CN100472723C - 电极形成方法 - Google Patents

电极形成方法 Download PDF

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CN100472723C
CN100472723C CNB2005101080521A CN200510108052A CN100472723C CN 100472723 C CN100472723 C CN 100472723C CN B2005101080521 A CNB2005101080521 A CN B2005101080521A CN 200510108052 A CN200510108052 A CN 200510108052A CN 100472723 C CN100472723 C CN 100472723C
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electrode
ito
thickness
light transmission
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CN1755899A (zh
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吉田和广
长谷川恭孝
加贺广持
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Toyoda Gosei Co Ltd
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Abstract

本发明提供一种透光性高、电阻低的透光性电极的制造方法。半导体发光元件(100)是在蓝宝石衬底上依次层叠了缓冲层(102)、非掺杂GaN层(103)、高载流子浓度n+层(104)、n型层(105)、发光层(106)、p型层(107)、p型接触层(108)而形成的，具有在至少存在氧的气氛下利用电子束蒸镀法或者离子电镀法形成、且之后进行烧制而形成的由ITO构成的透光性电极(110)。

Description

电极形成方法
技术领域
本发明涉及一种层叠III族氮化物类化合物半导体而形成的半导体元件的电极形成方法，特别涉及形成由氧化铟锡(ITO)构成的透光性电极的方法。
背景技术
目前，III族氮化物类化合物半导体元件一般使用非导电性的蓝宝石衬底，n电极、p电极都形成在半导体元件层一侧。在此，在所谓的正装式III族氮化物类化合物半导体元件中，在p型层表面使用例如由合金化了的金(Au)和钴(Co)构成的薄膜透光性电极，从形成有电极的一侧取出光。但是，Au/Co薄膜透光性电极的光透射率为60％左右，光取出效率不充分。
另一方面，作为III族氮化物类化合物半导体元件的透光性电极，人们提出了使用氧化铟锡(ITO)。
【专利文献1】日本特许第3394488号公报
【专利文献2】日本特开2003-17748号公报
关于氧化铟锡(ITO)，用于III族氮化物类化合物半导体元件时的特性还不十分清楚，而且，需要开发用于形成电极的最佳条件。
发明内容
因此，本发明的目的在于，提供一种作为III族氮化物类化合物半导体发光元件的透光性电极而由氧化铟锡(ITO)构成的电极的形成方法。
为了解决上述课题，根据方案1所记载的方法，其特征在于：层叠了III族氮化物类化合物半导体而形成的半导体元件的电极的形成方法，由以下步骤构成：在至少导入了氧气的、且氧气压力为0.06Pa～0.1Pa的低压真空室内，通过电子束蒸镀或离子电镀法来蒸镀氧化铟锡，所述电极由所述氧化铟锡构成。
如下所示，本发明人发现：通过在存在氧的气氛下利用电子束蒸镀法或者离子电镀法蒸镀ITO，能形成最佳的透光性电极。之后，利用加热进行ITO的烧制，由此，能形成透光性高、电阻率低的电极。另外还发现，如果在形成ITO时使氧气大于或等于0.06Pa，则不进行烧制，就能形成透光性高、电阻率低的电极。
虽然需要与由ITO构成的透光性电极接近来形成用于引线接合的所谓的焊盘电极，但是，本发明人还发现：例如如果在金的厚膜电极和ITO之间设置镍(Ni)、钛(Ti)、铬(Cr)和铝(Al)，则能提高接合度。
附图说明
图1是表示本发明实施例2的半导体发光元件100的结构的剖视图。
符号说明如下：
100半导体发光元件     101蓝宝石衬底            102缓冲层
103非掺杂GaN层        104高载流子浓度n+层      105n型层
106发光层             107p型层                 108p型接触层
110透光性p电极(ITO)   130保护膜                140n电极
具体实施方式
作为本发明的主要特征的ITO，Sn的比例以2～20％为好。ITO的厚度以10nm～10μm为好。如果小于10nm，则电流的扩散不充分，而且容易产生剥离。另外，如果超过10μm，则光透射性劣化。ITO的厚度，更理想的是100nm～5μm，最好是200nm～2μm。
ITO膜形成时的氧气压力，理想的是0.01Pa～10Pa，更理想的是0.03Pa～2Pa，最好是0.05Pa～1Pa。如果大于或等于0.01Pa，则能形成电阻值低的电极。另外，利用后工序的烧制，能得到大于或等于80％的光透射度。如果使氧气压力大于或等于0.06Pa，则不经过后工序的烧制也能得到大于或等于90％的光透射度。烧制可以在300℃～1000℃下进行。如果低于300℃，则烧制的效果不充分，如果超过1000℃，则将导致半导体元件的特性劣化。更理想的是500℃～900℃，最好是600℃～800℃。另外，烧制最好是在惰性气体气氛下，特别是在氮气气氛下进行。
对于用于引线接合的焊盘电极，可以用厚膜的金(Au)形成。厚度在0.5～3μm的范围内任意地设定。在主要由金(Au)形成焊盘电极时，如果在与由ITO构成的透光性电极之间形成镍(Ni)、钛(Ti)、铬(Cr)或铝(Al)，则焊盘电极与由ITO构成的透光性电极的接合度提高。特别是在使用了镍(Ni)时，接合度变得更高。
本发明涉及的III族氮化物类化合物半导体发光元件，除了与上述发明的主要结构有关的限定之外，可以采用任意的结构。另外，发光元件可以是发光二极管(LED)、激光二极管(LD)，光电耦合器、其它任意的发光元件。特别是，作为本发明涉及的III族氮化物类化合物半导体发光元件的制造方法，可以使用任意的制造方法。
具体地讲，作为晶体生长的衬底，可以使用蓝宝石、尖晶石、Si、SiC、ZnO、MgO或者III族氮化物类化合物单晶体等。作为使III族氮化物类化合物半导体层晶体生长的方法，分子束气相生长法(MBE)、有机金属气相生长法(MOVPE)、氢化物气相生长法(HVPE)、液相生长法等是有效的。
在发光层为多重量子阱构造时，可以包含由至少包含铟(In)的III族氮化物类化合物半导体AlxGayIn1-x-yN(0≤x<1，0<y≤1)构成的阱层。发光层的结构，例如包括由掺杂或非掺杂的GayIn1-yN(0<y≤1)构成的阱层、由带隙比该阱层大的任意组成的III族氮化物类化合物半导体AlGaInN构成的阻挡层。作为优选例，为非掺杂的GayIn1-yN(0<y≤1)的阱层和由非掺杂的GaN构成的阻挡层。
电极形成层等III族氮化物半导体层可以由III族氮化物类化合物半导体形成，该III族氮化物类化合物半导体是至少用AlxGayIn1-x-yN(0≤x≤1，0≤y≤1，0≤x+y≤1)来表示的2元类、3元类或4元类半导体构成。另外，这些III族元素的一部分也可以用硼(B)、铊(T1)置换，还可以用磷(P)、砷(As)、锑(Sb)、铋(Bi)置换一部分氮(N)。
另外，在使用这些半导体来形成n型的III族氮化物类化合物半导体层时，作为n型杂质可以添加Si、Ge、Se、Te、C等，作为p型杂质可以添加Zn、Mg、Be、Ca、Sr、Ba等。
根据以上的本发明的方法，能有效地、或者合理地解决上述课题。
【实施例1】
首先，为了示出由本发明的电极形成方法带来的提高ITO的光透射性和抑制薄膜电阻的效果，进行以下的实验。以氧化锡和氧化铟的混合物(氧化锡5％)为靶，利用电子束蒸镀法在蓝宝石衬底上形成膜厚300nm的ITO。此时，在使蒸镀装置内部形成小于或等于1×10-2Pa的高真空后，以4种压力导入氧气，分别形成ITO。氧气压力采用0.0Pa(即不导入氧气)、0.005Pa、0.015Pa、0.06Pa、0.1Pa的5种。之后，对波长470nm的蓝色光的光透射性和薄膜电阻进行测量。接着，分别在氮气气氛下以400℃烧制10分钟，之后再次测量光透射性和薄膜电阻。其结果示于表1中。另外，光透射性是以蓝宝石衬底的光透射性为100％时的相对值。
(续下一页)
表1
Figure C200510108052D00071
在形成ITO时不导入氧气的情况下，光透射性在烧制的前后存在显著的差别。即，在烧制前，光透射性停留在65％，但是烧制后，达到100％。另一方面，薄膜电阻为100Ω/□左右，在烧制前后几乎没有差别。
在存在0.005Pa的氧气的情况下形成ITO时，光透射性在烧制的前后存在显著的差别。即，在烧制前，光透射性停留在60％，但是烧制后，达到90％。另外，薄膜电阻在烧制前后几乎没有差别，为27Ω/□左右，虽然还有改善的余地，但还是比较好的。
在存在0.015Pa的氧气的情况下形成ITO时，光透射性在烧制的前后存在显著的差别。即，在烧制前光透射性停留在57％，但是烧制后达到88％。另外，薄膜电阻在烧制前后几乎没有差别，为16Ω/□左右，是极为良好的。
在存在0.06Pa的氧气的情况下形成ITO时，光透射性、薄膜电阻在烧制的前后都几乎没有差别，是极为良好的。即，光透射性为93％左右，薄膜电阻也为16Ω/□左右。
在存在0.1Pa的氧气的情况下形成ITO时，光透射性、薄膜电阻都是极为良好的。即，光透射性在烧制的前后都为96％左右，薄膜电阻从烧制前的14Ω/□减小到8Ω/□，改善了薄膜电阻。
以上的结果是，ITO因烧制而再结晶，从而光透射性变好，通过在存在微量的氧气的情况下形成ITO，在化学量论上(stoichiometric)成为理想的ITO组成，由此，可以说明电阻值得到了抑制。如上所述，根据本发明，作为透光性电极能可形成极为良好的ITO膜。
【实施例2】
图1表示本发明实施例涉及的半导体发光元件100的示意剖视图。对于半导体发光元件100，如图1所示，在厚度约300μm的蓝宝石衬底101之上，形成有由氮化铝(AlN)构成的膜厚约15nm的缓冲膜层102，在缓冲膜层102之上形成有由非掺杂的GaN构成的膜厚约500nm的层103，在层103上形成有由掺杂了1×1018/cm3的硅(Si)构成的膜厚约5μm的n型接触层104(高载流子浓度n+层)。
另外，在该n型接触层104之上形成有掺杂了1×1017/cm3的硅(Si)的膜厚25nm的由n型Al0.15Ga0.85N构成的n型层105。进而，在n型层105之上层叠有3对膜厚3nm的由非掺杂In0.2Ga0.8N所构成的阱层1061、和膜厚20nm的由非掺杂GaN构成的阻挡层1062，而形成多重量子阱构造的发光层106。
进而，在该发光层106之上形成有由掺杂了2×1019/cm3的Mg的膜厚25nm的p型Al0.15Ga0.85N构成的p型层107。在p型层107之上形成有由掺杂了8×1019/cm3的Mg的膜厚100nm的p型GaN构成的p型接触层108。
另外，在p型接触层108之上形成有由ITO构成的透光性p电极110，在n型接触层104上形成有n电极140。透光性p电极110由与p型接触层108直接接合的膜厚约300nm的ITO构成。
厚膜p电极120，是通过从透光性p电极110之上依次层叠膜厚约30nm的由镍(Ni)构成的第一层121、膜厚约1.5μm的由金(Au)构成的第二层122、膜厚约10nm的由铝(Al)构成的第三层123而构成的。
多层构造的n电极140，是通过从n型接触层104部分露出的部分之上层叠膜厚约18nm的由钒(V)构成的第一层141、和膜厚约100nm的由Al???构成的第二层142而构成的。
半导体发光元件，在蓝宝石衬底上依次外延生长了缓冲层102、非掺杂GaN层103、高载流子浓度n+层104、n型层105、发光层106、p型层107、p型接触层108，在进行了用于形成n电极140的刻蚀之后，如下面这样进行电极形成。
首先，用光致抗蚀剂形成掩膜，该掩膜在要形成透光性p电极(ITO)110的区域形成了窗口，之后，以氧化锡和氧化铟的混合物(氧化锡5％)为靶，利用电子束蒸镀法在氧气压力为0.06Pa下形成了膜厚300nm的由ITO构成的透光性p电极110。接着，在氮气气氛下进行600℃、5分钟的烧制。之后，除去光致抗蚀剂。
接着，用光致抗蚀剂形成掩膜，该掩膜在要形成厚膜p电极120的区域形成了窗口，之后，在透光性p电极110之上依次形成膜厚约30nm的由镍(Ni)构成的第一层121、膜厚约1.5μm的由金(Au)构成的第二层122、膜厚约10nm的由铝(Al)构成的第三层123。然后，除去光致抗蚀剂。
完全一样地用光致抗蚀剂形成掩膜，该掩膜在要形成厚膜n电极140的区域形成了窗口，之后，在露出高载流子浓度n+层103的区域形成膜厚约18nm的由钒(V)构成的第一层141、和膜厚约100nm的由铝(Al)构成的第二层142。然后，除去光致抗蚀剂。
接着，对透光性p电极(ITO)电极110、厚膜p电极120、n电极140进行加热处理。最后，形成由SiO2构成的保护膜130。并且，保护膜130也可以使用SiNx来替代SiO2。
【比较例】
准备如下这样形成的比较用的半导体发光元件：即，在上述实施例中，代替透光性p电极(ITO)110，而通过从最下层依次层叠
Figure C200510108052D00101
的Co、
Figure C200510108052D00102
的Au、
Figure C200510108052D00103
的Co、的Au这样的4层而形成薄膜透明电极，并代替厚膜p电极120，而从最下层依次形成膜厚40nm的Au、膜厚30nm的Cr、膜厚650nm的Au、膜厚10nm的Al。然后，与上述半导体发光元件100比较物性。此时，安装在Ag基座上，并用透明银浆料覆盖。
具有层叠了4层Au/Co/Au/Co并合金化了透明电极的比较用的半导体发光元件，驱动电压为3.15V，光度为77mcd，全放射束为3.4mW，与此相对，本发明涉及的图1的半导体发光元件100，驱动电压为3.27V，光度为146mcd，全放射束为7.6mW。即，相对于具有Au/Co薄膜透明电极的半导体元件，本发明的具有由ITO构成的透光性电极的半导体发光元件，驱动电压几乎没有变化，而且光度和全放射束显著提高。

Claims (1)

1.一种电极形成方法，是层叠III族氮化物类化合物半导体而形成的半导体元件的电极的形成方法，该方法的特征在于，由以下步骤构成：
在至少导入了氧气的、氧气压力为0.06Pa～0.1Pa的低压真空室内，通过电子束蒸镀或离子电镀法来蒸镀氧化铟锡，所述电极由所述氧化铟锡构成。
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