Recombination luminescence in alkali metal sulfates

In this paper we present the results of investigation of the nature of intrinsic luminescence caused by photon excitation in a wide spectral range from 10.3 eV to 4 eV at a temperature of 15–300 K. It is shown that in alkali metal sulfates the main emission band formed after excitation by X-rays and photons with an energy of 9–11 eV and 4–7.5 eV at 15–300 K is located in the spectral range of 3.65–3.9 eV. When the sulfates are excited by 4–7.75 eV photons, in addition to the emission band at 3.65–3.9 eV the other effective long-wave band at 3.1–2.5 eV appears. It is assumed that the 3.65–3.9 eV radiation results from the recombination of electrons with unevenly located holes of SO₄⁻ type. The long-wave emission bands in the alkali metal sulfates may be connected with the formation of electron-hole trapping centers after irradiation by photons with energies above 4.4 eV.     

Photoluminescence spectra of MnIn2S4

MnIn₂S₄ single crystals grown by the directional crystallization method were investigated by using the temperature and excitation power dependencies of photoluminescence (PL) spectra. PL spectra consist of one broad band resulting from donor-acceptor pair recombination. The analysis of the temperature quenching of the PL intensity yields one defect donor level with a thermal ionization energy of about 0.17 eV. The broad band of PL spectra indicates that radiative recombination is related to multiphonon optical processes. The energy of the involved phonon was found to be around 0.025 eV and the energy of the acceptor level is about 0.86 eV.     

PL characterization of GaN scintillator for radioluminescence-based dosimetry

Via photoluminescence (PL) measurements, we have investigated GaN (which is a widely employed material in optoelectronics) to be used as scintillator for developing implantable dosimetric probes. The studied Si-doped n-type GaN samples have common dominant band-edge emission at room temperature, with a strong doping-dependence on their PL spectra. Si-doped GaN with 10¹⁸ cm⁻³ concentration exhibits a non-negligible yellow luminescence (YL) or red luminescence broad band contribution, which is probably due to Ga vacancy native defect. However, heavily-doped GaN (1.5 × 10¹⁹ cm⁻³) has much more intense band-edge emission, with no significant contributions of lower-energy bands. The dominant band-edge emission peak remains unchanged at 3.4 eV for both concentrations, and may be accounted for by considering combined effects of band-gap narrowing and Fermi level rising. It has also been demonstrated by back-side PL collection that, due to bulk self-absorption, the dominant peak is shifted to 3.25 eV DAP (donor–acceptor-pair) or e–A (conduction-band-to-acceptor) band. At low temperatures (up to 200 K), PL intensity of heavily-doped GaN is dominated by a DBE (donor-bound exciton) line (D⁰X_A at 3.467 eV for T = 10 K). When further increasing the temperature, band-to-band recombination becomes dominant with red-shift of the emission peak in connection with gap narrowing. The shift in peak wavelength from 10 K to room temperature is about 5 nm, while the corresponding PL integrated intensity is decreased only by 30%. Irradiating samples at room temperature to a 200 Gy dose with 6 MeV photon and electron beams causes a slight increase on defect-related DAP or e–A line and YL broad band, but the effect is not noticeable for heavily-doped GaN.     

Photoluminescence studies on energy transfer processes in cerium-doped Gd3Al2Ga3O12 crystals

We have measured photoluminescence properties of cerium-doped Gd₃Al₂Ga₃O₁₂ (Ce:GAGG) crystals at low temperatures with use of synchrotron radiation. Excitation spectra for the Ce³⁺ 5d–4f emission exhibit prominent peaks at Gd³⁺ intra-4f absorption bands. The Gd³⁺ intra-4f emission band is observed at 3.91 eV, but is not in resonance with the lowest energy Gd³⁺ intra-4f absorption band at 3.95 eV. The temperature dependence of the Gd³⁺ emission intensity is not correlated with that of the Ce³⁺ emission intensity. Decay curves of the Ce³⁺ emission were also measured at 9 K under excitation at various photon energies. The decay curve is remarkably changed, depending on the excitation photon energies. The present results give us hints to understand the whole of energy transfer processes in Ce:GAGG crystals.     

Novel nano-structured glasses containing semiconductor quantum dots: controlling the photoluminescence with phonons and photons

Effects of temperatures and excitation intensities on the photoluminescence properties of PbS quantum dots precipitated in the glass were investigated. Peak wavelength of the near-infrared photoluminescence shifted towards the short wavelength side with an increase in temperature and excitation intensity. The largest shift in the peak wavelength of the photoluminescence bands was approximately 90 nm. The temperature coefficient of band gap energy (deduced from the photoluminescence wavelength) of quantum dots varied from 230 to 28 μeV/K under the excitation intensity of 50–600 mW. The integrated photoluminescence intensity also showed similar dependencies on temperature and excitation intensity. The shifts of the photoluminescence with changes in the temperature and excitation intensity were associated with the trapping and re-activation of charge carriers at defect sites located at the QDs/glass interface and inside the glass matrix.     

Room temperature PL characterization of micro and nanocrystalline diamond grown by MPCVD from Ar/H2/CH4 mixtures

A photoluminescence (PL) study at room temperature was accomplished as a complement to well-established structural and morphological characterization techniques such as μ-Raman, FTIR, XRD, XPS or SEM. Considering the wide electronic band gap of pure diamond (5.45 eV), the near ultraviolet excitation (325 nm) from an HeCd laser source was selected. The observed nanocrystalline diamond (NCD) and microcrystalline CVD diamond (MCD) samples were obtained by microwave plasma (MPCVD) from hydrogen poor Ar/H₂/CH₄ mixtures. The PL spectrum of both NCD and MCD samples is dominated by the 1.681 eV emission with significant intensity and energy variations. The well-known 1.681 eV band related to the Si-vacancy colour centre is much more pronounced in MCD. In addition, for NCD, the band shifts to higher energies with thickness, suggesting two mechanisms for the silicon incorporation: co-deposition from the plasma and diffusion from the substrate. The samples were further characterized by μ-Raman spectroscopy, X-ray diffraction and scanning electron microscopy, structurally and morphologically.     

Visible light induced photocatalytic performance of Mn-SnO2@ZnO nanocomposite for high efficient cationic dye degradation

In this work, we have synthesized Mn-doped SnO₂@ZnO nanocomposite for photo degradation of Methylene blue and Rhodamine B dyes upon visible light irradiation. The crystal structure, functional group, optical absorption, defect related emission, morphology, purity and binding energy state of synthesized samples were identified by using various analytical tools. The crystal structure revealed the rutile tetragonal, hexagonal wurtzite for SnO₂ and ZnO samples and the average crystal sizes were found in the range of 23.3 nm to 16.7 nm for the synthesized samples. The optical absorption peaks were shifted to higher wavelength side and optical band gap values were found between 3.52 eV and 2.77 eV which confirm the formation of hetero-junction of SnO₂@ZnO composites. The field emission scanning electron spectroscopy (FESEM) revealed the spherical grain morphology for pure and composite samples. The energy dispersive spectra (EDS) and element mapping confirms the purity of the synthesized samples. The X-ray photoelectron spectroscopy (XPS) revealed that the composition and energy state of Mn⁴⁺, Sn⁴⁺ and Zn²⁺ for composite samples. The photocatalytic degradation results clearly indicate that the Mn-doped SnO₂@ZnO nanocomposite has higher degradation efficiency of 98% and 92% for the Methylene blue and Rhodamine B dyes, respectively and is higher than the other synthesized samples. The present study reveals a low cost and highly efficient photo-catalyst which works up on visible light irradiation for the purification of waste water from industries.

     

Mechanism of bright red emission in Si nanoclusters

A bright photoluminescence around 1.7?eV is observed for post-annealed samples of 1?MeV Si(2+) implanted in an SiO(2) matrix. A super-linear power dependence of photoluminescence intensity accompanied by pulse shortening under continuous wave laser excitation is recorded without any spectral narrowing. An emission process comprised of an initial non-radiative recombination (time constant ～280-315?ps) of excited carriers in the defect states in SiO(2) matrices to the conduction band minima of nc-Si, followed by a slower process of radiative recombination in the direct band transition for nc-Si along with a non-radiative Auger recombination (time constant ～2.67?ns) is proposed.     

Radiative recombination in Cu2ZnSnSe4 monograins studied by photoluminescence spectroscopy

In this study we investigated the optical properties of Cu₂ZnSnSe₄ monograin powders that were synthesized from binary compounds in the liquid phase of flux material (KI) in evacuated quartz ampoules. The monograin powder had p-type conductivity. Radiative recombination processes in Cu₂ZnSnSe₄ monograins were studied using photoluminescence spectroscopy. The detected low-temperature (T = 10 K) photoluminescence band at 0.946 eV results from band-to-impurity recombination in Cu₂ZnSnSe₄. The ionization energy of the corresponding acceptor defect was found to be 69 ± 4 meV. Additional photoluminescence bands detected at 0.765 eV, 0.810 eV and 0.860 eV are proposed to result from Cu₂SnSe₃ phase whose presence in the as-grown monograins was detected by Raman spectroscopy and SEM analysis. Considering photoluminescence results, it is proposed that the optical bandgap energy of Cu₂ZnSnSe₄ is around 1.02 eV at 10 K.     

Photoluminesence studies of CdTe/SnO2 and CdTe/CdS heterojunctions: The influence of oxygen and the CdCl2 heat treatment

The influence of oxygen and annealing in the presence of CdCl₂ on the photoluminescence (PL) spectra of CdTe, component of SnO₂/CdTe heterojunction (HJ), has been studied in a temperature range of 17-100 K. The changes in the photoluminescence spectra were studied as a function of excitation intensity. Analysis of the PL spectra was carried out with considerations of spectra obtained from CdS/CdTe heterojunctions. CdTe side PL (SnO₂/CdTe HJ) consisted of 1.450 eV-DA defect band and 1.243 eV band (17 K). Annealing resulted in the disappearance of 1.243 eV band in oxygen containing samples. Interface PL for the unannealed samples consisted of mainly the 1.264 eV and a trace of the defect band. The CdCl₂ treatment is responsible for an almost symmetrical 1.416 eV band.     

Combustion synthesis of Eu2?+? and Dy3?+? activated Sr3(VO4)2 phosphor for LEDs

Combustion synthesis and photoluminescence (PL) characterization of Sr₃(VO₄)₂:Eu,Dy phosphors are presented in this paper. PL emission of Sr₃(VO₄)₂:Eu phosphor shows green broad emission band centring at 511 nm and a red sharp band at 614 nm by excitation wavelength of 342 nm. The PL emission spectrum of Sr₃(VO₄)₂:Dy phosphor exhibits an intense blue emission peak at 479 nm, yellow broad band centring at 573 nm and red band at 644 nm by the excitation wavelength of 426 nm in near visible blue region. The excitation wavelength of Eu (342 nm) and Dy (426 nm) activated Sr₃(VO₄)₂ phosphor are well matched with the excitation of near UV excited solid state lighting and blue chip excitation of light emitting diodes, respectively. The effect of Eu^2 +and Eu^3 +ions concentration on the emission intensity of Sr₃(VO₄)₂ was also investigated. The Sr₃(VO₄)₂:Eu is a potential green and red emitting phosphor as well as Sr₃(VO₄)₂:Dy is blue and yellow emitting phosphor for solid state lighting i.e. white LEDs. The XRD and SEM characteristics of Sr₃(VO₄)₂ materials was also reported in this paper.     

UV–VUV spectroscopy of rare earth doped persistent luminescence materials

The electronic and defect energy level structure of polycrystalline SrAl₂O₄:Eu²⁺,R³⁺ persistent luminescence materials were studied with thermoluminescence and UV–VUV synchrotron radiation emission and excitation spectroscopy. Theoretical calculations using the density functional theory (DFT) were carried out simultaneously with the experimental work. The experimental band gap energy (E_g) value of 6.6 eV agrees very well with the DFT value of 6.4 eV. The 4f⁷ → 4f⁶5d¹ excitation bands of Eu²⁺ were found rather similar irrespective of the R³⁺ co-dopant. The trap level energy distribution depended strongly on the R³⁺ co-dopant except for the shallowest trap energy above the room temperature remaining the same, however. The different processes in the mechanism of persistent luminescence from SrAl₂O₄:Eu²⁺,R³⁺ was constructed and discussed.     

Lateral features of Cu(In0.7Ga0.3)Se2-heterodiodes in the μm-scale by confocal luminescence and focused light beam induced currents

Polycrystalline Cu(In,Ga)Se₂ films (CIGSe) show substantial local variations of properties not only in regime of 10-100 nm but also in the scale length of few microns. We have analyzed optoelectronic properties of CIGSe heterodiodes by confocal luminescence and focused light beam induced currents (LBIC) versus temperature and excitation level with < 1 μm lateral resolution and we observe a strong dependence of the size of local patterns on excitation flux and a considerable dependence of the yield and the spectral shape of luminescence and of microscopic LBI currents on temperature. From experiments we derive activation energies for rates of non-radiative recombination of (2-7) meV and for minority carrier mobilities of about (60-70) meV. These energies are compared with local variations of band edges resulting from potential fluctuations which are formulated after an approach from literature and which has been fitted to experimental shifts of PL peaks and squeezing of PL spectra versus excitation flux. We estimate tunnel barriers for radiative transitions of trapped electrons of about (30-70) meV. Correlating our different results we attribute the activation energy for minority transport in CIGSe reflecting local variations of the conduction band edge mainly to spatial fluctuations of the optical band gap as a consequence of spatially varying elemental composition, and to variations of splitting of the quasi-Fermi levels introduced by spatially varying defect densities.     

The electronic structure and luminescence properties of Ce3+ doped Sr10[(PO4)5.5(BO4)0.5]BO2 under UV/VUV and X-ray excitation

The apatite related compound Sr₁₀[(PO₄)_5.5(BO₄)_0.5]BO₂ (SrBPO) doped with Ce³⁺ was synthesized via solid state reaction method. Undoped SrBPO shows blue-green emission under ultraviolet (UV) and X-ray excitation due to the defects in the host. When excited by vacuum ultraviolet–ultraviolet (VUV–UV) light or X-ray, Ce³⁺ doped SrBPO shows a broad emission band peaking at 450 nm originating from 5d–4f transition of Ce³⁺ and defects in the host. The phosphor exhibits strong excitation bands in UV range and a weak broad excitation band in VUV region. The site occupation of Ce³⁺ was proposed based on fluorescence decay curves. Electronic structure shows the compound is an indirect semiconductor with a band gap of 3.04 eV. The extremely small density of states of [PO₄]³⁻ or [BO₄]⁵⁻ group near Fermi level or in the conduction band is a possible origin of the weak excitation band in the VUV range. A possible mechanism was proposed to explain the luminescence properties observed.     

Luminescent properties of Eu3+ activated MLa2(MoO4)4 based (M = Ba,Sr and Ca) novel red-emitting phosphors

Eu³⁺-activated novel red phosphors, MLa₂(MoO₄)₄ (M = Ba, Sr and Ca) were synthesized by the conventional solid state method. The excitation and emission spectra indicate that these phosphors can be effectively excited by UV (395 nm) and blue (466 nm) light, and exhibit a satisfactory red performance at 614 nm. Upon excitation with a 466 nm light, our synthesized phosphors have stronger emission intensity than the sulfide red phosphors used in white LEDs. Due to high emission intensity and a good excitation profile, the Eu³⁺-doped CaLa₂(MoO₄)₄ phosphor may be a promising candidate in solid-state lighting applications.     

The copper influence on the PL spectra of CdTe thin film as a component of the CdS/CdTe heterojunction

The influence of annealing in the presence of CdCl₂ and a thin copper layer deposited onto CdTe on the photoluminescence spectra of CdTe, as a component of CdS/CdTe heterojunction, has been studied for two excitation wavelengths: 0.337 μm and 0.6328 μm. The behavior of the PL was studied as a function of the measurement temperature and excitation intensity. At 0.6328 μm excitation, the interface PL consists of a known 1.43X band, and the chloride annealing enhances radiative transitions at 1.536 eV. The intensity of the 1.536 eV transitions increases when Cu is present. The PL of as-deposited CdTe films prepared in the presence of oxygen has the 1.45X band attenuated when excited with 0.337 μm excitation wavelength.     

The preparation,characterization and optical properties of Cd2V2O7 and CdCO3 compounds

Cadmium vanadium oxides (Cd₂V₂O₇) and Cadmium carbonates (CdCO₃) were synthesized via a facile hydrothermal method. X-ray diffraction (XRD), Raman spectroscopy, infrared spectrometer (IR), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) were employed to characterize the structure, morphology and chemical state of the samples, respectively. The photoluminescence (PL) properties of the as-synthesized Cd₂V₂O₇ and CdCO₃ were measured at room temperature using an excitation wavelength of 325 nm. The Cd₂V₂O₇ shows two visible light emission centers located at 589 and 637 nm, which are supposed to be relevant to local defects in Cd₂V₂O₇. The CdCO₃ shows three emission centers located at 408, 530 and 708 nm, which are supposed to be relevant to the electron transition from the conduction band to valence band and defect related energy level.     

Observation of phosphorescence from fluorescent organic material Bebq2 using phosphorescent sensitizer

Absorption, emission and excitation spectra of bis(10-hydroxybenzo [h] quinolinato)-beryllium (Bebq₂) were studied using polystyrene film doped with 5 wt% Bebq₂, N,N-di(naphthalene-1-yl)-N,N-diphenyl-benzidene (NPB) film doped with 60 wt% Bebq₂, and neat film. The monomer and aggregate of Bebq₂ give fluorescence at 492 and 511 nm at 12 K, respectively. A strong T₁ emission with a vibronic structure was observed from Bebq₂ below 70 K by heavily doping with phosphorescent tris(2-phenylpyridine) iridium [Ir(ppy)₃]. The T₁ energy of Bebq₂ was estimated to be 2.26 eV from the onset of the 573 nm 0–0 vibronic emission band. The energy transfer mechanism from Ir(ppy)₃ to the T₁ state of Bebq₂ is discussed.     

Temperature dependence of photocapacitance spectrum of CIGS thin-film solar cell

Deep levels in Cu(In_1 − x,Ga_x)Se₂ (CIGS) are studied by transient photocapacitance (TPC) spectroscopy by varying the Ga concentration, x, from 0.38 to 0.7. The TPC spectra of CIGS thin-film solar cells at 140 K exhibited a defect level with an optical transition energy of about 0.8 eV. The spectrum shape in the sub-bandgap region is independent of the Ga concentration. Therefore, the optical transition energy to the defect level is almost constant with about 0.8 eV from the valence band. The TPC signals for defect level are quenched by increasing temperature. The activation energy of thermal quenching is estimated to be about 0.3 eV. The thermal and optical activation processes are explained using configuration coordinate diagram.     

Luminescence of Bi3+ in the orthorhombic perovskites CaB4+O3 (B4+=Zr,sn): Crossover from localized to D-state emission

The optical properties of Bi³⁺ in the orthorhombic perovskites CaZrO₃ and CaSnO₃ are investigated. The Stokes shift of Bi³⁺ emission in CaZrO₃ is small (∼0.80 eV) with the peak wavelength of the emission band occurring in the ultraviolet. This emission is attributed to the localized ³P_0,1 → ¹S₀ optical transition. In contrast, the Stokes shift of the Bi³⁺ emission in CaSnO₃ is large (>1 eV) with the emission band peaking in the visible. The emission band is also considerably broadened in CaSnO₃. It is claimed that Bi³⁺ luminescence in CaSnO₃ corresponds with the Bi³⁺ (6s²) -Sn⁴⁺ (5s^°) charge transfer emission (D-state emission). The energy of the ¹S₀→³P₁ (A-band) excitation band in both perovskites are very nearly the same. Physical reasoning is advanced for the occurrence and lack thereof of the D-state emission in these perovskites.