near-UV Light-emitting Diodes Research Articles

Mechanoluminescence and photoluminescence properties of Eu3+ -activated SrGa2 O4 phosphors.

Red-emitting Eu3+ activated SrGa2 O4 phosphors were synthesized using a conventional solid-state reaction method. The structural, optical, and luminescence properties were systematically investigated. The synthesized phosphors are single phase with a monoclinic structure. There are no significant changes in the phase and the crystal structure of the host matrix after incorporating Eu3+ ions. The undoped and Eu3+ doped SrGa2 O4 phosphors exhibited good mechanoluminescence (ML) emission without any irradiation with ultraviolet (UV) or gamma rays. Eu3+ -activated SrGa2 O4 phosphors have prominent red emission attributed to 5 D0 → 7 F2 forced electric dipole transition excited at 395 nm. The colour coordinates and purity of the SrGa2 O4 : 0.08 Eu3+ phosphor were calculated to be (0.6102, 0.3810) and 97.6%, respectively. The quantum efficiency is 12.68%, and was better than that of commercially available red phosphors. The ML and photoluminescence studies revealed that the synthesized phosphors can act as potential candidates for stress sensors, UV or near-UV light-emitting diodes (NUV LEDs) and components of phosphor-converted white light-emitting diode (pc-WLED) applications.

Multi-color luminescence of Sm3+ -doped Na2 YMg2 V3 O12 phosphor potentially applicable in white-LEDs.

A novel multi-color emitting Na2 YMg2 V3 O12 :Sm3+ phosphor was synthesized using a solid-state reaction, and its crystal structure, luminescence properties, and thermal stability were studied. Charge transfer within the (VO4 )3- groups in the Na2 YMg2 V3 O12 host led to a broad emission band between 400 and 700 nm, with a maximum at 530 nm. The Na2 Y1-x Mg2 V3 O12 :xSm3+ phosphors exhibited a multi-color emission band under 365 nm near-ultraviolet (near-UV) light, consisting of the green emission of the (VO4 )3- groups and sharp emission peaks at 570 nm (yellow), 618 nm (orange), 657 nm (red), and 714 nm (deep red) of Sm3+ ions. The optimal doping concentration of Sm3+ ions was found to be 0.05 mol%, and the dipole-dipole (d-d) interaction was primarily responsible for the concentration quenching phenomenon. Using the acquired Na2 YMg2 V3 O12 :Sm3+ phosphors, commercial BaMgAl10 O17 :Eu2+ blue phosphor, and a near-UV light-emitting diode (LED) chip, a white-LED lamp was designed and packaged. It produced bright neutral white light, manifesting a CIE coordinate of (0.314, 0.373), a color rendering index (CRI) of 84.9, and a correlated color temperature (CCT) of 6377 K. These findings indicate the potential of Na2 YMg2 V3 O12 :Sm3+ phosphor to be used as a multi-color component for solid-state illumination.

Dazzling Red-Emitting Europium(III) Ion-Doped Ca2LaHf2Al3O12 Garnet-Type Phosphor Materials with Potential Application in Solid-State White Lighting.

Bright red-emitting phosphors with high color purity and high photoluminescence quantum yield (PLQY) are highly demanded for the fabrication of high-performance warm-white light-emitting diodes (LEDs). Herein, we demonstrated a novel efficient Eu3+-activated Ca2LaHf2Al3O12 garnet phosphor with excellent luminescence properties for near-ultraviolet (near-UV) excited warm-white LEDs. The Ca2LaHf2Al3O12:Eu3+ phosphors exhibited an intense excitation spectrum in the near-UV region with a maximum around 394 nm, and they produced dazzling red luminescence peaking at 592, 614, 659, and 711 nm due to the 5D0 → 7FJ (J = 1-4) transitions of Eu3+ ions when the excitation wavelength was set at 394 nm. Luminescent properties have been studied as a function of Eu3+ doping concentration, and the highest emission intensity was achieved at 50 mol % Eu3+, while the dipole-dipole interaction brought the concentration quenching effect. The Ca2LaHf2Al3O12:50%Eu3+ sample exhibited CIE chromaticity coordinates of (0.6419, 0.3575) with a color purity of 92.7%, and its PLQY was measured to be 64%. The thermal stability and activation energy of Ca2LaHf2Al3O12:50%Eu3+ phosphors were also discussed and analyzed. Finally, we made a near-UV chip-based white LED device in which the Ca2LaHf2Al3O12:50%Eu3+ phosphor was utilized as a red ingredient. A bright warm-white light emission was realized from this LED device under 80 mA driving current, accompanied by a high color rendering index (CRI) of 88.3, a low correlation color temperature of 3853 K, and good CIE chromaticity coordinates of (0.3909, 0.3934). These results revealed that these red-emitting Ca2LaHf2Al3O12:Eu3+ phosphors have promising application prospect in near-UV-excited warm-white LEDs with high a CRI.

Sensitivity of indium molar fraction in InGaN quantum wells for near-UV light-emitting diodes

InGaN-based quantum wells (QWs) have higher threading dislocation density (TDD) in InGaN Light-emitting diode (LED). Despite of higher TDD, variation of Indium (In) molar fraction in the QW generate localized excitons with higher Indium composition, thus preventing bound carriers from non-radiative recombination. In this work, the sensitivity of the Indium molar fraction in InGaN QWs is explored for near-ultraviolet (UV) LEDs. The theoretically calculated results show that as the Indium composition increases in InGaN QWs, the radiative recombination increases along with an increase in carrier injection efficiency. The reduced non-radiative recombination for higher Indium composition leads to the enhanced spontaneous emission rate and internal quantum efficiency (IQE). For lowered Indium composition, the peak emission wavelength of the InGaN LEDs shift toward the shorter wavelength and the performances degrade drastically. Hence for shorter UV LEDs, the AlGaN-based device structure should be a suitable choice.

Near-UV light emitting diode with on-chip photocatalysts for purification applications.

A new design for light-emitting diodes (LEDs) with on-chip photocatalysts is presented for purification applications. An array of disk-shaped TiO2, with a diameter of several hundred nanometers, combined with SiO2 pedestals was fabricated directly on the surface of an InGaN-based near-ultraviolet (UV) LED using a dry etching process. The high refractive-index contrast at the boundary and the circular shape can effectively confine the near-UV light generated from the LED through multiple internal reflections inside the TiO2 nanodisks. Such a feature results in the enhancement of light absorption by the photocatalytic TiO2. The degradation of the organic dye malachite green was monitored as a model photocatalytic reaction. The proposed structure of LEDs with TiO2/SiO2 nanodisk/pedestal array exhibited a photocatalytic activity that was three times higher than the activity of LEDs with a TiO2 planar layer. The integration of photocatalytic materials with near-UV LEDs in a single system is promising for various purification applications, such as sterilization and disinfection.

Methyl Benzoylformate Derivative Norrish Type I Photoinitiators for Deep-Layer Photocuring under Near-UV or Visible LED

We designed and prepared a series of methyl benzoylformate (MBF) derivatives Norrish type I photoinitiators (MBFs) for light-emitting diode (LED)-induced photopolymerization through computer simula...

Cyan-emitting Ba0.45Ca2.5La6(SiO4)6: 0.05 Eu2+ and Ba1.45Ca1.5La6(SiO4)6:0.05 Eu2+ solid-solution phosphors for white light-emitting diodes

Two cyan-emitting phosphors with different bandwidths were successfully synthesized through the high-temperature solid-state method in a reducing atmosphere. The crystal structures, morphologies, and luminescence properties of the as-prepared phosphors were investigated. The Rietveld refinements of the powder X-ray diffraction (XRD) data demonstrated the single phase of the samples, and two crystallographic sites of La3+ were observed in the crystal structure. Under the excitation of UV light, both Ba0.45Ca2.5La6(SiO4)6: 0.05 Eu2+ and Ba1.45Ca1.5La6(SiO4)6: 0.05 Eu2+ phosphors emitted cyan light due to the 4f65 d1→4f7 transitions of the Eu2+ ion. The emission spectra could be well fitted by two component Gaussian peaks corresponding to two different coordination environments of the Eu2+ ions. The temperature-dependent photoluminescence spectra show a large difference on the thermal stability between the two phosphors. The two phosphors exhibit effective absorption of near-UV light and their internal quantum efficiencies (IQEs) were calculated as 31.5% and 42.4% under 295 nm UV-light excitation. The experimental results indicate that the novel cyan phosphors might have potential applications in white light-emitting diodes (LEDs) based on the near-UV LED chip.

Improved performance of InGaN/GaN Near-UV light-emitting diodes with staircase hole injector

We report the enhanced performance of near-ultraviolet (NUV) InGaN/GaN multiple quantum-well (MQW) light-emitting diodes (LEDs) with a staircase hole injector (SHI). Simulation results indicate that the internal electrostatic field in the QW of the LED-SHI is decreased owing to the reduced sheet charge density at the interface between QW and quantum barrier (QB) caused by the smaller In content difference. Additionally, the SHI structure in the QBs suppresses the ballistic or quasi-ballistic hole transport, thus enhancing efficient hole injection into the QWs. The radiative output power of an LED-SHI is increased by 25.3% at 300 mA over that of conventional LEDs with GaN QBs. The droop of internal quantum efficiency (IQE) an LED-SHI at 300 A·cm−1 is 6.1%, while the LED with GaN QBs has an IQE droop of 17.7%. The reduced IQE droop and increased radiative output power in the LED-SHI is attributed to the reduced hole overflow, increased hole injection into the MQW and the decreased electrostatic field in the MQWs. The results show that the SHI structure in the LED is promising for improved performance in high-power GaN-based NUV LEDs.

Eu3+-activated Ln2TeO6 (Ln = La, Y) as a novel red-emitting phosphor for warm white LEDs

Novel red-emitting phosphor Ln2TeO6:Eu3+ (Ln = La, Y) was synthesized through a high temperature solid-state reaction method. The material was characterized by X-ray diffraction patterns, Raman spectra, diffuse reflection spectra, photoluminescence excitation and emission spectra, the Commission International de L’Eclairage (CIE) chromaticity coordinates, luminescence decay curves, and temperature-dependent emission spectra. Ln2TeO6:Eu3+ (Ln = La, Y) emitted red light under the excitation of the near-UV and blue light and the concentration quenching mechanism was determined. Combined those phosphors with near-UV chips, the as-fabricated light emitting diode (LED) lamp gave bright red light under a forward bias current. These results demonstrated that Ln2TeO6:Eu3+ (Ln = La, Y) have promising application in phosphor-converted near-UV LED.

Ultra-high color rendering warm-white light-emitting diodes based on an efficient green-emitting garnet phosphor for solid-state lighting

High light-quality and low color temperature are two crucial factors for a comfortable healthy illumination. Phosphor-converted white light-emitting diodes (LEDs) could be readily realized by combining near-UV (380–420 nm) LED chips with tri-color phosphors, and thus near-UV-excitable inorganic phosphors with efficient visible luminescence are highly demanded for fabricating high-performance near-UV-pumped white LEDs. Herein, we demonstrated a novel highly efficient green-emitting phosphor based on Ce3+/Tb3+ ions co-activated Ca2GdHf2Al3O12 (abbreviated as: CGHAO) garnet compound, which enabled the realization of ultra-high color rendering warm-white LEDs. Notably, the CGHAO:Ce3+,Tb3+ phosphors could be efficiently excited by near-UV light around 408 nm and exhibited intense green emissions around 543 nm with high internal quantum efficiency of 82.7% and external quantum efficiency of 60.6%. The energy transfer from Ce3+ to Tb3+ ions was studied in detail, and the composition of CGHAO:Ce3+,Tb3+ phosphors was optimized. Utilizing the optimal CGHAO:0.04Ce3+,0.4Tb3+ green phosphor as color converter, a prototype near-UV-pumped white LED device was fabricated, and upon 120 mA driving current it demonstrated bright warm-white light with excellent CIE chromaticity coordinates of (0.391, 0.360), low correlated color temperature of 3575 K, ultra-high color rendering index (Ra = 94.4, R12 = 89.0, and R9 = 80.6) and good luminous efficacy of 27.40 lm·W−1. This work offers a new strategy for designing efficient LED phosphors for high-color-quality solid-state lighting.

Growth of high-quality near-ultraviolet light-emitting diodes used InGaN/GaN multiple quantum wells

High-quality near-ultraviolet (UV) light-emitting diodes (LEDs) used InGaN/GaN multiple quantum wells (MQWs) have been grown on ScMgAlO4 substrates by plasma enhanced metalorganic chemical vapor deposition (PEMOCVD). The structural properties and optoelectronic properties of InGaN/GaN MQWs are characterized carefully. The full-width at half-maximums (FWHMs) for GaN(0002) and GaN(10–12) X-ray rocking curves are 180 and 190 arcsec, respectively, indicating high crystalline quality of GaN epitaxial films. The as-grown InGaN/GaN MQWs with sharp and abrupt hetero-interfaces have been also obtained and confirmed by high-resolution X-ray diffraction and high-resolution transmission electron microscopy measurements. Meanwhile, there is a photoluminescence peak at 385 nm with an FWHM of 23.2 nm at 300 K and the internal quantum efficiency (IQE) for these InGaN/GaN MQWs is measured to be as high as 79.8%, revealing the high optoelectronic properties. This work sheds light on the preparation of high-performance near-UV LEDs for the application of UV curing, lighting, etc.

High-efficiency near-UV light-emitting diodes on Si substrates with InGaN/GaN/AlGaN/GaN multiple quantum wells

High quantum efficiency LEDs with InGaN/GaN/AlGaN/GaN MQWs have been demonstrated. The proposed GaN interlayer barrier can not only increase the concentration and the spatial overlap of carriers, but also improve the quality of the MQWs.

Design of Iodonium Salts for UV or Near-UV LEDs for Photoacid Generator and Polymerization Purposes.

Iodonium salts are well established photoacid generators, cationic photoinitiators, as well as additives commonly used in photoredox catalytic cycles. However, as a strong limitation, iodonium salts are characterized by low light absorption properties for λ > 300 nm so that these latter cannot be activated with cheap, safe, and eco-friendly near UV or even visible light emitting diodes (LEDs). To overcome this drawback, the covalent linkage of an iodonium salt to a chromophore absorbing at longer wavelength is actively researched. With aim at red-shifting the absorption spectrum of the iodonium salt, the synthesis of new compounds combining within a unique chemical structure both the chromophore (here the naphthalimide scaffold) and the iodonium salt is presented. By mean of this strategy, a polymerization could be initiated at 365 nm with the modified iodonium salts whereas no polymerization could be induced with the benchmark iodonium salt i.e., Speedcure 938 at this specific wavelength. To examine the effect of the counter-anion on the photoinitiating ability of these different salts, five different counter-anions were used. Comparison between the different anions revealed the bis(trifluoromethane)sulfonimide salt to exhibit the best photoinitiating ability in both the free radical polymerization of acrylates and the cationic polymerization of epoxides. To support the experimental results, molecular orbital calculations have been carried out. By theoretical calculations, the initiating species resulting from the photocleavage of the iodonium salts could be determined. The cleavage selectivity and the photochemical reactivity of the new iodoniums are also discussed.

Degradation mechanisms of bias stress on nitride-based near-ultraviolet light-emitting diodes in salt water vapor ambient

Degradation mechanisms of nitride-based near-ultraviolet (near-UV) light-emitting diodes (LEDs) were systematically analyzed by applying forward- and reverse-bias stresses to them in a salt water vapor ambient. The surface temperature of the forward-bias stress sample was higher than that of the reverse-bias stress sample. The high temperature of the forward-bias stress sample accelerated the chemical reaction of the device structure with salt water vapors and led to faster degradation. Composition analyses of the sample surface and cross-section were conducted to investigate the failure mechanism. The analyses results indicated that the erosion of the indium–tin–oxide layer enhanced the diffusion of the conducting metal into the LED crystal. The proposed method can effectively characterize the quality of near-UV LEDs in a short duration.

Effects of InAlN underlayer on deep traps detected in near-UV InGaN/GaN single quantum well light-emitting diodes

Two types of near-UV light-emitting diodes (LEDs) with an InGaN/GaN single quantum well (QW) differing only in the presence or absence of an underlayer (UL) consisting of an InAlN/GaN superlattice (SL) were examined. The InAlN-based ULs were previously shown to dramatically improve internal quantum efficiency of near-UV LEDs, via a decrease in the density of deep traps responsible for nonradiative recombination in the QW region. The main differences between samples with and without UL were (a) a higher compensation of Mg acceptors in the p-GaN:Mg contact layer of the sample without UL, which correlates with the presence of traps with an activation energy of 0.06 eV in the QW region, (b) the presence of deep electron traps with levels 0.6 eV below the conduction band edge (Ec) (ET1) and at Ec 0.77 eV (ET2) in the n-GaN spacer underneath the QW, and the presence of hole traps (HT1) in the QW, 0.73 eV above the valence band edge in the sample without UL (no traps could be detected in the sample with UL), and (c) a high density of deep traps with optical ionization energy close to 1.5 eV for the LEDs without UL. Irradiation with 5 MeV electrons led to a strong decrease in the electroluminescence (EL) intensity in the LEDs without UL, while for the samples with UL, such irradiation had little effect on the EL signal at high driving current, although the level of driving currents necessary to have a measurable EL signal increased by about an order of magnitude. This is despite the 5 times higher starting EL signal of the sample with UL. Irradiation also led to the appearance in the LEDs with UL of the ET1 and HT1 deep traps, but with concentration much lower than without the UL, and to a considerable increase in the Mg compensation ratio.

Fast UV-Curing Encapsulation for GaN-Based Light-Emitting Diodes

Due to the high refractive index of nitrides, encapsulation is necessary to improve the light extraction efficiency for GaN-based light-emitting diodes (LEDs). Traditional thermal-curing encapsulant needs to be heated for several minutes to form a dome-shaped lens, which is time-consuming. In this paper, we have developed a novel kind of silicon-based ultraviolet (UV)-curing encapsulant, for which only 20 s of near-UV (NUV) light radiation at room temperature is needed. The composition of the encapsulants is optimized to enhance light extraction ability. For 392-nm NUV LEDs packaged by this UV-curing encapsulant, the light output power is enhanced by 10.0%. Moreover, the LEDs packaged by UV-curing and thermal-curing encapsulant presented similar stability and reliability after 480 h of the aging test under a high driving current of 200 mA. This paper demonstrates the potential of silicon-based UV-curing encapsulants for the package of NUV, blue and white LEDs, which is time- and cost-effective for the LED industry.

Eu3+ -tetrakis β-diketonate complexes for solid-state lighting application.

Eu3+ -β-diketonate complexes are used, for example, in solid-state lighting (SSL) or light-converting molecular devices. However, their low emission quantum efficiency due to water molecules coordinated to Eu3+ and low photostability are still problems to be addressed. To overcome such challenges, we synthesized Eu3+ tetrakis complexes based on [Q][Eu(tfaa)4 ] and [Q][Eu(dbm)4 ] (Q1=C26 H56 N+ , Q2=C19 H42 N+ , and Q3=C17 H38 N+ ), replacing the water molecules in the tris stoichiometry. The tetrakis β-diketonates showed desirable thermal stability for SSL and, under excitation at 390nm, they displayed the characteristic Eu3+ emission in the red spectral region. The quantum efficiencies of the dbm complexes achieved values as high as 51%, while the tfaa complexes exhibited lower quantum efficiencies (28-33%), but which were superior to those reported for the tris complexes. The structures were evaluated using the Sparkle/PM7 model and comparing the theoretical and the experimental Judd-Ofelt parameters. [Q1][Eu(dbm)4 ] was used to coat a near-UV light-emitting diode (LED), producing a red-emitting LED prototype that featured the characteristic emission spectrum of [Q1][Eu(dbm)4 ]. The emission intensity of this prototype decreased only 7% after 30h, confirming its high photostability, which is a notable result considering Eu3+ complexes, making it a potential candidate for SSL.

395 nm GaN-based near-ultraviolet light-emitting diodes on Si substrates with a high wall-plug efficiency of 52.0%@350 mA.

The high-performance 395 nm GaN-based near-ultraviolet (UV) light emitting diodes (LEDs) on Si substrates have been obtained by designing an AlN buffer layer to decrease the dislocations density of the GaN layer. By adopting a multi-layer structure with a high- and low-V/III ratio alternation, a high-quality AlN buffer layer has been obtained with a small full-width at half-maximum (FWHM) for AlN(0002) X-ray rocking curve (XRC) of 648 arcsec and a small root-mean-square roughness of 0.11 nm. By applying the optimized AlN buffer layer, the high-quality GaN layer with GaN(0002) and GaN(10-12) XRC FWHM of 260 and 270 arcsec have been obtained, and the high-performance GaN-based near-UV LED wafers and chips have been fabricated accordingly. The as-fabricated near-UV LED chips exhibit a light output power of 550 mW with a forward voltage of 3.02 V at 350 mA, corresponding to a wall-plug efficiency of 52.0%. These chips with outstanding performance are of paramount importance in the application of curing, sterilization, efficient white lighting, etc.

Tunable emission with efficient energy transfer in Na2SrSi2O6:Ce3+, Tb3+ phosphor for near-UV LED

Two series of Na2SrSi2O6:Ce3+ and Na2SrSi2O6:Ce3+, Tb3+ phosphors were synthesized via high-temperature solid-state reaction. The obtained Na2SrSi2O6:Ce3+ phosphors exhibit an intense excitation peak at 284 and 360 nm, which was suited to the dominant emission band of a NUV light-emitting-diode (LED) chip. In the Ce3+ single doped system, the critical quench concentration of the phosphor was approximately 4 mol% and a dipole-dipole interaction was verified for the concentration quench mechanism. In addition, Tb3+ ions were introduced as a sensitizer, and the effects of introducing the Tb3+ ions are investigated by measuring the photoluminescence emission and excitation spectra, the PL decay curves, and the quantum efficiencies. Results confirm the occurrence of non-radiative energy transfer from Ce3+ to Tb3+ with an efficiency of over 60%, indicating that the developed phosphor can be used as a potential white-light-emitting phosphor for near-UV LED.

Mn4+-activated BaLaMgSbO6 double-perovskite phosphor: a novel high-efficiency far-red-emitting luminescent material for indoor plant growth lighting.

In the present work, novel high-efficiency Mn4+-activated BaLaMgSbO6 (BLMS) far-red-emitting phosphors used for plant growth LEDs were successfully synthesized via a solid-state reaction method. X-ray diffraction (XRD), photoluminescence (PL), temperature-dependent PL, CIE color coordinates, and lifetimes as well as internal quantum efficiency (IQE) were used to characterize the phosphor samples. The excitation spectrum of the as-obtained BLMS:Mn4+ phosphors presented two wide bands covering 250–550 nm and the emission spectrum exhibited a far-red emission band in the range of 650–800 nm peaked at 700 nm. Concentration-dependent PL properties of BLMS:Mn4+ phosphors were studied. The optimal doping concentration of Mn4+ ions was 0.6 mol%, and the concentration quenching mechanism was determined to be the nonradiative energy transfer among the nearest-neighbor Mn4+ activators. Impressively, the BLMS:0.6%Mn4+ sample showed an outstanding IQE of 83%. In addition, luminescence thermal quenching characteristics were also analyzed. Furthermore, the PL spectrum of BLMS:0.6%Mn4+ sample was compared with the absorption spectrum of phytochrome PFR. Finally, after combining BLMS:0.6%Mn4+ phosphors with a 365 nm near-UV LED chip, a far-red light-emitting diode (LED) device was successfully achieved to demonstrate its possible applications in plant growth LEDs.