Dispersion studies and electronic transitions in nickel phthalocyanine thin films

Thin films of the organic semiconductor nickel phthalocyanine (NiPc) are structurally investigated using X-ray diffraction and infrared light absorption. The optical absorption and dispersion studies of nickel phthalocyanine were investigated using spectrophotometric measurements of transmittance and reflectance at normal incidence in the wavelength range 190–2100 nm. The absorption spectra recorded in the UV-VIS region show two well-defined absorption bands of the phthacyanine molecules, namely, the Soret and the Q-band. The Davydove splitting of the main absorption peak in the metal phthalocyanines correlates with the relative tendencies of the metal to out-of-plane bonding. The refractive index n as well as the absorption index k were calculated and showed an independent of the film thickness in the film thicknesses range 400–770 nm. The refractive index n showed an anomalous dispersion in the absorption region as well as normal dispersion in the transparent region. Some of the important optical absorption such as the molar extinction coefficient, the oscillator strength, the electric dipole strength have been evaluated. The analysis of the spectral behavior of the absorption coefficient α in the absorption region revealed two indirect allowed transitions with corresponding energies 2.77±0.03 and 1.66±0.02 eV. An energy band diagram has been proposed to account for the optical transitions of NiPc thin film. All previous parameters were as well obtained for films annealed at 523 K for 2 h. Discussion of the obtained results and their comparison with the previously published data are also given.     

Optical absorption studies of copper phthalocyanine thin films

The optical absorption of thermally evaporated copper phthalocyanine (CuPc) was studied in the UV-VIS-NIR region. The absorption spectra recorded in the UV-VIS region show two well-defined absorption bands of the phthalocyanine molecules, namely, the Soret (B) and the Q-band . The Q-band shows its characteristic splitting (Davydov splitting) of the main absorption peak in the metal phthalocyanine correlates with the relative tendencies of the metal to out-of-plane bonding. Some of the important spectral characteristics such as the molar extinction coefficient (ε_molar), the oscillator strength (f), the electric dipole strength (q²) and absorption half-bandwidth (Δλ) of the principle optical transitions were evaluated. The analysis of the spectral behavior of the absorption coefficient α in the absorption region revealed two indirect allowed transitions with corresponding energies 2.95±0.03 and 1.55±0.02 eV.The spectra of the infrared absorption allow characterization of vibration modes for the powder, as-deposited material and thin films of CuPc annealed at 423 K for two hours. Discussion of the obtained results and their comparison with the previous published data are also given.     

Structural and optical properties of thermal evaporated magnesium phthalocyanine (MgPc) thin films

X-ray powder diffraction (XRD) of MgPc indicated that the material in the powder form is polycrystalline with monoclinic structure. Miller indices, h k l, values for each diffraction peak in XRD spectrum were calculated. Thermal evaporation technique was used to deposit MgPc thin films. The XRD studies were carried out for MgPc thin films where the results confirm the amorphous nature for the as-deposited films. While, polycrystalline films orientated preferentially to (1 0 0) plane with an amorphous background were obtained for films annealed at 623 K for 3 h. Optical properties of MgPc thin films were characterised by using spectrophotometric measurements of transmittance and reflectance in the spectral range from 190 to 2500 nm. The refractive index, n, and the absorption index, k, were calculated. According to the analysis of dispersion curves, the parameters, namely; the optical absorption coefficient (α), molar extinction coefficient (?_molar), oscillator energy (E_os), oscillator strength (f), and electric dipole strength (q²) were also evaluated. The recorded absorption measurements in the UV-vis region show two well defined absorption bands of phthalocyanine molecule; namely the Q-band and the Soret (B-band). The Q-band showed its splitting characteristic (Davydov splitting), and ΔQ was obtained as 0.15 eV. The analysis of the spectral behaviour of the absorption coefficient (α), in the absorption region revealed indirect transitions. The transport and the near onset energy gaps were estimated as respectively 2.74 ± 0.02 and 1.34 ± 0.01 eV.     

Optical properties and the dispersion parameters of new zinc Phthalocyanine benzofuran derivative prepared by non-vacuum spin coating technique

The optical properties of 2(3),9(10),16(17),23(24)-tetrakis-{6-(-benzofuran-2-carboxylate)-hexylthio} phthalocyaninatozinc(II) {Zn[Pc(b-S(CH₂)₆OCOBz-furan)₄], (ZnPcBzF) thin film prepared by spin coating method were investigated. The optical constants of the prepared film were determined using spectrophotometric measurements of the transmittance and reflectance at normal incidence in the spectral range 200–800 nm. The analysis of the spectral behavior of the absorption coefficient in the intrinsic absorption region revealed two direct allowed optical band gap of 2.58 and 3.87 eV. The dispersion of the refractive index was discussed in terms of the single oscillator using Sellmeier dispersion formula. The high frequency dielectric constant (ε_∞) and the lattice dielectric constant (ε_L) were estimated. From the optical constants analysis, the optical conductivity was also considered. Discussion of the obtained results and their comparison with the previous published data were also given. The obtained results of this new zinc phthalocyanine benzofuran derivative (ZnPcBzF) support the desirable feature for the microelectronic and optoelectronic devices.     

Effect of gamma irradiation on the optical properties of nano-crystalline InP thin films

Thin films of InP were prepared onto glass and quartz substrates using laser ablation technique. Some of the prepared films were irradiated using a ⁶⁰Co γ -ray source irradiation with a total dose of 100 kGy at room temperature. The as deposited and irradiated films were identified by scanning electron microscopy, SEM and X-ray diffraction, XRD. The SEM images have shown a nano-flower like structure for the as deposited films and influenced by the irradiation dose. The Optical characterizations of the as deposited and irradiated InP films were studied using spectrophotometric measurements of transmittance T(λ) and reflectance, R(λ) at normal incidence of light in the spectral range from 200 nm to 2500 nm. The refractive index, n, and the absorption index, k values were calculated using a modified computer program based on minimizing (ΔT)² and (ΔR)² simultaneously, within the desired accuracy. Analysis of the dispersion of the refractive index in the range 900 ≤ λ ≤ 2500 was discussed in terms of the single oscillator model. The optical parameters, such as the dispersion energy, E_d, the oscillator energy, E_o, the high frequency dielectric constant, _∞ and the lattice dielectric constant, _L were evaluated for the as deposited and irradiated films. The allowed optical transitions were found to be direct for the as deposited and irradiated films with energy gaps of 1.35 eV and 1.54 eV, respectively.     

Structural and optical properties of thermally evaporated thin films

Chalcogenide glass Se₅₅Ge₃₀As₁₅ have amorphous structure in both as-deposited and annealed conditions. The optical properties of the as-deposited and annealed films were studied using spectrophotometric measurements of transmittance, T(λ), and reflectance, R(λ), at normal incidence of light in the wavelength range 200–2500 nm. Neither annealing temperature nor film thickness can influence spectral response on refractive index and absorption index of films. The type of electronic transition responsible for optical properties is indirectly allowed transition with energy gap of 1.94 eV and phonon energy of 40 meV. The dispersion of the refractive index is discussed in terms of the single oscillator Wemple–Didomenico (WD) model. The width of band tails of localized states into the gap (ΔE), the single oscillator energy (E_o), the dispersion energy (E_d), the optical dielectric constant (ε_∞), the lattice dielectric constant (ε_L), the plasma frequency (ω_p) and the free charge carrier concentration (N) were estimated.     

Dynamics of redox processes and electrochromism of films of zirconium (IV) phthalocyanines with out-of-plane β-dicarbonyl ligands

The electrochromic properties of the mixed-ligand zirconium phthalocyanine complex films have been investigated. Voltammetric characteristics, absorption spectra of films as a function of potential, and curves of current and absorption at the Q-band maximum in the case of their reversible oxidation in 1 N KCl against time have been measured. An analysis of the time-current dependence allowed us to find that the dynamics of the reversible oxidation of phthalocyanine complexes in such films are determined by the codiffusion in their bulk of positive and negative carriers (as Cl^? anions) with effective diffusion coefficient D_eff = ~ 10^? 13 cm²/s. The same value of D_eff has been obtained from measurements of the curve of optical density in the region of the Q-band maximum against time.     

Optical and photoelectric properties of TlInS2 layered single crystals

Single crystals of the layered compound TlInS₂ were grown by direct synthesis of their constituents. The spectral and optical parameters have been determined using spectrophotometric measurements of transmittance and reflectance in the wavelength range 200–2500 nm. Absorption spectra of thin layers of TlInS₂ crystals are used to study the energy gap and the interband transitions of the compound in the energy region 2–2.4 eV. The dispersion curve of the refractive index shows an anomalous dispersion in the absorption region and a normal one in the transmitted region. The direct and indirect band gaps were determined to be 2.34 and 2.258 eV, respectively. Photoconductivity measurements at room temperature resolve the structure that can be identified with the optical transition.     

Effect of In-content on the optical properties of a-Se films

The optical transmission spectra of amorphous (a-) Se_1−xIn_x films, with x = 0.0, 0.05, 0.18 and 0.35, that prepared by thermal evaporation from their corresponding bulk ingots, are recorded over the spectral region of 500–2500 nm. A simple straight forward procedure proposed by Swanepeol has been applied to determine the two components of the complex refractive index (). The dispersion of is examined in terms of the Wemple and DiDomenico model and is discussed in terms of In-content. An estimation of various optical parameters such as, the optical energy gap (E_g = 1.96–1.33 eV), single oscillator energy (E_o = 3.95–3.16 eV), oscillator dispersion energy (E_d = 22.6–31.6 eV), lattice oscillator strength (E_l = 0.38–0.61 eV) and wavelength at zero material dispersion (λ_c = 2.0569–2.0879 μm) have been given and discussed in relation to the coordination number, hydrostatic density and formed chemical bonds that are introduced in the network of a-Se with the introduction of up to 35 at.% In.     

Structural and optoelectronic properties of amorphous GaN thin films

Amorphous gallium nitride (a-GaN) thin films were deposited on glass substrate by electron beam evaporation technique at room temperature and high vacuum using N ₂ as carrier gas. The structural properties of the films was studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). It was clear from XRD spectra and SEM study that the GaN thin films were amorphous. The absorbance, transmittance and reflectance spectra of these films were measured in the wavelength range of 300–2200 nm. The absorption coefficient spectral analysis in the sharp absorption region revealed a direct band gap of E _g = 3:1 eV. The data analysis allowed the determination of the dispersive optical parameters by calculating the refractive index. The oscillator energy E ₀ and the dispersion energy E _d, which is a measure of the average strength of inter-band optical transition or the oscillator strength, were determined. Electrical conductivity of a-GaN was measured in a different range of temperatures. Then, activation energy of a-GaN thin films was calculated which equalled E _a = 0:434 eV.     

Optical characterization of CuIn5S8 crystals by ellipsometry measurements

Optical properties of CuIn₅S₈ crystals grown by Bridgman method were investigated by ellipsometry measurements. Spectral dependence of optical parameters; real and imaginary parts of the pseudodielectric function, pseudorefractive index, pseudoextinction coefficient, reflectivity and absorption coefficients were obtained from the analysis of ellipsometry experiments performed in the 1.2–6.2 eV spectral region. Analysis of spectral dependence of the absorption coefficient revealed the existence of direct band gap transitions with energy 1.53 eV. Wemple–DiDomenico and Spitzer–Fan models were used to find the oscillator energy, dispersion energy, zero-frequency refractive index and high-frequency dielectric constant values. Structural properties of the CuIn₅S₈ crystals were investigated using X-ray diffraction and energy dispersive spectroscopy analysis.     

Dispersive optical constants of a-Se100−xSbx films

Thin films of amorphous Se_100−xSb_x (x=5,10 and 20 at%) system are deposited on a silicon substrate at room temperature (300 K) by thermal evaporation technique. The optical constant such as refractive index (n) has been determined by a method based on the envelope curves of the optical transmission spectrum at normal incidence by a Swanpoel method. The oscillator energy (E_o), dispersion energy (E_d) and other parameters have been determined by the Wemple–DiDomenico method. The absorption coefficient (α) has been determined from the reflectivity and transmitivity spectrum in the range 300–2500 nm. The optical-absorption data indicate that the absorption mechanism is a non-direct transition. We found that the optical band gap, E_g^opt, decreases from 1.66±0.01 to 1.35±0.01 eV with increase Sb content.     

Evolution of the optical properties of single-crystal La1−x SrxMnO3

An ellipsometric method is used to study the dispersion of the real ɛ ₁(ω) and imaginary ɛ ₂(ω) parts of the complex dielectric permittivity of single-crystal La_1−x Sr_xMnO₃ (x=0.1, 0.2, and 0.3) for energies from 100 meV to 5 eV at room temperature. It is found that, when lanthanum is replaced by strontium, the optical spectrum changes fundamentally. A shift in the main features of the spectrum of initial LaMnO₃ at 1.9 and 4.7 eV to lower energies takes place, as well as a partial redistribution of the optical-conductivity spectral weight in the band gap region E<1.7 eV. For compositions with x=0.2 and 0.3, a fine structure of the interband absorption is observed against a background of non-Drude optical conductivity at low energies. Fiz. Tverd. Tela (St. Petersburg) 41, 1445–1449 (August 1999)     

Optical limiting of near-IR radiation in a system based on magnesium phthalocyanine

Nanocrystals of magnesium phthalocyanine in the β-and X-crystalline forms and the magnesium phthalocyanine C₆₀ fullerene system are studied in the near-IR spectral region. The absorption spectra of new nanocomposites are measured. The possibilities of using these systems for optical limiting in the near-IR spectral region (at the wavelength λ=1047 nm) are investigated. The relation between the photoconductivity and nonlinear absorption of phthalocyanine in different crystalline forms is discussed.     

Measurement of the spectral dispersion curves of low birefringence polymer fibres

A method is suggested to overcome the difficulties of measuring the spectral dispersion of low birefringence fibres, that produce small optical path difference, δ<3λ, where δ is the optical path difference and λ is the wavelength of light used. This method depends on variable wavelength interferometry (VAWI). The suggested method is used to measure the spectral dispersion of birefringence of polypropylene fibre with a draw ratio 4 (low birefringence fibre). This method is also used to measure the spectral dispersion of birefringence of a polyester staple from ICI (high birefringence fibre). Also, the conventional VAWI method is used to measure the spectral dispersion of this fibre to confirm the results obtained by the suggested method. Microinterferograms are given for illustration.     

Mix-substituted phthalocyanines of a “push–pull”-type and their metal complexes as prospective nanostructured materials for optoelectronics

To study the influence of structural features of phthalocyanine (Pc) derivatives on their physico-chemical properties in bulk and thin films, 23 new phthalocyanines with different quantity and ratio of donor (alkyloxy-groups, in fragment “A”) and acceptor (Cl-, in fragment “B”) substituents in one molecule of the A₃B, ABAB and AABB types with varied length of alkyloxy-substituents and their metal complexes were designed and synthesized. A comparative analysis of spectral, mesomorphic and photoelectric properties of these mix-substituted phthalocyanines of a “push–pull” type was performed. It was shown that non-peripheral substitution by alkyloxy-fragments in hetero-substituted Pcs (similar to homo-substituted Pc) leads to red-shifting of the Q-band into near-IR region. The intensity of photoluminescence, position of peaks and their splitting are strongly connected with chemical structure of Pcs and the type of solvent. In contrast to non-mesogenic octyloxy-Pc (A4) having alkyloxy-substituents in non-peripheral positions, 22 of 23 synthesized compounds possess columnar mesomorphism. The change of donor–acceptor ratio can influence the type of mesophase. A new approach to the creation of materials for optoelectronics is proposed and implemented, which includes design of compounds possessing vitrification from mesophase with maintenance of a columnar order, absorption in the near IR-region of the spectrum and good performance electrophysical characteristics simultaneously.     

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.     

Photochemistry of tetrasulphonated magnesium phthalocyanine in water and DMSO solutions by Raman, femtosecond transient absorption, and stationary absorption spectroscopies

Photochemical and photophysical behavior of the tetrasulphonated magnesium phthalocyanine MgPcS₄ has been studied by Raman spectroscopy, femtosecond transient absorption, and stationary UV–VIS absorption spectroscopies. It has been shown also that the dimerization equilibrium constant K for the tetrasulfonated magnesium phthalocyanine is strongly shifted towards monomeric form in DMSO solutions compared to aqueous systems. The Raman and emission spectra recorded in the range of 294–77 K combined with the femtosecond transient absorption reveal spectral features that provide unique information about the primary photochemical and photophysical events of magnesium phthalocyanines in liquid solutions as well as in the crystal frozen matrices.     

基于透射光谱确定溅射Al2O3薄膜的光学（已撤稿）

基于反应磁控溅射Al₂O₃薄膜的紫外—可见—近红外透射实验光谱,采用Swanepoel方法结合Wemple-DiDomenico色散模型,方便地导出了Al₂O₃薄膜在200—1100 nm波长范围内的光学常数,包括折射率、色散常数、膜层厚度、吸收系数及能量带隙.研究发现反应磁控溅射Al₂O₃薄膜具有高折射率(1.556— 1.76,测试波长为550 nm)、低吸收和直接能量带隙(3.91—4.20 eV)等光学特性,而且其光学常数对薄膜制备过程中的重要工艺参数——膜层后处理温度表现出强烈的依赖性.此外,在膜层的弱吸收和中等吸收光谱区域内,计算得到的折射率色散曲线与分光光度法的测试结果基本符合,说明本实验中所建立的计算方法在确定反应磁控溅射Al₂O₃薄膜光学常数方面的可靠性. 关键词： 光学常数 Swanepoel方法 2O₃薄膜')" href="#">Al₂O₃薄膜 热处理     

Coupled ultrathin InAs layers in GaAs as a tool for the determination of band offsets

We have determined the band offsets at the highly strained InAs/GaAs heterointerface by photoluminescence excitation (PLE) measurements of the symmetric and antisymmetric states in two coupled ultrathin InAs layers embedded in a GaAs matrix. The conduction band offset ΔE_ccould be separated from the valence band offsets, since in a 32 monolayer (ML) barrier sample, the splitting between the heavy-hole exciton transitions is solely determined by ΔE_c. Knowing ΔE_c, the heavy-hole (hh) and light-hole (lh) band offsets ΔE_hhand ΔE_lhcould subsequently be determined from the coupling-induced shift and splitting in samples with a 16, 8 and 4 ML barrier. We find a conduction band offset of 535 meV, a conduction band offset ratio ofQ_c= 0.58 and a strain induced splitting between the hh and lh subbands of 160 meV.