RESUMO
Wide-spectrum displays require narrow-band red phosphors activated by Mn4+, but most of them, such as K2SiF6:Mn4+, have long fluorescence decay lifetimes (>7 ms) that hinder their use in fast-response backlights. Interestingly, K2LiAlF6:0.05Mn4+ has a shorter fluorescence lifetime (3.43 ms), but its disadvantage is that its luminescence intensity is relatively weak. So, in this study, the luminescence intensity of K2LiAlF6:0.05Mn4+ is improved by doping with Zn2+. The experimental results show that enhancement of the luminous intensity is as high as 39%, the fluorescence lifetime is only increased by 13% (3.89 ms), and it is still less than 4 ms. Through experiments and differential charge density calculations, it has been revealed that the luminescence intensity improvement is due to an increased crystalline quality during the synthesis process. Specifically, the co-doping of Zn2+ reduces the formation of impurity ions Mn2+ and Mn3+ and the generation of K+ vacancies caused by nonequivalent doping. We demonstrate the advantage of this phosphor over K2SiF6:Mn4+ in terms of response speed by using a camera. It emits only weak red light after the blue chip stops working for 5 ms, indicating its potential application in next-generation fast-response displays.
RESUMO
Although Mn4+-activated fluoride phosphors have high luminescence quality, their poor water resistance and thermal fluorescence properties significantly limit their practical applications. Here, we propose a surfactant modification strategy by adding the surfactant cetyltrimethylammonium bromide (CTAB) to the synthesis and modifying the surface of the phosphor with ethylene diamine tetraacetic acid (EDTA) to obtain a phosphor with excellent luminescence thermal properties and water resistance, K2TiF6:Mn4+-xCTAB-EDTA (KTFM-xC-E) phosphors. The experimental and X-ray diffraction Rietveld refinement results confirm that the phosphor has higher structural rigidity and thus improved thermal stability. The surface modification with EDTA resulted in the formation of a dilute Mn4+ shell layer on the phosphor surface, which prevented the inward hydrolysis of the phosphor and resulted in excellent water resistance. Therefore, we have successfully modified K2TiF6:Mn4+ (KTFM) phosphors using low-cost surfactants, which also provides new ideas for other commercial high-quality phosphors.
RESUMO
Mn4+-doped fluoride red light phosphors are widely utilized in various fields, and their luminous performance is influenced by their stability in high humidity and temperature environments. By incorporating TEOAH+ (TEOAH+ = (HOCH2CH2)3NH+) into the Na2TiF6 matrix, Na3HTiF8:Mn4+,TEOAH+ with improved thermal stability and water resistance was synthesized. Enhancement in the luminescence thermal stability is supported by its strong negative thermal quenching (NTQ) effect, which is attributed to the phonon-induced mechanism wherein the probability of radiative transitions increases much faster than the probability of non-radiative transitions. Additionally, the integrated emission intensity of the optimal sample Na3HTiF8:Mn4+,0.15TEOAH+ was maintained at 70.1% after being immersed in water for 360 min, which may be attributed to the addition of TEOAH+ cations in the structure, thus increasing its structural rigidity. The prototype light-emitting diode (LED) has a narrow emission band, 88.6% color gamut, and 83.1 lm W-1 light efficiency, according to the National Television Standards Committee (NTSC). The qualities of the phosphor make it an ideal candidate for back-lighting devices.
RESUMO
The luminescence properties and thermal stability of phosphors are key properties for practical applications. A series of K2SiF6: Mn4+, Na+ @ GQDs (KSF: Mn4+, Na+ @ GQDs, KSF = K2SiF6, GQDs = graphene quantum dots; here, Cl-contained graphene quantum dots are used) red light phosphors have been synthesized by using a combination of H2O2-free and hydrothermal coating methods. The fluorescence thermal stability and fluorescence intensity of the optimal phosphor are greatly improved by doping the matrix with Na+ and coating it with GQDs. The strong negative thermal quenching (NTQ) effect and the color stability of the phosphor at variable temperatures result in good thermal stability. The strong NTQ effect is attributed to the phonon-induced transition mechanism. The high thermal stability makes the optimal sample ideal for high-power light LEDs (WLEDs). The test results show that the prototype WLED with the optimal sample as the red light component produces warm white light. The light has high luminescent efficiency (101.6 lm W-1), low correlated color temperature (CCT = 3978 K), and high color rendering index (R a = 92.2).
RESUMO
A new type of monoethanolamine (MEA) and Mn4+ co-doped KTF : MEAH+, Mn4+ (K2TiF6 : 0.1MEAH+, 0.06Mn4+) red emitting phosphor was synthesized by an ion exchange method. The prepared Mn4+ co-doped organic-inorganic hybrid red phosphor exhibits sharp red emission at 632 nm and the emission intensity at room temperature is 1.43 times that of a non-hybrid control sample KTF : Mn4+ (K2TiF6 : 0.06Mn4+). It exhibits good luminescent thermal stability at high temperatures, and the maximum integrated PL intensity at 150 °C is 2.34 times that of the initial value at 30 °C. By coating a mixture of KTF : MEAH+, Mn4+, a yellow phosphor (YAG : Ce3+) and epoxy resin on a blue InGaN chip, a prototype WLED (white light-emitting diode) with CCT = 3740 K and R a = 90.7 is assembled. The good performance of the WLED shows that KTF : MEAH+, Mn4+ can provide a new choice for the synthesis of new Mn4+ doped fluoride phosphors.
RESUMO
Mn4+-doped fluoride phosphors are efficient narrowband red-emitting phosphors for white light-emitting diodes (WLEDs) and backlight displays. However, erosion by moisture is the main obstacle that limits their application. In this work, LNSF:Mn4+ (Li0.06Na1.94Si0.94Mn0.06F6) with high quantum yield (QY), luminescent thermal stability, and waterproofness was synthesized using the H2O2-free reaction method at room temperature. Compared to NSF:Mn4+(Na2Mn0.06Si0.94F6), the QY value, luminescence thermal stability, and water resistance of LNSF:Mn4+ are obviously improved by codoping of Li+ because of the formation of charge-carrier transfer (CT) and rare-Mn4+ layer induced by codoping of Li+. The former produces the negative thermal quenching (NTQ) effect, which results in the improvement of the luminescent thermal stability. The latter can inhibit the hydrolysis of Mn4+ on the surface of the sample, which leads to the enhancement of waterproofness. The formation mechanism of the rare-Mn4+ layer is discussed. A prototype WLED emitting the ideal warm white light (CCT = 3173 K, Ra = 90.4) was assembled by coating a mixture of LNSF:Mn4+, yellow emitting phosphor (YAG:Ce3+), and epoxy resin on the blue light InGaN chip, indicating that the performance of the WLED can be improved by using LNSF:Mn4+.
RESUMO
Herein, a series of NSF:0.05Mn4+,0.04K+@GQD (NSF: Na2SiF6, GQDs: Cl-containing graphene quantum dot) phosphors was prepared. Double enhancement effects on the luminescent intensity and thermal stability triggered by the GQD coating were observed for the optimal sample as follows: (a) its PL intensity was 1.72 times that of the uncoated control sample and (b) its luminescent thermal stability was greatly enhanced, with integrated PL intensities of 120, 150 and 180 °C to 179.7%, 175.8%, and 119.3% of the initial value at 25 °C, respectively. It is proposed that the above-mentioned behaviors involve a change in some of the thermal energy into light energy via a phonon-induced mechanism. The thermal stability analysis results showed that the optimal sample is suitable for application in high-power WLEDs. Specifically, warm white light with a low correlated color temperature, high luminescent efficiency and high color rendering index was obtained from the prototype WLEDs using the optimal sample as a red-emitting component.
