxygens are non-bridging; by merging these 4 oxygens into two, the framework topology of scapolite is obtained. The triclinic symmetry of hyalotekite observed at room temperature is obtained from a hypothetical tetragonal parent structure via a sequence of displacive phase transitions. Some of these transitions are associated with cation ordering, either Pb-Ba ordering in the large cation sites, or B-Be and Si-B ordering on tetrahedral sites. Others are largely displacive but affect the coordination of the large cations (Pb, Ba, K, Ca). High-resolution electron microscopy suggests that the undulatory extinction characteristic of hyalotekite is due to a fine mosaic microstructure. This suggests that at least one of these transitions occurs in nature during cooling, and that it is first order with a large volume change. A diffuse superstructure observed by electron diffraction implies the existence of a further stage of short-range cation ordering which probably involves both (Pb,K)-Ba and (BeSi,BB)-BSi.

Influence of Equatorial Diatom Processes on Si Deposition and Atmospheric CO(2) Cycles at Glacial/Interglacial Timescales

The causes of the glacial cycle remain unknown, although the primary driver is changes in atmospheric CO(2), likely controlled by the biological pump and biogeochemical cycles. The two most important regions of the ocean for exchange of CO(2) with the atmosphere are the equatorial Pacific and the Southern Ocean ( SO), the former a net source and the latter a net sink under present conditions. The equatorial Pacific has been shown to be a Si(OH)(4)-limited ecosystem, a consequence of the low source Si(OH)(4) concentrations in upwelled water that has its origin in the SO. This teleconnection for nutrients between the two regions suggests an oscillatory relationship that may influence or control glacial cycles. Opal mass accumulation rate (MAR) data and delta(15)N measurements in equatorial cores are interpreted with predictions from a one- dimensional Si(OH)(4)-limited ecosystem model (CoSINE) for the equatorial Pacific. The results suggest that equatorial Pacific surface CO(2) processes are in opposite phase to that of the global atmosphere, providing a negative feedback to the glacial cycle. This negative feedback is implemented through the effect of the SO on the equatorial Si(OH)(4) supply. An alternative hypothesis, that the whole ocean becomes Si(OH)(4) poor during cooling periods, is suggested by low opal MAR in cores from both equatorial and Antarctic regions, perhaps as a result of low river input. terminations in this scenario would result from blooms of coccolithophorids triggered by low Si(OH)(4) concentrations.

Size-Fractionated Nitrogen Uptake Measurements in the Equatorial Pacific and Confirmation of the Low Si-High-Nitrate Low-Chlorophyll Condition

The equatorial Pacific Ocean is the largest natural source of CO(2) to the atmosphere, and it significantly impacts the global carbon cycle. Much of the large flux of upwelled CO(2) to the atmosphere is due to incomplete use of the available nitrate (NO(3)) and low net productivity. This high-nutrient low-chlorophyll (HNLC) condition of the equatorial upwelling zone (EUZ) has been interpreted from modeling efforts to be due to low levels of silicate ( Si( OH) 4) that limit the new production of diatoms. These ideas were incorporated into an ecosystem model, CoSINE. This model predicted production by the larger phytoplankton and the picoplankton and effects on air-sea CO(2) fluxes in the Pacific Ocean. However, there were no size-fractionated rates available for verification. Here we report the first size-fractionated new and regenerated production rates (obtained with (15)N - NO(3) and (15)N - NH(4) incubations) for the EUZ with the objective of validating the conceptual basis and functioning of the CoSINE model. Specifically, the larger phytoplankton ( with cell diameters > 5 mu m) had greater rates of new production and higher f-ratios (i.e., the proportion of NO(3) to the sum of NO(3) and NH(4) uptake) than the picoplankton that had high rates of NH(4) uptake and low f-ratios. The way that the larger primary producers are regulated in the EUZ is discussed using a continuous chemostat approach. This combines control of Si(OH)(4) production by supply rate (bottom-up) and control of growth rate ( or dilution) by grazing ( top-down control).