Two-wave mixing of ion-implanted photorefractive waveguides in near-stoichiometric Fe:LiNbO3 crystals

We report on the two-wave mixing of light in photorefractive waveguides in H ion-implanted Fe-doped near-stoichiometric lithium niobate crystals. For pump light of 632.8 nm wavelength a gain coefficient as high as 15 cm⁻¹ is found. A response time of the order of a few seconds is achieved for micro-watt input powers.     

Rib waveguides based on Zn-substituted LiNbO3 films grown by liquid phase epitaxy

The fabrication of epitaxially grown Zn-substituted LiNbO₃ (Zn:LiNbO₃) waveguide films and rib waveguides is reported and detailed investigations about microstructure, morphology and optical waveguide properties are provided. Zn:LiNbO₃ films were grown on congruent X-cut LiNbO₃ substrates by a modified liquid phase epitaxy in solid–liquid coexisting solutions. The homogeneously Zn-substituted films exhibit high crystalline perfection and extremely flat surfaces with averaged surface roughness of rms = 0.2–0.3 nm. At the film/substrate interface a Zn-containing transient layer has been observed, which allows the growth of elastically strained Zn:LiNbO₃ film lattices. X-ray diffraction reciprocal-space measurements prove the pseudomorphic film growth. The refractive index difference between substrate and film depends on the zinc substitution content, which increase with rising growth temperatures. For films with 5.3 mol% Zn (Δn_o ≈ +5 × 10⁻³) only ordinary ray propagation was observed, while for films with 7.5 mol% Zn (Δn_o ≈ +8 × 10⁻³, Δn_e ≈ +5 × 10⁻³) both modes, TM and TE propagate. Stress-induced refractive index changes are in the order of Δn ≈ 10⁻⁴. In rib waveguide microstructures singlemode propagation with nearly symmetrical field distribution has been observed. To demonstrate the potential of the proton exchange-assisted dry-etching technique interferometer microstructures were fabricated.     

Optical properties of Sm doped Mg:LiNbO3 and Zn:LiNbO3 single crystals

Sm³⁺ doped Mg:LiNbO₃ and Zn:LiNbO₃ are grown by Czochralski method. Optical transmittance and emission spectra are measured and Judd-Ofelt theory is applied to determine phenomenological intensity parameters, oscillator strengths, radiant transition rates, total radiant lifetimes, and branching ratios. The calculations show that Judd-Ofelt parameters with the relation of Ω₄ > Ω₂ > Ω₆ exist, and ΣΩ_ξ (ξ = 2, 4 and 6) in Sm:Zn:LiNbO₃ decreases. Fluorescence spectra indicate that visible fluorescence of Sm³⁺ is made up of 570, 606, 613 and 654 nm emission bands in these crystals under 409 nm excitation.     

Hydrothermal synthesis and characterization of LiNbO3 crystal

Lithium niobate crystal was successfully synthesized via hydrothermal synthesis method using LiOH·H₂O or LiNO₃ and Nb₂O₅ as starting materials in water or ammonia solution. X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectra and Scanning electron microscopy (SEM) were used to characterize the as-prepared samples. The synthesis conditions such as crystallization temperature and time as well as ammonia concentration (when using LiNO₃ as Li source) were investigated. The results demonstrate that the crystallization and purity of the as-prepared samples were increased with the increase of time when temperature was at 260 °C. When using LiNO₃ as Li source a basic solution was necessary to synthesize LiNbO₃. In the present work ammonia solution was used instead of water to obtain alkalescence solvent. XRD results revealed that the as-prepared samples had a hexagonal structure. FT-IR results displayed that the LiNbO₃ phase could be completely formed and no secondary phase was found under proper conditions. SEM picture showed that the morphology of the sample was more perfect and bigger with increasing reaction time.     

Material properties and growth control of undoped and Sn-doped In2O3 thin films prepared by using ion beam technologies

Undoped (IO) and Sn-doped In₂O₃ (ITO) films have been deposited on glass and polymer substrates by an advanced ion beam technologies including ion-assisted deposition (IAD), hybrid ion beam, ion beam sputter deposition (IBSD), and ion-assisted reaction (IAR). Physical and chemical properties of the oxide films and adhesion between films and substrates were improved significantly by these technologies. By using the IAD method, non-stoichiometry and microstructure of the films were controlled by changing assisted oxygen ion energy and arrival ratio of assisted oxygen ion to evaporated atoms. Relationships between structural and electrical properties in ITO films on glass substrates were intensively investigated by using the IBSD method with changing ion energy, reactive gas environment, and substrate temperature. Smooth-surface ITO films (R_rms ≤ 1 nm and R_p-v ≤ 10 nm) for organic light-emitting diodes were developed with a combination of deposition conditions with controlling microstructure of a seed layer on glass. IAR surface treatment enormously enhanced the adhesion of oxide films to polymer substrate. The different dependence of IO and ITO films' properties on the experimental parameters, such as ion energy and oxygen gas environment, will be intensively discussed.     

Pyroelectric Ta-modified LiNbO3 thin films and devices for thermal infrared detection

High-performance pyroelectric infrared (IR) detectors have been fabricated using tantalate-doped lithium niobate LiNb_1 − xTa_xO₃ (abbreviated as LNT, with x = 0-1.0) thin films deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by diol-based sol-gel processing, in which, tantalate (Ta) is adopted as dopant in lithium niobate. The randomly oriented LNT thin film exhibits a relatively small dielectric constant and a large pyroelectric coefficient. The pyroelectric characteristics of detectors with various tantalate contents, as a function of modulation frequency, were investigated. It was found that LiNb_0.8Ta_0.2O₃ had the largest voltage responsivity of 7020 (V/W) at 70 Hz, and a specific detectivity (D^?) of 7.76 × 10⁷ cm Hz^1/2/W at 200 Hz. These results indicate that the LNT thin film with x = 0.20 is most suitable for application as high-performance pyroelectric thin-film detectors.     

Photoluminescence properties of ion beam synthesized β-FeSi2

Effects of structural changes near the interface, the implantation dose and the precipitate morphology on photoluminescence (PL) properties of ion-beam synthesized (IBS) β-FeSi₂ have been investigated. The intrinsic PL spectrum attributed to the interband transition of β-FeSi₂ was found by examining the dependence of the PL peak energy on temperature and the excitation power.     

Structures and light emission properties of nanocrystalline FeSi2/Si formed by ion beam synthesis with a metal vapor vacuum arc ion source

Thin layers of nanocrystalline FeSi₂ embedded in Si structures have been formed by Fe implantation using a metal vapor vacuum arc (MEVVA) ion source under various implantation and thermal annealing conditions. The microstructures were studied in details and correlated with the photoluminescence (PL) properties. It is found that higher lattice coherence between the FeSi₂ nanocrystals and the Si matrix is associated with better light emission efficiency. Multiple-cycle implantation schemes were introduced and it is shown that with appropriate process design the dose quenching effect can be suppressed to achieve light emission enhancement in higher dose samples. De-convolution of the PL spectra into two or three peaks was performed and their temperature and excitation power dependence were analyzed. The analysis results indicate that the 1.55-μm emission really originated from FeSi₂ and that the emission peaks are likely donor- or accepted-level-related. MOS structures with the incorporation of implanted nanocrystalline FeSi₂ were fabricated. Electroluminescence (EL) spectra from these devices showed two peak features of which one peak corresponds to FeSi₂ emission and the other corresponds to enhanced Si band-edge emission. Clear room-temperature EL signals from these device structures were observed. A model is proposed to qualitatively understand the temperature dependence of the EL spectra.     

The effect of In ion on the optical characteristics of Er in Er/Yb:LiNbO3 crystal

The effect of In³⁺ ion on the optical characteristics of Er³⁺ ion in Er/Yb:LiNbO₃ crystal under 980 nm excitation has been investigated. The Er and Yb contents in the crystals were measured by an inductively coupled plasma atomic emission spectrometer (ICP-AES). A significant enhancement of 1.54 μm emission was observed for Er/Yb:LiNbO₃ crystal doped with 1 mol% In₂O₃. The studies on the UV-vis absorption and the OH⁻ absorption spectra indicate that the threshold concentration of In³⁺ ion decreases with the Er/Yb doping in Er/Yb/In:LiNbO₃ crystal. The 1 mol% In₂O₃ doping results in the reduction of absorption cross section in the UV-vis region, meaning the formation of Er³⁺ cluster sites. The enhancement of 1.54 μm emission is attributed to the larger probabilities of the cross relaxation processes ⁴S_3/2 + ⁴I_15/2 → ⁴I_9/2 + ⁴I_13/2 (Er), ⁴S_3/2 + ⁴I_15/2 → ⁴I_13/2 + ⁴I_9/2 (Er) and ⁴I_9/2 + ⁴I_15/2 → ⁴I_13/2 + ⁴I_13/2 (Er) induced by Er³⁺ cluster sites.     

Synthesis of MoO3 nanobelts by medium energy nitrogen ion implantation

Ion implantation has been revealed as a potential technique to modify the surface of materials. In this work, MoO₃ nanobelts were synthesized on MoO₃ whisker surfaces by means of ion implantation with 60 keV nitrogen ions at a dose of 1 × 10¹⁶ atom/cm² and characterized by scanning electron microscopy, Raman spectroscopy, and transmission electron microscopy. The result showed that the nanostructures of MoO₃ occurred over the whisker surfaces and had belt-like shapes. The size of the synthesized MoO₃ nanobelts mostly ranged from 20 to 60 nm in width and 300 to 800 nm in length. The nanobelts were found to have an orthorhombic crystal structure with growth preferential in the [001] direction. The growth process of the nanobelts based on the common vapor-solid mechanism is discussed.     

Scintillation properties of Ce-doped LuLiF4 and LuScBO3

The crystals of 1 mol% Ce-doped LuLiF₄ (Ce:LLF) grown by the micro-pulling down (μ-PD) method and 1 mol% Ce-doped LuScBO₃ (Ce:LSBO) grown by the conventional Czochralski (Cz) method were examined for their scintillation properties. Ce:LLF and Ce:LSBO demonstrated ∼80% transparency at wavelengths longer than 300 and 400 nm, respectively. When excited by ²⁴¹Am α-ray to obtain radioactive luminescence spectra, Ce³⁺ 5d-4f emission peaks were detected at around 320 nm for Ce:LLF and at around 380 nm for Ce:LSBO. In Ce:LSBO, the host luminescence was also observed at 260 nm. By recording pulse height spectra under γ-ray irradiation, the absolute light yield of Ce:LLF and Ce:LSBO was measured to be 3600±400 and 4200±400 ph/MeV, respectively. Decay time kinetics was also investigated using a pulse X-ray equipped streak camera system. The main component of Ce:LLF was ∼320 ns and that of Ce:LSBO was ∼31 ns. In addition, the light yield non-proportionality and energy resolution against the γ-ray energy were evaluated.     

A novel technique to prepare LiNbO3 at low temperature

Fresh niobium hydroxide was first precipitated from NbF₅ solution using an aqueous ammonium hydroxide under basic conditions. Then a simple procedure of mixing lithium and niobium hydroxides together and heating at a low temperature (400 °C) produced pure ultrafine single phase LiNbO₃ (LN). In the literature, this is the lowest temperature so far reported on the formation of LN. The phase content and lattice parameters are determined by X-ray diffraction (XRD). The average particle size and morphology were studied by transmission electron microscopy (TEM).     

RBS/channelling study of ion-implanted and proton-exchanged LiNbO3:Nd:MgO planar waveguides

We present a structural study of two Nd³⁺/MgO codoped LiNbO₃ waveguides fabricated by two different methods: ion-implantation and proton-exchange. Rutherford backscattering spectrometry in combination with channelling was used to study the influence of the waveguide fabrication method on the possible modification of the LiNbO₃ crystal structure within the waveguiding layer. The results show that the ion-implanted waveguide mainly maintains the same properties as the virgin crystal, apart from a deterioration of a thin surface layer, whilst the proton-exchanged waveguide exhibits a quite different behaviour, although its surface is less damaged.     

Variations of microstructures and electrical properties of Bi4Ti3O12/SrTiO3/(La0.5, Sr0.5)CoO3/MgO epitaxial thin films by annealing

Epitaxial thin films of a heterostructure with Bi₄Ti₃O₁₂(BIT)/SrTiO₃(ST) were successfully grown with a bottom electrode consisting of La_0.5Sr_0.5CoO₃(LSCO) on MgO(001) substrates using pulsed laser deposition. The grown BIT and ST (001) planes were parallel to the growth surface with the orientation relationship of BIT <110>//ST <010>. In the as-deposited film, the BIT (001) plane appeared to expand to relieve a lattice mismatch with the ST (001) plane. However, annealing for 20-40 min induced the BIT (001) plane to contract horizontally with its c-axis expanding, which was associated with a local perturbation in the layer stacking of the BIT structure. This structural distortion was reduced in the film annealed for 1 h, with restoration of the periodicity of the layer stacking. Correspondingly, the dielectric constant of the as-deposited film was increased from 292 to 411 by annealing for 1 h. In parallel, the film was paraelectric but became more ferroelectric, with the remanent polarization and the coercive field changing from 0.1 μC/cm² and 14 kV/cm to 1.7 μC/cm² and 69 kV/cm, respectively.     

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.     

Optical properties of TiO2 thin films after Ag ion implantation

Metal plasma ion implantation has being successfully developed for improving the electronic and optical properties of semiconductor materials. Prior to deposition, a TiO₂ colloidal suspension was synthesized by microwave-induced thermal hydrolysis of the titanium tetrachloride aqueous solution. The TiO₂ thin film was optimized to obtain a high-purity crystalline anatase phase by calcinations at 550 °C. The TiO₂ coating was uniform without aggregation, which provided good photo conversion efficiency. Ag ion implantation into the as-calcined TiO₂ thin films was conducted with 1 × 10¹⁵ ~ 1 × 10¹⁶ ions/cm² at 40 keV. The peak position and intensity of the photoluminescence and UV-Vis absorption spectra are quite sensitive to Ag doping. The optical characterization showed a shift in optical absorption wavelength towards infrared ray side, which was correlated with the structure variation of the Ag⁺ implanted TiO₂. Due to the strong capability of forming compounds between the energetic silver ions and TiO₂, the photoluminescence emission and UV-Vis absorption efficiencies were improved.     

Control of crystallographic orientation of LiNbO3 films grown by electron-cyclotron resonance plasma sputtering on TiN films

We investigated the orientation of domains in LiNbO₃ (LN) thin films grown by electron-cyclotron resonance plasma sputtering on TiN films with various crystalline states. Deposition at 400 °C on an amorphous TiN produced partially crystallized and apparently c-axis-oriented LN. When TiN crystallized at 460 °C to become polycrystalline grains, the roughened surface randomized the orientation of LN. At 600 °C, the reaction of TiN with oxygen atoms supplied from the plasma created a TiO_x layer. Rapid thermal annealing of amorphous LN films at 460 °C was the best solution for removing these disorientation factors, but annealing of amorphous LN on poly-crystalline TiN yielded no c-axis-oriented domains.     

Optically induced three-dimensional nonlinear photonic lattices in LiNbO3:Fe crystal

We fabricate three-dimensional nonlinear photonic lattices in self-defocusing iron-doped lithium niobate photorefractive crystal for the first time by an improved Michelson interferometer device. The experimental setup is simple and inexpensive. The period of the induced photonic lattices can be dominated easily. We analyze the three-dimensional nonlinear photonic lattices by plane wave guiding and far field diffraction pattern imaging. The induced nonlinear photonic lattices can exist stably for a long time in the photorefractive crystal.     

Influence of metal plasma ion implantation on photo-sensitivity of anatase TiO2 thin films

Nano-scale TiO₂ thin films were synthesized by using sol-gel and spin-coating techniques on glass substrates for photo-catalytic applications. The Ti(IV) butoxide-based TiO₂ thin films were optimized for transforming into the high-purity crystalline anatase phase when calcined at 500 °C. To further enhance the photo-catalysis sensitivity of TiO₂ thin films for use in visible light environments, a metal plasma ion implantation process was implemented to modify the band gap electron configuration of Ti. Various transition metal atoms such as Ni, Cu, V, and Fe were ionized and accelerated at 20 keV to impinge on the surface of TiO₂ substrates at a dosage of 5 × 10¹⁵ ions/cm². ESCA analysis confirmed the binding energy shift of Ti by 0.8-1.2 eV, which accounted for the increased effective positive charge of Ti, resulting in more effective electron trapping capability and, thus, the electron-hole pair separation. In addition, the absorption spectroscopy demonstrated that optical absorption in the visible light regime occurred in specimens implanted with transition metal ions, likely due to the formation of extra impurity energy levels within the original TiO₂ band gap energy structure. Among all tested implant materials, the band gap energy of TiO₂ was effectively reduced by Cu and Fe ion implantation by 0.9-1.0 eV, which was sufficient enough to excite valence electrons over the band gap in visible light environments. The feasibility of the metal-doped TiO₂ thin films for effective applications under visible light irradiation was further confirmed by using super-hydrophilicity contact-angle measurement.     

Thermoluminescence properties of Ce-doped LiSr4(BO3)3 phosphor

Borates LiSr₄(BO₃)₃ were synthesized by high-temperature solid-state reaction. The thermoluminescence (TL) and some of the dosimetric characteristics of Ce³⁺-activated LiSr₄(BO₃)₃ were reported. The TL glow curve is composed of only one peak located at about 209 °C between room temperature and 500 °C. The optimum Ce³⁺ concentration is 1 mol% to obtain the highest TL intensity. The TL kinetic parameters of LiSr₄(BO₃)₃:0.01Ce³⁺ were studied by the peak shape method. The TL dose response is linear in the protection dose ranging from 1 mGy to 1 Gy. The three-dimensional thermoluminescence emission spectra were also studied, peaking at 441 and 474 nm due to the characteristic transition of Ce³⁺.