Hole Trapping Centers Research Articles

Suppression of the hole trap for high-quality amino-phosphine based InP quantum dots

InP quantum dots (QDs) have emerged as promising nanomaterials in various fields due to their exceptional optical properties. However, its wide emission linewidth limits further application. In this study, we synthesized high-quality InP/ZnSe/ZnS QDs by suppressing hole defects. The unreacted In precursors during nucleation easily enter ZnSe in the subsequent shelling process, forming a hole trapping center that adversely affects the photo-excitons radiative recombination. Our results demonstrate that the presence of In ions in ZnSe shell enhances exciton-phonon coupling, broadens the fluorescence emission spectrum, and weakens exciton binding energy. The optimized InP QDs exhibit a line width of 44 nm and 90% PLQY at 630 nm. Furthermore, our investigation into the interaction between shell hole defects and core exciton function provides valuable insights for designing and preparing another high-performance core-shell heterojunction QDs.

Formation of a combined electron-hole emission state in the LiRbSO4 – Eu phosphor

In the irradiated phosphor 4 LiRbSO Eu , the mechanisms of formation of the induced or combined electron-emitting state at 3.1-2.94 eV were studied using optical and thermal activation spectroscopy methods. It has been shown experimentally that the combined electron-emitting state of the phosphor is formed from the electron states of impurity and intrinsic electron and hole trapping centers of 24Eu SO   and 34 4 SO SO . Electron and hole trapping centers are created by irradiating the phosphor with photons exceeding the width of the forbidden band of the matrix, where free electrons are created in the conduction band and a hole in the valence band. The trapping center is formed by the capture of free electrons by impurities and anionic complexes according to the reaction 3 2 Eu e Eu      ,2 34 4 SO e SO    . In one process with electron centers, holes in the form of 24SO are localized. Thus, impurity and intrinsic 2 4Eu SO   and 34 4 SO SO  electron-hole trapping centers are formed. Similarly, trapping centers are formed as a result of charge transfer from the excited anion of the 24SO complex to the 3Eu  impurities and to the neighboring 2 4 SO anions according to the reaction ( 2 3 O Eu   ) and ( 2 24O SO  ), and localized holes are also formed in one act along with it. Combined electron-emitting states consisting of impurity and intrinsic electron states are excited by photons with energies of ~4.0 eV and ~4.5 eV.

Low temperature recombination luminescence of Mg3Y2Ge3O12:Tb3+

A study was conducted to examine the recombination processes in persistent phosphor Mg3Y2Ge3O12:Tb3+ garnet at low temperatures. Photoluminescence (PL), recombination luminescence (RL), electron paramagnetic resonance (EPR), and EPR detected by PL or RL were measured.In samples with low Tb3+ concentration, a broad PL and RL band around 400–450 nm and characteristic Tb3+ lines were observed. However, in samples with high Tb3+ concentration, only Tb3+ lines were present. Both the broad-band and the line components exhibit long-lasting tunneling luminescence with hyperbolic decay. After 263 nm UV irradiation signals of intrinsic electron (F-type) and hole (V-type) trapping centres were observed in the EPR spectra. Such signals were also observed in RL-detected EPR spectra, indicating that the broad RL band at low Tb3+ concentrations originates from tunneling recombination between these intrinsic traps. At high Tb3+ concentrations, the RL-EPR spectrum was not observed, suggesting that intrinsic electron and Tb-related hole trapping centres probably participate in the tunneling recombination.

Long-lived carriers-promoted photocatalytic deuteration of halides with D2O as the deuterium source over Cu doped quantum dots

Deuterium labeling is a highly valuable yet challenging subject of research in various scientific fields. Conventional deuteration methods often involve harsh reaction conditions and suffer from limited reactivity and selectivity. Herein, we report a visible light–driven C–X (X = halogen) to C–D (D = deuterium) exchange strategy over copper-doped cadmium sulfide quantum dots (Cu-CdS QDs) under mild conditions, eliminating the need for noble metal catalysts and expensive deuterium sources. The conversion of aryl halides into deuterated products using Cu-CdS QDs reaches up to 99%, which is four times higher than that achieved using pristine CdS QDs. The substantial enhancement in the photocatalytic activity of the QDs can be primarily attributed to the generation of long-lived charge carriers (approximately 6 μs) induced by Cu doping. Mechanistic studies reveal that the Cu dopants considerably retard the recombination of photoinduced carriers by creating intermediate energy levels that serve as hole trapping centers in CdS QDs, thereby improving the electron utilization efficiency in energetically demanding photoreduction reactions. Additionally, the introduction of Cu increases the energy offset between the conduction band of CdS QDs and molecular acceptors, facilitating the electron transfer process. Upon visible light irradiation, a series of aryl halides can be efficiently converted into the desired deuterated compounds using D2O as the deuterium source. This work demonstrates that regulating charge carrier dynamics in ultrasmall QD-based photocatalysts is a promising strategy for promoting organic transformations.

Identification of shallow trap centers in InSe single crystals and investigation of their distribution: A thermally stimulated current spectroscopy

Identification of trap centers in semiconductors takes great importance for improving the performance of electronic and optoelectronic devices. In the present study, we employed the thermally stimulated current (TSC) method within a temperature range of 10–280 K to explore trap centers in InSe crystal—a material with promising applications in next-generation devices. Our findings revealed the existence of two distinct hole trap centers within the InSe crystal lattice located at 0.06 and 0.14 eV. Through the leveraging the Tstop method, we offered trap distribution parameters of revealed centers. The results obtained from the experimental methodology employed to investigate the distribution of trap centers indicated that one of the peaks extended between 0.06 and 0.13 eV, while the other spanned from 0.14 to 0.31 eV. Notably, our research uncovers a remarkable variation in trap density, spanning one order of magnitude, for every 10 and 88 meV of energy variation. The results of our research present the characteristics of shallow trap centers in InSe, providing important information for the design and optimization of InSe-based optoelectronic devices.

Trap engineering in bismuth activated NaLu(Gd)GeO4 persistent phosphors by doping Ln3+

Persistent phosphors, as a promising material for information storage and encryption, have garnered considerable attention owing to their rapid access and low-energy consumption. However, the lack of effective trap control in storage phosphors has resulted in limited storage capacity. In this study, we have prepared a series of NaLu(Gd)GeO4:Bi3+,Ln3+ (Ln = Eu, Tb, Dy, Pr, Sm, Er, Nd, Ho, Tm, and Yb) materials exhibiting tunable multimode and multicolor stimuli-responsive luminescence. The enhanced thermo-stimulated luminescence of five times is obtained in NaLuGeO4:Bi3+,Eu3+ relative to NaLuGeO4:Bi3+, where Bi3+ not only serves as the luminescent center but also as the hole trap center, and trace amounts of Eu3+ act as electron traps to form stable electron-hole pair traps together with Bi3+ hole traps. We propose a new method to improve trap density by constructing electron-hole pair traps via utilizing Bi3+ and Ln3+ as both trap makers and luminescence centers. Density functional theory calculations provide detailed information on the band structures of the matrix and electronic properties, which has confirmed the types of traps and then supports persistent luminescence mechanisms. Particularly, our phosphors are used as optical storage medium for multilevel optical data recording in a single physical layer through managing traps via setting the temperature. This study provides valuable insights for the design and fabrication of next-generation optical information storage and encryption materials.

Luminescence and Electron–Hole-Trapping Centers in α-Ca2P2O7−Mn

The mechanisms of formation of induced intrinsic and impurity radiative states, which consist of intrinsic and impurity electron–hole-trapping center states in irradiated Ca2P2O7−Mn and Ca2P2O7 phosphates, were investigated using thermoactivation and vacuum-ultraviolet spectroscopy methods. These centers are excited at photon energies of 4.0 eV and 4.5 eV, which are within the matrix’s transparency region. New radiative-induced states at 3.06 eV and 2.92 eV are demonstrated to be generated upon the excitation of anions by photons with energies of 5.0 and 5.64 eV. This process is due to charge transfer from the ion to the impurities, specifically Mn2+(O2−−Mn2+) and the neighboring ion O 2−−(P2O7)4−. Furthermore, upon the excitation of matrix anions with photon energies exceeding the band gap (8.0–8.25 eV), electron-trapping by impurities such as Mn2+ and (P2O7)4− ions results.

Indirect evidence of Bi3+ valence change and dual role of Bi3+ in trapping electrons and holes for multimode X-ray imaging, anti-counterfeiting, and non-real-time force sensing

Discovering bismuth based smart materials that can respond to thermal, mechanical, and wide range X-ray to infrared photon excitation remains a challenge. Such materials have various uses like in advanced information encryption. In this work, valence state change between Bi2+, Bi3+, and Bi4+, and the dual role of Bi3+ in trapping electrons and holes have been studied in Bi3+ or/and Ln3+ (Ln=Tb or Pr) doped LiScGeO4 family of compounds by vacuum referred binding energy (VRBE) diagram construction, thermoluminescence, and spectroscopy. Electron release from Bi2+ has been evidenced. It can be used to experimentally determine the VRBE in the Bi2+ 2P1/2 ground state and to realize Bi3+ negative quenching luminescence. Particularly, a new force induced charge carrier storage phenomenon has been discovered for non-real-time force recording. Wide range of emission tailorable afterglow, unique Bi3+ ultraviolet-A, white, and infrared afterglow have been demonstrated by using Bi3+ as a hole trapping and recombination center and using energy transfer processes from Bi3+ to Tb3+, Pr3+, Dy3+, or Cr3+. Proof-of-concept advanced anti-counterfeiting, information encryption, and X-ray imaging will be demonstrated. This work not only develops smart storage phosphors, but more importantly unravels the valence change between Bi2+, Bi3+, or Bi4+ and how it can affect the trapping and release of charge carriers with thermal, optical, or mechanical excitation. This work therefore can promote the discovery and development of Bi3+ based smart materials for various applications.

X-ray assisted point defects creation in micron-size Zn, Mo oxide particles at liquid nitrogen temperature

Charge trapping processes induced by the X-ray irradiation in the heavy Mo doped ZnO and MoO3 micropowders synthesized by the hydrothermal growth method were investigated in detail. Electron paramagnetic resonance (EPR) and thermally stimulated luminescence (TSL) were applied in a correlated manner to discover the role of the Mo doping in the charge trapping processes in ZnO. Thermally unstable oxygen- and molybdenum-related charge trapping centers were studied. Molybdenum and oxygen created electron-hole trapping pairs in some cases were observed. Some part of the hole trapping centers seemed to be directly connected with the creation of Mo5+. The correlation between EPR and TSL data was found.

Control of positive and negative photo- and thermal-responses in a single PbI2@CH3NH3PbI3 micro/nanowire-based device for real-time sensing, nonvolatile memory, and logic operation.

CH3NH3PbI3 has shown great potential for photodetectors and photovoltaic devices due to its excellent positive response to visible light. However, its real-time response characteristics hinder its application in optical memory and logic operation; moreover, the presence of excessive PbI2 is a double-edged sword. Herein, we constructed a dual-terminal device using a single CH3NH3PbI3 micro/nanowire with two Ag electrodes, and then in situ introduced PbI2 quantum dots (QDs) as hole trap centres by thermal decomposition at 160 °C. An anomalous negative photoconductivity (NPC) effect for sub-bandgap light below the PbI2 bandgap is obtained. Importantly, an electrically erasable nonvolatile photomemory can be realized. Furthermore, the device also exhibits an abnormal positive thermal resistance (PTR)-related thermomemory effect, and the thermal-induced high-resistance state (HRS) can be erased by a large bias or an illumination of 365 nm super-bandgap UV light. Additionally, logical "OR" gate operations are achieved through a combination of 650 nm sub-bandgap light and a 70 °C temperature-induced HRS, as well as a large bias and 365 nm super-bandgap light-triggered low-resistance state. These effects are attributed to the excitation and injection of holes in QDs and structural defect traps. This multifunctional device, integrating real-time sensing, nonvolatile memory, and logical operation, holds significant potential for novel electronic and optoelectronic applications.

Ultraclean surface restoration and giant photoresponse enhancement of violet phosphorus

Violet phosphorus (VP), a recently developed kind of layered material, features exotic in-plane anisotropy, alluring thickness-dependent bandgap, and better thermal stability than its phosphorus allotropes. Such a broad variety of functionalities indicates VP is a promising candidate for advanced nanophotonics. However, its hydrophilic surface-induced air instability hinders further exploration and extensive device integration for photodetection and beyond. Herein, we report the successful restoration of the clean VP surfaces through nitrogen plasma combined with vacuum thermal annealing. Via manipulation of plasma excitation power, we can also achieve thickness etching and nondestructive p-doping to VP, paving the way for fabrication and engineering of VP photodetectors. As a proof-of-concept, plasma-treated VP photodetectors have been fabricated. Stemming from the plasma treatment-induced p-doping and hole trapping centers, the VP photodetectors exhibit giant photoresponse enhancement, reaching a high responsivity of 1.923 A/W, and is dramatically improved by 1300% compared with that before plasma treatments, which envisions high-sensitivity photodetection for next-generation more-than-Moore optoelectronics.

Intrinsic emissions and formation of electron-hole trapping centres in excited Li2SO4

Vacuum ultraviolet and thermal activation spectroscopies were used to study the nature of intrinsic emission and the mechanisms of the formation of electron and hole trapping centres in irradiated Li2SO4 powders and crystals. The obtained results along with excitation spectra showed that recombination emission at 3.8–4.2 eV and 4.5–5.5 eV occurs when an electron passes from the second and third sub-bands of the valence band formed from the 2p state of oxygen to the conduction band. It has been determined that Li2SO4 electron and hole trapping centres are created when electrons are trapped in the SO42– anionic sites. The holes are localised in the form of SO4 – radicals. The spectral position and intensity of individual emission bands are dependent on the crystallographic arrangement of localised holes.

Experimental and theoretical study on the green persistent luminescence phosphor Ca5Ga6O14:Bi3+

In this study, we developed a type of green persistent luminescence (PersL) material Ca5Ga6O14:Bi3+, which could be excited by UV light ranging from 270 nm to 360 nm with peak at 325 nm and exhibited a broad afterglow band peaking at 515 nm with the duration of about 11 min, which can be ascribed to the electron transitions between the 6s orbital and the 6p orbitals of Bi3+ ion. The thermoluminescence investigation and the First-principle calculation results revealed that the 6s orbital of Bi3+ was about 0.2 eV above the valence band maximum, while the 6p orbitals were 0.6–1.0 eV below the conduction band minimum. Moreover, we found that O vacancies and −2 charged Ga vacancies could form defect levels just above valence band and serve as the hole-trap centers, playing the key role in the process of the afterglow of Ca5Ga6O14:Bi3+. The possible afterglow mechanism was discussed in detail. This work offers an efficient way to construct Bi3+ doped PersL phosphors with desired properties.

Steady-state and dynamic characteristics of deep UV luminescence in rock salt-structured MgxZn1−xO

Temperature-dependent cathodoluminescence spectra were measured for rock salt-structured MgxZn1−xO films with x = 0.95–0.61. The Mg0.95Zn0.05O film exhibited the shortest deep UV peak wavelength of 199 nm (6.24 eV) at 6 K. Relatively high equivalent internal quantum efficiencies of 0.9%–11% were obtained. The Tauc plots, which were obtained from temperature-dependent optical transmittance measurements, exhibited large Stokes-like shifts of 0.7–0.9 eV at 6–300 K. Time-resolved photoluminescence (PL) signals at 7 K exhibited fast and slow decay components. The fast decay component had PL lifetimes of 2.59–3.08 ns, and the slow decay component far exceeded the measurement time range of 12.5 ns. The fast decay constant reflected the transfer lifetime of the photoexcited carriers to certain trapping centers. These centers were tentatively ascribed to Zn-related isoelectronic trapped-hole centers and may be a cause of the large Stokes-like shifts. The signals at 300 K exhibited very short PL lifetimes of 120–180 ps. The PL lifetimes were mainly attributed to the nonradiative recombination lifetime. Simultaneous decreases in the Zn-related isoelectronic trapped-hole centers and the nonradiative recombination centers were found to be necessary to improve the DUV emission properties of RS-MgxZn1−xO films.

Specific Features of Formation of Electron and Hole Trapping Centers in Irradiated CaSO4-Mn and BaSO4-Mn

Spectroscopic and thermoactivation methods were used to study the processes of accumulation of electron and hole trapping centers and energy transfer of electronic excitations to impurities in CaSO4-Mn and BaSO4-Mn. It is shown that electronic trapping centers are created during the excitation of an anionic complex as a result of charge transfer from O2−→SO42− to closely spaced anionic complexes SO42− in CaSO4 and BaSO4. In CaSO4 and BaSO4, energy transfer from the host to impurities occurs at the moment of charge transfer from the excited anionic complex to the combined radiative electronic state at 2.95–3.1 eV. This combined state is formed from electronic trapping centers Mn+-SO4− and SO43−-SO4−. It was found that the emerging combined radiative states at 2.95–3.1 eV of sulfates, which are formed as a result of charge transfer from the excited anionic complexes to the excited state of impurities, Tl+,Cu+,and Mn2+, occupy the same energy levels as the intrinsic electronic trapping center SO43− of the host at 2.95–3.17 eV. Experimental results show that during UV photon irradiation, anionic complexes are excited mainly near impurities in sulfates.

Electron-hole trapping centers in Na2SO4 with a transition metal impurity Mn

The Na 2 SO 4 samples were obtained by slow evaporation method. The mechanisms of the formation of electron and hole trapping centers are investigated by spectroscopic methods. Intrinsic recombination emission of 2.9–3.1 eV and impurity emission of 1.85 eV are excited at 4.0–4.5 eV. Intrinsic SO 3− 4 −SO − 4 and impurity Mn + − SO − 4 trapping centers were revealed. The local levels corresponding between the electron and hole trapping center are 4.0–4.5 eV. The decay of intrinsic and impurity trapping centers was recorded at temperatures of 130–150 K and 280–350 K.

Electron Tunneling Charging upon Sunlight for Near‐Infrared Persistent Luminescence

AbstractFor the conventional persistent luminescence (PersL) charging processes, carriers are photo‐pumped to the conduction band (CB) or high‐energy excited states (HES) under short‐wavelength UV or coherent near‐infrared (NIR) laser excitation. Herein, electron tunneling charging behavior is reported in Cr3+, Sm3+ co‐doped NIR PersL magnetoplumbite SrGa12O19, which allows for efficient charging by incoherent visible light. First, the electrons are efficiently captured by the neighboring GaII‐O2− electron–hole trap centers via a tunneling process, and then these excited electrons are transferred to shallow traps via a persistently energetic optical pump. This work further optimizes the PersL performance via engineering the energy band through partial substitution of In3+ for Ga3+. Consequently, tunneling charging occurring near the neighboring Cr3+‐traps dimers enables Sr(Ga,In)12O19:Cr3+,Sm3+ to display brighter NIR PersL (≈760 nm, peak; ≈100 nm, FWHM) than gallate spinel under sunlight irradiation. This work provides insights into electron tunneling charging under low‐energy excitation for NIR PersL, which may inspire more PersL explorations for practical applications.

Thermal annealing of neutron irradiation generated paramagnetic defects in transparent Al2O3 ceramics

It is fundamentally important to understand, control, and predict the effect of irradiation on the structure and optical properties of functional materials. In this work, the thermal stability of fast-neutron induced point defects has been investigated in polycrystalline transparent alumina ceramics. The results of a combined study of electron paramagnetic resonance (EPR) and photoluminescence spectroscopy are presented in this paper. The EPR signals related to different trapped-hole centers as well as electron-type F+ centers have been observed after neutron irradiation. Rapid decay of the total EPR signal intensity occurs after annealing in 600–750 K temperature range. The selective luminescence bands related to the F- and F2-type centers are detected under irradiated corundum ceramics photoexcitation within relevant defect absorption bands (i.e. intracenter excitation/emission).

Enhancement in photocatalytic H2 evolution utilizing the synergistic effect between dual cocatalysts and heterojunctions

Expediting electrons-holes separation and surface reaction kinetics is deemed to be pivotal factor to determine the photocatalytic performance. Decoration of reductive and oxidative cocatalysts on semiconductors is a resultful approach for motivating electrons-holes separation and surface reaction kinetics. In this work, a ternary 2.4%-(CoSe2@NiS-1)/CdS photocatalyst was developed. Among this compound, reductive cocatalyst CoSe2 not only acted as electron trapping center by extracting photogenerated electrons, but also constructed Schottky junction with CdS to accelerate migration of photogenerated carriers and inhibit the backflow. Meanwhile, oxidative cocatalyst NiS forming p-n type heterojunction with CdS served as hole-trap center to boost transport and consumption of photoinduced holes. Integrating of dual cocatalysts and heterojunctions played synergistic effect in promoting the photocatalytic performance and photo-corrosion stability. 2.4%-(CoSe2@NiS-1)/CdS achieved H2 evolution of 1413.9 μmol and maintained at 85.47% after six cycles. It's expected that this work can provide an insight into designing high active solar energy conversion system.

Low-temperature recombination luminescence of La-doped Ca2SnO4

Low-temperature ultraviolet-excited photoluminescence (PL) and recombination luminescence (RL) properties of La-doped Ca2SnO4 have been investigated by luminescence, electron paramagnetic resonance (EPR) and optically-detected magnetic resonance (ODMR) techniques. Two PL and RL bands at 340 nm and 450 nm have been observed. PL excitation spectra measurements with a synchrotron source showed a significant difference between the 450 nm and the 340 nm PL bands. The 450 nm band has a long-lasting hyperbolic decay, while the 350 nm band shows a fast decay. Assuming an excitonic nature of the 340 nm band, the band gap of the Ca2SnO4:La has been estimated to be approximately 5.5 eV. ODMR measurements suggest that the low-temperature RL band at 450 nm is caused by tunnelling recombination of electron trap and hole trap centres, and the recombination energy is transferred to Sn2+ luminescence centres.