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.     

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.     

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.     

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.     

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.     

Improved sidewall morphology on dry-etched SiO2 masked GaN features

A number of different methods have been investigated for minimizing sidewall roughness on dry etched GaN features formed using high density plasmas. In many instances, striations on dry etched mesas are a result of roughness in the initial photoresist mask employed, and this roughness is transferred sequentially to the dielectric mask and then to the GaN. Flood exposure of the photoresist, optimization of the bake temperature, choice of plasma chemistry, and ion flux/energy for patterning the dielectric mask all influence the final GaN sidewall morphology.     

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.     

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.     

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.     

ICP刻蚀对光刻胶掩模及刻蚀图形侧壁的影响

采用AZ1500光刻胶作为掩模对GaAs和InP进行ICP刻蚀,研究了刻蚀参数对光刻胶掩模及刻蚀图形侧壁的影响。结果表明,光刻胶的碳化变性与等离子体的轰击相关,压强、ICP功率和RF功率的增加以及Cl2比例的减小都会加速光刻胶的碳化变性,Cl2/Ar比Cl2/BCl3更易使光刻胶发生变性。对于GaAs样品刻蚀,刻蚀气体中Cl2含量越高,刻蚀图形侧壁的横向刻蚀越严重。Cl2/BCl3对GaAs的刻蚀速率比Cl2/Ar慢,但刻蚀后样品的表面粗糙度比Cl2/Ar小。刻蚀InP时的刻蚀速率比GaAs样品慢,且存在图形侧壁倾斜现象。该工作有助于推动在器件制备工艺中以光刻胶作为掩模进行ICP刻蚀,从而提高器件制备效率。     

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.     

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.     

Effects of Ar and O2 additives on photopatternable sol-gel etching in an SF6-based plasma for planar lightwave circuit fabrication

We present a novel study of the interaction of SF₆-based plasmas with sol-gel materials in a parallel plate reactive ion etching (RIE) system. The purpose of these experiments was to obtain quantitative measures and optimisation of the RIE parameters, which can be used in the microfabrication of planar lightwave circuit (PLC) devices. The sulfur hexafluoride chemistry is chosen due to its excellent etching properties of SiO₂, which is one of the components of the photopatternable sol-gel materials and is not present in typical photoresist materials. Fast process etching rate and good selectivity is achieved by varying SF₆ flow and power delivered to the electrodes. The study also reveals a marginal influence of oxygen and argon flow on the character of the sol-gel etching. The experimental data obtained can be used as a reference for any sol-gel devices fabricated using widely available RIE reactors.     

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.     

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.     

Selective etching of (Ba,Sr)TiO3 thin films over silicon in an inductively coupled plasma

In this work, we investigated etching characteristics of BST thin films and higher selectivity of BST over Si using inductive coupled O₂/Cl₂/Ar plasma (ICP) system. The maximum etch rate of BST thin films and selectivity of BST over Si were 61.5 nm/min at a O₂ addition of 1 sccm, 9.52 at a O₂ addition of 4 sccm into the Cl₂(30%)/Ar(70%) plasma, respectively. Plasma diagnostics was performed by Langmuir probe (LP), optical emission spectroscopy (OES) and quadrupole mass spectrometry (QMS). These results confirm that the increased etch rates at O₂ addition of 1 sccm is the result of the enhanced chemical reaction between BST and Cl radicals and an ion bombardment effect.     

Comparison of etching characteristics of SiO2 with ArF photoresist in C4F6 and C4F8 based dual-frequency superimposed capacitively coupled plasmas

In this study, we compared the C₄F₆ and C₄F₈ based plasma etching characteristics of silicon dioxide and ArF photoresist (PR) in a dual-frequency superimposed capacitively coupled plasma (DFS-CCP) etcher under different high- and low-frequency combinations (f_HF/f_LF), while varying the process parameters such as the dc self-bias voltage (V_dc), O₂ flow, and CH₂F₂ flow rate in the C₄F₈/CH₂F₂/O₂/Ar and C₄F₆/CH₂F₂/O₂/Ar plasmas. The silicon oxide etch rates increased significantly in both chemistries with increasing f_HF and O₂ flow rate. The silicon oxide etch rates were higher in the C₄F₈/CH₂F₂/O₂/Ar than in the C₄F₆/CH₂F₂/O₂/Ar plasmas, but the PR etch rate was much higher in the C₄F₆/CH₂F₂/O₂/Ar than in the C₄F₈/CH₂F₂/O₂/Ar plasmas under the present experimental conditions. The slower oxide etch rate in the C₄F₆ based plasmas was attributed to the thicker steady-state fluorocarbon layer on the silicon oxide surface, while the faster PR etch rate in the C₄F₈ based plasmas was ascribed to the higher F radical density in the plasma.     

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.     

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.     

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.