CN1092404C - 制造发光效率增加了的发光二极管的方法 - Google Patents
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Abstract
公开了一种由碳化硅制造发光效率增加了的发光二极管的方法,该方法包括在碳化硅一部分的一个方向上导向一激光束,和激光足以使得它撞击的碳化硅汽化,籍此形成碳化硅部分的切割线;然后,干法刻蚀碳化硅部分以除去激光切割碳化硅部分时产生的副产品。也公开了由此得到的晶片和二极管的结构。
Description
本发明涉及发光二极管的制造方法,更具体地说,涉及一种利用激光切割碳化硅衬底晶片上由碳化硅和氮化镓制成的各个二极管的一种方法。
术语“激光”是“受激发射光放大”的缩写。激光在可见光谱或其它电磁光谱部分产生相干单色光束。由于具有单一的波长和频率,激光束具有极高的能量。由于能量高,在很多工业应用中,激光束用于难加工材料的切割或者可能或必须按严格控制的图案切割或划线的物体。
由于半导体器件的生产需要在很小的范围内有相对准确的容差和图案,因此在生产过程中已尝试用激光对半导体材料形成图案,切割,或别的方式处理。然而,至今为止这种努力取得成果很小。主要问题有两个:第一,激光的能量损坏制造中的器件。第二,激光和被处理的材料尤其是被切割的材料之间的反应会产生副产品,这些副产品留在被制造结构的表面,以后必须除去这些副产品。假如没有可用的或满足要求的除去技术,这些副产品就会使由此形成的器件性能下降或甚至损坏。
发光二极管是一种在p-n结上加电势差时发射包括可见光的半导体器件。有多种方法制造发光二极管和一些关联的结构,但这些已是众所周知的,在此所要描述的发明适用于其中的大部分或全部。因此,以后这些方法除非必需用于解释本发明外将不会加以详细讨论。作为例子,Sze的<半导体器件物理>第二版(1981)第12-14章完整地解释了各种光量子器件,包括LED。
然而熟悉半导体材料和由这些材料制成的器件的人都知道,发光二极管能产生的光的颜色通常是由半导体材料的性质,最主要是由带隙决定的。带隙表示了各个原子价带和导带之间的能量跃迁。根据量子力学原理,价带和导带之间的跃迁受限于精确的带隙或受限于与同样是表征材料以及其掺杂剂和杂质特性的带隙有关的确定的中间态。简言之,材料的带隙限制了基于带隙跃迁所发射的光的颜色。
熟悉半导体材料、光以及它们之间相互作用的人都知道,跃迁发射光子的能量与它的频率有关,E=hυ,这里“E”是光子能量,“h”是普朗克常数,“υ”是频率。这样,通常以电子伏特“eV”表示的带隙能量宽度把它能产生的光子限制在一定的能量从而把光子限制在一定的频率。
其次,光子的频率和波长成反比关系,λ=c/υ,这里“c”是光速,“λ”是产生的波长。
由于这些限制,带隙小的材料只能产生波长长,频率低的光子,这些光子在可见光谱的红(770-622nm)、橙(622-597nm)、黄(597-577nm)波段。波长大约在525纳米的光具有更纯的绿色,因此要产生这种光子,半导体材料的带隙要在2.36eV左右。类似,发射较纯蓝色光的波长在470纳米量级,这样需要带隙为2.64eV或更大的半导体材料。当然,给特定的颜色或颜色的边界指定特定的波长在某种程度上是任意的,应该把这看成是一种说明性的而不能看成是绝对的。
仅有少数半导体材料具有合适的带隙能产生这种光。两种可选的材料是碳化硅(α-SiC的带隙是2.86eV)和氮化镓(3.36eV)。
人们对碳化硅的理论特性的认识已经有一些年月,但只是在最近十年体晶生长、外延生长、器件制造等技术有了长足的发展的情况下才由碳化硅生产出能工作的器件,这些发展大部分是由本发明的共同受让人提出的。碳化硅有极高的熔点(大约2830℃),物理硬度极大(通常用作研磨剂),具有超过150种晶体形状,它们中的大部分是由相对很小的热力学差别来划分的。
氮化镓以及和它相关的第三族氮化物(即元素周期表中的第三族)是其它可选材料,但是,直到今天还没有找到令人满意的能用作适当器件衬底的氮化镓或其它第三族氮化物的大体积单晶的生长方法。因此,氮化镓器件一般是在蓝宝石(Al2O3)上制成,而最近在碳化硅上制成。
迄今为止制造发射蓝光谱区光的LED的最成功的努力是使用“台式”(mesa)结构。“台式”一词通常指器件的衬底横截面积比有源区面积大的结构,该有源区一般在衬底上由两个或多个外延层形成。当在单个晶片上制作多个器件时,常规的台式结构在有源区之间提供了物理隔离,这是目前批量生产这种器件的最常用的方法。台阶之间的间距提供了器件之间机械隔离的空间。一般地,使用一些能工作在这样硬材料上的工具完成机械隔离,例如,钻石锯或最近提出的共同未决的转让申请序列号为08/290,458放电机器(“EDM”),该申请于1994年8月15日提出。一般说,EDM用于把大体积单晶分割成衬底晶片,钻石锯用于从晶片切割已形成于晶片上的各个芯片。
然而,在某种环境下,台式结构限制了制造工艺和成品器件的效率。由于倾向于需要相当大的晶片面积百分比来形成各个台阶之间的隔离,台式结构降低了制造效率。这样,在能减少台阶隔离面积的条件下,相应地有源器件结构所占的晶片面积百分比就会增加。然而迄今为止,钻石锯在能减少台阶隔离面积方面仍存在限制因素。
钻石锯切割也易于在各个LED芯片上产生相当的表面光洁度,这些光滑表面易于激励LED内部光的反射而不是光的外部发射。从这一方面考虑,熟悉器件的人都明白,光是从器件的结发射的,为了能成为可见光,它必须传到和离开器件的边缘。这样,由于光在内部反射,减少了所得到的器件的外部量子效应。
共同未决的共同转让申请序列号08/081,688提出一种增加发光效率的技术,该申请于1993年6月23日提出,它描述了一种利用光学方法增加这种二极管发光效率的扩展外延层。
然而,当试图使用激光切割碳化硅或氮化镓等材料时发现激光反应产生预期的和料想不到的问题。预期的问题包括不希望的副产品和对器件形成的损坏。料想不到的问题来自碳化硅所特有的缺点。具体地说,在其它的材料中,对于器件,尤其是对于其晶体结构的损坏能改变该材料产生的色强,但并不改变颜色本身。相反,若在碳化硅上产生一定类型的损伤,尤其是点缺陷,它们将易于形成复合中心,这些复合中心把二极管发射的可见光从蓝色变成绿色。这样,尽管希望以可控方式能产生碳化硅的绿色LED(例如见共同未决申请序列号08/290020,该申请于1994年8月12日提交),但当希望发射蓝光的LED时,产生绿LED是很不利的。
关于一般激光切割,尤其是碳化硅及氮化镓的激光切割的问题,迄今为止没有满意的解决方案。
因此,本发明的一个目的是提供一种用碳化硅和氮化镓制造发光二极管的方法。该方法增加了量子效率并且通过去掉了台式结构及产生台式结构所必需的技术从而能以更高的生产率来生产。
本发明通过用碳化硅制造增加了发光效率的发光二极管来达到这个目的。在第一方面,本方法包括在碳化硅的一部分的一个表面上对一激光束的导向,在此部分上激光足以使得它撞击的碳化硅汽化,籍此形成该碳化硅部分的切割。然后,干法刻蚀碳化硅以除去激光切割碳化硅部分时产生的副产品。
在另一方面,本发明包括一高效的发光二极管,该二极管包括碳化硅衬底和在衬底上形成p-n结的至少两个外延层。外延层的侧边缘和衬底的侧壁重合。作成欧姆接触以在结的两端加电势,形成的结的特征在于:当在p-n结的两端加一电势差时,结产生可见光谱蓝光区的光发射。
在又一个方面,本发明包括一高效的发光二极管,该二极管的重合的外延层侧边缘具有网状表面。
在又一方面,本发明包括碳化硅发光二极管前体结构,该结构包括一由在其上有形成p-n结于其间的至少两个外延层的碳化硅衬底组成的晶片,以及在晶片里的多个沟槽。
通过以下的详细描述和附图,前述的和其它的目标以及本发明的优越性将变得更明显。
图1是根据本发明的一个发光二极管的透视图;
图2是根据本发明的一个二极管前体结构的晶片的透视图;
图3是图2中沿3-3的横截面视图,该图说明了衬底、外延层、和沟槽。
本发明是一种利用碳化硅制造增加发光效率的发光二极管的方法。在第一方面,本方法包括在碳化硅的一部分的一个表面上一激光束的导向,在此部分激光足以使得它撞击的碳化硅汽化,籍此形成碳化硅部分的切割。然后,干法刻蚀碳化硅以除去激光切割碳化硅部分时产生的副产品。
更具体地说,已经发现激光在下述的激光导向步骤工作最有效,该步骤包括对能量等于或大于被切割的碳化硅带隙的波长的光导向。尽管申请人并不希望受到任何特殊理论的限制,但看起来对应于能量小于碳化硅带隙的波长的激光在切割和汽化碳化硅时效率很低,这也许是因为吸收度的原因,因此需要极高的功率,而这就趋于弊大于利。
这样,激光导向步骤包括在6H碳化硅部分引导波长为433纳米或更短的光,或在3C碳化硅部分引导波长为539纳米或更短的光,该碳化硅的带隙为2.3eV。类似,对带隙为3.26eV的4H碳化硅,波长应为380纳米或更短,对带隙为2.99eV的15R碳化硅,波长应为415纳米或更短。
对氮化镓和它的3.36eV带隙,最好是波长为369纳米或更短的光,可以是适当的方法步骤,其与上述的方法步骤或者一致或者类似。
在本发明的优选实施方式中,激光导向步骤包括波长为355纳米或266纳米的激光导向。熟悉激光器件的人将意识到355纳米是三倍频的钕钇铝金刚砂(“Nd:YAG”)激光,而266纳米代表同样激光的四倍频率。该激光应具有至少250毫瓦的输出功率,而最好大约为800毫瓦。对直径大约为0.4mil(1000mil=1英寸)的一束光,在切割材料上能产生大约77至247千瓦/平方厘米的功率密度。
一些晶体材料的特性和两倍、三倍、四倍或其它倍乘激光频率的技术已被很好地了解,在此就不另外加以详细描述。然而,作为并不是限定性的例子,美国专利号3,949,323;4,884,277;和5,144,630说明了这些特性和技术的一部分。
如前所述,迄今为止妨碍半导体材料的激光切割得到广泛应用的一个缺点是它产生的熔渣材料,该材料保留在切割半导体材料的表面,特别是布满器件前体的晶片。这些副产品最后或多或少地损坏或毁坏晶片上的器件前体。
迄今为止,还没有获得满意的除去熔渣的技术。然而,在本发明中,已经发现干法刻蚀步骤(避免“湿”--即,溶液--化学的步骤)将除去激光切割碳化硅部分时产生的副产品。特别是,干法刻蚀可以除去切割过程中形成的点缺陷,该点缺陷将降低碳化硅二极管产生的光颜色。在优选实施方式中,干法刻蚀碳化硅部分步骤包括用含氟的气体如三氟化氮、氮氧化物、三氟化氨、氧气、六氟化硫、四氟化碳、或它们的混合气体刻蚀步骤。干法刻蚀碳化硅的示例技术在美国专利号4,865,685和4,981,551中阐明,该专利在这里完全作为参考。当干法刻蚀氮化镓时,最好选用含氯气体,如Cl2(一般和H2混合)、BCl3、和SiCl4。
如刚才所述,本发明可应用于切割碳化硅的任何部分,但是最好包括在单晶碳化硅衬底上的激光导向,在该衬底上至少有两个碳化硅外延层,这些外延层之间形成发光p-n结。本方法最好包括在晶片的一个表面引导激光束,该晶片由大量邻接的碳化硅发光二极管前体组成,以一定的图案沿着晶片表面引导激光束从而在邻接的发光二极管前体之间形成大量的沟槽。然后,如刚才所述干法刻蚀晶片以除去激光束切割晶片时产生的副产品。不消说激光可以从晶片的前端或后端切割晶片,前端是器件前体部分而后端是衬底部分。
本发明还可以包括沿着切割线将被切割的碳化硅部分分离,从而形成两个碳化硅部分。当切割一个晶片时,本方法还包括干法刻蚀晶片步骤之后的沿沟槽分离晶片步骤。这种分离形成了所需要的各个LED或LED组。现今,分离可以直接用商用分离机器完成。例如,加利福尼亚州圣罗沙Dynatex的DX2+断晶片机。当然,这种商用器件是示例性而不是限定本发明的技术。
由于本发明方法的有效性,它还可以包括在晶片上导向激光的步骤之前在晶片上的二极管前体上加金属接触的步骤。和台式技术相比这提供了更有效的平面工艺的可能性和优势。
在本方法的优选实施方式中,导向激光步骤还包括Q开关激光,由此构成激光产生的沟槽内壁结构。关于激光技术的其它方面,Q开关在激光技术领域已得到很好的理解,将在其它场合进行详细讨论。优选的开关频率在大约1KHz的量级,最好大约为3KHz。这种开关频率为优选的激光频率提供了最大的功率输出。
在另一方面,本发明包括高效的发光二极管。这种二极管在图1中10所示。在这种实施方式中,二极管包括碳化硅衬底11和图1中层12和13所示的至少两个外延层。不消说,存在包括更进一步或另外的用于各种目的的外延层的器件结构。这样,这里关于两层的说明和讨论是用于解释本发明的而不仅是限定性的。
如图1所示,12和13外延层的边缘和11衬底的侧壁重合。换句话说,本发明以非台式结构制造二极管。如前所述,台式结构降低了从任意给定晶片表面积能生产的有源器件数目。与此相反,通过晶片前体结构本发明大大提高了生产潜力。
在二极管10上加上欧姆接触14和15,尽管图1显示出背部接触14完全覆盖了二极管的底部,在优选实施方式中该接触不完全覆盖底面以防止寄生光吸收。顶部接触15仅覆盖表面的小部分。
当两端加上电势时p-n结产生可见光谱的蓝光区发射。蓝光碳化硅发光二极管的本质和结构在美国专利号4,918,497和5,027,168里得到清楚的说明,这些专利和本发明一起共同转让,在这里完全作为参考。具体地说,在蓝光发光二极管中,16所示的结产生约450和490纳米的光发射。在本发明的优选实施方式中,外延层可以包括和所引用的参考专利中所述结构一致的碳化硅或氮化镓。
当把本发明引入绿光发光二极管时(例如、“用碳化硅制成的真绿光发光二极管”序列号08/290,020,1994年8月12日申请,在这里完全作为参考),该结将产生大约520至540纳米之间的光发射。对氮化镓二极管,光发射大约在350至550纳米之间。
在本方法的优选实施方式中,外延层的侧壁以及,如果需要的话,衬底11的侧壁,是网状结构。即,它们具有带有图案的表面。在本发明前面所指的“Q开关”方法步骤可以产生这种类似描述的网状边缘,关于这种边缘的最类似的描述(尽管肯定不是一个限定性的描述)是该网状边通过一系列的逐个的钻孔以形成纵向切割线而形成。这种切割边缘更类似于柱面钻孔边缘而不是镜像表面。如背景部分所述,钻石锯产生的光滑表面和其它机械切割技术易于激励光的内部反射而不是外部发射。这样,本发明的激光切割技术在所需要的边缘产生网状结构增加了形成器件的效率。
在又一方面,本发明包括图2中以20表示的晶片所示的碳化硅发光二极管前体结构。图3是一放大了的晶片20的横截面视图,该视图显示了晶片包括一在其上形成p-n结24的至少两个外延层22和23的碳化硅衬底21。一个示例性的晶片包括具有网状结构侧壁的多个沟槽25。更进一步,在一示例性的实施方式中,在8.5mil厚度的晶片中沟槽的高宽比为6∶1,该高宽比大于钻石锯在这样薄的晶片上所能完成的高宽比。大的高宽比提供了很多优点。包括更大的暴露侧壁,结果是增加了效率,也增加了从任意给定的晶片面积形成更多器件的能力。
图3不一定是按比例示出的,但是在本发明的典型实施方式中,晶片的厚度大约为8.5mil,沟槽的宽大约为1mil,深大约为6mil。前体结构可以更进一步包括图3所示的金属化背部接触26和顶部欧姆接触27。
如前述的实施方式,外延层可以包括碳化硅或氮化镓。
尽管,在此使用“氮化镓”这个词语,应该明白本发明适用于各种III族元素的氮化物,例如共同未决申请序列号08/309,251的于1994年9月20日申请的“具有III族氮化物有源区和长寿命的垂直几何发光二极管”和序列号为08/307,173的也于1994年9月20申请的“具有III族氮化物有源区的低应变激光结构”中描述的III族氮化物。这些专利完全作为在这里描述的技术的参考,以上描述的技术将适用于这种器件的制造,也适用于完全由碳化硅制成的器件的制造。类似,本发明的方法步骤可以应用于所有器件而不仅局限于在此讨论的示范的LED。
再有,一些生长碳化硅体单晶和碳化硅外延层的技术在以前的共同转让的或仅许可于本应用的受让人的专利中描述。这些示例性的专利包括体单晶生长(No.4,866,005)、外延生长(No.4912,064)、碳化硅的干法刻蚀(Nos.4865,685和4,981,551)、和发光二极管的特殊结构(Nos.4918,497;5,027,168;和5,338,944)的专利。
说明书中已提出了本发明的优选的和示例性的实施方式,同样是说明性的,并不局限于此,在以下的权利要求中提出本发明的范围。
Claims (13)
1.一种由碳化硅制造发光效率增加了的发光二极管的方法,该方法包括:
在碳化硅的一部分的一个方向上导向一激光束以在其撞击的碳化硅中形成切割线;以及
此后除去激光切割碳化硅部分时产生的副产品;
其特征在于:
激光足以使得它撞击的碳化硅汽化;以及
除去副产品的步骤包括干法刻蚀碳化硅。
2.根据权利要求1的方法,其中激光导向步骤包括对具有其能量等于或大于被切割的碳化硅带隙的波长的激光的导向。
3.根据权利要求1的方法,其中干法刻蚀碳化硅部分的步骤包括使用含氟气体进行反应离子刻蚀。
4.根据权利要求1的方法,其中在碳化硅部分激光导向步骤包括在其上形成p-n结的至少两个碳化硅外延层的单晶碳化硅衬底上的激光的导向。
5.根据权利要求1的方法,还包括沿着切割线分离被切割碳化硅部分从而形成两个碳化硅部分。
6.根据权利要求1的方法,其中导向激光束步骤包括:
在一晶片的一个表面导向激光束,该晶片由多个邻接的碳化硅发光二极管前体组成,激光足以使得它撞击的碳化硅汽化,籍此形成碳化硅部分的切割线;
以一定的图案沿着晶片表面导向激光束从而在邻接的发光二极管前体之间形成多个沟槽;以及
干法刻蚀晶片以除去激光束切割晶片时产生的副产品。
7.根据权利要求6的方法,其中在一晶片的一个表面导向激光束步骤包括在晶片背部衬底表面导向激光束。
8.根据权利要求6的方法,其中在一晶片的一个表面导向激光束步骤包括在晶片前部器件表面导向激光束。
9.根据权利要求6的方法,还包括在晶片上导向激光步骤之前在晶片上的二极管前体加金属接触的步骤。
10.一种由氮化镓制造发光效率增加了的发光二极管的方法,该方法包括:
在一晶片的一个表面上导向激光束,该晶片由多个邻接的氮化镓发光二极管前体组成,导向激光束在所撞击氮化镓中形成切割线;
以一定的图案沿着晶片表面导向激光束从而在邻接的发光二极管前体之间形成多个沟槽;以及
然后干法刻蚀晶片以除去激光束切割晶片时产生的副产品;
其特征在于:
激光足以使得它撞击的氮化镓汽化;以及
除去副产品的步骤包括干法刻蚀晶片。
11.根据权利要求10的方法,还包括在干法刻蚀晶片步骤之后沿沟槽分离晶片。
12.根据权利要求10的方法,还包括在晶片上导向激光步骤之前在晶片上的二极管前体加金属接触的步骤。
13.根据权利要求10的方法,其中激光导向步骤包括对具有其能量等于或大于被切割的氮化镓带隙的波长的激光的导向。
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JP2780744B2 (ja) * | 1992-11-06 | 1998-07-30 | 信越半導体株式会社 | GaAlAs発光素子の製造方法 |
DE4305296C3 (de) * | 1993-02-20 | 1999-07-15 | Vishay Semiconductor Gmbh | Verfahren zum Herstellen einer strahlungsemittierenden Diode |
US5432808A (en) * | 1993-03-15 | 1995-07-11 | Kabushiki Kaisha Toshiba | Compound semicondutor light-emitting device |
US5387776A (en) * | 1993-05-11 | 1995-02-07 | General Electric Company | Method of separation of pieces from super hard material by partial laser cut and pressure cleavage |
US5393993A (en) * | 1993-12-13 | 1995-02-28 | Cree Research, Inc. | Buffer structure between silicon carbide and gallium nitride and resulting semiconductor devices |
-
1994
- 1994-10-07 US US08/319,803 patent/US5631190A/en not_active Expired - Lifetime
-
1995
- 1995-10-02 KR KR1019970702278A patent/KR100369751B1/ko not_active IP Right Cessation
- 1995-10-02 AT AT95935696T patent/ATE174724T1/de not_active IP Right Cessation
- 1995-10-02 AU AU37612/95A patent/AU3761295A/en not_active Abandoned
- 1995-10-02 WO PCT/US1995/012622 patent/WO1996011504A1/en active IP Right Grant
- 1995-10-02 CN CN95196058A patent/CN1092404C/zh not_active Expired - Lifetime
- 1995-10-02 EP EP95935696A patent/EP0786150B1/en not_active Expired - Lifetime
- 1995-10-02 JP JP8512632A patent/JPH11505666A/ja active Pending
- 1995-10-02 DE DE69506734T patent/DE69506734T2/de not_active Expired - Lifetime
-
1997
- 1997-05-20 US US08/859,675 patent/US5912477A/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
EP0786150B1 (en) | 1998-12-16 |
AU3761295A (en) | 1996-05-02 |
US5631190A (en) | 1997-05-20 |
US5912477A (en) | 1999-06-15 |
JPH11505666A (ja) | 1999-05-21 |
DE69506734D1 (de) | 1999-01-28 |
KR100369751B1 (ko) | 2003-04-11 |
KR970706617A (ko) | 1997-11-03 |
CN1163014A (zh) | 1997-10-22 |
ATE174724T1 (de) | 1999-01-15 |
WO1996011504A1 (en) | 1996-04-18 |
DE69506734T2 (de) | 1999-07-15 |
EP0786150A1 (en) | 1997-07-30 |
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