CN103531672B - 具有孔隙的外延结构及其成长方法 - Google Patents
具有孔隙的外延结构及其成长方法 Download PDFInfo
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- 150000004767 nitrides Chemical class 0.000 claims description 9
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- 239000004065 semiconductor Substances 0.000 claims description 9
- 229910002601 GaN Inorganic materials 0.000 claims description 6
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 238000001451 molecular beam epitaxy Methods 0.000 claims description 5
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- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
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- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
本发明揭露一种具有孔隙结构的外延结构及其成长方法。外延成长方法包含以下步骤:形成牺牲层于基材上;图案化牺牲层,以在基材上形成多个间隔排列的凸起物;在裸露部分的基材上外延成长第一外延层,使第一外延层覆盖凸起物的一部分;蚀刻移除凸起物,以形成多个孔隙;以及在第一外延层上外延成长第二外延层,使孔隙被第一外延层及第二外延层包覆。
Description
技术领域
本发明是有关于一种外延结构以及一种外延成长方法,且特别是有关于一种具有孔隙的外延层以及此外延层的外延成长方法。
背景技术
近年来,发光二极管(Light Emitting diode)的技术快速发展。为了提高发光二极管的光取出率,图案化蓝宝石基板(Patterned sapphire substrate)技术已广泛被使用于现有氮化镓发光二极管产品中。然而为求进一步提升光取出效率,更有先进技术开发出于氮化镓外延材料中制造具有孔隙结构的发光二极管。在制造具有孔隙结构的发光二极管的已知技术中,很难精确地控制孔隙的体积大小及形状,因此造成孔隙型发光二极管的品质不稳定。有鉴于此,目前亟需一种新的制造方法,其能改善上述问题。
发明内容
因此,本发明的一目的是提供一种外延成长方法,以能在外延层中形成孔隙结构,且能够精准地控制孔隙的型态。此外延成长方法,包含下述步骤。首先,提供一基材。随后,形成一牺牲层于基材上。接着,图案化牺牲层,以在基材上形成多个间隔排列的凸起物,并且使凸起物之间的基材表面裸露出。随后,在裸露部分的基材上外延成长一第一外延层,使第一外延层覆盖每一凸起物的一部分,并露出每一凸起物的顶面。在外延成长第一外延层之后,蚀刻移除凸起物,以形成多个露出基材表面的孔隙。然后,在第一外延层上外延成长一第二外延层,使孔隙被第一外延层及第二外延层包覆。
在一实施方式中,基材为一蓝宝石基板或硅基板。
在一实施方式中,第一外延层包含周期表IIIA族的氮化物半导体材料(groupIIIA nitride semiconductor)。
在一实施方式中,第二外延层包含周期表IIIA族的氮化物的半导体材料。
在一实施方式中,第一外延层及第二外延层是氮化镓所构成。
在一实施方式中,第一外延层及第二外延层是以氢化物气相外延制程(hydridevapor phase epitaxy process)、有机金属化学气相沉积制程(metal organic chemicalvapor deposition process)或分子束外延制程(molecular beam epitaxy process)形成。
在一实施方式中,第二外延层成长时,其水平方向的成长速率大于铅垂方向的成长速率。
在一实施方式中,牺牲层为一无机材料层。
在一实施方式中,牺牲层包含氧化硅或氮化硅。
在一实施方式中,每一凸起物的一最大高度为约0.5μm至约3μm,每一凸起物的一底部宽度为约0.5μm至约5μm。
在一实施方式中,每一凸起物的一锥形角(taper angle)为小于或等于约90度。
在一实施方式中,图案化牺牲层的步骤包含以感应耦合等离子反应离子蚀刻(Inductively Coupled Plasma Reactive Ion Etching,ICP RIE)牺牲层。
在一实施方式中,凸起物是以湿式蚀刻法移除。
在一实施方式中,湿式蚀刻法所用的蚀刻剂包含氟化铵(NH4F)以及氟化氢(HF)。
在一实施方式中,每一孔隙的开口面积为每一孔隙底部面积的约5%至约50%。
在一实施方式中,基材表面还包括一缓冲层。
本发明的另一目的是揭露一种外延结构。此外延结构包含一基材、一第一外延层、一第二外延层以及一封闭气室。第一外延层配置在基材上方。第二外延层配置在第一外延层上。封闭气室埋设在第一外延层和第二外延层中,封闭气室具有一底部以及一顶部,封闭气室的底部和顶部分别形成在第一外延层和第二外延层中,且封闭气室的顶部的宽度小于底部的宽度。
在一实施方式中,封闭气室的顶部包含一圆弧面,且封闭气室的底部实质上为一平面。
在一实施方式中,封闭气室的一纵剖面为梯形。
在一实施方式中,封闭气室包含一阶梯状侧壁,且顶部及底部实质上为相对的两平面。
在一实施方式中,上述的外延结构还包含一缓冲层,缓冲层位在基材与第一外延层之间,且封闭气室的底部接触缓冲层。
在一实施方式中,上述的外延结构还包含一图案化牺牲层配置在基材上,且图案化牺牲层的上表面形成封闭气室的底部。
在一实施方式中,该封闭气室的高度为约0.5μm至约3μm,该封闭气室的底部的宽度为约0.5μm至约5μm。
附图说明
为让本发明的上述和其他目的、特征、优点与实施例能更明显易懂,所附附图的说明如下:
图1绘示本发明一实施方式的外延成长方法的流程图;
图2A-图2F绘示本发明一实施方式的外延成长方法中各制程阶段的剖面示意图;
图2G绘示本发明一实施方式的步骤150所形成的孔隙的上视示意图;
图3A-图3D绘示本发明另一实施方式的外延成长方法中制程阶段的剖面示意图;
图3E-图3H绘示本发明另一实施方式的外延成长方法中制程阶段的剖面示意图;
图4A-图4F绘示本发明又一实施方式的外延成长方法中制程阶段的剖面示意图;
图5A-图5B绘示本发明再一实施方式的外延成长方法中制程阶段的剖面示意图。
【主要元件符号说明】
100 方法
110、120、130 步骤
140、150、160 步骤
210 基材
212 缓冲层
220 牺牲层
222 凸起物
222a 残留部分凸起物
222t 顶面
224 孔隙
224a 开口
224b 底部
231 第一外延层
232 第二外延层
H 高度
W 宽度
α 锥形角
具体实施方式
为了使本发明的叙述更加详尽与完备,下文针对了本发明的实施方式与具体实施例提出了说明性的描述;但这并非实施或运用本发明具体实施例的唯一形式。以下所揭露的各实施例,在有益的情形下可相互组合或取代,也可在一实施例中附加其他的实施例,而无须进一步的记载或说明。
在以下描述中,将详细叙述许多特定细节以使读者能够充分理解以下的实施例。然而,可在无此等特定细节的情况下实践本发明的实施例。在其他情况下,为简化附图,熟知的结构与装置仅示意性地绘示于图中。
图1绘示本发明一实施方式的外延成长方法100的流程图,外延成长方法100至少包含步骤110至步骤160。图2A-图2F绘示方法100中各制程阶段的剖面示意图。在此揭露的外延成长方法可应用于制造发光二极管或制造平面显示器。
在步骤110中,提供基材210,如图2A所示。基材210可例如为蓝宝石基板、硅基板或其他适合于外延成长的基板。
在步骤120中,在基材210上形成牺牲层220,如图2B所示。在一实施方式中,牺牲层220为无机材料层。牺牲层220可例如为氧化硅或氮化硅等无机材料所制成。
在步骤130中,对牺牲层220进行图案化,以形成多个凸起物222。这些凸起物222彼此间隔地排列在基材210上,两个凸起物222之间的间隙让基材210的表面裸露出。
在一实施方式中,可先在牺牲层220上形成具有一定图案的光阻层,光阻层覆盖欲形成凸起物222的区域,并暴露出其他部分的牺牲层220。然后,再通过蚀刻制程来移除暴露出的牺牲层220,而形成凸起物222。具体而言,是通过光阻层的图案来决定凸起物222的上视轮廓。关于凸起物222的剖面形状,可经由适当的蚀刻技术来控制凸起物222的剖面形状。在一具体实例中,利用感应耦合等离子反应离子蚀刻(Inductively Coupled PlasmaReactive Ion Etching,ICP RIE)的制程技术来蚀刻暴露出的牺牲层220。感应耦合等离子反应离子蚀刻技术能够同时提供具方向性的离子轰击蚀刻以及不具方向性的反应性离子蚀刻,所以能够形成半球形状的凸起物222。通过调整ICP RIE中的制程参数,能够分别控制离子轰击的蚀刻速率和反应性离子的蚀刻速率,而形成不同剖面形状的凸起物222,例如可形成梯形剖面的凸起物222或矩形剖面的凸起物,下文将更详细叙述。
在一较佳实施例中,每一凸起物222的锥形角(taper angle)α是小于或等于约90度,每一凸起物的一最大高度H为约0.5μm至约3μm,每一凸起物的一底部宽度为W约0.5μm至约5μm。凸起物222的外观形状决定后续步骤中的孔隙形状,下文将更详细叙述。
在步骤140中,在裸露出的基材210上外延成长第一外延层231,使第一外延层231覆盖凸起物222的一部分,但凸起物222的顶面222t是曝露在第一外延层231之外,如图2D所示。详言之,在外延成长第一外延层231时,第一外延层231会沿着凸起物222的表面外延成长。若不终止外延成长制程,第一外延层231将会完全覆盖凸起物222。因此,本发明的一特征在于,在第一外延层231完全覆盖凸起物222之前,终止第一外延层231的外延成长,使凸起物的顶面222t曝露出来,避免第一外延层231完全包覆凸起物222。
在一实施方式中,第一外延层231包含周期表IIIA族的氮化物半导体材料(groupIIIA nitride semiconductor),例如氮化镓。第一外延层231可通过氢化物气相外延制程(hydride vapor phase epitaxy process)、有机金属化学气相沉积制程(metal organicchemical vapor deposition process)或分子束外延制程(molecular beam epitaxyprocess)来形成。
在步骤150中,蚀刻移除凸起物222,而形成多个孔隙224,并使基材210的一部分表面露出,如图2E所示。因为凸起物的顶面222t是曝露在第一外延层231之外,所以可利用湿式蚀刻制程来移除这些凸起物222,而形成孔隙224。蚀刻剂可例如为包含氟化铵(NH4F)以及氟化氢(HF)的混合溶液。详言之,孔隙224的位置、体积及外观形状大致上是取决于凸起物222的位置、体积及形状以及第一外延层231覆盖凸起物222的程度。因此,根据本发明的实施方式,能够通过步骤130中图案化牺牲层220的步骤,控制凸起物222的形状、体积以及排列方式,而得以事先精准地控制步骤140所形成的孔隙224的型态。
图2G绘示本发明一实施方式的步骤150中所形成的孔隙224的上视示意图。在本实施方式中,在移除凸起物222之后,孔隙开口224a的面积为孔隙底部224b的面积的约5%至约50%,更明确地为约15%至约40%。若孔隙开口224a的面积小于孔隙底部224b的面积的约5%,则很难在步骤150中迅速地移除凸起物222。反之,若孔隙开口224a的面积大于孔隙底部224b的面积的约50%,则第一外延层231覆盖凸起物222的程度不足,而不利于后续的步骤160。因此,根据本发明的诸多实施例,孔隙开口224a的面积较佳为孔隙底部224b的面积的约5%至约50%,更佳为约15%至约40%。
在步骤160中,于第一外延层231上外延成长第二外延层232,使孔隙224被第一外延层231及第二外延层232包覆,如图2F所示。换言之,在步骤160中,通过外延成长第二外延层232,使孔隙224变成埋设在第一外延层231与第二外延层232中的封闭气室(closed aircell)。第二外延层232的形成方法可与前文第一外延层231中所述的方法相同。在一实施方式中,第二外延层232包含周期表IIIA族的氮化物的半导体材料(group III nitridesemiconductor)。在一实例中,第二外延层232的材料与第一外延层231的材料相同,例如同样为氮化镓。在其他实施方式中,为了特别考量整体的光学路径,第二外延层232的折射率不同于第一外延层231的折射率。
在另一实施方式中,第二外延层232成长时的水平方向成长速率大于第一外延层231的水平方向成长速率。水平方向的成长速率可通过外延制程时的温度及压力来控制。在一实例中,第二外延层232成长时的温度大于第一外延层231的成长温度,而且第二外延层232成长时的压力小于第一外延层231的成长压力。为了使第一外延层231的膜层结构具有较佳的立体结构,故此时的成长环境为低温高压。此外,第二外延层232相对于第一外延层231而言,则是需要较佳的平坦化能力以及较易水平生长的结构,以覆盖孔隙224。第二层的成长环境相较于第一外延层231是较高温且低压的。
如前文步骤130及步骤140中所述,可通过形成不同剖面形状的凸起物222,而得到不同形状的孔隙224。图3A-图3D绘示本发明另一实施方式的外延成长方法中制程阶段的剖面示意图。图3A-图3D绘示的实施方式中,可形成具有梯形剖面的凸起物222,如图3A所示。然后,再外延成长第一外延层231;第一外延层231仅覆盖凸起物222的一部分,如图3B所示。接着,移除凸起物222而形成孔隙224,如图3C所示。随后,再外延成长第二外延层232将梯形剖面形状的孔隙224包覆其中,如图3D所示。相似地,图3E-图3H绘示的实施方式中,能够形成阶梯状剖面形状的孔隙224。
图4A-图4F绘示本发明又一实施方式的外延成长方法中制程阶段的剖面示意图。在图4A中,提供基材210。在图4B中,形成缓冲层212于基材210的表面上。在图4C中,在缓冲层212上形成多个凸起物222。然后,如图4D所示,在缓冲层212上外延成长第一外延层231。接着,如图4E所示,移除凸起物222而形成孔隙224。随后,如图4F所示,外延成长第二外延层232而将孔隙224包覆。
图5A-图5B绘示本发明再一实施方式的外延成长方法中制程阶段的剖面示意图。在本实施方式中,步骤110至步骤140可与前文关于图2A-图2D的叙述相同。然后,如图5A所示,在步骤150中仅蚀刻移除凸起物222的一部分,而不移除全部的凸起物222。详言之,在蚀刻移除凸起物222的过程中,在完全移除凸起物222之前,终止蚀刻程序,使凸起物222的一部分222a残留在基材上。随后,再进行步骤160的外延成长第二外延层232,使孔隙224被第一外延层231及第二外延层232包覆。换言之,根据本实施方式,能够在第一外延层231及第二外延层232中形成封闭气室以及埋设其中的凸起物残留部分222a。在一实施例中,凸起物的残留部分222a的折射率与第一外延层231及/或第二外延层232的折射率不同,因此能够作为另一个光学介质,改变图2F绘示的结构中的光学路径及光学特性。
虽然本发明已以实施方式揭露如上,然其并非用以限定本发明,任何熟悉此技艺者,在不脱离本发明的精神和范围内,当可作各种的更动与润饰,因此本发明的保护范围当视所附的权利要求书所界定的范围为准。
Claims (18)
1.一种具有孔隙结构的外延成长方法,其特征在于,包含:
提供一基材;
形成一牺牲层于该基材上;
图案化该牺牲层,并在该基材上形成多个间隔排列的凸起物,并且裸露出所述多个凸起物间的基材表面;
在该裸露出的基材上外延成长一第一外延层,使该第一外延层覆盖所述多个凸起物的一部分,并露出每一所述凸起物的顶面;
蚀刻移除每一所述多个凸起物的一部分,每一所述凸起物的一残留部分留在该基材上,形成多个露出所述残留部分的表面的孔隙;以及
在该第一外延层上外延成长一第二外延层,使该第一外延层及该第二外延层包覆所述多个孔隙和每一所述残留部分。
2.根据权利要求1所述的具有孔隙结构的外延成长方法,其特征在于,该基材为一蓝宝石基板或硅基板。
3.根据权利要求1所述的具有孔隙结构的外延成长方法,其特征在于,该第一外延层包含周期表IIIA族的氮化物半导体材料。
4.根据权利要求3所述的具有孔隙结构的外延成长方法,其特征在于,该第二外延层包含周期表IIIA族的氮化物的半导体材料。
5.根据权利要求4所述的具有孔隙结构的外延成长方法,其特征在于,该第一外延层及该第二外延层是氮化镓所构成。
6.根据权利要求5所述的具有孔隙结构的外延成长方法,其特征在于,该第一外延层及该第二外延层是以氢化物气相外延制程、有机金属化学气相沉积制程或分子束外延制程形成。
7.根据权利要求6所述的具有孔隙结构的外延成长方法,其特征在于,该第二外延层成长时的水平方向成长速率大于第一外延层的水平方向成长速率。
8.根据权利要求7所述的具有孔隙结构的外延成长方法,其特征在于,该第二外延层成长时的温度大于第一外延层的成长温度。
9.根据权利要求7所述的具有孔隙结构的外延成长方法,其特征在于,该第二外延层成长时的压力小于第一外延层的成长压力。
10.根据权利要求1所述的具有孔隙结构的外延成长方法,其特征在于,该牺牲层为一无机材料层。
11.根据权利要求10所述的具有孔隙结构的外延成长方法,其特征在于,该牺牲层包含氧化硅或氮化硅。
12.根据权利要求1所述的具有孔隙结构的外延成长方法,其特征在于,每一所述凸起物的一最大高度为0.5μm至3μm,每一所述凸起物的一底部宽度为0.5μm至5μm。
13.根据权利要求12所述的具有孔隙结构的外延成长方法,其特征在于,形成所述多个凸起物的步骤中,每一所述凸起物的一锥形角为小于或等于90度。
14.根据权利要求13所述的具有孔隙结构的外延成长方法,其特征在于,图案化该牺牲层的步骤包含以感应耦合等离子反应离子蚀刻该牺牲层。
15.根据权利要求1所述的具有孔隙结构的外延成长方法,其特征在于,所述多个凸起物是以湿式蚀刻法移除。
16.根据权利要求15所述的具有孔隙结构的外延成长方法,其特征在于,该湿式蚀刻法所用的蚀刻剂包含氟化铵以及氟化氢。
17.根据权利要求1所述的具有孔隙结构的外延成长方法,其特征在于,每一所述孔隙的开口面积为每一所述孔隙底部面积的5%至50%。
18.根据权利要求1至17中任一项权利要求所述的具有孔隙结构的外延成长方法,其特征在于,该基材表面还包括一缓冲层。
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CN102194941A (zh) * | 2010-11-16 | 2011-09-21 | 华灿光电股份有限公司 | 内置空腔的高效率发光二极管及其制备方法 |
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US7445673B2 (en) | 2004-05-18 | 2008-11-04 | Lumilog | Manufacturing gallium nitride substrates by lateral overgrowth through masks and devices fabricated thereof |
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TWI299917B (en) | 2006-03-17 | 2008-08-11 | Epistar Corp | Light-emitting diode and method for manufacturing the same |
US7560364B2 (en) | 2006-05-05 | 2009-07-14 | Applied Materials, Inc. | Dislocation-specific lateral epitaxial overgrowth to reduce dislocation density of nitride films |
TWI396297B (zh) | 2007-01-24 | 2013-05-11 | Tera Xtal Technology Corp | 發光二極體結構及其製造方法 |
US9000464B2 (en) * | 2012-03-01 | 2015-04-07 | Design Express Limited | Semiconductor structure for substrate separation and method for manufacturing the same |
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CN102034907A (zh) * | 2009-09-28 | 2011-04-27 | 上海宇体光电有限公司 | 一种提高GaN基LED发光效率的图形掩埋方法 |
CN102315347A (zh) * | 2010-07-05 | 2012-01-11 | 展晶科技(深圳)有限公司 | 发光二极管磊晶结构及其制造方法 |
CN102194941A (zh) * | 2010-11-16 | 2011-09-21 | 华灿光电股份有限公司 | 内置空腔的高效率发光二极管及其制备方法 |
CN102280533A (zh) * | 2011-06-23 | 2011-12-14 | 西安神光安瑞光电科技有限公司 | 氮化镓衬底材料制造方法 |
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US20150228853A1 (en) | 2015-08-13 |
US20170154769A1 (en) | 2017-06-01 |
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US9673353B2 (en) | 2017-06-06 |
US20140008766A1 (en) | 2014-01-09 |
US20150228854A1 (en) | 2015-08-13 |
CN103531672A (zh) | 2014-01-22 |
US9892911B2 (en) | 2018-02-13 |
US9601661B2 (en) | 2017-03-21 |
US9041159B2 (en) | 2015-05-26 |
TWI474510B (zh) | 2015-02-21 |
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