CN1624945A - 制造光半导体器件的方法 - Google Patents

制造光半导体器件的方法 Download PDF

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CN1624945A
CN1624945A CNA2004101001845A CN200410100184A CN1624945A CN 1624945 A CN1624945 A CN 1624945A CN A2004101001845 A CNA2004101001845 A CN A2004101001845A CN 200410100184 A CN200410100184 A CN 200410100184A CN 1624945 A CN1624945 A CN 1624945A
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resin
resin bed
vulcabond
optical semiconductor
polycarbodiimide
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CN100401538C (zh
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末广一郎
堀田佑治
贞瀬直树
釜田卓
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Nitto Denko Corp
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Abstract

本发明提供了一种制造光半导体器件的方法，其包括：(1)在导体上分别装配的一个或更多光半导体元件上形成树脂层；和(2)压模步骤(1)中形成的树脂层。

Description

制造光半导体器件的方法
技术领域
本发明涉及一种制造光半导体器件的方法。
背景技术
已知光半导体器件包括由两种或更多种以折射率从光半导体元件侧向最外层递减排列的树脂层包封的光半导体元件，以便能够具有改善的光取出(takeout)效率(参见专利文献1)。
专利文献1：JP10-65220A(权利要求1)
至今为止直接接触光半导体元件的第一包封树脂由浸泡或铸封(potting)形成。然而，迄今为止浸泡或铸封的树脂封装具有缺陷：以预定量在每个光半导体元件上滴加液态树脂的操作较麻烦，包封元件的密封形状不规则易于导致不均匀发光。
发明内容
本发明的一个目的是提供一种制造光半导体器件的方法，可以容易和均匀地进行一个或更多个光半导体元件的树脂封装。
根据下列说明书本发明的其它目的和特征将变得明显。
本发明涉及制造光半导体器件的方法，这包括：
(1)在一个或更多个各自装配在导体上的光半导体元件上形成树脂层；知
(2)压模步骤(1)中形成的树脂层。
根据本发明，光半导体元件的树脂封装可以容易和均匀地进行，可以得到光取出效率均匀的优质光半导体器件。
附图说明
图1图解说明了本发明步骤(1)的一个具体实施方式，其中在光半导体元件上形成树脂层。
图2图解说明了本发明步骤(1)的另一个具体实施方式，其中在光半导体元件上形成树脂层。
图3图解说明了本发明步骤(2)一个具体实施方式，其中用冲模机压模树脂层。
图4是图解本发明得到的发光二极管阵列的一个具体实施方式的剖面图。
附图中使用的参考数字分别表示下列。
1：树脂
2：光半导体元件
3：基板
4：层压机
5：铸模
6：电线
7：导体
8：冲模机(stamper)
9：LED阵列
10：LED薄片
11：第一树脂层
12：第二树脂层
具体实施方式
本发明制造半导体器件的方法包括：
(1)在一个或更多个各自装配在导体上的光半导体元件上形成树脂层；和
(2)压模步骤(1)中形成的树脂层。
在步骤(1)中，光半导体元件没有特别限制，只要它们是普通用于光半导体器件的。其实例包括氮化镓(GaN，折射率，2.5)、磷化镓(GaP；折射率，2.9)和砷化镓(GaAs；折射率，3.5)。其中优选GaN，因为它发射蓝光，由此可以与磷光体(phosphor)共同使用制造白色LED。
在其上装配每个光半导体元件的导体没有特别限制，只要它是普通用于光半导体器件的。使用的导体可以是具有预定形状的引线框，或可以是已经通过蚀刻以具有预定形状的导体。
在其上装配一个或更多个光半导体元件和导体的基板也没有特别限制。然而，考虑到更显著地发挥本发明的效果，本发明中优选器件包括一个基板和装配在其上的两个或更多个导体和两个或更多个光半导体元件。
考虑到提高从光半导体元件的光取出效率，优选构成步骤(1)中树脂层的树脂(该树脂以下有时可以称为″第一树脂″)的折射率为1.6或更高，更优选1.7-2.1。
包封光半导体元件的树脂实例包括聚醚砜、聚酰亚胺、芳族聚酰胺、聚碳化二亚胺和环氧树脂。
考虑到在低温和低压的处理容易程度，优选这些用作构成步骤(1)中树脂层的树脂为聚碳化二亚胺。更优选为通式(1)代表的聚碳化二亚胺：
Figure A20041010018400051
(其中R代表二异氰酸酯残基，R1代表单异氰酸酯残基，n是1-100的整数)。
在本发明中，通过使一种或更多种二异氰酸酯进行缩聚反应并用单异氰酸酯封端得到的聚合物，获得通式(1)代表的聚碳化二亚胺。
通式(1)中，R代表用作原料的二异氰酸酯的残基，R1代表用作另一原料的单异氰酸酯的残基。符号n是1-100的整数。
用作原料的二异氰酸酯和单异氰酸酯可以是芳族或脂肪族。二异氰酸酯和单异氰酸酯各自可以由一种或更多种芳族异氰酸酯单独构成或一种或更多种脂肪族异氰酸酯单独构成，或可以包含芳族异氰酸酯和脂肪族异氰酸酯的组合。考虑到获得具有较高折射率的聚碳化二亚胺，本发明中优选使用芳族异氰酸酯。即，优选二异氰酸酯和单异氰酸酯中的至少一种包含芳族异氰酸酯或由一种或更多种芳族异氰酸酯构成，或者二异氰酸酯和单异氰酸酯各自由一种或更多种芳族异氰酸酯构成。更优选其中二异氰酸酯包含脂肪族异氰酸酯和芳族异氰酸酯的组合，并且单异氰酸酯由一种或更多种芳族异氰酸酯构成的情况。特别优选是其中二异氰酸酯和单异氰酸酯各自由一种或更多种芳族异氰酸酯构成的情况。
本发明中使用的二异氰酸酯的实例包括六亚甲基二异氰酸酯、十二亚甲基二异氰酸酯、2，2，4-三甲基六亚甲基二异氰酸酯、4，4′-二氯六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯、四甲基苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、环己基二异氰酸酯、赖氨酸二异氰酸酯、甲基环己烷2，4′-二异氰酸酯、4，4′-二苯基甲烷二异氰酸酯、4，4′-二苯醚二异氰酸酯、2，6-甲苯基二异氰酸酯、2，4-甲苯基二异氰酸酯、萘二异氰酸酯、1-甲氧基苯基2，4-二异氰酸酯、3，3′-二甲氧基-4，4′-二苯基甲烷二异氰酸酯、4，4′-二苯醚二异氰酸酯、3，3′-二甲基-4，4′-二苯醚二异氰酸酯、2，2-双[4-(4-异氰酸根合苯氧基(isocyanatophenoxy))苯基]六氟丙烷和2，2-双[4-(4-异氰酸根合苯氧基)苯基]丙烷。
考虑到使聚碳化二亚胺具有较高的折射率并且易于控制，在这些二异氰酸酯中优选使用选自甲苯基二异氰酸酯、4，4′-二苯基甲烷二异氰酸酯、萘二异氰酸酯、六亚甲基二异氰酸酯和十二亚甲基二异氰酸酯中的至少一种。更优选为萘二异氰酸酯。
那些二异氰酸酯可以单独使用或以其两种或更多种的混合物使用。然而考虑到耐热性，优选使用两种或三种二异氰酸酯的混合物。
用作原料的一种或更多种二异氰酸酯优选包含一种或更多种芳族二异氰酸酯，其含量基于全部二异氰酸酯优选为10mol％或更大(上限，100mol％)。这些二异氰酸酯合乎需要地为上述列举的作为优选实例。
本发明中可使用的单异氰酸酯的实例包括环己基异氰酸酯、异氰酸苯酯、对硝基苯基异氰酸酯、对和间甲苯基异氰酸酯、对甲酰基苯基异氰酸酯、对异丙基苯基异氰酸酯和1-萘基异氰酸酯。
优选的单异氰酸酯为芳族单异氰酸酯，因为芳族单异氰酸酯互相不反应，用该单异氰酸酯聚碳化二亚胺封端可以高效地进行。更优选使用1-萘基异氰酸酯。
那些单异氰酸酯可以单独使用或以其两种或更多种的混合物使用。
考虑到储存稳定性，用于封端的单异氰酸酯的量优选为1-10mol每100mol使用的二异氰酸酯成分。
可以通过在预定溶剂中在形成碳二亚胺催化剂的存在下，经过缩聚反应转化一种或更多种作为原料的二异氰酸酯至碳二亚胺，并用单异氰酸酯封端得到的碳二亚胺聚合物，制备本发明的聚碳化二亚胺。
进行二异氰酸酯缩聚反应的温度通常为0-150℃，优选10-120℃。
在其中结合使用脂肪族二异氰酸酯和芳族二异氰酸酯作为原料的二异氰酸酯的情况中，优选在低温反应二异氰酸酯。反应温度优选为0-50℃，更优选为10-40℃。因为脂肪族二异氰酸酯和芳族二异氰酸酯的缩聚进行充分，优选使用该范围中的反应温度。
在其中期望反应混合物中过量存在的芳族二异氰酸酯进一步与由脂肪族二异氰酸酯和芳族二异氰酸酯形成的聚碳化二亚胺反应的情况下，反应温度优选为40-150℃，更优选50-120℃。只要反应温度在该范围之内，可以使用任何所需溶剂平稳地进行反应。因此优选该反应温度范围。
反应混合物中二异氰酸酯浓度优选为5-80％(重量)。只要二异氰酸酯浓度在该范围之内，可以充分形成碳二亚胺，并易于控制反应。因此优选该二异氰酸酯浓度范围。
用单异氰酸酯封端可以通过将单异氰酸酯加入至由二异氰酸酯形成碳二亚胺的初始、中间或最后阶段或形成碳二亚胺的整个过程的反应混合物中。单异氰酸酯优选为芳族单异氰酸酯。
至于形成碳二亚胺的催化剂，可以有利地使用任何已知的含磷化合物催化剂。其实例包括膦杂环戊烯(phospholene)氧化物例如1-苯基-2-膦杂环戊烯1-氧化物、3-甲基-2-膦杂环戊烯1-氧化物、1-乙基-2-膦杂环戊烯1-氧化物、3-甲基-1-苯基-2-膦杂环戊烯2-氧化物和这些的3-膦杂环戊烯异构体。
用于制备聚碳化二亚胺的溶剂(有机溶剂)是已知的溶剂。其实例包括卤代烃例如四氯乙烯、1，2-二氯乙烷和氯仿，酮溶剂例如丙酮、甲基乙基酮、甲基异丁基酮和环己酮，环醚溶剂例如四氢呋喃和二噁烷，以及芳烃溶剂例如甲苯和二甲苯。这些溶剂可以单独使用或以其两种或更多种的混合物使用。这些溶剂还用于溶解得到的聚碳化二亚胺。
反应终点可以用红外光谱分析(IR分析)根据由碳二亚胺结构(N＝C＝N)(2,140cm-1)导致的吸收的出现和由异氰酸酯(2,280cm-1)导致的吸收的消失来确定。
形成碳二亚胺反应完成后，通常以溶液形式得到聚碳化二亚胺。然而，可以将得到的溶液倾注到不良溶剂例如甲醇、乙醇、异丙醇或己烷中，以沉淀聚碳化二亚胺并除去未反应的单体和催化剂。
在制备已经以沉淀物回收的聚碳化二亚胺溶液中，以预定方式洗涤并干燥沉淀物，然后再次溶解在有机溶剂中。通过进行该操作，聚碳化二亚胺溶液可以具有改善的储存稳定性。
在其中聚碳化二亚胺溶液包含副产物的情况下，例如，可以用适当的吸附剂通过吸附除去副产物而纯化溶液。吸附剂的实例包括氧化铝凝胶、硅胶、活性碳、沸石、活性氧化镁、活性矾土、漂白土、活性粘土和分子筛碳。这些吸附剂可以单独使用或其两种或更多种结合使用。
通过如上所述方法，得到本发明聚碳化二亚胺。考虑到使构成步骤(1)中树脂层的聚碳化二亚胺具有较高的折射率，优选聚碳化二亚胺的主链结构由芳族和脂肪族二异氰酸酯构成，其端基已经用芳族单异氰酸酯封端。更优选其主链结构由一种或更多种芳族二异氰酸酯构成，其端基已经用芳族单异氰酸酯封端。
具体地，聚碳化二亚胺中，优选通式(1)中R代表的二异氰酸酯残基的10mol％或更多(上限，100mol％)为一种或更多种芳族二异氰酸酯残基，通式(1)中R1代表的单异氰酸酯残基为一种或更多种芳族单异氰酸酯残基。二异氰酸酯残基优选为选自甲苯基二异氰酸酯、4，4′-二苯基甲烷二异氰酸酯、萘二异氰酸酯、六亚甲基二异氰酸酯和十二亚甲基二异氰酸酯中的至少一种，更优选为萘二异氰酸酯残基。芳族单异氰酸酯残基优选为1-萘基异氰酸酯残基。
用于进行在一个或更多个光半导体元件上形成包含第一树脂的树脂层的步骤的方法实例包括：如图1所示，用例如层压机4层压片状树脂1至其上装配了光半导体元件2的基板3上的方法；和如图2所示，其中例如用铸造模5施加树脂1至其上装配有光半导体元件2的基底3上，然后固化的方法。在每个图1和2中，根据常规技术光半导体元件2各自已经通过电线6连接至导体7。
在图1所示方法中，通过，例如，在溶剂中溶解树脂，用例如铸模、旋涂或辊涂技术将得到的树脂溶液形成为具有适当厚度的薄膜，然后在一定温度干燥薄膜使得可以除去溶剂，不引发固化反应，而得到片状树脂。已经形成为薄膜的树脂溶液的干燥温度不能无条件地确定，因为它随树脂和溶剂的种类而改变。然而，优选温度为20-350℃，更优选50-200℃。当考虑到光半导体元件的高度和用冲模机模制时，经过加热干燥得到的片状树脂的厚度优选为约150-400μm。还可以使用两种或更多种这样的树脂片互相叠置。
在其中使用层压机等通过热压粘接熔化和层压片状树脂至基板的情况下，优选树脂加热至优选70-250℃，更优选100-200℃，优选在0.1-10MPa层压，更优选0.5-5MPa。当使用层压机时，优选其转速为100-2,000rpm，更优选500-1,000rpm。
在图2所示方法中，用于铸模的模具条件包括优选加热温度为30-80℃，更优选50-60℃，优选线速度为0.5-8m/min。施加后干燥温度优选为20-350℃，更优选100-200℃，干燥周期优选为10-60分钟。
如上所述例举说明的步骤(1)之后为步骤(2)。本发明特征主要在步骤(2)中。通过压模(1)中形成的树脂层，可以容易地用均匀的树脂层包封光半导体元件，可以得到具有均匀的光取出效率的光半导体器件。
可以用冲模机等压模树脂层。在本发明中，例如，使用的冲模机可以是通过激光加工形成聚酰亚胺片或聚碳酸酯片进入预定模具的冲模机，或者是通过用金属例如镍电镀该模具作为底版(master)(原版)的冲模机。
用冲模机压模树脂层可以如图3所示的方式进行。调整冲模机8使得可以在光半导体元件2上方形成具有凹进或突出的树脂层。该装配件插入加热压板和另一个加热压板之间的间隙，然后加热/压制，从而可以热固化并模制步骤(1)中形成的树脂层。使用冲模机能够用具有均匀形状的树脂层一次包封许多光半导体元件。
加热/压制条件的实例包括优选在70-250℃加热，更优选100-200℃，压制压力优选为0.1-10MPa，更优选0.5-5MPa，该加热/压制时间优选为5秒-3分钟，更优选10秒-1分钟。
通过在光半导体元件上模制树脂层成为具有凹进或突出的形状，可以用产生的透镜改善光取出效率和光线调节。
本发明中优选在步骤(2)后进一步进行下列步骤(3)：
(3)在步骤(2)压模的树脂层上(以下简称″第一树脂层″)形成包含具有折射率低于构成第一树脂层的第一树脂的第二树脂的第二树脂层。
第二树脂没有特别限制，只要已经考虑其折射率进行选择。具体地，选择第二树脂使得它具有低于第一树脂的折射率。然而，考虑到增加在树脂层界面的光取出效率，第一树脂和第二树脂的比折射率(specific refractive index)差值{[(第一树脂折射率)-(第二树脂折射率)]/(第一树脂折射率)×100}优选为5-35％。
第二树脂的实例包括与上述列举作为第一树脂实例相同的树脂。然而，考虑到易于模制和低成本，优选为环氧树脂。
第一树脂层和第二树脂层可以适当地包含光散射填料，例如二氧化硅，以及添加剂例如荧光剂。
可以用适当地选自已知方法例如注入模制、铸模、压铸、浸泡和用分散器铸封的方法形成第二树脂层。
根据需要可以在第二树脂层的外侧上进一步形成一个或更多树脂层。在这种情况下，优选得到的多个树脂层按照树脂折射率向最外面树脂层降低的次序排列。
如本发明所述，通过用冲模机在光半导体元件上压模树脂层，可以容易并均匀地用树脂包封光半导体元件，可以得到具有均匀光取出效率的优质光半导体器件。因此，本发明制备的光半导体器件优选是包含基板和装配在其上的多个光半导体元件(特别是发光二极管阵列)的光半导体器件。本发明得到的发光二极管阵列的一个实例如图4所示。在图4中，在LED阵列9上的LED薄片10和导体7已经由使用冲模机压模的第一树脂层11包封，并且第一树脂层11已经用第二树脂层12包封。
实施例
将参考下列实施例更详细地解释本发明，但是不应解释为本发明局限于这些实施例。
在下列实施例中，全部合成反应是在氮气流中进行的。用FT/IR-230(由Nippon Bunko K.K.生产)进行IR分析。
聚碳化二亚胺制备实施例
向500mL装有搅拌器、滴液漏斗、回流冷凝器和温度计的四颈烧瓶引入29.89g(171.6mmol)甲苯基二异氰酸酯(异构体混合物，T-80，由Mitsui-TakedaChemical生产)、94.48g(377.52mmol)的4，4′-二苯基甲烷二异氰酸酯、64.92g(308.88mmol)的萘二异氰酸酯和184.59g甲苯。将这些成分混合在一起。
向其中加入8.71g(51.48mmol)1-萘基异氰酸酯和0.82g(4.29mmol)3-甲基-1-苯基-2-膦杂环戊烯2-氧化物。搅拌下将得到的混合物加热至100℃，并保持2小时。
由IR分析确定反应的进程。具体地，跟踪可归因于异氰酸酯的N-C-O伸缩振动(2,280cm-1)吸收量降低和可归因于碳二亚胺的N＝C＝N伸缩振动(2,140cm-1)吸收量增加。在用IR分析确定反应终点后，冷却反应混合物至室温。因此，得到聚碳化二亚胺溶液(用于对比实施例1)。在该聚碳化二亚胺中，100mol％二异氰酸酯残基是芳族二异氰酸酯残基。该聚碳化二亚胺由如上所述通式(1)代表，其中n为15-77。
随后，将聚碳化二亚胺溶液涂布至由用脱模剂(氟化硅氧烷)处理的聚(对苯二甲酸乙二醇酯)薄膜构成的隔离物(厚度，50μm)(由TorayIndustries，Inc生产)。在130℃加热该涂层1分钟，然后在150℃加热1分钟。此后，除去隔离物以得到临时固化的片状聚碳化二亚胺(厚度，50μm)。
在150℃的固化炉中固化得到的片状聚碳化二亚胺。用多波长Abbe’s折射计(DR-M4，由ATAGO生产)在589nm波长和25℃的温度下检测固化树脂折射率。发现固化树脂的折射率是1.748。
实施例1
将上述制备实施例得到的四片临时固化的片状聚碳化二亚胺堆叠起来以产生具有50mm×30mm尺寸和厚度200μm的片。层压该片至包含其上装配的GaN的具有7×18个LED薄片(2.5mm×2.2mm节距)、并且尺寸为50mm×30mm的基板。用层压机在500rpm的转速100℃的辊温度和0.5MPa的辊压力进行层压。由此，形成第一树脂层。
随后，将具有2.5×2.2mm距离的、4×4排列的直径为0.74mm和深度0.17mm的凹进处的冲模机(由聚酰亚胺制成)叠加至第一树脂层上，以在200℃和1.5MPa下压模第一树脂层1分钟。
然后叠加环氧树脂(NT-8006，由Nitto Denko生产；折射率，1.560)作为低折射率树脂层(第二树脂层)，并在120℃固化5小时。由此，得到表面式装配类型的发光二极管阵列。
高折射率树脂层的厚度以突出部分测量为175μm，总树脂厚度是300μm。因为高折射率树脂层的折射率是1.748，该树脂层和低折射率树脂层之间的折射率差值是0.188。
在得到的发光二极管阵列中，每个发光二极管发射的光线量(绝对能量)从前面测量平均值为0.13μW/cm2/nm，其标准偏差是0.025μW/cm2/nm。
对比实施例1
以和实施例1中相同的方法制造发光二极管阵列，除了滴加聚碳化二亚胺溶液到每个LED薄片上以形成第一树脂层。
在得到的发光二极管阵列中，由每个发光二极管放射的光线量从前面测量平均为0.08μW/cm2/nm，其标准偏差为0.019μW/cm2/nm。
结果说明因为实施例1没有如对比实施例1中进行的要求滴加预定量树脂到每个LED薄片上，实施例1的制备方法较简单，从而得到的二极管阵列具有从每个LED薄片的光取出效率的降低的不均匀性。
本发明制造的光半导体器件适用于例如个人电脑、手机等的面光源。
虽然已经参考其具体实施方案详细描述本发明，在不脱离其精神和范围的情况下可以作出的多种变化和改变对于本领域熟练技术人员来说是显而易见的。
本申请基于日本专利申请号2003-406400(2003年12月4日提交)，其内容此处引入作为参考。

Claims (5)

1.一种制造光半导体器件的方法，所述方法包括：
(1)在一个或更多个各自装配在导体上的光半导体元件上形成树脂层；和
(2)压模在步骤(1)中形成的树脂层。
2.权利要求1的方法，其中步骤(2)是用冲模机进行的。
3.权利要求1的方法，进一步包括，在步骤(2)后：
(3)在步骤(2)压模的树脂层上形成包含具有折射率低于构成压模树脂层树脂的第二种树脂的第二树脂层。
4.权利要求1的方法，其中在步骤(1)中形成的树脂层包含由通式(1)代表的聚碳化二亚胺：
(其中R代表二异氰酸酯残基，R1代表单异氰酸酯残基，n是1-100的整数)。
5.权利要求1的方法，其中光半导体器件是发光二极管阵列。
CNB2004101001845A 2003-12-04 2004-12-03 制造光半导体器件的方法 Expired - Fee Related CN100401538C (zh)

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