On Relationships between Plasma Chemistry and Surface Reaction Kinetics Providing the Etching of Silicon in CF4, CHF3, and C4F8 Gases Mixed with Oxygen.

In this work, we discuss the effects of component ratios on plasma characteristics, chemistry of active species, and silicon etching kinetics in CF4 + O2, CHF3 + O2, and C4F8 + O2 gas mixtures. It was shown that the addition of O2 changes electrons- and ions-related plasma parameters rapidly suppresses densities of CFx radicals and influences F atoms kinetics through their formation rate and/or loss frequency. The dominant Si etching mechanism in all three cases is the chemical interaction with F atoms featured by the nonconstant reaction probability. The latter reflects both the remaining amount of fluorocarbon polymer and oxidation of silicon surface.

On Relationships between Gas-Phase Chemistry and Reactive Ion Etching Kinetics for Silicon-Based Thin Films (SiC, SiO2 and SixNy) in Multi-Component Fluorocarbon Gas Mixtures.

This work summarizes the results of our previous studies related to investigations of reactive ion etching kinetics and mechanisms for widely used silicon-based materials (SiC, SiO2, and SixNy) as well as for the silicon itself in multi-component fluorocarbon gas mixtures. The main subjects were the three-component systems composed either by one fluorocarbon component (CF4, C4F8, CHF3) with Ar and O2 or by two fluorocarbon components with one additive gas. The investigation scheme included plasma diagnostics by Langmuir probes and model-based analysis of plasma chemistry and heterogeneous reaction kinetics. The combination of these methods allowed one (a) to figure out key processes which determine the steady-state plasma parameters and densities of active species; (b) to understand relationships between processing conditions and basic heterogeneous process kinetics; (c) to analyze etching mechanisms in terms of process-condition-dependent effective reaction probability and etching yield; and (d) to suggest the set gas-phase-related parameters (fluxes and flux-to-flux ratios) to control the thickness of the fluorocarbon polymer film and the change in the etching/polymerization balance. It was shown that non-monotonic etching rates as functions of gas mixing ratios may result from monotonic but opposite changes in F atoms flux and effective reaction probability. The latter depends either on the fluorocarbon film thickness (in high-polymerizing and oxygen-less gas systems) or on heterogeneous processes with a participation of O atoms (in oxygen-containing plasmas). It was suggested that an increase in O2 fraction in a feed gas may suppress the effective reaction probability through decreasing amounts of free adsorption sites and oxidation of surface atoms.

Dry Etching Performance and Gas-Phase Parameters of C6F12O + Ar Plasma in Comparison with CF4 + Ar.

This research work deals with the comparative study of C6F12O + Ar and CF4 + Ar gas chemistries in respect to Si and SiO2 reactive-ion etching processes in a low power regime. Despite uncertain applicability of C6F12O as the fluorine-containing etchant gas, it is interesting because of the liquid (at room temperature) nature and weaker environmental impact (lower global warming potential). The combination of several experimental techniques (double Langmuir probe, optical emission spectroscopy, X-ray photoelectron spectroscopy) allowed one (a) to compare performances of given gas systems in respect to the reactive-ion etching of Si and SiO2; and (b) to associate the features of corresponding etching kinetics with those for gas-phase plasma parameters. It was found that both gas systems exhibit (a) similar changes in ion energy flux and F atom flux with variations on input RF power and gas pressure; (b) quite close polymerization abilities; and (c) identical behaviors of Si and SiO2 etching rates, as determined by the neutral-flux-limited regime of ion-assisted chemical reaction. Principal features of C6F12O + Ar plasma are only lower absolute etching rates (mainly due to the lower density and flux of F atoms) as well as some limitations in SiO2/Si etching selectivity.

A Study on the Etching and Surface Characteristics of SiOC Thin Films After C6F12O Plasma Etching.

Silicon oxycarbide (SiOC) film was etched using a CF4/C6F12O/O2 mixed gas plasma through an inductively coupled plasma etcher. Changes in the dielectric constant and surface chemical bonding properties were investigated using ellipsometry and Fourier transform infrared spectroscopy. Plasma diagnosis was carried out using a double Langmuir probe, ultraviolet detector, and residual gas analyzer. The physical and chemical plasma properties of CHF3 and C6F12O exhibited similar trends. However, the C6F12O mixed plasma exhibited a smaller change in dielectric constant compared to that of a conventional CHF3 mixed plasma, because of the lower ion density, ion energy flux, and UV intensity and thinner fluorocarbon-based polymer formation. Therefore, the liquefied C6F12O gas can substitute for the existing etching process gas and reduce the change in dielectric constant.

Plasma Parameters and Etching Characteristics of SiOxNy Films in CF4 + O2 + X (X = C4F8 or CF2Br2) Gas Mixtures.

In this work, we carried out the study of CF4 + O2 + X (X = C4F8 or CF2Br2) gas chemistries in respect to the SiOxNy reactive-ion etching process in a low power regime. The interest in the liquid CF2Br2 as an additive component is motivated by its generally unknown plasma etching performance. The combination of various diagnostic tools (double Langmuir probe, quadrupole mass-spectrometry, X-ray photoelectron spectroscopy) allowed us to compare the effects of CF4/X mixing ratio, input power and gas pressure on gas-phase plasma characteristics as well as to analyze the SiOxNy etching kinetics in terms of process-condition-dependent effective reaction probability. It was found that the given gas systems are characterized by: (1) similar changes in plasma parameters (electron temperature, ion current density) and fluxes of active species with variations in processing conditions; (2) identical behaviors of SiOxNy etching rates, as determined by the neutral-flux-limited process regime; and (3) non-constant SiOxNy + F reaction probabilities due to changes in the polymer deposition/removal balance. The features of CF4 + CF2Br2 + O2 plasma are lower polymerization ability (due to the lower flux of CFx radicals) and a bit more vertical etching profile (due to the lower neutral/charged ratio).

Application of Si and SiO2 Etching Mechanisms in CF4/C4F8/Ar Inductively Coupled Plasmas for Nanoscale Patterns.

An investigation of the etching characteristics and mechanism for both Si and SiO2 in CF4/C4F8/Ar inductively coupled plasmas under a constant gas pressure (4 mTorr), total gas flow rate (40 sccm), input power (800 W), and bias power (150 W) was performed. It was found that the variations in the CF4/C4F8 mixing ratio in the range of 0-50% at a constant Ar fraction of 50% resulted in slightly non-monotonic Si and SiO2 etching rates in CF4-rich plasmas and greatly decreasing etching rates in C4F8-rich plasmas. The zero-dimensional plasma model, Langmuir probe diagnostics, and optical emission spectroscopy provided information regarding the formation-decay kinetics for the plasma active species, along with their densities and fluxes. The model-based analysis of the etching kinetics indicated that the non-monotonic etching rates were caused not by the similar behavior of the fluorine atom density but rather by the opposite changes of the fluorine atom flux and ion energy flux. It was also determined that the great decrease in both the Si and SiO2 etching rates during the transition from the CF4/Ar to C4F8/Ar gas system was due to the deposition of the fluorocarbon polymer film.

Silicon Surface Modification Using C4F8+O2 Plasma for Nano-Imprint Lithography.

The investigation of C4F8+O2 feed gas composition on both plasma parameters and plasma treated silicon surface characteristics was carried out. The combination of plasma diagnostics by Langmuir probes and plasma modeling indicated that an increase in O2 mixing ratio results in monotonically decreasing densities of CF(x) (x = 1-3) radicals as well as in non-monotonic behavior of F atom density. The surface characterization by X-ray photoelectron spectroscopy and contact angle measurements showed that the C4F8+O2 mixtures with less than 60% 02 result in modification of Si surfaces due to the deposition of the FC polymer films while the change of O2 mixing ratio in the range of 30%-60% provides an effective adjustment of the surface characteristics such as surface energy, contact angle, etc.

Characteristics of room temperature silicon nitride deposited by internal inductively coupled plasma chemical vapor deposition.

The parallel inductively coupled plasma chemical vapor deposition system is used to directly control the activated radical and charged species in the plasma of a silicon nitride thin film, which is deposited at room temperature for flexible displays. By controlling the plasma characteristics of silicon nitride with plasma heating at 85 °C, this new technique produced low hydrogen content silicon nitride thin films at room temperature (25 °C). Deposition rates and refractive indices of the films ranged from 6.8 nm/min to 4.57 nm/min and from 2.125 to 1.749 with NH3 variation and ranged from 5.12 nm/min to 4.105 nm/min and from 1.81 to 1.92 with N2 variation, respectively. In the optical emission spectra of the plasmas investigated at fixed RF powers (1000 W), the peaks corresponding to the radical and charged species of SiH4, N2, and NH3 were related to the changes of the deposition rate and refractive index of the films. Current-voltage measurements with MIM capacitors revealed that these films had dielectric breakdown fields higher than 8 MV/cm, and FTIR showed their lower hydrogen contents than the conventional PECVD films.

Micro electro-mechanical system piezoelectric cantilever array for a broadband vibration energy harvester.

Limited energy sources of ubiquitous sensor networks (USNs) such as fuel cells and batteries have grave drawbacks such as the need for replacements and re-charging owing to their short durability and environmental pollution. Energy harvesting which is converting environmental mechanical vibration into electrical energy has been researched with some piezoelectric materials and various cantilever designs to increase the efficiency of energy-harvesting devices. In this study, we focused on an energy-harvesting cantilever with a broadband vibration frequency. We fabricated a lead zirconate titanate (PZT) cantilever array with various Si proof masses on small beams (5.5 mm x 0.5 mm x 0.5 mm). We obtained broadband resonant frequencies ranging between 127 Hz and 136 Hz using a micro electro-mechanical system (MEMS) process. In order to obtain broadband resonant characteristics, the cantilever array was comprised of six cantilevers with different resonant frequencies. We obtained an output power of about 2.461 µW at an acceleration of 0.23 g and a resistance of 4 kΩ. The measured bandwidth of the resonant frequency was approximately 9 Hz (127-136 Hz), which is about six times wider than the bandwidth of a single cantilever.

Surface modification of polypropylene separators in lithium-ion batteries using inductively coupled plasma treatment.

We describe herein an improvement in the surface wettability of plasma-treated separators for use in lithium-ion batteries. We treated the separators with an O2/Ar inductively coupled plasma to increase their surface energy. The plasma treatment on the separator and plasma diagnostic experiments were performed in an inductively coupled plasma (ICP) reactor. The fraction of Ar in the O2/Ar plasma was changed from 0% to 100%. The plasma diagnostics were performed using optical emission spectroscopy and a double Langmuir probe. To confirm the morphological change of the separator membrane by the plasma treatment, we used the scanning electron microscopy. The surface energy measurements were performed using the drop method. We found that the plasma treatment transformed the separator from a hydrophobic membrane to a hydrophilic one, thereby achieving high separator wettability. After the treatment of the separators with O2/Ar plasma, the batteries exhibited better cycle performance and rate capacity than those employing the untreated ones.

On the etching characteristics and mechanisms of HfO2 thin films in CF4/O2/Ar and CHF3/O2/Ar plasma for nano-devices.

The study of etching characteristics and mechanisms for HfO2 and Si in CF4/O2/Ar and CHF3/O2/Ar inductively-coupled plasmas was carried out. The etching rates of HfO2 thin films as well as the HfO2/Si etching selectivities were measured as functions of Ar content in a feed gas (0-50% Ar) at fixed fluorocarbon gas content (50%), gas pressure (6 mTorr), input power (700 W), bias power (200 W), and total gas flow rate (40 sccm). Plasma parameters as well as the differences in plasma chemistries for CF4- and CHF3-based plasmas were analyzed using Langmuir probe diagnostics and 0-dimensional plasma modeling. It was found that, in both gas systems, the non-monotonic (with a maximum at about 15-20% Ar) HfO2 etching rate does not correlate with monotonic changes of F atom flux and ion energy flux. It was proposed that, under the given set of experimental conditions, the HfO2 etching process is affected by the factors determining the formation and decomposition kinetics of the fluorocarbon polymer layer. These factor are the fluxes of CF(x) (x = 1, 2) radicals, O atoms and H atoms.

Design and fabrication of vibration based energy harvester using microelectromechanical system piezoelectric cantilever for low power applications.

We fabricated dual-beam cantilevers on the microelectromechanical system (MEMS) scale with an integrated Si proof mass. A Pb(Zr,Ti)O3 (PZT) cantilever was designed as a mechanical vibration energy-harvesting system for low power applications. The resonant frequency of the multilayer composition cantilevers were simulated using the finite element method (FEM) with parametric analysis carried out in the design process. According to simulations, the resonant frequency, voltage, and average power of a dual-beam cantilever was 69.1 Hz, 113.9 mV, and 0.303 microW, respectively, at optimal resistance and 0.5 g (gravitational acceleration, m/s2). Based on these data, we subsequently fabricated cantilever devices using dual-beam cantilevers. The harvested power density of the dual-beam cantilever compared favorably with the simulation. Experiments revealed the resonant frequency, voltage, and average power density to be 78.7 Hz, 118.5 mV, and 0.34 microW, respectively. The error between the measured and simulated results was about 10%. The maximum average power and power density of the fabricated dual-beam cantilever at 1 g were 0.803 microW and 1322.80 microW cm(-3), respectively. Furthermore, the possibility of a MEMS-scale power source for energy conversion experiments was also tested.

Neural network modeling of deposition rate characteristics of low temperature silicon nitride deposited by inner two parallel coil inductively coupled plasma chemical vapor deposition.

In this study, a neural network model for silicon nitride (SiN) deposition process is proposed. SiN thin films were deposited by a direct inner two parallel inductively coupled plasma chemical vapor deposition (ICPCVD) system that can control the activated radical and charged species in plasma. This system can produce SiN thin films at low temperature for flexible displays. The input parameters considered for deposition conditions were the N2 gas flow rate, NH3 gas flow rate, and substrate temperature. These were varied within the ranges of 0-20 sccm, 0-20 sccm, and 100-300 degrees C, respectively. For those of input parameters and the output of deposition rate, we developed a back propagation neural network model with a pre-processor. It is shown that the model accuracy and learning speed of the proposed model are better than those of a conventional neural network model. In the experiments conducted, it was found that the deposition rate increased as the flow rates of ammonia (NH3) and nitrogen (N2) increased up to a certain amount. On the contrary, when the flow rates of NH3 and N2 went over a certain amount, the deposition rate decreased. It was also found that an increase in temperature resulted in an increase in the deposition rate.

Electrical and mechanical characteristics of room temperature deposited silicon nitride using two inner parallel cylindrical coils inductively coupled plasma chemical vapor deposition.

For investigating silicon nitride (SiN) thin film deposition process at room temperature without additional substrate heating, we studied inductively coupled plasma chemical vapor deposition with two inner parallel cylindrical coils which can activate the more radicals and charged species in the plasma. We investigated the influence of plasma RF power on the characteristics of room temperature deposited SiN films. Deposition rates, dielectric constant, refractive index, and stress of the films ranged from 4.5 nm/min to 8.3 nm/min, 8.4 to 10, 1.8 to 2.1, and 0.54 to 0.15, respectively. According to the FTIR measurements, the concentration of the Si--H and N--H bonds was decreased as the RF power increased, and the Si--H bonds tended to disappear at RF power over 500 W. This reduction in the hydrogen content was accompanied by the increases in the deposition rate and refractive index. It was confirmed that the breakdown field could be also maximized to 10 MV/cm.

Formation of metal and dielectric liners using a solution process for deep trench capacitors.

We demonstrated the feasibility of metal and dielectric liners using a solution process for deep trench capacitor application. The deep Si trench via with size of 10.3 microm and depth of 71 microm were fabricated by Bosch process in deep reactive ion etch (DRIE) system. The aspect ratio was about 7. Then, nano-Ag ink and poly(4-vinylphenol) (PVPh) were used to form metal and dielectric liners, respectively. The thicknesses of the Ag and PVPh liners were about 144 and 830 nm, respectively. When the curing temperature of Ag film increased from 120 to 150 degrees C, the sheet resistance decreased rapidly from 2.47 to 0.72 Omega/sq and then slightly decreased to 0.6 Omega/sq with further increasing the curing temperature beyond 150 degrees C. The proposed liner formation method using solution process is a simple and cost effective process for the high capacity of deep trench capacitor.

Micromachining of a bimorph Pb(Zr,Ti)O3 (PZT) cantilever using a micro-electromechanical systems (MEMS) process for energy harvesting application.

We designed and fabricated a bimorph Pb(Zr,Ti)O3 (PZT) cantilever with an integrated Si proof mass to obtain a low resonant frequency for an energy harvesting application. The cantilevers were fabricated on the micro-electromechanical systems (MEMS) scale. A mode of piezoelectric conversions were d31 and d33 mode in cantilever vibration Therefore, we designed and fabricated a single cantilever with d31 unimorph, d31 bimorph, d33 unimorph, and d33 bimorph modes. Finally, we fabricated a device with beam dimensions of about 5,400 microm x 480 microm x 14 microm (< +/- 5%), and an integrated Si proof mass with dimensions of about 1,481 microm x 988 microm x 450 microm (< +/- 5%). In order to measure the d31 and d33 modes, we fabricated top and bottom electrodes. The distance between the top electrodes was 50 microm and the resonant frequency was 89.4 Hz. The average powers of the d31 unimorph, d31 bimorph, d33 unimorph, and d33 bimorph modes were 3.90, 9.60, 21.42, and 22.47 nW at 0.8 g (g = 9.8 m/s2) and optimal resistance, respectively.

Vibration energy harvester with sustainable power based on a single-crystal piezoelectric cantilever array.

We designed and fabricated a bimorph cantilever array for sustainable power with an integrated Cu proof mass to obtain additional power and current. We fabricated a cantilever system using single-crystal piezoelectric material and compared the calculations for single and arrayed cantilevers to those obtained experimentally. The vibration energy harvester had resonant frequencies of 60.4 and 63.2 Hz for short and open circuits, respectively. The damping ratio and quality factor of the cantilever device were 0.012 and 41.66, respectively. The resonant frequency at maximum average power was 60.8 Hz. The current and highest average power of the harvester array were found to be 0.728 mA and 1.61 mW, respectively. The sustainable maximum power was obtained after slightly shifting the short-circuit frequency. In order to improve the current and power using an array of cantilevers, we also performed energy conversion experiments.

Design and fabrication of a PZT cantilever for low frequency vibration energy harvesting.

In this study, a PZT cantilever with a Si proof mass is designed and fabricated for a low frequency energy harvesting application. A mathematical model of a multi-layer composite beam was derived and applied in a parametric analysis of the piezoelectric cantilever. Finally, the dimensions of the cantilever were determined for the resonant frequency of the cantilever. Our cantilever design was based on MATLAB and ANSYS simulations. For this simulation, the proof mass volumes were varied from 0 to 0.5 mm3 and resonant frequencies were calculated from 833.5 Hz to 125.5 Hz, respectively. Based on simulation, we fabricated a device with beam dimensions of about 4.10 mm x 0.48 mm x 0.012 mm, and an integrated Si proof mass with dimensions of about 0.481 mm x 0.48 mm x 0.45 mm. The resonant frequency, maximum peak voltage, and highest average power of the cantilever device were 224.8 Hz, 4.8 mV, and 2.24 nW, respectively.