A preliminary study of SF6 based inductively coupled plasma etching techniques for beta gallium trioxide thin film

Beta phase Gallium trioxide (β-Ga₂O₃) thin film was grown by metal organic chemical vapor deposition technology. Mixture gases of SF₆ and Ar were used for dry etching of β-Ga₂O₃ thin film by inductively coupled plasma (ICP). The effect of SF₆/Ar (etching gas) ratio on etch rate and film etching damage was studied. The etching rate and surface roughness were measured using F20-UN thin film analyzer and atomic force microscopy showing that the etching rate in the range between 30 nm/min and 35 nm/min with an improved surface roughness was obtained when the reactive mixed gas of SF₆/Ar was used. The analysis of X-ray diffraction and transmission spectra further confirmed the non-destructive crystal quality. This work demonstrates that the properly proportioned mixture gases of SF₆/Ar is suitable for the dry etching of β-Ga₂O₃ thin film by ICP and can serve as a guide for future β-Ga₂O₃ device processing.     

CHF3-O2 reactive ion etching of 4H-SiC and the role of oxygen

Reactive ion etching of 4H-SiC was performed using a CHF₃-O₂ plasma. The etch rate and mean surface roughness were investigated as a function of the ratio of the O₂ flow rate to the total gas flow rate. It was found that oxygen plays an indirect role in contributing to the etching of SiC. An optimum O₂ fraction of 20% was found to give a maximum etch rate of 35 nm/min. On the other hand, the root-mean-square (RMS) surface roughness was found to increase from 1.31 to 2.34 nm when the O₂ fraction increased from 0% to 80%. Auger electron spectroscopy results for the samples etched at the optimum condition of 20% O₂ fraction revealed the presence of oxygen on the etched surface in a form of an oxide-like layer (SiO_x). No carbon residue (carbon rich-layer) and aluminum were found. Based on our results, the role of O₂ in the reactive ion etching of 4H-SiC will be presented.     

Deep dry etching of borosilicate glass using SF6 and SF6/Ar inductively coupled plasmas

Deep reactive ion etching (DRIE) of borosilicate glass was carried out using SF₆ and SF₆/Ar plasmas in an inductively coupled plasma (ICP) reactor. Electroplated Ni on Cu (≅50 nm)/Cr (≅100 nm)/glass structure using patterned SU-8 photoresist mask with a line spacing of 12-15 μm was used as a hard-mask for plasma etching. Plasma etching of borosilicate glass was performed by varying the various process parameters such as the gas chemistry, the gas flow ratio, the top electrode power, and the dc self-bias voltage (V_dc). In the case of using SF₆ gas only, the profiles of the etched channel showed the undercut below the Ni hard-mask due to a chemical etching and the microtrenching at the bottom of the etched channel. An optimized process using the SF₆ plasmas showed the glass etch rate of ≅750 nm/min. The addition of the Ar gas to the SF₆ gas removed the undercut and microtrenching but decreased the etch rate to ≅540 nm/min. The increasing and decreasing time-dependent etch rates with the etch depth in the SF₆ (200 sccm) and SF₆(60%)/Ar(40%) plasmas, respectively, were ascribed to the different ion-to-neutral flux ratios leading to the different etch process regime.     

Chemical conversion of C2 F6 and uniformity of etching SiO2 in a radial flow plasma reactor

Plasma etching of SiO₂} with C₂}F₆} in a radial flow reactor was investigated to determine relationships between chemical aspects of the discharge, operating parameters such as power and flow rates, and uniformity of etching over a large area. The chemical conversion of C₂}F₆} in the discharge was monitored by infrared spectrometry of the exhaust gases, as a function of discharge power and gas flow rate. The input gas was found to be transformed mainly to CF₂} and a polymeric material, and at sufficiently long residence times (∼1 sec) a "steady state " was achieved. At the steady state condition C₂}F₆} was found to be ∼60% converted. The amount of conversion was not influenced by the presence of SiO₂} being etched, however, the production of CF₄} was reduced by the presence of SiO₂}. For a known flow rate and reactor dimensions the concentrations of species as a function of radial position in the reactor were calculated. It was demonstrated that the etch rate of SiO₂} was dependent on this radial concentration profile. Uniform etching was obtained if the etching zone lay entirely within the "steady state" region of the discharge. Reduced etch rates or polymerization on the substrates was observed if large concentration gradients (rich in C₂}F₆}existed in the etching zone. It was concluded that the etch rate of SiO₂} is dependent then on the local gas composition in the discharge, and can be manipulated by means of adjusting power and gas flow rates.     

Chromium etching characteristics using a planar type plasma reactor

The dry etching characteristics of Cr film in the CCl₄/O₂ mixed gas plasma have been investigated with a variety of etching parameters in the planar type reactor with the 13.56 MHz rf power. Moreover the dry etching resistance of EB resists and variation of the feature size on a 12.5 and 15 cm Cr-Mask are described. The etch rate of Cr film depends strongly on the etchant gas composition ratio, the electrode separation and the electrode surface materials. In the cathode coupling mode with a gas pressure of 0.2 Torr, a gas flow rate of CCl₄/O₂ of 0.5, electrode separation of 80 mm and rf power density of 0.38 W/cm², the following results are obtained: (1) The etch rate of Cr film is about 30 nm/min, Paper presented partially at 23rd Annual Electronic Materials Conference, University of California, Santa Barbara, California, June 24, 1981.     

Chemical contribution of oxygen to silicon carbide plasma etching kinetics in a distributed electron cyclotron resonance (DECR) reactor

This paper deals with the influence of the oxygen additive on the fluorinated plasma etch rate of silicon carbide. The assumption according to which the oxygen has a direct contribution to silicon carbide etching, by chemical reaction with carbon atoms, is generally reported in the literature. Our etching experiments are performed in a distributed electron cyclotron resonance reactor, on both 3C- and 6H-SiC. An SF₆/O₂ gas mixture (avoiding the presence of C species in the plasma), fluorine saturation conditions and constant ion bombardment energy and flux are used, allowing the study of O₂ contribution exclusively. In these conditions, our results demonstrate the neutrality of O₂ on SiC etching mechanisms. These results will be discussed reinfored both by several other experimental observations.     

ICP刻蚀损伤对金属场板结构SiC肖特基二极管电学性能的影响

本文通过电感耦合等离子体（ICP）系统地研究了各种刻蚀参数对4H-SiC刻蚀的影响,并进一步研究了刻蚀损伤对金属场板结构4H-SiC肖特基二极管电学性能的影响。研究表明刻蚀速率和SiC表面形貌都会受到ICP功率、RF功率、压强和刻蚀气体流量的影响。在高的ICP偏压下,观察到了刻蚀损伤（刻蚀坑和刻蚀锥）的形成。更深入的研究表明,这些刻蚀损伤的形成和SiC自身的缺陷有关。这些刻蚀损伤的存在会导致SiC肖特基二极管正反向I-V性能发生恶化。在刻蚀损伤严重的情况下,对比正反向I-V测试结果发现,在0~50V的绝对电压范围内,正向电流甚至远小于反向电流。     

Low bias dry etching of III-nitrides in Cl2-based inductively coupled plasmas

Cl₂-based inductively coupled plasmas (ICP) with low additional dc self-biases (?100V) produce convenient etch rates (500–1500Å·min^?1) for III-nitride electronic device structures. A systematic study of the effects of additive gas (Ar, N₂, H₂), discharge composition, process pressure, and ICP source power and chuck power on etch rate and surface morphology has been performed. The general trends are to go through a maximum in etch rate with percent Cl₂ in the discharge for all three mixtures, and to have an increase (decrease) in etch rate with source power (pressure). Since the etching is strongly ion-assisted, anisotropic pattern transfer is readily achieved. Maximum etch selectivities of approximately six for InN over the other nitrides were obtained.     

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.     

Controlled beam dry etching of InP by using Br2-N2 Gas

Indium phosphide dry etching is carried out using a reactive beam extracted from a Br₂-N₂ gas discharge plasma. Keeping the N₂ gas pressure constant at 0.23 mTorr, the Br₂ gas pressure was varied from 0 to 0.1 mTorr and the sample temperature was varied from 40 to 200°C. The etched shapes and etching rates are investigated in terms of the etching beam composition. Two distinct types of etching mechanisms come into play depending on the Br₂ gas pressure. Smooth vertical side walls and a temperature independent etching rate can be obtained at a Br₂ gas pressure of 0.04 mTorr or less and a temperature above 100°C, where the etching is induced by the ambient Br₂ gas species and N₂ beam. Undercut etching with a temperature dependent etching rate is seen at a Br₂ gas pressure of 0.07 mTorr or higher, where the etching beam contains both N₂ and Br₂ gas species. Neutralized Br species generated by the discharge of the Br₂ gas are shown to form the undercut. A waveguide corner mirror with a loss of less than 1 dB is made by using an etching beam with no neutralized Br species.     

Etching of mesa structures in HgCdTe

Mesa structures were etched in HgCdTe using different Br₂/HBr/Ethylene glycol (EG) formulations. Etch rate and degree of anisotropy (A) were studied in detail for all of the combinations. Addition of EG to the conventional etchant gave A>0.5, with controllable etch rates. Optimum etchant composition was determined to be 2% Br₂ in a 3:1 mixture of EG:HBr. This composition resulted in a good anisotropy factor of ∼0.6 and a reasonably optimum etch rate of ∼2.5 μm/min, with rms surface roughness of ∼2 nm. Kinetics of the etching reaction have also been studied for the optimum etchant concentration and an etching mechanism has been proposed.     

Role of N2 during chemical dry etching of silicon oxide layers using NF3/N2/Ar remote plasmas

In this work, the role of N₂ gas during the chemical dry etching of silicon oxide layers in NF₃/N₂/Ar remote plasmas was investigated by analyzing the species in the plasma, the reaction by-products in the exhaust, and the chemical properties of the etched surface. Increasing the N₂ gas flow rate resulted in an initial increase in the oxide etch rate up to a maximum value, followed by a subsequent decrease. The increased etch rate of the silicon oxide layers was not ascribed to the increased surface arrival rate of fluorine, but to the enhanced oxygen removal from the silicon oxide caused by the formation of NO₂ molecules. Presumably, the NO radicals formed from the added N₂ gas react chemically with the oxygen in the oxide, leading to the breaking of the Si-O bonds and the effective removal of oxygen, which in turn enhances the formation of SiF₄ resulting in an increased etch rate.     

A comparative study of wet and dry selective etching processes for GaAs/AIGaAs/lnGaAs pseudomorphic MODFETs

The etching characteristics of Al_xGa_1-xAs in citric acid/H₂O₂ solutions and SiCl₄/SiF₄ plasmas have been studied. Using a 4:1 solution of citric acid/H₂O₂ at 20° C, selectivities of 155, 260, and 1450 have been obtained for GaAs on Al_xGa_1-xAs withx = 0.3,x = 0.45, andx = 1.0, respectively. Etch rates of GaAs in this solution were found to be independent of line widths and crystal orientations for etched depths up to 1000?. GaAs etch profiles along [110] and [110] directions displayed different slope angles as expected. Selective reactive ion etching (SRIE) using SiCl₄/SiF₄ gas mixtures at 90 mTorr and -60 V self-biased voltage yielded selectivities between 200 and 500 forx values ranging from 0.17 to 1.0. SRIE etch rates for GaAs were relatively constant for etch depths of less than 1000?. At greater etch depths, etch rates varied by up to 76% for line widths between 0.3 and 1.0μm. Both selective wet etch and dry etch processes were applied to the fabrication of pseudomorphic GaAs/AIGaAs/lnGaAs MODFETs with gate lengths ranging from 0.3 to 2.5 μm on heterostructures with an embedded thin AlAs etch stop layer. A threshold voltage standard deviation of 13.5 mV for 0.3 μ gate-length MODFETs was achieved using a 4:1 citric acid/H₂O₂ solution for gate recessing. This result compares favorably with the 40 mV obtained using SRIE, and is much superior to the 230 mV achieved using the nonselective etch of 3:1:50 H₃PO₄: H₂O₂: H₂O. This shows that selective wet etching using citric acid/H₂O₂ solutions in conjunction with a thin Al_xGa_1-xAs(x ≥ 0.45) etch stop layer provides a reasonably simple, safe, and reliable process for gate recessing in the fabrication of pseudomorphic MODFETs.     

Cl2 chemical dry etching of GaAs under high vacuum conditions—Crystallographic etching and its mechanism

Cl₂ chemical dry etching for GaAs substrates of {111}A, {111}B, {110} and {100} orientations was accomplished under high vacuum conditions. The etch rate for different substrate orientations was {111}B > {110} = {100} > {111}A for temperatures below 450° C, and was nearly equal for temperatures above 450° C. For {111}B, {110} and {100} substrates, the etch rate depends strongly on the substrate temperature above 450° C and below 150° C. Two activation energies for etching (10.0 kcal/mol below 150° C and 16.0 kcal/mol above 450° C) were obtained. Between 150 and 450° C, the etch rate depends weakly on the substrate temperature. However, for {111}A substrate, the etch rate increased monotonically with increasing substrate temperature above 300° C. The activation energy corresponds to that for the other substrates above 450° C. These results are caused by the surface chemical reaction of GaAs/Cl₂. By using these etching properties, a vertical side wall was fabricated without ion bombardment.     

Selective chemical etching of polycrystalline SiGe alloys with respect to Si and SiO2

Polycrystalline SiGe etches that are selective to silicon dioxide as well as silicon are needed for flexibility in device fabrication. A solution of NH₄OH, H₂O₂, and H₂O has been found to selectivity etch polycrystalline silicon-germanium alloys over both silicon and silicon dioxide. Optimum composition of the solution was determined by maximizing etch rates for SiGe films with several germanium compositions. The dependence of etch rates on germanium content, etching temperature, and doping concentration are reported. The etch rate and selectivity are approximately exponentially proportional to the germanium content. Etching was found to be insensitive to deposition method, doping method, and annealing conditions of the SiGe films. In addition, etching leaves a smooth silicon substrate surface after removal of SiGe films.     

Plasma etching of copper films at low temperature

Experimental verification of a low temperature (<20 °C), reactive plasma etch process for copper films is presented. The plasma etch process, proposed previously from a thermochemical analysis of the Cu-Cl-H system, is executed in two steps. In the first step, copper films are exposed to a Cl₂ plasma to preferentially form CuCl₂, which is volatilized as Cu₃Cl₃ by exposure to a H₂ plasma in the second step. Plasma etching of thin films (9 nm) and thicker films (400 nm) of copper has been performed; chemical composition of sample surfaces before and after etching has been determined by X-ray photoelectron and flame atomic absorption spectroscopies.     

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

High density plasma etching of mercury cadmium telluride using CH₄/H₂/Ar plasma chemistries is investigated. Mass spectrometry is used to identify and monitor etch products evolving from the surface during plasma etching. The identifiable primary etch products are elemental Hg, TeH₂, and Cd(CH₃)₂. Their relative concentrations are monitored as ion and neutral fluxes (both in intensity and composition), ion energy and substrate temperature are varied. General insights are made into surface chemistry mechanisms of the etch process. These insights are evaluated by examining etch anisotropy and damage to the remaining semiconductor material. Regions of process parameter space best suited to moderate rate, anisotropic, low damage etching of HgCdTe are identified.     

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.     

Effect of dry etching on surface properties of III-nitrides

Dry etched InAlN and GaN surfaces have been characterized by current-voltage measurement, Auger electron spectroscopy, and atomic force microscopy. Electron cyclotron resonance discharges of BCl₃. BCl₃/Ar, BCl₃/N₂, or BCl₃/N₂ plus wet chemical etch all produce nitrogen surfaces that promote leakage current in rectifying gate contacts, with the BCl₃/N₂ plus wet chemical etch producing the least disruption on the surface properties. The conductivity of the immediate InAlN or GaN surface can be increased by preferential loss of N during BCl₃ plasma etching, leading to poor rectifying contact characteristics when the gate metal is deposited on this etched surface. Careful control of plasma chemistry, ion energy, and stoichiometry of the etched surface are necessary for acceptable pinch-off characteristics. Hydrogen passivation during the etch was also studied.