CN107978661B - 一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片及制备方法 - Google Patents
一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片及制备方法 Download PDFInfo
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Abstract
一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片及制备方法,属于半导体发光器件技术领域。由(0001)面蓝宝石衬底、低温GaN缓冲层、氮极性GaN模板层、n‑GaN电子注入层、多量子阱有源层、极化诱导p型掺杂空穴注入层组成,其中氮极性GaN模板层中有SiNx掩膜层,极化诱导p型掺杂空穴注入层上设置有p电极,n‑GaN电子注入层有一裸露台面,在其上设置有n电极;本发明采用斜切的蓝宝石衬底,提高外延片的晶体质量及表面平整度;氮极性GaN模板层中原位插入SiNx掩膜,有效阻挡位错同时降低非故意掺杂的浓度,提高内量子效率;采用Al组分线性增加的掺Mg的AlGaN制作形成为极化诱导p型掺杂空穴注入层,提高空穴的浓度,提高电注入效率。
Description
技术领域
本发明属于半导体发光器件技术领域,具体涉及一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片及制备方法。
背景技术
GaN,AlN,InN及其合金化合物都是直接带隙半导体,其禁带宽度可以在0.7eV到6.2eV之内连续调节,对应的发光波长从红外一直延伸到紫外波段,是制备LED的理想材料。但是目前为止,唯一适合作为p型掺杂剂的Mg其室温下在GaN中的激活能高达200meV。这就导致室温下Mg的激活效率不会超过1%,而过高的掺杂浓度又会引入其他问题,如表面退化,极性反转等。因此p型GaN中的空穴浓度很难超过1018cm-3。低的空穴浓度会引入高的串联电阻,在大电流下工作还会导致Droop效应的产生。因此氮化物材料的p型掺杂成为了阻碍大功率高效率LED发展的瓶颈之一。
发明内容
本发明的目的就是为解决上述p型材料中Mg激活效率低问题,用氮极性(外延方向为轴方向)Al组分线性增加的掺Mg的AlGaN代替传统掺Mg的GaN作为空穴注入层制备蓝紫光LED。该器件结构利用了AlGaN薄膜中自发极化强度随Al组分增加而增加的特性,在Al组分线性增加的AlGaN薄膜中形成负的空间极化电荷,利用极化电荷对空穴的吸引能力诱导Mg受主中的空穴发生电离。由此产生的空穴的浓度仅和薄膜内空间电荷的密度有关,不受热激活能量的限制,从而实现提高Mg受主激活率,提升LED性能的目的。
本发明的技术方案是:
本发明所设计的一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片(见附图1和附图说明),其特征在于:其从下至上依次由高温氮化处理、带有斜切角的(0001)面蓝宝石衬底1、低温GaN缓冲层2、氮极性GaN模板层3、n-GaN电子注入层5、多量子阱有源层6、极化诱导p型掺杂空穴注入层7组成,其中氮极性GaN模板层3中有SiNx掩膜层4,极化诱导p型掺杂空穴注入层7上有p电极8,将部分表面蚀刻至裸露出n-GaN电子注入层5,其上面有n电极9.
如上所述的一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片,其特征在于:所述的(0001)面蓝宝石衬底1具有一定的斜切角(即蓝宝石衬底1的生长面与蓝宝石(0001)晶面具有一定的夹角),斜切方向为偏[1010]轴方向,斜切角为0.2~4°。
如上所述的一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片,其特征在于:芯片中除(0001)面蓝宝石衬底1,p电极8,n电极9外,均采用MOCVD外延完成,外延过程中,外延生长方向为氮化物的方向,所述外延生长方向对应的晶面为面。
如上所述的一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片,其特征在于:所述的SiNx掩膜层4位于氮极性GaN模板层3当中,由氨气和硅烷原位生成。
如上所述的一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片,其特征在于:多量子阱有源层6由阱层Inx3Ga1-x3N和垒层GaN交替生长组成,对数在2~5对之间,每个阱层的厚度为2~4nm,每个垒层的厚度为10~15nm,其中0.1≤x3≤0.2。
如上所述的一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片,其特征在于:所述的极化诱导p型掺杂空穴注入层7由掺Mg的AlGaN材料构成,其中Al的组分沿外延生长方向逐渐升高,即从Alx1Ga1-x1N到Alx2Ga1-x2N逐渐过渡,其中0≤x1<x2≤1,厚度为50~100nm。
如上所述的一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片,其特征在于:低温GaN缓冲层2的厚度为10~30nm,氮极性GaN模板层3的厚度为2~3μm,SiNx掩膜层4位于氮极性GaN模板3当中,其距离蓝宝石衬底1为100~500nm,n-GaN电子注入层5的厚度为0.5~1μm,InGaN基多量子阱有源区6中每个阱层Inx3Ga1-x3N的厚度为2~4nm、每个垒层GaN的厚度为10~15nm,极化诱导p型掺杂空穴注入层7的厚度为50~100nm,p电极层8的厚度为10~30nm,n电极层9的厚度为60~100nm。
一种如上所述的带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片的制备方法,其步骤如下:
(1)为了使外延生长方向沿氮化物的方向进行,首先将带有斜切角的(0001)面蓝宝石衬底在氨气和氮气的混合气氛下进行原位的高温氮化处理(氨气和氮气的体积比为1:2~1:3,氮化温度为1020~1080℃,氮化处理的时间120~240s),之后采用MOCVD方法的蓝宝石衬底上依次外延生长低温GaN缓冲层2(生长温度520~560℃,厚度10~30nm,生长源为氨气和三乙基镓)、氮极性GaN模板层3(生长温度1050~1100℃,厚度100~500nm,生长源为氨气和三甲基镓)、SiNx掩膜层4(生长温度1020~1080℃,生长时间30~120s,生长源为氨气和硅烷,为多孔结构)、氮极性GaN模板层3(与前面生长氮极性GaN模板层的工艺条件相同,厚度1.5~2.5μm)、n-GaN电子注入层5(生长温度1020~1050℃,厚度0.5~1μm,生长源为氨气和三甲基镓,掺杂源为硅烷,掺杂浓度为1018~1019/cm3)、多量子阱有源层6(量子阱由阱层Inx3Ga1-x3N和垒层GaN交替生长组成,对数在2~5对之间,每个阱层的厚度为2~4nm,每个垒层的厚度为10~15nm,其中0.1≤x3≤0.2,阱层Inx3Ga1-x3N生长源为氨气、三甲基铟和三乙基镓,垒层GaN的生长源为氨气和三甲基镓)、极化诱导p型掺杂空穴注入层7(由掺Mg的、Al组分沿外延方向线性增加的AlGaN制成,生长过程中通过线性的减少Ga源的流量同时线性增加Al源的流量实现Al组分的线性变化,生长温度980~1020℃,厚度50~100nm,生长源为氨气、三甲基镓和三甲基铝,掺杂源为二茂镁,掺杂浓度为1019~1020/cm3),从而制备得到氮极性蓝紫光LED结构;
(2)在极化诱导p型掺杂空穴注入层7上表面一侧的区域用ICP方法刻蚀至裸露出n-GaN电子注入层5,得到n-GaN台面;在未刻蚀的极化诱导p型掺杂空穴注入层7上制备p电极8(厚度10~30nm),在露出的n-GaN台面上制备n电极9(厚度60~100nm);p电极的材料可以是Au、Pt等单层材料,Ni-Au、Ni-Pt等二元合金复合材料或Ti-Pt-Au、Ni-Pt-Au等三元复合材料,n电极的材料可以是Ti-Al二元合金复合材料、Ti-Al-Au三元合金复合材料或者Ti-Al-Ni-Au四元合金复合材料,制备电极的方法可采用热蒸镀、电子束蒸镀或磁控溅射方法(n电极指n-GaN台面上生长的电极,没有掺杂;p电极指极化诱导p型掺杂空穴注入层7上生长的电极,没有掺杂)。
本发明的效果和益处:本发明采用带有一定斜切角度的(0001)面蓝宝石作为衬底,通过斜切可以在衬底表面形成原子级的台阶,促进LED芯片在整个外延过程中生长模式向台阶流模式发展,从而提高外延的晶体质量及表面平整度;本发明在氮极性GaN模板层中原位插入具有多孔结构的SiNx掩膜层,从而大幅降低外延层中的位错密度及非故意掺杂的浓度,提高LED的内量子效率;本发明采用氮极性Al组分线性增加的掺Mg的AlGaN代替传统掺Mg的GaN作为蓝紫光LED的空穴注入层,依靠极化电场诱导产生空穴,具有空穴浓度高、温度稳定性好的特点,可以有效提高空穴的浓度及热稳定性,从而提高LED的发光效率;同时Al组分线性增加会导致AlGaN的禁带宽度从下到上逐渐增加,再加上极化电场的作用,使得p型AlGaN在作为空穴注入层的同时起到电子阻挡层的作用,避免了额外制作电子阻挡层,简化了器件结构和工艺。
附图说明
图1:本发明所述带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片的结构示意图;
图2:实施例1制备的氮极性极化诱导p型掺杂的AlGaN及氮极性p型GaN空穴浓度随温度变化对比图;
图3:本发明所述带有极化诱导p型掺杂层的LED能带结构示意图,极化诱导p型掺杂层在作为空穴注入层的同时可以阻挡电子溢出有源区;
图4:实施例1制备的氮极性LED在不同电流注入下的发光谱图。
图中,1为蓝宝石衬底、2为低温GaN缓冲层、3为氮极性GaN模板层、4为SiNx掩膜层、5为n-GaN电子注入层、6为多量子阱有源层、7极化诱导p型掺杂空穴注入层、8为p电极、9为n电极。
具体实施方式
以下结合技术方案和附图详细叙述本发明的具体实施例。
实施例1:
1.采用MOCVD方法,首先将商用带有斜切角的(0001)面蓝宝石衬底(圆形,直径2英寸,斜切方向为偏轴方向,斜切角为0.8°)进行高温氮化,之后在衬底上一次性外延制备N极性蓝紫光LED结构,如图1所示。具体结构如下:在高温氮化的蓝宝石衬底1上依次制备低温GaN缓冲层2(厚度10nm)、氮极性GaN模板层3(厚度300nm)、原位SiNx掩膜层4(生长时间为120s)、氮极性GaN模板层3(厚度1.7μm)、n-GaN电子注入层5(Si掺杂浓度2×1018/cm3,厚度0.5μm)、InGaN多量子阱有源层6(量子阱对数为2对,即阱-垒-阱-垒层结构,垒层为GaN,厚度13nm,阱层为In0.1Ga0.9N,厚度2nm)、极化诱导p型掺杂空穴注入层7(Al组分从下到上为从0到0.3线性增加,Mg掺杂浓度2×1019/cm3,厚度75nm)。
氮化的温度为1050℃,反应压强为600mbar,氮化用的气体为体积比1:3的氨气和氮气混合气;低温GaN缓冲层2生长温度为560℃,反应压强为600mbar,生长源为氨气和三乙基镓;氮极性GaN模板层3生长温度为1080℃,反应压强为300mbar,生长源为氨气和三甲基镓;SiNx掩膜层4生长温度为1050℃,反应压强为100mbar,生长源为氨气和硅烷;n-GaN电子注入层5生长温度为1050℃,反应压强为300mbar,生长源为氨气和三甲基镓,掺杂源为硅烷;多量子阱有源层6垒层GaN和阱层InGaN的生长温度分别为870℃和775℃,反应压强为400mbar,垒层的生长源为氨气和三甲基镓,阱层生长源为氨气、三甲基铟和三乙基镓;极化诱导p型掺杂空穴注入层7生长温度为1020℃,反应压强为150mbar,生长源为氨气、三甲基镓和三甲基铝,掺杂源为二茂镁;器件各层具体生长参数见表1。
2.用ICP方法(刻蚀气体为流量比为9:1的氯气和氯化硼,极板功率100w)在极化诱导p型掺杂空穴注入层7上表面一侧的区域刻蚀至裸露出n-GaN电子注入层5,得到n-GaN台面;分别采用热蒸镀方法在未刻蚀的极化诱导p型掺杂空穴注入层7上制备Ni-Au二元合金复合材料的p电极层8(厚度30nm,Ni层厚度为10nm,Au层厚度为20nm,蒸发源分别为Ni金属和Au金属)、在露出的n-GaN台面上制备Ti-Al二元合金复合材料的n电极层9(厚度120nm,Ti层厚度为20nm,Al层厚度为100nm,蒸发源分别为Ti金属和Al金属),从而得到氮极性蓝紫光LED芯片。电极的具体制备工艺见表2。
3.图2所示为本发明器件中所涉及的极化诱导p型掺杂的AlGaN与普通p型GaN空穴浓度随温度变化的对比图。由图中数据可知,在测量的温度范围内(150~450K)极化诱导掺杂得到的样品比普通的p型GaN的空穴浓度更高,而且极化诱导掺杂样品的空穴几乎不随温度的变化而改变。
4.图3所示为器件的能带结构示意图,多量子阱有源区和极化诱导p型掺杂空穴注入层之间存在较大的导带带阶,有源区的电子想要溢出有源区需要克服很高的势垒,因此极化诱导p-Alx1Ga1-x1N空穴注入层7可以起到阻挡电子的作用。
5.图4所示为器件在不同驱动电流下的电致发光谱,此时器件的p电极连接直流电源的正极,n电极连接负极。在20mA、25mA、30mA、35mA和40mA的正向电流下,发光谱在430nm处均显示出蓝紫光发射峰。
表1:带有极化诱导p型掺杂层的氮极性蓝紫光LED各层生长参数
表1附注:TMGa代表三甲基镓;TEGa代表三乙基镓;TMIn代表三甲基铟;TMAl代表三甲基铝;Cp2Mg代表二茂镁;SiH4代表硅烷;NH3代表高纯氨气。
表2:器件电极制备工艺参数
Claims (3)
1.一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片,其从下至上依次由具有一定的斜切角,斜切方向为偏轴方向,斜切角为0.2~4°的c面蓝宝石衬底(1)、低温GaN缓冲层(2)、氮极性GaN模板层(3)、n-GaN电子注入层(5)、多量子阱有源层(6)、极化诱导p型掺杂空穴注入层(7)组成;其中氮极性GaN模板层(3)中有SiNx掩膜层(4);极化诱导p型掺杂空穴注入层(7)上设置有p电极(8);n-GaN电子注入层(5)有一裸露台面,在其上设置有n电极(9);其特征在于:InGaN基量子阱有源区(6)由阱层Inx3Ga1-x3N和垒层GaN交替生长组成,对数在2~5对之间,其中0.1≤x3≤0.2;并且该芯片的制备步骤如下:
(A)将带有斜切角的(0001)面蓝宝石衬底(1)在氨气和氮气的混合气氛下进行原位的高温氮化处理,之后采用MOCVD方法的蓝宝石衬底上依次外延生长低温GaN缓冲层(2)、氮极性GaN模板层(3)、SiNx掩膜层(4)、氮极性GaN模板层(3)、n-GaN电子注入层(5)、多量子阱有源层(6)、极化诱导p型掺杂空穴注入层(7),从而制备得到氮极性蓝紫光LED结构;氨气和氮气的体积比为1:2~1:3,氮化温度为1020~1080℃,氮化处理的时间120~240s;
(B)在极化诱导p型掺杂空穴注入层(7)上表面一侧的区域用ICP方法刻蚀至n-GaN电子注入层(5),得到裸露的n-GaN台面;在未刻蚀的极化诱导p型掺杂空穴注入层(7)上制备p电极(8),在裸露的n-GaN台面上制备n电极(9);从而制备得到带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片;
其中,低温GaN缓冲层(2)的生长温度为520~560℃,生长源为氨气和三乙基镓;氮极性GaN模板层(3)的生长温度为1050~1100℃,生长源为氨气和三甲基镓;SiNx掩膜层(4)的生长温度为1020~1080℃,生长时间30~120s,生长源为氨气和硅烷,为多孔结构;n-GaN电子注入层(5)的生长温度为1020~1050℃,生长源为氨气和三甲基镓,掺杂源为硅烷,掺杂浓度为1018~1019/cm3;多量子阱有源层(6)阱层Inx3Ga1-x3N的生长源为氨气、三甲基铟和三乙基镓,垒层GaN的生长源为氨气和三甲基镓;极化诱导p型掺杂空穴注入层(7)由掺Mg的AlGaN材料构成,其中Al的组分沿外延生长方向逐渐升高,即从Alx1Ga1-x1N到Alx2Ga1-x2N逐渐过渡,其中0≤x1<x2≤0.3;生长过程中通过线性的减少Ga源的流量同时线性增加Al源的流量实现Al组分的线性变化,生长温度980~1020℃,厚度50~100nm,生长源为氨气、三甲基镓和三甲基铝,掺杂源为二茂镁,掺杂浓度为1019~1020/cm3。
2.如权利要求1所述的一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片,其特征在于:低温GaN缓冲层(2)的厚度为10~30nm,氮极性GaN模板层(3)的厚度为2~3μm,SiNx掩膜层(4)位于氮极性GaN模板(3)当中,其距离蓝宝石衬底(1)为100~500nm,n-GaN电子注入层(5)的厚度为0.5~1μm,InGaN基多量子阱有源区(6)中每个阱层Inx3Ga1-x3N的厚度为2~4nm、每个垒层GaN的厚度为10~15nm,极化诱导p型掺杂空穴注入层(7)的厚度为50~100nm,p电极层(8)的厚度为10~30nm,n电极层(9)的厚度为60~100nm。
3.如权利要求1所述的一种带有极化诱导p型掺杂层的氮极性蓝紫光LED芯片,其特征在于:p电极材料为Au、Pt、Ni-Au、Ni-Pt、Ti-Pt-Au或Ni-Pt-Au,n电极材料为Ti-Al、Ti-Al-Au或Ti-Al-Ni-Au,p电极和n电极采用热蒸镀、电子束蒸镀或磁控溅射方法制备。
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