Nonpolar a-plane GaN grown on r-plane sapphire using multilayer AlN buffer by metalorganic chemical vapor deposition

Mirror-like and pit-free non-polar a-plane (1 1 −2 0) GaN films are grown on r-plane (1 −1 0 2) sapphire substrates using metalorganic chemical vapor deposition (MOCVD) with multilayer high-low-high temperature AlN buffer layers. The buffer layer structure and film quality are essential to the growth of a flat, crack-free and pit-free a-plane GaN film. The multilayer AlN buffer structure includes a thin low-temperature-deposited AlN (LT-AlN) layer inserted into the high-temperature-deposited AlN (HT-AlN) layer. The results demonstrate that the multilayer AlN buffer structure can improve the surface morphology of the upper a-plane GaN film. The grown multilayer AlN buffer structure reduced the tensile stress on the AlN buffer layers and increased the compressive stress on the a-plane GaN film. The multilayer AlN buffer structure markedly improves the surface morphology of the a-plane GaN film, as revealed by scanning electron microscopy. The effects of various growth V/III ratios was investigated to obtain a-plane GaN films with better surface morphology. The mean roughness of the surface was 1.02 nm, as revealed by atomic force microscopy. Accordingly, the multilayer AlN buffer structure improves the surface morphology and facilitates the complete coalescence of the a-plane GaN layer.     

Characterization of wide-band-gap semiconductors (GaN, SiC) by defect-selective etching and complementary methods

Two defect-selective etching approaches used for revealing and analysis of defects in wide-band-gap semiconductors (GaN, SiC) are described in detail: (i) orthodox etching in molten salts (KOH, NaOH) and hot acids (H₂SO₄,H₃PO₄) and (ii) electroless photo-etching (photoelectrochemical or PEC) in aqueous solutions of KOH. Characteristic features of these two techniques, their reliability and limitation in revealing different types of defects (dislocations, stacking faults, micro-defects and electrically active chemical non-homogeneities) will be discussed. Examples of the use of both etching approaches to reveal defects in bulk and epitaxial layers of different crystallographic orientation are given. Numerous references to previous work on calibration of the etch features by means of TEM, X-ray diffraction, Raman and PL methods are cited.     

Optimization of inductively coupled plasma deep etching of GaN and etching damage analysis

Inductively coupled plasma (ICP) etching of GaN with an etching depth up to 4 μm is systemically studied by varying ICP power, RF power and chamber pressure, respectively, which results in etch rates ranging from ∼370 nm/min to 900 nm/min. The surface morphology and damages of the etched surface are characterized by optical microscope, scanning electron microscope, atomic force microscopy, cathodoluminescence mapping and photoluminescence (PL) spectroscopy. Sub-micrometer-scale hexagonal pits and pillars originating from part of the structural defects within the original GaN layer are observed on the etched surface. The density of these surface features varies with etching conditions. Considerable reduction of PL band-edge emission from the etched GaN surface indicates that high-density non-radiative recombination centers are created by ICP etching. The density of these non-radiative recombination centers is found largely dependent on the degree of physical bombardments, which is a strong function of the RF power applied. Finally, a low-surface-damage etch recipe with high ICP power, low RF power, high chamber pressure is suggested.     

Dry etching of MgCaO gate dielectric and passivation layers on GaN

MgCaO films grown by rf plasma-assisted molecular beam epitaxy and capped with Sc₂O₃ are promising candidates as surface passivation layers and gate dielectrics on GaN-based high electron mobility transistors (HEMTs) and metal-oxide semiconductor HEMTs (MOS-HEMTs), respectively. Two different plasma chemistries were examined for etching these thin films on GaN. Inductively coupled plasmas of CH₄/H₂/Ar produced etch rates only in the range 20-70 Å/min, comparable to the Ar sputter rates under the same conditions. Similarly slow MgCaO etch rates (∼100 Å/min) were obtained with Cl₂/Ar discharges under the same conditions, but GaN showed rates almost an order of magnitude higher. The MgCaO removal rates are limited by the low volatilities of the respective etch products. The CH₄/H₂/Ar plasma chemistry produced a selectivity of around 2 for etching the MgCaO with respect to GaN.     

Morphologies of latent and etched heavy-ion tracks in {111} CaF2

Structure details of latent tracks created by U, Pb and Au ions (energies 6.9, 28.7 and 11.1?MeV/A, respectively) in {111} CaF₂ have been extracted by means of scanning force microscopy and transmission electron microscopy. The revealed structure has assisted in the interpretation of the etching behaviour of tracks created in {111} CaF₂ by 9.2?MeV/A Bi ions. In the latter experiments, irradiated fragments were immersed for short durations in a 3:1 10% HCl/96% H₂SO₄ solution and the morphology of the formed etch pits was derived by high-resolution scanning electron microscopy and scanning force microscopy. Three conclusions emerged. First, ion-induced surface hillocks exhibit no resistance against etchant attack. Second, the primary etching diameter of the track coincides with the nanometric width of the structurally altered track core. Third, the structure of the etch pits, 3-faced symmetric pyramidal depressions with {122} faces, indicates that etching across the track halo, a few tens of nanometers wide strained crystal, is dominated by surface energies of crystal faces.     

Dry etching characteristics of GaN using Cl2/BCl3 inductively coupled plasmas

ICP power/RF power, operating pressure, and Cl₂/BCl₃ gas mixing ratio are altered to investigate the effect of input process parameters on the etch characteristics of GaN films. The etch selectivity of GaN over SiO₂ and photoresist is studied. Although higher ICP/RF power can obtain higher GaN/photoresist etch selectivity, it can result in faceting of sidewall and weird sidewall profile due to photoresist mask erosion. Etch rates of GaN and SiO₂ decrease with the increase of operating pressure, and etch selectivity of GaN over SiO₂ increases with the increasing operating pressure at fixed ICP/RF power and mixture component. The highest etch selectivity of GaN over SiO₂ is 7.92, and an almost vertical etch profile having an etch rate of GaN close to 845.3 nm/min can be achieved. The surface morphology and root-mean-square roughness of the etched GaN under different etching conditions are evaluated by atomic force microscopy. The plasma-induced damage of GaN is analyzed using photoluminescence (PL) measurements. The optimized etching process, used for mesa formation during the LED fabrication, is presented. The periodic pattern can be transferred into GaN using a combination of Cl₂/BCl₃ plasma chemistry and hard mask SiO₂. Patterning of the sapphire substrate for fabricating LED with improved extraction efficiency is also possible using the same plasma chemistry.     

Wet chemical etching method for BST thin films annealed at high temperature

As a traditional etchant, pure buffered hydrofluoric acid (BHF), does not possess the ability to etch BST thin films annealed at high temperature, even though it works greatly on as-deposited Ba_0.5Sr_0.5TiO₃ (BST) films. In this paper, we developed an etchant by mixing BHF and strong acid (HNO₃, HCl, H₂SO₄ and H₃PO₄) and use it successfully on BST films annealed with high temperature. The experimental results show that a 1-8 wt% of strong acid acts as an efficient catalyst and the etching speed is significantly improved. The etched BST films show little distortions and smooth etching edges were recorded.     

Structural and optical properties of GaN thin films grown on Al2O3 substrates by MOCVD at different reactor pressures

GaN thin films grown by MOCVD on (0 0 0 1) Al₂O₃ substrates at different growth pressures were characterized by field-emission scanning electron microscopy, atomic force microscopy, micro-Raman, and photoluminescence at room temperature. It was found that there is an optimum pressure of 76 Torr at which the structural and optical properties of the GaN samples are superior. On the other hand samples grown at higher pressure exhibited hexagonal surface pits and surface spirals. The results showed that the growth pressure strongly influences the morphology, and significantly affects the structural and optical properties of the GaN epilayers.     

Effect of chemical etching on the Cu/Ni metallization of poly (ether ether ketone)/carbon fiber composites

Poly(ether ether ketone)/carbon fiber composites (PEEK/Cf) were chemical etched by Cr₂O₃/H₂SO₄ solution, electroless plated with copper and then electroplated with nickel. The effects of chemical etching time and temperature on the adhesive strength between PEEK/Cf and Cu/Ni layers were studied by thermal shock method. The electrical resistance of some samples was measured. X-ray photoelectron spectroscopy (XPS) was used to analyze the surface composition and functional groups. Scanning electron microscopy (SEM) was performed to observe the surface morphology of the composite, the chemical etched sample, the plated sample and the peeled metal layer. The results indicated that CO bond increased after chemical etching. With the increasing of etching temperature and time, more and more cracks and partially exposed carbon fibers appeared at the surface of PEEK/Cf composites, and the adhesive strength increased consequently. When the composites were etched at 60 °C for 25 min and at 70-80 °C for more than 15 min, the Cu/Ni metallization layer could withstand four thermal shock cycles without bubbling, and the electrical resistivity of the metal layer of these samples increased with the increasing of etching temperature and time.     

Multiple UV-blue luminescence emissions in electrochemical anodic etched n-type silicon wafer

This very paper is focusing on the preparation of porous nanostructures in n-type silicon (1 1 1) wafer by chemical etching technique in alkaline aqueous solutions of 5 M NaOH, 5 M K₂CO₃ and 5 M K₃PO₄, and particularly, on its ultraviolet-blue photoluminescence emission. The anodic chemical etched silicon wafer has been characterized by means of optical microscopy, scanning electron microscopy, fluorescence spectroscopy, atomic force microscopy and Fourier transform infrared spectroscopy. This very surface morphology characterization has been clearly shown - the effect of anodic-chemical-etching procedure processed in K₂CO₃ or K₃PO₄ was much vigorous than that processed in NaOH. The FTIR spectra indicate that the silicon oxide was formed on the surface of electrochemical etched n-Si (1 1 1) wafers, yet not on that of the pure chemical etched ones anyhow. And an intense ultraviolet-blue photoluminescence emission is observed, which then differs well from the silicon specimen etched in alkaline solution with no anodic potential applied. The proper photoluminescence mechanism is discussed, and hence there may be a belief that the intense ultraviolet-blue photoluminescence emission would be attributed to the silicon oxide coating formed on silicon wafer in anodic-chemical-etching process.     

Dry etching of ITO by magnetic pole enhanced inductively coupled plasma for display and biosensing devices

The dry etching of indium tin oxide (ITO) layers deposited on glass substrates was investigated in a high density inductively coupled plasma (ICP) source. This innovative low pressure plasma source uses a magnetic core in order to concentrate the electromagnetic energy on the plasma and thus provides for higher plasma density and better uniformity. Different gas mixtures were tested containing mainly hydrogen, argon and methane. In Ar/H₂ mixtures and at constant bias voltage (−100 V), the etch rate shows a linear dependence with input power varying the same way as the ion density, which confirms the hypothesis that the etching process is mainly physical. In CH₄/H₂ mixtures, the etch rate goes through a maximum for 10% CH₄ indicating a participation of the radicals to the etching process. However, the etch rate remains quite low with this type of gas mixture (around 10 nm/min) because the etching mechanism appears to be competing with a deposition process. With CH₄/Ar mixtures, a similar feature appeared but the etch rate was much higher, reaching 130 nm/min at 10% of CH₄ in Ar. The increase in etch rate with the addition of a small quantity of methane indicates that the physical etching process is enhanced by a chemical mechanism. The etching process was monitored by optical emission spectroscopy that appeared to be a valuable tool for endpoint detection.     

Microstructuring of fused silica by laser-induced backside wet etching using picosecond laser pulses

The laser-induced backside wet etching (LIBWE) is an advanced laser processing method used for structuring transparent materials. LIBWE with nanosecond laser pulses has been successfully demonstrated for various materials, e.g. oxides (fused silica, sapphire) or fluorides (CaF₂, MgF₂), and applied for the fabrication of microstructures. In the present study, LIBWE of fused silica with mode-locked picosecond (t_p = 10 ps) lasers at UV wavelengths (λ₁ = 355 nm and λ₂ = 266 nm) using a (pyrene) toluene solution was demonstrated for the first time. The influence of the experimental parameters, such as laser fluence, pulse number, and absorbing liquid, on the etch rate and the resulting surface morphology were investigated. The etch rate grew linearly with the laser fluence in the low and in the high fluence range with different slopes. Incubation at low pulse numbers as well as a nearly constant etch rate after a specific pulse number for example were observed. Additionally, the etch rate depended on the absorbing liquid used; whereas the higher absorption of the admixture of pyrene in the used toluene enhances the etch rate and decreases the threshold fluence. With a λ₁ = 266 nm laser set-up, an exceptionally smooth surface in the etch pits was achieved. For both wavelengths (λ₁ = 266 nm and λ₂ = 355 nm), LIPSS (laser-induced periodic surface structures) formation was observed, especially at laser fluences near the thresholds of 170 and 120 mJ/cm², respectively.     

Chemical etching investigation of polycrystalline p-type 6H-SiC in HF/Na2O2 solutions

In this work, an experimental study on the chemical etching reaction of polycrystalline p-type 6H-SiC was carried out in HF/Na₂O₂ solutions. The morphology of the etched surface was examined with varying Na₂O₂ concentration, etching time, agitation speed and temperature. The surfaces of the etched samples were analyzed using scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) Fourier transform infrared spectroscopy (FT-IR) and photoluminescence. The surface morphology of samples etched in HF/Na₂O₂ is shown to depend on the solution composition and bath temperature. The investigation of the HF/Na₂O₂ solutions on 6H-SiC surface shows that as Na₂O₂ concentration increases, the etch rate increases to reach a maximum value at about 0.5 M and then decreases. A similar behaviour has been observed when temperature of the solution is increased. The maximum etch rate is found for 80 °C. In addition, a new polishing etching solution of 6H-SiC has been developed. This result is very interesting since to date no chemical polishing solution has been developed on the material.     

A study on the wet etching behavior of AZO (ZnO:Al) transparent conducting film

This paper studies the wet etching behavior of AZO (ZnO:Al) transparent conducting film with tetramethylammonium hydroxide (TMAH). The optimum optoelectronic film is prepared first using designated RF power, film thickness and controlled annealing heat treatment parameters. The AZO film is then etched using TMAH etchant and AZ4620 photoresist with controlled etchant concentration and temperature to examine the etching process effect on the AZO film optoelectronic properties. The experimental results show TMAH:H₂O = 2.38:97.62 under 45 °C at the average etch rate of 22 nm/min as the preferred parameters. The activation energy drops as the TMAH concentration rises, while the etch rate increases along with the increase in TMAH concentration and temperature. After lithography, etching and photoresist removal, the conductivity of AZO film dramatically drops from 2.4 × 10⁻³ Ω cm to 3.0 × 10⁻³ Ω cm, while its transmittance decreases from 89% to 83%. This is due to the poor chemical stability of AZO film against AZ4620 photoresist, leading to an increase in surface roughness. In the photoresist postbaking process, carbon atoms diffused within the AZO film produce poor crystallinity. The slight decreases in zinc and aluminum in the thin film causes a carrier concentration change, which affect the AZO film optoelectronic properties.     

Density functional study of hypophosphite adsorption on Ni (1 1 1) and Cu (1 1 1) surfaces

Surface structures and electronic properties of hypophosphite, H₂PO₂⁻, molecularly adsorbed on Ni(1 1 1) and Cu(1 1 1) surfaces are investigated in this work by density functional theory at B3LYP/6-31++g(d, p) level. We employ a four-metal-atom cluster as the simplified model for the surface and have fully optimized the geometry and orientation of H₂PO₂⁻ on the metal cluster. Six stable orientations have been discovered on both Ni (1 1 1) and Cu (1 1 1) surfaces. The most stable orientation of H₂PO₂⁻ was found to have its two oxygen atoms interact the surface with two PO bonds pointing downward. Results of the Mulliken population analysis showed that the back donation from 3d orbitals of the transition metal substrate to the unfilled 3d orbital of the phosphorus atom in H₂PO₂⁻ and 4s orbital's acceptance of electron donation from one lone pair of the oxygen atom in H₂PO₂⁻ play very important roles in the H₂PO₂⁻ adsorption on the transition metals. The averaged electron configuration of Ni in Ni₄ cluster is 4s^0.634p^0.023d^9.35 and that of Cu in Cu₄ cluster is 4s^1.004p^0.033d^9.97. Because of this subtle difference of electron configuration, the adsorption energy is larger on the Ni surface than on the Cu surface. The amount of charge transfers due to above two donations is larger from H₂PO₂⁻ to the Ni surface than to the Cu surface, leading to a more positively charged P atom in Ni_nH₂PO₂⁻ than in Cu_nH₂PO₂⁻. These results indicate that the phosphorus atom in Ni_nH₂PO₂⁻ complex is easier to be attacked by a nucleophile such as OH⁻ and subsequent oxidation of H₂PO₂⁻ can take place more favorably on Ni substrate than on Cu substrate.     

High-density plasma etching of indium-zinc oxide films in Ar/Cl2 and Ar/CH4/H2 chemistries

The dry etching characteristics of transparent and conductive indium-zinc oxide (IZO) films have been investigated using an inductively coupled high-density plasma. While the Cl₂-based plasma mixture showed little enhancement over physical sputtering in a pure argon atmosphere, the CH₄/H₂/Ar chemistry produced an increase of the IZO etch rate. On the other hand, the surface morphology of IZO films after etching in Ar and Ar/Cl₂ discharges is smooth, whereas that after etching in CH₄/H₂/Ar presents particle-like features resulting from the preferential desorption of In- and O-containing products. Etching in CH₄/H₂/Ar also produces formation of a Zn-rich surface layer, whose thickness (∼40 nm) is well-above the expected range of incident ions in the material (∼1 nm). Such alteration of the IZO layer after etching in CH₄/H₂/Ar plasmas is expected to have a significant impact on the transparent electrode properties in optoelectronic device fabrication.     

Formation mechanism of Si(1 0 0) surface morphology in alkaline fluoride solutions

Formation mechanism of Si(1 0 0) surface morphology in alkaline fluoride solutions was investigated both theoretically and experimentally. By analysis of Raman spectra of silicon wafer surfaces and three kinds of etching solutions (NaOH, NaOH/NH₄F, and NaOH/NH₄F/Na₂CO₃) with and without addition of Na₂SiO₃·9H₂O, no Si-F bond is formed, F⁻ and CO₃²⁻ ions accelerate the condensation of Si-OH groups. Based on experimental results, it is proposed that bare silicon and silicon oxide coexist at the wafer surface during etching process and silicon oxide of different structure, size, and site at the surface manufacture different surface morphology in alkaline fluoride solution.     

Photoluminescence activity of Yang and Secco etched multicrystalline silicon material

Ultraviolet and blue-green photoluminescence (PL) was investigated on multicrystalline silicon (mc-Si) samples chemically etched by Secco and Yang solutions. The samples were characterized by dislocation density (10⁵-10⁶ cm⁻²). The form of etched pits is triangular with Yang etch and like a honeycomb with Secco etch as observed with a scanning electron microscope (SEM). These textures of mc-Si wafers give a PL activity similar to that obtained with nanostructures of porous silicon (PS) as reported in the literature. The ultraviolet PL spectra observed with Yang etch shift to the blue-green spectrum range when applying Secco etch. In our experiments we have observed 3-5 μm diameter macro pores separated by a high density of nanowalls. These observations suggest that the origin of the PL activity are quantum dots resulting from the silicon nanocrystallites obtained after few minutes of chemical etching.     

Electrodeposited ruthenium oxide thin films for supercapacitor: Effect of surface treatments

Amorphous and porous ruthenium oxide thin films have been deposited from aqueous Ru(III)Cl₃ solution on stainless steel substrates using electrodeposition method. Cyclic voltammetry study of a film showed a maximum specific capacitance of 650 F g⁻¹ in 0.5 M H₂SO₄ electrolyte. The surface treatments such as air annealing, anodization and ultrasonic weltering affected surface morphology. The supercapacitance of ruthenium oxide electrode is found to be dependent on the surface morphology.     

Optimized ICP etching process for fabrication of oblique GaN sidewall and its application in LED

Inductively coupled plasma (ICP) etching of GaN is systemically investigated by changing ICP power/RF bias power, operating pressure, and Cl₂/BCl₃ gas mixing ratio. The hexagonal etch pits related to screw dislocation existing along GaN epitaxial layer were observed on the etched GaN surface after ICP etching. The intensity of band-edge emission is significantly reduced from the etched n-GaN surface, which reveals that plasma-induced damage are generated after ICP etching. The oblique sidewall is transferred into GaN using a combination of Cl₂/BCl₃ plasma chemistry and hard mask SiO₂. By adjusting ICP etching process parameters, oblique sidewalls with various oblique angles can be formed, allowing for conformal metal lines coverage across the mesa structures, which can play an important role in the interconnection of multiple microchips for light emitting diodes (LEDs) fabrication.