Dc Self-bias Research Articles

Deposition of hydrogenated amorphous carbon films by CH4/Ar capacitively coupled plasma using tailored voltage waveform discharges

We investigated the effects of tailored voltage waveform (TVW) discharges on the deposition of hydrogenated amorphous carbon (a-C:H) films in CH4/Ar capacitively coupled plasma. TVW discharges employ two driving radio frequencies (13.56 MHz and 27.12 MHz) and control their phase shifts to independently regulate ion bombardment energy (IBE) and ion flux. In this study, a-C:H films were deposited by changing DC-self bias with phase shift and constant applied voltage peak-to-peak. Additionally, we investigated phase-resolved optical emission spectroscopy (PROES) for plasma characterization. As a result, plasma-enhanced CVD (PECVD) for a-C:H films using TVW discharges realize control of film properties such as mass density, sp3 fraction, and H content, while keeping the deposition rate constant. Thus, it is suggested that TVW discharges realize the independent control of IBE and ion flux with high accuracy, highlighting its utility in a-C:H film depositions.

Magnetic enhancement of the electrical asymmetry effect in capacitively coupled plasmas

The development of real-time control strategies for key discharge parameters, such as densities, fluxes, and energy distributions, is of fundamental interest to many plasma sources. Over the last decade, multi-harmonic ‘tailored’ voltage waveforms have been successfully employed to achieve enhanced control of key parameters in a wide range of radio-frequency (RF) plasma sources through application of the electrical asymmetry effect (EAE). More recently, the analogous magnetic asymmetry effect (MAE) has been numerically and experimentally demonstrated to achieve a notable degree of control in parallel plate RF plasma sources. The MAE is achieved via selectively magnetising the charged species adjacent to one electrode, altering the charge flux to the surface and enforcing a DC self-bias to maintain quasineutrality. This study addresses the degree of control achieved by the MAE in a non-planar geometry via 2D fluid/kinetic simulations of a magnetised RF capacitively coupled plasma source employing two different magnetic topologies. The simultaneous application of the EAE and MAE is then presented for the same geometry, demonstrating a degree of non-linear behaviour dependant upon the applied magnetic topology. Control of the DC self-bias voltage ηdc is demonstrated for a single 600 Vpp , 13.56 MHz discharge in both ‘convergent’ (maximum on-axis field strength) and ‘divergent’ (minimum on-axis field strength) magnetic topolgies. MAE induced modulations of ηdc = 0.13 Vpp and ηdc = 0.03 Vpp are achieved for each magnetic topology, respectively, for magnetic field strengths between 50 and 1000 G. Simultaneous application of an EAE and MAE is achieved through a multi-harmonic ‘peak’-type tailored voltage waveform employing varying harmonic phase offsets between 0∘ ⩽ θ ⩽ 360∘ . The degree to which the DC self-bias voltage is modulated by the applied EAE is mediated by the orientation and magnitude of the applied magnetic field. The EAE induced DC self-bias modulations exhibit non-linear behaviour in response to a superimposed MAE, such that the resulting DC self-bias differs from an additive combination of the two effects alone Simultaneous application of the electrical and MAEs offers the possibility of further decoupling ion and electron dynamics in RF plasma sources, and represents an improvement over each approach in isolation.

Voltage waveform tailoring for high aspect ratio plasma etching of SiO2 using Ar/CF4/O2 mixtures: Consequences of low fundamental frequency biases

The use of non-sinusoidal waveforms in low pressure capacitively coupled plasmas intended for microelectronics fabrication has the goal of customizing ion and electron energy and angular distributions to the wafer. One such non-sinusoidal waveform uses the sum of consecutive harmonics of a fundamental sinusoidal frequency, f0, having a variable phase offset between the fundamental and even harmonics. In this paper, we discuss results from a computational investigation of the relation between ion energy and DC self-bias when varying the fundamental frequency f0 for capacitively coupled plasmas sustained in Ar/CF4/O2 and how those trends translate to a high aspect ratio etching of trenches in SiO2. The fundamental frequency, f0, was varied from 1 to 10 MHz and the relative phase from 0° to 180°. Two distinct regimes were identified. Average ion energy onto the wafer is strongly correlated with the DC self-bias at high f0, with there being a maximum at φ = 0° and minimum at φ = 180°. In the low frequency regime, this correlation is weak. Average ion energy onto the wafer is instead dominated by dynamic transients in the applied voltage waveforms, with a maximum at φ = 180° and minimum at φ = 0°. The trends in ion energy translate to etch properties. In both, the high and low frequency regimes, higher ion energies translate to higher etch rates and generally preferable final features, though behaving differently with phase angle.

Discharge characteristics of a low-pressure geometrically asymmetric cylindrical capacitively coupled plasma with an axisymmetric magnetic field

We investigate the discharge characteristics of a low-pressure geometrically asymmetric cylindrical capacitively coupled plasma discharge with an axisymmetric magnetic field generating an E × B drift in the azimuthal direction. Vital discharge parameters, including electron density, electron temperature, DC self-bias, and electron energy probability function (EEPF), are studied experimentally for different magnetic field strength (B) values. A transition in the plasma parameters is observed for a specific range of magnetic fields where the discharge is highly efficient with lower electron temperature. Outside this range of magnetic field, the plasma density drops, followed by an increase in the electron temperature. The observed behavior is attributed to the transition from geometrical asymmetry to magnetic field-associated symmetry due to reduced radial losses and plasma confinement in the peripheral region. The DC self-bias increases almost linearly from a large negative value to nearly zero, i.e., it turns into a symmetric discharge. The EEPF undergoes a transition from bi-Maxwellian for unmagnetized to Maxwellian at intermediate B and finally becomes a weakly bi-Maxwellian at higher values of B. The above transitions present a novel way to independently control the ion energy and ion flux in a cylindrical capacitively coupled plasma system using an axisymmetric magnetic field with an enhanced plasma density and lower electron temperature that is beneficial for plasma processing applications.

The electrical asymmetry effect in electronegative CF4 capacitive RF plasmas operated in the striation mode

The Electrical Asymmetry Effect (EAE) provides control of the mean ion energy at the electrodes of multi-frequency capacitively coupled radio frequency plasmas (CCP) by tuning the DC self-bias via adjusting the relative phase(s) between the consecutive driving harmonics. Depending on the electron power absorption mode, this phase control affects the ion flux in different ways. While it provides separate control of the mean ion energy and flux in the α-mode, limitations were found in the γ- and Drift-Ambipolar modes. In this work, based on experiments as well as kinetic simulations, the EAE is investigated in the striation-mode, which is present in electronegative CCPs driven by low frequencies. The discharge is operated in CF4 and is driven by two consecutive harmonics (4/8 MHz). The simulation results are validated against measurements of the DC self-bias and the spatio-temporally resolved dynamics of energetic electrons. To include heavy particle induced secondary electron emission realistically, a new computationally assisted diagnostic is developed to determine the corresponding secondary electron emission coefficient from a comparison of the DC self-bias obtained experimentally and from the simulations. Based on the validated simulation results, the EAE is found to provide separate control of the mean ion energy and flux in the striation mode, while the axial charged particle density profiles and the number of striations change as a function of the relative phase. This is understood based on an analysis of the ionization dynamics.

Spatial flux and energy asymmetry in a low pressure capacitively coupled plasma discharge excited by sawtooth waveform: A harmonic study

Plasma asymmetry generation in capacitively coupled plasma (CCP) discharges provides control over vital parameters that are useful in many plasma processing applications. In this article, using the particle-in-cell simulation technique, we investigated the spatial plasma asymmetry creation by a temporally asymmetric (sawtooth) waveform by varying its number of harmonics (N). The simulation results predict a non-linear increase in the plasma density and ion flux with an increase in N, i.e., it first decreases, reaching to a minimum value for a critical value of N and then increases almost linearly with a further rise in N. The ionization asymmetry increases with N, and higher harmonics on the instantaneous sheath position are observed for higher values of N. These higher harmonics generate multiple ionization beams that are generated near the expanding sheath edge and are responsible for an enhanced plasma density. The ion energy distribution function (IEDF) depicts a bi-modal shape for different values of N. DC self-bias is observed on the powered electrode, its magnitude with respect to the plasma potential decreases with increasing N, and therefore, the corresponding ion energy on the powered electrode decreases. The results conclude that by changing N of a sawtooth waveform in a collisionless CCP system, the ion flux asymmetry is not altered, whereas sheath symmetry could be significantly affected causing a systematic variation in the ion energy asymmetry. Due to an increase in the higher harmonic contents in the sawtooth waveform, a transition from broad bi-modal to narrow-shaped IEDFs is found.

Influence of magnetic field gradient on the capacitive argon discharge at 8 MHz and 40 MHz

A one-dimensional implicit particle-in-cell/Monte Carlo collision model is used to study the effects of magnetic field gradients on the capacitively coupled argon plasma at 8 MHz and 40 MHz. The magnetic field strength at the powered electrode is fixed at 10 G, while varies from 30 to 100 G at the grounded electrode. The simulations show that the magnetic field with variable gradient can produce controllable asymmetry in the plasma density and ion flux profiles to each electrode. Increasing the magnetic field gradient will generate a significant dc self-bias, which results in a large ion bombardment energy at the powered electrode. The magnetic field gradients have been demonstrated to be an approach to create the dc self-bias and also effectively improve the plasma density. It is also found that at a higher frequency of 40 MHz, the dc self-bias voltage decreases, due to the fact that high collision rate of electrons with background gas will disturb the cyclotron motion of electrons, so the effect of the magnetic field is weakened. As a result, the ability to independently control ion energy and flux is weakened.

Electron dynamics in planar radio frequency magnetron plasmas: III. Comparison of experimental investigations of power absorption dynamics to simulation results

In magnetized capacitively coupled radio-frequency (RF) discharges operated at low pressure the influence of the magnetic flux density on discharge properties has been studied recently both by experimental investigations and in simulations. It was found that the magnetic asymmetry effect allows for a control of the DC self-bias and the ion energy distribution by tuning the magnetic field strength. In this study, we focus on experimental investigations of the electron power absorption dynamics in the presence of a magnetron-like magnetic field configuration in a low pressure capacitive RF discharge operated in argon. Phase resolved optical emission spectroscopy measurements provide insights into the electron dynamics on a nanosecond-timescale. The magnetic flux density and the neutral gas pressure are found to strongly alter these dynamics. For specific conditions energetic electrons are efficiently trapped by the magnetic field in a region close to the powered electrode, serving as the target surface. Depending on the magnetic field strength an electric field reversal is observed that leads to a further acceleration of electrons during the sheath collapse. These findings are supported by two-dimensional particle in cell simulations that yield deeper insights into the discharge dynamics.

Voltage waveform tailoring for high aspect ratio plasma etching of SiO2 using Ar/CF4/O2 mixtures: Consequences of ion and electron distributions on etch profiles

The quality of high aspect ratio (HAR) features etched into dielectrics for microelectronics fabrication using halogen containing low temperature plasmas strongly depends on the energy and angular distribution of the incident ions (IEAD) onto the wafer, as well as potentially that of the electrons (EEAD). Positive ions, accelerated to high energies by the sheath electric field, have narrow angular spreads and can penetrate deeply into HAR features. Electrons typically arrive at the wafer with nearly thermal energy and isotropic angular distributions and so do not directly penetrate deeply into features. These differences can lead to positive charging of the insides of the features that can slow etching rates and produce geometric defects such as twisting. In this work, we computationally investigated the plasma etching of HAR features into SiO2 using tailored voltage waveforms in a geometrically asymmetric capacitively coupled plasma sustained in an Ar/CF4/O2 mixture at 40 mTorr. The tailored waveform consisted of a sinusoidal wave and its higher harmonics with a fundamental frequency of 1 MHz. We found that some degree of control of the IEADs and EEADs is possible by adjusting the phase of higher harmonics φ through the resulting generation of electrical asymmetry and electric field reversal. However, the IEADs and EEADs cannot easily be separately controlled. The control of IEADs and EEADs is inherently linked. The highest quality feature was obtained with a phase angle φ = 0° as this value generated the largest (most negative) DC self-bias and largest electric field reversal for accelerating electrons into the feature. That said, the consequences of voltage waveform tailoring (VWT) on etched features are dominated by the change in the IEADs. Although VWT does produce EEADs with higher energy and narrower angular spread, the effect of these electrons on the feature compared to thermal electrons is not large. This smaller impact of VWT produced EEADs is attributed to thermal electrons being accelerated into the feature by electric fields produced by the positive in-feature charging.

Application of similarity laws to dual-frequency capacitively coupled radio frequency plasmas with the electrical asymmetry effect

Similarity laws (SLs) are useful for correlation and prediction of plasma parameters at different scales, which have been verified for geometrically symmetric capacitive radio-frequency (rf) discharges in nonlocal kinetic regimes. In this work, we demonstrate the applicability of SLs to dual-frequency rf discharges and confirm that similarity relations still hold considering the electrical asymmetry effect (EAE). By simultaneously tuning the control parameters (the gas pressure p, discharge gap d, and driving frequency f), we examine the similarity relations in rf plasmas via fully kinetic particle-in-cell simulations with the external circuits coupled and solved self-consistently. The validity of the SL scalings in dual-frequency rf plasmas with the EAE is confirmed for parameters such as the electron/ion density, ion flux, dc self-bias, ion energy distribution function, and power absorption. Although adjusted by the EAE, the dc self-bias and ion energy distribution functions are identified as similarity invariants under similar discharge conditions. Furthermore, the plasma series resonance phenomenon, filamentation of power depositions of electrons and ions in bulk plasma, and electric field reversal are observed in dual-frequency discharges with the EAE, which can also be exactly replicated under similar discharge conditions. The results further extend the application of SL scaling to dual-frequency rf plasmas, providing a more comprehensive understanding of the scaling characteristics in rf plasmas.

Electron energy probability function measurement in a 2 MHz and 13.56 MHz dual-frequency capacitively coupled argon plasma

The effect of low-frequency power and high-frequency power on the electron energy probability function (EEPF) and the physical and electrical characteristics of plasma are experimentally investigated in a dual-frequency capacitively coupled plasma. RF powers of 2 MHz (low-frequency) and 13.56 MHz (high-frequency) are simultaneously applied to an electrode. EEPFs and DC self-bias voltages (V DC) are measured as one of the two RF powers is increased while the other is fixed. When the 2 MHz power increases at a fixed 13.56 MHz power, the electron density decreases, and the electron temperature increases with the decrease in the population of low-energy (below 5 V) electrons in the EEPF. Note that the increase in the low-frequency power is accompanied by a large decrease in V DC, which is related to the ion energy. On the other hand, when 13.56 MHz power increases at a fixed 2 MHz power, the electron density and the electron temperature significantly increase with the increase in the population of high-energy (above 5 V) electrons in the EEPF, while V DC decreases slightly. Experimental results show that the increase in the low-frequency power enhances the ion energy, and the increase in the high-frequency power enhances electron heating and ionization efficiency.

Experimental investigations of plasma dynamics in the hysteresis regime of reactive RF sputter processes

Reactive radio frequency (RF) sputter processes are highly relevant for thin film deposition, but there is no complete understanding of the fundamentals of their operation. While the Berg model describes the hysteresis regime considering the oxygen coverage of the boundary surfaces, a complete fundamental understanding of the plasma–surface interactions and their effects on the discharge is still missing. In this work, we provide such fundamental insights based on an extensive experimental analysis of the physics in the hysteresis regime of magnetized reactive sputter processes, where the same reactive gas admixture can lead to different discharge characteristics depending on the previous state of the plasma. A variety of plasma and surface diagnostics is used to reveal these insights. A low pressure capacitively coupled RF discharge (CCP, 13.56 MHz) with a magnetron-like magnetic field topology adjacent to the target is operated in argon gas with a variable admixture of O2. The applied RF power, the gas flows/pumping speed, as well as the neutral gas pressure are changed systematically to understand the effects of these external control parameters on the hysteresis regime. The magnetic asymmetry effect is found to play an important role, since an axially non-uniform magnetic field is used to realize a local electron confinement at the target. Similar to process control in applications, the DC self-bias is measured to stabilize the surface composition using a feedback controller with the oxygen gas flow as the manipulated variable.

Effects of magnetic field on the secondary electron asymmetry effect in capacitively coupled plasmas

The secondary electron asymmetry effect (SEAE) provides the opportunity to generate the dc self-bias voltage and asymmetric plasma response, where secondary electron emission coefficients at both electrodes are unequal. In this work, we use one-dimensional implicit particle-in-cell/Monte Carlo collision simulation to investigate the effects of the homogeneous and inhomogeneous magnetic field on the SEAE. The magnetic field is applied parallel to electrodes, and the discharge is operated in a geometrically and electrically symmetric capacitively coupled argon plasma. By comparing the simulation results of the effects of the homogeneous and inhomogeneous magnetic field on the SEAE, the homogeneous magnetic field can increase the dc self-bias voltage to a certain extent and has little effect on the plasma density distribution. The inhomogeneous magnetic field is more advantageous in generating the dc self-bias but at the cost of uneven plasma density distribution. In addition, by comparing the results of inhomogeneous magnetic fields with opposite gradients, we found that the value of the self-bias voltage can be changed by adjusting the magnetic field gradient. Aside from that the roles of two electrodes can be easily reversed by changing the slopes of the magnetic field gradient. The results suggest that such a configuration could be desired in the microelectronics industry, since the controllable self-bias voltage is needed for deposition and etching processes.

Ion energy distribution function in very high frequency capacitive discharges excited by saw-tooth waveform

Tailoring the ion energy distribution function (IEDF) is vital for advanced plasma processing applications. Capacitively coupled plasma (CCP) discharges excited using a non-sinusoidal waveform have shown its capability to control IEDF through the generation of plasma asymmetry and DC self-bias. In this paper, we performed a particle-in-cell simulation study to investigate the IEDF in a symmetric capacitive discharge excited by a saw-tooth-like current waveform at a very high frequency. At a constant driving frequency of 27.12 MHz, the simulation results predict that the ion energy asymmetry in the discharge scales with the discharge current amplitude. A transition from a single narrow ion energy peak to a bi-modal type IEDF is observed with an increase in the current density amplitude. Further studies at a constant current density and varying the fundamental excitation frequency show that the ion energy asymmetry enhances with a reduction in the driving frequency. Increase in the plasma asymmetry and significant DC self-bias at a lower driving frequency is observed to be one of the principal factors responsible for the observed asymmetry in the ion energy peaks. An investigation of DC self-bias and plasma potential confirms that the powered electrode energy peak corresponds to the DC self-bias with respect to the plasma potential, and the grounded electrode peak corresponds to the plasma potential. These results suggest that although lower driving frequency is beneficial for generating the discharge asymmetry and large DC self-bias, a narrow low energy IEDF is plausible in very high frequency driven CCP systems.

Investigations of the sheath in a dual-frequency capacitively coupled rf discharge by optically trapped microparticles

The sheath of a dual-frequency capacitively coupled rf discharge has been investigated with microparticles as probes based on two different methods: by the first method, intensity profiles of the emitted light of the discharge and the scattered light of the microparticles are used to study the effects of phase variation between the fundamental frequency (13.56 MHz) and its first harmonic (27.12 MHz) or a change in the dc self-bias, respectively, on the expansion of the sheath and the levitation height of microparticles in the sheath. These measurements show that the sheath width as well as the levitation height of the microparticles correlates with the dc self-bias as a function of the phase between the applied voltage harmonics. By a second method, profiles of the force acting on an optically trapped microparticle in an optical tweezer in the sheath were measured. On the basis of these force profiles, the strength of the electric field force as a function of pressure and the dependency on the distance of the probe to the rf electrode as well as the extent of the sheath are determined in both a single- and a dual-frequency discharge. From the results, it can be deduced that the sheath thickness and the electric field force in a dual-frequency discharge are influenced by both excitation frequencies and, thus, differ from a single-frequency discharge.

Comment on “A study on improvement of discharge characteristic by using a transformer in a capacitively coupled plasma” [Phys. Plasmas 22, 123504 (2015)

In the paper [Y.C. Kim et al., Phys. Plasmas 22, 123504 (2015)], the plasma density in radio frequency (RF) capacitively coupled plasma was increased by introducing a step-down ferrite-core transformer into a conventional type-T impedance matching network. The authors ascribed the increment in plasma density to the reduction of DC self-bias. Although this correlation was roughly right, but behaviors of the DC self-bias in the asymmetric RF discharge that was non-linearly interacted with the external circuit were not discussed. In practical applications, this approach of increasing plasma density will be limited by the rapid increase in power loss in step-down ferrite-core transformer operating in high-power 13.56 MHz discharges and the still high DC self-bias governed by the asymmetric geometry.

Space-charge induced particle reflection between hybrid AC/DC biased electrodes

Space-charge limited current flow between DC biased electrodes is a widely applicable problem in many areas of physics. Recently, radio-frequency biasing, together with DC self-bias formation, has been studied as a new concept for the extraction of charged particles from an upstream plasma source. Here, we compare particle extraction between systems using this hybrid AC/DC biasing, with conventional DC biased electrodes, and identify important similarity parameters. The injection current first leading to particle reflection strongly depends on the applied AC frequency and voltage magnitude, as well as the initial particle injection velocity, and is in general lower than the DC case. For injection currents above the AC limit, the system becomes unstable, and self-excited space-charge oscillations are generated. A critical parameter is the ratio of the average particle transit time between the electrodes to the AC period, γ = t L/T. As long as γ ≫ 1, the onset of particle reflection can be sufficiently delayed that the extracted current approaches the DC limit.

Non-linear effects and electron heating dynamics in radio-frequency capacitively coupled plasmas with a non-uniform transverse magnetic field

A non-uniform transverse magnetic field is used to increase the plasma density and create an asymmetry in radio frequency capacitively coupled plasmas for plasma sputtering and plasma vapor deposition. Based on one-dimensional particle-in-cell/Monte Carlo collision simulations, the effect of the magnetic field magnitude on the non-linear behavior and the electron heating dynamics is studied for a pure helium plasma at a pressure of 30 mTorr. The results show that increasing the magnetic field magnitude can generate a more positive DC self-bias. As a result, non-linear oscillations of the electron current density and the electric field close to the grounded electrode are enhanced. An electric field reversal is induced when the powered electrode sheath collapses to balance electron and ion fluxes toward this boundary due to the strong confinement of electrons. Anomalous energetic electron beams are observed propagating from the collapsed sheath toward the plasma bulk. It is shown that such beams are reflections of the beams originating from the opposite expanding sheath based on the analysis of single particle motions. We show that energetic electron beams can be reflected by the transverse magnetic field.

2D particle-in-cell simulations of geometrically asymmetric low-pressure capacitive RF plasmas driven by tailored voltage waveforms

The effects of the simultaneous presence of two different types of plasma asymmetry, viz, geometric and electrical, on low-pressure capacitively coupled argon discharges are studied by 2D3V graphics-processing-unit-based particle-in-cell/Monte Carlo simulations. The geometric asymmetry originates from the different powered vs grounded electrode surface areas, while the electrical asymmetry is established by applying peaks/valleys and sawtooth-up/-down driving voltage waveforms. While in geometrically symmetric discharges, the {peaks ↔ valleys} and the {sawtooth-down ↔ sawtooth-up} switching of the waveforms is equivalent to exchanging the powered and grounded electrodes, this transformation is violated when the geometric symmetry is broken. Under such conditions, the plasma characteristics and the DC self-bias generation behave differently, compared to the geometrically symmetric case. This leads to different sheath dynamics and, therefore, strongly influences the electron power absorption dynamics. For identical peak-to-peak voltages, the plasma density obtained for such tailored voltage waveforms is found to be higher compared to the classical single-frequency waveform case. Reduced plasma densities are found in the valleys- and sawtooth-down waveform cases, compared to the peaks- and sawtooth-up waveforms. By including realistic energy and material-dependent secondary electron emission (SEE) coefficients in the simulations, the electron-induced SEE is found to be reduced in the valleys- and sawtooth-down waveform cases, which explains the behaviour of the plasma density. Using such tailored waveforms in geometrically asymmetric discharges is also found to lead to the formation of different charged particle energy distributions at the boundary surfaces, compared to those in geometrically symmetric plasma sources.

Reactive ion etching of PbSe thin films in CH4/H2/Ar plasma atmosphere

In this work, we reported a reactive ion etching of PbSe thin films on silicon in CH4/H2/Ar plasma atmosphere. Various etching parameters that affect dc self-bias, the etching rate and the etching smoothness of the surface and sidewalls, including rf power, gas ratio, and process pressure, have been systematically investigated. It is found that the dc self-bias has an approximate linear relationship with rf power, but it decreases as the process pressure increases. The etching rate increases with increasing rf power and decreasing process pressure. Additionally, the etching rate increases to the maximum as CH4 percentage increases to 40%, beyond which it decreases with further increasing CH4 percentage due to formation of polymer. Furthermore, SEM results show that for all investigated samples except one etched in atmosphere with 60% CH4, the etched surfaces are smooth, and the sidewalls are vertical. The etched profile of sample etched in atmosphere with 60% CH4 is very rough, which should be attributed to formation of polymer as well.