Characterization of the CH4/H2/Ar high density plasma etching process for ZnSe

High density plasma etching of zinc selenide using CH₄/H₂/Ar plasma chemistries is investigated. Mass spectrometry, using through-the-platen sampling, is used to identify and monitor etch products evolving from the surface during etching. The identifiable primary etch products are Zn, Se, ZnH₂, SeH₂, Zn(CH₃)₂, and Se(CH₃)₂. Their concentrations are monitored as ion and neutral fluxes (both in intensity and composition), ion energy, and substrate temperature are varied. General insights about the surface chemistry mechanisms of the etch process are given from these observations. Regions of process parameter space best suited for moderate rate, anisotropic, and low damage etching of ZnSe are proposed. Code 6752 Code 6174     

Inductively coupled plasma etching of HgCdTe using a CH<Subscript>4</Subscript>-based mixture

We report results on a study on inductively coupled plasma (ICP) etching of HgCdTe using a CH₄-based mixture. Effects of key process parameters on etch rates were investigated and are discussed in this article in light of plasma parameter measurements, performed using a Langmuir probe. Process parameters of interest include ICP source power, substrate power, pressure, and CH₄ concentration. We show that the ICP etching technique allows us to obtain etch rates of about 200 nm/min, which is high enough to use this technique in a manufacturing process. We also observe that the ion bombardment has a strong influence on HgCdTe etch rate. Finally, we show that this etch rate is modified by the substitution of methane for hydrogen.     

Effects of CH2F2 and H2 flow rates on process window for infinite etch selectivity of silicon nitride to ArF PR in dual-frequency CH2F2/H2/Ar capacitively coupled plasmas

The process window for the infinite etch selectivity of silicon nitride (Si₃N₄) layers to ArF photoresist (PR) and ArF PR deformation were investigated in a CH₂F₂/H₂/Ar dual-frequency superimposed capacitive coupled plasma (DFS-CCP) by varying the process parameters, such as the low frequency power (P_LF), CH₂F₂ flow rate, and H₂ flow rate. It was found that infinitely high etch selectivities of the Si₃N₄ layers to the the ArF PR on both the blanket and patterned wafers could be obtained for certain gas flow conditions. The H₂ and CH₂F₂ flow rates were found to play a critical role in determining the process window for infinite Si₃N₄/ArF PR etch selectivity, due to the change in the degree of polymerization. The preferential chemical reaction of hydrogen with the carbon in the hydrofluorocarbon (CH_xF_y) layer and the nitrogen on the Si₃N₄ surface, leading to the formation of HCN etch by-products, results in a thinner steady-state hydrofluorocarbon layer and, in turn, in continuous Si₃N₄ etching, due to enhanced SiF₄ formation, while the hydrofluorocarbon layer is deposited on the ArF photoresist surface.     

Etch damage evaluation on (Bi4−xLax)Ti3O12 thin films during the etch process using inductively coupled plasma sources

The etching mechanism of (Bi_4−xLa_x)Ti₃O₁₂ (BLT) thin films in Ar/Cl₂ inductively coupled plasma (ICP) and plasma-induced damages at the etched surfaces were investigated as a function of gas-mixing ratios. The maximum etch rate of BLT thin films was 50.8 nm/min of 80% Ar/20% Cl₂. From various experimental data, amorphous phases on the etched surface existed on both chemically and physically etched films, but the amorphous phase was thicker after the 80% Ar/20% Cl₂ process. Moreover, crystalline “breaking” appeared during the etching in Cl₂-containing plasma. Also the remnant polarization and fatigue resistances decreased more for the 80% Ar/20% Cl₂ etch than for pure Ar plasma etch.     

Inductively coupled plasma reactive ion etching of SiC single crystals using NF<Subscript>3</Subscript>-based gas mixtures

Inductively coupled plasma reactive ion etching of SiC single crystals using NF₃-based gas mixtures was investigated. Mesas with smooth surfaces and vertical sidewalls were obtained, with a maximum etch rate of about 400 nm/min. Effects of CH₄ and O₂ addition to the NF₃ gas and the crystalline quality of substrates were studied during the SiC dry etching using various masks. Selectivity of the photoresist (PR) mask improved from about 0.2 to about 0.4 by the addition of 30% CH₄ during the RIE, although the etch rate decreased by 50–70%. Results also indicated that the substrate quality does not significantly affect the etch results.     

Mechanism of selective Si3N4 etching over SiO2 in hydrogen-containing fluorocarbon plasma

This paper describes the mechanism of selective Si₃N₄ etching over SiO₂ in capacitively-coupled plasmas of hydrogen-containing fluorocarbon gas, including CHF₃, CH₂F₂ and CH₃F. The etch rate of Si₃N₄ and SiO₂ is investigated as a function of O₂ percentage in all plasma gases. Addition of O₂ in feed gases causes plasma gas phase change especially H density. The SiO₂ etch rate decreases with increase of O₂ percentage due to the decline of CF_x etchant. The Si₃N₄ etch rate is found to be strong correlated to the H density in plasma gas phase. H can react with CN by forming HCN to reduce polymer thickness on Si₃N₄ surface and promote the removal of N atoms from the substrate. Thus the Si₃N₄ etch rate increases with H intensity. As a result, a relative high selectivity of Si₃N₄ over SiO₂ can be achieved with addition of suitable amount of O₂ which corresponds to the maximum of H density.     

Reactive ion etching of gallium nitride films

Reactive ion etching (RIE) was performed on gallium nitride (GaN) films grown by electron cyclotron resonance (ECR) plasma assisted molecular beam epitaxy (MBE). Etching was carried out using trifluoromethane (CHF₃) and chloropentafluoroethane (C₂ClF₅) plasmas with Ar gas. A conventional rf plasma discharge RIE system without ECR or Ar ion gun was used. The effects of chamber pressure, plasma power, and gas flow rate on the etch rates were investigated. The etch rate increased linearly with the ratio of plasma power to chamber pressure. The etching rate varied between 60 and 500Å/min, with plasma power of 100 to 500W, chamber pressure of 60 to 300 mTorr, and gas flow rate of 20 to 50 seem. Single crystalline GaN films on sapphire showed a slightly lower etch rate than domain-structured GaN films on GaAs. The surface morphology quality after etching was examined by atomic force microscopy and scanning electron microscopy.     

N2 effect on GaAs etching at 150 mTorr capacitively-coupled Cl2/N2 plasma

The role of N₂ on GaAs etching at 150 mTorr capacitively-coupled Cl₂/N₂ plasma is reported. A catalytic effect of N₂ was found at 20-25% N₂ composition in the Cl₂/N₂ discharges. The peak intensities of the Cl₂/N₂ plasma were monitored with optical emission spectroscopy (OES). Both atomic Cl (725.66 nm) and atomic N (367.05 nm) were detected during the Cl₂/N₂ plasma etching. With the etch rate and OES results, we developed a simple model in order to explain the etch mechanism of GaAs in the high pressure capacitively-coupled Cl₂/N₂ plasma as a function of N₂ ratio. If the plasma chemistry condition became positive ion-deficient at low % N₂ or reactive chlorine-deficient at high % N₂ in the Cl₂/N₂ plasma, the GaAs etch rate is reduced. However, if the plasma had a more balanced ratio of Cl₂/N₂ (i.e. 20-25% N₂) in the plasma, much higher etch rates (up to 150 nm/min) than that in pure Cl₂ (50 nm/min) were produced due to synergetic effect of neutral chlorine adsorption and reaction, and positive ion bombardment. Pure Cl₂ etching produced 14 nm of RMS surface roughness of GaAs. Introduction of ?20% N₂ gas in Cl₂/N₂ discharges significantly reduced the surface roughness to 2-4 nm. SEM photos showed that the morphology of photoresist mask was strongly degraded. Etch rate of GaAs slightly increased from 10 to 40 nm/min when RIE chuck power changed from 10 to 150 W at 12 sccm Cl₂/8 sccm N₂ plasma condition. The surface roughness of GaAs etched at 12 sccm Cl₂/8 sccm N₂ plasma was 2-3 nm.     

Reaction chemistry and resulting surface structure of HgCdTe etched in CH4/H2 and H2 ECR plasmas

We report on several new aspects of etching of Hg_1−xCd_xTe (x = 0.22), HgTe, and CdTe in CH₄/H₂/Ar plasmas generated by an electron cyclotron resonance plasma source. Using a residual gas analyzer, we have identified elemental Hg, TeH₂, Te(CH₃)₂, and Cd(CH₃)₂ as the primary reaction products escaping from a HgCdTe surface during the plasma exposure. We have also demonstrated that a bias is not needed to etch HgCdTe at moderate temperatures (30-40°C), as previously suggested by other researchers. We have also developed a technique that avoids the formation of hydrocarbon polymer films on a HgCdTe sample during etching. Moreover, we have examined by x-ray photoelectron spectroscopy analysis and ellipsometry the surface condition of HgCdTe resulting from etching with this technique at zero bias. After exposure to the CH₄/H₂Ar plasma (or to a H₂/Ar plasma only), the HgCdTe samples exhibited a depletion of the HgTe component in the near surface region (increase of the x-value). The depletion covered a range from virtually x = 1 after H₂/Ar (10:2 in sccm) etching to values 0.4 < x < 0.5 after CH₄/H₂Ar (7:7:2 in seem) etching. Exposures to the plasmas were found to result in surface roughening of HgCdTe, however, plasmas rich in H₂ were observed to cause significantly rougher surfaces than plasmas with small H₂/CH₄ ratios. This difference in the resulting surface condition is attributed solely to chemical effects since the respective ion energies are considered to be below the damage threshold for HgCdTe in both cases. We also investigated the etching of HgTe and CdTe single crystals. The etch rate of HgTe was found to be over one order of magnitude higher than that of CdTe under similar conditions. This large difference in etch rates is assumed to be responsible for the observed preferential etching of the HgTe component indicated by the HgTe depletion of the HgCdTe surface region.     

Effect of gas mixing ratio on etch behaviors of Ba2Ti9O20 (BTO) and Pt thin films in Cl2/Ar inductively coupled plasma

An investigation of the Ba₂Ti₉O₂₀ (BTO) and Pt thin films etch mechanism in the Cl₂/Ar inductively coupled plasma was carried out. It was found that an increase in Ar mixing ratio at fixed gas pressure and input power causes a fast decrease in the BTO etch rate (26.9-1.2 nm/min for 0-100% Ar) while the Pt etch rate increases slightly from 17.4-23.0 nm/min. Langmuir probe diagnostics and zero-dimensional plasma modeling provided the data on plasma parameters, steady-state composition and fluxes of active species on the etched surface. From the model-based analysis of etch kinetics, it was shown that the behavior of the BTO etch rate corresponds to the reaction-rate-limited etch regime, where the etch rate is limited neither by physical sputtering of the main material nor by the ion-stimulated desorption of low-volatile reaction products. The etch process of Pt appears in the transitional regime and is controlled by the neutral and ion fluxes together.     

Low-energy electron-enhanced etching of HgCdTe

Low-energy electron-enhanced etching (LE4) is applied to HgCdTe to eliminate ion-induced surface damage. First, LE4 results for patterned samples are illustrated. The LE4 mechanism is understood from a mechanistic study in terms of three etch variables: direct current (DC) bias, gas composition, and sample temperature. For this paper, the effects of DC bias (electron energy) and gas composition (CH₄ concentration) are summarized qualitatively, followed by quantitative evidence. Etch rate, the amount of polymer, surface stoichiometry, and surface roughness have specific relations with each etch variable under competition between pure LE4 and polymer deposition.     

ECR plasma etch fabrication of C-doped base InGaAs/InP DHBT structures: A comparison of CH4/H2/Ar vs BCl3/N2 plasma etch chemistries

We compare ECR plasma etch fabrication of self-aligned thin emitter carbondoped base InGaAs/InP DHBT structures using either CH₄/H₂/Ar or BCl₃/N₂ etch chemistries. Detrimental hydrogen passivation of the carbon doping in the base region of our structure during CH₄/H₂/Ar dry etching of the emitter region is observed. Initial conductivity is not recovered with annealing up to a temperature of 500°C. This passivation is not due to damage from the dry etching or from the MOMBE growth process, since DHBT structures which are ECR plasma etched in BCl₃/N₂ have the same electrical characteristics as wet etched controls. It is due to hydrogen implantation from the plasma exposure. This is supported with secondary ion mass spectroscopy profiles of structures which are etched in CH₄/D₂/Ar showing an accumulation of deuterium in the C-doped base region.     

Plasma and wet chemical etching of In0.5Ga0.5P

Dry and wet chemical etching of epitaxial In_{0, 5}Ga_0.5P layers grown on GaAs substrates by gas-source molecular beam epitaxy have been investigated. For chlorine-based dry etch mixtures (PCl₃/Ar or CC1₂F₂/Ar) the etching rate of InGaP increases linearly with dc self-bias on the sample, whereas CH₄/H₂-based mixtures produce slower etch rates. Selectivities of ≥500 for etching GaAs over InGaP are obtained under low bias conditions with PCl₃/Ar, but the surface morphologies of InGaP are rough. Both CC1₂F₂/Ar and CH₄/H₂/Ar mixtures produce smooth surface morphologies and good (≥10) selectivities for etching GaAs over InGaP. The wet chemical etching rates of InGaP in H₃PO₄:HC1:H₂O mixtures has been systemically measured as a function of etch formulation and are most rapid (∼1 μn · min⁻¹) for high HCl compositions. The etch rate,R, in a 1:1:1 mixture is thermally activated of the formR ∝ , whereE _a = 11.25 kCal · mole⁻¹. This is consistent with the etching being reaction-limited at the surface. This etch mixture is selective for InGaP over GaAs.     

用于非易失性相变存储器中Si2Sb2Te5在CF4/Ar等离子体下的反应离子刻蚀

Phase change random access memory（PCRAM） is one of the best candidates for next generation nonvolatile memory,and phase change Si₂Sb₂Te₅ material is expected to be a promising material for PCRAM.In the fabrication of phase change random access memories,the etching process is a critical step.In this paper,the etching characteristics of Si₂Sb₂Te₅ films were studied with a CF₄/Ar gas mixture using a reactive ion etching system.We observed a monotonic decrease in etch rate with decreasing CF4 concentration,meanwhile,Ar concentration went up and smoother etched surfaces were obtained.It proves that CF4 determines the etch rate while Ar plays an important role in defining the smoothness of the etched surface and sidewall edge acuity.Compared with Ge₂Sb₂Te₅, it is found that Si₂Sb₂Te₅ has a greater etch rate.Etching characteristics of Si₂Sb₂Te₅ as a function of power and pressure were also studied.The smoothest surfaces and most vertical sidewalls were achieved using a CF₄/Ar gas mixture ratio of 10/40,a background pressure of 40 mTorr,and power of 200 W.     

Influence of activated polymer on the etching rate of SiO2 in CF4 + H2 plasma

The reactive ion etching (RIE) of SiO₂ in CF₄ + H₂ plasma is considered. The influence of activated polymer on the RIE rate of SiO₂ in CF₄ + H₂ plasma is determined by extrapolation of experimentally measured kinetics of the etching rate. It is found that the increased surface coverage by CF₂ radicals suppresses the RIE rate of SiO₂ in CF₄ + H₂ plasma during the initial stages of the etching process. The formation of activated polymer becomes pronounced when adsorbed CF₂ radicals are slowly activated. The activated polymer intensifies the etching reaction and enhances the etching rate. At the same time, the activated polymer intensifies the polymerization reactions. The increased surface coverage by the polymer suppresses the RIE rate of SiO₂ in CF₄ + H₂ plasma at later stages of the etching process.     

Iron nitride mask and reactive ion etching of GaN films

One of the major GaN processing challenges is useful pattern transfer. Serious photoresist mask erosion and hardening are often observed in reactive ion etching of GaN. Fine pattern transfer to GaN films using photoresist masks and complete removal of remaining photoresist after etching are very difficult. By replacing the etch mask from conventional photoresist to a sputtered iron nitride (Fe-8% N) film, which is easily patterned by wet chemical etching and is very resistive to Cl based plasmas, GaN films can be finely patterned with vertical etched sidewalls. Successful pattern transfer is realized by reactive ion etching using Cl (H) containing plasmas. CHF₃/Ar, C₂ClF₅/Ar, C₂ClF₅/Ar/O₂, SiCl₄, and CHCl₃ plasmas were used to etch GaN. The GaN etch rate is dependent on the crystalline quality of GaN. Higher crystalline quality GaN films exhibit slower etch rates than GaN films with higher dislocation and stacking fault density.     

Dry etching characteristics of In1-x-y Ga x Al y as alloys in CCl2F2:Ar and CH4:H2:Ar discharges

The etching characteristics of InGaAlAs alloys lattice-matched to InP were investigated using low pressure (1 mTorr) electron cyclotron resonance CH₄:H₂:Ar or CCl₂F₂:Ar discharges with additional radiofrequency biasing of the samples. Using CCl₂F₂:Ar discharges with ≥250V negative bias it is possible to obtain equi-rate etching of the material for all compositions between In_0.53Ga_0.47As and In_0.52Al_0.48As. At lower bias values, formation of A1F₃ on the surface leads to an inhibition of the etch rates. By making use of the differential etch rates of InGaAlAs layers of different compositions in CH₄:H₂:Ar mixtures, it is possible to choose dc bias values that allow one to stop the etching at a pre-selected depth in a multi-layer structure. For example, for -150 V bias, one can etch through In_0.53Ga_0.47As, In_0.53Ga_0.40Al_0.07As and Ino.53Ga_0.30Al_0.17As layers, and stop at an underlying layer with composition In_0.53Ga_0.20Al_0.27As.     

Wet Etching of (0001) GaN/Al2O3 grown by MOVPE

H₃PO₄, NaOH, and KOH solutions are found to be useful for removing nitrogen depleted layers or damage induced by high temperature annealing or dry etching of metalorganic chemical vapor deposition-grown (0001)GaN/Al₂O₃. Solutions are selective to the (0001)plane of GaN. However, certain flat planes etched without etch pits are exposed by wet etching.     

Remote plasma etching of titanium nitride using NF3/argon and chlorine mixtures for chamber clean applications

To avoid plasma induced erosion of chamber hardware, the application of remote plasma sources to activate the etch gases was introduced. We present results on the etch behaviour of titanium nitride (TiN) using mixtures of NF₃, Cl₂ and argon. The gas mixture was excited in a remote plasma source and then routed through a reaction chamber to study the etch behaviour of TiN samples which simulate the situation at the chamber walls. The dependency of the TiN etch rate on temperature, gas flow, composition and pressure was examined. While the temperature (studied in the range 25-300 °C) turned out to be the most sensitive parameter, the general etch rate was mainly dependent on the availability of atomic fluorine. Etch products and NF₃/Cl₂ dissociation have been monitored by quadrupole mass spectrometry and infrared spectroscopy. While NF₃ showed a high decomposition up to 96%, chlorine decomposition was not observed. However the addition of chlorine increased the etch rates up to 260% in the low pressure/low temperature regime. Surface effects of chlorine addition are indicated by X-Ray Photoelectron Spectrometry and REM surface analysis.     

SiCl4-based reactive ion etching of ZnO and MgxZn1−xO films on r-sapphire substrates

SiCl₄-based reactive ion etching (RIE) is used to etch Mg_xZn_1−xO (0≤x≤0.3) films grown on r-plane sapphire substrates. The RIE etch rates are investigated as a function of Mg composition, RIE power, and chamber pressure. SiO₂ is used as the etching mask to achieve a good etching profile. In comparison with wet chemical etching, the in-plane etching anisotropy of Mg_xZn_1−xO (0≤x≤0.3) films is reduced in RIE. X-ray photoelectron spectroscopy measurements show that there is no Si and Cl contamination detected at the etched surface under the current RIE conditions. The influence of the RIE to the optical properties has been investigated.