MoS2 nanoparticle formation in a low pressure environment

Formation of MoS2 nanoparticles at pressures between 0.5 and 10 Torr has been studied. Two different chemistries for the particle nucleation are compared: one based on MoCl5 and H2S, and the other based on MoCl5 and S. In both cases particle formation has been studied in a thermal oven and in a radio-frequency discharge. Typically, the reaction rates at low pressures are too low for an efficient thermal particle production. At pressures below 10 Torr no particle production in the oven is achieved in H2S chemistry. In the more reactive chemistry based on sulfur, the optimal conditions for thermal particle growth are found at 10 Torr and low gas flows, using excess of hydrogen. In the radio-frequency discharge, nanoparticles are readily formed in both chemistries at 0.5 Torr and can be detected in situ by laser light scattering. In the H2S chemistry particles smaller than 100 nm diameter have been synthesized, the sulfur chemistry yields somewhat larger grains. Both in thermal and plasma-enhanced particle syntheses, using excess of hydrogen is beneficial for the stability and purity of the particles

Near-surface generation of negative ions in low-pressure discharges

Formation processes of negative ions in low-pressure plasmas are not yet fully understood: as a rule experiments reveal higher negative ion density than predicted by the models. In this work we report near-surface generation of negative ions. This hitherto neglected formation mechanism appears to be important in low-pressure discharges and can have large impacts on the bulk plasma chemistry. We monitor energy-resolved positive and negative ion fluxes arriving at the electrodes in an oxygen parallel-plate radio-frequency ~rf, 13.56 MHz! and dc glow plasmas by means of a quadrupole mass spectrometer. Negative ions formed in the plasma volume are observed by extracting them through an orifice in the anode of a dc glow discharge. Unexpectedly, we record large negative ion signals at the cathode of a dc discharge and at the grounded electrode of an rf discharge. These ions are formed in the plasma sheath, in collision processes involving high-energy species. We propose an efficient mechanism of negative ion generation due to ion pair formation in the sheath

Measurement of the gas temperature in fluorocarbon radio frequency discharges using infrared absorption spectroscopy

The translational gas temperature was measured in 13.56 MHz radio-frequency (rf) discharges in CF4 and CHF3. Infrared absorption spectra of CF4 and CF2 were recorded using a tunable diode laser and the gas temperature was deduced from the linewidths of the absorption lines of these molecules. It is shown that linewidth measurements yield a simple and direct method to determine the gas temperature, with an accuracy up to ~ 10 K. The results obtained in CF4 and CHF3 plasmas indicate that the translational temperatures of all particles investigated in these plasmas are, at most, 50 K above the room temperature. The temperature increases with increasing gas pressure and rf power, but it is independent of the flow rate. This is attributed to an increased heating rate of the gas. Moreover, it was found that the temperature rise is significantly smaller in CHF3 than in CF4, under the same plasma conditions. This can be attributed to a higher power dissipation by chemical conversion of the parent gas in a CHF3 discharge, as compared with a CF4 plasm

Voids in dust clouds suspended in the plasma sheath

Voids in dusty plasma are a new phenomenon, which is still not understood. In this work we have studied experimentally for first time voids in the sheath of a radio-frequency (RF) dusty plasma. Injecting big dust particles into the plasma, we form a dust cloud in the sheath. The behaviour of the cloud as a function of RF power and gas pressure is investigated using video imaging. Both dependencies show a threshold for the void formation. This threshold is characterised by a sudden decrease in the inter-particle distance, while in the non-void mode the distance increases with power and pressure. We have performed Langmuir probe measurements of the floating potential in the bulk plasma close to the sheath in order to estimate the form of the potential well trapping the dust grains

Near-surface generation of negative ions in low-pressure discharges

Formation processes of negative ions in low-pressure plasmas are not yet fully understood: as a rule experiments reveal higher negative ion density than predicted by the models. In this work we report near-surface generation of negative ions. This hitherto neglected formation mechanism appears to be important in low-pressure discharges and can have large impacts on the bulk plasma chemistry. We monitor energy-resolved positive and negative ion fluxes arriving at the electrodes in an oxygen parallel-plate radio-frequency ~rf, 13.56 MHz! and dc glow plasmas by means of a quadrupole mass spectrometer. Negative ions formed in the plasma volume are observed by extracting them through an orifice in the anode of a dc glow discharge. Unexpectedly, we record large negative ion signals at the cathode of a dc discharge and at the grounded electrode of an rf discharge. These ions are formed in the plasma sheath, in collision processes involving high-energy species. We propose an efficient mechanism of negative ion generation due to ion pair formation in the sheath

Production and destruction of CFx radicals in radio-frequency fluorocarbon plasmas

Spacially resolved densities of CF, CF2, and CF3¿ radicals in capacitively coupled 13.56 MHz radio-frequency (rf) discharges in CF4¿and CHF3 were determined by means of infrared absorption spectroscopy employing a tunable diode laser spectrometer. It was established that the stationary CF2 density and density profile in a CF4 plasma depend strongly on the electrode material. This is attributed to different sticking coefficients of CF2 on different surfaces. Furthermore, it was found that the densities of all CFx radicals increase near the electrodes at high gas pressures and rf powers in a CHF3 plasma. This leads to the conclusion that production of CFx radicals takes place in the sheath region close to the electrodes. It is proposed that collisions between ions and source gas molecules are responsible for this production of CFx radicals. In the presence of a destruction process in the plasma glow (e.g., by three-body recombination with other radicals) and the absence of a fast surface loss process this results in the observed increase of CFx densities near the electrodes. In order to study the radical kinetics time dependent measurements were performed during power modulation of the plasma. It was found that the decay time of the CF2 density in the afterglow of a CF4 plasma is much shorter than the corresponding decay time in a CHF3¿discharge. This suggests that the surface loss is relatively less important in the latter case, in agreement with measurements of spatial density distributions. This is explained by the presence of a (CFx)n layer, which is readily deposited on the electrodes in a CHF3 discharge, and by low sticking probabilities of CF and CF2 radicals on such a layer. © 1996 American Vacuum Societ

The chemistry of a CCl2F2 radio frequency discharge

A systematic study of the chemistry of stable molecules and radicals in a low pressure CCl2F2 radio frequency discharge for dry Si etching has been performed. Various particle densities have been measured and modeled. The electron density, needed as an input parameter to model the CCl2F2 dissociation, is measured by a microwave cavity method. The densities of stable molecules, like CClF3, CF4, 1,2-C2Cl2F4 and the etch product SiF4, are measured by Fourier transform absorption spectroscopy. The density of the CF2 radical is measured by means of absorption spectroscopy with a tunable diode laser. Its density is in the order of 1019 m-3. All density measurements are presented as a function of various plasma parameters. Moreover, optical emission intensities of Cl and F have been recorded as a function of plasma parameters. It appears that the feed gas (CCl2F2) is substantially dissociated (about 70%–90%) in the discharge. Based on the obtained data the dissociation rates of several molecules have been estimated. The measured total dissociation rate of CCl2F2 is 8×10-15 m3¿s-1. For this molecule the dissociation rate is substantially higher than the dissociative attachment rate (10-15 m3¿s-1). The dissociation rate for CClF3 is 2×10-15 m3¿s-1 and for CF4 about 3×10-16 m3¿s-1. The total dissociation rate of C2Cl2F4 is higher than 5 ×10-15 m3¿s-1, of which 2.5±0.5 × 10-15 m3¿s-1 is due to dissociative attachment. Furthermore it has been found that the presence of a silicon wafer strongly affects the plasma chemistry. Optical emission measurements show that the densities of halogen radicals are significantly depleted in presence of Si. Moreover, the densities of several halocarbon molecules display a negative correlation with the density of the etch product SiF4. © 1995 American Vacuum Societ