CN1137331A - 碳化硅与氮化镓间的缓冲结构及由此得到的半导体器件 - Google Patents

碳化硅与氮化镓间的缓冲结构及由此得到的半导体器件 Download PDF

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CN1137331A
CN1137331A CN94194481A CN94194481A CN1137331A CN 1137331 A CN1137331 A CN 1137331A CN 94194481 A CN94194481 A CN 94194481A CN 94194481 A CN94194481 A CN 94194481A CN 1137331 A CN1137331 A CN 1137331A
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约翰·A·埃德蒙得
伍拉迪米尔·德米特里夫
克尼斯·艾文
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Wolfspeed Inc
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Abstract

本发明公开了一种过渡晶体结构，用于在一个单晶碳化硅层和一个单晶氮化镓层之间提供优良的晶格匹配和热匹配。这种过渡晶体结构包括一个缓冲区，它由以下结构构成：一个第一氮化镓和氮化铝层，一个与所述第一层邻接的第二氮化镓和氮化铝层。第二层中氮化铝的克分子百分比与第一层中氮化铝的克分子百分比显著不同。一个单晶氮化镓层制作于所述第二氮化镓层上。最佳实施例中，缓冲区还包括一个位于一个碳化硅衬底上的氮化铝外延层。

Description

碳化硅与氮化镓间的缓冲结构 及由此得到的半导体器件
本发明涉及用氮化镓制作的半导体器件，尤其涉及一种使用碳化硅衬底制作氮化镓器件的方法。
本发明提供了一种氮化镓(GaN)结构和由此得到的器件。氮化镓是一种人们感兴趣的半导体化合物，因为它的直接带隙结构使得它具有高效率发射蓝光的潜力。
可见光谱中的蓝光部分和邻接的紫外线(UV)波长(大约500-350纳米；2.5-3.6eV)被认为是全部电磁波谱中的重要区域。虽然人们对制作发射蓝光、紫光或紫外线波长的半导体器件(或者对应的检测器件)感兴趣，但即使在最好情况下，尝试开发这种器件仍然困难，并且在大多数情况下是不成功的。目前，可获得许多发光二极管(“LED”，也称作“半导体光器件”)，这些发光二极管能发出从红外区到绿色波长(大约1000-500纳米；1.2-2.5eV)区域的光或电磁辐射。然而，正如熟悉彩色和彩色图像的产生的人都知道的那样，为了在合适的应用中提供全彩色图像和图形，也需要将蓝光作为可见光谱中的第三种基本颜色。
氮化镓(GaN)因为具有相对宽的直接带隙，因而是一种用于蓝色发光二极管的感兴趣的选择物。正如熟悉半导体材料与器件和半导体材料与光的相互作用的人们所知的那样，人眼所见到的光的颜色代表波长(或相应的频率)。反过来，波长和频率对应于一个给定的能量值。这样，可见光谱的特定颜色只能由可发生的需数量的能量跃迁的材料而产生。更简单地说，一种给定的半导体材料的发光二极管所能产生的颜色是这种材料带隙的一个直接函数。更宽的带隙允许更高的能量跃迁，从而又产生导致更高频率(更短波长)颜色的更高能量的光子(频率正比于能量跃迁且波长反比于频率)。
氮化镓有一个足够的带隙(3.4eV)，可发射可见光谱中的任何颜色，尤其是蓝光，但存在着某些固有的困难。使用氮化镓制作半导体发光二极管的一个困难是难于确定一种合适的衬底材料。正如熟悉这种器件的人所知，当电流(电子流)穿过半导体材料的p型层与n型层之间的结时，LED发射光。当电子和电子空位(空穴)复合时，将发射一种波长以某种方式与上述的材料带隙相对应的光子。通常所说的这种层必须具有单晶(外延)层特征。这就需要赖以生长的合适的衬底。因此，正如熟悉晶格生长的人们所知，衬底将对其上所发生的外延生长机制和质量产生显著影响。通常，为了发生一种所需的外延生长类型，衬底的晶格参数与外延层的晶格参数必须一致或者彼此相当接近。一个晶体层可以生长在一个非匹配衬底上，但将以非晶形式生长或者布满缺陷，这都将从根本上破坏它的可用的电特性或电光特性。同样道理，衬底材料及其晶向会显著影响氮化镓外延层的晶体结构。
由于氮化镓体衬底从未成功地制作过，因而对研究人员来说，为氮化镓确定一个合适的衬底是一项困难的工作。蓝宝石(Al2O3)可作为首选的衬底。迄今为止，虽然不尽完美，蓝宝石仍多少为氮化镓提供了一些有用的热匹配和晶格匹配。
蓝宝石有一个显著的缺点：缺乏导电性；即很难对蓝宝石进行掺杂来制作导电衬底。器件制造过程中，如果衬底缺乏导电性，那么所有与器件的电接触(LED通常有两个接触)，一定不能作在衬底上。结果是，制作于蓝宝石衬底上的氮化镓器件，一般至少需要放置两个电引线在它的同一表面上。
但常优先选用一种不同的LED结构，被称为“垂直”结构，这种结构要把LED制作于一个导电衬底上。在垂直LED中，电接触可以制作于器件的顶部和底部，而不需要在顶部制作两个电接触，或者在侧面上制作一个或全部两个电接触，对工程技术人员来说，与标准LED的顶部和底部接触安排相比，后者的配置通常是更困难的。
用于制作氮化镓，例如垂直GaN LED导电衬底的一种推荐可选材料是碳化硅(SiC)。碳化硅与氮化镓具有适宜的热匹配，即两种材料的线性膨胀系数很接近。碳化硅可进行导电性掺杂，且确实有能力作成蓝光发射器。例如可参见Edmond等人的美国专利号为4918497和5027168的专利文献，二者都已转让给了本发明的受让人。
碳化硅具有与氮化镓较好的，但又不完全相同的晶格匹配，然而，直接在SiC上制作高质量的GaN外延层是困难的。但是，与蓝宝石相比，SiC具有与GaN更为接近的晶格匹配(蓝宝石与GaN具有15％的晶格失配，SiC具有3.5％的晶格失配)。因而，将氮化镓置于碳化硅上的成功的垂直器件已作为商品出现。
Strite和Morkoc在“GaN，AlN，and InN：A Review”(J.Vac.Sci.Technol.B.，10(4)，July/August 1992，pp.1237-1266)中陈述了许多有关氮化镓的特性及其使用中存在的问题和试图解决这些问题的办法等方面的内容。
因此，本发明的一个目的是为制作这种垂直器件提供一种结构，在这种结构中，一个单晶碳化硅层和一个单晶氮化镓层之间具有优良的晶格匹配和热膨胀系数匹配。
为了达到这一目的，本发明使用了一种过渡晶体结构，这种结构可以在单晶碳化硅和单晶氮化镓层之间提供优良的晶格匹配和热匹配。这种过渡结构包括一个缓冲区，由以下两层构成：一个第一氮化镓和氮化铝(AlN)层和一个与第一层邻接的第二氮化镓和氮化铝层，其中，第二层中氮化铝的克分子百分比与第一层中氮化铝的克分子百分比显著不同。
在另一种实施方式中，本发明包括了含有缓冲层的器件原始结构，还有一种实施方式，本发明包括了含有新型缓冲层的各种垂直器件本身。
结合下述的说明及附图将会对本发明的上述及其他优点有更清楚的认识。
图1是依据本发明的一种过渡结构的原理剖视图；
图2是依据本发明的一种发光二极管的原理剖视图；
图3是另一种发光二极管的剖视原理图；
图4是包含本发明结构的发光二极管的第三种实施方式；
图5是依据本发明及所示组分给出的一种过渡晶体结构的一个二次离子质谱仪(SIMS)的深度分布；
图6是对本发明所述氮化镓外延层使用汞(Hg)接触的差分电容一电压测定法所测出的掺杂浓度与深度的关系曲线图；
图7至图9是不包含本发明的晶体表面的光学显微照片；
图10至图12是包含本发明结构的氮化镓晶体表面的光学显微照片。
本发明是用于在单晶碳化硅和一单晶氮化镓层之间提供优良晶格匹配和热(热膨胀系数)匹配的一种过渡晶体结构。图1示意性地给出了这种过渡结构的剖面图并概括地标以20。这种过渡结构的主要特征是一个用括号标示的缓冲区21。缓冲区由以下两层构成：一个第一氮化镓和氮化铝层22和一个与第一层22邻接的第二氮化镓和氮化铝层23。第二层23中氮化铝的克分子百分比与第一层22中氮化铝的克分子百分比显著不同。
由图1还可看出，过渡结构包括一个位于第二氮化镓和氮化铝层23上的单晶氮化镓层24、一个单晶碳化硅衬底25和一个碳化硅衬底上的氮化铝层26。
最佳实施例中，第一层22中氮化镓的百分比大于该层中氮化铝的克分子百分比。但在第二层23中，氮化铝的克分子百分比大于氮化镓的克分子百分比。虽然为了获得良好的效果，这并不是一种希望的结构，但这种结构的惊人成功之处在于：按通常分析可预料层中氮化镓的克分子百分比越高与纯氮化镓层的匹配越好。而在本发明中，直接与氮化镓外延层24相邻接的是具有较小氮化镓克分子百分比的层23。
图1所示的本结构的最佳实施例中，第一氮化镓和氮化铝层22中氮化铝的克分子百分比近似介于20％和50％之间，氮化铝的最佳克分子百分比约为30％。在第二层23中，氮化铝的克分子百分比近似介于60％和95％之间，最佳值约为90％。
正如本领域熟练人员所知及此处引用的一些参考文献中特别指出的那样，针对这一应用，衬底和任何缓冲层质量度量的一个指标是作出的所需氮化镓层的晶格质量，此处为层24。使用本发明的缓冲区21，形成的氮化镓层中的杂质浓度可低至约1×1016cm-3(参见图6)。
图1还表明在另一实施例中，本发明可以包含垂直器件原始结构，这一结构由一个碳化硅衬底25，衬底25上的缓冲区21和缓冲区上的一个单晶氮化镓层24构成。上面已指出，缓冲区21最好包括三层：碳化硅上的一个氮化铝层26；一个第一氮化镓和氮化铝层22，其中，氮化镓的克分子百分比大于氮化铝的克分子百分比；一个与第一层22邻接的第二氮化镓和氮化铝层23，其中，氮化铝的克分子百分比大于氮化镓的克分子百分比。
缓冲结构的优点以及使用这种缓冲结构制作的前述垂直器件的优点又可以从表示垂直发光二极管的不同实施例的图2、图3和图4中看出。图2示出了一个发光二极管30。二极管30包括一个单晶碳化硅衬底31，一个用括号标示的缓冲区32，一个具有一个第一导电类型的位于缓冲区32上的第一单晶氮化镓层33，一个位于第一层33上的第二单晶氮化镓层34，并具有与第一层相反的导电类型以便第一层33和第二层34之间形成一个p-n结。在衬底31和第二氮化镓层34上作出欧姆接触35和欧姆接触36。
在前一实施例中，过渡区32包括一个位于碳化硅衬底31上的氮化铝外延层37；一个第一氮化镓和氮化铝层40，其中，氮化镓的克分子百分比大于氮化铝的克分子百分比；一个与第一层邻接的第二氮化镓和氮化铝层41，其中，氮化铝的克分子百分比大于氮化镓的克分子百分比。
图2所示的实施例中，缓冲区32未被掺杂并作为一个绝缘层，因而所示的LED 30还包括短路接触42和短路接触43，用于提供一个衬底31和第一单晶氮化镓层33之间的电通路。
图3示出了总括标为45的依据本发明的又一个LED实施例。二极管45包括一个碳化硅衬底46，由平台标示的缓冲区47，一个第一氮化镓层48，一个具有与层48相反导电类型的第二氮化镓层49，以及一个位于氮化镓层48和49间的氮化镓合金层50。合金层50具有与第一氮化镓层同样的导电类型，使得p-n结形成于第二氮化镓层49和氮化镓合金层50之间。本领域将这种结构称为双异质结构，它用来帮助将整个器件中的电流约束在合金层区域以获得更高的效率。衬底46也和第一氮化镓层48具有相同的导电类型。
在最佳实施例中，合金层由铟镓氮(InGaN)组成，使得作成的器件峰值发射波长近似介于410纳米(nm)和470纳米之间。氮化镓也能高效率地发出其它颜色的光，包括绿光(例如470-560nm)。
图3也示出了一组短路接触51和52以及第二氮化镓层和碳化硅衬底46各自的欧姆接触53和54。
图4示出了依据本发明的又一个LED实施例，其中，缓冲区经过了导电性掺杂，因而不再使用短路接触，更准确地说，图4示出的一个二极管60带有一个碳化硅衬底61，用括号62标示出的缓冲结构，第一氮化镓层63，氮化镓合金层64和第二氮化镓层65。与氮化镓层65和碳化硅衬底61的欧姆接触分别示为欧姆接触66和67。与图3的实施例中一样，合金层64与第二氮化镓层65的导电性相反，于是形成了一个p-n结。但合金层64具有与第一GaN层63和SiC衬底61相同的导电性。
由于图4所示器件具有一个导电的缓冲结构，因而不需要图2和图3中给出的短路接触。
在本发明的一些具体例子当中，可厚至6微米的单晶氮化镓层被生长于6H碳化硅衬底上。X射线摆动曲线(θ-2θ扫描)的半宽是54弧秒(arc seconds)。首先可以观察到生长于SiC上光泵激的氮化镓层的受激发射。300K时受激发射的波长为376nm。
一般不是有意地将掺杂层掺杂至浓度约1016cm-3(Nd-Na)。对掺杂的n型层，净杂质浓度控制在1×1017cm-3和4×1018cm-3之间，对P型层，浓度Na-Nd控制在1×1017cm-3和2×1018cm-3之间。蓝色发光二极管使用这些层制作。在电发光光谱中可以观察到波长为375nm的边缘发射，并且在约410nm和470nm之间具有一个峰值。
由于本发明具有少数的晶体缺陷、导电的碳化硅衬底以及所得到的导电碳化硅上的优良氮化镓的组合，从而形成了一种质量极高的氮化镓器件。
碳化硅衬底可按照授予Carter等人的美国专利号4866005的专利文献中所记载的方式生长，而氮化镓、氮化镓合金和缓冲层都另外使用常规化学汽相淀积(CVD)工艺来生长。在CVD外延生长过程中，气流、压力和温度等各种参数虽然在不同系统之间可能并不相同，但对本领域普通技术人员而言，不需过多的试验也可使用其他系统以所述方式生长此处所提到的各种层。
图5是一个SIMS分布图，它进一步表明了本发明的结构特征。其中(从右向左看)，扫描显示了硅和碳(即SiC)的存在，接着是铝和氮(AlN)的氮化物，然后是镓、铝和氮(GaN和AlN)，最后是镓和氮(GaN)作为顶层。
图6是掺杂浓度与深度的关系曲线，从图中可以看出，本发明使用的碳化硅上生长的氮化镓外延层具有极低的本体杂质浓度(1E16)。
图7、图8和图9是在200倍和400倍之间的倍率拍摄的光学显微照片，如图所示，试图直接在碳化硅上生长氮化镓无法得到所期望的结果。
图10示出了一个氮化镓表面，如图所示，当使用比最优缓冲区稍差的缓冲区时，结果得到轻微的改善。
图11和图12也采用400倍率拍摄，从图中可以看出本发明的优点，特别是GaN晶体表面的相当光滑和无缺陷的晶体结构，与图7至图10相对照更能看出这一点。
通过附图和详细说明，已经公开了本发明的典型最佳实施例，虽然使用了具体的限定，但只用于一般描述性，而不是为了限定，下面的权利要求书将指出本发明的保护范围。

Claims (16)

1.一种过渡晶体结构，用于在单晶的碳化硅和一层单晶的氮化镓之间提供良好的晶格匹配和热匹配，所述过渡晶体结构包括：一个缓冲区，由以下两层构成：
一个第一氮化镓和氮化铝层；
一个与所述的第一层邻接的第二氮化镓和氮化铝层，其中，所述第二层中氮化铝的克分子百分比与所述第一层中氮化铝的克分子百分比显著不同；以及一个位于所述第二氮化镓和氮化铝层上的单晶氮化镓层。
2.根据权利要求1所述的结构，其中所述第一层中氮化镓的克分子百分比大于所述第一层中氮化铝的克分子百分比；以及
其中所述第二层中氮化铝的克分子百分比大于所述第二层中氮化镓的克分子百分比。
3.根据权利要求2所述的结构还包括一个单晶碳化硅衬底；以及
所述缓冲区还包括一个位于所述碳化硅衬底上的氮化铝外延层。
4.根据权利要求3所述的结构，其中，所述第一氮化镓和氮化铝层中氮化铝克分子百分比近似介于20％和50％之间。
5.根据权利要求3所述的结构，其中，所述第一氮化镓和氮化铝层中氮化铝克分子百分比约为30％。
6.根据权利要求3所述的结构，其中，所述第二氮化镓和氮化铝层中氮化铝克分子百分比近似介于60％和95％之间。
7.根据权利要求3所述的结构，其中，所述第二氮化镓和氮化铝层中氮化铝克分子百分比约为90％。
8.根据权利要求3所述的结构，其中，所述衬底选自由6H、4H或者3C多晶型的碳化硅构成的组中。
9.一种由权利要求1所述的过渡晶体结构制作的垂直发光二极管，它还包括：
一个用于所述缓冲区的单晶碳化硅衬底；
具有一个第一导电类型的所述缓冲区中的所述单晶氮化镓层；
一个位于所述单晶氮化镓层上的第二单晶氮化镓层，具有与所述第一导电类型相反的导电类型，所述单晶氮化镓层之间构成一个p-n结；以及
与所述衬底和所述第二氮化镓层的欧姆接触。
10.根据权利要求9所述的发光二极管，其中，所述缓冲区还包括一个位于所述碳化硅衬底上的氮化铝外延层。
11.根据权利要求9所述的发光二极管，其中，所述缓冲区进行了导电性掺杂。
12.根据权利要求9所述的发光二极管，其中，所述缓冲区是一个绝缘层，并且所述二极管还包括所述衬底和所述第一单晶氮化镓层间的短路接触。
13.根据权利要求9所述的发光二极管，它还包括一个位于所述第一和第二氮化镓层间的一个氮化镓合金外延层。
14.根据权利要求13所述的发光二极管，其中，所述氮化镓合金由铟镓氮组成。
15.根据权利要求9所述的发光二极管，峰值发射波长近似位于410纳米和470纳米之间。
16.根据权利要求9所述的发光二极管，峰值发射波长近似位于470纳米和560纳米之间。
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