CN107919430A - 用于led应用的无机结合剂中的磷光体 - Google Patents
用于led应用的无机结合剂中的磷光体 Download PDFInfo
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Classifications
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- H01L33/48—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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Abstract
描述了一种用于制作LED/磷光体结构的方法,其中蓝发光二极管(LED)管芯的阵列安装在底座晶片上。磷光体粉末与诸如丙烯酸酯或硝化纤维的有机聚合物结合剂混合。液体或糊状物混合物随后被沉积在LED管芯或其它衬底上成为基本均匀的层。有机结合剂随后通过在空气中烧掉或者经历O2等离子体工艺被移除,或者被溶解,留下烧结在一起的磷光体晶粒的多孔层。利用溶胶‑凝胶(例如TEOS或MTMS的溶胶‑凝胶)或者也称为水玻璃的液体玻璃(例如硅酸钠或硅酸钾)浸渍该多孔磷光体层,这浸透该多孔结构。该结构随后被加热以固化无机玻璃结合剂,留下鲁棒玻璃结合剂,除其它期望属性之外,该玻璃结合剂耐受变黄。
Description
技术领域
本发明涉及一种供发光二极管(LED)使用以对LED发射进行波长转换的磷光体层,并且具体地涉及一种利用无机玻璃结合剂形成该磷光体层以得到改进性能的技术。
背景技术
在LED上方提供磷光体层是常见的。典型地,磷光体被提供在蓝光LED上方以形成白光。通过磷光体泄漏的蓝光与磷光体光组合产生白光。有许多方式在LED上方提供磷光体层,并且下面描述一种现有技术的技术。
已知预先形成一层与硅树脂(silicone)混合的磷光体粉末,并且随后将该层层压在安装在底座晶片上的发射蓝光的LED管芯上。该晶片随后被切割(singulate)。得到的管芯发射白光。这描述于转让给本受让人并且通过引用结合于此的,Grigoriy Basin等人的美国专利申请公布20110031516和20110266569。其它技术也将磷光体粉末混合在有机聚合物结合剂(例如硅树脂或环氧树脂)中并且随后将该液体/糊状物层直接沉积(例如印刷、成型等)在LED上方。随后固化结合剂以使其硬化。
然而,来自LED的热和高通量趋于使磷光体颗粒周围的有机结合剂氧化,致使结合剂变黄并且使光颜色偏移。另外,高质量硅树脂和环氧树脂较昂贵,这对于大的远程磷光体部件而言是重要的问题。
需要的是一种用于形成磷光体层的工艺,该磷光体层或者可以直接形成于LED上方或者可以形成于透明衬底上,并且其不使用硅树脂或其它有机聚合物作为结合剂。
尽管无机玻璃对于磷光体粉末将是比较稳定和可靠的结合剂,熔化玻璃在形成磷光体-玻璃层所需的高温下化学反应性太高,这是由于玻璃将与磷光体,特别是红光氮化物磷光体化学反应。
用于形成玻璃层的溶胶-凝胶也可以被认为是替代硅树脂的候选物,但是溶胶-凝胶对于磷光体反应性也太高,导致光衰减。另外,溶胶-凝胶的低粘度将导致磷光体沉淀以及磷光体密度不均匀。还将存在其它问题。
发明内容
形成一种具有无机玻璃结合剂的磷光体层,该磷光体层可以被用作用于LED的远程磷光体或者用作LED上方的涂层以对LED光进行波长转换。在一个实施例中,LED发射蓝光,并且磷光体将该光转换为白光。
最初,磷光体粉末与诸如不昂贵的丙烯酸酯或硝化纤维的有机聚合物结合剂混合。混合物可以形成为具有宽粘度范围的糊状物。这种混合物随后容易丝网印刷在诸如薄玻璃衬底的透明衬底上。可替换地,混合物可以被丝网印刷在安装在底座晶片上的LED管芯上方。可以使用其它沉积技术。该层可以制成具有诸如+/-2%的精确厚度。
有机结合剂随后诸如在180-300摄氏度在空气中被烧掉。可替换地,混合物可以经历O2等离子体工艺。在任一情形中,聚合物被氧化并且蒸发。结合剂也可以被化学溶解。
得到的层是多孔的经烧结磷光体粉末层,其基本均匀地分布在透明衬底或LED上方。该多孔层比较脆弱并且受污染。
接着,利用溶胶-凝胶(例如TEOS或MTMS的溶胶-凝胶)或者也称为水玻璃的液体玻璃(例如硅酸钠或硅酸钾)浸渍该多孔层,这浸透(saturate)该多孔结构。
该结构随后被加热以固化无机玻璃结合剂。对于溶胶-凝胶的情形,加热致使溶胶-凝胶变得交联以形成硬的耐划伤的玻璃层。对于液体玻璃的情形,水成份蒸发,留下硬的层。可以使用其它玻璃质材料。
得到的无机结合剂材料在LED产生的高热量和通量下极为稳定,它耐受变黄,它导热性显著优于硅树脂或环氧树脂,它远没有硅树脂或环氧树脂那么昂贵,并且它具有更大的机械强度和耐划伤性。
公开了其它实施例。
附图说明
图1为现有技术的安装在底座上的蓝光或UV倒装芯片LED管芯的截面视图。
图2为说明排布(populate)有LED管芯阵列,诸如500-4000个LED的简化底座晶片的自上向下视图,其中晶片上所有LED管芯同时被加工。
图3说明具有层压或沉积在LED上方的磷光体层的图2的底座晶片。
图4说明排布有利用透镜封装的LED的图2的底座晶片,磷光体层被层压或沉积在透镜上方。
图5为沉积在衬底上的磷光体层的截面视图,其中磷光体粉末分布在聚合物结合剂中。该衬底可以是玻璃衬底或者是底座晶片上的LED管芯。
图6说明在聚合物结合剂通过在O2等离子体中氧化或者在空气中烘干而蒸发之后,留下多孔磷光体层的图5的磷光体层。
图7说明溶胶-凝胶玻璃、液体玻璃或其它合适透明无机结合剂材料浸透该多孔磷光体层,随后被固化以形成鲁棒无机结合剂。
图8说明图5的磷光体层被层压在排布有LED管芯的底座晶片上方。
图9说明在应用真空或其它形式的压力时,图8的磷光体层适形到LED管芯的形状。
图10为依据本发明一个实施例其上方形成有磷光体层的已完成的LED的截面视图,其中在切割之前磷光体层形成于底座晶片的整个表面上方。
图11为依据本发明另一实施例其上方形成有磷光体层的已完成的LED的截面视图,其中磷光体层作为瓦被贴附在LED管芯顶部上方。
图12为概述依据本发明一些实施例用于制作磷光体层的技术的流程图。
用相同附图标记标注相同或相似的元件。
具体实施方式
尽管磷光体层的本发明不依赖于其供任何特定LED使用,将描述LED结构的示例以说明供LED使用的磷光体层。
现有技术图1说明安装在底座晶片12一部分上的常规倒装芯片LED管芯10。在倒装芯片中,n和p接触都形成于LED管芯的同一侧上。
在本公开中,术语“底座晶片”旨在表示LED管芯阵列的支撑件,其中晶片上的电接触被结合到LED管芯上的电极,并且晶片稍后被切割以形成单个底座上的一个或多个LED,其中底座具有将连接到电源的电极。
LED管芯10由生长在诸如蓝宝石衬底的生长衬底上的,包括n-层14、有源层15和p-层16的半导体外延层形成。在图1中,生长衬底已经通过激光剥离、蚀刻、研磨,或者通过其它技术被移除。在一个示例中,外延层是基于GaN的,并且有源层15发射蓝光。发射UV光的LED管芯也适用于本发明。
金属电极18电接触p-层16,并且金属电极20电接触n-层14。在一个示例中,电极18和20为金垫,所述金垫被超声焊接到陶瓷底座晶片12上的阳极和阴极金属垫22和24。底座晶片12具有导电通路24,该导电通路引到底部金属垫26和28用于结合到印刷电路板。许多LED安装在底座晶片12上并且将稍后被切割以形成单独LED/底座。
LED的另外细节可以发现于受让人的美国专利No.6,649,440和6,274,399以及美国专利公布US2006/0281203A1和2005/0269582A1,所有这些通过引用结合于此。
图2为LED管芯10阵列安装在其上的示例性底座晶片12的自上向下简化视图(仅仅一个LED被编号,但是晶片12上所有正方形都是LED)。单个底座晶片12上可以存在500-4000个LED。晶片12上的所有LED将使用下文所述方法同时被加工。
图3说明LED管芯10安装在其上的底座晶片12的一部分。LED电极18和20结合到底座晶片12上的金属垫,该金属垫通过延伸穿过晶片12的通路而连接到晶片12底面上更鲁棒的垫。当晶片12稍后被切割时,底部垫可以被焊接到印刷电路板上的垫。
磷光体层38被示为在晶片12上方,这代表磷光体层38或者将被层压在晶片12上方或者磷光体层38将为与LED管芯10分离的远程层。在另一实施例中,磷光体层38可以被切割以形成瓦,并且每个瓦被贴附在LED管芯10上方。另外,在另一实施例中,在LED被切割之前,磷光体层38被层压在LED晶片上方。以此方式,磷光体的浪费很少。磷光体层38的其它用途被预想。
图4说明LED管芯10可以如何在其上成型半球形透镜36,从而在层压之后将磷光体层38与管芯10分离。这减小了磷光体上的热和通量的强度,并且改善随角度变化的颜色均匀性。
图5-7说明依据本发明一个实施例的磷光体层的形成。
在图5中,衬底40可以是透明玻璃板,或者是排布有LED管芯10的底座晶片12的表面,或者是任何其它合适衬底。如果磷光体层38(图3和4)旨在为用于远程磷光体应用的自支撑层,或者旨在被切割成瓦并贴附在LED管芯10上,则玻璃衬底是优选的。由透明玻璃板支撑并且与(多个)LED分离的远程磷光体对于使用互连LED阵列的高功率应用会是优选的,其中在该应用中所产生的光和热非常高;或者在下述情形中会是优选的,其中期望通过选择使用具有不同特性的各种远程磷光体板其中之一而可以选择发射的颜色。如果磷光体层38旨在被直接层压在底座晶片12上的LED上方或者层压在LED晶片上方,则衬底40将是排布有LED管芯10的底座晶片12或者将是LED晶片。
最初,磷光体粉末42与有机聚合物结合剂44混合,该结合剂为诸如丙烯酸酯、硝化纤维或者可以稍后被蒸发或溶解掉的其它商业上可获得的结合剂。由于磷光体粉末42的常规的小晶粒尺寸以及其在结合剂44中的密度的原因,磷光体粉末42在结合剂44中的分布相当均匀,这应在磷光体层38各处实现良好的颜色均匀性。磷光体晶粒尺寸和密度不是至关重要的;然而该密度应使得在结合剂44稍后被移除之后晶粒彼此接触。
磷光体粉末42可以为包括YAG、红、绿、黄、蓝、或橙色磷光体或者其组合的任何常规磷光体,这取决于应用以及LED。
由于聚合物结合剂44不必具有良好光学属性,它可以比硅树脂廉价得多。供磷光体使用的硅树脂约为$900US/kg。
混合的结合剂/磷光体可以形成糊状物或粘稠液体,其被喷涂、浸涂、旋涂或丝网印刷在衬底40上。厚度对于本发明不是至关重要的,但是磷光体粉末42的厚度和密度影响所发射的光颜色。沉积的层应具有+/-2%的厚度精度以实现良好的颜色均匀性。
在图6中,结合剂44经历诸如在空气气氛中180-300摄氏度的加热一段时间从而蒸发结合剂44。可替换地,O2等离子体可以用于氧化结合剂40以将结合剂44转换为气体,或者结合剂可以被化学溶解和加热。加热和移除结合剂44的组合导致磷光体粉末42晶粒被烧结在一起并且烧结到衬底40以形成比较均匀的磷光体粉末42层。磷光体粉末42形成多孔层或网状物(web)。
在图7中,多孔层随后用溶胶-凝胶(用于形成玻璃)或者也称为水玻璃的液体玻璃浸渍并且被浸透。这可以通过喷涂、浸涂或其它公知方法完成。
在浸透步骤之后,液体玻璃或溶胶-凝胶被固化以使材料脱水,留下围绕磷光体粉末42的鲁棒的玻璃结合剂48。在一些情形中,通过加热或在室温脱水更长时间来执行固化,或者使用化学固化剂来执行固化。
液体玻璃(硅酸钠或硅酸钾)是通过熔合各种份额的砂(SiO2)和碳酸钠(Na2CO3)来制成,其中碳酸钠中的CO2被驱赶走。这些份额的比例确定最终产物的属性。此产物被明确为SiO2/Na2O的比例以及在水中的浓度。钠也可以被钾或锂替代,从而获得不同属性。在将液体玻璃应用成为薄膜之后,水被蒸发,留下固态玻璃涂层。更低的SiO2/Na2O比例趋于更好地保持水并且因此更缓慢地蒸发。如果期望增加的耐用性,则更高比例的溶液(大约2.8-3.22)是优选的。完全脱水典型地要求在干燥工艺期间加热。硅酸盐层可以在250℃的温度被固化,该温度远低于发光材料可以承受的温度(氮化物基发光材料可以承受高达350℃的温度,并且YAG基发光材料可以承受甚至高得多的温度)。
使涂层耐用的另一种方法是利用化学硬化(setting)。在此方式中可以使用的化学硬化剂包括矿物酸和有机酸、CO2气体以及诸如碳酸氢钠的酸式盐。
当硅酸盐膜被完全脱水时,它们提供出色的高温耐性。大多数硅酸盐具有大约850℃的流点。在LED中将永远不会达到这种温度。
液体玻璃对于可见光是透明的,并且透射率在400nm之下迅速下降,在325nm表现大约40%的值。对于将蓝光转换为白光的LED,这个范围是足够的。
硅酸盐涂层可能易碎。如果要求更高的柔性度,典型地可以添加按重量计5%的丙三醇。丙三醇对蓝光具有非常高的透明度。可以添加其它材料,诸如乙二醇、丙二醇、乙醇等。
存在许多合适的溶胶-凝胶材料,诸如TEOS(正硅酸乙酯)、MTMS(甲基三甲氧基硅烷)和MTES(三乙氧基硅烷),所有这些统称为玻璃材料。溶胶-凝胶较不昂贵(低于$20US/kg),因此得到的磷光体层不如硅树脂结合剂中磷光体粉末那么昂贵。玻璃具有高的热和光热稳定性,并且在存在LED的高热量和通量的情况下耐受变黄。形成这种材料的溶胶-凝胶公知被用于将该材料沉积在衬底上。
溶胶-凝胶工艺是通常用于制作玻璃质涂层的湿法化学技术。在此工艺中,溶胶(或溶液)逐渐演化到形成既含有液相又含有固相的类似凝胶的网络。微米尺寸或亚微米尺寸玻璃颗粒变得交联,形成该凝胶。使用溶胶-凝胶形成TEOS、MTMS、MTES或其它玻璃层是公知的并且不需要详细描述。
干燥工艺用于从凝胶移除液相,得到无定形玻璃(连接的氧化硅网络或基体)。可以执行后续热处理(烧制)从而使玻璃致密以增强其机械属性。
由于在脱水之后将出现收缩,溶胶-凝胶或液体玻璃的厚度应被调节以确保在脱水之后完全覆盖磷光体粉末42。为了完全覆盖,多次应用和固化溶胶-凝胶或液体玻璃会是期望的。
该玻璃层可以形成为具有与高指数硅树脂的折射率相当的较高折射率,从而提供良好光提取。
作为将图5的膜直接沉积在LED管芯10上方或者将该膜沉积在玻璃衬底上的可替换方案,膜可以预先形成为柔性层,随后层压在LED管芯10和底座晶片12上方,如图8和9所示。
在一个实施例中,聚合物结合剂44和磷光体粉末42混合物的柔性层形成于可释放膜(衬底40的一实施例)上。该层可以被测试以确定其发光属性,并且被匹配到发射特定窄范围蓝光的LED管芯的特定料仓(bin)。如图8所示,以可释放膜面朝上的方式,随后将柔性层58层压在匹配的LED管芯10上。真空或机械的向下压力被用于确保不存在空气间隙并且使层58适形到LED管芯10。在层58被全部层压在LED管芯10上方之前或之后,移除该可释放膜。随后,如图9所示,执行图6和7的工艺从而形成含有磷光体粉末42的鲁棒的无机玻璃层59。
图10说明在半球形透镜60被成型在LED管芯10上方之后并且在底座晶片12被切割之后图9的结构(使用层压层58)。该结构可以发射白光或任何颜色的光。图10的结构也可以这样形成:通过喷涂、旋涂等将图5的层44/42直接沉积在LED管芯10上方,随后执行图6和7的工艺。
图11说明LED结构,其中图7的发光结构已经被切割以形成发光瓦40/42/48,并且每个瓦被贴附在LED管芯上方。在一个实施例中,LED管芯具有直接贴附在管芯顶表面上方的YAG瓦64,并且使用图5-7工艺形成的含有红光磷光体粉末的发光瓦40/42/48被贴附在YAG瓦64上方以形成较暖的白光。薄玻璃层、环氧树脂或硅树脂可以被用作粘合剂。
图12为概述依据本发明一些实施例的形成磷光体层的各种步骤的流程图。
在步骤70,制作LED晶片,诸如含有GaN基蓝光LED的晶片。
在步骤71,对LED晶片划片(dice),并且将LED管芯排布于底座晶片。
在步骤72,将磷光体粉末和有机结合剂的混合物形成为糊状物或液体用于丝网印刷或其它类型的沉积,或者形成为层压层。
在步骤73,将磷光体/结合剂混合物印刷或层压在玻璃板(例如,对于远程磷光体)或其它衬底上或者在LED管芯上方。
在步骤74,通过加热或使结合剂经历O2等离子体或其它处理而移除有机结合剂,留下多孔的经烧结磷光体粉末层。
在步骤75,通过喷涂、浸涂或其它工艺,利用液体玻璃、溶胶-凝胶或其它合适材料浸渍磷光体“网状物”。
在步骤76,诸如通过加热固化液体玻璃或溶胶-凝胶,以使溶胶-凝胶层交联和/或蒸发任何溶液,诸如液体玻璃中的水。
由于收缩的原因,可以多次执行步骤75和76。
尽管已经示出和描述了本发明的具体实施例,但是本领域技术人员将清楚可以进行改变和调适而不背离就更宽广方面而言的本发明,并且因此所附权利要求将落在本发明真实精神和范围内的所有这种改变和调适涵盖在它们的范围内。
Claims (3)
1.一种发光装置,包括:
安装在底座上的发光二极管(LED)管芯;
置于该发光二极管管芯上方的多孔磷光体层,其中该多孔磷光体层包括烧结在一起的磷光体晶粒;以及
基本上填充该多孔磷光体层中的空间的无机透明硅酸盐结合剂,该硅酸盐结合剂是通过固化被灌注在该多孔磷光体层中的溶胶-凝胶或液体玻璃而形成的。
2.如权利要求1所述的装置,其中该多孔磷光体层由玻璃衬底支撑,该玻璃衬底位于该发光二极管管芯上面。
3.一种结构,包括:
包括经烧结磷光体颗粒的多孔磷光体层;以及
基本上填充该多孔磷光体层中的空间的无机透明硅酸盐结合剂,该硅酸盐结合剂是在该多孔磷光体层形成之后通过固化被灌注在该多孔磷光体层中的溶胶-凝胶或液体玻璃而形成的。
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US20160233377A1 (en) | 2016-08-11 |
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CN107919430B (zh) | 2021-11-09 |
US9337398B2 (en) | 2016-05-10 |
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US20150041841A1 (en) | 2015-02-12 |
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US9537047B2 (en) | 2017-01-03 |
WO2013144777A1 (en) | 2013-10-03 |
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