Evidence for exciton binding at Ni impurity sites in ZnSe

A broad charge transfer band is observed in the photoluminescence excitation (PLE) spectrum of the 2.5 μ Ni²⁺ luminescence in ZnSe : Ni. This band lies above the highest energy d-d excitation bands and exhibits a ZPL at 1.8163 eV and LO(#38;0lambda;) phonon replicas at higher energy. In contrast, PLE spectra of Co²⁺ luminescence in ZnSe:Co contain only d-d excitation bands. The charge transfer band in ZnSe:Ni is interpreted as evidence for bound exciton formation at the Ni site. The recombination energy of this exciton is transferred efficiently to the excited d-band states of the Ni ion, leading to characteristic Ni²⁺d-d luminescence.     

The nature of the predominant acceptors in high quality zinc telluride

We report very sharp bound exciton luminescence spectra in high quality melt-grown very lightly compensated ZnTe, p-type with N_A-N_D in the low 10⁺¹⁵ cm^-3. Bound exciton localisation energies at seven shallow neutral acceptors with E_A between ~55 and ~150 meV are very insensitive to E_A. Optical absorption and dye laser luminescence excitation spectroscopy were necessary to obtain a full separation of the transitions due to different acceptors, together with a study of certain ‘two-hole’ luminescence satellites in which the acceptor is left in a series of orbital states after bound exciton decay. Two shallow acceptors are P_Te and As_Te, a third possibly Li_Zn while a fourth, relatively prominent in our best undoped crystals, may be a complex. A deeper, 150 meV acceptor, frequently reported in the ZnTe literature and electrically dominant in most of our undoped crystals has the Zeeman character of a point defect. We present clear evidence from our spectra that this energy does not represent the binding of a single hole at a doubly ionized cation vacancy, a popular attribution since 1963. This acceptor may be covered by another impurity, possibly Cu_Zn. We also report bound phonon effects, lifetime broadening of excited bound exciton states and observe a single unidentified donor with E_D ~18.5 meV. This energy is determined using selective dye laser excitation at the weak neutral donor bound exciton line and from the onset of valence band to ionized donor photo-absorption.     

Study of acceptor states in CdTe by donor-acceptor pair excitation luminescence

Excitation of donor-acceptor pair luminescence has been studied in CdTe doped with lithium or chlorine. The excitation spectrum of the lithium acceptor is determined and fitted with the effective mass theory of Baldereschi and Lipari. Revised values of the valence band parameters are deduced: μ = 0.8, δ = 0.054, Ry = 24 meV. The analysis of the 1.45 eV luminescence band in compensated Cl-doped crystals shows the existence of donor-acceptor pair transitions. Three acceptor centers are identified: E_A = 89, 111 and 119 meV, and the contribution of a deep donor (E_D > 40 meV) is demonstrated. Besides intracentre type excitation transitions of the 1.45 eV band have been observed in non-compensated chlorine-doped crystals. Thus several recombination channels and distinct acceptor states contribute to the composite 1.45 eV luminescence band.     

Electronic excitations and luminescence of SrMgF4 single crystals

The electronic and crystal structures of SrMgF₄ single crystals grown by the Bridgman method have been investigated. The undoped SrMgF₄ single crystals have been studied using low-temperature (T = 10 K) time-resolved fluorescence optical and vacuum ultraviolet spectroscopy under selective excitation by synchrotron radiation (3.7–36.0 eV). Based on the measured reflectivity spectra and calculated spectra of the optical constants, the following parameters of the electronic structure have been determined for the first time: the minimum energy of interband transitions E _g = 12.55 eV, the position of the first exciton peak E _n = 1 = 11.37 eV, the position of the maximum of the “exciton” luminescence excitation band at 10.7 eV, and the position of the fundamental absorption edge at 10.3 eV. It has been found that photoluminescence excitation occurs predominantly in the region of the low-energy fundamental absorption edge of the crystal and that, at energies above E _g , the energy transfer from the matrix to luminescence centers is inefficient. The exciton migration is the main excitation channel of photoluminescence bands at 2.6–3.3 and 3.3–4.2 eV. The direct photoexcitation is characteristic of photoluminescence from defects at 1.8–2.6 and 4.2–5.5 eV.     

Electronic excitations and luminescence in CsLiB6O10 crystals

The paper presents the results of a complex investigation into the dynamics of electronic excitations in the CsLiB₆O₁₀ crystal (CLBO) by low-temperature luminescence VUV spectroscopy with subnanosecond time resolution under photoexcitation by synchrotron radiation. Strong broad-band low-temperature photoluminescence (PL) of the CLBO crystal has been revealed. Data on the PL decay kinetics, time-resolved PL and PL excitation spectra, and reflectance spectra at 9.3 and 295 K are obtained. It is shown that the intrinsic PL of CsLiB₆O₁₀ in the 3.5-eV range is caused by radiative annihilation of self-trapped excitons. The channels of creation and decay of relaxed and unrelaxed excitons in cesium lithium borate are discussed. The band gap of CLBO is estimated as E _g≈8.5 eV. A monotonic increase in the excitation efficiency of intrinsic CLBO luminescence at exciting photon energies above 19 eV is identified as the photon multiplication process.     

Copper,the dominant acceptor in refined,undoped zinc telluride

Comparative measurements have been made of optical absorption and photoluminescence of refined undoped and Cu in-diffused ZnTe single crystals. Strong increases in a bound exciton BE line near 2.375 eV previously identified with the electrically dominant point defect acceptor ‘a’, with binding energy E_A ? 149 meV, suggests that this acceptor is substitutional Cu_Zn. Similarly strong increases in a relatively broad band at slightly higher energy suggests the simultaneous incorporation of shallow donors, possibly interstital Cu_I. These findings indicate that intrinsic defects such as V_Zn neither control the Fermi level in refined ZnTe nor produce shallow acceptors with E_A ? 250 meV, contrary to much previous speculation.     

Optical properties of amorphous CuInSe2

Optical absorption spectra of polycrystalline and amorphous CuInSe₂ thin films were measured at room temperature in the photon energy range from 0.8 to 2.1 eV. In amorphous CuInSe₂ the absorption coefficient follows the relation α(hv) = A(hv?E₀)/hv characteristic of optical transitions between extended states in both the valence and conduction band. The optical gap of E₀ = 1.38 ± 0.01 eV is larger than the fundamental gap energy of E_g = 1.01 ± 0.01 eV in crystalline CuInSe₂. A comparison of the results for CuInSe₂ with those for ZnSe is given.     

New high-energy luminescence bands from Co2+ in ZnSe

Three sharp absorption features in the energy range 2.36–2.55 eV have been detected in the transmission spectrum of Co-diffused ZnSe, and a number of luminescence transitions originating from the lowest of these states at 2.361 eV have been observed. Photoluminescence excitation spectra prove that these are high energy excited states of the Co²⁺_Zn impurity, a conclusion confirmed by comparison of measured and predicted luminescence energies. This represents the first identification of luminescence branching from a higher excited state of a transition metal ion in any semiconductor. The sharp, weakly phonon-coupled transitions involve either intra-impurity excitation or transitions from the impurity to localised states split off from a minimum in the conduction band. The implications of these observations for the mechanism of host-impurity energy transfer and for the nature of the excited state wavefunctions are discussed.     

Low-temperature time-resolved vacuum ultraviolet luminescent spectroscopy of KH2PO4 crystals with defects

Low-temperature photoluminescence (PL) of unactivated KDP crystals under selective synchrotron excitation is for the first time measured with subnanosecond time resolution. Time-resolved PL (2–6 eV) and PL excitation (4–35 eV) spectra, as well as PL kinetics, are measured at 7 K. From the acquired experimental data, luminescent bands related to intrinsic defects of the KDP lattice are identified; in particular, the long-wave band at 2.6 eV is assigned to L defects, and the band at 3.5–3.6 eV is attributed to D defects. An efficient energy transfer over the hydrogen sublattice is shown to take place in KDP at low temperatures. It results in the efficient excitation of L and D center photoluminescence in the fundamental absorption region, at electron transitions to the bottom levels of the conduction band, corresponding to the states of the hydrogen atom. The band gap E _g is evaluated to be 8.0–8.8 eV.     

Self-activated luminescence in zinc-sulfo-selenide crystals

The orange luminescence at 2.15eV of As-grown ZnS_0.52Se_0.48crystals has been studied. The peak energy, halfwidth and Gaussian band shape exhibit a temperature dependence which is similar to that of the self-activated (SA) luminescence of ZnS at 2.66 eVand to that of ZnSe at 2.03 eV, and which can be described satisfactorily by a configurational coordinate model. However, optically detected magnetic resonance experiments at 1.8 K show that the luminescence is due to the recombination of an electron thermally released from a donor state with a hole trapped at an A-center acceptor state. The temperature dependence of the thermoluminescence spectra above 77 K and their spectral shift under additional IR exposure are also consistent with radiative recombination involving distant donor-acceptor pairs.     

Manifestation of outgoing resonance in stokes and anti-stokes spectra of ZnTe and ZnMgTe quantum wires

The spectra of resonant light scattering by ZnTe quantum wires have been measured at excitation energies of 2.18–2.72 eV. The quantum wires have been grown on Si(100) and GaAs(100) substrates by molecular beam epitaxy. The effect of outgoing resonance with the electron transition energy E ₀ on the intensity of phonon lines of the Stokes spectrum and on the intensity ratio of the Stokes and anti-Stokes spectral lines has been studied. The energy E ₀ has been determined in ZnTe and ZnMgTe quantum wires from the edge luminescence spectra.     

Band-edge emission in CuI single crystals

The photoluminescence spectra of CuI single crystals have been studied at T = 4.2 K and at various excitation levels. The emission band of donor-acceptor pairs (DAP) with a maximum at about 4200 Å has been shown to possess a complex structure. Theoretical analyses and exciton spectroscopy data make it possible to calculate the ionization energies for the donors and acceptors participating in the formation of DAP, which are equal to E_D = = 0.045?0.065 eV and E_A = 0.155?0.170 eV, respectively. The fine structure of emission due to the annihilation of excitons bound on acceptor pairs (band maximum 4075 Å) has been detected and calculated. The energy of the longitudinal optical phonon participating in the exciton-phonon interaction (LO ? 18.7 meV) has been determined.     

Emission and excitation spectra of ZnO:Ga and ZnO:Ga,N ceramics

The spectral characteristics of ZnO:Ga and ZnO:Ga,N ceramics prepared by uniaxial hot pressing have been investigated. At room temperature, the edge (exciton) band at 3.12 eV dominates in the luminescence spectra of ZnO:Ga, while a wide luminescence band at 2.37 eV, which is likely to be due to zinc vacancies, is observed in the spectra of ZnO:Ga,N. Upon heating, the edge band maximum shifts to lower energies and the bandwidth increases. The extrapolated position of the edge-band maximum at zero temperature, E _m (0) = 3.367 ± 0.005 eV, is in agreement with the data for thin zinc oxide films. The luminescence excitation spectra in the range from 3 to 6.5 eV are reported and the mechanism of energy transfer to excitons and luminescence centers is considered.     

Influence of the thickness of CdTe and ZnTe layers on cathodoluminescence spectra of strained CdTe/ZnTe superlattices with quantum-dot layers

The influence of the thickness of ZnTe barrier layers on the cathodoluminescence spectra of strained CdTe/ZnTe superlattices containing layers of quantum dots with an average lateral size of approximately 3 nm has been investigated. In samples with thick barrier layers (30, 15 nm), the cathodoluminescence spectra of quantum dots exhibit one band with a maximum at E = 2.03 eV. It has been revealed that, at a barrier layer thickness of ∼3 nm, the luminescence band is split. However, at a ZnTe layer thickness of 1.5 nm, the luminescence spectrum also contains one band. The experimental results have been interpreted with allowance made for the influence of elastic biaxial strains on the energy states of light and heavy holes in the CdTe and ZnTe layers. For the CdTe/ZnTe heterostructure with quantum dots in which the thickness of the deposited CdTe layer is 1.5 monolayers and the thickness of the barrier layer is 100 monolayers, the cathodoluminescence spectrum contains 2LO-phonon replicas. This effect has been explained by the resonance between two-phonon LO states and the difference between the energy states in the electronic spectrum of wetting layer fragments.     

Structural and optical properties of CdS/Cu(In,Ga)Se<Subscript>2</Subscript> heterostructures irradiated by high-energy electrons*

Thin films of Cu(In, Ga)Se₂ (CIGS) with a Ga/(Ga + In) ratio of ~0.27 corresponding to the standard elemental composition for solar-energy transducers were grown on Mo-coated glass substrates by the Cu, In, Ga, and Se co-evaporation technique from different sources. Transmission (T), photoluminescence (PL), and photoluminescence excitation (PLE) spectra at 4.2 K were used to analyze electronic properties in the asgrown and electron-irradiated CIGS films. The band-gap energy (E_g) of the CIGS films measured using both transmission and PLE methods was found to be about 1.28 eV at 4.2 K. Two deep bands in the PL spectra of the irradiated CIGS films, P₁ at ~0.91 eV and P₂ at ~0.77 eV, have been detected. These bands are tentatively associated with copper atoms substituting indium (Cu_In) and indium vacancies V_In, respectively, as the simplest radiation-induced defects.     

ZnSe and copper-doped ZnSe nanocrystals (NCs): Optical absorbance and precise determination of energy band gap beside their exact optical transition type and Urbach energy

The using of a reliable and accurate new method (called in literature as derivation of absorption spectrum fitting (DASF)) for evaluation of the optical band gap (E_g) and also the exact nature of charge carriers optical transitions, is investigated in ZnSe and ZnSe:Cu nanocrystals (NCs) synthesized by rapid microwave irradiation. This method can be performed by using the output of UV–Visible spectroscopy. The obtained E_g values are within the range of 2.985–3.261 eV, depending to the microwave irradiation time and Cu dopant percentage (decreasing trend with increasing of irradiation time and Cu content). The DASF-based obtained results for ZnSe and ZnSe:Cu nanoparticles, showed the more precise values of band gap, with the same trend of previously qualitative reported data on the same samples. Also, the direct gap nature of their optical transitions was justified. To perform the method, there is no any need to the concentration of solutions and merely one need the direct absorption or transmission spectra. In other word, DASF technique was employed on ZnSe NCs to confirm its validity and to avoid non-precise reports on optical band gap which can affect on the device optimizations based on these samples. Moreover, using the values of E_g, refractive index and dielectric constant of each sample were obtained at the absorption edge. Also, the width of the tailing states in the gap (Urbach energy: E_Tail) was estimated and were within the range of 0.049–0.122 eV, which their very small values in compare with E_g imply to the sharp valence and conduction band edges; it means the good crystallinity nature of the produced samples.     

Luminescence and electronic excitations in KBe<Subscript>2</Subscript>BO<Subscript>3</Subscript>F<Subscript>2</Subscript> crystals

This paper reports on a study of the dynamics of electronic excitations in KBe₂BO₃F₂ (KBBF) crystals by low-temperature luminescent vacuum ultraviolet spectroscopy with nanosecond time resolution under photoexcitation by synchrotron radiation. The first data have been obtained on the kinetics of photoluminescence (PL) decay, time-resolved PL spectra, time-resolved PL excitation spectra, and reflection spectra at 7 K; the estimation has been performed for the band gap E _g = 10.6−11.0 eV; the predominantly excitonic mechanism for PL excitation at 3.88 eV has been identified; and defect luminescence bands at 3.03 and 4.30 eV have been revealed. The channels of generation and decay of electronic excitations in KBBF crystals have been discussed.     

Electron spin filtering in the GaAs/AlGaAs interface space charge field

The circularly polarized recombination radiation produced by optically oriented electrons in GaAs and viewed in the direction of and opposite to the pump light propagation was found to have opposite signs of polarization. The excitation was effected by photons of energy E_hv ≈ E _g + Δ through a transparent AlGaAs window. The opposite signs of circular polarization and its complex dependence on the luminescence wavelength are accounted for by the influence of the space charge field created by the depleted layer near the interface.     

Optically detected electron resonance in phosphorus-doped ZnTe

Samples of ZnTe showing near gap edge luminescence predominantly due to exciton recombination at shallow neutral acceptors and donor- acceptor pair recombination have been investigated using optically detected magnetic resonance (ODMR). Emission polarization changes at 2.318 eV were observed due to magnetic resonance of electrons at g_e = + 0.401 ± 0.004. The observations are consistent with the donor trapped electron resonance resulting from microwave induced changes in donor-acceptor pair photoluminescence.     

Luminescence of LaBr3: Ce,Hf crystals under photon excitation in the ultraviolet,vacuum ultraviolet,and X-ray ranges

This study has been carried out using synchrotron radiation, time-resolved luminescence ultraviolet and vacuum ultraviolet spectroscopy, optical absorption spectroscopy, and thermal activation spectroscopy. It has been found that, in scintillation spectrometric crystals LaBr₃: Ce,Hf characterized by a low hygroscopicity, along with Ce³⁺ centers in regular lattice sites, there are Ce³⁺ centers located in the vicinity of the defects of the crystal structure. It has also been found that the studied crystals exhibit photoluminescence (PL) of new point defects responsible for a broad band at wavelengths of 500–600 nm in the PL spectra. The minimum energy of interband transitions in LaBr₃ is estimated as E _g ～ 6.2 eV. The effect of multiplication of electronic excitations has been observed in the range of PL excitation energies higher than 13 eV (more than 2E _g ). Thermal activation studies have revealed channels of electronic excitation energy transfer to Ce³⁺ impurity centers.