Recent Advances in Cation-Engineered A3BX6 Metal Halide Perovskite for Enhanced Radiative Transition

Light-emitting diodes (LEDs) are currently undergoing rapid development as plant growth light sources in a plant factory with artificial lighting (PFAL). However, little is known about the effects of supplementary light and pulsed LEDs on plant growth, bioactive compound productions, and energy efficiency in lettuce. In this study, we aimed to determine the effects of supplementary white LEDs (study I) and pulsed LEDs (study II) on red leaf lettuce (Lactuca sativa L. ‘Sunmang’). In study I, six LED sources were used to determine the effects of supplementary white LEDs (RGB 7:1:1, 7:1:2, RWB 7:1:2, 7:2:1, 8:1:1, 8:2:0 [based on chip number] on lettuce). Fluorescent lamps were used as the control. In study II, pulsed RWB 7:2:1 LED treatments (30, 10, 1 kHz with a 50 or 75% duty ratio) were applied to lettuce. In study I, the application of red and blue fractions improved plant growth characteristics and the accumulation of antioxidant phenolic compounds, respectively. In addition, the application of green light increased plant growth, including the fresh and dry weights of shoots and roots, as well as leaf area. However, the substitution of green LEDs with white LEDs induced approximately 3.4-times higher light and energy use efficiency. In study II, the growth characteristics and photosynthesis of lettuce were affected by various combinations of duty ratio and frequency. In particular, biomass under a 1 kHz 75% duty ratio of pulsed LEDs was not significantly different from that of the control (continuous LEDs). Moreover, no significant difference in leaf photosynthetic rate was observed between any pulsed LED treatment utilizing a 75% duty ratio versus continuous LEDs. However, some pulsed LED treatments may potentially improve light and energy use efficiency compared to continuous LEDs. These results suggest that the fraction of red, blue, and green wavelengths of LEDs is an important factor for plant growth and the biosynthesis of bioactive compounds in lettuce and that supplementary white LEDs (based on a combination of red and blue LEDs) might be more suitable as a commercial lighting source than green LEDs. In addition, the use of suitable pulses of LEDs might save energy while inducing plant growth similar to that under continuous LEDs. Our findings provide important basic information for designing optimal light sources for use in a PFAL.

ABSTRACTRecently, a renewed research interest has emerged for the development of visible light, down-converting phosphors for application in white light emitting diodes (LEDs). In such devices, a blue GaN LED can act as the primary light source, exciting photoluminescence in a phosphor with subsequent broad-band emission occurring at lower energies. It was recently reported that use of a combinatorial approach to synthesize and screen potential inorganic phosphors for such an application could aid in identifying improved phosphors for blue to yellow down conversion. Using solution chemistry techniques developed by Symyx Technologies, solid state thin-film arrays (libraries) based on the garnet structure (A1-xBx)3(C1-yDy)5O12:Ce3+, where x and y = 0 to 1.0 and A, B = Y, Gd, or Lu; C., D = Al or Ga, were synthesized. X-ray diffraction was used to select library samples of the crystalline garnet phase. Libraries of these various garnets were then characterized, and their spectral properties compared to traditionally prepared bulk powder phosphors of similar composition. Emission and excitation trends show that as larger cations are substituted for Y (A = Y), emission and excitation are red-shifted and as larger cations are substituted for Al (C = Al), emission and excitation are blue-shifted. If smaller cations are substituted for Y and Al, an opposite trend is observed.

ABSTRACTRecently, renewed interest has emerged for the development of visible light, down-converting phosphors for application in white light emitting diodes (LEDs). In such devices, a blue GaN LED can act as a primary light source, serving as an efficient pump to excite photoluminescence in a phosphor with subsequent emission occurring at lower energies. The combination of blue light from the LED chip and emission from the phosphor(s) produces white light. It was recently reported that a combinatorial approach to synthesize and screen potential inorganic phosphors for use in white LEDs could aid in identifying improved phosphors for blue to yellow down conversion. Solid state thin-film arrays (libraries) based on the garnet structure (A1−x,Bx)3−z(C1−y,Dy)5O12:Ce3+z, where A, B = Y, Gd, Lu, La; C., D = Al, Ga; x and y = 0 to 1.0; and z = 0.03, were synthesized, and x-ray diffraction was used to select library samples of the crystalline garnet phase. Libraries of these various garnets were then characterized spectroscopically and their properties compared to traditionally prepared bulk powder phosphors of similar composition. Emission and excitation trends show that as larger cations are substituted for Y (A = Y), emission and excitation are red-shifted and as larger cations are substituted for Al (C = Al), emission and excitation are blue-shifted. If smaller cations are substituted for Y and Al an opposite trend is observed. Temperature dependence photoluminescence measurements and emission/excitation trends are also examined.

Considerations for the use of white light emitting diode (LED) sources to produce illumination for automotive forward lighting is presented. Due to their reliability, small size, lower consumption, and lower heat generation LEDs are a natural choice for automotive lighting systems. Currently, LEDs are being sucessfully employed in most vehicle lighting applications. In these applications the light levels, distributions, and colors needed are achievable by present LED technologies. However, for vehicle white light illumination applications LEDs are now only being considered for low light level applications, such as back-up lamps. This is due to the relatively low lumen output that has been available up to now in white LEDs. With the advent of new higher lumen packages, and with the promise of even higher light output in the near future, the use of white LEDs sources for all vehicle forward lighting applications is beginning to be considered. Through computer modeling and photometric evaluation this paper examines the possibilities of using currently available white LED technology for vehicle headlamps. It is apparent that optimal LED sources for vehicle forward lighting applications will be constructed with hereto undeveloped technology and packaging configurations. However, the intent here in exploring currently available products is to begin the discussion on the design possibilities and significant issues surrounding LEDs in order to aid in the design and development of future LED sources and systems. Considerations such as total light output, physical size, optical control, power consumption, color appearance, and the effects of white LED spectra on glare and peripheral vision are explored. Finally, conclusions of the feasibility of current LED technology being used in these applications and recommendations of technology advancements that may need to occur are made.

Eu3+ doped YVO4 is excellent traditional red phosphor, but shifting its efficient excitation band to a longer wavelength is necessary for application in white light-emitting diodes, and is a big challenge that calls for good solution. Following the observation that cation substitution usually is an effective way to manipulate the band-gap of phosphors, we carried out ab initio calculation for the band-gap of pure and Bi3+ doped LnVO4 (Ln = Y, Lu, and Sc). The results show that the band-gap decreases with the cationic radius from Y3+ to Sc3+, and the doping of Bi3+ further decreases their band-gaps. The experimental results on the Eu3+ doped and Eu3+, Bi3+ co-doped LnVO4 (Ln = Y, Lu, and Sc) phosphors confirm this. In particular, the excitation of Eu3+ and Bi3+ co-doped ScVO4 is shifted to approach 400 nm, which fulfills the excitation requirement of near-ultraviolet-based white light-emitting diodes, and implies that Eu3+ and Bi3+ co-doped ScVO4 should be a promising candidate as red phosphor in white light-emitting diodes.

Ag-Eu3+ co-doped fluoroborate glass phosphors doped with various Eu3+-concentrations were prepared by a melt-quenching technique. The luminescent properties of these glass phosphors were characterized by excitation and emission spectra. Broad excitation and emission bands located, respectively, at 300-450 nm and 390-700 nm originating from silver aggregates were observed. Strong red emissions were detected under 404 nm violet light-emitting diode (LED) excitation for those Ag-Eu3+ co-doped samples. It was found that these red emissions of Eu3+ well compensated the deficiency of the red spectral components in glasses containing Ag aggregates. In addition, it was confirmed that stable white light could be achieved from the combination of a specific Ag-Eu3+ co-doped fluoroborate glass phosphor and LEDs with different output wavelengths. By adjusting the luminescence intensity ratio of the glass phosphor to the 404 nm violet LED, tunable emitting color was realized, and the studied glass phosphors showed excellent emitting color stability toward LED drive currents. Our results demonstrated that this kind of easy fabrication, low-cost, and highly stable Ag-Eu3+ co-doped fluoroborate glass phosphors had potential application in white LED.

Recent years, white light emitting diodes (LEDs) have been one of the most promising light source in lots of applications, due to its excellent properties, such as high luminous efficacy, low power consumption, and environment-friendliness. However, the commercialized approach, which use blue or UV LEDs to excite some appropriate phosphors, has disadvantages in energy loss and low color rending index. In order to obtain high qulity phosphor free white LEDs, InGaN based micro- and nano-sized structures obtained by Selective Area Growth (SAG) method, is proposed. The quantum well (QWs) thickness and the Indium composition vary with position along the different facets of these structures, resulting in the emission of multiple wavelengths. Even though there is wavelength variation on the different facets, the variation is still not large enough to achieve white LEDs with high color rending index. Thus, we designed an asymmetric pyramid structure to enlarge the wavelength difference. Large Indium segregation and QWs thickness variation occur due to the large growth rate difference during the lateral overgrowth process. Additionally, the asymmetric pyramid can also reduce the dislocation density and improve the material quality by the lateral overgrowth. As a result, a well-designed asymmetric pyramid array is suitable for fabricating high quality white LED.

Solvent-free microwave-assisted synthesis of solid-state yellow carbon dots with visible-light excitation for dual applications in fingerprint visualization and white LEDs.

InGaN/GaN multiple quantum wells on selectively grown GaN microfacets and the applications for phosphor-free white light-emitting diodes

Preparation of N-doped carbon dots based on starch and their application in white LED

A novel orange-yellow-emitting polymethyl methacrylate derivative grafted with cationic iridium(III) complex units was synthesized and used as down-conversion luminescent materials in light-emitting diodes (LEDs). The polymer had a thermal decomposition temperature (Td) of 275 °C. With the temperature increasing from 20 to 100 °C, its photoluminescent intensity decreased to 76.8% with thermal quenching activation energy (Ea) of 0.2775 eV. A series of LEDs was fabricated by 460 nm blue GaN chips and the polymer blended in silicone at different concentrations. At 4.0 wt %, a cold white LED was obtained, the correlated color temperature (CCT) was 10,050 K, color rendering index (CRI) was 71.2, luminous efficiency (ηL) was 5.3 lm·w−1, and Commission Internationale de L’Eclairage (CIE) chromaticity coordinates were (0.30, 0.24). At 5.0 wt.%, the LED emitted neutral white light, its CCT was 4938 K, CRI was 75, ηL was 13.8 lm·w−1, and the CIE value was (0.34, 0.27). At 5.5 wt %, 6.0 wt %, 7.0 wt %, and 8.0 wt %, the LEDs all emitted warm white light; their CCTs were 3446, 3093, 2557, and 2337 K, respectively; their CRIs were 73.6, 71.8, 63.8, and 59.0, respectively; their ηL were 18.1, 16.3, 14.8, and 13.7 lm·w−1, respectively; and their CIE values were (0.36, 0.30), (0.40, 0.35), (0.45, 0.38), and (0.50, 0.42), respectively. At 9.0 wt %, the blue light of GaN chip was completely absorbed by the polymer and only the orange-yellow light of the polymer emitted. The results suggested the polymer was a promising orange-yellow-emitting phosphor candidate for white LEDs, especially for warm white LEDs.

A narrow band emission nitride SrLiAl3N4:Eu2+ (SLA) red phosphor prepared through a high-pressure solid state reaction was coated with organosilica layers in 400 ~ 600 nm thickness to improve its waterproof property. The coated samples showed excellent moisture resistance while retaining an external quantum efficiency (EQE) of 70% of its initial EQE after being aged for 5 days in harsh conditions. White light-emitting diodes (LEDs) of SLA red-phosphors and commercial Y3Al5O12:Ce3+ (YAG:Ce) yellow-phosphor on a blue-InGaN chip were shown high color rendition (CRI = 89, R9 = 69) and low correlated color temperature of 2406 K. All-inorganic CsPbX3 (X = Cl, Br, I) perovskite quantum dots (PQDs) with narrow emission bad were synthesized by hot injection methods. We propose an efficient and simple method to prevent the anion-exchange effect. We mixed green CsPbBr3 PQDs with purchased mesoporous silica. We applied the new PQD-based LEDs for backlight displays. Our white LED device for backlight display passed through a color filter with an NTSC value of 113% and Rec. 2020 of 85%. For lighting application, we used red perovskite quantum dots assisted by a yellow YAG:Ce phosphor were integrated on a blue chip. This warm white light with CCT (3328K), high color rendering index (CRI = 84.7) and a super high value of saturated red color component R9 as 96. Nitrides phosphors and all inorganic quantum dots were a good candidate for the application of white light LEDs with narrow emission band.

Manganese halides are emerging as promising alternatives to traditional inorganic phosphors and X-ray scintillators due to their low toxicity, high attenuation coefficients, high light yield, and cost-effective solution-processability. We synthesized a novel manganese chloride, (4CTP)2MnCl4 (4CTP = (4-chlorobenzyl)triphenylphosphonium), via solvent volatilization. The crystal exhibits a narrow-band (∼48 nm) green emission at 516 nm under ultraviolet or blue light excitation, attributed to the Mn2+ d-d transition, with a photoluminescence quantum yield (PLQY) of 95.7% and a nearest Mn···Mn distance of 9.909 Å. A white light-emitting diode (LED) for backlight displays was fabricated using (4CTP)2MnCl4, a 450 nm blue LED chip, and K2SiF6: Mn4+, achieving a color gamut of 112.1% at 20 mA. Substituting the red phosphor with (Sr, Ca)AlSiN3: Eu2+ produced a white LED for solid-state lighting with a color rendering index (CRI) of 92.4 and a correlated color temperature (CCT) of 4097 K. The crystal also demonstrated excellent X-ray scintillation properties (a light yield of 63,400 photons/MeV). A flexible (4CTP)2MnCl4@PMMA film enabled high-resolution X-ray imaging (10.4 lp/mm). This work showcases a simple route to develop high-performance manganese halides for LEDs and X-ray imaging.

Design of a broadband cyan-emitting phosphor with robust thermal stability for high-power WLED application

It is well known that the upconversion luminescence from lanthanide metal-organic frameworks (Ln-MOFs) is difficult to achieve, and thus, there are few reports on dual luminescence-based MOFs. Here, dual-mode light-emitting Ln-MOFs are synthesized using a low-cost hydrothermal method. Our results show that the obtained Ln-MOFs not only have high thermal stability (up to 420°) but also are stable in deionized water. The dual-mode up- and downconversion luminescence is simultaneously observed from Er-Eu-MOFs. The temperature-dependent fluorescence decay time is calculated to be ranging from 0.46 to 0.36 ms for temperatures from 100 to 300 K. We suggested that this phenomenon was because the number of phonons participating in the MOF matrix increases with temperature during the luminescence process, and the phonons interact with the electrons in the material. The values of the J-O parameters calculated from the emission spectra indicated that the symmetry around Eu3+ ions in Eu-MOF is the highest, which was also higher than that of Er-Eu-MOF. To explore the potential applications of Eu-MOFs in white light-emitting diodes (LEDs), red emission from Eu-MOFs was combined with blue, green, and yellow emissions from metal halide perovskites to achieve white light emission. White light with excellent color quality and vision performance was obtained. These findings demonstrate that Ln-MOFs are potentially successful materials for applications in white LEDs.