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.     

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.     

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.     

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.     

Effect of O2/CHF3 plasma treatment on n-type GaN grown on sapphire by MOCVD

Plasma-induced damage of n-type GaN in Cl₂/CH₄/Ar reactants and its recovery by the O₂/CHF₃ plasma treatment in reactive ion etching (RIE) system were studied by etching rate, self-bias voltage and Hall measurement. RIE of n-type GaN was performed at a radio frequency power of 250 W in Cl₂/CH₄/Ar ambient prior to in the O₂/CHF₃ plasma treatment. The effect of O₂/CHF₃ plasma treatment on electrical characteristics of n-type GaN was investigated by changing the ratio of O₂/CHF₃ flow rate. It is found that the damage caused by conventional RIE processing could be partly recovered by CHF₃/O₂ plasma treatment.     

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.     

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.     

Dry etching of GaN using chemically assisted Ion beam etching with HCI and H2/Cl2

The dry etching characteristics of GaN were investigated using chemically assisted ion beam etching (CAIBE) with HCI and H₂/Cl₂ gas. Etch rates using CAIBE/HC1 were investigated as a function of Ar ion beam energy and substrate temperature. These results were compared to CAIBE/C1₂. Etch rates were also investigated for CAIBE/H₂/Cl₂ for various ratios of H₂:C1₂. Highly anisotropic submicron lines are demonstrated using CAIBE/HC1. Auger electron spectroscopy was used to investigate surface stoichiometric changes of samples etched with CAIBE/HC1, CAIBE/H₂/Cl₂,, and CAIBE/C1₂. The diffusion of deuterium into GaN during etching was also investigated using secondary ion mass spectrometry.     

Gate oxide reliability concerns in gate-metal sputtering deposition process: an effect of low-energy large-mass ion bombardment

The effects of ion species/ion bombardment energy in sputtering deposition process on gate oxide reliability have been experimentally investigated. The use of xenon (Xe) plasma instead of argon (Ar) plasma in tantalum (Ta) film sputtering deposition for gate electrode formation makes it possible to minimize the plasma-induced gate oxide damage. The Xe plasma process exhibits 1.5 times higher breakdown field and five times higher 50%-charge-to-breakdown (Q_BD). In the gate-metal sputtering deposition process, the physical bombardment of energetic ion causes to generate hole traps in gate oxide, resulting in the lower gate oxide reliability. The simplified model providing a better understanding of the empirical relation between the gate oxide damage and the ion-bombardment energy to gate oxide in gate-metal sputtering deposition process is also presented.     

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.     

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.     

In-situ plasma cleaning of stainless steel III-V MOCVD growth systems

A plasma enhanced, in-situ, dry etching process for the cleaning of stainless steel III-V Metal Organic Chemical Vapor Deposition growth systems was investigated as a function of etchant gas, flow rate, electrode configuration, power density and plasma frequency. The plasma enhanced etching process was investigated using Ar, CH₄ (5% in H₂), CCl₂F₂ (Freon 12)/Ar and Cl₂/Ar plasmas with flows varying from 5 to 25 seem. The plasma was excited using three electrode configurations, and two radio frequency generators (90–460 KHz and 13.56 MHz), singly and in combination. The plasma power was varied over the range from 200 to 700 Watts (∼0.2W/cm² – 0.7W/cm²). The etching rates of GaAs, InP, As, and Mo were measured using a weight difference method. The Cl₂/Ar plasmas exhibited etching rates typically 5 to 10 times greater than that of CCl₂F₂ plasmas, which in turn is several times greater than that of the other etchant gases investigated. At 400 W, elemental As etch rates, as high as ∼180μm/hr and ∼20μm/hr were achieved using Cl₂ and CCl₂F₂ plasmas, respectively. InP/GaAs etch rates using Cl₂ were ∼30μm/hr and using CCl₂F₂ were ∼7μm/hr. Plasma characteristics and etch rate measurements are reported. The in-situ process investigated is a safe, cost effective and an efficient method for increasing reactor uptime.     

Effect of High-Density Plasma Process Parameters on Carrier Transport Properties in <Emphasis Type="Italic">p</Emphasis>-to-<Emphasis Type="Italic">n</Emphasis> Type Converted Hg<Subscript>0.7</Subscript>Cd<Subscript>0.3</Subscript>Te Layer

Exposure of p-type HgCdTe material to Ar/H₂-based plasma is known to result in p-to-n conductivity-type conversion. While this phenomenon is generally undesirable when aiming to perform physical etching for device delineation and electrical isolation, it can be used in a novel process for formation of n-on-p junctions. The properties of this n-type converted material are dependent on the condition of the plasma to which it is exposed. This paper investigates the effect of varying the plasma process parameters in an inductively coupled plasma reactive ion etching (ICPRIE) tool on the carrier transport properties of the p-to-n type converted material. Quantitative mobility spectrum analysis of variable-field Hall and resistivity data has been used to extract the carrier transport properties. In the parameter space investigated, the n-type converted layer carrier transport properties and depth have been found to be most sensitive to the plasma process pressure and temperature. The levels of both RIE and ICP power have also been found to have a significant influence.     

高Al组分AlGaN的ICP干法刻蚀

初步研究了采用Cl2 /Ar /He等离子体对MOCVD生长的背照射Al0. 45 Ga0. 55N材料的 ICP干法刻蚀工艺。采用离子束溅射生长的Ni作为刻蚀掩模,刻蚀速率随ICP直流偏压的增加而增加。采用传输线模型测量了刻蚀前后AlGaN材料方块电阻的变化,分析了干法刻蚀电学损伤与直流偏压的关系。用扫描电镜( SEM)观察了不同直流偏压下刻蚀台面形貌,并对其进行了分析。     

The effects of reactive ion etching-induced damage on the characteristics of ohmic contacts to n-Type GaN

The effects of reactive ion etching n-GaN surfaces with both SiCl₄ and Ar plasmas have been investigated using transmission line measurements. The measurements were made from ohmic contacts consisting of Al (as-deposited) and Ti/Al (as-deposited and rapid thermal annealed). The contact resistance, specific contact resistance, and sheet resistance were investigated as functions of the dc plasma self-bias voltage and etch time. The contact resistance extracted from contacts fabricated on surfaces etched with SiCl₄ was found to be improved over the unetched samples for all conditions investigated. Dry etching the surface with Ar severely degraded the contact resistance over the unetched sample except at the lower self-bias voltages. Rapid thermal annealing of etched samples prior to Al deposition was found to be effective in removing some of the reactive ion etching/SiCl₄-induced damage.     

Gallium arsenide surface chemistry and surface damage in a chlorine high density plasma etch process

In an effort to monitor ion-driven surface chemistry in the high density plasma etching of GaAs by Cl₂/Ar plasma chemistries, we have applied mass spectrometry and careful substrate temperature control. Etch product chlorides were mass analyzed while the substrate temperature was monitored by optical bandgap thermometry and as pressure (neutral flux), microwave power (ion flux) and rf bias of the substrate (ion energy) were varied. By ensuring that the substrate temperature does not deviate during process variations, the changes in product mass peak intensities are a direct measure of changes in the ionassisted surface chemistry which promotes anisotropic etching. Experimental results show that ion-assisted surface chemistry is optimum when sufficient Cl and Cl⁺ are present in the incident plasma flux. These conditions are met at low coupled microwave powers (<300 W) and low total process pressures (<1.0 mTorr) for input gas mixtures of 25% Cl₂ in Ar. Three mechanistic regions are identified for surface chemistry as a function of incident ion energy: 1) largely thermal chemistry for <50 eV; 2) ion-assisted chemistry for 50–200 eV; and 3) sputtering for >200 eV. Photoreflectance measurements of the surface Fermi level show significant damage for ion energies >75 eV. However, in situ and ex situ surface passivations can recover the surface Fermi level for up to 200 eV ion energies, in good correlation to the onset of sputtering and subsurface damage. Thus, anisotropic, low damage pattern transfer is possible for ion energies between 50 and 200 eV.     

Very Low Pressure Magnetron Reactive Ion Etching of GaN and Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ga<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>N Using Dichlorofluoromethane (Halocarbon 12)

In this work we report on the magnetron reactive ion etch (MRIE) technology for gallium nitride (GaN) and aluminum gallium nitride (Al _x Ga_1−x N) using dichlorodifluoromethane (CCl₂F₂), commonly known as halocarbon 12, with etch rates greater than 1,000 and 840 ?/min, respectively. Magnetic confinement of a very low pressure (10⁻⁴ Torr range) radio frequency (RF) discharge generates high-density plasmas, with low sheath voltages at the bounding surfaces, and very high dissociation of the source gas. Furthermore, the very low pressure of the etch process is characterized by long mean free paths so that sputtering contamination is reduced. MRIE chemistry has been monitored in situ by means of mass spectroscopy. Finally, we report on the successful fabrication of an indium gallium nitride (In _x Ga_1−x N) blue light emitting diode (LED), whose fabrication sequence included the MRIE etching of GaN in CCl₂F₂.     

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.     

Etching characteristics of photoresist and low-k dielectrics by Ar/O2 ferrite-core inductively coupled plasmas

We have investigated the characteristics of Ar/O₂ plasmas in terms of the photoresist (PR) and low-k material etching using a ferrite-core inductively coupled plasma (ICP) etcher. We found that the O₂/(O₂+ Ar) gas flow ratio significantly affected the PR etching rate and the PR to low-k material etch selectivity. Fourier transform infrared spectroscopy (FTIR) and HF dipping test indicated that the etching damage to the low-k material decreased with decreasing O₂/(O₂ + Ar) gas flow ratio.     

High-density plasma etch selectivity for the III–V nitrides

High-density plasma etching has been an effective patterning technique for the group-III nitrides due to ion fluxes which are 2–4 orders of magnitude higher than more conventional reactive ion etch (RIE) systems. GaN etch rates exceeding 0.68 μm/min have been reported in Cl₂/H₂/Ar inductively coupled plasmas (ICP) at −280 V dc-bias. Under these conditions, the etch mechanism is dominated by ion bombardment energies which can induce damage and minimize etch selectivity. High selectivity etch processes are often necessary for heterostructure devices which are becoming more prominent as growth techniques improve. In this study, we will report high-density ICP etch rates and selectivities for GaN, AlN, and InN as a function of plasma chemistry, cathode rf-power, ICP-source power, and chamber pressure. GaN:AlN selectivities >8:1 were observed in a Cl₂/Ar plasma at 10 mTorr pressure, 500 W ICP-source power, and 130 W cathode rf-power, while the GaN:InN selectivity was optimized at 6.5:1 at 5 mTorr, 500 W ICP-source power, and 130 W cathode rf-power.