SMOOTHING PHOSPHORS FOR AC LED LIGHTING
20170275533 ยท 2017-09-28
Assignee
Inventors
Cpc classification
International classification
Abstract
Disclosed are smoothing phosphors for AC LED lighting that are capable of prolonging the light emission time of an AC LED (or array of AC LEDs) during a cycle response to a phase change of the alternating current to substantially reduce flicker. The smoothing phosphor of the present teachings comprises a matrix represented by the formula: M.sub.(l-k-r-v)X.sub.(m-p)Al.sub.2(n-0.5x-0.5y)O.sub.3(n-0.5x-0.5y): Mn.sub.(x+p)O.sub.(x+p), Si.sub.yO.sub.2y, Eu.sub.k, R.sub.r, Li.sub.v wherein M is at least one of La.sub.2O.sub.3, Ce.sub.2O.sub.3, Gd.sub.2O.sub.3, Lu.sub.2O.sub.3, Ba.sub.2OF.sub.2, Sr.sub.2OF.sub.2, Ca.sub.2OF.sub.2, Ba.sub.2OCl.sub.2, Sr.sub.2OCl.sub.2, Ca.sub.2OCl.sub.2, BaO, SrO, CaO, or ZnO; provided that when M comprises BaO, SrO, CaO, or ZnO, M does not comprise La.sub.2O.sub.3, Ce.sub.2O.sub.3, Gd.sub.2O.sub.3, Lu.sub.2O.sub.3, Ba.sub.2OF.sub.2, Sr.sub.2OF.sub.2, Ca.sub.2OF.sub.2, Ba.sub.2OCl.sub.2, Sr.sub.2OCl.sub.2, or Ca.sub.2OCl.sub.2; X is at least one of MgO or ZnO; R is at least one of Sm, Pr, Tb, Dy, Er, or Ho; m=0 to 2; n=4 to 11; x=0.005 to 1; y=0.005 to 1; p=0 to 1; k=0 to 0.2; r=0 to 0.2; and v=0 to 0.2.
Claims
1. A smoothing phosphor for AC LED lighting, said smoothing phosphor comprising a matrix represented by the formula: M.sub.(l-k-r-v)X.sub.(m-p)Al.sub.2(n-0.5x-0.5y):O.sub.3(n-0.5x-0.5y):Mn.sub.(x+p)O.sub.(x+p), Si.sub.yO.sub.2y, Eu.sub.k, R.sub.r, Li.sub.v wherein: M is at least one of La.sub.2O.sub.3, Ce.sub.2O.sub.3, Gd.sub.2O.sub.3, Lu.sub.2O.sub.3, Ba.sub.2OF.sub.2, Sr.sub.2OF.sub.2, Ca.sub.2OF.sub.2, Ba.sub.2OCl.sub.2, Sr.sub.2OCl.sub.2, Ca.sub.2OCl.sub.2, BaO, SrO, CaO, or ZnO; provided that when M comprises BaO, SrO, CaO, or ZnO, M does not comprise La.sub.2O.sub.3, Ce.sub.2O.sub.3, Gd.sub.2O.sub.3, Lu.sub.2O.sub.3, Ba.sub.2OF.sub.2, Sr.sub.2OF.sub.2, Ca.sub.2OF.sub.2, Ba.sub.2OCl.sub.2, Sr.sub.2OCl.sub.2, or Ca.sub.2OCl.sub.2; X is at least one of MgO or ZnO; R is at least one of Sm, Pr, Tb, Dy, Er, or Ho; m=0 to 2; n=4 to 11; x=0.005 to 1; y=0.005 to 1; p=0 to 1; k=0 to 0.2; r=0 to 0.2; and v=0 to 0.2.
2. The smoothing phosphor of claim 1, wherein M is at least one of La.sub.2O.sub.3, Ce.sub.2O.sub.3, Gd.sub.2O.sub.3, Lu.sub.2O.sub.3, Ba.sub.2OF.sub.2, Sr.sub.2OF.sub.2, Ca.sub.2OF.sub.2, Ba.sub.2OCl.sub.2, Sr.sub.2OCl.sub.2, or Ca.sub.2OCl.sub.2, m=0, n=11, and p=0, and the matrix is represented by the formula: M.sub.l-k-r)Al.sub.(22-x-y)O.sub.(33-1.5x-1.5y):Mn.sub.xO.sub.x, Si.sub.yO.sub.2y, Eu.sub.k, R.sub.r, Li.sub.v.
3. The smoothing phosphor of claim 1, wherein M is at least of BaO, SrO, CaO, or ZnO, m=2, n=8, and the matrix is represented by the formula: M.sub.(l-k-r-v)X.sub.(2-p)Al(.sub.16-x-y)O.sub.(24-1.5x-1.5y):Mn.sub.(x+p)O.sub.(x+p), Si.sub.yO.sub.2y, Eu.sub.k, R.sub.r, Li.sub.v.
4. The smoothing phosphor of claim 1, wherein M is at least of BaO, SrO, CaO, or ZnO, m=1, n=5, and the matrix is represented by the formula: M.sub.(l-k-r-v)X.sub.(l-p)Al.sub.(10-x-y))O.sub.(15-1.5x-1.5y):Mn.sub.x+p)O.sub.(x+p), Si.sub.yO.sub.2y, Eu.sub.k, R.sub.r, Li.sub.v.
5. The smoothing phosphor of claim 1, wherein M is at least of BaO, SrO, CaO, or ZnO, m=1, n=7, and the matrix is represented by the formula: M.sub.(l-k-r-v)X.sub.(l-p)Al.sub.(14-x-y)O.sub.(21-1.5x-1.5y):Mn.sub.(x+p)O.sub.(x+p), Si.sub.yO.sub.2y, Eu.sub.k, R.sub.r, Li.sub.v.
6. The smoothing phosphor of claim 1, wherein M is at least of BaO, SrO, CaO, or ZnO, m=0, n=6, p=0, and the matrix is represented by the formula: M.sub.(l-k-r-v)Al.sub.(12-x-y)O.sub.(18-1.5x-1.5y):Mn.sub.xO.sub.x, Si.sub.yO.sub.2y, Eu.sub.k, R.sub.r, Li.sub.v.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] The present teachings are illustratively shown and described in reference to the accompany drawings, in which
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DETAILED DESCRIPTION OF THE INVENTION
[0022] The present teachings are directed to the creation of smoothing phosphors for AC LED lighting that are capable of reducing flicker of an AC LED (or array of LEDs). The smoothing phosphor of the present teachings comprises a matrix represented by the general formula: M.sub.(l-k-r-y)X.sub.(m-p)Al.sub.2(n-0.5x-0.5y)O.sub.3(n-0.5x-0.5y):Mn.sub.(x+p)O.sub.(x+p), Si.sub.yO.sub.2y, EU.sub.k, R.sub.r, Li.sub.v, wherein M is at least one of La.sub.2O.sub.3, Ce.sub.2O.sub.3, Gd.sub.2O.sub.3, Lu.sub.2O.sub.3, Ba.sub.2OF.sub.2, Sr.sub.2OF.sub.2, Ca.sub.2OF.sub.2, Ba.sub.2OCl.sub.2, Sr.sub.2OCl.sub.2, Ca.sub.2OCl.sub.2, BaO, SrO, CaO, or ZnO; provided that when M comprises BaO, SrO, CaO, or ZnO, M does not comprise La.sub.2O.sub.3, Ce.sub.2O.sub.3, Gd.sub.2O.sub.3, Lu.sub.2O.sub.3, Ba.sub.2OF.sub.2, Sr.sub.2OF.sub.2, Ca.sub.2OF.sub.2, Ba.sub.2OCl.sub.2, Sr.sub.2OCl.sub.2, or Ca.sub.2OCl.sub.2; X is at least one of MgO or ZnO; R is at least one of Sm, Pr, Tb, Dy, Er, or Ho; m=0 to 2; n=4 to 11; x=0.005 to 1; y=0.005 to 1; p=0 to 1; k=0 to 0.2; r=0 to 0.2; and v=0 to 0.2.
[0023] When an LED (or array of LEDs) are directly pumped or operated from AC, typically 110V/60 Hz or 230V/50 Hz, the instantaneous AC voltage applied has to exceed a minimum threshold value in order for current to flow through the LED (or array of LEDs), making the LED turn on and emit light. Given the AC LED (or array of AC LEDs) minimum threshold value, along with the sinusoidal waveform of AC, the AC LED turns on and off at the same frequency, causing the AC LED (or array of AC LEDs) to flicker when directly connected to an AC power source, thereby affecting the observed quality of light produced.
[0024] Flicker is the periodic change in the instantaneous light output of a light source. Flicker is measured using two different metrics, i.e. percent flicker and flicker index. Percent flicker, sometimes referred to as modulation index, is defined as the ratio of the maximum light intensity output value minus the minimum light intensity output value divided by the sum of the maximum and minimum light intensity output values for one AC cycle. Flicker index is defined as the ratio of the area under the light intensity output curve above the average light intensity output value to the total area of the light intensity output curve for one AC cycle. Although both metrics for flicker measurement are relative measures of the cyclic variation in light output of a light source, percent flicker does not take into account the waveform of the light source, nor the duty cycle, whereas flicker index does. Nonetheless, the presence of flicker can substantially impact the quality of light produced and thus perceived by a human observer.
[0025] By employing smoothing phosphors in accordance with the present invention, the light emission time of the AC LED (or array of LEDs) is prolonged during a cycle response to a phase change of the AC such that flicker can be reduced. Generally speaking, an AC LED operating at 50 to 120 Hz has an off period that is normally about 1 ms to about 10 ms. When a smoothing phosphor is used, the AC LED continues to emit light during this off period such that the flicker, otherwise produced, is substantially minimized. In order for a smoothing phosphor to be effective in the reduction of flicker of an AC LED, the smoothing phosphor should have an emission lifetime that is substantially similar to the off period of the AC LED. Ions having such an emission lifetime include Mn.sup.2+, Fe.sup.3+, 4f rare earth ions, or ions with s electrons in the out-shell, such as Bi.sup.3+ (6s.sup.2), Tl.sup.+ (6s.sup.2), Sb.sup.3+ (5s.sup.2), S.sub.n.sup.2+ (5.sub.s.sup.2), all of which involve spin-forbidden transitions, and thus provide a longer lifetime of emission. However, based on the emission spectrum of an AC LED, along with additional requirements for practical applications of AC LED lighting, Fe.sup.3+, 4f rare earth ions, or ions with s electrons in the out-shell are not suitable.
[0026] In general, Mn.sup.2+ ions emit light that is characteristically in the green or red region of the electromagnetic spectrum. Mn.sup.2+ has 5 electrons in its 3d shell, labeled as 3d.sup.5. The ground state of Mn.sup.2+ is S-state with zero total orbital angular momentum, total spin 5/2, and the spin multiplet, indicated as a superscript, of 6, thus labeled as .sup.6S.sub.0. The first excited state of free Mn.sup.2+ ions is .sup.4G. Above .sup.4G, are .sup.4P, .sup.4D, .sup.2I, .sup.4F, .sup.2D, etc. In the cubic crystal field, .sup.6S.sub.0 is represented as .sup.6A.sub.1. The excited state .sup.4G, having 9-fold orbital degeneracy, is split into .sup.4T.sub.1, .sup.4T.sub.2, .sup.4E, and .sup.4A.sub.1 in the cubic representation. A is an orbital singlet, E is a doublet, and Ts are triplets. It can be noticed that all spin-multiplets (S=4 or 2) of excited states are different from the ground state (S=6). Therefore, all the electronic transitions of Mn.sup.2+ are spin forbidden and thus illustrate an emission lifetime of Mn.sup.2+ that is substantially similar to the off period of an AC LED (or array of AC LEDs).
[0027] Furthermore, this also implies that the electronic transition probability of Mn.sup.2+ is relatively low, and thus the excitation of Mn.sup.2+ with that of AC LED emission is weaker than that of a spin allowed transition. To aid in the excitation of Mn.sup.2+ with that of AC LED emission, a host matrix with strong absorption of AC LED emission through Mn.sup.2+ was investigated. In addition, the host matrix should also entail a strong, broad, efficient emission in the spectral emission range of Mn.sup.2+, an emission lifetime that is also substantially similar to the off period of the AC LED, and have a high concentration quenching onset level of the emissive Mn.sup.2+ ions. In light of the foregoing characteristics, it was determined that suitable host matrices for Mn.sup.2+ is that of aluminate-based compounds having the general formula: M.sub.(l-k-r-v)X.sub.(m-p)Al.sub.2(n-0.5x-0.5y)O.sub.3(n-0.5x-0.5y), wherein M is at least one of La.sub.2O.sub.3, Ce.sub.2O.sub.3, Gd.sub.2O.sub.3, Lu.sub.2O.sub.3, Ba.sub.2OF.sub.2, Sr.sub.2OF.sub.2, Ca.sub.2OF.sub.2, Ba.sub.2OCl.sub.2, Sr.sub.2OCl.sub.2, Ca.sub.2OCl.sub.2, BaO, SrO, CaO, or ZnO; provided that when M comprises BaO, SrO, CaO, or ZnO, M does not comprise La.sub.2O.sub.3, Ce.sub.2O.sub.3, Gd.sub.2O.sub.3, Lu.sub.2O.sub.3, Ba.sub.2OF.sub.2, Sr.sub.2OF.sub.2, Ca.sub.2OF.sub.2, Ba.sub.2OCl.sub.2, Sr.sub.2OCl.sub.2, or Ca.sub.2OCl.sub.2; X is at least one of MgO or ZnO; m=0 to 2; n=4 to 11; x=0.005 to 1; y=0.005 to 1; p=0 to 1; k=0 to 0.2; r=0 to 0.2; and v=0 to 0.2. These suitable host matrices have hexagonal symmetry and contain Al-O spinel blocks, in which Al.sup.3+ occupies either tetrahedral or octahedral sites of the spinel blocks. Thus, when doped with Mn.sup.2+, M.sup.3+ of the host matrix is partially or fully replaced with that of Mn.sup.2+.
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[0029] It was further determined that the Mn.sup.2+ doped aluminate phosphors, possess a charge defect as a result of the oxygen vacancies created by the partial or full substitution of Mn.sup.2+ for that of Al.sup.3+. A charge defect refers to defects in the crystalline matrix of a phosphor as a result of the replacement, partial or full, of one atom for another in the matrix that is not an exact match in charge (valence state), thereby resulting in altered photoluminescent characteristics, such as e.g., decrease of emission intensity. Thus, in order to minimize the charge defects produced by such substitution, the smoothing phosphors of the present teachings are also further co-doped with Si.sup.4+. As an example,
[0030] The concentration of Mn.sup.2+ within the smoothing phosphor should be as a high as possible to maximize the excitation intensity of Mn.sup.2+. However with too high Mn.sup.2+ content, concentration quenching can occur, thereby reducing the emission intensity of the smoothing phosphor. Thus, there is a balance that exists between the excitation intensity, the emission intensity, and Mn.sup.2+ content of the smoothing phosphor. The role that Mn.sup.2+ content has on the emission intensity of the smoothing phosphors of the present teachings was investigated.
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[0032] Alternatively or in addition to the Mn-Mn pairs emission, the smoothing phosphors of the present teachings may also emit light in the red region of the electromagnetic spectrum with the further co-doping of rare earths such as Sm.sup.3+, Tb.sup.3+, Dy.sup.3+, Er.sup.3+, or Ho.sup.3+. For example,
[0033] In another aspect of the present teachings, the smoothing phosphors may be further co-doped with Eu.sup.2+ so as to enhance the excitation intensity, and thus the emission intensity, of Mn.sup.2+. The emission spectrum of Eu.sup.2+ overlaps with the excitation spectrum of Mn.sup.2+, therefore it is possible through energy transfer from Eu.sup.2+ to Mn.sup.2+ to increase excitation in the spectral range of about 360 to 410 nm of the smoothing phosphors of the present teachings. As an example,
[0034] Other exemplary smoothing phosphors in accordance with the present teachings are illustrated in
[0035] Other exemplary smoothing phosphors in accordance with the present teachings are illustrated in
[0036] A number of methods may be used to synthesize the smoothing phosphors of the present teachings such as, liquid mixing methods, solid chemical reaction methods, etc. Liquid mixing methods include methods such as co-precipitation and sol-gel techniques. In solid chemical reaction methods, a flux, such as H.sub.3BO.sub.3 or B.sub.2O.sub.3, is used to stimulate the solid chemical reaction. A solid chemical reaction method may include admixing various starting materials in a predetermined ratio and pre-sintering them in a furnace, followed by grinding and sintering in the furnace at a higher temperate. For example in instances of lab scale, one method may include weighing the starting materials of the smoothing phosphor into a weighing dish, followed by admixing the materials and grinding into a mortar with a pestle until uniform. The ground material is then placed in an alumina combustion boat and placed in an oven at around 900 C. in air or in a forming gas mixture of 97% N.sub.2, and 3% H.sub.2 at a rate of 50 cm.sup.3/min for four hours. The material is then cooled and ground again in a mortar with a pestle, followed by again placing the material into an alumina combustion boat and sintered at around 1350 C. to 1450 C. for four hours in the forming gas mixture of 97% N.sub.2 and 3% H.sub.2 at a rate of 50 cm.sup.3/min. The material is then cooled and ground to a powder of the desired particle size to yield a smoothing phosphor in accordance with the present teachings.
[0037] For the purposes of describing and defining the present teachings, it is noted that the term substantially is utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement or other representation. The term substantially is also utilized herein to present the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.
[0038] Although the teachings have been described with respect to various embodiments, it should be realized that these teachings are also capable of a wide variety of further and other embodiments within the spirit and scope of the appended disclosure.