CN105762243A - 一种p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器及其制备方法 - Google Patents
一种p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器及其制备方法 Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
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- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
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- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Abstract
本发明公开了一种pGaN/ZnO基多量子阱/nZnO结构的发光二极管及激光器及其制备方法,该发光二极管及激光器包括pGaN层、ZnO/ZnMgO多量子阱层、nZnO层和金属电极。其制备方法如下:首先采用分子束外延法在pGaN薄膜上先后制备ZnO/ZnMgO多量子阱层和nZnO层;然后分别在pGaN及nZnO区镀上金属电极。本发明所制备的器件采用ZnO/ZnMgO多量子阱作为有源层,可降低发光二极管及激光器的阈值并提高其发光效率;此外,为解决同质结构中高效稳定的pZnO难以实现的问题,本发明采用pGaN作为空穴注入层;同时,相比于其它p型材料,GaN具有与ZnO结构相同、外延失配低的优势。
Description
技术领域
本发明涉及一种发光二极管及激光器的制备方法,尤其涉及一种p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器及其制备方法,属于半导体光电子器件领域。
背景技术
近年来,短波长发光二极管、激光器等以其高效节能的优势,已成为半导体光电子领域的研究热点。ZnO作为宽禁带半导体材料,具有直接带隙能带结构,室温禁带宽度为3.37eV;除具有物理化学性质稳定、原料丰富等优点外,ZnO的激子束缚能高达60meV,远高于GaN(25meV)、ZnSe(22meV)等半导体材料,同时也高于室温热能(26meV),因此ZnO中具有很高的激子密度,这为实现室温高效发光提供可能。
然而就ZnO基发光二极管及激光器而言,目前研究报道的同质器件由于高效稳定的p-ZnO难以获得,导致其发光效率较低,不利于产业应用,制约了ZnO基材料的发展;而基于ZnO的异质器件,如较常采用p-NiO等作为空穴注入层,往往由于晶格失配较大,难以获得高质量的界面,同样导致发光性能不够理想。而p-GaN不仅具有稳定高效的p型导电性能,同时与ZnO的晶格失配小,非常合适作为ZnO基器件的空穴注入层。
此外,由于电子迁移率远高于空穴,ZnO基p-n结中电子空穴复合主要发生在p区,而p区一般采用了质量相对较差的p-ZnO或其它异质材料(如p-GaN、p-NiO等),导致发光效率降低及ZnO高激子束缚能的优势无法发挥,同样限制了ZnO基光电器件的应用。采用ZnO/ZnMgO多量子阱作为有源层可解决上述问题,但实现高质量的ZnO/ZnMgO多量子阱对制备方法等要求较高。目前,在ZnO基发光二极管及激光器领域,国际国内尚无p-GaN/ZnO/ZnMgO多量子阱/n-ZnO结构的报道。
发明内容
本发明的目的是针对现有结构的不足,提供一种低激发阈值、高发射效率的p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器及其制备方法。
本发明所述的发光二极管及激光器包括自下而上依次设置的p-GaN层、ZnO/ZnMgO多量子阱层、n-ZnO层,在p-GaN层和n-ZnO层上还分别设有第一电极、第二电极。
所述的ZnO/ZnMgO多量子阱层周期为3~10,ZnO层的厚度为3~5nm,ZnMgO层的厚度为5~10nm。所述的ZnMgO层中Mg摩尔组分为10%~20%。
其制备方法包括以下步骤:
1)采用分子束外延法在p-GaN薄膜上制备ZnO/ZnMgO多量子阱层,并预留生长第一电极的面积:
所述分子束外延法生长ZnO/ZnMgO多量子阱层,具体生长过程为ZnO层和ZnMgO层交替生长,其周期为3~10;ZnO层的厚度为3~5nm,以纯金属Zn和经射频活化的纯O2为生长源,衬底温度为500~750℃,Zn源炉温为250~300℃,氧气流量为1~3sccm;ZnMgO层的厚度为5~10nm,以纯金属Zn、纯金属Mg和经射频活化的纯O2为生长源,Mg源炉温330~380℃,其它生长条件与前述ZnO层相同;
2)采用分子束外延法在ZnO/ZnMgO多量子阱层上制备n-ZnO层:
所述分子束外延法生长n-ZnO层,以纯金属Zn和经射频活化的纯O2为生长源,或者以纯金属Zn、纯金属Ga和经射频活化的纯O2为生长源,衬底温度为500~750℃,Zn源炉温250~300℃,Ga源炉温300~500℃,氧气流量为1~3sccm,n-ZnO层的厚度为200~300nm;
3)在p-GaN预留面积处及n-ZnO上分别镀上第一电极和第二电极,电极厚度为70~100nm。
本发明所述的纯金属Zn的纯度≥99.9998%,纯金属Mg的纯度≥99.9999%,纯金属Ga的纯度≥99.99999%,纯O2的纯度≥99.9999%;所述的ZnMgO层中Mg摩尔组分为10%~20%;所述的p-GaN层为采用金属有机化学气相沉积法在蓝宝石衬底上生长的p-GaN薄膜,其空穴浓度高于5×1017cm-3。
ZnO/ZnMgO多量子阱中ZnO、ZnMgO层以及n-ZnO层的具体厚度可通过调整生长时间改变。
本发明的有益效果在于:
1.本发明采用p-GaN作为空穴注入层,其p型导电性能稳定可靠、商用易获得,且与ZnO外延失配小,具有诸多其它材料无可比拟的优势。
1)同为直接带隙宽禁带半导体材料,GaN室温禁带宽度为3.44eV;其p型掺杂的难题已解决,目前已实现广泛的商业应用。因此,p-GaN可作为稳定高效的空穴注入层。
2)GaN在结构方面与ZnO有诸多相似之处:两者的晶体结构相同,均为六方纤锌矿结构;晶格常数十分接近,a轴及c轴的晶格失配分别仅为1.8%和0.5%。相比于其它p型材料(如:NiO),GaN与ZnO形成异质结构时外延失配低,有利于提高界面质量。
2.本发明采用ZnO/ZnMgO多量子阱作为有源层,可以降低器件的激发阈值、提高其发射效率。
1)ZnMgO合金与ZnO晶格常数匹配带隙可调,是ZnO基量子阱结构中理想的势垒材料。ZnO的激子束缚能高达60meV,与GaN等相比,可实现更低阈值的受激发射;此外,由于量子限域效应,量子阱可获得更高的激子束缚能,因此,采用ZnO/ZnMgO多量子阱作为有源层,可实现低阈值发光。
2)量子阱结构中电子空穴被有效地限制在阱层中,相比于ZnO基p-n结器件,电子空穴复合区域由p区变为高质量的阱层,可实现高效率发光。
3.本发明采用分子束外延方法,可制备高质量ZnO/ZnMgO多量子阱及n-ZnO薄膜。
1)分子束外延法可精确控制外延层组成、结构及掺杂量,生长速度慢,能对薄膜厚度进行精确调控,是生长多量子阱结构的“利器”。在制备高质量薄膜及量子阱结构方面具有其它真空镀膜方法无法比拟的优势。
2)多量子阱结构中,随着阱层厚度减小量子限域效应增强,但厚度太小难以保证其质量;本发明所述阱层厚度为3-5nm,所制备ZnO/ZnMgO多量子阱具有明显的量子限域效应,且各层厚度可精确调控,界面平整。
本发明获得的发光二极管及激光器发光阈值低,且其制备方法基于MBE实现,精确可控,界面质量及外延层晶体质量高,有利于提高其发光效率。
附图说明
图1是p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器的结构示意图。
图中:1为蓝宝石衬底、2为p-GaN层、3为ZnO/ZnMgO多量子阱层(详细结构见右侧放大图,3-1为ZnO层、3-2为ZnMgO层)、4为n-ZnO层、5为第二电极、6为第一电极。
具体实施方式
以下结合附图及具体实施例对本发明做进一步阐述。
参照图1,本发明的p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器件,包括蓝宝石衬底1上生长的p-GaN层2、ZnO/ZnMgO多量子阱层3、n-ZnO层4和Au电极5、6。
实施例1
1)衬底清洗:将生长有p-GaN层的蓝宝石衬底依次放入丙酮、酒精和去离子水分别超声清洗10min,经去离子水冲洗后,用氮气吹干。
2)衬底预处理:将上述洗净的衬底放入分子束外延系统预处理室内烘烤3h,温度为300℃;随后放入高真空生长室内800℃高温处理30min。
3)采用分子束外延法在p-GaN层上沉积5个周期的ZnO/ZnMgO多量子阱,同时预留生长第一电极的面积,以纯金属Zn(纯度为99.9998%)为Zn源,纯金属Mg(纯度为99.9999%)为Mg源,经射频活化的纯O2(纯度为99.9999%)为O源,衬底温度为650℃,Zn源炉温250℃,Mg源炉温350℃,氧气流量为1sccm,射频功率为300W;ZnO层和ZnMgO层交替生长,阱层ZnO生长时间为120s,厚度约3nm,垒层ZnMgO生长时间为300s,厚度约8nm;
4)采用分子束外延法在ZnO/ZnMgO多量子阱层上制备n-ZnO薄膜,以纯金属Zn(纯度为99.9998%)为Zn源,经射频活化的纯O2(纯度为99.9999%)为O源,衬底温度为650℃,Zn源炉温250℃,氧气流量为1sccm,射频功率为300W;生长时间为3h,厚度约280nm;
5)在上述p-GaN预留面积处及n-ZnO区镀上金属Au电极,厚度为70nm。制得p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器。
实施例2
1)衬底清洗:将生长有p-GaN层的蓝宝石衬底依次放入丙酮、酒精和去离子水分别超声清洗10min,经去离子水冲洗后,用氮气吹干。
2)衬底预处理:将上述洗净的衬底放入分子束外延系统预处理室内烘烤3h,温度为300℃;随后放入高真空生长室内800℃高温处理30min。
3)采用分子束外延法在p-GaN层上沉积5个周期的ZnO/ZnMgO多量子阱,同时预留生长第一电极的面积,以纯金属Zn(纯度为99.9998%)为Zn源,纯金属Mg(纯度为99.9999%)为Mg源,经射频活化的纯O2(纯度为99.9999%)为O源,衬底温度为700℃,Zn源炉温250℃,Mg源炉温355℃,氧气流量为1.5sccm,射频功率为300W;ZnO层和ZnMgO层交替生长,阱层ZnO生长时间为160s,厚度约4nm,垒层ZnMgO生长时间为320s,厚度约9nm;
4)采用分子束外延法在ZnO/ZnMgO多量子阱层上制备n-ZnO薄膜,以纯金属Zn(纯度为99.9998%)为Zn源,纯金属Ga(纯度为99.99999%)为Ga源,经射频活化的纯O2(纯度为99.9999%)为O源,衬底温度为700℃,Zn源炉温250℃,Ga源炉温350℃,氧气流量为1sccm,射频功率为300W;生长时间为3h,厚度约300nm;
5)在上述p-GaN预留面积处及n-ZnO区镀上金属Au电极,厚度为100nm。制得p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器。
实施例3
1)衬底清洗:将生长有p-GaN层的蓝宝石衬底依次放入丙酮、酒精和去离子水分别超声清洗10min,经去离子水冲洗后,用氮气吹干。
2)衬底预处理:将上述洗净的衬底放入分子束外延系统预处理室内烘烤3h,温度为300℃;随后放入高真空生长室内800℃高温处理30min。
3)采用分子束外延法在p-GaN层上沉积8个周期的ZnO/ZnMgO多量子阱,同时预留生长第一电极的面积,以纯金属Zn(纯度为99.9998%)为Zn源,纯金属Mg(纯度为99.9999%)为Mg源,经射频活化的纯O2(纯度为99.9999%)为O源,衬底温度为700℃,Zn源炉温250℃,Mg源炉温360℃,氧气流量为2sccm,射频功率为300W;ZnO层和ZnMgO层交替生长,阱层ZnO生长时间为180s,厚度约5nm,垒层ZnMgO生长时间为400s厚度约10nm;
4)采用分子束外延法在ZnO/ZnMgO多量子阱层上制备n-ZnO薄膜,以纯金属Zn(纯度为99.9998%)为Zn源,纯金属Ga(纯度为99.99999%)为Ga源,经射频活化的纯O2(纯度为99.9999%)为O源,衬底温度为700℃,Zn源炉温250℃,Ga源炉温400℃,氧气流量为2sccm,射频功率为300W;生长时间为2.5h,厚度约240nm;
5)在上述p-GaN预留面积处及n-ZnO区镀上金属Au电极,厚度为100nm。制得p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器。
Claims (6)
1.一种p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器,其特征在于,包括自下而上依次设置的p-GaN层(2)、ZnO/ZnMgO多量子阱层(3)、n-ZnO层(4),在p-GaN层(2)和n-ZnO层(4)上还分别设有第一电极(6)、第二电极(5)。
2.根据权利要求1所述的p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器,其特征在于,所述的ZnO/ZnMgO多量子阱层(3)周期为3~10,ZnO层的厚度为3~5nm,ZnMgO层的厚度为5~10nm。
3.制备权利要求1所述的p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器的方法,其特征在于包括以下步骤:
1)采用分子束外延法在p-GaN薄膜(2)上制备ZnO/ZnMgO多量子阱层(3),并预留生长第一电极的面积:
所述分子束外延法生长ZnO/ZnMgO多量子阱层(3),具体生长过程为ZnO层和ZnMgO层交替生长,其周期为3~10;ZnO层的厚度为3~5nm,以纯金属Zn和经射频活化的纯O2为生长源,衬底温度为500~750℃,Zn源炉温为250~300℃,氧气流量为1~3sccm;ZnMgO层的厚度为5~10nm,以纯金属Zn、纯金属Mg和经射频活化的纯O2为生长源,Mg源炉温330~380℃,其它生长条件与前述ZnO层相同;
2)采用分子束外延法在ZnO/ZnMgO多量子阱层(3)上制备n-ZnO层(4):
所述分子束外延法生长n-ZnO层(4),以纯金属Zn和经射频活化的纯O2为生长源,或者以纯金属Zn、纯金属Ga和经射频活化的纯O2为生长源,衬底温度为500~750℃,Zn源炉温250~300℃,Ga源炉温300~500℃,氧气流量为1~3sccm,n-ZnO层(4)的厚度为200~300nm;
3)在p-GaN(2)预留面积处及n-ZnO(4)上分别镀上第一电极(6)和第二电极(5),电极厚度为70~100nm。
4.根据权利要求3所述的p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器的制备方法,其特征在于:所述的纯金属Zn的纯度≥99.9998%,纯金属Mg的纯度≥99.9999%,纯金属Ga的纯度≥99.99999%,纯O2的纯度≥99.9999%。
5.根据权利要求3所述的p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器的制备方法,其特征在于:步骤1)中所述的ZnMgO层中Mg摩尔组分为10%~20%。
6.根据权利要求1所述的p-GaN/ZnO基多量子阱/n-ZnO结构的发光二极管及激光器,其特征在于,所述的p-GaN层(2)为采用金属有机化学气相沉积法在蓝宝石衬底(1)上生长的p-GaN薄膜,其空穴浓度高于5×1017cm-3。
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