Donor-acceptor Pair Luminescence Research Articles

Bridgman-Grown (Cd,Mn)Te and (Cd,Mn)(Te,Se): A Comparison of Suitability for X and Gamma Detectors.

This study explores the suitability of (Cd,Mn)Te and (Cd,Mn)(Te,Se) as room-temperature X-ray and gamma-ray detector materials, grown using the Bridgman method. The investigation compares their crystal structure, mechanical and optical properties, and radiation detection capabilities. Both crystals can yield large-area single crystal samples measuring approximately 30 × 30 mm2. In low-temperature photoluminescence analysis, both materials showed defect states, and annealing in cadmium vapors effectively eliminated donor-acceptor pair luminescence in (Cd,Mn)Te but not in (Cd,Mn)(Te,Se). Moreover, harder (Cd,Mn)(Te,Se) exhibited a higher etch pit density compared to softer (Cd,Mn)Te. X-ray diffraction examination revealed uniform lattice constant distribution in both compounds, with variations at a part per million level. (Cd,Mn)Te crystals demonstrated excellent single crystal properties with narrower omega scan widths, while (Cd,Mn)(Te,Se) exhibited a high contribution of block-like structures with significantly larger misorientation angles. Spectroscopic evaluations revealed better performance of a pixelated (Cd,Mn)Te detector, in comparison to (Cd,Mn)(Te,Se), achieving a mean full width at half maximum of 14% for the 122 keV gamma peak of Co-57. The reduced performance of the (Cd,Mn)(Te,Se) detector may be attributed to deep trap-related luminescence or block-like structures with larger misorientation angles. In conclusion, Bridgman-grown (Cd,Mn)Te emerges as a more promising material for X-ray and gamma-ray detectors when compared to (Cd,Mn)(Te,Se).

Donor-acceptor pair transitions in MgAl2O4 spinel

The luminescence of the well-known spinel-structured functional compound MgAl2O4 was studied at cryogenic temperatures below 10 K in a wide spectral range from near-IR to VUV under synchrotron radiation and electron beam excitation. The most intense luminescence band at ∼5 eV, which origin remained largely unknown up to now, showed characteristic behaviour of the donor-acceptor pair (DAP) centres and was assigned to the so-called antisite defects. The antisite DAPs are formed by position-swapped cations AlMg● and MgAl′, which define the inversion degree of the spinel structure and, to the best of our knowledge, always exceed 10% (>1.5 × 1021 cm−3) in the synthetic solids. Full data set allowed confirming that extremely high concentration of these intrinsic defects is the main reason for the strong 5-eV luminescence, which mechanism includes the electron transfer from MgAl′ to AlMg● (excitation) following by that from VO● to MgAl× (emission). Irradiation with He + ions up to fluences of 1017 cm−2 randomly displaced cations to empty sites of the spinel lattice resulting in more intragap defect levels, which induce a non-radiative energy relaxation channel quenching closely spaced while unaffecting distant DAP luminescence.

High-resolution photoluminescence study on donor-acceptor pair (DAP) recombination in silicon crystals co-doped with phosphorous and gallium

Before lower purity, lower cost silicon (Si) materials, such as compensated Si, can play a role in the terawatt-level (TW) capacity of photovoltaics, a better understanding of the fundamental properties of impurities in compensated Si is essential. In this work, high-resolution photoluminescence (PL) has been used to study the charge carrier radiative recombination through Donor-Acceptor pairs (DAPs) in phosphorus (P) and gallium (Ga) co-doped Si material grown for solar cell applications. The high spectral resolution of our PL system, 0.06 meV, enables us to overcome hitherto prior issues of overlapping spectral lines, giving access to extremely fine structures associated with DA pair (DAP) recombination. Our results confirm the presence of three broad bands and a discrete line structure related to DAP luminescence. The comparison of the discrete line structure due to DAPs recombination in the PL spectra with the theoretically predicted one allows the accurate determination of the Ga ionization energy. Temperature-dependent PL is then used to understand the thermally-induced changes in the DAP luminescence. In particular, we observe that the radiative recombination channel remains active for distant DAPs up to ∼40 K, unlike that for close-range DAPs for which the radiative channel is quenched after only slight increases in the temperature range 10–25 K. Furthermore, the analysis of the temperature dependent changes in the PL intensity of the broad DAP bands up to ∼200 K is used to derive the ionization energy of P donors in compensated Si material. In light of this important information, the significance of using high resolution PL to analyse spectral features in compensated Si is demonstrated.

Inorganic luminescent pigments

Abstract Inorganic luminescent pigments (luminescent materials, luminophores, phosphors) as synthetically generated crystalline compositions absorb energy followed by emission of light with lower energy, respectively, longer wavelengths. The light emission occurs often in the visible spectral range. External energy is necessary to enable luminescent materials to generate light. Luminescent pigments are divided into fluorescent and phosphorescent pigments. This classification goes back to different energy transitions. Emission based on allowed optical transitions, with decay times in the order of µs or faster is defined as fluorescence. Emission with longer decay times is called phosphorescence. The occurrence of fluorescence or phosphorescence as well as the decay time depend on structure and composition of a specific luminophore. There are four luminescence mechanisms discussed for inorganic luminescent materials: center luminescence, charge-transfer luminescence, donor–acceptor pair luminescence, and long-afterglow phosphorescence. The emission of luminescent light can have its origin in different excitation mechanisms such as optical excitation (UV radiation or even visible light), high-voltage or low-voltage electroluminescence and excitation with high energy particles (X-rays, γ-rays). Inorganic luminescent pigments are used mainly in fluorescent lamps, cathode-ray tubes, projection television tubes, plasma display panels, light-emitting diodes (LEDs) and for X-ray and γ-ray detection. The pigment particles are dispersed for the applications in specific binder systems. They are applied in form of thin layers and by means of luminophore/solvent suspensions, containing adhesive agents, on a substrate.

ZnO and ZnO:Ga Ceramics for Advanced Scintillators

The undoped ZnO reveals narrow luminescence bands located close to fundamental absorption edge, known as near band luminescence (NBL) and defects related wide luminescence band within visible range of spectrum. NBL decay is in sub-nanosecond range and it is promising for fast scintillator development. However, the defects luminescence decay is in microsecond range and it is disturbing for fast scintillators. Dopants strongly change the luminescence properties, mainly the intensity and decay time and that is the cause for intense study of doped ZnO luminescence properties. Thus the study of luminescent properties of undoped ZnO and doped ZnO:Ga ceramics was carried out. The dependence of the radioluminescence intensity on temperature and spectrum of near band edge luminescence were examined. NBL spectra comparison of ZnO and ZnO:Ga ceramics with ZnO:Ga single crystal allowed drawn out that at 300 K the donor-acceptor pair luminescence is dominant. It was suggested that the reabsorption within band edge spectral region could significantly affected the near band luminescence intensity and spectral position at 300 K. The significant impact of gallium on the ZnO luminescence is observed. The decay kinetics of luminescence were studied in picosecond range and the two-stage luminescence decay was found for undoped ZnO. The fastest decay stage time is determined to be within 37 – 57 ps. One stage decay kinetics of NBL was determined for ZnO:Ga ceramic and decay time of 17 ps was estimated.

Emission dynamics of hybrid plasmonic gold/organic GaN nanorods

We studied the emission of bare and aluminum quinoline (Alq3)/gold coated wurtzite GaN nanorods by temperature- and intensity-dependent time-integrated and time-resolved photoluminescence (PL). The GaN nanorods of ∼1.5 μm length and ∼250 nm diameter were grown by plasma-assisted molecular beam epitaxy. Gold/Alq3 coated GaN nanorods were synthesized by organic molecular beam deposition. The near band-edge and donor-acceptor pair luminescence was investigated in bare GaN nanorods and compared with multilevel model calculations providing the dynamical parameters for electron–hole pairs, excitons, impurity bound excitons, donors and acceptors. Subsequently, the influence of a 10 nm gold coating without and with an Alq3 spacer layer was studied and the experimental results were analyzed with the multilevel model. Without a spacer layer, a significant PL quenching and lifetime reduction of the near band-edge emission is found. The behavior is attributed to surface band-bending and Förster energy transfer from excitons to surface plasmons in the gold layer. Inserting a 5 nm Alq3 spacer layer reduces the PL quenching and lifetime reduction which is consistent with a reduced band-bending and Förster energy transfer. Increasing the spacer layer to 30 nm results in lifetimes which are similar to uncoated structures, showing a significantly decreased influence of the gold coating on the excitonic dynamics.

Shallow acceptor state in ZnO realized by ion irradiation and annealing route

Activation of shallow acceptor state has been observed in ion irradiated and subsequently air annealed polycrystalline ZnO material. Low temperature photoluminescence (PL) spectrum of the sample exhibits clear signature of acceptor bound exciton (ABX) emission at 3.360 eV. The other two samples, pristine and ion irradiated (without annealing), however, do not show acceptor related PL emission in the nearby energy region. Electron transition from shallow donor (most probable site is interstitial zinc for undoped ZnO) to such newly formed shallow acceptor state creates new donor-acceptor pair (DAP) luminescence peak ∼ 3.229 eV. ABX and DAP peak energy positions confirm that the acceptor is N related. The acceptor exciton binding energy has been estimated to be 180 ± 15 meV which is in conformity with earlier reports. The activation of shallow acceptors without any source of atomic nitrogen can only be possible through diffusion of molecular nitrogen inside the sample during annealing. The N2 molecules get trapped at bulk defect sites incorporated by ion irradiation and subsequent annealing. X-ray diffraction (XRD) and Raman spectroscopic (RS) investigation have been employed to probe the changing defective nature of the ZnO samples. Irradiation induced increased disorder has been detected (both by XRD and RS) which is partially removed/modified by annealing at 300 °C. Simultaneous activation of molecular nitrogen acceptor in purposefully defective ZnO is the key finding of this work. Results presented here provide a simple but controlled way of producing shallow acceptor state in ZnO. If optimized through suitable choice of ion, its energy and fluence as well as the annealing temperature, this methodology can trigger further scope to fabricate devices using ZnO epitaxial thin films or nanowires.

Photoluminescence Blinking and Reversible Electron Trapping in Copper-Doped CdSe Nanocrystals.

Single-particle photoluminescence blinking is observed in the copper-centered deep-trap luminescence of copper-doped CdSe (Cu(+):CdSe) nanocrystals. Blinking dynamics for Cu(+):CdSe and undoped CdSe nanocrystals are analyzed to identify the effect of Cu(+), which selectively traps photogenerated holes. Analysis of the blinking data reveals that the Cu(+):CdSe and CdSe nanocrystal "off"-state dynamics are statistically identical, but the Cu(+):CdSe nanocrystal "on" state is shorter lived. Additionally, a new and pronounced temperature-dependent delayed luminescence is observed in the Cu(+):CdSe nanocrystals that persists long beyond the radiative lifetime of the luminescent excited state. This delayed luminescence is analogous to the well-known donor-acceptor pair luminescence of bulk copper-doped phosphors and is interpreted as revealing metastable charge-separated excited states formed by reversible electron trapping at the nanocrystal surfaces. A mechanistic link between this delayed luminescence and the luminescence blinking is proposed. Collectively, these data suggest that electron (rather than hole) trapping/detrapping is responsible for photoluminescence intermittency in these nanocrystals.

Influence of substrate activation process on structural and optical properties of ZnS thin films

ZnS thin films were deposited on glass substrates by a chemical bath deposition method using a substrate activation process in which aluminum ions become “contaminants” that act as a nucleation center for active components within the deposition solution. The structure and morphology results demonstrate that the films have a ZnS sphalerite crystal structure with a particle size less than 15 nm, and the films consist of small homogeneous grains. The effects of the substrate activation process on the band gap energies and donor-acceptor pair luminescence process were also investigated. A green emission centered at 502 nm was produced due to donor-acceptor transitions from the aluminum acceptor to the ionized and substitution aluminum centers (Al3+).

Selective area growth of GaN nanorods by using molecular beam epitaxy: Effect of growth temperature and Ga flux

Gallium-nitride (GaN) nanorods (NRs) were selectively grown on patterned Ti/Si(111) substrates by using plasma-assisted molecular beam epitaxy. The effects of the growth temperature and the Ga flux on the optical properties of the GaN NRs were investigated. Both the length and the diameter of the GaN NRs decreased with increasing growth temperature whereas the diameter of the GaN NRs remained constant and the length increased with increasing Ga flux. The photoluminescence spectra of GaN NRs grown under different experimental conditions exhibited emission peaks corresponding to neutral-donor-bound excitons (DOX), donor-acceptor pair (DAP), and yellow luminescence (YL) bands at 3.477, 3.26, and 2.25 eV, respectively. Results demonstrate that the variation in the diameters of the GaN NRs has a greater influence on the defect concentration than the lengths of the NRs.

The role of defects in fluorescent silicon carbide layers grown by sublimation epitaxy

Donor-acceptor co-doped SiC is a promising light converter for novel monolithic all-semiconductor white LEDs due to its broad-band donor-acceptor pair luminescence and potentially high internal quantum efficiency. Besides sufficiently high doping concentrations in an appropriate ratio yielding short radiative lifetimes, long nonradiative lifetimes are crucial for efficient light conversion. The impact of different types of defects is studied by characterizing fluorescent silicon carbide layers with regard to photoluminescence intensity, homogeneity and efficiency taking into account dislocation density and distribution. Different doping concentrations and variations in gas phase composition and pressure are investigated.

CuIn<sub>1-x</sub>Ga<sub>x</sub>Se<sub>2</sub> Thin Films Prepared by Co-Evaporation Technique

The optical properties of Cu-poor CuIn1-xGaxSe2 thin films with different gallium contents grown by co-evaporated technique were studied. Measurements of photoluminescence and photoreflectance were performed on the samples. The photoluminescence and photoreflectance emission peaks observed around 1.1 eV are attributed to donor-acceptor pair luminescence. These donor-acceptor pair emissions are considered to originate from relatively shallow acceptor and donor energy levels. With increasing gallium content, the emission peaks shift towards higher levels of photon energy, and the linewidths of the luminescence spectra for the samples become wider, which we attributes to the greater statistical disorder between indium and gallium. Moreover, the conversion efficiency of the CuIn1-xGaxSe2-based solar cells is obtained. The measured results coincide with the inference given by the photoluminescence spectra.

Donor-acceptor pair luminescence in B and P compensated Si co-doped with Ga

The electrical activity of Ga impurities in a high concentration range in B and P highly compensated Si co-doped with Ga for photovoltaic applications has been investigated through the analysis of donor-acceptor pair luminescence. We have identified the fine structure due to the pair luminescence between P-donors and Ga-acceptors based on a comparison with a theoretical spectrum using their generally accepted ionization energies in low concentration ranges in uncompensated Si. The fine structure showed no dependence on dopant concentrations in the P and Ga concentration ranges from 7 × 1016 to 4 × 1017 cm−3 and from 5 × 1016 to 3 × 1017 cm−3, respectively, which leads us to suggest that both P and Ga impurities act as isolated donors and acceptors without noticeable reduction of ionization energies due to high doping.

Compensation effects in GaN:Mg probed by Raman spectroscopy and photoluminescence measurements

Compensation effects in metal organic chemical vapour deposition grown GaN doped with magnesium are investigated with Raman spectroscopy and photoluminescence measurements. Examining the strain sensitive E2(high) mode, an increasing compressive strain is revealed for samples with Mg-concentrations lower than 7 × 1018 cm−3. For higher Mg-concentrations, this strain is monotonically reduced. This relaxation is accompanied by a sudden decrease in crystal quality. Luminescence measurements reveal a well defined near band edge luminescence with free, donor bound, and acceptor bound excitons as well as a characteristic donor acceptor pair (DAP) luminescence. Following recent results, three acceptor bound excitons and donor acceptor pairs are identified. Along with the change of the strain, a strong modification in the luminescence of the dominating acceptor bound exciton and DAP luminescence is observed. The results from Raman spectroscopy and luminescence measurements are interpreted as fingerprints of compensation effects in GaN:Mg leading to the conclusion that compensation due to defect incorporation triggered by Mg-doping already affects the crystal properties at doping levels of around 7 × 1018 cm−3. Thereby, the generation of nitrogen vacancies is introduced as the driving force for the change of the strain state and the near band edge luminescence.

Step-Flow Growth of Fluorescent 4H-SiC Layers on 4 Degree Off-Axis Substrates

Homoepitaxial layers of fluorescent 4H-SiC were grown on 4 degree off-axis substrates by sublimation epitaxy. Luminescence in the green spectral range was obtained by co-doping with nitrogen and boron utilizing donor-acceptor pair luminescence. This concept opens possibilities to explore green light emitting diodes using a new materials platform.

Study of donor–acceptor pair luminescence in highly doped and compensated Cz silicon

AbstractThe photoluminescence (PL) of highly doped and compensated Czochralski silicon has been investigated. The low‐temperature PL spectra show a donor‐to‐acceptor zero‐phonon broad band and clearly distinguished phonon replica shifting to the blue side with increasing the net doping concentration in silicon crystal. The data are consistent with DAP luminescence involving an acceptor level of about 46 meV above the valence band edge in silicon. The analysis of temperature evolution of the PL spectra indicate that the observed PL spectra are due to a donor–acceptor pair recombination with a donor level located at 46 meV. The redshift of this band with increasing excitation power was also observed. The dependence of the emission peak energy on the excitation power is characteristic of highly compensated material in which potential fluctuations influence the band structure.

Near-band luminescence of CdZnTe detector crystals

The near-band luminescence due to both neutral donor and neutral acceptor bound excitons (D0 Ex), (A0Ex) and its phonon replicas as well as luminescence of donor-acceptor pair (DAP) and deep energy level due to undefined defect state (A band) were studied in CZT detector crystals. The near-band luminescence correlation with detector characteristics was analyzed and the results could be applied for nondestructive detector material selection. It is obtained that some parameters such as a presence and intensity of A and DAP luminescence bands, the decay kinetics in A0Ex-1LO and DAP luminescence bands, are most important characteristics for detector material characterization.

Photoluminescence characteristics of as-synthesized and annealed ZnS:Cu,Al nanocrystals

As-synthesized ZnS:Cu,Al nanocrystals with average size of 2–3 nm show abroad emission band peaking at 445 nm (blue) and a shoulder at around 540 nm (green). Annealing the nanocrystals in nitrogen gas results in a reduction in the intensity of the blue emission while enhancing the intensity of the green emission band. The maximum of the green emission is first redshifted to around 590 nm when the annealing temperature is increased to 400 °C, and later blueshifted to 564 and 500 nm for the samples annealed at 500 °C and 600 °C for 1 h, respectively. The lower phase-transition temperature (from zinc blende to wurtzite) and the donor–acceptor pair luminescence process in nanocrystals are discussed.

Time-Resolved Microphotoluminescence Study of Cu(In,Ga)Se2

The carrier recombination processes in Cu(In1-x,Gax)Se2 (CIGS) thin films were investigated by time-resolved microscopic-photoluminescence (µ-PL) measurement at room temperature. For films with x = 0.45, the spatial distribution of the donor–acceptor pair luminescence is much larger than the grain size. The PL decay lifetime is directly correlated with the µ-PL intensity, but the spectral shape is identical regardless of the sample position. These results suggest that the nonuniform distribution of nonradiative recombination centers mainly affects the carrier recombination in CIGS thin films. At relatively high Ga concentrations (x ≥0.7), the spatial inhomogeneity in µ-PL intensity is enhanced and decay accelerated, suggesting an increase in the density of nonradiative recombination centers. Thus, suppression of nonradiative recombination is critical to enhancing the performance of CIGS-based solar cells.

Donor-Acceptor Pair Luminescence of P-Al and N-Al Pairs in 3C-SiC and the Ionization Energy of the P Donor

The analysis of the donor-acceptor pair luminescence of P-Al and N-Al pairs obtained recently for the cubic 3C polytype of SiC is viewed in some detail. A detailed consideration is given to the fitting procedure applied to the P-Al and N-Al spectra. Fit with theoretical models of spectra of type I and type II are applied to both N-Al and P-Al experimental spectra, and it is demonstrated that only contribution from P on Si site is observable in the presented samples. The accuracy of the obtained phosphorus ionization energy of 48.1 meV is also discussed.