Elucidating surface properties of dry-etched ZnO using H2/CH4 and H2/CH4/Ar plasma

This paper reports a study of reactive ion etching (RIE) of n-ZnO in H₂/CH₄ and H₂/CH₄/Ar gas mixtures. Variables in the experiment were gas flow ratios, radio-frequency (rf) plasma power, and total pressure. Structural and electrical parameters of the etched surfaces and films were determined. Both the highest surface roughness and highest etching rate of ZnO films were obtained with a maximum rf power of 300 W, but at different gas flow ratios and working pressures. These results were expected because increasing the rf power increased the bond-breaking efficiency of ZnO. The highest degree of surface roughness was a result of pure physical etching by H₂ gas without mixed CH₄ gas. The highest etching rate was obtained from physical etching of H₂/Ar species associated with chemical reaction of CH₄ species. Additionally, the H₂/CH₄/Ar plasma treatment drastically decreased the specific contact and sheet resistance of the ZnO films. These results indicated that etching the ZnO film had roughened the surface and reduced its resistivity to ohmic contact, supporting the application of a roughened transparent contact layer (TCL) in light-emitting diodes (LEDs).     

Comparison of CH4/H2 and C2H6/H2 inductively coupled plasma etching of ZnO

CH₄/H₂-based discharges are attractive for dry etching of single crystal ZnO because of their non-corrosive nature. We show that substitution of C₂H₆ for CH₄ increases the ZnO etch rate by approximately a factor of 2 both with and without any inert gas additive. The C₂H₆/H₂/Ar mixture provides a strong enhancement over pure Ar sputtering, in sharp contrast to the case of CH₄/H₂/Ar. The threshold ion energy for initiating etching is 42.4 eV for C₂H₆/H₂/Ar and 59.8 eV for CH₄/H₂/Ar. The etched surface morphologies were smooth, independent of the chemistry and the Zn/O ratio in the near-surface region was unchanged within experimental error after etching with both chemistries. The plasma etching improved the band-edge photoluminescence intensity and suppressed the deep level emission from the bulk ZnO under our conditions, due possibly to removal of surface contamination layer.     

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.     

Dry etching of bulk single-crystal ZnO in CH4/H2-based plasma chemistries

The effect of inert gas additive (He, Ar, Xe) to CH₄/H₂ discharges for dry etching of single crystal ZnO was examined. The etch rates were higher with Ar or Xe addition, compared to He but in all cases the CH₄/H₂-based mixtures showed little or no enhancement over pure physical sputtering under the same conditions. The etched surface morphologies were smooth, independent of the inert gas additive species and the Zn/O ratio in the near-surface region decreases as the mass number of the additive species increases, suggesting preferential sputtering of O. The plasma etching improved the band-edge photoluminescence intensity from the ZnO for the range of ion energies used here (290-355 eV), due possibly to removal of surface contamination layer.     

Dry etching of CuCrO2 thin films

Highly conducting films of p-type CuCrO₂ are attractive as hole-injectors in oxide-based light emitters. In this paper, we report on the development of dry etch patterning of CuCrO₂ thin films. The only plasma chemistry that provided some chemical enhancement was Cl₂/Ar under inductively coupled plasma conditions. Etch rates of ∼500 Å min⁻¹ were obtained at chuck voltages around −300 V and moderate source powers. In all cases, the etched surface morphologies were improved relative to un-etched control samples due to the smoothing effect of the physical component of the etching. The threshold ion energy for the onset of etching was determined to be 34 eV. Very low concentrations (≤1 at.%) of residual chlorine were detected on the etched surfaces but could be removed by simple water rinsing.     

Effect of H2 and O2 plasma etching treatment on the surface of diamond-like carbon thin film

In this study, we investigated the surface properties of diamond-like carbon (DLC) films for biomedical applications through plasma etching treatment using oxygen (O₂) and hydrogen (H₂) gas. The synthesis and post-plasma etching treatment of DLC films were carried out by 13.56 MHz RF plasma enhanced chemical vapor deposition (PECVD) system. In order to characterize the surface of DLC films, they were etched to a thickness of approximately 100 nm and were compared with an as-deposited DLC film. We obtained the optimum condition through power variation, at which the etching rate by H₂ and O₂ was 30 and 80 nm/min, respectively. The structural and chemical properties of these thin films after the plasma etching treatment were evaluated by Raman and Fourier transform infrared (FT-IR) spectroscopy. In the case of as-deposited and H₂ plasma etching-treated DLC film, the contact angle was 86.4° and 83.7°, respectively, whereas it was reduced to 35.5° in the etching-treated DLC film in O₂ plasma. The surface roughness of plasma etching-treated DLC with H₂ or O₂ was maintained smooth at 0.1 nm. These results indicated that the surface of the etching-treated DLC film in O₂ plasma was hydrophilic as well as smooth.     

Comparison of plasma chemistries for the dry etching of bulk single-crystal zinc-oxide and rf-sputtered indium-zinc-oxide films

The dry etching characteristics of bulk, single-crystal zinc-oxide (ZnO) and rf-sputtered indium-zinc-oxide (IZO) films have been investigated using an inductively coupled high-density plasma with different plasma chemistries. The introduction of interhalogens such as ICl, IBr, BI₃, and BBr₃ to the Ar plasma produced no enhancement of the ZnO and IZO etch rates with respect to physical sputtering in a pure argon atmosphere under the same experimental conditions. In these plasma chemistries, the etch rate of both materials increased with source power and ion energy, indicating that ion bombardment plays an important role in enhancing desorption of etch products. Except in Ar/CH₄/H₂ discharges, the ZnO etch rate was very similar to that of IZO, which indicates that zinc and indium atoms are driven by a similar plasma etching dynamic. CH₄/H₂-containing plasmas produced higher etch rates for IZO than for ZnO due to the preferential desorption of the group III etch products. Application of the CH₄/H₂/Ar plasma to the etching of deep features in bulk, single-crystal ZnO produced highly anisotropic profiles although some trenches were observed near the sidewalls.     

The influence of H2/(H2 + Ar) ratio on microstructure and optoelectronic properties of microcrystalline silicon films deposited by plasma-enhanced CVD

Hydrogenated microcrystalline silicon films were deposited by glow discharge decomposition of SiH₄ diluted in mixed gas of Ar and H₂. By investigating the dependence of the film crystallinity on the flow rates of Ar and H₂, we showed that the addition of Ar in diluted gas markedly improves the crystallinity due to an enhanced dissociation of SiH₄. The infrared-absorption spectrum reveals that the fraction of SiH bonding increases with increasing the rate ratio of H₂/(H₂ + Ar). The surface roughness of the films increases with increasing the flow rate ratio of H₂/(H₂ + Ar), which is attributed to the decrease of massive bombardment of Ar ions in the plasma. Refractive index and absorption coefficient of the films were obtained by simulating the optical transmission spectra using a modified envelope method. Electrical measurements of the films show that the dark conductivity increases and the activation energy decreases with the ratio of H₂/(H₂ + Ar). A reasonable explanation is presented for the dependence of the microstructure and optoelectronic properties on the flow rate ratio of H₂/(H₂ + Ar).     

Influence of crystallization on the spectral features of nano-sized ferroelectric barium strontium titanate (Ba0.7Sr0.3Tio3) thin films

Ferroelectric barium strontium titanate (Ba_0.7Sr_0.3TiO₃)(BST) thin films have been prepared from barium 2-ethylhexanoate [Ba[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂]_, strontium 2-ethylhexanoate [Sr[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂] and titanium(IV) isopropoxide [TiOCH(CH₃)₂]₄ precursors using a modified sol-gel technique. The precursor except [TiOCH(CH₃)₂]₄ were synthesized in the laboratory. Transparent and crack-free films were fabricated on pre-cleaned quartz substrates by spin coating. The structural and optical properties of films annealed at different temperatures have been investigated. The as-fired films were found to be amorphous that crystallized to the tetragonal phase after annealing at 550 °C for 1 h in air. The lattice constants “a” and “c” were found to be 3.974 A and 3.990 A, respectively. The grain sizes of the films annealed at 450, 500 and 550 °C were found to be 30.8, 36.0 and 39.8 nm respectively. The amorphous film showed very high transparency (∼95%), which decreases slightly after crystallization (∼90%). The band gap and refractive index of the amorphous and crystalline films were estimated. The optical dispersion data are also analyzed in the light of the single oscillator model and are discussed.     

Atomic force microscopy investigation of surface roughness generated between SiO2 micro-pits in CHF3/Ar plasma

The present paper investigates the surface roughness generated by reactive ion etching (RIE) on the location between silicon dioxide (SiO₂) micro-pits structures. The micro-pit pattern on polymethyl methacrylate (PMMA) mask was created by an electron beam lithography tool. By using PMMA as a polymer resist mask layer for pattern transfer in RIE process, the carbon (C) content in etching process is increased, which leads to decrease of F/C ratio and causes domination of polymerization reactions. This leads to high surface roughness via self-organized nanostructure features generated on SiO₂ surface which was analyzed using atomic force microscopy (AFM) technique. The etching chemistry of CHF₃ plasma on PMMA masking layer and SiO₂ is analyzed to explain the polymerization. The surface root-mean-square (RMS) roughness below 1 nm was achieved by decreasing the RF power to 150 W and process pressure lower than 10 mTorr.     

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.     

SnO2/TiO2 mixed oxide particles synthesized in doped premixed H2/O2/Ar flames

SnO₂/TiO₂ mixed oxides with primary particle size ranging between 5 nm d_p 12 nm were synthesized by doping a H₂/O₂/Ar flame with Sn(CH₃)₄ and Ti(OC₃H₇)₄ co-currently. The effects of “flow coordinate,” concentration and flame configurations were investigated with respect to particle size and morphology of the generated mixed oxides. In situ characterization of the mixed oxides was performed using the particle mass spectrometer (PMS), while XRD, TEM, BET and UV–Vis were performed ex situ. Results obtained showed that primary particle size of mixed oxides can be controlled by varying experimental parameters. The mixed oxides have interesting properties compared to those of the pure oxides of TiO₂ and SnO₂, which were also synthesized in flames earlier. Band gap tuning opportunities are possible using mixed oxides.     

Enhancement of long-term stability of pentacene thin-film transistors encapsulated with transparent SnO2

The long-term stability of pentacene thin-film transistors (TFTs) encapsulated with a transparent SnO₂ thin-film prepared by ion beam-assisted deposition (IBAD) was investigated. After encapsulation process, our organic thin-film transistors (OTFTs) showed somewhat degraded field-effect mobility of 0.5 cm²/(V s) that was initially 0.62 cm²/(V s), when a buffer layer of thermally evaporated 100 nm SnO₂ film had been deposited prior to IBAD process. However, the mobility was surprisingly sustained up to 1 month and then gradually degraded down to 0.35 cm²/(V s) which was still three times higher than that of the OTFT without any encapsulation layer after 100 days in air ambient. The encapsulated OTFTs also exhibited superior on/off current ratio of over 10⁵ to that of the unprotected devices (∼10⁴) which was reduced from ∼10⁶ before aging. Therefore, the enhanced long-term stability of our encapsulated OTFTs should be attributed to well protection of permeation of H₂O and O₂ into the devices by the IBAD SnO₂ thin-film which could be used as an effective inorganic gas barrier for transparent organic electronic devices.     

Dry etching of zinc-oxide and indium-zinc-oxide in IBr and BI3 plasma chemistries

The dry etching characteristics of bulk single-crystal zinc-oxide (ZnO) and RF-sputtered indium-zinc-oxide (IZO) films have been investigated using an inductively coupled high-density plasma in Ar/IBr and Ar/BI₃. In both plasma chemistries, the etch rate of ZnO is very similar to that of IZO, which indicates that zinc and indium atoms are driven by a similar plasma etching dynamics. IBr and BI₃-based plasmas show no enhancement of the etch rate over pure physical sputtering under the same experimental conditions. The etched surface morphologies are smooth, independent of the discharge chemistry. From Auger electron spectroscopy, it is found that the near-surface stoichiometry is unchanged within experimental error, indicating a low degree of plasma-induced damage.     

Surface characterization and luminescent properties of SrAl2O4:Eu,Dy nano thin films

SrAl₂O₄:Eu²⁺, Dy³⁺ thin films were grown on Si (1 0 0) substrates in different atmospheres using the pulsed laser deposition (PLD) technique. The effects of vacuum, oxygen (O₂) and argon (Ar) deposition atmospheres on the structural, morphological and photoluminescence (PL) properties of the films were investigated. The films were ablated using a 248 nm KrF excimer laser. Improved PL intensities were obtained from the unannealed films prepared in Ar and O₂ atmospheres compared to those prepared in vacuum. A stable green emission peak at 520 nm, attributed to 4f⁶5d¹→4f⁷ Eu²⁺ transitions was obtained. After annealing the films prepared in vacuum at 800 °C for 2 h, the intensity of the green emission (520 nm) of the thin film increased considerably. The amorphous thin film was crystalline after the annealing process. The diffusion of adventitious C into the nanostructured layers deposited in the Ar and O₂ atmospheres was most probably responsible for the quenching of the PL intensity after annealing.     

Investigation of IrO2-SnO2 thin film evolution from aqueous media

The thermal evolution process of IrO₂-SnO₂/Ti mixed oxide thin films of varying noble metal content has been investigated under in situ conditions by thermogravimetry-mass spectrometry, Fourier transform infrared emission spectroscopy and cyclic voltammetry. The gel-like films prepared from aqueous solutions of the precursor salts Sn(OH)₂(CH₃COO)_2−xCl_x and H₂IrCl₆ on titanium metal support were heated in an atmosphere containing 20% O₂ and 80% Ar up to 600 °C.The thermal decomposition reactions practically take place in two separate temperature ranges from ambient to about 250 °C and between 300 and 600 °C. In the low temperature range the liberation of solution components and - to a limited extent - an oxidative cracking reaction of the acetate ligand takes place catalyzed by the noble metal. In the high temperature range the evolution of chlorine as well as the decomposition of surface species formed (carbonyls, carboxylates, carbonates) can be observed. The acetate ligand shows extreme high stability and is decomposed in the 400-550 °C range, only.Since the formation and decomposition of the organic surface species can significantly influence the morphology (and thus the electrochemical properties) of the films, the complete understanding of the film evolution process is indispensable to optimize the experimental conditions of electrode preparation.     

Fabrication and characterization of La-doped HfO2 gate dielectrics by metal-organic chemical vapor deposition

La-doped HfO₂ gate dielectric thin films have been deposited on Si substrates using La(acac)₃ and Hf(acac)₄ (acac = 2,4-pentanedionate) mixing sources by low-pressure metal-organic chemical vapor deposition (MOCVD). The structure, thermal stability, and electrical properties of La-doped HfO₂ films have been investigated. Inductive coupled plasma analyses confirm that the La content ranging from 1 to 5 mol% is involved in the films. The films show smaller roughness of ∼0.5 nm and improved thermal stability up to 750 °C. The La-doped HfO₂ films on Pt-coated Si and fused quartz substrates have an intrinsic dielectric constant of ∼28 at 1 MHz and a band gap of 5.6 eV, respectively. X-ray photoelectron spectroscopy analyses reveal that the interfacial layer is Hf-based silicate. The reliable value of equivalent oxide thickness (EOT) around 1.2 nm has been obtained, but with a large leakage current density of 3 A/cm² at V_g = 1V + V_fb. MOCVD-derived La-doped HfO₂ is demonstrated to be a potential high-k gate dielectric film for next generation metal oxide semiconductor field effect transistor applications.     

Characterization of TiO2/Au/TiO2 films deposited by magnetron sputtering on polycarbonate substrates

Transparent and conducting TiO₂/Au/TiO₂ (TAuT) films were deposited by reactive magnetron sputtering on polycarbonate substrates to investigate the effect of the Au interlayer on the optical, electrical, and structural properties of the films. In TAuT films, the Au interlayer thickness was kept at 5 nm. Although total thickness was maintained at 100 nm, the stack structure was varied as 50/5/45, 70/5/25, and 90/5/5 nm.In XRD pattern, the intermediate Au films were crystallized, while all TAuT films did not show any diffraction peaks for TiO₂ films with regardless of stack structure. The optical and electrical properties were dependent on the stack structure of the films. The lowest sheet resistance of 23 Ω/□ and highest optical transmittance of 76% at 550 nm were obtained from TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm films. The work function was dependent on the film stack. The highest work function (4.8 eV) was observed with the TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm film stack. The TAuT film stack of TiO₂ 90 nm/Au 5 nm/TiO₂ 5 nm films is an optimized stack that may be an alternative candidate for transparent electrodes in flat panel displays.     

Characterization of interface between CuInSe2 and In2O3

CuInSe₂/In₂O₃ structures were formed by depositing CuInSe₂ films by stepwise flash evaporation onto In₂O₃ films, which were grown by DC reactive sputtering of In target in presence of (Ar+O₂) gas mixture. Phase purity of the CuInSe₂ and In₂O₃ films was confirmed by Transmission Electron Microscopy (TEM) studies. X-ray diffraction (XRD) results on CuInSe₂/In₂O₃/glass structures showed sharp peaks corresponding to (112) plane of CuInSe₂ and (222) plane of In₂O_3. Rutherford Backscattering Spectrometry (RBS) investigations were carried out on CuInSe₂/In₂O₃/Si structures in order to characterize the interface between In₂O₃ and CuInSe₂. The results show that the CuInSe₂ films were near stoichoimetric and In₂O₃ films had oxygen deficient composition. CuInSe₂/In₂O₃ interface was found to include a ∼20 nm thick region consisting of copper, indium and oxygen. Also, the In₂O₃/Si interface showed the formation of ∼20 nm thick region consisting of silicon, indium and oxygen. The results are explained on the basis of diffusion/reaction taking place at the respective interfaces.