CN106367062B - 白光led用全光谱荧光粉及其制备方法和白光led发光装置 - Google Patents
白光led用全光谱荧光粉及其制备方法和白光led发光装置 Download PDFInfo
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
- C09K11/7727—Sulfates
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Abstract
本发明公开了一种白光LED用全光谱荧光粉,其化学组成式为Ca0.94Zn1‑xOS:0.03Ce3+,0.03Na+,xMn2+。此外,还公开了该荧光粉的制备方法和使用该荧光粉的白光LED发光装置。本发明的白光LED用全光谱荧光粉发光亮度高、化学稳定性和温度猝灭特性良好、激发和发射范围较宽。它在蓝光激发下可获得一系列不同色温的高效白光,能够满足通用照明领域对于不同类型光源的需求,同时具有显色性能好、能量转换率高、色温均匀性好并且不易发生光衰的优点。
Description
技术领域
本发明属于发光材料技术领域;涉及一种LED荧光粉及其制备方法和发光装置,更具体地,涉及一种白光LED用全光谱荧光粉及其制备方法和白光LED发光装置。
背景技术
近年来,白光LED作为一种新型的固态照明光源,由于其环保、节能、可靠性高、寿命长等优点受到人们的关注。它的诸多优点在普通照明、信号灯、液晶显示器背景光源等诸多领域得到了广泛的应用,并有望取代目前使用的各式灯泡和荧光灯,成为新一代的绿色照明光源。
白光是一种混色光,白光的实现可以采取不同颜色匹配原理,混合多颜色的单色光合成白光。在CIE中任意两个非互补色以任意比例混合将产生中间色,通过三个线性无关的颜色相混合成的中间色位于以此三点为顶点所围成的三角形内。依据发光学和光度学原理,实现白光可由全光谱和黄光混合,也可由红、绿、蓝三基色光混合。
当前合成白光LED主要有以下四种方式。一是三基色LED芯片组合方案:将蓝、绿、红三种LED芯片与荧光粉组装成白光LED产生白光,该方案属于LED芯片p-n结的电致发光。但是,这种方案由于使用的LED芯片数量为单芯片方案的3倍,高芯片密度会使工作温度的升高而使荧光粉发光效率严重下降,且不同荧光粉的吸收不同,从而导致所产生白光的色坐标的发生漂移,并且该种方案的成本较高使其推广应用难度较大。二是蓝光LED芯片与多基色荧光粉组合方案:在蓝光LED中一并封装蓝、绿、红三种荧光粉构成白光LED。该方案利用蓝光LED发射的长波紫外或紫外光激发红、绿、蓝三基色荧光粉复合产生白光该方案的特点是荧光体选择的种类丰富,可获得显色性好的白光,但由于荧光粉互相混合阻碍其对发射源的充分吸收,导致效率较低,还不能满足商业上的照明应用。三是量子阱白光LED:量子阱是指由两种不同的半导体材料相间排列形成的、具有明显量子限制效应的电子或空穴的势阱。如果材料薄层交替生长形成多层结构,那么会形成许多分离的量子阱,则称为多量子阱。多量子阱途径是在芯片发光层的生长过程中掺杂不同杂质以控制结构不同的量子阱,通过不同量子阱发出的多种光子复合发射白光。该方法提高了发光效率,可降低成本,降低包装及电路的控制难度,但技术难度相对较大。第四种方式,也是目前可实现产业化的是光转换型白光LED的主流方案是InGaN蓝色LED芯片和Ce3+激活的稀土石榴石(YAG)黄色荧光粉组合得到;具体来说,这种方案是在蓝色全光谱LED芯片上涂敷能被全光谱激发的Ce3+激活的YAG黄色荧光粉,芯片发出的全光谱与荧光粉发出的黄光互补形成白光。这种白光LED制作原理简单且发光效率高,已经在许多领域获得应用。然而这种方案的一个致命的缺点就是该荧光粉中的发射光谱不具连续性,缺少有效红光成份导致发射谱不全,所获得的白光显色指数还较低,应用受到了一定的限制,难以满足特定低色温照明的要求,特别是一些对色温性和显色性要求较高的领域和艺术照明、医用照明等领域,因此需要通过开发色温更好的全光谱荧光粉,以提高白光的显色性和可调能力。
在目前的全光谱荧光材料中,能够在显色性和稳定性方面都能达到应用要求的荧光粉还很少见。已有的白光LED用荧光粉体系包括硅酸盐体系、硅基氮(氧)化物体系、磷酸盐体系、铝酸盐体系以及硫化物体系。这些荧光粉存在下列缺陷。首先,硅酸盐体系荧光粉化学和热稳定性较好,但封装成品显色指数普遍不高。其次,硅基氮(氧)化物体系荧光粉激发波长宽、温度稳定性好,发光性能优良;但是这类荧光粉在制备过程中需要高温高压等苛刻条件,增加了安全隐患。再次,磷酸盐体系荧光粉发光效率高,稳定性好;但这类荧光粉需要通过高温固相合成技术和火焰喷雾热解技术制备,条件同样较为苛刻,成本较高。第四,铝酸盐体系荧光粉亮度高,发射峰宽,成本低;但是工业化生产中存在合成温度较高,荧光粉颗粒度较大等问题,严重阻碍了其在白光LED中的进一步应用。第五,硫化物体系荧光粉激发波段较宽,并且发光亮度较好。然而,由于硫化物稳定性和抗紫外光辐射能力较差,白光LED使用寿命不长;同时,这类荧光粉对湿度敏感,稳定性较差。
另一方面,使用上述荧光粉和红绿两色荧光粉封装的白光LED通常会因为所使用的荧光粉体系不同,发射光谱半峰宽较窄,导致封装成品显示指数普遍不高。同时,全光谱荧光粉在封装的白光LED中往往存在光衰。采用这些方案制备的暖白光LED光源,在使用过程中,随着时间延长,色温发生显著漂移,暖白光向正白光逐渐转变。
因此,基于现有的荧光粉基质和掺杂离子进行改进,以得到能够与蓝光激发LED相匹配的荧光粉是LED发光材料面临的重要课题,相关发光材料和发光装置的发展对于白光LED的发展具有重要的意义。本发明主要针对目前蓝光激发下白光LED中缺少单一基质全光谱高显色性荧光粉的问题,选择硫氧化物为基质材料开展研究。
发明内容
本发明目的之一是克服现有技术的不足,提供一种发光亮度高、化学稳定性和温度猝灭特性良好、激发和发射范围较宽的白光LED用全光谱荧光粉。
本发明目的之二是提供一种制备上述白光LED用全光谱发光材料的制备方法。该制备方法简单、易于操作、设备成本低且无污染。
本发明目的之三是提供一种显色性能好、能量转换率高、色温均匀性好并且不易发生光衰的暖色调白光LED发光装置。
为实现上述目的,本发明的白光LED用全光谱荧光粉以硫氧化物为基质,以三价Ce为主激活剂及能量传递的供体,以二价Mn为能量传递的受体,得到一种发光亮度高、化学稳定性和温度猝灭特性良好、激发和发射范围较宽的白光LED用全光谱荧光粉。
白光LED用全光谱荧光粉的化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中0.003≤x≤0.09。优选地,本发明的白光LED用全光谱荧光粉的化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中0.009≤x≤0.05。更优选地,本发明的白光LED用全光谱荧光粉的化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中0.02≤x≤0.04。最优选地,本发明的白光LED用全光谱荧光粉的化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中x=0.03,即Ca0.94Zn0.97OS:0.03Ce3+,0.03Na+,0.03Mn2+。
另一方面,本发明提供了一种制备上述白光LED用全光谱荧光粉的方法,该方法包括下列步骤:
1)按通式Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+的化学计量比准确称取原料,其中0.003≤x≤0.09,并充分研细混匀,得到原料混合物;
2)将步骤1)得到的原料混合物在氩气气氛中高温煅烧,从而得到烧结体;
3)将步骤2)得到的烧结体研磨成为粉末。
在步骤1)中,原料选自钙、锌、铈和锰的单质、氧化物、氯化物、硫化物、碳酸盐、硫酸盐、磷酸盐、硝酸盐,以及其它合适盐类。在一个优选的实施方式中,原料来自钙、锌、铈和锰的氧化物、氯化物、碳酸盐、硝酸盐。在一个更优选的实施方式中,原料来自钙、锌、铈和锰的氧化物和硫化物。
此外,在步骤1)中,可以任选地加入反应助熔剂,所述的反应助熔剂可以是钙、锶、锂、硅、铝和铈的卤化物、硫酸盐、碳酸盐以及三氧化二硼或硼酸的一种或多种以上。优选地,所述的反应助熔剂可以是锂和铈的卤化物、硫酸盐、碳酸盐的一种或多种以上。最优选地,所述的反应助熔剂选自锂的碳酸盐。基于原料的总重量,助熔剂的加入量一般为0-10wt%。在一个优选的实施方式中,助熔剂的加入量为5wt%。
在一个优选的实施方式中,按通式Ca0.94Zn0.97OS:0.03Ce3+,0.03Na+,xMn2+的化学计量比称取碳酸钙、硫化锌、氧化铈、碳酸钠以及碳酸锰,其中0.003≤x≤0.09;优选0.009≤x≤0.05;更优选0.02≤x≤0.04;以及最优选x=0.03。
在步骤2)中,将步骤1)得到的混合物放入坩埚中,其中坩埚优选为刚玉坩埚或铂坩埚。然后,将装有原料混合物的坩埚放入高温炉中,在氩气气氛中高温煅烧,然后冷却至室温,从而得到烧结体。
步骤2)中所述高温指的是900-1200℃的温度,优选950-1150℃的温度,最优选1000-1100℃的温度。高温煅烧时间一般是1小时至72小时,优选是2小时至48小时,进一步优选是3小时至24小时,最优选是3小时至6小时。
步骤2)得到的烧结体通常样品颗粒形貌不规则,颗粒度较大,粒径分布不均匀。因此,可以通过步骤3)的常规研磨步骤改善白光LED用全光谱荧光粉的颗粒度大小以及粒径分布均匀度。研磨时间一般为5分钟至2小时,优选10分钟至1小时,更优选15分钟至30分钟。这种研磨手段是本领域技术人员所熟知的。
上述制备方法简单、易于操作、设备成本低且无污染。所制备得到的白光LED用全光谱荧光粉发光亮度高、化学稳定性和温度猝灭特性良好、激发和发射范围较宽,在蓝光波段有较宽的强激发,并可与蓝光芯片组装成白光LED器件,能够在较大程度上满足产业需求。
又一方面,本发明提供了一种显色性能好、能量转换率高、色温均匀性好并且不易发生光衰的暖色调白光LED发光装置。
所述白光LED发光装置包括封装基板、蓝光LED芯片以及能够有效吸收LED芯片发光并释放全光谱的荧光粉;其中,全光谱荧光粉为上述本发明的白光LED用全光谱荧光粉,其化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中0.003≤x≤0.09。优选地,化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中0.009≤x≤0.05。更优选地,化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中0.02≤x≤0.04。最优选地,化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中x=0.03,即Ca0.94Zn0.97OS:0.03Ce3+,0.03Na+,0.03Mn2+。
其中,蓝光LED芯片为InGaN半导体芯片,其发光峰值波长为455nm。
LED发光装置通过下列原理产生白光,即将LED芯片固定于封装基板上,连通电极并将荧光粉以涂覆或点胶的方式直接或间接涂于蓝光LED芯片(InGaN半导体芯片)表面,利用蓝光激发荧光粉产生白光。
本发明的暖色调白光LED发光装置具有显色性能好、能量转换率高、色温均匀性好并且不易发生光衰的优点。
与现有技术相比,本发明具有下列优势:
1)本发明的白光LED用全光谱荧光粉发光亮度高、化学稳定性和温度猝灭特性良好、激发和发射范围较宽,在蓝光波段有较宽的强激发,并可与蓝光芯片组装成白光LED器件,能够在较大程度上满足产业需求。
2)本发明的制备方法简单、易于操作、设备成本低且无污染;可产生巨大的社会效益和经济效益,适合普遍推广使用。
3)本发明的白光LED用全光谱荧光粉,在蓝光激发下可获得一系列不同色温的高效白光,能够满足通用照明领域对于不同类型光源的需求,同时具有显色性能好、能量转换率高、色温均匀性好并且不易发生光衰的优点。
具体实施方式
实施例1:
该实施例的白光LED用全光谱荧光粉的化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中x=0.006,具体表达式为Ca0.94Zn0.94OS:0.03Ce3+,0.03Na+,0.006Mn2+。
按Ca0.94Zn0.97OS:0.03Ce3+,0.03Na+,0.03Mn2+中各元素计量比,准确称取0.4704gCaCO3,0.4844g ZnS,0.0258g CeO2,0.0159g Na2CO3,0.0035g MnCO3,0.0500g Li2CO3,高纯度粉末原料,置于玛瑙研钵中研磨30分钟左右,使原料充分混合均匀。将混合原料转移到氧化铝坩埚中,并把刚玉小坩埚置于氩气气氛的高温反应炉中,1100℃烧结3小时,自然冷却后取出,再次研磨30分钟左右,即得单一相Ca0.94Zn0.994OS:0.03Ce3+,0.03Na+,0.006Mn2+荧光粉。
实施例8:
该实施例的白光LED用全光谱荧光粉的化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中x=0.009,具体表达式为Ca0.94Zn0.991OS:0.03Ce3+,0.03Na+,0.009Mn2+。
按Ca0.94Zn0.991OS:0.03Ce3+,0.03Na+,0.009Mn2+中各元素计量比,准确称取0.4704gCaCO3,0.4830g ZnS,0.0258g CeO2,0.0159g Na2CO3,0.0052g MnCO3,0.0500g Li2CO3,高纯度粉末原料,置于玛瑙研钵中研磨30分钟左右,使原料充分混合均匀。将混合原料转移到氧化铝坩埚中,并把刚玉小坩埚置于氩气气氛的高温反应炉中,1100℃烧结4小时,自然冷却后取出,再次研磨15分钟左右,即得单一相Ca0.94Zn0.991OS:0.03Ce3+,0.03Na+,0.009Mn2+荧光粉。
实施例2-7和比较例1-2。
在实施例2-7中,除了原料粉末的组成和所得全光谱荧光粉的化学组成式不同之外,其余的工艺条件参数均与实施例1的制备方法相同。
实施例1-8所获得的白光LED用全光谱荧光粉的化学组成式、发射光谱的峰值位置和Ce3+/Mn2+的相对发光强度的测试结果如表1所示。
表1
本发明的白光LED用全光谱荧光粉的激发波长为455nm,与商业化的蓝光LED芯片可以很好地匹配。所有的样品发射光谱均有两个峰,分别归属于Ce3+和Mn2+的发射峰,Ce3+的发射峰峰值为524nm,Mn2+的峰值波长落在565-575nm波长范围内,且随着Mn2+浓度的增加,本发明的白光LED用全光谱荧光粉Ce3+/Mn2+的相对发光强度显著提高。比较例1则仅存在Ce3 +的发射峰,而不存在565-575nm的发射峰。比较例2的Ce3+/Mn2+的相对发光强度最高。
白光LED发光装置应用实施例
按照下列方法制备本发明的暖色调白光LED发光装置。所述白光LED发光装置包括蓝光LED芯片以及能够有效吸收LED芯片发光并发射全光谱的本发明的白光LED用全光谱荧光粉;其中,全光谱荧光粉分别为上述实施例1-3和实施例5的白光LED用全光谱荧光粉,其化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中x=0.003,0.006,0.009,0.03。其中,蓝光LED芯片为InGaN半导体芯片,其发光峰值波长为455nm。。将发明的白光LED用全光谱荧光粉均匀分散在折射率1.41,透射率99%的硅胶中,涂在芯片上,得到本发明的暖色调白光LED发光装置。
采用实施例1-3和实施例5和8以及比较例1-2的白光LED用全光谱荧光粉封装的暖色调白光LED的光效及光色数据。具体参见表2。
表2
从上表可以看出,本发明的白光LED用全光谱荧光粉在蓝光激发下可获得一系列不同色温的高效暖色调白光,能够满足通用照明领域对于不同类型光源的需求,由本发明的白光LED用全光谱荧光粉所制备的暖色调白光LED发光装置显色性能好,色温均匀性好。而比较例1和2的白光LED发光分别偏红和偏绿,白光纯度稍低。另一方面,在大量试验中,发明人发现本发明的白光LED用全光谱荧光粉的化学稳定性和温度猝灭特性良好。经过500小时老化后,实施例1-3和实施例5和8的CIE-X和CIE-Y坐标数值变化均不超过0.005;色温变化不超过100K;显色指数变化不超过5。而比较例1和2的CIE-X和CIE-Y坐标数值变化均超过0.01;色温变化均超过150K;显色指数变化均超过10。
以上所述仅为本发明的优选实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均包含在本发明的保护范围之内。
Claims (10)
1.一种白光LED用全光谱发射荧光粉,其特征在于,其化学组成式为Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+,其中0.003≤x≤0.09。
2.根据权利要求1所述的荧光粉,其中,0.009≤x≤0.05。
3.根据权利要求2所述的荧光粉,其中,0.02≤x≤0.04。
4.根据权利要求3所述的荧光粉,其中,x=0.03。
5.一种制备权利要求1-4任一项所述的白光LED用全光谱荧光粉的方法,包括下列步骤:
1)按通式Ca0.94Zn1-xOS:0.03Ce3+,0.03Na+,xMn2+的化学计量比准确称取原料,其中x值如权利要求1-4所述,并充分研细混匀,得到原料混合物;
2)将步骤1)得到的原料混合物在氩气气氛中高温煅烧,从而得到烧结体;
3)将步骤2)得到的烧结体研磨成为粉末。
6.根据权利要求5所述的制备方法,其中,在步骤1)中,所述原料来自钙、锌、铈和锰的氧化物和硫化物。
7.根据权利要求5所述的制备方法,其中,在步骤1)中,可以任选地加入反应助熔剂,所述的反应助熔剂选自锂的碳酸盐。
8.根据权利要求5所述的制备方法,其中,在步骤2)中,所述高温指的是1000-1100℃的温度;所述高温煅烧时间是3小时至6小时。
9.一种白光LED发光装置,包括封装基板、蓝光LED芯片以及荧光粉,其特征在于,所述荧光粉为权利要求1-4任一项所述的白光LED用全光谱发射荧光粉。
10.根据权利要求9所述的白光LED发光装置,其中,所述蓝光LED芯片为InGaN半导体芯片。
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CN102899033B (zh) * | 2012-11-16 | 2014-11-26 | 湖南师范大学 | 一种制备含有二价铕离子红色荧光粉的方法 |
CN103881703B (zh) * | 2014-03-25 | 2016-04-06 | 陕西科技大学 | 一种白光led用单一基质荧光粉的制备方法 |
CN103965894B (zh) * | 2014-05-23 | 2016-02-24 | 四川大学 | 一种白光led用硅酸盐单基质白光荧光粉及其制备方法 |
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