Optical recording using hydrogen phthalocyanine thin films

Vacuum sublimed thin films of the blue dye hydrogen phthalocyanine (H₂Pc) were incorporated into various optical recording structures. The dye was shown to be thermally, hydrolytically, and oxidatively stable. In all cases, the writing mechanisms are dependent on the sublimation of H₂Pc. Several recording structures which take advantage of the sublimation property of H₂Pc are demonstrated, including pit forming and bubble forming media. These H₂Pc-based optical recording structures show very high optical contrast and low writing threshold energies. In addition, very thin films (50–75Å) of H₂Pc were incorporated into a tellurium-based medium, which significantly enhanced the writing contrast observed in that medium.     

Electrospinning preparation and photophysical properties of one-dimensional (1D) composite nanofibers doped with erbium(III) complexes

1D composite nanofibers of poly(vinylpyrrolidone) (PVP, M_W≈60,000) doped with three Er(III) complexes were prepared by electrospinning. They demonstrated strong near-infrared (NIR) photoluminescence (PL) at 1535 nm and ternary Er(TTA)₃Phen (denoted as Er2, where TTA=2-thenoyltrifluoroacetonate; Phen=1,10-phenanthroline) fibers (Er2/PVP) exhibited maximum PL intensity. The crystal structure of Er2 complex has been determined by X-ray diffraction measurements. Er2 doped in fibers exhibited better thermal stability of NIR PL than the pure Er2 complex. These luminescent composite fibers have potential application in optical amplifiers.     

Electrical transport properties of thermally evaporated phthalocyanine (H2Pc) thin films

Thin films of H₂Pc of various thicknesses have been deposited onto glass substrates using thermal evaporation technique at room temperature. The dark electrical resistivity measurements were carried out at different temperatures in the range 298-473 K. An estimation of mean free path (l_o) of charge carriers in H₂Pc thin films was attempted. Measurements of thermoelectric power confirm that H₂Pc thin films behave as a p-type semiconductor. The current density-voltage characteristics of Au/H₂Pc/Au at room temperature showed ohmic conduction mechanism at low voltages. At higher voltages the space-charge-limited conduction (SCLC) accompanied by an exponential trap distribution was dominant. The temperature dependence of current density allows the determination of some essential parameters such as the hole mobility (μ_h), the total trap concentration (N_t), the characteristic temperature (T_t) and the trap density P(E).     

Effect of peripheral ligands on the optical limiting property of homoleptic sandwich-type rare earth metal diphthalocyanines

The optical limiting property of sandwich-type rare earth metal diphthalocyanines, Eu[Pc(R)₈]₂[R=n-C₇H₁₅,OC₅H₁₁], was investigated via fluence-dependent transmittance measurements. The measurements were performed using collimated 10-ns pulses generated from a frequency-doubled Nd:YAG laser at 532-nm wavelength. The results demonstrated that Eu[Pc(OC₅H₁₁)₈]₂ exhibited better optical limiting behavior than Eu[Pc(C₇H₁₅)₈]₂. This is attributed to the enhanced delocalization of the π-conjugated system in Eu[Pc(OC₅H₁₁)₈]₂ because of the stronger electron-donating ability of alkoxy relative to that of alkyl. Received: 4 May 2001 / Accepted: 10 August 2001 / Published online: 17 October 2001     

Highly Bright and Photostable Li(Gd,Y)F4:Yb,Er/LiGdF4 Core/Shell Upconversion Nanophosphors for Bioimaging Applications

Intense green‐emitting Li(Gd,Y)F₄:Yb,Er/LiGdF₄ core/shell (C/S) upconversion nanophosphors (UCNPs) with a tetragonal bipyramidal morphology are synthesized. The morphology and UC luminescence of the Li(Gd,Y)F₄:Yb,Er UCNPs are significantly affected by the Li precursors, and bright UC green‐emitting Li(Gd,Y)F₄:Yb,Er UCNPs with a tetragonal bipyramidal shape, i.e., UC tetragonal bipyramids (UCTBs), are synthesized using LiOH·H₂O as a Li precursor. A LiGdF₄ shell is grown on the Li(Gd,Y)F₄:Yb,Er UCTBs, and the C/S UCNPs exhibit 4.7 times higher luminescence intensity than core UCTBs. The C/S UCNPs show a high absolute UC quantum yield of 4.6% under excitation with 980 nm near infrared (NIR) light, and the UC luminescence from the C/S UCNPs is stable under continuous irradiation with the 980 nm NIR laser for 1 h. The hydrophobic surfaces of the as‐synthesized C/S UCNPs are modified to hydrophilic surfaces by using poly(acrylic acid) (PAA) for bioimaging applications. They are applied to human cervical adenocarcinoma (HeLa) cell imaging and SK‐MEL‐2 melanoma cell imaging and in vivo imaging, including subcutaneous and intramuscular imaging, and UC luminescence images with high signal‐to‐noise ratio are obtained. Furthermore, sentinel‐lymph‐node imaging is successfully conducted with the PAA‐capped Li(Gd,Y)F₄:Yb,Er/LiGdF₄ C/S UCNPs under illumination with NIR light.     

The effect of adsorbed o-chloranil on the surface photovoltage of metal-free phthalocyanine films

The surface photovoltage of metal-free phthalocyanine (H₂Pc) films with known concentrations of adsorbed o-chloranil (o-CA) is reported, and monolayer coverages (≈10¹⁵ molecules/cm²) of o-CA result in the inversion of the sign of the photovoltage, an increase of approximately two orders of magnitude in the photovoltaic relaxation time, and a broadening of the phthalocyanine Q-band into the near IR. Higher coverages of o-CA resulted in samples with no photovoltage within the experimental detection limits. All of these observations are consistent with the formation of charge transfer complexes ($\text{H}{}_2\text{Pc}{}^{\mathrm{+}}\text{o-CA}{}^{\mathrm{?}}$) at these surfaces, which results in the consequent alternate decay mechanism for the photoexcited H₂Pc molecule: H₂p_c¹+o-CA^?→_k3H₂P_c⁺+o-CA^??, H₂P_c¹+o-CA^??→_k5H₂P_c+o-CA^?.The experimental evidence indicates that k^?1₃ is less than 7 nsec and k^?1₅ is roughly 0.6 msec for monolayer o-CA coverages.     

Electrical and optical properties of ZnO thin films prepared by magnetron rf sputtering—influence of Al, Er and H

The influence of Al, Er and H in ZnO thin films (ZnO:Al, ZnO:Er and ZnO:H) deposited by magnetron sputtering at different substrate temperatures, T_s, on their optical, structural and electrical properties was investigated. X-ray diffraction (XRD) analyses show an improvement of the crystalline structure with increasing T_s. The optical band gap, , of the films, from transmission and reflection spectra, ranged from 3.27 to 3.41 eV. The Urbach band tail width was also calculated. Incorporation of Al and Er resulted in a reduced and an increased resistivity, ρ, respectively, and an increase in the Urbach tail width in both cases. However, sputtering in an Ar+H₂ gas mixture led to an increase in ρ and an improvement in the structural order of the films. A discussion of the influence of T_s and of Al, Er and H on the properties is presented.     

Ultrafast third-order optical nonlinearity of several sandwich-type phthalocyaninato and porphyrinato europium complexes

The third-order optical nonlinearity of two sandwich-type phthalocyaninato and porphyrinato europium com- plexes, including double- and triple-deckers （Eu[Pc（OC5H11）8]2, Eu2（Pc）（TPP）2, Pc=phthalocyanine, TPP=5, 10, 15, 20- tetraphenylporphyrinate）, was investigated by using the femtosecond time-resolved optical Kerr gate method at 830 nm wavelength. Their second-order hyperpolarizability is estimated to be 0.74× 10^-30esu and 3.0× 10^-3esu respectively. This exhibits an evident enhancement in comparison with 0.47×10^-30esu for one-decker Eu（Pc）（acac） （acac=acetylacetonate）, which is also measured under the same conditions. The enhancement is attributed to the introduction of lanthanide metal to the large π-conjugated system, intermacrocycle interaction and two-photon resonance etc.     

UV-visible spectral study on the stability of lead phthalocyanine complexes

UV-visible electronic spectral study has been done on lead phthalocyanine (PbPc), lead tetranitro phthalocyanine (PbTNP) and lead tetraamino phthalocyanine (PbTAP) in dimethyl sulphoxide (DMSO) and H₂SO₄ media. Metal free phthalocyanine (H₂Pc) is insoluble in DMSO and soluble in conc. H₂SO₄. The study has been extended to H₂Pc to compare the stability of phthalocyanine structure with the PbPc complexes in H₂SO₄ medium. PbPc complexes are stable in DMSO, and all the complexes are more stable in 36 N H₂SO₄ than in 30 N and 28 N H₂SO₄ media. Further, complete demetallation and degradation of the phthalocyanine structure have been observed for all the PbPc complexes in 36 N H₂SO₄ medium within a week's time. The stability of these complexes is compared with H₂Pc in H₂SO₄ medium. The decomposition reactions in H₂SO₄ media for H₂Pc, PbPc, PbTNP and PbTAP are followed spectrophotometrically and rate constants were calculated. The decomposition reactions were found to follow the first-order kinetics with respect to the concentration of their respective phthalocyanine derivatives.     

DFT and DFT-D studies on molecular structure of double-decker phthalocyaninato-terbium(III) complex

A molecular structure of a double-decker phthalocyaninato-terbium(III) anion (TbPc₂^?) is optimised by density functional theory (DFT) and DFT with a dispersion interaction (DFT-D) method. The DFT-D method such as B3LYP-D and B97-D functional sets estimates phthalocyaninato (Pc) ions to be planar although B3LYP and PBE1PBE make them concave. In addition, the planar structure corresponds to an experimental X-ray crystallographic result. On the other hand, an optimised geometry of Pc^2? dimer by B3LYP-D estimates the convex Pc^2? structure due to the dispersion interaction between outer aromatic rings. These results suggest the importance of the dispersion interaction for the structure of TbPc₂^?.     

Near-infrared broadband luminescence and energy transfer in Bi–Tm–Er co-doped lanthanum aluminosilicate glasses

The Bi–Tm–Er co-doped SiO₂–Al₂O₃–La₂O₃ (SAL) glasses, which exhibited a broadband near-infrared (NIR) emission, were investigated by the optical absorption and photoluminescence spectra. A super broadband NIR emission extending from 0.95 to 1.6 μm with a full-width at half-maximum (FWHM) of 430 nm which covered the whole O, E, S, C and L bands, was observed in Bi–Tm–Er co-doped samples under 808 nm excitation, as a result of the overlap of the Bi-related emission band (centered at 1270 nm) and the emission from Tm^{3+ 3}H₄→³F₄ transition (1450 nm) as well as Er^{3+ 4}I_13/2→⁴I_15/2 transition (1545 nm). In addition, a super broadband emission with amplitude relatively flat from 0.95 to 2.1 μm has been observed. The possible energy transfer between Bi-related centers, Tm³⁺ ions and Er³⁺ ions was proposed.     

NIR to visible upconversion emission from Dy: ZBLYAN glasses

This paper reports on the near infrared (730-783 nm) to the visible upconversion emissions at 482 nm (⁴F_9/2→⁶H_15/2), 576 nm (⁴F_9/2→⁶H_13/2) and 662 nm (⁴F_9/2→⁶H_11/2) from the Dy³⁺doped 53ZrF₄-20BaF₂-2LaF₃-2YF₃-3AlF₃-19NaF-1DyF₃ glasses. We have also carried out a systematic study on the normal emission properties of these glasses in order to understand their performance both as a NIR upconverted visible luminescent and as normal visible fluorescent optical systems of technical importance. With an increase in Dy³⁺ concentration beyond a particular value (1 mol%), activator-activator interaction becomes a significant cause of concentration quenching in the luminescence properties. The dependence of the emission spectra on the excitation wavelengths has also been examined and 451 nm was found to be the ideal excitation wavelength in the measurement of normal fluorescence spectra. In the case of NIR upconverted visible emission, we have observed that the NIR excitation at 783 nm as the suitable pump wavelength in demonstrating prominent visible emission colours from these glasses. The relevance in undertaking these optical materials lies in their potential for upconversion laser application in the visible wavelength region. The NIR upconversion phenomenon has been explained in terms of energy level schemes due to excited state absorption (ESA) and energy transfer upconversion (ETU) processes.     

Hydrogenation effect on enhancement of photoluminescence of Er and Si nanocrystallites in Er-doped SiO2 synthesized by laser ablation

Significant enhancement of photoluminescence (PL) was attained for Er ions and Si nanocrystallites (nc-Si) in SiO₂ films by two kinds of hydrogenation, using H₂ molecules or H atoms. Er-doped SiO₂ films containing Er impurities and a high density of nc-Si were fabricated by laser ablation of Er films deposited on Si substrate in an O₂ gas atmosphere, followed by annealing at high temperatures in flowing Ar gas. Hydrogenation at 300–500 °C was found to effectively increase the PL intensity of Er ions as well as that of nc-Si. In particular, the hydrogen atom treatment dramatically shortens the hydrogenation time for the enhancement of Er PL compared to the hydrogen molecule treatment. Spectra of electron spin resonance showed a decrease in residual defects, namely, P_b-type defects located at the interfaces between nc-Si and SiO₂ by hydrogenation. These results clearly show the effectiveness of hydrogen passivation for Si nanostructures; i.e., the increase in the Er PL and nc-Si PL due to hydrogen passivation of the nonradiative recombination centers located at the interfaces between nc-Si and SiO₂. PACS 78.67.Bf; 71.20.Eh; 76.30.Mi; 81.15.Fg     

Effect of Er doping on optical band gap energy of TiO2 thin films prepared by spin coating

In order to evaluate the effect of Er doping in the range of 0–1.0 mol% on optical indirect band gap energy (E_g) of the film, the Er-doped TiO₂ (Er-TiO₂) thin films were spin-coated onto fluorine-doped SnO₂ coated (FTO) glasses. Glancing angle X-ray diffraction (GAXRD) results indicated that the films whose thickness was 550 nm consisted of pure anatase and FTO substrate. The anatase (101) TiO₂ peaks became broader and weaker with the rise in Er content. The apparent crystallite size decreased from 12 nm to 10 nm with increasing the amount of Er from 0 mol% to 1.0 mol%. UV–vis spectrophotometry showed that the values of E_g decreased from 3.25 eV to 2.81 eV with the increase of Er doping from 0 to 0.7 mol%, but changed to 2.89 eV when Er content was 1.0 mol%. The reduction in E_g might be attributed to electron and/or hole trapping at the donor and acceptor levels in the TiO₂ band structure.     

1.53 μm electroluminescence from ErF3-doped organic light-emitting diodes

Near-infrared (NIR) organic light-emitting devices (OLEDs) are demonstrated by employing erbium fluoride (ErF₃)-doped tris-(8-hydroxyquinoline) aluminum (Alq₃) as the emitting layer. The device structure is ITO/N,N′-di-1-naphthyl-N,N′-diphenylbenzidine (NPB)/Alq₃: ErF₃/2,2′,2″-(1,3,5-phenylene)tris(1-phenyl-1H-benzimidazole) (TPBI)/Alq₃/Al. Room-temperature electroluminescence around 1530 nm is observed due to the ⁴I_13/2–⁴I_15/2 transition of Er³⁺. Full width at half maximum (FWHM) of the electroluminescent (EL) spectrum is ～50 nm. NIR EL intensity from the ErF₃-based device is ～4 times higher than that of Er(DBM)₃Phen-based device at the same current. Alq₃–ErF₃ composite films are investigated by the measurements of X-ray diffraction (XRD), absorption, photoluminescence (PL) and PL decay time. Electron-only devices are also fabricated. The results indicate that energy transfer mechanism and charge trapping mechanism coexist in the NIR EL process.     

Energy transfer in Er:Eu:Yb co-doped tellurite glasses: Yb as enhancer and quencher

Energy transfer has been studied from Er³⁺ to Eu³⁺ ions on excitation with NIR photons (796 and 980 nm) with and without Yb³⁺ ions. It is found that in one case the presence of Yb³⁺ enhances the fluorescence yield (980 nm excitation) whereas in the other case it quenches (796 nm excitation). Energy transfer from Er³⁺ ion's levels ⁴S_3/2 and ²H_11/2 is verified by decay curve analysis in both the cases. The nature of interaction between the donor (Er) and the acceptor (Eu) ions is found to be dipole-dipole. The energy transfer parameters viz. transfer probability, critical distance etc. have been calculated.     

Upconversion emission in Er<Superscript>3+</Superscript>-doped lead niobium germanate thin-film glasses produced by pulsed laser deposition

Thin films of Er³⁺-doped lead–niobium germanate have been produced by pulsed laser deposition from Er³⁺-doped 25PbO₂–25Nb₂O₅–50GeO₂ (mol%) transparent glasses with an Er content in the range 0.5–3 wt%. The room-temperature infrared to visible upconversion properties of these thin films have been investigated under 800-nm laser excitation. An energy transfer upconversion mechanism has been identified to be responsible for the population of the ⁴S_3/2:²H_11/2 excited level, from which an intense green emission occurs. A rate equation analysis supports the proposed mechanism.     

Visible and NIR luminescence of nanocrystalline β-Ga2O3:Er prepared by solution combustion synthesis

In this paper we report on facile solution combustion synthesis of erbium doped β-Ga₂O₃ with urea as fuel. The product was characterized using powder X-ray diffraction and transmission electron microscopy (TEM). X-ray diffraction and TEM showed that the material is nanostructured. Luminescence properties of β-Ga₂O₃:Er are studied with excitation in near infrared (Nd:YAG laser at 1064 nm) and visible (argon laser at 514.5 nm). A strong NIR emission of Er³⁺ in the window of minimal optical loss in silica based optical fibers, due to the ⁴I_13/2→⁴I_15/2 transition at 1.55 μm has been observed. Codoping with Yb³⁺ significantly increases the intensity of that important emission.     

Crystal growth and optical properties of Cr3+, Er3+, RE3+: Gd3Ga5O12 (RE=Tm,Ho, Eu) for mid-IR laser applications

In this paper we report on the optical properties of triply Cr³⁺, Er³⁺, and RE³⁺ (RE=Tm, Ho, Eu) doped Gd₃Ga₅O₁₂ crystals that were grown by the Czochralski method. Optical absorption, near-infrared (NIR), and mid-infrared (mid-IR) fluorescence spectra were characterized for the fabricated crystals and corresponding luminescence decay measurements under 654 nm excitation were also carried out. Based on the analysis of energy transfer process between Er and RE (RE=Tm, Ho, Eu) ions, the energy transfer efficiency (ETE) values were evaluated, correspondingly. From the spectral data of all the studied crystals, it is observed that the co-doped Cr³⁺ ion highly increases the absorption pump power and the three kinds of co-doped RE³⁺ ions depopulate the Er:⁴I_13/2 energy level effectively. The spectral analysis shows that titled rare earth doped crystals are promising materials for ～3.0 μm mid-IR laser applications and among them Cr,Er,Eu:GGG is relatively more suitable due to its excellent optical properties compared with others.     

Nonlinear optical properties of erbium doped zinc oxide (EZO) thin films

Undoped and Erbium (Er) doped zinc oxide (EZO) thin films were deposited on glass substrate by sol–gel method using spin coating technique with different doping concentration. EZO films were characterized using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), UV–VIS-NIR transmission and single beam z scan method under illumination of frequency doubled Nd:YAG laser. The deposited films were found to be well crystallized with hexagonal wurtzite structure having a preferential growth orientation along the ZnO (002) plane. A blue-shift was observed in the band gap of EZO films with increasing Er concentration. All the films exhibited a negative value of nonlinear refractive index (n₂) at 532 nm which is attributed to the two photon absorption and weak free carrier absorption. Third order nonlinear optical susceptibility, χ⁽³⁾ values of EZO films were observed in the remarkable range of 10^? 6 esu. EZO (0.4 at.%) sample was found to be the best optical limiter with limiting threshold of 1.95 KJ/cm².