Organic–inorganic composites consisted of poly(3,4-ethylenedioxythiophene) and Prussian Blue analogues

The organic–inorganic material consisted of poly(3,4-ethylenedioxythiophene) (pEDOT) and copper hexacyanoferrate (Cuhcf) was synthesized. The pEDOT film with Fe(CN)₆^3−/4− as counter-ions potentiodynamically polarized in aqueous CuCl₂ electrolyte brings about stable hybrid material (pEDOT/Cuhcf) performing single redox activity of Fe^II/III at a formal potential E_f = 0.61 V (vs. Ag/AgCl/0.1 M KCl) and less clearly shaped two redox coming from copper ions entrapped inside the film. XPS ex situ measurements show three different binding energies for copper (Cu 2p_3/2: 932.2, 934.8 and 936.3 eV) and two for iron (Fe 2p_3/2: 708.2 and 709.0 eV). Spectroelectrochemical measurements allowed to establish an order in the energy band gap (E_g) for the investigated hybrids pEDOT/Mehcf (Me = Fe, Co, Ni, Cu) as follows: E_{g(pEDOT/Fehcf)} = 1.40 eV < E_{g(pEDOT/Cohcf)} = 1.48 eV < E_{g(pEDOT/Nihcf)} = 1.52 eV < E_{g(pEDOT/Cuhcf)} = 1.6 eV. The hybrid materials were examined as electrodes for electrocatalytic reduction of H₂O₂. Copper centres in pEDOT/Cuhcf as well as high spin iron centres in pEDOT/Fehcf were found to be electrocatalytically active towards hydrogen peroxide reduction.     

Photocatalytic Property and Electronic Structure of Lanthanide-based Oxysulfides

Lanthanide-based oxysulfides and sulfide, LnTaO_3.5S_0.5, Ln₁₀OS₁₄ (Ln = La, Pr, Nd, Sm) and La₄In₅S₁₃, were successively synthesized by sulfurization in a flowing H₂S. The sulfurization decreased the band-gap energies from >4 eV to <3eV, because of the formation of occupied S3p orbitals on the top of valence band. In accordance with the small band gap, the H₂ evolution from a 0.01 M Na₂S and 0.01 M Na₂SO₃ solution system was observed under irradiation of light up to >500 nm. The rate of H₂ evolution under light irradiation of >500 nm increased in the order of Ni/LaTaO_3.5S_0.5 < Ru/La₁₀OS₁₄ < Pt/La₄In₅S₁₃.     

Optical properties and new carbon forms of sputtered amorphous carbon films

Amorphous carbon films were deposited by r.f. magnetron sputtering at various bias voltages V_b applied on Si substrate. We studied the optical properties of the films using in situ spectroscopic ellipsometry (SE) measurements in the energy region 1.5–5.5 eV. From the SE data analysis the dielectric function ε(ω) of the a-C films was obtained, providing information about the electronic structure and the bonding configuration of a-C films. Based on the SE data the films are classified in three categories. In Category I and II belong the films developed with V_b≥0 V (rich in sp² bonds) and −100≤V_b<0 V (rich in sp³ bonds), respectively. The dielectric function of the films belonging in these two categories can be described with two Lorentz oscillators located in the energy range 2.5–5 eV (π–π^*) and 9–12 eV (σ–σ^*). A correlation was found between the oscillator strength and the sp² and sp³ contents. The latter were calculated by analyzing the ε(ω) with the Bruggeman effective medium theory. In films deposited with V_b<−100 V (Category III), the formation of a new and dense carbon phase was detected which exhibits a semi-metallic optical behavior and the ε(ω) can be described with two oscillators located at ∼1.2 and ∼5.5 eV.     

Low-cost flame synthesized La2/3Cu3Ti4O12 electro-ceramic and extensive investigation on electrical,impedance, modulus,and optical properties

An environmentally-friendly synthesis route and low-cost starting materials are more appropriate for the production of ceramic materials at the industry level. With this concern we prepared the La_2/3Cu₃Ti₄O₁₂(LCTO), which is isostructural of CaCu₃Ti₄O₁₂ (CCTO), using the low-cost TiO₂ instead of a high-cost of titanium source (titanium isopropoxide or titanium chloride) using a low-cost wet-chemical route. Although, there are lots of synthetic methods reported for LCTO fabrication in terms of duration, cheap reagents, energy consumption, feasibility, etc. The present method is far better than the others. The prepared ceramic samples were sintered at 1050 ^°C/12 h and studied their structural, morphology and impedance, and modulus studies for further confirmation. The prepared LCTO ceramic shows the pure phase with the cubic type of morphology. The homogenous distribution of all the elements was observed through dispersive X-ray analysis. X-ray photoelectron spectroscopy studies revels that La is in +3 oxidation state, Cu is in a +2 oxidation state, and Ti is multiple (+3 and + 4) oxidation state. The LCTO ceramic displayed the very high dielectric constant (∼3852) and dielectric loss (0.322), at 1 kHz and at room temperature. Calculated the activation energy using the impedance and modulus data and it shows the superior to that of CCTO ceramic synthesized by the same method. The prepared samples exhibited Debye-type relaxation, which is evoked from the impedance and modulus studies. The calculated optical energy bandgap of LCTO (2.06 eV) is found to be lesser than that of the well-known structure of perovskites (BaTiO₃ (3.28 eV), PbTiO₃ (3.18 eV), LiNbO₃ (3.78 eV) and BiFeO₃ (2.67 eV) as well as structure of spinel CoCr₂O₄ (3.10 eV) and LuFe₂O₄ (2.18 eV)) materials.     

Porous titanium dioxide supported on glass microbubbles to prepare a low-density photocatalyst for AR1 degradation

Low-density TiO₂(C)/GB hollow powders were synthesized by loading anatase TiO₂ onto glass microbubbles. CTAB (cetyltrimethyl ammonium bromide) was used to produce pores in the supported TiO₂. A TiO₂ layer with a thickness greater than 100 nm was tightly loaded onto the glass microbubbles. CTAB led to a slight expansion of the bandgap energy from 3.22 eV (TiO₂(0)/GB) to 3.41 eV (TiO₂(3.0)/GB). The E_CB and the E_VB values were ?0.32 and 2.91 V for the TiO₂(1.5)/GB, respectively. Both the average pore size (from 5.59 to 9.44 nm) and the total pore volume (from 0.0799 to 0.1283 cm³/g) of TiO₂(C)/GB increased with an increasing amount of CTAB. The hole-electron recombination efficiency was in the sequence of TiO₂(1.5)/GB< TiO₂(3.0)/GB< TiO₂(0)/GB. The AR1 degradation efficiency varied with the CTAB amount, and the maximum degradation efficiency was obtained for TiO₂(1.5)/GB. The TiO₂(C)/GB hollow powders were suspended in an AR1 solution during the degradation process, and TiO₂(C)/GB floated on the water surface after treatment to ensure fast solid-water separation. The reaction rate constants were 1.79 × 10^?2 and 1.21 × 10^?2 min^?1 for TiO₂(1.5)/GB and the unsupported TiO₂ powders, respectively. TiO₂(1.5)/GB had a stronger activity than the TiO₂ powders.     

Surfacial proton conducting CeO2 nanosheets

Proton conducting ceramic fuel cells (PCFCs) have been attracting much more attentions due to is affordable ionic conductivity lower operating temperatures (<600 °C). CeO₂ nanosheets expose mainly to the (111) plane exhibit a super proton conductivity of 0.3 S cm^?1 and a maximum power density of 948 mWcm^?2 at 550 °C. In these two morphologies of CeO₂, the difference in Ce³⁺/Ce⁴⁺ ratios and the formation of oxygen vacancies on the surface are mainly responsible for proton transport. Theoretical calculation proves that protons can move more easily on the CeO₂ (111) facet with smaller binding energy (0.14 eV) and lower energy barrier for H–O formation (1.7 eV) than on other facets, also superior proton conduction for the nanosheet morphology over the nano-particles. This work has developed a morphological methodology for high proton surface conduction to design highly efficient ionic transport for advanced CFCs and electrochemical devices.     

Ion-Exchange Properties of lon-Sieve-Type Manganese Oxides Prepared by Using Different Kinds of Introducing Ions

Abstract

Three ion-sieve-type manganese oxides, HMnO(Li), HMnO(Na), and HMnO(K), were prepared by acid treatments of Li⁺-, Na⁺-, and K⁺-introduced manganese oxides, respectively. Three oxides were obtained from γ-MnO² and the corresponding alkali metal hydroxides by heating at 600°C. The ion-exchange properties of the adsorbents were investigated by pH titration, K_d measurements, and the adsorption of metal ions from seawater. The selectivity sequences of alkali metal ions were Na⁺ < Cs⁺ < Rb⁺ < K⁺ < Li⁺ for HMnO(Li) and Li⁺ Na⁺ < Cs⁺ < K⁺ < Rb⁺ for HMnO(Na) and HMnO(K). The high selectivity of Li⁺ on HMnO(Li) can be ascribed to an ion-sieve effect of spinel-type manganese oxide which was produced from LiMn₂O₄ Since HMnO(Na) and HMnO(K) had [2 × 2] tunnels of edge-shared [MnO₆] octahedra, the high selectivities of K⁺ and Rb⁺ on these samples were used to explain that the sizes of the [2 × 2] tunnels were suitable for filling ions of about 1.4 Å in radius in a stable configuration. The order of metal-ion uptake from seawater was Sr²⁺ < K⁺ < Mg²⁺ < Ca²⁺ < Na⁺ < Li⁺ for HMnO(Li), Li⁺ < Sr²⁺ < Mg²⁺ < Ca²⁺ < Na⁺ < K⁺ for HMnO(Na), and Li⁺ < Sr²⁺ < Ca²⁺ < Mg²⁺ < K⁺ < Na⁺ for HMnO(K).     

Phase stability,microstructure, and dielectric properties of quaternary oxides In12Ti10A2BO42 (A: Ga or Al; B: Mg or Zn)

Quaternary oxides In₁₂Ti₁₀Al₂MgO₄₂ (ITAM), In₁₂Ti₁₀Al₂ZnO₄₂ (ITAZ), In₁₂Ti₁₀Ga₂MgO₄₂ (ITGM), and In₁₂Ti₁₀Ga₂ZnO₄₂ (ITGZ), were synthesized by the solid-state reaction method and the dielectric behavior is reported. The samples were submitted to different sintering temperatures (1473-1773 K) for 24 hours and the phase stability and microstructure were analyzed by X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). It is found that the phase decomposition occurs above of 1573 K. Microstructure images showed an increase in the grains size as sintering temperature was raised. The dielectric permittivity as a function of temperature and frequency showed acceptable dielectric constant (15-30) and low dielectric loss (tan δ << 1) values in a wide range of temperature. The band gap obtained by the optical spectrum analysis is about 3.5 eV indicating good dielectric insulating compounds. Furthermore, the electrical conductivity, the activation energy, and the conduction mechanisms are analyzed and discussed in a whole range of temperature. The good dielectric values, ε′ (15-20) and tan δ (~0.004), and their behavior (almost independent of the frequency and temperature) almost constant within a wide range of temperature make these quaternary oxides interesting in electroceramic applications.     

Thermal desorption of deuterium from modified carbon nanotubes and its correlation to the microstructure

The process of deuterium desorption from single-wall carbon nanotubes (SWNTs) modified by atomic (D) and molecular (D₂) deuterium treatment was investigated in an ultrahigh vacuum environment using thermal desorption mass spectroscopy (TDMS). Microstructural and chemical analyses of SWNT material, modified by this deuterium interaction, were performed by means of a combination of scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results disclose characteristic features in the TDMS spectra of deuterium evolved from the SWNT material, which can be correlated to the microstructure of nanocarbon material modified by D-treatment. The TDMS spectra of deuterium originating from the large diameter rope type nanotube structures, resulting from a prolonged low-pressure (D + D₂) gas mixture treatment, exhibit three overlapping desorption peaks: a dominant one with a desorption activation energy (E_des) of approx. 2.86 eV and lower intensity peaks at E_des of ∼1.50 and 2.46 eV. On the other hand, the TDMS spectra of deuterium taken from the “coral reef”-like carbon nanostructures, obtained after prolonged treatment of SWNTs to a high-pressure (D + D₂) gas mixture produced at high temperature, reveal the coexistence of four superimposed desorption peaks with E_des ranging from 1.23 to 4.4 eV. A dominant desorption peak with E_des ≈ 4.4 eV, can be attributed to bulk diffusion of D trapped within this nanocapsule bulk structure.     

Effect of Calcination Temperature on the Structural and Optical Properties of (ZnO)0.8 (ZrO2)0.2 Nanoparticles

Calcination temperature has influenced the structural and optical features of nanocrystalline (ZnO)_0.8 (ZrO₂)_0.2 series. Indeed, at present, general research in the approach to synthesis of (ZnO)_0.8 (ZrO₂)_0.2 nanoparticles by combustion using zinc nitrate hexahydrate (Zn (NO₃)₂·6H₂O) and zirconium (11) nitrate pentahydrate (Zr (NO₃)₂·5H₂O) is still in its infancy. A Thermogravimetric (TG) assessment was performed to determine the precursor of the conduction. Characterizations such as energy dispersive X-ray analysis (EDX), X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–Visible, Fourier transform infrared spectroscopy (FTIR), and photoluminescence (PL) spectroscopy were carried out. The crystallite size of the binary oxides (ZnO)_0.8 (ZrO₂)_0.2 on the maximum expansion of ZnO–ZrO₂ nanoparticle was studied using Scherrer’s equation. Due to calcination, significant modifications were observed in terms of the size of the particles, the absorption spectra, and the intensity of the photoluminescence. In the XRD result, an increment in crystallinity was observed from 10.20 nm to 28.00 nm while the FTIR findings showed the removal of the polymer as well as the presence of nanoparticles metals. The optical band gap results indicated a decline in energy band gap between (3.27 and 3.12) eV for (ZnO)_0.8 and (4.89–4.51) eV for (ZrO₂) _0.2 nanoparticles. A photoluminescence result showed two individual peaks at 655 nm (1.89 eV) and 715 nm (1.73 eV) respectively. The study also showed the application which can be a suitable choice to be used in solar cell applications.

     

Magnetic characteristics and optical band alignments of rare earth (Sm+3, Nd+3) doped garnet ferrite nanoparticles (NPs)

Yttrium iron garnet (YIG) nanoparticles (NPs) doped with rare earth (RE) metal ions (Y_2.5Sm_0.5Fe₅O₁₂, Y_2.5Nd_0.5Fe₅O₁₂) were successfully synthesized by sol-gel auto combustion approach. The cubic crystalline structure and morphology of the prepared garnet ferrite NPs were analyzed by X-ray diffractometer (XRD) and field emission scanning electron microscopy (FESEM). The cubic crystalline garnet phase of the synthesized YIG, Sm-YIG and Nd-YIG samples was successfully achieved at 950 °C sintering temperature. The force constant and absorption bands were estimated by using Fourier transform infrared spectroscopy (FTIR). The doping effect of RE metal ions on the chemical states of YIG were examined by x-ray photoelectron microscopy (XPS). The valence band (from 12.63 eV to 13.22 eV), conduction band (from 10.89 eV to 11.34 eV) edges and optical bandgap values of RE doped YIG samples were calculated using UV–Vis spectroscopy and ultraviolet photo electron spectroscopy (UPS). The magnetic analysis of the prepared NPs was studied using vibrating sample magnetometer (VSM). The XPS analysis of RE doped YIG samples exhibit the existence of RE (Sm⁺³, Nd⁺³) contents on the surface of YIG ferrite by decreasing the oxygen lattice in garnet structure. The optical bandgap (from 1.74 eV to 1.88 eV) explains the semiconducting nature of the synthesized NPs. The UPS results confirm the valence band position of YIG doped samples. The saturation magnetization and remanence of RE doped garnet ferrite samples increased from 13.45 to 18.83 emu/g and 4.06–6.53 emu/g, respectively.     

Structural and optical properties of magnesium nitride formed by a novel electrochemical process

The electrochemical formation of magnesium nitride (Mg₃N₂) films in LiCl-KCl containing Li₃N at 723 K was investigated. From a thermodynamic point of view, a potential-pN³⁻ diagram was constructed for the Mg-N system in an analogous fashion to Pourbaix diagrams for aqueous solutions. As a result, the thermodynamically stable region of Mg₃N₂ in LiCl-KCl-Li₃N was identified. XRD analysis revealed that Mg₃N₂ film was obtained by potentiostatic electrolysis of a magnesium electrode between 0.4 and 0.8 V (versus Li⁺/Li), and the structure of obtained Mg₃N₂ was anti-bixbyite (a = 1.001 nm). Reflectance measurements clarified that assuming direct transition, the bandgap energy was 3.15 eV and assuming indirect transition, the bandgap energy was 2.85 eV.     

Hierarchical Organization of TiO2 Nanostructures in Low‐Temperature Solution Processes

Nanostructured TiO₂ thin films were prepared via a low‐temperature solution processing. We have previously calculated the degree of supersaturation (s) for TiO₂ precursor solution to systematically tailor the development of TiO₂ nanostructures in the range of s = 70–200. In this article, we focused more on a lower supersaturation regime (s < 70), from which we were able to obtain various shapes and sizes of nanostructures of TiO₂ thin films. A film consisting of “rutile” phase nanoblades was observed when the degree of supersaturation was s = 15–70. To further lower the supersaturation (s < 15), hydrothermal processing had to be used, for which a film consisting of “rutile” phase nanorods was obtained. The resulting thin films were evaluated for band gap energies and dielectric properties. The band gap energy for those rutile thin films decreased from 3.22 to 2.99 eV when the supersaturation was lowered from s = 70 to 15. The dielectric constant (k) of the rutile film processed from s = 50 showed the best performance with k~50 at 1 MHz.     

Low temperature reaction of point defects in ion irradiated 4H–SiC

The low temperature evolution of point defects induced in SiC by ion irradiation was investigated by deep level transient spectroscopy. The defects were introduced by irradiation with a 7.0 MeV beam of C⁺ ions at a fluence of 6 × 10⁹ cm^? 2. Annealing was then performed in the temperature range of 330–400 K in order to study the change in point defect structure with temperature. The low temperature annealing performed was observed to induce a change in the produced defects. The deep levels related to the S_x (E_C ? 0.6 eV) and S₂ defects (E_C ? 0.7 eV) recovered with annealing while, simultaneously, a new level, S₁ (E_C ? 0.4 eV), was formed. The activation energy of the S₁ defect is 0.94 eV, while the annealing of both the S_x and S₂ levels occurred with activation energy of 0.65 eV.     

Hydrolysis mechanism of crosslinks formed between hydroxymethylated 2-substituted 4,6-diamino-s-triazines and cotton

Hydrolysis resistance and mechanism of reaction products of hydroxymethylated 2-substituted (X) 4,6-diamino-s-triazines (MXT) with cotton fabrics has been studied. Finishing reagents used were MXT having the following substituents: X = CH₃O? (MMT), (CH₃)₂CHO? (MIPT), CH₃? (MAG), C₂H₅NH? (MEM), HOC₂H₄NH? (MHEM), and (HOC₂H₄)₂N? (MBHEM). For comparison, trimethylolmelamine (TMM), dimethylolurea (DMU), dimethylolethyleneurea (DMEU), and dimethylol-ethyltriazone (DMET) were used. Hydrolysis was carried out in buffer and NaOH solutions of various pH's for 30 min at 80°C. The order of hydrolysis resistance of crosslinked reagents was determined from the nitrogen contents retained. It was as follows: pH 1, MROT < MRNT < MRT; pH ≧ 2, MROT > MRT > MRNT; pH ≦ 13, MROT > MRNT; pH 14, MROT < MRT < MRNT, where MROT is hydroxymethylated 2-alkoxy (MMT, MIPT), MRT is hydroxymethylated 2-alkyl (MAG), and MRNT is hydroxymethylated 2-alkylamino-4,6-diamino-s-triazine (MEM, MHEM, MBHEM). This fact can be explained in terms of the basicity constant (p^K_b) of crosslinked MXT with cotton (approximately p^K_b) of 2-substituted 4,6-diamino-s-triazine (XT). The hydrolysis rates of crosslinked MMT, MAG, and MEM were determined at pH 2. The activation energies were 21.8 for MMT, 20.9 for MAG, and 21.0 kcal/mole for MEM.     

Binding Properties of a Polymer Having Amidoxime Groups with Proton and Metal Ions

Abstract

The proton-binding behavior of a polymer having amidoxime groups was examined by the potentiometric titration method. Adsorptive properties of the polymer for UO₂(VI), Mg(II), Fe(II), Ni(III), Co(II), Ni(II), Cu(II), and Zn(II) were also examined at very low concentrations in the 1–9 pH range. The amidoxime polymer possesses adsorptive affinities of the following order: (Mg(II), Ca(II)) < Zn(II) < Co(II) < Ni(II) < Cu(II) < UO₂(VI). These adsorptive affinities are reasonably explained by the proton-binding and the metal ion-complexing abilities of the ligand, and are discussed from the standpoint of uranium recovery from seawater.     

Preparation and characterization of SnO2 nanoparticles in aqueous solution of [EMIM][EtSO4] as a low cost ionic liquid using ultrasonic irradiation

A facile, template-free, room temperature and environmentally benign green route for the preparation of SnO₂ nanoparticles in aqueous solution of 1-ethyl-3-methylimidazolium ethyl sulfate, [EMIM][EtSO₄], room-temperature ionic liquid (RTIL), via ultrasonic irradiation is proposed. The X-ray diffraction (XRD) studies display that the products are excellently crystallized in the form of tetragonal rutile structure. Energy dispersive X-ray spectroscopy (EDX) investigations reveal the products are pure. The morphology of as-prepared nanoparticles was characterized by scanning electron microscopy (SEM). Diffuse reflectance spectra (DRS) of the products exhibit band gap energy of about 3.98 eV which shows blue shift of 0.38 eV that can be attributed to quantum confinement effect of SnO₂ nanoparticles. A possible formation mechanism of the SnO₂ nanoparticles using ultrasonic irradiation in aqueous solution of the RTIL is presented.     

Evolution of TiOx-SiOx nano-composite during annealing of ultrathin titanium oxide films on Si substrate

This paper discusses the formation of the TiO_x-SiO_x nano-composite phase during annealing of ultrathin titanium oxide films (~27 nm). The amorphous titanium oxide films are deposited on silicon substrates by sputtering. These films are important for high-k dielectrics and sensing applications. Annealing of these films at 750 °C in the O₂ environment (for 15–60 min) resulted in the polycrystalline rutile phase. The films exhibit Raman peaks at 150 cm⁻¹ (B_1g), 435 cm⁻¹ (E_g), and 615 cm⁻¹ (A_1g) confirming the rutile phase. The signature TO (1078 cm⁻¹) and LO (1259 cm⁻¹) infrared active vibrational modes of Si–O–Si bond confirms the presence of silicon-oxide. The X-ray photoelectron spectra of the TiO_x films show multiple peaks corresponding to Ti metal (453.8 eV); Ti⁴⁺ state (458.3 eV (Ti 2p_3/2) and 464 eV (Ti 2p_1/2)); and Ti³⁺ state (456.4 eV (Ti 2p_3/2) and 460.8 eV (Ti 2p_1/2)). The O1s XPS spectra peaks at 530–533 eV can be attributed to Ti–O and Si–O bonds of the TiO_x-SiO_x nano-composite phase in the annealed films. The depth profiling XPS study shows that the top surface of the annealed film is mainly TiO_x and the amount of SiO_x increases with the depth.     

Equilibrium studies of the extraction of zirconium(IV) from sulfuric acid solutions with Di(2-ethylhexyl)phosphoric acid

Equilibrium studies were made at 25°C in the extraction of zirconium(IV) from sulfuric acid solutions with di(2-ethylhexyl)phosphoric acid (D2EHPA, HR) dissolved in kerosene. The reaction stoichiometry was numerically determined and the compositions of the extracted species were found to be ZrR₄ and ZrR₄(HR) at low loading ratios of D2EHPA (α < 0.09), but became ZrR₄ and ZrR₄(HR)₃ at relatively higher loading ratios (0.10 < α < 0.32). The equilibrium constants for the formation of these species were also obtained. Furthermore, numerical treatment of the experimental data excluded the existence of polynuclear complexes under the conditions studied (α < 0.32).     

Free-exciton luminescence spectrum broadening due to excitonic complex in diamond

The excitation density evolution of a band-edge luminescence spectrum of diamond in the photon energy region 5.14 to 5.40 eV was investigated at 190, 240 and 290 K with the fifth harmonic (5.82 eV) of a pulsed YAG laser in the excitation density range 2.2 to 272 mJ/cm². A broadening of a free-exciton luminescence (FE) spectrum with the peak energy (E_peak) of 5.28 eV due to the growth of the low-energy tail was observed with increasing excitation density. From a detailed spectrum analysis, it is found that the broadening originates in excitonic complex (EC) luminescence (E_peak = 5.26 eV) in addition to electron-hole plasma (EHP) luminescence (E_peak = 5.23 eV). The EC luminescence intensity was observed to be proportional to the 1.5 power of the FE luminescence intensity, which is the same manner as in the case of the EC luminescence in crystalline silicon. The excitation density dependence of the EHP luminescence intensity is discussed with percolation theory.