The etching characteristics of Al2O3 thin films in an inductively coupled plasma

In this study, the etching characteristics of ALD deposited Al₂O₃ thin film in a BCl₃/N₂ plasma were investigated. The experiments were performed by comparing the etch rates and the selectivity of Al₂O₃ over SiO₂ as functions of the input plasma parameters, such as the gas mixing ratio, the DC-bias voltage, the RF power, and the process pressure. The maximum etch rate was obtained at 155.8 nm/min under a 15 mTorr process pressure, 700 W of RF power, and a BCl₃ (6 sccm)/N₂ (14 sccm) plasma. The highest etch selectivity was 1.9. We used X-ray photoelectron spectroscopy (XPS) to investigate the chemical reactions on the etched surface. Auger electron spectroscopy (AES) was used for the elemental analysis of the etched surfaces.     

Long wavelength Ce emission in Y6Si3O9N4 phosphors for white-emitting diodes

Y₆Si₃O₉N₄:Ce³⁺ phosphor was prepared by a solid-state reaction in reductive atmosphere. X-ray powder diffraction (XRD) analysis confirmed the formation of Y₆Si₃O₉N₄:Ce³⁺. Scanning electron microscopy (SEM) observation indicated that the microstructure of the phosphor consisted of irregular fine grains with an average size of about 5 μm. Photoluminescence (PL) measurements showed that the phosphor can be efficiently excited by near ultraviolet (UV) or blue light excitation, and exhibited bright green emission peaked at about 525 nm. Compared with Ce³⁺-doped Y₄Si₂O₇N₂ phosphors, Ce³⁺-doped Y₆Si₃O₉N₄ phosphors showed longer wavelengths of both excitation and emission. The Y₆Si₃O₉N₄:Ce³⁺ is a potential green-emitting phosphor for white LEDs.     

Synthesis and characterization of Ca3Co4O9 thin films prepared by sol-gel spin-coating technique on Al2O3(001)

Ca₃Co₄O₉ thin films are deposited on Al₂O₃(001) substrates using a sol-gel spin-coating process. X-ray diffraction shows that the film exhibits a single phase of Ca₃Co₄O₉ with the (00l) planes parallel to the film surface. The temperature dependence of magnetic susceptibility showed as expected the existence of two magnetic transitions similar to those observed in bulk samples: a ferrimagnetic and a spin-state transition around 19 and 375 K, respectively. At 5 K the magnetization curves along the c-axis of the Al₂O₃(001) show that the remanent magnetization and coercive field are close to those obtained for films grown by pulsed laser deposition, which evidences the interest to use such an easy technique to grow complex thin films oxides.     

Effect of Si3N4-particles addition in Ag-Cu-Ti filler alloy on Si3N4/TiAl brazed joint

A novel composite filler alloy was developed by introducing Si₃N_4p (p = particles) into Ag-Cu-Ti filler alloy. The brazing of Si₃N₄ ceramics and TiAl intermetallics was carried out using this composite filler alloy. The typical interfacial microstructure of brazed joints was: TiAl/AlCu₂Ti reaction layer/Ag_(s,s) + Al₄Cu₉ + Ti₅Si_3p + TiN_p/TiN + Ti₅Si₃ reaction layer/Si₃N₄. Effects of Si₃N_4p content in composite filler alloy on the interfacial microstructure and joining properties were investigated. The distribution of Ti₅Si_3p and TiN_p compounds in Ag-based solid solution led to the decrease of the mismatch of the coefficient of thermal expansion (CTE) and the Young's modulus between Si₃N₄ and TiAl substrate. The maximum shear strength of 115 MPa was obtained when 3 wt.% Si₃N_4p was added in the composite filler alloy. The fracture analysis showed that the addition of Si₃N_4p could improve the mechanical properties of the joint.     

Preparation and thermoelectric properties of nc-Si:(Al2O3 + SiO2) composite film

A composite film of nanocrystalline Si (nc-Si) embedded in (Al₂O₃ + SiO₂) has been prepared on a quartz substrate by thermally evaporating a 400 nm thick Al film on a quartz substrate and annealing in air at 580 °C for 1 h. During annealing, the Al reacts with the SiO₂ of the quartz substrate and produces nc-Si, which is embedded in the (Al₂O₃ + SiO₂) film. The average size of nc-Si is ~ 22 nm and the thickness of the nc-Si:(Al₂O₃ + SiO₂) composite film is ~ 810 nm. It is found that the prepared film is thermoelectric with a Seebeck coefficient of − 624 μV/K at 293 K and − 225 μV/K at 413 K.     

In2O3-ZnO transparent conductive oxide film deposition on polycarbonate substrates

Amorphous transparent conductive oxide films in the In-Zn-O system were deposited on polycarbonate (PC) substrates by simultaneous DC sputtering of an In₂O₃ target and a ZnO target with either 4 wt% Al₂O₃ or 7.5 wt% Ga₂O₃ impurities. Although the resistivity of the amorphous, non-doped In-Zn-O film on PC was about one order of magnitude higher than that on the glass substrate, the resistivity of the In-Zn-O films with Ga₂O₃ impurities on PC substrates was reduced to the level of the non-doped In-Zn-O films on glass substrates. The addition of Al₂O₃ or Ga₂O₃ to the In-Zn-O films also induced the widening of the optical band gap, which would improve transparency at blue wavelengths.     

Investigation of brittle failure in transparent conductive oxide and permeation barrier oxide multilayers on flexible polymers

An oxide multilayer structure—consisting of an indium zinc oxide (IZO) conductive layer, a silicon oxide (SiO_x, x = 1.8) water vapor permeation barrier, and an aluminum oxide (Al₂O₃) interlayer—coated on polyethylene terephthalate (PET) is proposed as a transparent flexible substrate for display and photovoltaic applications. Vital properties of the multilayer, such as the low water vapor impermeability of the SiO_x barrier and the high conductance of the IZO film, degraded considerably because of the crack formation in bend geometries, attributed to the large difference between elastic properties of the oxide films and polymers. In order to suppress the crack formation, a 10-nm-thick Al₂O₃ interlayer was sputtered on Ar ion-beam treated PET surfaces prior to a SiO_x plasma-enhanced chemical vapor deposition (PECVD) process. Changes in the conductance and water vapor impermeability were investigated at different bending radii and bending cycles. It was found that the increases in resistance and water vapor transmission rate (WVTR) were significantly suppressed by the ion-beam PET pretreatment and by the sputtered Al₂O₃ interlayer. The resistance and WVTR of IZO/SiO_x/Al₂O₃/PET systems could be kept low and invariable even in severely bent states by choosing the SiO_x thickness properly. The IZO (135 nm)/SiO_x (90 nm)/Al₂O₃ (10 nm)/PET system maintained a resistance of 3.2 × 10^− 4 Ω cm and a WVTR of < 5 × 10^− 3 g m² d^− 1 after 1000 bending cycles at a bending radius of 35 mm.     

Deposition and characterization of pulsed direct current magnetron sputtered Al95.5Cr2.5Si2 (N1 − xOx) thin films

Aluminum rich oxynitride thin films were prepared using pulsed direct current (DC) magnetron sputtering from an Al_95.5Cr_2.5Si₂ (at.%) target. Two series of films were deposited at 400 °C and 650 °C by changing the O₂/(O₂ + N₂) ratio in the reactive gas from 0% (pure nitrides) to 100% (pure oxides). The films were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and nanoindentation. The results showed the existence of three different regions of microstructure and properties with respect to the oxygen concentration. For the samples deposited at 650 °C in the nitrogen rich region (O₂/(O₂ + N₂) ≤ 0.08), the formation of the h-AlN (002) and Al-N bond were confirmed by XRD and XPS measurements. The hardness of the films was around 30 GPa. In the intermediate region (0.08 ≤ O₂/(O₂ + N₂) ≤ 0.24), the presence of an amorphous structure and the shifting of the binding energies to lower values corresponding to non-stoichiometric compounds were observed and the hardness decreased to 12 GPa. The lowering of mechanical properties was attributed to the transition of the clean target to the reacted target under non-steady state deposition conditions. In the oxygen rich region (0.24 ≤ (O₂/(O₂ + N₂) ≤ 1), the existence of α-Al₂O₃-(113), α-Al₂O₃-(116) and Al-O bonds confirmed the domination of this phase in this region of deposition and the hardness increased again to 30-35 GPa. Films deposited at 400 °C showed the same behavior except in the oxygen rich region, where hardness remains low at about 12-14 GPa.     

Photoluminescence behaviors in ZnGa2O4 thin film phosphors deposited by a pulsed laser ablation

ZnGa₂O₄ thin film phosphors have been deposited using a pulsed laser deposition technique on Si (1 0 0) and Al₂O₃ (0 0 0 1) substrates at a substrate temperature of 550 °C with various oxygen pressures 100, 200 and 300 mTorr, and various substrate temperatures of 450, 550 and 650 °C with a fixed oxygen pressure of 100 mTorr. The films grown under different deposition conditions have been characterized using microstructural and luminescent measurements. Under the different substrate temperatures, ZnGa₂O₄ thin films show the different crystallinity and luminescent intensity. The crystallinity and photoluminescence (PL) of the ZnGa₂O₄ films are highly dependent on the deposition conditions, in particular, oxygen pressure, substrate temperature, a kind of substrates. The luminescent spectra show a broad band extending from 350 to 600 nm peaking at 460 nm. The PL brightness data obtained from the ZnGa₂O₄ films grown under optimized conditions have indicated that the sapphire is one of the most promised substrates for the growth of high quality ZnGa₂O₄ thin film phosphor.     

Fabrication of nanostructure Al2O3/ZrO2 (Y2O3) eutectic by combustion synthesis melt-casting under ultra-high gravity

A novel method for preparing Al₂O₃/ZrO₂ (Y₂O₃) eutectic was developed by combining combustion synthesis with melt-casting under ultra-high gravity (CSMC-UHG). The application of UHG = 800 g resulted in a high relative density of 99.8%, and an orientation-growth along the UHG direction. The microstructure was composed of aligned growth regimes containing a triangular dispersion of orderly ZrO₂ rods in Al₂O₃ matrix with a spacing of 300 nm. The eutectic had a high fracture toughness up to 17.9 MPa·m^1/2, which was mainly attributed to the nanostructure and the elastic bridge effects of the aligned ZrO₂ rods.     

Electronic structure and photoluminescence properties of Eu-activated Ca4Si2O7F2

The blue-emitting phosphors Ca_(4−x)Eu_xSi₂O₇F₂ (0 < x ? 0.05) have been prepared by solid-state reaction and the photoluminescence properties have been studied systematically. The electronic structure of calcium fluoride silicate Ca₄Si₂O₇F₂ was calculated using the CASTEP code. The calculation results of electronic structure show that Ca₄Si₂O₇F₂ has an indirect band gap with 5 eV. The top of the valence band is dominated by O 2p and Si 3p states, while the bottom of the conduction band is mainly composed of Ca 3d states. Under the 350 nm excitation, the obtained sample shows a broad emission band in the wavelength range of 400-500 nm with peaks of 413 nm and 460 nm from two different luminescence centers, respectively. The relative intensity of the two peaks changes with the alteration of the Eu²⁺ concentration. The strong excitation bands of the powder in the wavelength range of 200-420 nm are favorable properties for the application as lighting-emitting-diode conversion phosphor.     

High-rate deposition of high-quality Sn-doped In2O3 films by reactive magnetron sputtering using alloy targets

Sn-doped In₂O₃ (ITO) films were deposited on heated (200 °C) fused silica glass substrates by reactive DC sputtering with mid-frequency pulsing (50 kHz) and a plasma control unit combined with a feedback system of the optical emission intensity for the atomic O* line at 777 nm. A planar In-Sn alloy target was connected to the switching unit, which was operated in the unipolar pulse mode. The power density on the target was maintained at 4.4 W cm^− 2 during deposition. The feedback system precisely controlled the oxidation of the target surface in “the transition region.” The ITO film with lowest resistivity (3.1 × 10^− 4 Ω cm) was obtained with a deposition rate of 310 nm min^− 1 and transmittance in the visible region of approximately 80%. The deposition rate was about 6 times higher than that of ITO films deposited by conventional sputtering using an oxide target.     

Sr3.5Mg0.5Si3O8Cl4: Eu bluish-green-emitting phosphor for NUV-based LED

Sr₄Si₃O₈Cl₄:Eu²⁺ and Sr_3.5Mg_0.5Si₃O₈Cl₄:Eu²⁺ phosphors were prepared by a conventional solid state reaction (SS). Excited by 370 nm near-ultraviolet light, the phosphors show an efficient bluish-green wide-band emission centering at 484 nm, which originates from the 4f5d¹ → 4f⁷ transition of Eu²⁺ ion. The excitation spectra of the phosphors are a broad band extending from 250 nm to 400 nm. Mg²⁺-codoping greatly enhances the bluish-green emission of the phosphors. An LED was fabricated by coating the Sr_3.5Mg_0.5Si₃O₈Cl₄:0.08Eu²⁺ phosphor onto an ~ 370 nm-emitting InGaN chip. The LED exhibits bright bluish-green emission under a forward bias of 20 mA. The results indicate that Sr_3.5Mg_0.5Si₃O₈Cl₄:0.08Eu²⁺ is a candidate as a bluish-green component for fabrication of NUV-based white LEDs.     

Enhanced mechanical response of hybrid alloy AZ31/AZ91 based on the addition of Si3N4 nanoparticles

The main aim of this study was to simultaneously increase tensile strength and ductility of AZ31/AZ91 hybrid magnesium alloy with Si₃N₄ nanoparticles. AZ31/AZ91 hybrid alloy nanocomposite containing Si₃N₄ nanoparticle reinforcement was fabricated using solidification processing followed by hot extrusion. The nanocomposite exhibited similar grain size to the monolithic hybrid alloy, reasonable Si₃N₄ nanoparticle distribution, non-dominant (0 0 0 2) texture in the longitudinal direction, and 13% higher hardness than the monolithic hybrid alloy. Compared to the monolithic hybrid alloy (in tension), the nanocomposite simultaneously exhibited higher yield strength, ultimate strength, failure strain and work of fracture (+12%, +5%, +64% and +71%, respectively). Compared to the monolithic hybrid alloy (in compression), the nanocomposite exhibited higher yield strength and ultimate strength, lower failure strain and higher work of fracture (+35%, +4%, −6% and +6%, respectively). The beneficial effects of Si₃N₄ nanoparticle addition on the enhancement of tensile and compressive properties of AZ31/AZ91 hybrid alloy are investigated in this paper.     

Characteristics of SiOxNy films deposited by inductively coupled plasma enhanced chemical vapor deposition using HMDS/NH3/O2/Ar for water vapor diffusion barrier

SiO_xN_y thin films were deposited by inductively coupled plasma enhanced chemical vapor deposition (ICP-PECVD) using hexamethyldisilazane (HMDS, 99.9%)/NH₃/O₂/Ar at a low temperature, and examined for use as a water vapor diffusion barrier. The film characteristics were investigated as a function of the O₂:NH₃ ratio. An increase in the O₂:NH₃ ratio decreased the level of impurities such as -CH_x, N-H in the film through a reaction with oxygen. Thereby, a more transparent and harder film was obtained. In addition, an increase in the O₂:NH₃ ratio decreased the nitrogen content in the film resulting in a more SiO₂-like SiO_xN_y film. Using SiO_xN_y fabricated with an O₂:NH₃ ratio of 1:1, a multilayer thin film consisting of multiple layers of SiO_xN_y/parylene layers was formed on a polyethersulfone (PES, 200 μm) substrate, and its water vapor transmittance rate (WVTR) was investigated. A WVTR < 0.005 g/(m² day) applicable to organic thin film transistors or organic light emitting diodes was obtained using a multilayer composed of SiO_xN_y (260 nm)/parylene (< 1.2 μm) on the PES.     

Deposition and characterization of TiAlN/Si3N4 superhard nanocomposite coatings prepared by reactive direct current unbalanced magnetron sputtering

Superhard nanocomposite coatings of TiAlN/Si₃N₄ with varying silicon contents were synthesized using reactive direct current (DC) unbalanced magnetron sputtering. The Si and TiAl targets were sputtered using an asymmetric bipolar-pulsed DC power supply and a DC power supply, respectively, in Ar+N₂ plasma. The structural and mechanical properties of the coatings were characterized using X-ray diffraction (XRD) and nanoindentation techniques, respectively. The elemental composition of the TiAlN/Si₃N₄ nanocomposite coatings was determined using energy-dispersive X-ray analysis and the bonding structure was characterized by X-ray photoelectron spectroscopy. The surface morphology of the coatings was studied using atomic force microscopy. The XRD data showed that the nanocomposite coatings exhibited (1 1 1) and (2 0 0) reflections of cubic TiAlN phase. The broadening of the diffraction peaks with an increase in the silicon content in the nanocomposite coatings, suggested a decrease in the average crystallite size. The TiAlN/Si₃N₄ nanocomposite coatings exhibited a maximum hardness of 43 GPa and an elastic modulus of 350 GPa at a silicon concentration of approximately 11 at%. The hardness and the elastic modulus of the nanocomposite coatings decreased significantly at higher silicon contents. Micro-Raman spectroscopy was used to characterize the structural changes as a result of heating of the nanocomposite coatings in air (400-850 °C) and in vacuum (900 °C). The Raman data of the nanocomposite coatings annealed in air and vacuum showed better thermal stability as compared to that of the TiAlN coatings. Similarly, the nanocomposite coatings deposited on mild steel substrates exhibited improved corrosion resistance.     

Lightweight geopolymer made of highly porous siliceous materials with various Na2O/Al2O3 and SiO2/Al2O3 ratios

The syntheses of lightweight geopolymeric materials from highly porous siliceous materials viz. diatomaceous earth (DE) and rice husk ash (RHA) with high starting SiO₂/Al₂O₃ ratios of 13.0-33.5 and Na₂O/Al₂O₃ ratios of 0.66-3.0 were studied. The effects of fineness and calcination temperature of DE, concentrations of NaOH and KOH, DE to RHA ratio; curing temperature and time on the mechanical properties and microstructures of the geopolymer pastes were investigated. The results indicated that the optimum calcination temperature of DE was 800 °C. Increasing fineness of DE and starting Na₂O/Al₂O₃ ratio resulted in an increase in compressive strength of geopolymer paste. Geopolymer pastes activated with NaOH gave higher compressive strengths than those with KOH. The optimum curing temperature and time were 75 °C and 5 days. The lightweight geopolymer material with mean bulk density of 0.88 g/cm³ and compressive strength of 15 kg/cm² was obtained. Incorporation of 40% RHA to increase starting SiO₂/Al₂O₃ and Na₂O/Al₂O₃ ratios to 22.5 and 1.7 and enhanced the compressive strength of geopolymer paste to 24 kg/cm² with only a marginal increase of bulk density to 1.01 g/cm³. However, the geopolymer materials with high Na₂O/Al₂O₃ (>1.5) were not stable in water submersion.     

A yellow-emitting Ca3Si2O7: Eu phosphor for white LEDs

A series of yellow-emitting phosphors based on a silicate host matrix, Ca_3 − xSi₂O₇: xEu²⁺, was prepared by solid-state reaction method. The structure and photoluminescent properties of the phosphors were investigated. The XRD results show that the Eu²⁺ substitution of Ca²⁺ does not change the structure of Ca₃Si₂O₇ host and there is no impurity phase for x < 0.12. The SEM images display that phosphors aggregate obviously and the shape of the phosphor particle is irregular. The EDX results reveal that the phosphors consist of Ca, Si, O, Eu and the concentration of these elements is close to the stoichiometric composition. The Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be excited at a wavelength of 300-490 nm, which is suitable for the emission band of near ultraviolet or blue light-emitting-diode (LED) chips. The phosphors exhibit a broad emission region from 520 to 650 nm and the emission peak centered at 568 nm. In addition, the shape and the position of the emission peak are not influenced by the Eu²⁺ concentration and excitation wavelength. The phosphor for x = 0.045 has the strongest excitation and emission intensity, and the Ca_3 − xSi₂O₇: xEu²⁺ phosphors can be used as candidates for the white LEDs.     

Hydrogen etching of Si3N4 layers with plasma assisted hot wire CVD

In order to develop sustainable processes for clean manufacturing environment for thin film or other solar cell production, we studied the hydrogen etching of silicon nitride (Si₃N₄) films on flat crystalline silicon (c-Silicon) substrates. With an arrangement primarily constructed for hot wire CVD (HWCVD) deposition of thin silicon films also cleaning processes with atomic hydrogen were studied with a simplified three wire assembly. The three filaments could be biased independently by different potential. A variation of hydrogen pressure and flow was performed to find out conditions of high etching rates for the Si₃N₄ layers. The etching rate was simply determined by measuring the time for total removal of the film, since this could be easily detected by the change of the anti-reflection property. Etching rates of 0.1 nm/s have been obtained under 15 Pa and a flow of 50 sccm. An intensive study was carried out of the direct current (DC) plasma hot wire CVD conditions.     

Flame aerosol deposition and annealing of Y3Al5O12:Tb phosphor coatings

Sub-micrometer-sized powders of Y₃Al₅O₁₂:Tb phosphor (d_SEM = 320 nm) were prepared by flame-assisted spray pyrolysis of aqueous precursors in a premixed propane/air flame and in situ deposited onto quartz substrates. Phosphor screens with densities of up to 0.7 mg cm⁻² could be produced within 20 min. As-deposited coatings were amorphous and required a thermal post-treatment. After annealing in an oven for 2 h (T ≥ 900 °C), the yttrium aluminum garnet phase (YAG:Tb) was obtained. Alternatively, the phosphor coatings were treated by an impinging flame in the same setup used for the deposition. Quasi-amorphous Y₃Al₅O₁₂:Tb coatings demonstrated bright green photoluminescence upon flame annealing at T ≈ 1100 °C for just several minutes and could outperform YAG:Tb when excited in the wavelength ranges 205–220 nm and 230–260 nm. For example, brightness of emission from the quasi-amorphous coatings was up to five times higher than that of the fully crystalline YAG:Tb phosphor at a technically important wavelength of 254 nm.