CN1482690A - 氮化镓系化合物半导体发光器件 - Google Patents

氮化镓系化合物半导体发光器件 Download PDF

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Publication number
CN1482690A
CN1482690A CNA03145867XA CN03145867A CN1482690A CN 1482690 A CN1482690 A CN 1482690A CN A03145867X A CNA03145867X A CN A03145867XA CN 03145867 A CN03145867 A CN 03145867A CN 1482690 A CN1482690 A CN 1482690A
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China
Prior art keywords
electrode
compound semiconductor
gallium nitride
type
semiconductor layer
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CNA03145867XA
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CN1240142C (zh
Inventor
Д
中村修二
山田孝夫
֮
妹尾雅之
山田元量
板东完治
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Nichia Corp
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Nichia Corp
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Priority claimed from JP12489093A external-priority patent/JP2803742B2/ja
Priority claimed from JP12931393A external-priority patent/JP2748818B2/ja
Priority claimed from JP20727493A external-priority patent/JP2783349B2/ja
Priority claimed from JP23468593A external-priority patent/JP2770717B2/ja
Priority claimed from JP23468493A external-priority patent/JP2697572B2/ja
Priority claimed from JP25317193A external-priority patent/JP2770720B2/ja
Priority claimed from JP872794A external-priority patent/JP3154364B2/ja
Application filed by Nichia Corp filed Critical Nichia Corp
Publication of CN1482690A publication Critical patent/CN1482690A/zh
Publication of CN1240142C publication Critical patent/CN1240142C/zh
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Abstract

一种氮化镓系化合物半导体发光器件，在绝缘衬底上至少依次层叠的n型氮化镓系化合物半导体层和p型氮化镓系化合物半导体层，所述p型氮化镓系化合物半导体层的侧面为发光观察面，其特征在于：在所述p型氮化镓系化合物半导体层的整个表面上形成有透光的第一电极，同时在所述第一电极上形成有贯通该第一电极的一部分的切口状窗口；在所述窗口上形成有与第一电极电连接的焊接用第二电极，以及所述第二电极与p型氮化镓系化合物半导体层粘结得比第一电极牢固。

Description

氮化镓系化合物半导体发光器件
本申请是申请号为98118311.5、发明名称为“氮化镓系III-V族化合物半导体器件及其制造方法”、申请日为94年4月28日的发明专利申请的分案申请。
技术领域
本发明涉及具有欧姆电极的氮化镓系化合物半导体发光器件。
背景技术
近年来，采用GaN、GaAlN、InGaN、InAlGaN等氮化镓系III-V族化合物半导体材料的发光器件备受关注。这类发光器件通常具有在衬底上将n型氮化镓系化合物半导体层与掺p型掺杂剂的氮化镓系化合物半导体层叠层的结构。
已往，掺p型掺杂剂的氮化镓III-V族化合物半导体层仍是高阻i型，因而，已有的器件就是所谓的MIS结构。最近，将高阻i型层转化为低阻p型层的技术，例如已被特开平2-257676号、特开平3-218325号以及特开平5-183189号所揭示，由此可以制造出p-n结型氮化镓系III-V族化合物半导体发光器件。
但是，为了实现此类p-n结型氮化镓化合物半导体器件，在p型层和/或n型层上形成与之接触的电极方面尚存在各种问题。
现在，因受制造方面的制约，在p-n结型氮化镓系III-V族化合物半导体发光器件化合物半导体层内的最上层具有p型化合物半导体层。另外，作为此类器件的衬底，一般使用透明的蓝宝石衬底。与其它半导体发光器件中使用的GaAs、GaAlP等半导体衬底不同，因蓝宝石是绝缘的，为给化合物半导体层施加预定的电流使器件执行其发光机能，不能把电极直接固定在衬底本身上。p电极和n电极必须各自与p型化合物半导体层和n型化合物导体层形成直接接触。为保证向整个p型化合物半导体层施加均匀电流，以便得到来自器件的均匀发光，须将p型层基本上全面覆盖地形成p电极。但是，因为已有p电极是不透光的，为避免所发的光被p型电极衰减，外部量子效率变坏，不能从与形成p型化合物半导体层和n型化合物半导体层的衬底相反的一侧观察已有发光器件的发光。
但是，对于此类已有化合物半导体发光器件固定在引线架上的情况，为使未形成化合物半导体层的衬底面朝上，必须将p电极和n电极朝下安装于2个引线架上。即，必须将一个半导体芯片横跨安装于2个引线架上。此时，为了避免p型化合物半导体层与n型化合物半导体层的电短路，必须确保2个引线架有一定间隔，自然而然地不得不把半导体的一个芯片尺寸加大到1mm2以上。因而，以已有的器件结构而论，由一枚晶片所得到的芯片数目必然减少。另外，2个引线架还需要非常精密的位置配合，并需要氮化镓系化合物半导体的精细的腐蚀技术。
其次，就n电极而论，如上所述，为实现p-n结型氮化镓系III-V族化合物半导体发光器件，是最近提出的课题。在已有的MIS型结构的发光器件中，因为关键是利用电极与高阻的i型层的肖特基势垒，几乎未对n电极给予关注。
作为已有MIS构造的氮化镓系III-V族化合物半导体发光器件的n电极材料，例如已被特开昭55-9442号披露的铝或铝合金。另外也往往使用铟。由此可见，不管用铝或铟均难以得到与n型氮化镓系III-V族化合物半导体层十分满意的欧姆接触，还有，发觉由于退火使电极变质而容易失去导电性。
总而言之，已往尚没有达到与氮化镓系III-V族化合物半导体层十分满意的欧姆接触的电极材料。
发明目的
因而，本发明之目的在于提供一种设有与氮化镓系化合物半导体层形成欧姆接触电极的氮化镓系化合物半导体发光器件。
本发明的氮化镓系化合物半导体发光器件在绝缘衬底上至少依次层叠的n型氮化镓系化合物半导体层和p型氮化镓系化合物半导体层，所述p型氮化镓系化合物半导体层的侧面为发光观察面，其特征在于：在所述p型氮化镓系化合物半导体层的整个表面上形成有透光的第一电极，同时在所述第一电极上形成有贯通该第一电极的一部分的切口状窗口；在所述窗口上形成有与第一电极电连接的焊接用第二电极，以及所述第二电极与p型氮化镓系化合物半导体层粘结得比第一电极牢固。
附图说明
图1是表示将本发明的第一实施方案的发光器件安装在引线架上的状态示意断面图；
图2是表示本发明的p电极的电流-电压特性曲线图(图中X轴的1刻度为0.5V，Y轴的1刻度为0.2mA)；
图3是本发明第2实施方案的发光器件的平面图；
图4是沿图3的IV-IV线的断面图；
图5是表示本发明的第2实施方案的一个变形例的斜视图；
图6是表示本发明第3实施方案的发光器件的断面图；
图7是表示本发明第3方案的第1变形例的断面图；
图8是表示本发明第3方案的第2变形例的断面图；
图9是表示本发明第3方案的第3变形例的平面图；
图10是表示本发明第4实施方案的半导体发光器件的断面图；
图11A～图11D是与比较例一起表示本发明的各种不同的n电极的电流-电压特性曲线图(图中X轴1刻度为0.5V、Y轴1刻度为50μA)；
图12A～图12D是表示本发明的另一些n电极与比较例相比的电流-电压特性曲线图(图中X轴1刻度为0.5V、Y轴1刻度为50μA)；
图13A～图13D是与比较例一起表示本发明各种不同的n电极的电流-电压特性曲线图(图中X轴1刻度为0.5V、Y轴1刻度为50μA)；
图14A～图14D是与比较例一起表示本发明的另一些不同的n电极的电流-电压特性曲线图(图中X轴1刻度为0.5V、Y轴1刻度为50μA)；
图15是说明n电极粘结试验的图；
图16是表示本发明第5实施方案的半导体发光器件的一部分断面图；以及
图17是与比较例一起表示本发明第5实施方案的各种不同的n电极的电流-电压特性曲线图(图中X轴1刻度为0.5V、Y轴1刻度为50μA)。
具体实施方式
关于本发明，氮化镓系III-V族化合物半导体是指诸如GaN、GaAlN、InGaN、InAlGaN之类的包括镓在内的周期表第III族元素的氮化物半导体。这些化合物半导体可用化学式
    InxAlyGa1-x-yN表示，其中0≤X≤1、0≤Y≤1 X+Y≤1。
另外，在本发明中，所谓欧姆接触采用的是半导体领域中通常的含意。
在本发明中，所谓电极的透光性是指从氮化镓系III-V族化合物半导体发光器件发出的光有1％以上透过电极，并非意味着电极必须是无色透明的。透光性电极通常要使从氮化镓系III-V族化合物半导体发光器件发出的光透过20～40％或更多。
还有，在本发明中，金属材料为含2种以上金属的情况，将2种以上的金属预先合金化也可以，将各金属层层叠起来也行。在金属材料为含2种以上的金属的情况下，对各种金属虽无特别的限制，最好所含的各种金属至少为0.1原子％。
以下，参照附图对本发明加以详细说明。在所有的图中，同一部位用同一标号表示。
图1示意地表示本发明第1实施方案的氮化镓系III-V族化合物半导体发光器件10。
该发光器件(LED)10具有由蓝宝石等材料构成的透明绝缘性的衬底11。形成一层n型氮化镓系III-V族合物半导体层12，例如0.5μm～10μm厚，将整个衬底11的一主面11a覆盖住。在n型半导体层12中，虽然不掺入n型掺杂剂也可以，但最好掺入硅(Si)、锗(Ge)、硒(Se)、硫(S)、碲(Te)等n型掺杂剂。
在n型半导体层12的表面上，形成一层例如0.01μm～5μm厚的p型氮化镓系III-V族化合物半导体层13。在p型半导体层13中掺入锌(Zn)、镁(Mg)、铍(Be)、锶(Sr)、钡(Ba)等p型掺杂剂，再在400℃以上的温度下退火(关于退火请参阅涉及本受让人的申请特开平5-183189号公报[对应于转让给本受让人的1992年1月2日申请的美国专利申请系列号N0.07/970,145(此内容作为本说明书的揭示内容而插入本说明书)])。
将p型半导体层13与n型半导体层12的表面层腐蚀去掉一部分，露出部分n型半导体层12的表面。
在n型半导体层的露出面上，形成n电极14。
几乎全面覆盖住p型半导体层，形成本发明的p电极15。该p电极是由金属材料构成的透光性的欧姆电极。对形成p电极15的金属材料无特别限制。例如，p电极材料可以含有从金、镍、铂、铝、锡、铟、铬、钛中选出的1种或2种以上的金属。能获得满意的欧姆接触的金属材料包含从铬、镍、金、钛及铂组成的组中选出的至少2种金属。最好的金属材料包含金及镍。对金及镍的形成来说，最好先将镍层直接与p型半导体层13接触，再在其上形成金层。
如上所述，对金属材料含2种以上金属的情况下，具有各种金属层的叠层结构也可，预先合金化也行。具有叠层结构的金属材料经后述的退火可形成合金。
对p电极15，可在p型半导体层13上用例如蒸镀、溅射等通常的被覆技术形成金属材料层，再经退火进行调整。退火优选在400℃以上的温度进行。在400℃以下的温度下进行退火，显示出金属材料层与p型半导体层难以形成满意的欧姆接触的倾向。不用说，退火应在氮化镓系III-V族化合物半导体分解温度(约1200℃)以下的温度进行。退火时间优选为0.01分～30分。
本退火的效果与上述的US-SN 07/970,145中记载的效果相同。即，若将气相生长法生长的含p型掺杂剂的氮化镓系III-V族化合物半导体层在400℃以上的温度退火后，则其电阻率会急剧下降。经过退火，因将与半导体结晶中的受主结合的氢原子赶出，而使受主杂质激活。所以，因将电极在400℃以上的温度退火，实际上增加了掺入p型杂质的氮化镓系III-V族化合物半导体载流子的浓度，而易于得到欧姆接触。与p型半导体层13呈欧姆接触的优选材料，不管有无透光性，是含镍及金的金属材料。
用于p电极15的金属材料最好这样形成：使退火后的厚度变成0.001μm～1μm。由于退火，在金属材料向p型半导体层13的内部扩散的同时，还有一部分向外逸散，因而使厚度变薄。在退火后通过将金属材料的最终厚度调节到0.001μm～1μm厚，可以使p电极有理想的透光性。超过1μm的厚度，虽无特别的障碍，但这样一来，电极有逐渐显现金属色泽的倾向，使透光性下降。p电极15的厚度若薄于上述范围，从透光性之观点看是好的，但厚度过薄会使电极15与p型半导体层13的接触电阻有增加的倾向。这样，p电极的厚度就优选为0.005μm～0.2μm，最好为0.01μm～0.2μm。
本发明的p电极是透光的，并与p型半导体层形成理想的欧姆接触，而使发光器件的正向电压降低，使器件的发光效率提高。
实验例1
在掺锌的p型GaN层上，依次蒸镀一层镍以及在其上的一层金，厚度各为0.1μm，在600℃退火，在将其合金化之同时，得到变得透明的p电极。其厚度为0.03μm。该p电极的电流电压特性由图2中的曲线A表示。由该图可知，本p电极与p型氮化镓系III-V族化合物半导体形成了良好的欧姆接触。
那么，对具备此种透光性的欧姆p电极15的本发明的发光器件10，可通过p电极15进行发光观察。从而，如图1所示，作为使用氮化镓系化合物半导体以外的半导体形成的发光器件的装置，一般在所用的杯状引线架18之上，将基片11未形成半导体层的底面，即与第1主面11a相对的第2主面11b朝向引线架安装。
p电极15以在其一部分上所形成的焊盘17的部位与被连接在另一引线架(金属柱)19上的金丝一类的焊丝21相连接。n电极通过金丝一类的焊丝20与杯状引线架18相连接。
在本发明的优选实施方案中，焊盘17最好由单质金、或含金而不含铝或铬的2种以上的金属构成的金属材料形成。至于含金而不含铝或铬的金属材料可以列举出金，以及含金和钛、镍、铟和/或铂的材料。由此类金属材料构成的焊盘与p电极的粘结性是良好的，在与金丝的丝焊时，与由金丝形成的焊球的粘结性也是良好的。而且，这种金属材料在退火时，或在为发光而向器件通电的过程中，几乎不向p电极迁移不使p电极变质(透光性下降)。而含铝或铬的金属材料在通电中，在比较短的时间(例如500小时)就发生向p电极的迁移，使p电极变质。
实验例2
在图1所示的具有作为基片11的蓝宝石基片、作为n型半导体层12的厚度为4μm的n型GaN层、作为p型半导体层13的厚度为1μm的掺镁的p型GaN层的器件的p电极15之上形成的由各种金属材料构成的焊盘。p电极是经依次蒸镀厚度各为0.1μm的镍层和金层，在600℃退火，使之合金化同时变得透明，得到厚度为0.05μm的电极。
更具体的说，用下列表1所示的焊盘材料在p电极上形成焊盘。即在p电极上直接形成表1的列中所示的金属层，再在其上蒸镀表1的行中所示的金属层，在p电极退火过程之同时进行退火形成焊盘。焊丝是金丝。
使如此得到的发光器件连续发光500小时，检验焊盘对p电极的影响。将结果一并记载于表1中。
                       表1
在表1中，标记VG是“很好”之省略、表示器件在500小时发光后，焊盘完全不变色，仍保持初期的透光性，而且p电极与p型半导体的欧姆接触特性不变的情况，标记G是“好”之省略，表示在焊盘周围的电极部分虽稍稍变色，但发光未到明显减弱的程度，而且p电极与p型半导体层的欧姆接触没有变化的情况，标记B是“坏”之省略，表示p电极失掉了透光性，p电极与p型半导体也失去欧姆接触特性的情况。但是，不管p电极是否变色，与金球的粘结性变坏，将难以进行丝焊的焊盘用符号“-”表示。
如表1所示，例如用Ni-Au形成p电极的情况，用与p电极材料相同的材料即Ni-Au形成焊盘时，p电极一点也不变色而仍保持原有的透光性。另外，用单质金形成焊盘的情况也能得到相同的结果。可是Cr或Al都容易向p电极中迁移，即使p电极含金，p电极的特性也会变坏。
实验例3
除用Au-Ti形成p电极(这种p电极的欧姆特性稍稍劣于Ni-Au电极)以外，进行与实验例2相同的实验。其结果是对用单质金或用Au-Ti形成焊盘的情况，为VG；对用金与除铝或铬以外的金属(即，镍、钛、铟、或铂)构成的金属材料形成的情况，结果为G；对用金与铝或铬构成的金属材料形成的情况下，结果为B。
实验例4
除用Au-Al形成p电极(这种电极的欧姆特性稍稍劣于Ni-Au)以外，进行与实验例2相同的实验。其结果是，对用单质金形成焊盘的情况，为VG；对用金与除铝或铬以外的金属(即镍、钛、铟、或铂)构成的金属材料形成的情况下，结果为G，但用金与铝构成的金属材料形成焊盘的情况，与p电极虽属同一材料，但结果仍为B。还有，用金与铬构成的金属材料情况下，其结果也是B。
图3是依本发明第2实施方案的半导体发光器件的平面图。图4是沿图3的IV-IV线的断面图。本实施方案特别涉及p电极用的焊盘之改进。如图所示，在半导体基片的方形的第1主面上形成有透光性p电极15，其上设置切口311，以露出p型半导体层13的一部分表面。焊盘32通过切口311与p型半导体层13牢固粘结，同时与p电极形成电连接。图示的实施方案，焊盘32不但填满了切口311，而且还延伸到切口311周围的p电极的部分表面。切口部311，因而焊盘32最好设在离设置在n型半导体层12上的n电极14最远的位置(这种情况，也适用于图1的器件)。因此，外加电流可以扩展到整个p型半导体层13，使器件均匀发光。就图示例来说，在平面方形晶片的对角线上，切口部(窗)311形成在透光性p型电极15的角部，而n电极14则形成在n型半导体层12上的角部。
对焊盘32来说，与p型半导体层13形成欧姆接触当然好，但因通过p电极15已达到与p型半导体层13的欧姆接触，如果与p电极15能实现电连接，不形成欧姆接触也行。但是，焊盘32是用与p型半导体层13粘接得比p电极15还牢固的导电性金属材料形成。由于焊盘32与p型半导体层13粘结得比p电极15还牢固，在引线丝焊接时，这样即使拉拽金丝等的焊丝，也能防止焊盘32和/或p电极15被剥离。作为这样的焊盘用的金属材料，可以举出是单纯铝、或含铬、铝和金之中至少二种金属的金属材料。形成焊盘32的金属材料含有两种以上金属的情况下，如上所述，可以预先使它们合金化。也可以例如依次层叠各金属层，在p电极退火时，同时合金化。这些金属材料，虽然不能与p型半导体层13形成良好的欧姆接触，但与p型半导体层13粘结牢固，丝焊时不会被剥离。因而，可使之薄膜化，薄至显示出有透光性。这样的薄膜焊盘，因能使器件所发出的光透过，就不会使器件的发光量有明显地下降。还有，将焊盘32做成多层结构，用比与p型半导体层13粘合得更牢固的材料，形成与p型电极15直接接触的层，而用与焊丝材料粘附性更优良的金属形成最上层。
实验例5
在一层p型GAN层上，蒸镀层叠总厚度为0.01μm的Ni-Au，形成1000个透光性焊盘。另一方面，分别蒸镀总厚为0.01μm的Cr-Al、Al-Au、Cr-Au或纯Al，各形成1000个透光性的焊盘。在这些焊盘上用金丝进行丝焊之后，拿开该金丝，通过检测焊盘剥离的数目，来测定合格率。虽然由Ni-Au构成的焊盘的合格率约为60％，但其它材料构成的焊盘的合格率都在98％以上。
还有，通过形成厚焊盘32，由于其厚度较大，可使之提高与p型半导体层13的附着力。厚焊盘没有显示透光性，例如用与p电极相同的材料形成的话，但可实现欧姆接触。
图5，除切除透光性p电极15之角部，形成切口部312以外，表明与图4器件是同样的器件。另外，在图5中，为了清楚地示出切口部312，没有将焊盘表示出来。
图6除用绝缘透明保护膜(保护膜411)覆盖薄透光性p电极15外，表明与图1所示发光器件相同。保护膜具有让90％以上的光透过的透明度。另外，保护膜由于是绝缘性的，丝焊时在n电极14上形成保留其上的金属球，即使与p电极相接触，也能防止两者电短路。还有，由于保护膜是透明的，能让器件发出的透过p电极的光透过，就不会降低器件的外部量子效率(光输出效率)。再有，与防止刺伤薄的p电极15的同时，保护膜还能防止丝焊时，因拉拽焊丝而使焊盘17和p电极被剥离。
形成保护膜的材料，只要透明绝缘，就没有特别限制，令人满意的是，包括氧化硅、氧化钛、氧化铝和氮化硅。这些材料不论膜厚如何都无色透明，又是绝缘的。所以，用这些材料形成的保护膜，透过p电极的光几乎不会被衰减。保护膜可采用常规的蒸镀或溅射技术形成。对保护膜的厚度虽然不作特别限制，但一般为0.001μm至10μm。
还有，在n电极14与焊盘17之间的区域，丝焊时，由焊丝形成的金属球也容易使n电极14与p电极15桥接。所以，在图6中，保护膜要全面地覆盖该区域。
图7，保护膜(保护膜412)除覆盖p电极15的整个露出面，p型半导体层13的露出端面以及n型半导体层的露出端面外，都和图6所示结构同样。因此，图7发光器件的可靠性也比图6器件的可靠性又提高了。
图8，除n电极14与焊丝的焊接部和焊盘17的焊接部外，连续的保护膜(保护膜413)大致上覆盖全晶片以外，表明与图6结构都相同。这样一来，通过在焊盘17的表面上也形成了保护膜，焊盘17成了被保护膜压着的状态，因而防止了焊盘17从p电极15上剥离。此外，因保护膜也形成在n电极14上，所以，也防止了n电极14从n型半导体层12上被剥离。这样，就提供了可靠性特别优良的器件。
图9，除n电极14和焊盘17形成在平面矩形晶片对角线上的对角部之外，都与图8所示结构相同。采用这种电极配置，可以取得与图3所说明的优点相同的优点。
下面，说明有关本发明的n电极。
本发明的n电极用包含钛和铝与/或金的金属材料，例如，包含钛和铝的材料、包含钛和金的材料、或者包含钛、金与铝的材料形成。这些金属，可以预先合金化，也可以是由各金属层层叠的结构。用这些金属材料形成的电极，退火后，实现了与n型氮化镓系III-V族化合物半导体层的优良欧姆接触。
在上述退火温度，最好在400℃以上，退火可以进行0.01分钟到30分钟。
一般，氮化镓系III-V族化合物半导体即使没有掺杂剂掺入，由于在结晶中形成氮晶格空位，还是具有成为n型的性质。在化合物半导体的生长过程中，由于掺入硅、锗、硒、硫等的n型掺杂剂，表现出最好的n导电型。而且，氮化镓系III-V族化合物半导体，通常采用有机金属气相生长法(MOCVD，或MOVPE)、氢化物气相生长法(HDCVD)、分子束外延(MBE)这样的气相生长法生长。就这些气相生长法来说，采用例如，用作镓源的三甲基镓、用作氮源的氨或联氨等含氢原子化合物，还用氢气等气体用作携带气体。含氢原子的这些气体，在氮化镓系III-V族化合物半导体生长中被热分解放出氢，氢被吸收到生长的半导体中，与氮晶格空位或n型掺杂剂结合，阻碍了它们作为施主的作用。如果在400℃以上的温度使n电极材料或p电极材料退火，半导体结晶中捕集的氢元素会被赶出，于是，结晶中的n型掺杂剂或者p型掺杂剂被激活，有效地增加了结晶中电子载流子浓度或空穴载流子浓度，可以认为实现了与电极的欧姆接触。这样退火的效果和上述特开平5-183189号公告或USSN07/970145所记载的将p型掺杂剂掺入氮化镓系III-V族化合物半导体的效果是一样的。在该公告中，记载表明，掺入了p型掺杂剂的氮化镓系III-V族化合物半导体，从400℃的退火温度开始，电阻率慢慢降低，在700℃以上的退火温度则电阻率不变。然而本发明的n型氮化镓系III-V族化合物半导体，在400℃退火开始，虽然慢慢降低电阻率，但没有发现急烈的电阻率下降，在600℃下退火，电阻率约变为初始电阻率的1/2，即使在该温度以上进行退火，电阻率也不再降低。
对n电极的退火温度，以500℃以上为好，600℃以上为更好。n电极材料含铝时，退火温度用较低的温度就足够了，优选在450℃以上，最好在500℃以上。退火温度的上限，与p电极退火的上限温度一样，是不到氮化镓系III-V族化合物半导体分解的温度。对n电极的总厚度虽然没有特别限制，但通常为50埃以上，优选为0.01μm到5μm之间。
包含钛和铝与/或金的本发明n电极材料以各金属层的叠层结构为好。这时，可以让钛层在n型氮化镓系III-V族化合物半导体层上直接接触。这是由于，钛与n型氮化镓系III-V族化合物半导体能形成极优良的欧姆接触之故。这种情况下，钛层可以形成厚度为20A到0.3μm范围。另外，铝或金层的总厚度以比钛层厚为好。因此，退火时钛表面迁移之后，在进行丝焊时就能防止与n电极焊丝或焊球的附着强度的降低。
包含钛与金、或者钛与金和铝的本发明的n型电极材料还比由钛与铝组成的n电极材料的抗氧化性能好，与丝焊时形成的金球附着更牢固。还有，含金的本发明的n电极材料，可以把最上层做成金层的叠层结构。当然，这是因为金层和金球粘结得非常坚固。
图10表示设有本发明n电极的双异质结构的发光器件。该器件，例如在由蓝宝石构成的基片11上，使例如由非掺杂的GaN构成的厚度为0.02至0.5μm的缓冲层介于其间(未图示)，形成例如厚度为1μm至10μm的n型氮化镓系III-V族化合物半导体层51。
在n型半导体层51上，形成由n型氮化镓系III-V族化合物半导体，例如掺入硅等的n型掺杂剂的n型GaAlN构成的第1盖层52。该盖层52，通常厚度为0.01至5μm，较好为0.1至4μm。
第1盖层52之上又形成与盖层52半导体组分不同的氮化镓系III-V族化合物半导体构成的有源层(发光层)53。该有源层53可以用掺入n型或者p型掺杂剂，优选为掺硅等n型掺杂剂的低电阻率InaGa1-aN(0＜a＜1)来形成。有源层53厚度在10A至1.5μm间，较好为0.01至0.2μm间。
有源层53上再形成与有源层53有不同半导体组分的p型氮化镓系III-V族化合物半导体，例如掺镁等的p型掺杂剂的GaAlN构成的第2盖层54。第2盖层54通常厚度在0.01μm以上，较好为0.1至1μm。
第2盖层54之上，形成由p型氮化镓系III-V族化合物半导体，例如p型GaN构成的接触层55，其上还形成p电极56。p电极56用任何导电性合适的金属材料形成均可。显示良好欧姆特性而用作电极材料，可以举出的是含镍和金的金属材料。可以将镍和金预先做成合金，但是将各金属层层叠的结构(这时可使镍层与接触层直接接触)则更好。不言而喻，有关上述各实施方案的本发明透光性欧姆p电极15特别是焊盘32也都能用于图10的器件上。p电极56经过金属球59与焊丝60连接。
晶片从接触层55，沿其深度方向，到n型半导体层51的表面部位为止的部分由腐蚀除去，使n型半导体层51部分露出。再在该n型半导体层51的露出表面上，形成了本发明的n电极57。n电极57通过金属球58与焊丝61相连接。
实验例6
在直径2英寸的蓝宝石基片上，形成厚度4μm掺硅的n型GaN层，其表面上，蒸镀大小10μm的各种n电极材料每种各1000个，在450℃下做退火。全部测定由同一材料构成的电极之间的电流-电压特性。结果表示于图11A～11D的线A～D。图11A对应于按0.01∶1的厚度比依次层叠钛与铝所得的电极，图11B是用含有1重量％钛的Al-Ti合金形成的电极，图11C是由钛单独构成的电极，图11D是由铝单独构成的电极。这些图是表示各自代表的电流-电压特性曲线图，而由铝和钛构成的电极，如图11A、图11B所示那样，与n型GaN层形成良好的欧姆接触。还有，那些各1000个的电极全部表示出了如图11A、图11B所示的欧姆特性。另一方面，单独钛或单独铝构成的电极，分别如图11C、图11D所示的那样，哪个也没有表示出良好的欧姆特性，各1000个电极之中，能呈现如图11A或11B所示的那种欧姆特性的电极只不过几个。
而且，用显微镜观察了退火后的电极表面，由单独钛或单独铝构成的电极，其表面积90％以上都变质发黑了。
实验例7
在直径2英寸的蓝宝石基片上，形成厚度为0.2μm掺硅的n型Ga0.9Al0.1N层。在该表面上，按100μm大小，改变钛与铝的叠层结构n电极材料的钛层与铝层厚度之比，每种蒸发各自1000个，并在450℃下退火。测定由同一材料构成电极的电流～电压特性。结果如图12A～12D的线A～D所示。图12A～图12D分别对应于钛与铝按0.001∶1的厚度比，铝与钛按0.001∶1的厚度比，钛与铝接1∶0.001的厚度比，以及铝与钛按1∶0.001的厚度比，各自依次层叠所得的电极。这些图清楚表明不管钛与铝的含有比率如何，全都有良好的欧姆特性。还有，使钛层直接接触n型半导体层的Ti-Al电极全部呈现表示于图12A和12C的良好欧姆特性，但使铝层直接与n型半导体层接触的Al-Ti电极，没有呈现满意欧姆特性的各有几个。还有，无论哪一个电极也都未变质。
实验例8
在掺硅的n型GaAlN层上，首先蒸镀厚为0.03μm的钛，其上蒸镀厚为0.5μm的铝，再在其上蒸镀厚为0.5μm的金之后，将这个叠层结构以各种温度退火5分钟。在图13A～13D中用线A～D表示结果。图13A对应于退火温度300℃的情况，图13B是退火温度为400℃的情况，图13C是退火温度为500℃的情况，而图13D则对应于退火温度为600℃的情况。从这些图知道，退火温度为300℃的情况下，电极与n型半导体层之间没有表现出良好的欧姆特性(图13A)；退火温度为400℃以上的情况下，表现出满意的欧姆特性(图13B～13D)。还有，用钛、铝和金的合金形成n电极，也得到同样的结果。
实验例9
在掺硅的n型GaN层上除蒸镀厚度为0.03μm的钛，其上再蒸镀厚度为0.5μm的金以外，进行与实验例8同样的实验。在图14A～14D用线A～D表示结果，图14A是对应于退火温度为300℃时情况，图14B是退火温度为400℃的情况，图14C是退火温度为500℃的情况，而图14D则对应于退火温度为600℃的情况。从各个图知道，退火温度在300℃的情况下，电极与n型半导体层之间没有表现出良好的欧姆特性(图14A)；退火温度在400℃以上的情况下，表现出满意的欧姆特性(图14B～14D)。还有，用钛与金的合金形成电极也得到了同样的结果。
若将图14A～14D和图13A～13D作比较，对含钛与金的电极材料再外加铝，即使用较低的退火温度也可知能获得显示满意欧姆特性的n电极。所谓用较低温度获得满意的欧姆特性，这就是能抑制氮化镓系III-V族化合物半导体的热分解，对保持其结晶性这点上特别有利。
实验例10
为了研究n电极和金球的粘结强度，进行了以下实验。
通过参照图15，在掺硅的n型GaN层71上，形成由Al构成的薄膜、或由Ti-Al、Ti-Au、Ti-Au-Al或者Ti-Al-Au构成的多层膜(各多层膜从左起依次层叠)，做成各自直径120μm大小每种100个，在500℃下退火，形成n电极72。接着，将各n电极放置在空气中一天提供表面氧化。然后，各n电极上球焊金丝74。形成了直径100μm的金球73。此后，从金球的正侧面放一把刃具75，在刃具75加负荷，水平地拉刮球73，使球73剥落，或者未被剥落而毁坏为止。结果表示在表2中。表2中，各种负荷下的数值，表示从电极上剥落球的个数，而球不被剥落而毁坏，记作“毁坏”。
                       表2
如表2所示，由钛和金或钛和铝及金构成的n电极，比由钛和铝构成的n电极，耐氧化性能更优越，因而，也就表现出与金球有更强的粘结力。并且，由钛和铝及金构成n电极的场合，金作为最上层比铝作为最上层的场合，也清楚表现出更强的粘结力。
由钛和铝构成的n电极材料有良好欧姆特性，是由于防止了因氧化而降低金属球与n电极材料层的粘结力，其表面上最好层叠比铝有高熔点的高熔点金属材料层。这样的高熔点金属材料包括金、钛、镍、铂、钨、钼、铬和/或铜。最好是金、钛、和/或镍。这些材料和由钛与铝构成的第1金属材料层的粘合性非常好，不会与第1材料层剥离，而且，与丝焊时形成金属球的粘结也良好。特别是，第2高熔点金属材料以包含金为好。最好是包含金和金以外的高熔点金属(优选为钛和/或镍)材料。这些高熔点金属材料，既可预先合金化，也可以是各金属层层叠的结构。这时，以金做最上层为好，这是已经说过的。形成这样的叠层膜之后，按上述条件进行退火，就得到n电极。第2高熔点金属材料能防止包含在下层金属材料中的铝向n电极表面迁移，从而能防止铝氧化。
图16表示这种叠层结构的n电极57。图16中，n电极57是由钛和铝叠层结构组成的第1薄膜57a，以及在其上形成的例如叠层结构的高熔点金属材料组成的第2薄膜57b所构成。
实验例11
掺硅的n型GaN层上，蒸镀厚度为0.03μm钛，其上再蒸镀厚度0.1μm铝，形成第1薄膜后，在铝层上除依次蒸镀厚度0.03μm的钛、0.03μm的镍、以及0.5μm的金外，进行与实验例8同样的实验。结果表示为图17A～17D中的线A～D。图17A对应于退火温度为300℃的情况、图17B是退火温度为400℃的情况、图17C是退火温度为500℃的情况，而图17D是退火温度为600℃的情况。由各图可知，退火温度为300℃的情况下，电极与n型半导体层之间没有表现出良好的欧姆特性(图17A)，退火温度在400℃以上的情况下，则表现出满意的欧姆特性(图17B～17D)。还有，采用600℃退火温度也知道不会使欧姆特性劣化。
实验例12
为了研究n电极和金球的粘结强度，使用下面表3所示的电极材料，进行与实验例10同样的实验，将结果合并记在表3内。
                      表3
Figure A0314586700201
从表3可知，高熔点金属材料使钛和铝构成的金属材料的耐氧化性提高了，也使其与金球的粘结性提高了。
还有，上述的本发明的n电极，不言而喻，适用于图1以及图3到图9各器件的n电极14，能提高这些器件的特性。
以下记载本发明的实施例
实施例1
在蓝宝石基片上，依次层叠由非掺杂GaN构成的缓冲层(厚度0.02μm)、掺硅n型GaN层(厚4μm)、以及掺镁的p型GaN层(厚1μm)制备成2英寸直径的晶片。接着，为露出n型GaN层的n电极形成部，而腐蚀除去p型GaN层。
接着，掩蔽露出的n型GaN层部分之后，在整个p型GaN层上，蒸镀厚度为0.03μm镍，接着其上蒸镀厚度为0.07μm的金。接着，掩蔽该蒸镀膜，在露出的n型GaN层表面部分蒸镀铝。
然后，将所得的晶片在500℃下进行10分钟退火处理，随着镍和金合金化，变为透光性。退火后的p电极厚度为0.07μm，呈现透光性。
将该晶片切成350μm方形芯片，把一个芯片安装在图1所示杯形的引线架上，进行预定的丝焊，就制成了发光二极管。该二极管的发光输出，20mA下为80μw，正向电压为4V。
还有，由2英寸晶片切开的芯片个数，约为16000个，从这些芯片得到的发光二极管除去接触不好的产品之后的合格率在95％以上。
附带说，用实施例1获得的晶片，与已有技术同样地把p电极和n电极分别与引线架直接接触配置(制作在蓝宝石基片上)芯片时，芯片尺寸最小也要有1mm见方。跨在2条引线架上安装该1mm见方的芯片，进行所需的电极连接，而制成发光二极管。该发光二极管，用20mA电流，发光输出为40μw，而大家都知道横向发光不输出。而且，2英寸晶片切成的芯片个数不超过2000个，由这些芯片得到的发光二极管，除去接触不好的产品之后的合格率仅为60％。
因此，根据本发明，由于p型半导体层的电极是由实现欧姆接触金属构成的，而且是透光性的，所以能提供一种容许从氮化镓系化合物半导体层一侧观察发光的发光器件。还可以证实，由于不会降低发光器件的外部量子效率(光取出效率)，就是能有效地取出发射的光。并且，根据本发明，还可确认：能缩小1个芯片的尺寸、特别提高生产性，有增加合格率以及降低生产成本的效果。
实施例2
除用600℃进行退火外，都进行实施例1的工艺过程。所得到的p型电极大致上和实施例1电极有同样的厚度，并表现出同样的透光性。而且，制成的发光二极管呈现与实施例1二极管大致相同的发光输出、正向电压，另外合格率也是大体一样。
实施例3
p型GaN层上，除依次蒸镀厚度0.5μm的铬、厚度为0.5μm的镍以外，进行实施例1的工艺过程。所得到的p型电极的厚度为0.7μm，并呈现同样的透光性。并且，制成的发光二极管表现出与实施例1发光二极管大致相同的发光输出和正向电压，且合格率也大致相同。
实施例4
p型GaN层上，除依次蒸镀厚度为0.01μm的铂、厚度为0.1μm的钛以外，进行实施例1的工艺过程。所得到的p型电极具有0.07μm的厚度，并呈现同样的透光性。并且，制成的发光二极管表现出与实施例1的发光二极管大致相同的发光输出和正向电压，且合格率也大致一样。
实施例5
在直径2英寸的蓝宝石基片上，依次层叠GaN缓冲层、掺硅n型GaN层、掺硅GaAlN盖层、掺锌和硅的InGaN有源层、掺镁GaAlN盖层，以及掺镁p型GaN接触层，而形成双异质结构的晶片。
接着，对具有图10示出结构的1芯片施行腐蚀，露出部分的n型GaN层。用预定的掩模，在各个露出的n型GaN层上蒸镀100埃的钛，其上再蒸镀厚度0.5μm的金，形成直径100μm的多层膜。
将所得的晶片，在氮气氛中，600℃下，退火5分钟，使多层膜转化成n电极。用晶片探针测定n电极间的电流～电压特性，显示了图12D示出的欧姆特性。
接着，在p型接触层上，用常规方法形成p电极之后，把晶片切成芯片。于是，由2英寸晶片得到15000个芯片。
采用管芯焊接法，把各芯片安置在引线架上，再用球焊机在p和n电极上连接金丝。在15000个芯片之中，在球焊中球和n电极都没有剥离。并且，焊接后，任意抽出20个芯片，由于拉拽各条金丝时，在整个金球从n电极剥落前，金丝就断了。
实施例6
作为n电极材料，除蒸度100的钛，其上再蒸底厚度的0.4μm的铝以外，与实施例5同样制做，得到15000个发光芯片。用晶片探针测定所有n电极的电流～电压特性，给出了图11A示出的特性。并且，在15000个芯片之内，在球焊的过程中，金球和n电极没有剥离。而且，在焊接后，任意抽出20个芯片，拉拽各条金丝时，所有金球都在从n电极剥落之前金丝就断了。
实施例7
作为n电极，除蒸镀厚度为0.5μm的含1％钛的Ti-Al合金以外；作法与实施例5相同，从而得到15000个发光芯片。用晶体探针测定全部n电极的电流～电压特性，给出了图11B示出的特性。而且，15000个芯片之内，在球焊中，金球与n电极没有剥离。并且，在焊接后，任意抽出20个芯片，拉拽各条金丝时，所有金球都在从n电极上剥落之前金丝就断了。
实施例8
将实施例5的发光芯片，在p电极和n电极处与有2条引线的架粘结。这种情况下，p电极和n电极通过各自的铟粘结剂粘结。粘结后，拉拽n电极和连接的引线架时，在铟与引线架的界面发生了剥离。
本实施例表示了本发明的n电极用焊锡、铟、金合金等常用的粘结剂与引线架直接牢固粘合。
实施例9
在该实施例中，除了蒸镀100的钛、在其上蒸镀厚度为0.1μm的铝以形成第1薄膜，再在其上形成厚度为0.1μm的钛和0.1μm的镍作为第2薄膜以外，n型电极材料的其它制作方法都与实施例5相同。由此得到15000个发光芯片。用晶片探针测定全部n型电极的电流～电压特性，给出了图13D示出的特性。并且，15000个芯片之内，在球焊中，金球和n电极都滑有剥离。而且，焊接后，随机抽出20个芯片，拉拽各个金丝时，所有金球都在从n电极剥落之前金丝就断了。
实施例10
作为n电极材料的第2薄膜，除蒸镀厚度为0.1μm的钛以及厚度为0.4μm的金以外，都与实施例9同样制作，得到15000个发光芯片。根据晶片探针测定全部n电极的电流～电压特性，给出图14D示出的特性。并且，15000个芯片之中，在球焊中，金球和n电极没有剥离。而且，焊接后，随机抽出20个芯片，拉拽各金丝时，所有金球都在从n电极剥落之前金丝就已断了。
实施例11
作为n电极的第2薄膜，除蒸镀厚度为0.1μm的钛、厚度为0.1μm的铬，以及厚度为0.4μm的金以外，都与实施例9同样制作，得到15000个发光芯片。根据晶片探针测定的全部n电极的电流～电压特性，给出图13C或13D示出的特性。并且，15000个芯片中，在球焊中，金球和n电极都不会剥离。而且，焊接后，随机抽出20个芯片，拉拽各金丝时，在整个金球从n电极剥落前，金丝就已断了。
实施例12
将实施例9的发光芯片，在p电极和n电极处与2引线架粘结。这种情况下，p电极和n电极通过各自铟粘结剂粘结。粘结之后，拉拽与n电极连接的引线架时，铟和引线架的界面发生剥离。
以上虽然参照本发明的具体实施方案作出说明，但本发明不应仅限于此。各个实施方案，就其适用的范围来说，也能适用于其他实施方案。而且，例如，把本发明可加到p-n同质结或p-n双异质结的氮化镓系III-V族化合物发光器件上，也适用于p-n单异质结的氮化镓系III-V族化合物半导体发光器件。此外，本发明不但适用于发光二极管，而且也适用于激光二极管等其他发光器件、还有太阳电池、光电二极管等对600nm以下波长敏感的光敏器件。本发明主要是提供与氮化镓系化合物半导体为欧姆接触的电极材料。因而，本发明能够适用于基片上具有p型氮化镓系化合物半导体层和/或n型氮化镓系化合物半导体层的任何半导体发光器件。该基片不限于蓝宝石等绝缘性基片，也可用碳化硅(SiC)、硅(Si)、氧化锌(ZnO)、砷化镓(GaAs)、磷化镓(GaP)等半导体基片。

Claims (5)

1.氮化镓系化合物半导体发光器件，在绝缘衬底上至少依次层叠的n型氮化镓系化合物半导体层和p型氮化镓系化合物半导体层，所述p型氮化镓系化合物半导体层的侧面为发光观察面，其特征在于：
在所述p型氮化镓系化合物半导体层的整个表面上形成有透光的第一电极，同时在所述第一电极上形成有贯通该第一电极的一部分的切口状窗口；在所述窗口上形成有与第一电极电连接的焊接用第二电极，以及
所述第二电极与p型氮化镓系化合物半导体层粘结得比第一电极牢固。
2.如权利要求1所述的氮化镓系化合物半导体发光器件，其特征在于：所述第二电极用粘结性比所述第一电极好的p型氮化镓系化合物半导体层形成。
3.如权利要求2所述的氮化镓系化合物半导体发光器件，其特征在于：所述第二电极由从Cr、Al、Au中选出的至少2种材料或由Al单独构成。
4.如权利要求1所述的氮化镓系化合物半导体发光器件，其特征在于：所述第二电极的膜厚大于所述第一电极的膜厚。
5.如权利要求1所述的氮化镓系化合物半导体发光器件，其特征在于：所述第一电极由Ni和Au构成。
CNB03145867XA 1993-04-28 1994-04-28 氮化镓系化合物半导体发光器件 Expired - Lifetime CN1240142C (zh)

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JP12931393A JP2748818B2 (ja) 1993-05-31 1993-05-31 窒化ガリウム系化合物半導体発光素子
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JP20727493A JP2783349B2 (ja) 1993-07-28 1993-07-28 ｎ型窒化ガリウム系化合物半導体層の電極及びその形成方法
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JP23468493A JP2697572B2 (ja) 1993-09-21 1993-09-21 窒化ガリウム系化合物半導体発光素子
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JP23468593A JP2770717B2 (ja) 1993-09-21 1993-09-21 窒化ガリウム系化合物半導体発光素子
JP25317193A JP2770720B2 (ja) 1993-10-08 1993-10-08 窒化ガリウム系化合物半導体発光素子
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