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.     

Etch characteristics of GaN and BN materials in chlorine-based plasmas

Reactive ion etching (RIE) was performed on GaN and BN thin films using chlorine-based plasmas. The optimum chemistry was found to be BCl₃/Cl₂/N₂/Ar and Cl₂/Ar at 30 and 40 mtorr for GaN and BN etching, respectively. X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) analysis of the GaN and BN etched surfaces show a decrease in the surface nitrogen atomic composition and an increase in chlorine impurity incorporation with increasing self-dc bias. A photo-assisted RIE (PA-PIE) process using an IR filtered Xe lamp beam was then used and resulted in improved etch rates and surface composition. Optical emission spectroscopy (OES) measurements have also shown photoenhancement of the etch 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.     

Selective dry etching of (Sc2O3)x(Ga2O3)1−x gate dielectrics and surface passivation films on GaN

(Sc₂O₃)_x(Ga₂O₃)_1?x films grown by molecular beam epitaxy show promise for use as surface passivation layers and gate dielectrics on GaN-based high electron mobility transistors. Completely selective, low-damage, dry etching of (Sc₂O₃)_x(Ga₂O₃)_1?x films with respect to GaN can be achieved with low-power inductively coupled plasmas of CH₄/H₂/Ar with etch rates in the range 200–300 Å/min. The incident ion energies are of order 100 eV, and no roughening of the underlying GaN was observed under these conditions. Similar etch rates were obtained with Cl₂/Ar discharges under the same conditions, but GaN showed rates almost an order of magnitude higher.     

Electron cyclotron resonance plasma etching of materials for magneto-resistive random access memory applications

Dry etching of multilayer magnetic thin film materials is necessary for the development of sensitive magnetic field sensors and memory devices. The use of high ion density electron cyclotron resonance (ECR) plasma etching for NiFe, NiFeCo, TaN, and CrSi in SF₆/Ar, CH₄/H₂/Ar, and Cl₂/Ar plasmas was investigated as a function of microwave source power, rf chuck power, and process pressure. All of the plasma chemistries are found to provide some enhancement in etch rates relative to pure Ar ion milling, while Cl₂/Ar provided the fastest etch rate for all four materials. Typical etch rates of 3000Å/min were found at high microwave source power. Etch rates of these metals were found to increase with rf chuck power and microwave source power, but to decrease with increasing pressure in SF₆/Ar, CH₄/H₂/Ar, and Cl₂/Ar. A significant issue with Cl₂/Ar is that it produces significant metal-chlorine surface residues that lead to post-etch corrosion problems in NiFe and NiFeCo. However, the concentration of these residues may be significantly reduced by in-situ H₂ or O₂ plasma cleaning prior to removal of the samples from the etch reactor.     

A Study on Modified Silicon Surface after CHF3/C2F6 Reactive Ion Etching

The effects of reactive ion etching (RIE) of SiO₂ layer in CHF₃ / C₂F₆ on the underlying Si surface have been studied by X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometer, Rutherford backscattering spectroscopy, and high resolution transmission electron microscopy. We found that two distinguishable modified layers are formed by RIE : (i) a uniform residue surface layer of 4 nm thickness composed entirely of carbon, fluorine, oxygen, and hydrogen with 9 different kinds of chemical bonds and (ii) a contaminated silicon layer of about 50 nm thickness with carbon and fluorine atoms without any observable crystalline defects. To search the removal condition of the silicon surface residue, we monitored the changes of surface compositions for the etched silicon after various post treatments as rapid thermal anneal, O₂, NF₃, SF₆, and Cl₂ plasma treatments. XPS analysis revealed that NF₃ treatment is most effective. With 10 seconds exposure to NF₃ plasma, the fluorocarbon residue film decomposes. The remained fluorine completely disappears after the following wet cleaning.     

Characterization of reactive ion etching-induced damage to n-GaN surfaces using schottky diodes

Dry etch-induced damage has been investigated using Pd Schottky diodes fabricated on n-type GaN surfaces that were etched by reactive ion etching in SiCl₄ and Ar plasmas. Damage was evaluated by measuring the current-voltage, current-voltage-temperature, and capacitance-voltage characteristics of the diodes. A plasma chemistry that includes a chemical etching component (SiCl₄) was found to significantly reduce the degree of induced damage in comparison to a chemistry that uses only a physical component (Ar). The effective barrier height, ideality factor, reverse breakdown voltage, reverse leakage current, and the effective Richardson coefficient of diodes etched under various plasma conditions are presented. The degree of etch-induced damage was found to depend strongly on the plasma self-bias voltage but saturates with etch time after an initial two-minute etch period. Rapid thermal annealing was found to be effective in improving the diode characteristics of the etched GaN samples.     

Dry etch selectivity of Gd2O3 to GaN and AlN

Gd₂O₃ is a promising gate dielectric for GaN, but little is known of its dry etching characteristics. We achieved Gd₂O₃ etch rates up to ～600 Å · min^?1 in high density Cl2-based discharges, with maximum selectivities of ～15 over GaN and ～4 over AlN. Pure Cl₂ discharges produced reverse selectivities for both Gd₂O₃/GaN and Gd₂O₃/AlN, with typical values between 0.1–0.4. When a rare gas additive such as Ar or Xe was added to the plasma chemistry, the nitrides etched faster than the oxide. This indicates that volatile etch products (GaCl₃, AlCl₃, N₂) form in Cl₂-based plasmas once the GaN or AlN bonds are broken by ion bombardment, but that GdCl_x species are not volatile. In conjunction with the low efficiency for Gd₂O₃ bond-breaking at low ion energies, this leads to low selectivity.     

A comparative study on a high aspect ratio contact hole etching in UFC- and PFC-containing plasmas

An etching of a SiO₂ contact hole with a diameter of 0.19 μm and an aspect ratio of 13, using C₄F₆/Ar/O₂/CH₂F₂ and c-C₄F₈/Ar/O₂/CH₂F₂ plasmas, was performed for a feasibility test of the use of unsaturated fluorocarbons (UFCs) as an alternative to perfluorocarbon (PFC) gases for a high aspect ratio contact hole etching. The etch profile of the contact hole obtained in the C₄F₆/Ar/O₂/CH₂F₂ plasma was shown to have 23% lower degree of bowing than that in the c-C₄F₈/Ar/O₂/CH₂F₂ plasma. The Kelvin and chain contact resistances of the contact holes etched in the C₄F₆/Ar/O₂/CH₂F₂ plasma were 10-12% higher than those in the c-C₄F₈/Ar/O₂/CH₂F₂ plasma, but they were within the device spec. The integration of device with 0.1 μm design rule using C₄F₆/Ar/O₂/CH₂F₂ and c-C₄F₈/Ar/O₂/CH₂F₂ plasmas during the contact hole etching was also conducted, and it was found that etch profiles, metal coverage, and bottom critical dimensions of the contact in the C₄F₆/Ar/O₂/CH₂F₂ plasma were nearly identical to those in the c-C₄F₈/Ar/O₂/CH₂F₂ plasma, suggesting that the use of C₄F₆ gas as an etchant gas for a high aspect ratio contact hole etching can be a good alternative to PFC gases.     

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.     

Reactive ion etching of dielectrics and silicon for photovoltaic applications

This paper investigates the reactive ion etching of SiO₂, Si₃N₄, and Si using CHF₃/O₂ plasma. In particular, we have characterized the time and rf power dependence of the carrier lifetimes in n‐ and p‐type FZ Si. The time dependence of reactive ion etching (RIE) at different rf powers provide insight into the two competing processes of damage accumulation and damage removal in the near‐surface region of the Si during plasma etching. The carrier lifetime, measured using the quasi‐steady‐state photoconductance (QSSPC) technique, has a quadratic dependence on the rf power, which can be related to changes in the dc self‐bias generated by the plasma at different rf powers. The change in carrier lifetime is similar in both n‐ and p‐type Si of the same doping concentration. Using this fact, together with the electronic properties of defects obtained by deep level transient spectroscopy (DLTS), we have modeled the injection‐dependence of the measured carrier lifetimes using the Shockley–Read–Hall model. The isochronal annealing behavior of plasma etched Si has also been studied. Copyright © 2006 John Wiley & Sons, Ltd.     

Mechanism of porous low-k film damage induced by plasma etching radicals

The etching damage on nano-clustering silica (NCS) film due to etching radicals was investigated using a method of radical treatments in RIE plasma. NCS coated-side of the wafer was turned downward and put at 0.65 mm above the wafer stage to investigate only the influence of radicals. Etching radicals, which comes from CF₄, diffuse into NCS film and reduce Si-CH₃ bonds and Si-CH₃ loss is proportional to the amount of diffused fluorine in NCS film. Several Si-CH₃ bonds are converted to Si-F bonds then. As a result, the low-k performance is degraded and especially the leakage current heavily increases. We proposed a method for estimating the degree of the sidewall damage due to etching radicals using blanket wafers. The degree of sidewall damage is proportional to the value of CR^−0.5, where C is the damage diffusion coefficient, which is derived from Si-CH₃ decrement ratio from a radical treatment result and R is the etching rate, which is derived from a RIE treatment result under the same plasma condition. The value of CR^−0.5 depends on the etching condition and must be decreased as much as possible in order to reduce the sidewall damage during RIE. For example, lower gas pressure, higher RF power, and higher CF₄/Ar gas flow ratio were desirable for the sidewall damage reduction.     

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.     

Low-Dimensional Waveguide Grating Fabrication in GaN with Use of SiCl<Subscript>4</Subscript>/Cl<Subscript>2</Subscript>/Ar-Based Inductively Coupled Plasma Dry Etching

Optimized fabrication of submicron-sized features in gallium nitride (GaN) with the use of inductively coupled plasma (ICP) dry etching, based on SiCl₄/Cl₂/Ar gas mixture, is presented. Dense periodic patterns, i.e., 400-nm-period gratings, were transferred into a gallium nitride waveguide under different etching conditions. ICP power, radiofrequency (RF) power, chamber pressure, and Ar/Cl₂ gas mixing ratio were altered during the experiment. Depths of fabricated grating couplers up to 670 nm were achieved. The most suitable etching conditions are discussed with the assessment based on etching selectivity, scanning electron microscopy (SEM) observation of grating tooth slope, hard-mask erosion process, and etched surface morphology.     

Characterization of GaN films etched using reactive ion etching technique by secondary ion mass spectrometry

We investigated GaN films etched by using reactive ion etching (RIE) technique to fabricate the GaN-based devices. The samples were grown on sapphire substrate by metal organic chemical vapor deposition (MOCVD), and Ti/Al contacts were formed on n-GaN surfaces after etching processes. The effects of the kinds of reactive gases were evaluated by secondary ion mass spectrometry (SIMS). The results showed that in the sample etched using BCl₃ gas, the signal from boron contaminations was strongly detected at the interface between the contact metal and n-GaN, and we found that additional etching in Cl₂ plasma after etching with BCl₃ gas was essential to make a good contact.     

Chemically assisted ion beam etching of gallium nitride

Chemically assisted ion beam etching of gallium nitride (GaN) grown by metalorganic chemical vapor deposition has been characterized using an Ar ion beam and Cl₂gas. The etch rate of GaN was found to increase linearly with Ar ion beam current density, increase linearly then saturate with Ar ion beam energy, vary slightly with Cl₂ flow rate, and lastly, increase moderately with substrate temperature. Etch rates as high as 330 nm/min were obtained at high beam energies and 210 nm/min at a more nominal level of 500 eV. The anisotropy of etched profiles improved in the presence of Cl₂ in comparison to those etched by Ar ion milling only. Elevated substrate temperatures further enhanced the anisotropy to obtain near-vertical profiles for fairly deep-etched structures. Auger electron spectroscopy was used to investigate etch-induced surface changes. Oxygen contamination was observed on the as-etched surface but a dilute HC1 treatment restored the stoichiometry of the material to its unetched state.     

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.     

H2-based dry plasma etching for mesa structuring of HgCdTe

An experimental study has been carried out on the performance of n-type x = 0.31 HgCdTe photoconductive detectors in order to evaluate two different etching techniques; dry plasma etching, in the form of H₂/CH₄ reactive ion etching (RIE), and wet chemical etching using bromine in hydrobromic acid. Two-dimensional laser beam-induced current (LBIC) imaging was employed as an in-line process monitoring tool to evaluate the lateral extent of reactive ion etching (RIE) induced doping changes in the HgCdTe epilayer following mesa delineation. Responsivity and noise measurements were performed on fabricated mid-wavelength infrared (MWIR) photoconductive devices to evaluate the influence dry plasma etching has on material properties. For a signal wavelength of 3 μm, 60° field of view, and a temperature of 80 K, background limited D _λ ^* performance was recorded for wet chemical processed devices but not for the dry plasma processed devices. The D _λ ^* values obtained for wet chemical and dry plasma etched photoconductive detectors were 2.5×10¹¹ cmHz^1/2W⁻¹ and 1.0×10¹⁰ cmHz^1/2W⁻¹, respectively. Mercury annealing, which has been shown to restore the electrical properties of dry plasma processed HgCdTe, could be used to lessen the influence that RIE dry plasma etching has on photoconductor detector performance.     

Final polishing of Ga-polar GaN substrates using reactive ion etching

Reactive ion etching of {0001} oriented plate-like GaN single crystals has been investigated using SiCl₄:Ar:SF₆ chemistry. The reactive ion etching process is highly chemical. Large anisotropy of the etching rate and of the morphology has been established on (000 ) N-polar and (0001) Ga-polar sides of the GaN crystals, with remarkably higher rate on the N-polar side. Atomic force microscopy measurements have shown smooth surface and good polishing effect obtained on Ga-polar side, while N-polar surface exhibits an increased roughness of a factor of 10 after RIE.