Comparison of ECR plasma chemistries for etching of InGaP and AlGaP

Etch rates for InGaP and AlGaP are examined under electron cyclotron resonance (ECR) conditions in Cl₂/Ar, BCl₃/Ar, BCl₃/N₂, ICl/Ar, and IBr/Ar discharges. All the plasmas except IBr/Ar provide rapid etching of InGaP at rates above 1 μm min⁻¹. ICl/Ar provides the highest etch rates. Unlike the Cl₂/Ar and BCl₃-based chemistries, the rates in ICl/Ar and IBr/Ar are almost independent of microwave power in the range 400–1000 W. Much lower rates were obtained for AlGaP in every discharge due to the greater difficulties in bond breaking that must precede formation and desorption of the etch products.     

Etching characteristics of ZnO thin films in chlorine-containing inductively coupled plasmas

This study examined the plasma etching characteristics of ZnO thin films etched in BCl₃/Ar, BCl₃/Cl₂/Ar and Cl₂/Ar plasmas with a positive photoresist mask. The ZnO etch rates were increased in a limited way by increasing the gas flow ratio of the main etch gases in the BCl₃/Ar, BCl₃/Cl₂/Ar and Cl₂/Ar plasmas at a fixed dc self-bias voltage (V_dc). However, the ZnO etch rate was increased more effectively by increasing the V_dc. Optical emission spectroscopy (OES) and X-ray photoelectron spectroscopy (XPS) analyses of the ZnO surfaces etched at various Cl₂/(Cl₂ + Ar) mixing ratios revealed the formation of the ZnO_xCl_y reaction by-products as a result of the increased etch rate with increasing Cl₂ addition, compared with 100% Ar⁺ sputter etching. This suggests that at Cl₂/Ar flow ratios ⩾20%, the ZnO etch process is controlled by an ion-assisted removal mechanism where the etch rate is governed by the ion-bombardment energy under the saturated chlorination conditions.     

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.     

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.     

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.     

Plasma chemistries for high density plasma etching of SiC

A variety of different plasma chemistries, including SF₆, Cl₂, ICl, and IBr, have been examined for dry etching of 6H-SiC in high ion density plasma tools (inductively coupled plasma and electron cyclotron resonance). Rates up to 4500?-min⁻¹ were obtained for SF₆ plasmas, while much lower rates (≤800?·min⁻¹) were achieved with Cl₂, ICl, and IBr. The F₂-based chemistries have poor selectivity for SiC over photoresist masks (typically 0.4–0.5), but Ni masks are more robust, and allow etch depths ≥10 μm in the SiC. A micromachining process (sequential etch/deposition steps) designed for Si produces relatively low etch rates (<2,000?-min⁻¹) for SiC.     

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.     

Model‐Based Analysis of the ZrO2 Etching Mechanism in Inductively Coupled BCl3/Ar and BCl3/CHF3/Ar Plasmas

The etching mechanism of ZrO₂ thin films and etch selectivity over some materials in both BCl₃/Ar and BCl3/CHF3/Ar plasmas are investigated using a combination of experimental and modeling methods. To obtain the data on plasma composition and fluxes of active species, global (0‐dimensional) plasma models are developed with Langmuir probe diagnostics data. In BCl3/Ar plasma, changes in gas mixing ratio result in nonlinear changes of both densities and fluxes for Cl, BCl2, and BCl2⁺. In this work, it is shown that the nonmonotonic behavior of the ZrO2 etch rate as a function of the BCl3/Ar mixing ratio could be related to the ion‐assisted etch mechanism and the ion‐flux‐limited etch regime. The addition of up to 33% CHF₃ to the BCl₃‐rich BCl3/Ar plasma does not influence the ZrO2 etch rate, but it non‐monotonically changes the etch rates of both Si and SiO2. The last effect can probably be associated with the corresponding behavior of the F atom density.     

The fabrication and dry etching of poly-Si/TaN/Mo gate stack in the metal inserted poly-Si stack structure

The Mo-based metal inserted poly-Si stack (MIPS) structure is an appropriate choice for metal gate and high-k integration in sub-45 nm gate-first CMOS device. A novel metal nitride layer of TaN or AlN with high thermal stability has been introduced between Mo and poly-Si as a barrier material to avoid any reaction of Mo during poly-Si deposition. After Mo-based MIPS structure is successfully prepared, dry etching of poly-Si/TaN/Mo gate stack is studied in detail. The three-step plasma etching using the Cl₂/HBr chemistry without soft landing step has been developed to attain a vertical poly-Si profile and a reliable etch-stop on the TaN/Mo metal gate. For the etching of TaN/Mo gate stack, two methods using BCl₃/Cl₂/O₂/Ar plasma are presented to get both vertical profile and smooth etched surface, and they are critical to get high selectivity to high-k dielectric and Si substrate. In addition, adding a little SF₆ to the BCl₃/O₂/Ar plasma under the optimized conditions is also found to be effective to smoothly etch the TaN/Mo gate stack with vertical profile.     

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.     

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.     

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.     

Etching of As- and P-based III–V semiconductors in a planar inductively coupled BCl<Subscript>3</Subscript>/Ar plasma

A parametric study of the etch characteristics of Ga-based (GaAs, GaSb, and AlGaAs) and In-based (InGaP, InP, InAs, and InGaAsP) compound semiconductors in BCl₃/Ar planar inductively coupled plasmas (ICPs) was performed. The Ga-based materials etched at significantly higher rates, as expected from the higher volatilities of the As, Ga, and Al trichloride, etch products relative to InCl₃. The ratio of BCl₃ to Ar proved critical in determining the anisotropy of the etching for GaAs and AlGaAs, through its effect on sidewall passivation. The etched features in In-based materials tended to have sloped sidewalls and much rougher surfaces than for GaAs and AlGaAs. The etched surfaces of both AlGaAs and GaAs have comparable root-mean-square (RMS) roughness and similar stoichiometry to their unetched control samples, while the surfaces of In-based materials are degraded by the etching. The practical effect of the Ar addition is found to be the ability to operate the ICP source over a broader range of pressures and to still maintain acceptable etch rates.     

ICP dry etching of ZnO and effects of hydrogen

Two different plasma chemistries for etching ZnO were examined. Both Cl₂/Ar and CH₄/H₂/Ar produced etch rates which increased linearly with rf power, reaching values of 1200 Å/min for Cl₂/Ar and 3000 Å/min for CH₄/H₂/Ar. The evolution of surface morphology, surface composition, and PL intensity as a function of energy during etching were monitored. The effect of H in ZnO was studied using direct implantation at doses of 10¹⁵–10¹⁶ cm⁻², followed by annealing at 500–700 °C. The hydrogen shows significant outdiffusion at 500 °C and is below the detection limits of SIMS after 700 °C anneals. SEM of the etched features showed anisotropic sidewalls, indicative of an ion-driven etch mechanism.     

The behaviour of boron molecular ion implants into silicon

Implants of boron molecular ions into silicon have been studied using a variety of experimental techniques, but with emphasis on sheet resistance annealing characteristics and transmission electron microscopy. Boron halide compound molecules have been implanted and equivalent dose sequential implants of atomic species used as control conditions. The implants studied were B⁺, BCl₂⁺, BCl⁺, Cl⁺ + B⁺, BF₂⁺, BF⁺ and B⁺ + F⁺ at 25 keV/B atom and B⁺, BBr₂⁺ and Br₂⁺ + B⁺ at 12 keV/B atom.The implantation of molecular ions enables conditions of varying damage to be studied with constant dose, dose rate and energy of the dopant species. In addition to damage effects the halogen atoms produce species effects in the implanted zone. The escape of the halogen atoms has been measured as a function of the annealing temperature.The significant differences which exist between the behaviour of silicon implanted with these various conditions are considered with reference to the damage structures observed by transmission electron microscopy. The boron-fluorine molecular implants are shown to offer some advantages as a means of implanting boron.     

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.     

Reactive sputter etching of Al in BCl3

Etching of Al is studied in pure BCl₃ as well as in mixtures with other gases in the reactive sputter etching mode in a cryopumped system. Etch rate, selectivity with respect to positive photoresist, SiO₂ and Si and etch profiles are investigated as a function of gas composition, gas pressure, flow rate and plasma power. Plasma chemical processes are monitored by quadrupole mass spectroscopy as well as by optical emission spectroscopy. Perfectly square Al-profiles can be etched if etch rates are kept below 1000 A/min. Al-patterns running over steep steps can also be clearly defined if a certain amount of overetching can be tolerated. The experimental data indicate that the etch process is reactant supply limited. Anisotropic etching is achieved by either a ‘surface inhibitor mechanism’ or the formation of a sidewall protecting film.     

Study of Surface Treatments on InAs/GaSb Superlattice LWIR Detectors

We report on the comparison of mesa sidewall profiles of InAs/GaSb strained-layer superlattice (SLS) detector structures (λ _{50% cutoff} ≈ 14 μm at V _bias = 0 V and T = 30 K) obtained after (a) a conventional BCl₃-based inductively coupled plasma etch, (b) a chemical etch (H₂O₂:HCl:H₂O, 1:1:4), and (c) a combination of both etches. We found that the smoothest sidewall profile with reasonable undercut (~5 μm) was obtained after chemical etch only. The chemical etch was optimized primarily using an n-type GaSb substrate. During this process, numerous chemical etchants were examined. GaSb n-type substrates were chosen for this study in preference over InAs substrates due to their high chemical reactivity and the complicated composition of the native oxide. In addition, SLS detectors are usually grown on GaSb substrates and, after hybridization of the focal-plane array to the readout integrated circuit, the GaSb substrate is etched away using a combination of wet and dry etching techniques. We found that H₂O₂:HCl:H₂O (1:1:4) etching solution provided the smoothest etched surface of GaSb, with a root-mean-square roughness of 1.59 nm.     

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.     

Sequential Vacuum Evaporated Copper Metal Halides for Scalable,Flexible, and Dynamic X-Ray Detection

Copper metal halides have emerged as a strong contender in the scintillator field due to the self-trapped excitons (STEs) mechanism. However, their development has been hindered by the preparation process. Single crystals have long growth cycles and cannot achieve large areas and flexibility. Quantum dots have a low yield and can easily cause chemical pollution, and the thickness of films prepared by the spin coating cannot be controlled. To address these challenges, a new method for preparing Cs₃Cu₂Cl₅ using sequential vacuum evaporation is developed. This allows successful preparation of large-area (≈100 cm²) and flexible films. The STEs mechanism of Cs₃Cu₂Cl₅ gives it unique properties such as a large Stokes shift that reduces self-absorption effects, and a wide full width at half-maximum that improves coupling with photodiodes. Therefore, Cs₃Cu₂Cl₅ is applied to X-ray imaging with a light yield of ≈30 000 photons MeV⁻¹, a spatial resolution of over 10 lp mm⁻¹, and a low detection limit below 0.8 µGy_air s⁻¹. In addition, the flexible Cs₃Cu₂Cl₅ film enables effective dynamic imaging and clear imaging on non-planar objects. It also exhibits good resistance to harsh environments, maintaining good imaging performance after 150 days. It is believed that sequential vacuum evaporation provides an important idea for preparing scintillators.