Prediction of etching results and etching stabilization by applying principal component regression to emission spectra during in-situ cleaning

A method to predict etching results by analyzing plasma emission spectra during in-situ cleaning was investigated, where the plasma emission spectra indicate the surface condition of etching reactor walls. Plasma-wall interaction was evaluated by using both principal component regression of plasma emission spectra and attenuated-total-reflection Fourier-transform infrared spectroscopy. We found that differences in the amount of silicon oxide deposition on the reactor wall affected radical composition in the plasma during in-situ cleaning and consequently affected the etching results. Etching result predictions using the plasma spectra corresponded very well to the etching result measurements, which are used to improve etching stability.     

Applying RF current harmonics for end-point detection during etching multi-layered substrates and cleaning discharge chambers with NF3 discharge

The present paper reports the results of studying the characteristics of the etching process of multi-layered materials (Si₃N₄/SiO₂/Si and SiO₂/Si) and of cleaning technological chambers covered with silicon nitride films (Si₃N₄) in a NF₃ RF capacitive discharge. The process of chamber cleaning was monitored with a mass spectrometer. The gas pressure, RF voltage amplitude, current-voltage phase shift, ohmic current as well as the second harmonic of the RF current were also recorded. The opportunity of using these parameters for end-point detection of etching and plasma cleaning is discussed. It is found that the second harmonic of the RF current may be successfully used for end-point detection of multi-layered materials etching and to monitor the cleaning process of technological chambers. The cleaning of chambers of complicated design may possess a double-stage pattern.     

Process optimization of CF4/Ar plasma etching of Au using I-optimal design

In this paper, reactive ion etching of Au is performed with CF₄/Ar gases, and process optimization method is suggested using a statistically established process model. The I-optimal design was employed to set up the etching experiment with operating parameters, namely, gas composition, RF power and chamber pressure. Its analysis was performed on individual parameters of the etch rate, selectivity, and profile. In addition, process optimization, including all three responses of interest, is provided simultaneously. We confirmed that a nonvolatile by-product AuF_x was re-deposited on the surface, but controlling the amount of carbon fluoride provided a good etch rate with a satisfactory sidewall profile by reducing by-products. Although RF power is closely related with etch rate, increased power gives poor selectivity due to increased physical etching. Pressure and gas flows strongly interact with each other, affecting sidewall characteristics. Suggested optimization simultaneously considers three responses of interests, which is crucial in process development and optimization for quickly ramping up high volume manufacturing.     

Process control of high rate microcrystalline silicon based solar cell deposition by optical emission spectroscopy

Silicon thin-film solar cells based on microcrystalline silicon (μc-Si:H) were prepared in a 30 × 30 cm² plasma-enhanced chemical vapor deposition reactor using 13.56 or 40.68 MHz plasma excitation frequency. Plasma emission was recorded by optical emission spectroscopy during μc-Si:H absorber layer deposition at deposition rates between 0.5 and 2.5 nm/s. The time course of SiH^? and H_β emission indicated strong drifts in the process conditions particularly at low total gas flows. By actively controlling the SiH₄ gas flow, the observed process drifts were successfully suppressed resulting in a more homogeneous i-layer crystallinity along the growth direction. In a deposition regime with efficient usage of the process gas, the μc-Si:H solar cell efficiency was enhanced from 7.9 % up to 8.8 % by applying process control.     

Influence of contaminations on the performance of thin-film silicon solar cells prepared after in situ reactor plasma cleaning

This paper addresses the influence of the chemical memory effect (CME) of in situ plasma cleaning by using the fluorinated gases on the properties of subsequently deposited thin-film silicon solar cells and discusses methods to avoid or reduce this effect. Secondary ion mass spectrometry (SIMS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) profiles analysis showed a high impurity concentration in the intrinsic (i)-layer of p-i-n solar cells prepared directly after in situ cleaning. With increasing number of cell depositions these contaminations decrease and the solar cell performance recovers to the standard value. Restoring solar cell performance is accompanied by a decrease of contaminants concentration in the i-layer. The intentional variation of the F-content in the i-layer obtained by adding SiF₄ to the process gas mixture during a-Si:H i-layer preparation reveals that for solar cells a fluorine content above 1.5 × 10¹⁹ cm^− 3 is critical. We applied NF₃ or SF₆ + O₂ as cleaning gases and optimized the cleaning procedure. In case of using NF₃ as the cleaning gas, the CME was less pronounced as compared to the SF₆ + O₂ case and by additional procedures, like increasing the total gas flow rate during deposition, hydrogen plasma treatment of reaction chamber, the high solar cell quality could be achieved directly after in situ reactor cleaning. Low concentration of impurities in such cells was observed. Also the long-term illumination test (light-soaking for 1000 h, AM1.5 radiation) shows the same stabilized efficiency as compared to reference cells.     

Removal of Nano-sized Particles Using Carbon Dioxide (CO2) Gas Cluster Cleaning without Pattern Damage

As pattern size of semiconductor device becomes less than 20 nm, the removal of particles smaller than 10 nm without pattern damages requires new physical dry cleaning technology. CO₂ gas cluster cleaning is an alternative dry cleaning process to meet these cleaning requirements. To demonstrate gas cluster cleaning performance, particle removal efficiency (PRE) and gate structure pattern damages were evaluated. When pressurized and low temperature CO₂ gas was passed through a convergence–divergence (C–D) nozzle, high energy CO₂ gas clusters were generated at high speed in a vacuum atmosphere. The cleaning force of the CO₂ gas cluster is related to the flow rate of the CO₂ gas. The optimum CO₂ gas flow rate for the particle removal without pattern damage was found to be 6 L/min (LPM). Removal efficiency for 50 nm silica particles was greater than 90%, and no pattern damage was observed on 60 nm poly-Si and a-Si gate line patterns. It was confirmed that the CO₂ gas cluster cleaning force could be controlled by the CO₂ gas flow rate supplied to nozzle.     

Micro-fabrication techniques applied to aluminosilicate glass surfaces: Micro-indentation and wet etching process

Micro-indentation and HF etching were explored as micro-fabrication techniques applied to glass surfaces. The effects of the aluminosilicate glass composition and of the etching conditions on the etching rate were investigated. It was found that the etching rate increased with increasing the ratio of Al₂O₃ to SiO₂ in the aluminosilicate glass. Etching parameters, such as pH, concentration and temperature of HF acid, had effects on etching rate. However, the effects of these parameters were much smaller at indented area than at non-indented area. The results indicated that the etching rate difference between the two areas, which is one of the key factors in the micro-fabrication technique, could be controlled with these parameters. And the phenomena can be well explained in terms of etching and leaching mechanism of aluminosilicate glass.     

Plasma-surface interactions for advanced plasma etching processes in nanoscale ULSI device fabrication: A numerical and experimental study

Plasma-surface interactions in Cl- and Br-based plasmas have been studied for advanced front-end-of-line (FEOL) etching processes in nanoscale ULSI device fabrication. A Monte Carlo-based atomic-scale cellular model (ASCeM) was developed to simulate the feature profile evolution on nanometer scale during Si etching in Cl₂ and Cl₂/O₂ plasmas, including surface oxidation, inhibitor deposition, and ion reflection and penetration on surfaces. A classical molecular dynamics (MD) simulation for Si/Br and Si/HBr as well as Si/Cl systems was also developed, along with an improved Stillinger-Weber interatomic potential model for Si/halogen interactions, to clarify surface reaction kinetics on atomic scale during Si etching in Cl₂ and HBr plasmas. The numerical results revealed the origin of profile or surface anomalies such as microtrench, roughness, and residue, and also etching fundamentals such as etch yield, product stoichiometry, and atomistic surface structures. Moreover, the etching of high-k dielectric and metal electrode materials, such as HfO₂ and TaN, was investigated in BCl₃- and Cl₂-containing plasmas with and without rf biasing, to gain an understanding of the etch mechanisms and to achieve anisotropic and selective etching of metal/high-k gate stacks.     

Vacuum lithography using plasma polymerization and plasma development

A completely dry lithography has been proposed which involves plasma polymerization of methyl methacrylate (MMA) and plasma development with CCl₄. It was called vacuum lithography because all processes were performed in a vacuum. However, the developed pattern had a lower resolution than patterns produced by conventional lithography with a wet process. After several technical refinements, the quality of the resist and the developed pattern was markedly improved. In this paper, recent results will be reported.A gas-flow-type reactor was used instead of a bell-jar-type reactor because the morphology of plasma-polymerized MMA (PPMMA) varied with each experimental run which was performed with the same gas and discharge parameters. The monomer vapour was introduced downstream of the argon discharge, and the polymerized film was formed on the substrate placed further downstream in the mixed gas.The development of pattern was performed by etching with an Ar-O₂ mixture and with hydrogen gas instead of CCl₄ gas, because the etching rate of the resist was too high in a CCl₄ plasma and a clear pattern was not obtained. The evaluated sensitivity and γ value of PPMMA were 1000 μC cm^?2 and 1 respectively. MMA containing 5% tetramethyltin was also used as a monomer gas for plasma polymerization downstream of the argon discharge. In this case the sensitivity and γ value were 10 μC cm^?2 and 2 respectively.     

Test of a ring imaging Cherenkov counter

We have tested a ring imaging Cherenkov counter with readout of the projection chamber type. A specific detector response of N₀ = 80 cm^?1 was measured which corresponds to 8 photoelectrons per event in 1.60 m long nitrogen radiator. The resolution of the ring radius was measured to be Δr/r = 3.6%. The crosstalk between neighboring wires due to photons generated in the avalanche process was estimated to contribute up to 50% per hit. It was reduced considerably by inserting shielding walls between the wires and by adding C₂H₆ or iC₄H₁₀ to the CH₄-TMAE gas mixture.     

Control of plasma process instabilities during thin silicon film deposition

Fourier transform infrared absorption spectroscopy (FTIR), optical emission spectroscopy (OES), self-bias voltage and plasma impedance controls were applied as in situ process diagnostics during the deposition of amorphous silicon thin-films. The diagnostic abilities of OES and FTIR are compared. The FTIR in-situ direct measurement of silane concentration in exhaust line is more precise than OES control. All in situ process diagnostics clearly indicates the inconsistency of plasma properties and therefore of deposition conditions. The drifts are comparable with the film deposition time. The FTIR measurement of reactant concentration in the process chamber evidence that the strong silane concentration drop (about 50%) in a plasma is the cause of the short-term drift of OES signals (SiH? emission), plasma impedance and self-bias voltage signals. The influences of the deposition chamber geometry and technological parameters on process drifts are considered. The decrease of the gas residence time in the reactor leads to a decrease of Initial Transient State phenomena. Finally, the improvement of solar cell performance based on thin silicon films is demonstrated when drifts are reduced.     

The gas flux distribution in the XHV chamber of the vacuum primary standard developed by PTB

The ultimate pressure in the XHV calibration chamber of the PTB primary standard CE3, whose operation is based on the continuous expansion of gas, has been reduced by the use of a relatively large orifice area. Thus, the gas density and flux distributions cannot be taken as uniform in the calibration chamber. To eliminate this drawback we examined the gas flux distribution by Direct Simulation using the Monte Carlo method. This paper describes the gas flux distribution over the chamber walls, which was simulated, recorded and related to the idealized conditions. This allows determining the gauge position correction factor K_gi for each of the gauge ports. Using these factors, it is possible to eliminate the systematic deviation of the gas flow parameters from those under the idealized Maxwellian conditions and to improve the uncertainty budget.     

Optimized inductively coupled plasma etching for poly(methyl-methacrylate-glycidly-methacrylate) optical waveguide

Optical loss is a crucial quality for the application of polymer waveguide devices. The optimized oxygen inductively coupled plasma etching conditions, including antenna power, bias power, chamber pressure, O₂ flow rate and etching time for the fabrication of smooth vertical poly(methyl-methacrylate-glycidly-methacrylate) channel waveguide were systematically investigated. Atomic force microscopy and scanning electron microscopy were used to characterize the etch rate, surface roughness and vertical profiles. The increment of etch rate with the antenna power, bias power and O₂ flow rate was observed. Bias power and chamber pressure were found to be the main factor affecting the interface roughness. The vertical profiles were proved to be closely related to antenna power, bias power and O₂ flow rate. Surface roughness increment was observed when the etching time increased.     

Control of oxidation on NiSix during etching and ashing processes

The oxidation on nickel silicide (NiSi_x) during plasma etching and oxygen ashing is investigated for stable contact resistance on NiSi_x. NiSi_x exposed by various processes is observed by X-ray photoelectron spectroscopy. The oxidation on NiSi_x is promoted by the fluorine that remains during etching and the oxide thickness on n⁺ NiSi_x is greater than that on p⁺ NiSi_x. The remaining fluorine after etching can be decreased by in-situ nitrogen plasma treatment during the post-etching process. Therefore, the oxidation progress with exposure to air and the difference in oxidation on NiSi_x between n⁺ and p⁺ can be suppressed.     

Electrical, optical and surface properties of P2S5/(NH4)2Sx+ Se-treated doped-channel field-effect transistors with double etch-stop layers

This work describes doped-channel field-effect transistors (DCFETs), featuring both low-high doped-channels and double AlAs etch-stop layers used in a selective etch recessed-gate process. A developed highly selective wet etching process is applied as a gate-recess technique to fabricate DCFETs. Selective wet etching using citric acid/H₂O₂/NH₄OH/H₂O solutions in conjunction with double thin AlAs etch-stop layers is a reasonably simple, safe, and reliable process for gate recessing in the fabrication of the DCFETs herein. Surface passivation using P₂S₅/(NH₄)₂S_x+ Se on GaAs Schottky barrier diodes, formed by Pt/Au contacts, is examined for the first time and the results are compared with those of unpassivated devices. For the passivated Pt/Au gate device, the two-terminal gate-drain breakdown (source floating) at − 1 mA/mm is 17 V, and the device provides an excellent combination of transconductance and output current. The X-ray photoelectron spectroscopy, secondary ion mass spectrometry, and photoluminescence results are highly consistent with the Schottky barrier measurements and the device performance.     

Hrtem study of nanocrystalline zirconia powders

Zirconia powders with grain sizes between 4 and 35 nm were synthesized by the gas condensation technique. Different qualities (grain size, grain size distribution) of powders have been observed and can be attributed to different synthesis conditions (mainly temperature gradients) within the UHV chamber. The existence of necks between single particles has been observed. These necks are due to a first sintering process during the oxidation of the metal/ suboxide clusters condensed on the walls in the synthesis chamber. Several stages of this sintering process are documented by high-resolution micrographs. Furthermore, some particles exhibit a shell-like structure with monoclinic ZrO₂ in the outer region and tetragonal ZrO₂ in the inner region. This is an indication of (i) the martensitic phase transition character of zirconia in general, and (ii) the existence of a critical particle size in n-ZrO₂ responsible for the metastability of a tetragonal polymorph in nanosized zirconia powder. Lattice distortions in some directions can be concluded from image reconstruction of the digitized micrograph of a single nanosized ZrO₂ particle.     

Influence of C<Subscript>4</Subscript>F<Subscript>8</Subscript>/Ar/O<Subscript>2</Subscript> plasma etching on SiO<Subscript>2</Subscript> surface chemistry

The plasma assisted etching of SiO₂ in a commercial RF reactor with a variety of C₄F₈/Ar/O₂ chemistries has been studied by XPS, SIMS and FTIR. A simple model of surface reactions is proposed. In particular, the role of oxygen in the etch process has been investigated. According to our experiments, oxygen inhibits the formation of CFH based polymeric films on the surface. As the etching process is due to an exchange reaction between the oxygen in the SiO₂ and the gaseous fluorine species in the plasma, the presence of oxygen in the etch hinders this process by occupying adsorption sites on the surface. The results would confirm that argon does not participate in chemical reactions with the SiO₂ substrate but provides energy for reactions in which F, C and O are involved. The results also indicate that a thick fluorocarbon layer only forms on the surface in the absence of oxygen, regardless of the oxygen source. Consequently, only when the SiO₂ layer has been substantially removed does this film form.     

Characteristics of bottom-gate low temperature nanocrystalline silicon thin film transistor fabricated by hydrogen annealing of gate dielectric layer

Thin film transistors having nanocrystalline silicon as an active layer were fabricated by catalytic-CVD at a low process temperature (≤ 200 °C). The tri-layer of the bottom-gate TFT was deposited continuously inside the Cat-CVD reactor. In order to improve the quality of the gate dielectric layer an in-situ hydrogen annealing step was introduced in between the silicon nitride and the nanocrystalline silicon deposition steps. The in-situ hydrogen annealing was effective in reducing the hysteresis in the C-V characteristics and in enhancing the breakdown voltage by decreasing the defects inside the SiN_x film.     

Source d'ions lourds multicharges caprice 10 GHz pour tous les elements metalliques et Gazeux

A new compact multiply charged E.C.R. ion source completely enclosed by an iron return yoke is described. A new coaxial 10 GHz microwave accessibility is operating. This allows a very compact two stages source in an entirely removable vacuum chamber and a very easy increasing possibility of the axial magnetic field value. Then two different working modes are possible.A classical mode (ω_ce = ω_rf, 100% cw, rf power 300 W, coils supply 20 kW) gives same performance than all the other reliable larger 10 GHz sources.A second mode (100% cw, rf power 600 W, coils supply 33 kW) operates with an additional resonant surface ω_ce = 2 ω_rf and increases by a factor 3 or 4 all currents on high charge states. Total extraction current is multiplied by a factor of 4 just as it would do by using a classical 20 GHz source by increase in density. This new resonant surface is unfortunately stopped in its radial part by the wall of the vacuum chamber due to a too low 10 GHz sextupole (0,4 T). Presently a better sextupole (0,8 T) is being built in order to work with both whole resonant surfaces inside the plasma chamber and perhaps so to improve charge states distribution by rising the plasma life time.On the other hand both the removable vacuum chamber and the coaxial rf feeder are well fitted to produce all metallic ions in long run and high intensity by working without any insulator inside the plasma chamber and by a good cleaning possibility. One shows cw spectra of 10 metallic elements from Al to Au and one can observe an exponential decrease for Ca, Ag and Au. This remark indicates a possible easy way to yield high charge states of all metals. One can expect to regulate all the easiest elements like Al, Si, Fe, Ni, Mo, Ta and W for 100 h. For example a good (within 1%) regulation of a 15 μA ₅₆²⁶Fe⁷⁺ for 10 h is partly shown.     

Plasmachemical synthesis of maghemite nanoparticles in atmospheric pressure microwave torch

The powder of γ − Fe₂O₃ nanoparticles was synthesized in microwave torch at atmospheric pressure from 0.05 sccm of Fe(CO)₅ vapors in 670 sccm of argon. The optimization of the torch reactor design and deposition conditions allowed continual synthesis of γ − Fe₂O₃ nanoparticles at low power consumption. The synthesized powder was collected at the reactor walls and analyzed by TEM, X-ray diffraction and Raman spectroscopy without any further purification or treatment. The mean diameter of NPs, as observed by TEM, was 12 nm with a 90% confidence interval 5.5-22 nm.