Characterization of low refractive index SiOCF:H films designed to enhance the efficiency of light emission

An anti-reflection (AR) coating was deposited on the surface of flat panel displays to increase the efficiency of the light emission. The use of low reflective index material can decrease the thickness of the optical coating layer. In this work, low refractive index SiOCF:H films were deposited on P-type (100) Si and glass substrates by the plasma enhanced chemical vapor deposition (PECVD) method using an SiH₄, CF₄ and N₂O gas mixture. The refractive index of the SiOCF:H film continuously decreased with increasing deposition temperature and rf power, exhibiting a minimum value of 1.3854. As the rf power was increased, the fluorine content of the film increased linearly to 5.41% at an rf power of 180 W. The rms surface roughness decreased to 1.0 nm with increasing rf power, with the optimum conditions being observed for the film deposited at an rf power of 140 W.     

Asymmetrical single-mode silica waveguide deposited by PECVD

Silicon oxynitride (SiON) layer and SiO₂ buffer layer were deposited on silicon wafers by PECVD technique using SiH₄, N₂O and N₂. The refractive index of SiON films measured at a wavelength of 1552 nm using a prism coupler, could be continuously varied from 1.4480 to 1.4508. Optical planar waveguides with a thickness of 6 μm and a refractive index contrast (Δn) of 0.36% have been obtained. In addition, etching experiments were performed using ICP dry etching equipment on thick SiON films grown on Si substrates covered with a thick SiO₂ buffer layer. In order to measure optical properties, a polarization maintaining single-mode fiber was used for the input and a microscope objective for the output at 1.55 μ m. A low-loss and low propagation SiON-based waveguide was fabricated with easily adjustable refractive index of core layer.     

Deposition of Europium Oxide on Si and its optical properties depending on thermal annealing conditions

We investigate the influence of the ambient gas during thermal annealing on the photoluminescence (PL) properties of europium compound thin films on Si substrates. The films were deposited by radio-frequency magnetron sputtering and subsequently annealed in N₂ or O₂ ambient gas by rapid thermal annealing (RTA). The results of X-ray diffraction indicate that the resulting europium compound annealed in N₂ ambient have several silicate phases such as EuSiO₃ and Eu₂SiO₄ compared to those annealed in O₂ ambient. The spectral results revealed that a broad luminescence associated with Eu²⁺ ions, with a maximum intensity at 600 nm and a FWHM of 110 nm, was observed from the thin film annealed at 1000 °C in N₂ ambient. However, a series of narrow PL spectra from Eu³⁺ ions were observed from the film annealed in O₂ ambient.     

Influence of Post-Annealing on the Characteristics of Pb(Zr,Ti)O3 Thin Films Deposited by Liquid Delivery MOCVD Using a Cocktail Solution

Ferroelectric PZT thin films were deposited by liquid delivery MOCVD using a cocktail solution. The cocktail solution consisted of Pb(METHD)₂, Zr(METHD)₄ and Ti(MPD)(METHD)₂ diluted with ethylcyclohexane. The films deposited on Pt/Ti/SiO₂/Si at a substrate temperature of 500°C consisted of PZT, PbO and PbPt_x, and showed poor properties. However, after annealing at 450°C in air for thirty minutes, the PbPt_x phase disappeared while the volume of the PbO phase increased. The hysteresis properties were also improved by annealing at 450°C. After annealing at 600°C in air for thirty minutes, the PbPt_x and the PbO phases disappeared perfectly and the PZT thin films showed good hysteresis properties with the remanent polarization of 30 μC/cm² and the coercive field of 88 kV/cm.     

Integration of H2 barriers for ferroelectric memories based on SrBi2Ta2O9 (SBT)

Abstract

In this study, integration of an hydrogen barrier into a FeRAM process flow is investigated. It is reported in the literature that ferroelectric properties can be maintained after hydrogen annealing by using IrO_x as a top electrode [16][17][18]. Advantage of materials like IrO_x is less catalytic activity compared to Pt. However, we found that IrO_x is not a promising candidate for top electrode barrier. (Pt)/IrO_x/SBT/Pt capacitors are prone to shorting or exhibit high leakage. IrO_x films are very easily reduced by reducing ambient which will result in peeling off. Also, IrO_x films tend to oxidize Ti or TiN layers immediately. Therefore, other barrier materials or layer sequences like Ir/IrO_x have to be considered.

For protection of the entire capacitor an Encapsulation Barrier Layer (EBL) is required. In this study, LPCVD SiN is used. LPCVD SiN is a standard material in CMOS technology. Production tools are available and it is well known as hydrogen barrier. By modifying the deposition process and using a novel process sequence, no visual damage of the capacitors after SiN-deposition and FGA is seen. Also, no degradation of electrical properties after capacitor formation as well as after SiN-deposition and FGA is observed. However, after metal 1 and metal 2 processing, 2P_r values at 1.8V are reduced from 12μC/cm²to 2μC/cm². Polarization at 5.0V is not affected.     

Dielectric properties of ZnNb2 O 6 -TiO 2 mixture thin films

ZnNb₂O₆-TiO₂ mixture thin films with multilayer structures were fabricated via a sol-gel spin coating process. TiO₂ layers were deposited on the pre-crystallized ZnNb₂O₆ layers in order to suppress the formation of the ixiolite phase which always forms in the bulk system. The phase constitution of the thin films, confirmed by X-ray diffraction (XRD), could be controlled by the annealing temperatures, which, in turn, influenced the dielectric properties of the thin films. TiO₂ layers crystallized as the anatase phase and then transformed to the rutile phase at temperatures higher than 725^∘C. Dielectric constants of the mixture thin films, measured at 1 MHz with an MIM (metal-insulator-metal) structure, increased from 27 to 41 with dielectric losses below 0.005 as the annealing temperature increased from 700^∘C to 900^∘C. The increase in the dielectric constants was understood to originate from the increasing amounts of the rutile phase. Temperature coefficients of capacitance (TCC) were also measured between 25^∘C and 125^∘C, which showed a decreasing manner from positive values to negative values with increasing annealing temperatures. When annealed at 850^∘C, the TCC of the thin films could be tuned to be approximately 0 ppm/^oC with dielectric constant and dielectric loss of 36 and 0.002, respectively.     

Growth and characterization of UHV sputtering HfO2 film by plasma oxidation and low temperature annealing

Ultra-thin (∼4.0 nm) HfO₂ films were fabricated by plasma oxidation of sputtered metallic Hf films with post low temperature annealing. Advantage of this fabrication process is that the pre-deposition of Hf metal can suppress the formation of interfacial layer between HfO₂ film and Si substrate. The as-deposited HfO₂ films were subsequently treated by rapid thermal annealing at different temperatures in N₂ to investigate the effects of thermal annealing on the physical and electrical properties of HfO₂ film. A SiO₂-rich interface layer was observed after higher temperature rapid thermal annealing and the phase change of HfO₂ film from amorphous into crystalline occurred at about 700^∘C. As a result of higher temperature annealing, effective dielectric constant and leakage current were significantly influenced by the formation of interface layer and the crystallization of HfO₂ film.     

Fabrication of Er3+/Pr3+ Co-doped soda-lime glass thin films using RF magnetron sputtering method and optical property characterization

Er^3+/Pr³⁺ co-doped soda-lime glass thin films have been fabricated using RF magnetron sputtering method and their structural and optical properties have been studied. Deposition rate, crystallinity, and composition of glass thin films were investigated by scanning electron microscopy, transmission electron microscopy, and electron probe micro area analysis. Refractive index, birefringence and binding characteristics have been investigated using a prism coupler and X-ray photoelectron spectroscopy. Er³⁺/Pr³⁺ co-doped soda lime glass thin films were prepared by changing substrate temperature (room temp. ∼550^∘C), RF power (90 W–130 W), and Ar/O₂ gas flow ratio at processing pressure of 4 mTorr. Glass thin films could be obtained at the optimized processing condition at 350^∘C, RF power of 130 W, and gas flow of Ar:O₂ = 40:0 with maximum deposition rate of 1.6 μm/h. Refractive index and birefringence increased from 1.5614 to 1.5838 and from 0.000154 to 0.000552, respectively, as the content of Pr³⁺ increased. Binding energy of Pr3d also increased as the content of Pr³⁺ increased.     

Development of ferroelectric Pb(ZrxTi1−x)O3 thin films by metallo-organic decomposition process and rapid thermal annealing

Polycrystalline Pb(Zr_0.5Ti_0.5)O₃ thin films with good ferroelectric properties have been prepared by metallo-organic decomposition (MOD) process, using acetate-based precursors, and followed by two different kinds of annealing process, independently, including oven annealing and rapid thermal annealing (RTA). The experimental procedures were described for the films deposited on Pt-coated silicon substrates. There were distinct differences between oven annealing and RTA process, in terms of structures, morphologies, and electrical properties of the films. The films with RTA process showed denser and smoother surface, finer grain sizes, and much higher dielectric constant (1200–1400), remnant polarization of 30–35 μC/cm² and lower coercive field of 65–85 kv/cm in the entire annealing temperature range of this study. At an annealing temperature of 550°C, RTA processed films showed identical XRD patterns of perovskite phase and clear ferroelectricity; however, it was not possible to realize the perovskite structure and ferroelectricity in the films oven-annealed at that temperature. These acetate-derived PZT films with RTA process were reproducible, showed high quality in uniformity and homogeneity.     

Low Temperature Process for Synthesis of (100) Textured Pb(Zr0.48Ti0.52)O3 Thin Films on Si Substrate by Laser Lift-Off Transferring Technique

(100) textured Pb(Zr_0.48Ti_0.52)O₃ (PZT) films were prepared on silicon substrates by MOD process and laser lift-off technique. Textured PZT films were first grown on (001) Sapphire substrate, using Ba(Mg_1/3Ta_2/3)O₃ (BMT) materials as buffer layer. The (100) textured PZT/BMT/Sapphire films were attached to Si substrate using a transient-liquid-phase Pd-In bonding process, and then were separated from Sapphire substrates by a laser lift-off process, in which, a 38 ns pulse from excimer laser (248 nm) at 600 mJ/cm² fluence melted BMT buffer layer, expelling the Sapphire. The crystallinity of the surface of films was further improved by laser annealing. X-ray diffraction analysis of the PZT films showed that the crystallographic structure of films is maintained during laser lift-off process. Electrical testing of the films after laser lift-off process followed by laser annealing demonstrated that the ferroelectric properties are retained for the transferred films (P_r = 9μ C/cm² and E_c = 74 kV/cm).     

Effect of a hydrogen ratio in electrical and optical properties of hydrogenated Al-doped ZnO films

This study examined the effect of the hydrogen ratio on the electrical and optical properties of hydrogenated Al-doped zinc oxide (AZO) thin films deposited by rf magnetron sputtering using a ceramic target (98 wt% ZnO, 2 wt% Al₂O₃). Various AZO films on glass were prepared by changing the H₂/(Ar?+?H₂) ratio at room temperature. The AZO/H films showed a lower resistivity and a higher carrier concentration and mobility than the AZO films. However, the resistivity and mobility of the AZO/H films increased and decreased with increasing H₂ flow ratio, respectively. As a result, the AZO/H films grown with 2% H₂ addition showed excellent electrical properties with a resistivity of 4.98?×?10⁴ Ωcm. The UV-measurements showed that the optical transmission of the AZO/H films was >85% in the visible range with a wide optical band gap. In addition, the effect of H₂ flow ratio on the structure and composition of hydrogenated AZO thin films have also been studied.     

Preparation and electrical properties of 0.4Pb(Zn1/3Nb2/3)O3-0.6Pb(Zr0.4Ti0.6)O3 thin films by 2-step annealing method

Films of (1−x)Pb(Zn_1/3Nb_2/3)O₃-xPb(Zr_0.4Ti_0.6) O₃ (x = 0.6, 40PZN-60PZT) were deposited on Pt/TiO₂/ SiO₂/Si substrate through spin coating. Using a combination of homogeneous precursor solution preparation and two-step pyrolysis process, we were able to obtain the 40PZN-60PZT thin films of perovskite phase virtually without pyrochlore phase precipitation after annealing above 650^∘C. But since annealing done at the high temperatures for extended time can cause diffusion of Pt, TiO₂ and Si, and precipitation of nonstoichiometric PbO, we adopted 2-step annealing method to circumvent these problems. The 2-step annealed films show dense microstructure than the 1-step films annealed at higher temperature. Furthermore, the root-mean-square surface roughness of 220 nm thick films which are annealed at 720^∘C for 1 min and then annealed at 650^∘C for 5 min was found to be 3.9 nm by atomic force microscopy as compared to the 12 nm surface roughness of the film annealed only at 720^∘C for 5 min. The electrical properties of 2-step annealed films are virtually same and those of the 1-step annealed films annealed at high temperature. The film 2-step annealed at 720^∘C for brief 1 min and with subsequent annealing at 650^∘C for 5 min showed a saturated hysteresis loop at an applied voltage of 5 V with remanent polarization (P _r) and coercive voltage (V _c) of 25.3 μC/cm² and 0.66 V respectively. The leakage current density was lower than 10⁻⁵A/cm² at an applied voltage of 5 V.     

Influence of Gas Flow Ratio in PE‐CVD Process on Mechanical Properties of Silicon Nitride Film

This paper investigates the influence of gas flow ratio in the preparation of submicron‐thick silicon nitride (SiN_x) films on their elastic properties. SiN_x films with a thickness ranging from 0.14 to 0.69 µm were deposited by plasma‐enhanced chemical vapor deposition (PE‐CVD) onto 10‐µm‐thick single‐crystal silicon (SCS) specimens by changing the gas flow ratio of monosilane (SiH₄) to ammonia (NH₃) to nitrogen (N₂). A uniaxial tensile tester operated under an atomic force microscope (AFM) characterized the Young's modulus of SiN_x films and the fracture strength of SiN_x/SCS laminated specimens. The Young's modulus of SiN_x films ranged from 99.5 to 144.3 GPa, which increased with the gas flow ratio but was independent of the film thickness. Nano‐indentation tests were also carried out to examine the Poisson's ratio of SiN_x films in addition to the tensile tests. The Poisson's ratio was found to be 0.19 to 0.27, on average. Auger spectroscopy revealed that an increase of the atomic content ratio of nitrogen (N) to silicon (Si) in SiN_x films yielded higher elastic constants of the films. © 2008 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Preparation and characterization of PZT ferroelectric thin films by plasma enhanced metalorganic chemical vapor deposition

Abstract

PZT thin films with a uniform distribution of components were prepared by plasma enhanced chemical vapor deposition (PECVD) using Pb(C₂H₅)₄, Z (O-i-C₄H₉)₄, Ti(O-i-C₃H₇)₄, and oxygen. The crystallization of films was occure after annealing in the temperature range between 450 and 550°C under O₂ ambient for 1 hr. The significant change of Pb concentration in PECVD PZT thin films was not observed in the relation to annealing temperature and time. The dielectric constant PECVD PZT thin films increased with the Ti content, showed the maximum value in the vicinity of morphotropic phase boundary (MPB) composition of PZT material, and decreased with the Ti content. The leakage current density of PZT (65/35) thin film of 180 nm in thickness was 3·37 × 10^?7 A/cm² at the applied voltage of 3 V. Remanent polarization increased with increasing of Zr content in the film and coercive field was nearly independent of the composition. The typical values of electrical properties were ε_r = 570, E_c = 90 kV/cm, and P_r = 19 μC/cm² in the PECVD PZT (54/46) thin film of 220 nm in thickness.     

Formation of Silicate-Added (Bi,La)4Ti3O12 Films on LaAlO3/Si(100) Structures

We fabricated MFIS (metal-ferroelectric-insulator-semiconductor) diodes with ((Bi,La)₄Ti₃O₁₂: BLT) films and lanthanum silicate (La₂SiO₅: LSO)-added BLT films formed on LaAlO₃/Si(100) structures. LaAlO₃ films were prepared by an MBD (molecular beam deposition) method. After the film deposition, they were subjected to ex site N₂ annealing in a rapid thermal annealing (RTA) furnace at 800°C for 1 min. BLT films and LSO-added BLT films were deposited on these LaAlO₃/Si structures using a sol-gel technique. The memory windows of BLT and LSO-added BLT films were 3.0 V and 2.1 V, respectively. It was found from the current density-voltage (I-V) characteristics that the insulation property of the LSO-added BLT film was superior to that of the BLT film. We conclude from these results that LaAlO₃ is an excellent candidate of a buffer layer for forming ferroelectric-gate FETs and that the LSO-added BLT film is suitable for low voltage operation of the FETs.     

CuO formation control as a function of mixed ratio of Cu-free powders in the synthesis of YBCO superconductors on Cu substrates

YBa₂Cu₃O_x (Y123) superconducting films were fabricated on Cu substrates using a simple screen-printing method, from Cu-free powders (Y₂O₃ and BaCO₃). In the process, CuO, which causes superconducting properties of Y123 films to deteriorate, was formed on the film surface. By varying the atomic ratio of Y to Ba (Y:Ba = 1:1∼1:4), the ratio needed to prevent CuO formation was found for the film surface that had been heat-treated at 980^∘C for 17 s. The film, with the ratio of Y to Ba (Y:Ba = 1:1), is reheat-treated at 930^∘C for 9 min 30 s to form a superconducting Y123 phase. It was possible to prevent CuO formation by controlling the ratio of Cu-free powders in the mixture and to fabricate YBCO superconductors on Cu substrates using a two-step heat-treatment.     

Characteristics of Bi4Ti3O12 thin films on ITO/glass and Pt/Si substrates prepared by R.F. sputtering and rapid thermal annealing

Bi₄Ti₃O₁₂ thin films are deposited on ITO/glass and Pt/Ti/Si(100) substrates by R.F. magnetron sputtering at room temperature. The films are then heated by a rapid thermal annealing (RTA) process conducted in oxygen atmosphere at temperatures ranging from 550–700^∘C. X-ray diffraction examination reveals that the crystalinity of the films grown on Pt/Ti/Si is better than that of the films grown on ITO/glass under the same fabrication conditions. SEM observation shows that the films grown on Pt/Ti/Si are denser than those grown on ITO/glass substrates. Interactive diffusion between the Bi₄Ti₃O₁₂ film and the ITO film increases with the increase of annealing temperature. The optical transmittance of the thin film annealed at 650^∘C is found to be almost 100% when the effect of the ITO film is excluded. The relative dielectric constants, leakage currents and polarization characteristics of the two films are compared and discussed.     

Effects of rapid thermal annealing in different ambients on structural, electrical, and optical properties of ZnO thin films by sol-gel method

We studied the effects of rapid thermal annealing in different ambients on the structural, electrical and optical properties of the sol-gel derived ZnO thin films. All the films after annealing showed highly degree of (002) oriented in the X-ray diffractometry (XRD) patterns. The effects of annealing ambients on electrical properties of the films were studied. Carrier concentration, resistivity and mobility were found to be distinguished after annealed in different ambients. The sample with the lowest resistivity of 0.095 ??·cm and the largest mobility of 105.1 cm²/v·s was achieved after annealing in vacuum. XPS results indicated that more oxygen vacancies existed on the ZnO surface when annealed in vacuum than that in O₂.     

The electronic structures for the optical absorption of Hf-O-N thin films

The local structures of Hf-O-N thin films were analyzed using an extended X-ray absorption fine structure (EXAFS) study on Hf L _III-edge and first-principles calculations. Depending on their composition and atomic configurations, Hf₄O₈ (CN: 7.0), Hf₄O₅N₂ (CN: 6.25) and Hf₄O₂N₄(CN: 5.5) were suggested as the local structures of Hf-O-N thin films. The optical band gaps of Hf-O-N thin films were compared with the calculated band gap. And to investigate the optical absorption, the effects of film compositions on the valence bands of Hf-O-N thin films were analyzed by comparing the experimental valence band with the valence band.     

Preparation and characterization of SrBi2Ta2O9 thin films by low-oxygen-concentration annealing technique

SrBi₂Ta₂O₉ thin films were successfully prepared at a low annealing temperature using a low-oxygen-concentration annealing technique. It was possible to obtain a single perovskite phase at 600 °C in 0.7% oxygen concentration and fluorite phase was observed at 600 °C in 100% oxygen. In addition, the SrBi₂Ta₂O₉ thin films annealed at 650 °C in 0.7% oxygen were well crystallized and composed of dense crystal grains with a size of 70 nm. The remanent polarization and leakage current density of the SrBi₂Ta₂O₉ thin film obtained using this new technique were 7 μC/cm² and 3 × 10⁻⁹ A/cm² (at 5 V), respectively. The final remanent polarization after 10⁹ switching cycles was nearly constant. © 1999 Scripta Technica, Electr Eng Jpn, 129(4): 1–6, 1999