CN105428481B - 氮化物底层及其制作方法 - Google Patents

氮化物底层及其制作方法 Download PDF

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CN105428481B
CN105428481B CN201510921684.3A CN201510921684A CN105428481B CN 105428481 B CN105428481 B CN 105428481B CN 201510921684 A CN201510921684 A CN 201510921684A CN 105428481 B CN105428481 B CN 105428481B
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aln
layers
nitride
cushions
substrate
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CN105428481A (zh
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林文禹
陈圣昌
钟志白
徐宸科
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Quanzhou Sanan Semiconductor Technology Co Ltd
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Xiamen Sanan Optoelectronics Technology Co Ltd
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Abstract

本发明提供了一种氮化物底层结构及其制作方法，采用具有一开放式条状孔洞的溅射式AlN层作为缓冲层，从而在氮化物薄膜生长于该缓冲层之前提供应力释放的路径，可以提升氮化物底层结构的晶格质量并且改善表面裂纹。本发明同时提供了一种采用该氮化物底层结构的发光二极管结构。

Description

氮化物底层及其制作方法
技术领域
本发明涉及半导体制备领域，具体为一种可以改善表面裂纹的氮化物底层结构及其制作方法。
背景技术
发展深紫外发光二极管，生长高晶格质量且无裂纹的 AlN 材料是首要克服的关键技术，目前在蓝宝石衬底上使用 V/III 渐变法 (V/III multi-growth modemodification)、脉冲式 NH3法 (NH3 pulsed flow method)、两步法 (two-step method)、三步法 (three-step method)以及高低温交替法( low and high temperaturealternation) 等皆可以得到一定程度的晶格质量且近乎无裂纹的 AlN 薄膜。
越来越多的试验结果证实，在蓝宝石衬底上使用溅射式(Sputter) AlN 材料作为进一步生长氮化物薄膜的缓冲层，可以得到高品质的底层材料，并且对于发光二极管的光输出功率有较大的提升。例如，在蓝宝石衬底上溅射AlN层作为缓冲层，再采用MOCVD生长AlN薄膜于该溅射式AlN缓冲层上，可以大幅降低XRD (102) 衍射半波宽。然而，溅射式 AlN缓冲层表面非常平整，不会形成不连续的薄膜表面，无法提供应力释放的路径，导致表面裂纹严重。
发明内容
为了解决氮化物薄膜生长在溅射式AlN缓冲层上会出现表面裂纹严重的问题，本发明提供了一种氮化物底层结构，采用具有一开放式条状孔洞的溅射式AlN层作为缓冲层，从而在氮化物薄膜生长于该缓冲层之前提供应力释放的路径，可以提升氮化物底层结构的晶格质量并且改善表面裂纹。
本发明的技术方案为：氮化物底层结构，从下至上依次包括：衬底，溅射式AlN缓冲层，MOCVD 生长的AlxIn1-x-yGayN层（0≤x≤1，0≤y≤1），其中所述溅射式AlN缓冲层具有平坦的表面，其内部具有条状孔洞，用以提供应力释放的路径。
优选地，所述孔洞与所述AlN缓冲层的侧壁连通。
优选地，所述溅射式AlN缓冲层的厚度为1 μm以下。
优选地，所述孔洞的深度为0.1~05μm，宽度为100~500μm。
本发明同时提供一种氮化物底层的制作方法，包括步骤：1）提供衬底，在其表面上形成条状材料层；2）在所述条状材料层及衬底上溅镀AlN材料层，形成平坦的薄膜；3）从所述衬底端以激光束来回扫描，使所述条状材料层分解，从而形成表面平坦、内部具有条状孔洞的溅射式AlN缓冲层；4）采用MOCVD在所述溅射式AlN缓冲层上形成AlxIn1-x-yGayN层（0≤x≤1，0≤y≤1）；其中，所述条状材料层的能隙E1、激光束的能隙E2和AlN缓冲层的能隙E3的关系为：E1＜E2＜E3。
进一步地，所述步骤3）中还包括：湿法蚀刻去除所述AlN材料层分解后产生的残余物，形成与所述AlN缓冲层的侧壁连通的条状孔洞。
优选地，所述条状材料层选用氮化镓。
优选地，所述步骤3）中选用波长为248nm的激光束。
本发明还提供了另一种氮化物底层的制作方法，包括步骤：1）提供衬底，在其表面上溅镀AlN材料层，形成平坦的薄膜；2）从所述衬底端以激光束来回扫描，使所述AlN材料层内部部分分解，从而形成表面平坦、内部具有条状孔洞的溅射式AlN缓冲层；3）采用MOCVD在所述溅射式AlN缓冲层上形成AlxIn1-x-yGayN层（0≤x≤1，0≤y≤1）；其中，所述激光束的能隙E2和AlN缓冲层的能隙E3的关系为： E2＞E3。
进一步地，所述步骤2）中还包括：湿法蚀刻去除所述AlN材料层分解后产生的残余物，形成与所述AlN缓冲层的侧壁连通的条状孔洞。
优选地，所述步骤2）中选用波长为193nm的激光束。
前述氮化物底层结构可应用于发光二极管，特别是深紫外发光二极管。采用前述制作方法可以获得高晶格质量且无裂纹的 AlN 底层，然后再进行各外延材料层的生长，从而获得高发光效率的发光二极管。
本发明的其它特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本发明而了解。本发明的目的和其他优点可通过在说明书、权利要求书以及附图中所特别指出的结构来实现和获得。
附图说明
附图用来提供对本发明的进一步理解，并且构成说明书的一部分，与本发明的实施例一起用于解释本发明，并不构成对本发明的限制。此外，附图数据是描述概要，不是按比例绘制。
图1为根据本发明实施的一种氮化物底层结构示意图。
图2为根据本发明实施的一种氮化物发光二极管示意图。
图3为根据本发明实施的一种制作氮化物底层的流程图。
图4~8为根据图3所示流程图制作氮化物底层的各个过程结构示意图。
图9为根据本发明实施的另一种制作氮化物底层的流程图。
具体实施方式
在本发明被详细描述之前，应当注意在以下的说明内容中，类似的组件是以相同的编号来表示。
参看图1，本发明氮化物底层100的一个较佳实施例，包含一衬底110、一采用PVD生长在该衬底110上的溅射式AlN缓冲层120，一采用MOCVD生长的AlxIn1-x-yGayN层140（0≤x≤1，0≤y≤1）。其中，衬底110衬底1的选取包括但不限于蓝宝石、氮化铝、氮化镓、硅、碳化硅，其表面结构为平面结构，在本实施例中，选用蓝宝石平片衬底。溅射式AlN缓冲层120具有平坦的上表面120a，内部具有条状孔洞结构130，该条状孔洞130与溅射式AlN缓冲层120的侧壁连通，以释放应力。在本实施例之氮化物底层结构中，保留溅射式AlN缓冲层能够提升后续诸如AlN等氮化物薄膜晶格质量的优点，并导入开放式条状孔洞层以达到应力释放，解决氮化物薄膜表面裂纹问题。
图2显示了一种生长于上述氮化物底层结构100上的LED结构，至少还包括n型半导体层200、有源层300和p型半导体层400。一般，AlN材料层可允许实现低至约200 纳米波长的光发射，特别适用于进行深紫外LED生长。在该实施例中，氮化物底层结构100的AlxIn1-x- yGayN层140选用AlN材料，n型半导体层200、有源层300和p型半导体层400形成于AlN底层100上，采用AlGaN材料，可实现波长为210~365nm的高品质紫外LED。
图3显示了根据本发明实施的一种制作氮化物底层的流程图，其包括步骤S110~140，下面结合图4~8进行说明。
参看图4，在蓝宝石平片衬底110上形成条状材料层150，该条状材料层选用低能隙材料。在本实施例中选用GaN材料，先采用MOCVD方法或PVD方法在蓝宝石平片衬底110上沉积一GaN材料层，然后再进行图案化处理形成条状结构。
参看图5，在该条状材料层150和衬底110的表面溅镀AlN材料层，形成一平坦的薄膜120。
参看图6和7，使用激光束由蓝宝石衬底110一端入射，回来扫描将条状材料层150分解，并湿法蚀刻去除该条状材料层分解后的残余物，得到一个具有开放式条状孔洞层130的溅射式AlN缓冲层120。在本实施例中，选用波长为248nm、光斑直径为0.3mm的激光束进行扫描，条状材料层150的能隙E1（能隙为3.4）、激光束的能隙E2（能隙为5）和AlN缓冲层120的能隙E3（能隙为6.1）的关系为：E1＜E2＜E3，故条状材料层150可以被较快分解，而保持溅射式AlN缓冲层140完整，再采用湿法蚀刻去除该条状GaN材料层经激光分解后产生的残余Ga金属，从而获得表面平坦、内部具有的溅射式AlN缓冲层120，该条状孔洞的深度为0.1~0.5μm，宽度约为300μm。
参看图8，采用MOCVD 在射式AlN缓冲层120生长AlN层130，藉由嵌入的开放式条状孔洞可达良好的应力释放。
一般，在氮化物外延薄膜中导入孔洞层，需采用图型化衬底 (PSS) 或二次外延。在AlN底层结构中，由于AlN 外延侧向生长速率很低，形成孔洞后继续将薄膜长平，须生长厚度为5~10μm的AlN外延层。在本实施例中，首先在衬底110与溅射式AlN缓冲层120之间形成条状低能隙材料层150，然后采用激光从衬底一侧进行扫描，使该能隙材料层150分解，保留了溅射式AlN缓冲层表面非常平整的特性，同时在内部形成了用于释放应力的开放式孔洞层，后续可直接采用MOCVD在该溅射式AlN缓冲层上形成无裂纹的AlN薄膜，避免了生长很厚的AlN、进行二次生长等问题。
图9显示了根据本发明实施的另一种制作氮化物底层的流程图，其包括步骤S210~230。首先，在蓝宝石平片衬底的表面上溅镀AlN材料层，形成平坦的薄膜；接着，从该衬底端以激光束来回扫描，使该AlN材料层内部部分分解，湿法蚀刻去除该AlN材料层分解后产生的残余物，从而形成表面平坦、内部具有条状孔洞的溅射式AlN缓冲层；然后，采用MOCVD在所述溅射式AlN缓冲层上形成AlxIn1-x-yGayN层。在本实施例中，采用波长为193nm、光斑直接为0.5mm的激光束进行扫描该溅镀AlN材料层，因此，激光束的能隙E2和AlN缓冲层的能隙E3的关系满足E2＞E3，达到可以分解部分AlN材料层的目的，从而获得表面平坦、内部具有条状孔洞的溅射式AlN缓冲层120，该条状孔洞的深度为0.01~0.1μm，宽度约为500μm。
在本实施例中，采用直接采用能隙大于AlN材料的激光束进行扫描，可省略实施例1中的步骤S110，其形成的孔洞深度较浅。
很明显地，本发明的说明不应理解为仅仅限制在上述实施例，而是包括利用本发明构思的所有可能的实施方式。

Claims (13)

1.氮化物底层，从下至上依次包括：衬底，溅射式AlN缓冲层，MOCVD 生长的AlxIn1-x- yGayN层，其中0≤x≤1，0≤y≤1，其特征在于：所述溅射式AlN缓冲层具有平坦的表面，其内部具有条状孔洞，用于在生长所述AlxIn1-x-yGayN层之前提供应力释放的路径。
2.根据权利要求1所述的氮化物底层，其特征在于：所述孔洞与所述AlN缓冲层的侧壁连通。
3.根据权利要求1所述的氮化物底层，其特征在于：所述溅射式AlN缓冲层的厚度为1 μm以下。
4.根据权利要求1所述的氮化物底层，其特征在于：所述孔洞的高度为0.01~0.5μm。
5.氮化物底层的制作方法，包括步骤：
1）提供衬底，在其表面上形成条状材料层；
2）在所述条状材料层及衬底上溅镀AlN材料层，形成平坦的薄膜；
3）从所述衬底端以激光束来回扫描，使所述条状材料层分解，从而形成表面平坦、内部具有条状孔洞的溅射式AlN缓冲层；
4）采用MOCVD在所述溅射式AlN缓冲层上形成AlxIn1-x-yGayN层，0≤x≤1，0≤y≤1；
其中，所述条状材料层的能隙E1、激光束的能隙E2和AlN缓冲层的能隙E3的关系为：E1＜E2＜E3。
6.根据权利要求5所述的氮化物底层的制作方法，其特征在于：所述条状材料层选用氮化镓。
7.根据权利要求6所述的氮化物底层的制作方法，其特征在于：所述步骤3）中还包括：湿法蚀刻去除所述条状材料层经激光分解后产生的残余Ga金属，形成与所述AlN缓冲层的侧壁连通的条状孔洞。
8.根据权利要求5所述的氮化物底层的制作方法，其特征在于：所述激光束选用波长为248nm的激光。
9.氮化物底层的制作方法，包括步骤：
1）提供衬底，在其表面上溅镀AlN材料层，形成平坦的薄膜；
2）从所述衬底端以激光束来回扫描，使所述AlN材料层内部部分分解，从而形成表面平坦、内部具有条状孔洞的溅射式AlN缓冲层；
3）采用MOCVD在所述溅射式AlN缓冲层上形成AlxIn1-x-yGayN层，0≤x≤1，0≤y≤1；
其中，所述激光束的能隙E2和AlN缓冲层的能隙E3的关系为： E2＞E3。
10.根据权利要求9所述的氮化物底层的制作方法，其特征在于：所述激光束选用波长为193nm的激光。
11.根据权利要求9所述的氮化物底层的制作方法，其特征在于：所述步骤2）中还包括：湿法蚀刻去除所述AlN材料层分解后产生的残余物，形成与所述AlN缓冲层的侧壁连通的条状孔洞。
12.发光二极管，从下至上依次包括：衬底，溅射式AlN缓冲层，MOCVD 生长的AlxIn1-x- yGayN层，0≤x≤1，0≤y≤1，n型半导体层，有源层和p型半导层，其特征在于：所述溅射式AlN缓冲层具有平坦的表面，其内部具有条状孔洞，以在生长所述AlxIn1-x-yGayN层的过程中释放应力。
13.根据权利要求12所述的发光二极管，其特征在于：所述发光二极管的发光波长为365nm~210nm。
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