技术领域technical field
本发明属于发光二极管的技术领域，具体地涉及一种高光效发光二极管外延片及其制备方法、LED。The invention belongs to the technical field of light-emitting diodes, and in particular relates to a high-efficiency light-emitting diode epitaxial wafer, a preparation method thereof, and an LED.
背景技术Background technique
发光二极管(LED)作为新一代的照明光源，由于其长寿命、节能度高、绿色环保等显著特征，被广泛应用于照明领域。Light-emitting diodes (LEDs), as a new generation of lighting sources, are widely used in the field of lighting due to their outstanding features such as long life, high energy saving, and environmental protection.
III 族氮化物 LED 采用InGaN/GaN多量子阱作为有源区，理论上可以覆盖从近紫外到近红外的宽光谱区，使其在固态照明中非常具有吸引力。一般来讲，生长长波长LED的量子阱的温度大约在700-800℃，利用相对较低的温度下进行，来提高量子阱层中的铟含量。然而，降低温度所带来的不良影响，亦会导致之后的AlGaN层的晶体质量的显著降低。另外由于InGaN与AlGaN的晶格失配，导致量子阱层的量子限制斯塔克效应会显著降低氮化物基LED的发光强度。III-nitride LEDs use InGaN/GaN multiple quantum wells as the active region, which can theoretically cover a wide spectral region from near-ultraviolet to near-infrared, making them very attractive for solid-state lighting. Generally speaking, the temperature for growing the quantum wells of long-wavelength LEDs is about 700-800°C, and the relatively low temperature is used to increase the indium content in the quantum well layer. However, adverse effects brought about by lowering the temperature will also lead to a significant decrease in the crystal quality of the subsequent AlGaN layer. In addition, due to the lattice mismatch between InGaN and AlGaN, the quantum confinement Stark effect of the quantum well layer will significantly reduce the luminous intensity of the nitride-based LED.
因此，在InGaN阱层上沉积AlGaN层，首先因晶格失配导致极化电场引起的内部电场，而压电场在量子阱中的量子限制斯塔克效应会显著降低氮化物基LED的发光强度，其次AlGaN层的势垒高度不够，电子溢流增加，LED的发光效率下降。Therefore, depositing the AlGaN layer on the InGaN well layer, firstly, the internal electric field caused by the polarization electric field due to lattice mismatch, and the quantum confinement Stark effect of the piezoelectric field in the quantum well will significantly reduce the luminous intensity of the nitride-based LED. Secondly, the barrier height of the AlGaN layer is not enough, the electron overflow increases, and the luminous efficiency of the LED decreases.
发明内容Contents of the invention
为了解决上述技术问题，本发明提供了一种高光效发光二极管外延片及其制备方法、LED，用于解决现有技术中的技术问题。In order to solve the above-mentioned technical problems, the present invention provides a high-efficiency light-emitting diode epitaxial wafer, its preparation method, and LED, which are used to solve the technical problems in the prior art.
第一方面，本发明实施例提供以下技术方案，一种高光效发光二极管外延片，包括衬底以及依次沉积在所述衬底上的第一半导体层、有源层以及第二半导体层；In the first aspect, the embodiments of the present invention provide the following technical solutions, a high-efficiency light-emitting diode epitaxial wafer, including a substrate, a first semiconductor layer, an active layer, and a second semiconductor layer sequentially deposited on the substrate;
所述有源层包括M个周期性交替排布的势阱层以及复合势垒层，所述复合势垒层包括沿着外延方向依次层叠的第一势垒子层、第二势垒子层与第三势垒子层，所述第一势垒子层包括沿着外延方向依次层叠的GaN层与Ga2O3层，所述第二势垒子层为N型AlGaON层，所述第三势垒子层为BInGaN层，所述第二势垒子层中Si元素的掺杂浓度范围为1E17atoms/cm3~1E18 atoms/cm3。The active layer includes M periodic and alternately arranged potential well layers and composite barrier layers, the composite barrier layer includes a first barrier sublayer, a second barrier sublayer and athird barrier sublayer stacked in sequence along the epitaxial direction, the first barrier sublayer includes a GaN layer and aGa2O3 layer stacked in sequence along the epitaxial direction, the second barrier sublayer is an N-type AlGaON layer, the third barrier sublayer is a BInGaN layer, and the doping concentration range of the Si element in the second barrier sublayer It is 1E17 atoms/cm3 ~1E18 atoms/cm3 .
相比现有技术，本申请的有益效果为：首先，通过设置第一势垒子层可以减少势阱层、第三势垒子层与第二势垒子层之间的晶格失配，以提高复合势垒层的晶体质量，减少电子与空穴发生非辐射复合，其次，本发明中的第二势垒子层的势垒高度高于现有技术中AlGaN层的势垒高度，可以减少电子溢流，提高电子与空穴的辐射复合效率，降低发光二极管的droop效率，同时在第二势垒子层中掺杂的Si可以屏蔽由极化电场引起的内部电场，降低量子限制斯塔克效应，提高电子和空穴的空间重叠度，因此本发明提高复合势垒层的势垒高度，减少电子溢流，降低有源层极化效应，提高有源层的发光效率。Compared with the prior art, the beneficial effects of the present application are as follows: firstly, by setting the first potential barrier sublayer, the lattice mismatch between the potential well layer, the third potential barrier sublayer and the second potential barrier sublayer can be reduced, so as to improve the crystal quality of the composite barrier layer and reduce the non-radiative recombination of electrons and holes; The Si doped in the barrier layer can shield the internal electric field caused by the polarization electric field, reduce the quantum confinement Stark effect, and increase the spatial overlap of electrons and holes. Therefore, the present invention increases the barrier height of the composite barrier layer, reduces electron overflow, reduces the polarization effect of the active layer, and improves the luminous efficiency of the active layer.
较佳的，所述复合势垒层的厚度范围为5nm ~50nm，所述第一势垒子层、所述第二势垒子层与所述第三势垒子层的厚度比范围为1:1:1~1:20:1，所述GaN层与所述Ga2O3层的厚度比范围为1:1~1:10。Preferably, the thickness of the composite barrier layer ranges from 5 nm to 50 nm, the thickness ratio of the first barrier sublayer, the second barrier sublayer and the third barrier sublayer ranges from 1:1:1 to1 :20:1, and the thickness ratio of the GaN layer to theGa2O3 layer ranges from 1:1 to 1:10.
较佳的，所述势阱层为InGaN层，所述势阱层的厚度范围为1nm ~10nm，所述势阱层中In组分范围为0.01~0.5。Preferably, the potential well layer is an InGaN layer, the thickness of the potential well layer ranges from 1 nm to 10 nm, and the In composition in the potential well layer ranges from 0.01 to 0.5.
较佳的，所述第二势垒子层中Al组分范围为0.01~0.5、O组分范围为0.01~0.2，所述第三势垒子层中B组分范围为0.01~0.2、In组分范围为0.01~0.1。Preferably, the Al composition in the second barrier sublayer ranges from 0.01 to 0.5, the O composition ranges from 0.01 to 0.2, the B composition in the third barrier sublayer ranges from 0.01 to 0.2, and the In composition ranges from 0.01 to 0.1.
较佳的，所述势阱层与所述复合势垒层交替排布的周期M取值范围为：1≤M≤20。Preferably, the value range of the period M in which the potential well layers and the composite barrier layers are alternately arranged is: 1≤M≤20.
较佳的，所述第一半导体层包括依次沉积在所述衬底上的缓冲层、非掺杂GaN层、N型GaN层，所述第二半导体层包括依次沉积于所述有源层上的电子阻挡层、P型GaN层。Preferably, the first semiconductor layer includes a buffer layer, a non-doped GaN layer, and an N-type GaN layer deposited on the substrate in sequence, and the second semiconductor layer includes an electron blocking layer and a P-type GaN layer deposited on the active layer in sequence.
第二方面，本发明实施例还提供以下技术方案，一种高光效发光二极管外延片的制备方法，包括以下步骤：In the second aspect, the embodiments of the present invention also provide the following technical solutions, a method for preparing a high-efficiency light-emitting diode epitaxial wafer, comprising the following steps:
提供一衬底；providing a substrate;
在所述衬底上沉积第一半导体层；depositing a first semiconductor layer on the substrate;
在所述第一半导体层上交替沉积M个周期的势阱层以及复合势垒层，以形成有源层，所述复合势垒层包括沿着外延方向依次层叠的第一势垒子层、第二势垒子层与第三势垒子层，所述第一势垒子层包括沿着外延方向依次层叠的GaN层与Ga2O3层，所述第二势垒子层为N型AlGaON层，所述第三势垒子层为BInGaN层，所述第二势垒子层中Si元素的掺杂浓度范围为1E17atoms/cm3~1E18 atoms/cm3；M periods of potential well layers and composite barrier layers are alternately deposited on the first semiconductor layer to form an active layer. The composite barrier layer includes a first barrier sublayer, a second barrier sublayer and athird barrier sublayer stacked in sequence along the epitaxial direction, the first barrier sublayer includes a GaN layer and a Ga2O layer stacked in sequence along the epitaxial direction, the second barrier sublayer is an N- type AlGaON layer, the third barrier sublayer is a BInGaN layer, and the Si element in the second barrier sublayer The doping concentration range is 1E17 atoms/cm3 ~1E18 atoms/cm3 ;
在最后一个周期的所述复合势垒层上沉积第二半导体层。A second semiconductor layer is deposited on the composite barrier layer of the last cycle.
较佳的，所述复合势垒层的生长温度范围为800℃~1000℃，生长气氛N2/H2/NH3比例范围为1:1:1~1:10:20，生长压力范围为50torr~300torr，所述势阱层的生长温度范围为700℃~900℃，生长压力范围为50torr~300torr。Preferably, the growth temperature of the composite barrier layer ranges from 800°C to 1000°C, the ratio of N2 /H2 /NH3 in the growth atmosphere ranges from 1:1:1 to 1:10:20, the growth pressure ranges from 50 torr to 300 torr, the growth temperature of the potential well layer ranges from 700°C to 900°C, and the growth pressure ranges from 50 torr to 300 torr.
较佳的，所述在所述衬底上沉积第一半导体层的步骤中，在所述衬底上依次沉积缓冲层、非掺杂GaN层、N型GaN层，以形成第一半导体层；Preferably, in the step of depositing the first semiconductor layer on the substrate, a buffer layer, a non-doped GaN layer, and an N-type GaN layer are sequentially deposited on the substrate to form the first semiconductor layer;
所述在最后一个周期的所述复合势垒层上沉积第二半导体层的步骤中，在最后一个周期的所述复合势垒层上依次沉积电子阻挡层、P型GaN层，以形成第二半导体层。In the step of depositing a second semiconductor layer on the composite barrier layer in the last period, an electron blocking layer and a P-type GaN layer are sequentially deposited on the composite barrier layer in the last period to form a second semiconductor layer.
第三方面，本发明实施例还提供以下技术方案，一种LED，包括上述的高光效发光二极管外延片。In the third aspect, the embodiments of the present invention also provide the following technical solution, an LED comprising the above-mentioned epitaxial wafer of a high-luminous-efficiency light-emitting diode.
附图说明Description of drawings
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the accompanying drawings used in the embodiments or prior art descriptions. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other accompanying drawings can also be obtained according to these drawings without paying creative labor.
图1为本发明实施例提供的高光效发光二极管外延片的结构图；FIG. 1 is a structural diagram of a high-efficiency light-emitting diode epitaxial wafer provided by an embodiment of the present invention;
图2为本发明实施例提供的复合势垒层的结构图；FIG. 2 is a structural diagram of a composite barrier layer provided by an embodiment of the present invention;
图3为本发明实施例提供的高光效发光二极管外延片的制备方法的流程图。FIG. 3 is a flow chart of a method for preparing a high-efficiency light-emitting diode epitaxial wafer provided by an embodiment of the present invention.
附图标记说明：Explanation of reference signs:
以下将结合说明书附图对本发明作进一步说明。The present invention will be further described below in conjunction with the accompanying drawings.
具体实施方式Detailed ways
下面详细描述本发明的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本发明的实施例，而不能理解为对本发明的限制。Embodiments of the present invention are described in detail below, examples of which are shown in the drawings, wherein the same or similar reference numerals designate the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the figures are exemplary and are intended to explain the embodiments of the present invention and should not be construed as limitations of the present invention.
在本发明实施例的描述中，需要理解的是，术语“长度”、“宽度”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明实施例和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。In the description of the embodiments of the present invention, it should be understood that the orientations or positional relationships indicated by the terms "length", "width", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the embodiments of the present invention and simplifying the description. configuration and operation, and therefore should not be construed as limiting the invention.
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明实施例的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be interpreted as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, a feature defined as "first" and "second" may explicitly or implicitly include one or more of these features. In the description of the embodiments of the present invention, "plurality" means two or more, unless otherwise specifically defined.
实施例一Embodiment one
如图1所示，本发明第一实施例提供了一种高光效发光二极管外延片，包括衬底1以及依次沉积在所述衬底1上的第一半导体层、有源层5以及第二半导体层；As shown in FIG. 1 , the first embodiment of the present invention provides a high-efficiency light-emitting diode epitaxial wafer, including a substrate 1 and a first semiconductor layer, an active layer 5, and a second semiconductor layer sequentially deposited on the substrate 1;
如图2所示，所述有源层5包括M个周期性交替排布的势阱层51以及复合势垒层52，所述复合势垒层52包括沿着外延方向依次层叠的第一势垒子层521、第二势垒子层522与第三势垒子层523，所述第一势垒子层521包括沿着外延方向依次层叠的GaN层5211与Ga2O3层5212，所述第二势垒子层522为N型AlGaON层，所述第三势垒子层523为BInGaN层，所述第二势垒子层522中Si元素的掺杂浓度范围为1E17atoms/cm3~1E18 atoms/cm3。As shown in FIG. 2 , the active layer 5 includes M periodic and alternately arranged potential well layers 51 andcomposite barrier layers 52. The composite barrier layer 52 includes a first barrier sublayer 521, a second barrier sublayer 522, and a third barrier sublayer 523 stacked in sequence along the epitaxial direction. N-type AlGaON layer, the third barrier sublayer 523 is a BInGaN layer, and the doping concentration of Si element in the second barrier sublayer 522 ranges from 1E17 atoms/cm3to 1E18 atoms/cm3 .
具体的，在本发明中，首先，通过设置第一势垒子层521可以减少势阱层51、第三势垒子层523与第二势垒子层522之间的晶格失配，以提高复合势垒层52的晶体质量，减少电子与空穴发生非辐射复合，其次，本发明中的第二势垒子层522的势垒高度高于现有技术中AlGaN层的势垒高度，可以减少电子溢流，提高电子与空穴的辐射复合效率，降低发光二极管的droop效率，同时在第二势垒子层522中掺杂的Si可以屏蔽由极化电场引起的内部电场，降低量子限制斯塔克效应，提高电子和空穴的空间重叠度，因此本发明提高复合势垒层52的势垒高度，减少电子溢流，降低有源层5极化效应，提高有源层5的发光效率。Specifically, in the present invention, first, the lattice mismatch between the potential well layer 51, the third barrier sublayer 523, and the second barrier sublayer 522 can be reduced by setting the first barrier sublayer 521, so as to improve the crystal quality of the composite barrier layer 52 and reduce the non-radiative recombination of electrons and holes. The droop efficiency of the light-emitting diode, while the Si doped in the second barrier sublayer 522 can shield the internal electric field caused by the polarization electric field, reduce the quantum confinement Stark effect, and increase the spatial overlap of electrons and holes. Therefore, the present invention increases the barrier height of the composite barrier layer 52, reduces electron overflow, reduces the polarization effect of the active layer 5, and improves the luminous efficiency of the active layer 5.
在本实施例中，所述复合势垒层52的厚度范围为5nm ~50nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比范围为1:1:1~1:20:1，所述GaN层5211与所述Ga2O3层5212的厚度比范围为1:1~1:10。In this embodiment, the thickness of the composite barrier layer 52 is in the range of 5 nm to 50 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is in the range of 1:1:1 to 1:20:1, and the thickness ratio of the GaN layer 5211 to the Ga2 O3 layer 5212 is in the range of 1:1 to 1:10.
在本实施例中，所述势阱层51为InGaN层，所述势阱层51的厚度范围为1nm ~10nm，所述势阱层51中In组分范围为0.01~0.5。In this embodiment, the potential well layer 51 is an InGaN layer, the thickness of the potential well layer 51 ranges from 1 nm to 10 nm, and the In composition in the potential well layer 51 ranges from 0.01 to 0.5.
在本实施例中，所述第二势垒子层522中Al组分范围为0.01~0.5、O组分范围为0.01~0.2，所述第三势垒子层523中B组分范围为0.01~0.2、In组分范围为0.01~0.1。In this embodiment, the Al composition in the second barrier sublayer 522 ranges from 0.01 to 0.5, the O composition ranges from 0.01 to 0.2, the B composition in the third barrier sublayer 523 ranges from 0.01 to 0.2, and the In composition ranges from 0.01 to 0.1.
在本实施例中，所述势阱层51与所述复合势垒层52交替排布的周期M取值范围为：1≤M≤20。In this embodiment, the value range of the cycle M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is: 1≤M≤20.
在本实施例中，所述第一半导体层包括依次沉积在所述衬底1上的缓冲层2、非掺杂GaN层3、N型GaN层4，所述第二半导体层包括依次沉积于所述有源层5上的电子阻挡层6、P型GaN层7。In this embodiment, the first semiconductor layer includes a buffer layer 2, an undoped GaN layer 3, and an N-type GaN layer 4 sequentially deposited on the substrate 1, and the second semiconductor layer includes an electron blocking layer 6 and a P-type GaN layer 7 deposited on the active layer 5 in sequence.
为了方便后续的光电测试以及便于理解，在本申请中引入若干实验组与对照组。In order to facilitate subsequent photoelectric tests and facilitate understanding, several experimental groups and control groups are introduced in this application.
其中，实验组包括实验组一到实验组十五，实验组一到实验组十五均采用如实施例一所述的一种高光效发光二极管外延片，且其均包括如实施例一所述的有源层5，对照组则采用现有技术中的LED外延片，其结构与实施一大致相同，但区别如下：对照组中的有源层5具体为AlGaN量子阱层，且AlGaN量子阱层厚度为10nm；Wherein, the experimental group includes the experimental group 1 to the experimental group 15, and the experimental group 1 to the experimental group 15 all adopt a kind of high light-efficiency light-emitting diode epitaxial wafer as described in the first embodiment, and they all include the active layer 5 as described in the first embodiment, and the control group adopts the LED epitaxial wafer in the prior art, and its structure is roughly the same as that in the first implementation, but the difference is as follows: the active layer 5 in the control group is specifically an AlGaN quantum well layer, and the thickness of the AlGaN quantum well layer is 10nm;
具体的，实验组一中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为10。Specifically, the thickness of the composite barrier layer 52 in the experimental group 1 is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second potential barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third potential barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the period M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is 10.
实验组二中的所述复合势垒层52的厚度为2nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in the experimental group 2 is 2 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second potential barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third potential barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the period M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is 10.
实验组三中的所述复合势垒层52的厚度为50nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in the experimental group three is 50 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second potential barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third potential barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the period M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is 10.
实验组四中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:1:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in experimental group four is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:1:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second potential barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third potential barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the period M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is 10.
实验组五中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:20:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in the experimental group five is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:20:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second potential barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third potential barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the period M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is 10.
实验组六中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:1，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in experimental group six is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:1, and the doping concentration of the Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second potential barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third potential barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the period M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is 10.
实验组七中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:10，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in experimental group 7 is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:10, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second potential barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third potential barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the period M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is 10.
实验组八中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为1E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in the eighth experiment group is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of the Si element in the second barrier sublayer 522 is 1E17 atoms/cm3, the Al composition in the second potential barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third potential barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the period M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is 10.
实验组九中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为1E18 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in the experimental group nine is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 1E18 atoms/cm3, the Al composition in the second potential barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third potential barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the period M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is 10.
实验组十中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.01、O组分为0.01，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in the experimental group ten is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second barrier sublayer 522 is 0.01, the O composition is 0.01, the B composition in the third potential barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the cycle M of the alternating arrangement of the potential well layers 51 and the composite barrier layers 52 is 10.
实验组十一中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.5、O组分为0.2，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in the eleventh experiment group is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second barrier sublayer 522 is 0.5, the O composition is 0.2, the B composition in the third barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the cycle M of the alternate arrangement of the potential well layers 51 and the composite barrier layers 52 is 10.
实验组十二中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.01、In组分范围为0.01，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in the experimental group twelve is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third barrier sublayer 523 is 0.01, and the In composition range is 0.01, and the cycle M of the alternate arrangement of the potential well layers 51 and the composite barrier layers 52 is 10.
实验组十三中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.2、In组分范围为0.1，所述势阱层51与所述复合势垒层52交替排布的周期M为10。The thickness of the composite barrier layer 52 in the experimental group thirteen is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second potential barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third potential barrier sublayer 523 is 0.2, and the In composition range is 0.1, and the period M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is 10.
实验组十四中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为1。The thickness of the composite barrier layer 52 in experimental group fourteen is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the cycle M of the alternate arrangement of the potential well layers 51 and the composite barrier layers 52 is 1.
实验组十五中的所述复合势垒层52的厚度为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比为1:2，所述第二势垒子层522中Si元素的掺杂浓度为5E17 atoms/cm3，所述第二势垒子层522中Al组分为0.1、O组分为0.1，所述第三势垒子层523中B组分为0.1、In组分范围为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M为20。The thickness of the composite barrier layer 52 in the experimental group fifteen is 10 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is 1:8:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 is 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is 5E17 atoms/cm3, the Al composition in the second barrier sublayer 522 is 0.1, the O composition is 0.1, the B composition in the third barrier sublayer 523 is 0.1, and the In composition range is 0.05, and the cycle M of the alternate arrangement of the potential well layers 51 and the composite barrier layers 52 is 20.
将上述若干实验组以及对照组中的高光效发光二极管外延片制备为10×24mil尺寸的芯片，并在120 mA/ 60 mA电流下测试，测试结果表1所示。The high-efficiency light-emitting diode epitaxial wafers in the above-mentioned several experimental groups and the control group were prepared into chips with a size of 10×24 mil, and tested at a current of 120 mA/60 mA. The test results are shown in Table 1.
表1Table 1
将对照组所提供的LED外延片的光效作为基准，因此其提升光效为0%，而实验组一相比对照组，其光效提升了5.0%，实验组二相比对照组，其光效提升了2.3%，实验组三相比对照组，其光效提升了2.8%，实验组四相比对照组，其光效提升了2.0%，实验组五相比对照组，其光效提升了3.1%，实验组六相比对照组，其光效提升了2.8%，实验组七相比对照组，其光效提升了3.2%，实验组八相比对照组，其光效提升了2.0%，实验组九相比对照组，其光效提升了3.2%，实验组十相比对照组，其光效提升了1.8%，实验组十一相比对照组，其光效提升了3.5%，实验组十二相比对照组，其光效提升了1.3%，实验组十三相比对照组，其光效提升了3.3%，实验组十四相比对照组，其光效提升了1.2%，实验组十五相比对照组，其光效提升了3.6%。The luminous efficiency of the LED epitaxial wafer provided by the control group is used as a benchmark, so its luminous efficiency is 0%. Compared with the control group, the luminous efficiency of the experimental group 1 is increased by 5.0%. Compared with the control group, the luminous efficiency of the experimental group 2 is increased by 2.3%. Compared with the control group, the luminous efficiency of the experimental group 7 increased by 3.2%, compared with the control group, the luminous efficiency of the experimental group 8 increased by 2.0%, the luminous efficiency of the experimental group 9 increased by 3.2% compared with the control group, the luminous efficiency of the experimental group 10 increased by 1.8% compared with the control group, the luminous efficiency of the experimental group 11 increased by 3.5% compared with the control group, the luminous efficiency of the experimental group 12 increased by 1.3% compared with the control group, and the luminous efficiency of the experimental group 13 increased by 3.3% compared with the control group. Compared with the control group, the light efficiency of the experimental group 15 increased by 3.6%.
因此可知，实验组一所提供的高光效LED外延片相比对照组，其光效提升最大，提升了5.0%，且对应的，所述复合势垒层52的厚度优选为10nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比优选为1:8:1，所述GaN层5211与所述Ga2O3层5212的厚度比优选为1:2，所述第二势垒子层522中Si元素的掺杂浓度优选为5E17atoms/cm3，所述第二势垒子层522中Al组分优选为0.1、O组分优选为0.1，所述第三势垒子层523中B组分优选为0.1、In组分范围优选为0.05，所述势阱层51与所述复合势垒层52交替排布的周期M优选为10。Therefore, it can be seen that compared with the control group, the high luminous efficiency LED epitaxial wafer provided by the experimental group 1 has the largest luminous efficiency improvement of 5.0%, and correspondingly, the thickness of the composite barrier layer 52 is preferably 10 nm, and the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 is preferably 1:8:1.2o3The thickness ratio of layer 5212 is preferably 1:2, and the doping concentration of Si element in the second barrier sublayer 522 is preferably 5E17 atoms/cm3The Al composition in the second barrier sublayer 522 is preferably 0.1, the O composition is preferably 0.1, the B composition in the third barrier sublayer 523 is preferably 0.1, and the In composition range is preferably 0.05. The cycle M of the alternate arrangement of the potential well layers 51 and the composite barrier layers 52 is preferably 10.
值得说明的是，在本发明的另一些实施例中，还提供以下方案，一种LED，包括如实施例一所述的高光效发光二极管外延片。It is worth noting that, in some other embodiments of the present invention, the following solutions are also provided, an LED comprising the epitaxial wafer of a high-luminous-efficiency light-emitting diode as described in Embodiment 1.
实施例二Embodiment two
如图3所示，本发明第二实施例提供了一种高光效发光二极管外延片的制备方法，包括以下步骤：As shown in Figure 3, the second embodiment of the present invention provides a method for preparing a high-efficiency light-emitting diode epitaxial wafer, including the following steps:
S01、提供一衬底1；S01, providing a substrate 1;
其中，所述衬底1可选用蓝宝石衬底、SiO2蓝宝石复合衬底、硅衬底、碳化硅衬底、氮化镓衬底、氧化锌衬底中的一种；Wherein, the substrate 1 can be selected from one of a sapphire substrate, a SiO2 sapphire composite substrate, a silicon substrate, a silicon carbide substrate, a gallium nitride substrate, and a zinc oxide substrate;
具体的，在本实施例中衬底1选用蓝宝石衬底，蓝宝石是目前最常用的GaN基LED衬底材料，蓝宝石衬底具有制备工艺成熟、价格较低、易于清洗和处理，高温下有很好的稳定性。Specifically, in this embodiment, the substrate 1 is selected from a sapphire substrate. Sapphire is currently the most commonly used GaN-based LED substrate material. The sapphire substrate has a mature manufacturing process, low price, easy cleaning and handling, and good stability at high temperatures.
在本实施例中，采用中微A7 MOCVD(Metal-organic Chemical Vapor Deposition金属有机气相沉积，简称MOCVD)设备，高纯H2(氢气)、高纯N2(氮气)、高纯H2和高纯N2的混合气体中的一种作为载气，高纯NH3作为N源，三甲基镓(TMGa)及三乙基镓(TEGa)作为镓源，三甲基铟(TMIn)作为铟源，三甲基铝(TMAl)作为铝源，硅烷(SiH4)作为N型掺杂剂，二茂镁(CP2Mg)作为P型掺杂剂进行外延生长。In this embodiment, Zhongwei A7 MOCVD (Metal-organic Chemical Vapor Deposition, referred to as MOCVD) equipment is used, one of high-purityH2 (hydrogen), high-purityN2 (nitrogen), high-purityH2 and high-purityN2 is used as a carrier gas, high-purity NH3 is used as N source, trimethylgallium (TMGa) and triethylgallium (TEGa) are used as gallium source, trimethylindium (TMIn ) as an indium source, trimethylaluminum (TMAl) as an aluminum source, silane (SiH4 ) as an N-type dopant, and dimagnesocene (CP2 Mg) as a P-type dopant for epitaxial growth.
S02、在所述衬底1上沉积第一半导体层；S02, depositing a first semiconductor layer on the substrate 1;
其中，在所述衬底1上依次沉积缓冲层2、非掺杂GaN层3、N型GaN层4，以形成所述第一半导体层。Wherein, a buffer layer 2 , a non-doped GaN layer 3 and an N-type GaN layer 4 are sequentially deposited on the substrate 1 to form the first semiconductor layer.
首先，在所述衬底1上沉积缓冲层2；First, depositing a buffer layer 2 on the substrate 1;
具体的，缓冲层2具体为AlN/GaN缓冲层，选用在应用材料PVD中沉积缓冲层，其厚度为15 nm，采用AlN/GaN缓冲层提供了与衬底1取向相同的成核中心，释放了GaN和衬底1之间的晶格失配产生的应力以及热膨胀系数失配所产生的热应力，进一步的生长提供了平整的成核表面，减少其成核生长的接触角使岛状生长的GaN晶粒在较小的厚度内能连成面，转变为二维外延生长。Specifically, the buffer layer 2 is an AlN/GaN buffer layer. The buffer layer is deposited in the applied material PVD, and its thickness is 15 nm. The AlN/GaN buffer layer provides a nucleation center with the same orientation as the substrate 1, releasing the stress caused by the lattice mismatch between GaN and the substrate 1 and the thermal stress caused by the mismatch of thermal expansion coefficient. Further growth provides a flat nucleation surface, reducing the contact angle of its nucleation growth, so that the island-shaped GaN crystal grains can be connected into a plane within a smaller thickness. into two-dimensional epitaxial growth.
之后，需要对已沉积缓冲层2的衬底1进行预处理；Afterwards, the substrate 1 on which the buffer layer 2 has been deposited needs to be pretreated;
具体地，将已镀完缓冲层2的衬底1转入MOCVD中，在H2气氛进行预处理1min~10min，处理温度为1000℃～1200℃，再对衬底1进行氮化处理，提升缓冲层2的晶体质量，并且可以有效提高后续沉积GaN外延层的晶体质量。Specifically, the substrate 1 that has been plated with the buffer layer 2 is transferred to MOCVD, pretreated inH2 atmosphere for 1 min to 10 min, and the treatment temperature is 1000°C to 1200°C, and then the substrate 1 is nitrided to improve the crystal quality of the buffer layer 2, and can effectively improve the crystal quality of the subsequently deposited GaN epitaxial layer.
接着，在缓冲层2上沉积非掺杂GaN层3；Next, depositing a non-doped GaN layer 3 on the buffer layer 2;
其中，非掺杂GaN层3生长温度为1050℃~1200℃，压力100torr~600 torr，厚度为1um~5um；Wherein, the growth temperature of the non-doped GaN layer 3 is 1050°C~1200°C, the pressure is 100torr~600torr, and the thickness is 1um~5um;
具体的，非掺杂GaN层3生长温度1100℃，生长压力150 torr，生长厚度2um~3um，非掺杂GaN层3生长温度较高，压力较低，制备的到GaN的晶体质量较优，同时厚度随着GaN厚度的增加，压应力会通过堆垛层错释放，线缺陷减少，晶体质量提高，反向漏电降低，但提高GaN层厚度对Ga源材料消耗较大，大大提高了LED的外延成本，因此目前LED外延片通常非掺杂GaN层3生长2um~3um，不仅节约生产成本，而且GaN材料又具有较高的晶体质量。Specifically, the growth temperature of the non-doped GaN layer 3 is 1100°C, the growth pressure is 150 torr, and the growth thickness is 2um~3um. The growth temperature of the non-doped GaN layer 3 is higher and the pressure is lower, and the crystal quality of the prepared GaN is better. At the same time, as the thickness of the GaN increases, the compressive stress will be released through stacking faults, the line defects will be reduced, the crystal quality will be improved, and the reverse leakage will be reduced. The growth of layer 3 is 2um~3um, which not only saves the production cost, but also the GaN material has higher crystal quality.
最后，在非掺杂GaN层3上沉积N型GaN层4；Finally, an N-type GaN layer 4 is deposited on the non-doped GaN layer 3;
其中，N型GaN层4生长温度为1050℃~1200℃，压力100torr~600torr，厚度为2um~3um，Si掺杂浓度为1E19atoms/cm3~5E19 atoms/cm3；Among them, the growth temperature of the N-type GaN layer 4 is 1050°C~1200°C, the pressure is 100torr~600torr, the thickness is 2um~3um, and the Si doping concentration is 1E19 atoms/cm3 ~5E19 atoms/cm3 ;
具体的，N型GaN层4生长温度为1120℃，生长压力100torr，生长厚度为2um~3um，Si掺杂浓度为2.5E19atoms/cm3，首先N型GaN层4为LED发光提供充足电子，其次N型GaN层4的电阻率要比P-GaN上的透明电极的电阻率高，因此足够的Si掺杂，可以有效的降低N型GaN层4的电阻率，最后N型GaN层4足够的厚度可以有效释放应力LED的发光效率。Specifically, the growth temperature of the N-type GaN layer 4 is 1120°C, the growth pressure is 100 torr, the growth thickness is 2um~3um, and the Si doping concentration is 2.5E19atoms/cm3 . The thickness can effectively release the luminous efficiency of the stress LED.
S03、在所述第一半导体层上交替沉积M个周期的势阱层51以及复合势垒层52，以形成有源层5，所述复合势垒层52包括沿着外延方向依次层叠的第一势垒子层521、第二势垒子层522与第三势垒子层523，所述第一势垒子层521包括沿着外延方向依次层叠的GaN层5211与Ga2O3层5212，所述第二势垒子层522为N型AlGaON层，所述第三势垒子层523为BInGaN层，所述第二势垒子层522中Si元素的掺杂浓度范围为1E17atoms/cm3~1E18 atoms/cm3；S03. Alternately deposit M periods of potential well layers 51 and composite barrier layers 52 on the first semiconductor layer to form the active layer 5. The composite barrier layer 52 includes a first barrier sublayer 521, a second barrier sublayer 522, and a third barrier sublayer 523 sequentially stacked along the epitaxial direction, and the first barrier sublayer 521 includes GaN layers 5211 and GaN layers sequentially stacked along the epitaxial direction.2o3layer 5212, the second barrier sublayer 522 is an N-type AlGaON layer, the third barrier sublayer 523 is a BInGaN layer, and the doping concentration range of the Si element in the second barrier sublayer 522 is 1E17 atoms/cm3~1E18 atoms/cm3;
具体的，所述复合势垒层52的厚度范围为5nm ~50nm，所述第一势垒子层521、所述第二势垒子层522与所述第三势垒子层523的厚度比范围为1:1:1~1:20:1，所述GaN层5211与所述Ga2O3层5212的厚度比范围为1:1~1:10，所述势阱层51为InGaN层，所述势阱层51的厚度范围为1nm ~10nm，所述势阱层51中In组分范围为0.01~0.5，所述第二势垒子层522中Al组分范围为0.01~0.5、O组分范围为0.01~0.2，所述第三势垒子层523中B组分范围为0.01~0.2、In组分范围为0.01~0.1，所述势阱层51与所述复合势垒层52交替排布的周期M取值范围为：1≤M≤20。Specifically, the thickness of the composite barrier layer 52 ranges from 5 nm to 50 nm, the thickness ratio of the first barrier sublayer 521, the second barrier sublayer 522 and the third barrier sublayer 523 ranges from 1:1:1 to 1:20:1, and the GaN layer 5211 and the Ga2o3The thickness ratio of the layer 5212 ranges from 1:1 to 1:10, the potential well layer 51 is an InGaN layer, the thickness of the potential well layer 51 ranges from 1 nm to 10 nm, the In composition in the potential well layer 51 ranges from 0.01 to 0.5, the Al composition in the second barrier sublayer 522 ranges from 0.01 to 0.5, the O composition ranges from 0.01 to 0.2, and the B composition in the third barrier sublayer 523 ranges from 0.01 to 0.5. 01~0.2, the range of In composition is 0.01~0.1, and the value range of period M in which the potential well layers 51 and the composite barrier layers 52 are alternately arranged is: 1≤M≤20.
同时，所述复合势垒层52的生长温度范围为800℃~1000℃，生长气氛N2/H2/NH3比例范围为1:1:1~1:10:20，生长压力范围为50torr~300torr，所述势阱层51的生长温度范围为700℃~900℃，生长压力范围为50torr~300torr，且在本实施例中，势阱层51的厚度优选为3.5nm，生长温度优选为795℃，生长压力优选为200 torr，In组分优选为0.15。At the same time, the growth temperature of the composite barrier layer 52 ranges from 800°C to 1000°C, the growth atmosphere N2 /H2 /NH3 ratio ranges from 1:1:1 to 1:10:20, the growth pressure ranges from 50 torr to 300 torr, the growth temperature range of the potential well layer 51 ranges from 700°C to 900°C, and the growth pressure ranges from 50 torr to 300 torr, and in this embodiment, the thickness of the potential well layer 51 is preferably is 3.5 nm, the growth temperature is preferably 795° C., the growth pressure is preferably 200 torr, and the In component is preferably 0.15.
S04、在最后一个周期的所述复合势垒层52上沉积第二半导体层；S04, depositing a second semiconductor layer on the composite barrier layer 52 in the last period;
其中，在最后一个周期的所述复合势垒层52上依次沉积电子阻挡层6和P型GaN层7，以形成所述第二半导体层。Wherein, the electron blocking layer 6 and the P-type GaN layer 7 are sequentially deposited on the composite barrier layer 52 in the last period to form the second semiconductor layer.
首先，在最后一个周期的所述复合势垒层52上沉积电子阻挡层6；First, an electron blocking layer 6 is deposited on the composite barrier layer 52 of the last period;
其中，电子阻挡层6为AlInGaN层，其厚度10nm~40nm，生长温度900℃~1000℃，压力100torr~300torr，其中Al组分范围为0.005~0.1，In组分范围为0.01~0.2；Wherein, the electron blocking layer 6 is an AlInGaN layer with a thickness of 10nm~40nm, a growth temperature of 900°C~1000°C, and a pressure of 100torr~300torr, wherein the range of the Al composition is 0.005~0.1, and the range of the In composition is 0.01~0.2;
具体的，电子阻挡层6厚度为15 nm，其中Al组分浓度沿外延层生长方向由0.01渐变至0.05，In组分浓度为0.01，生长温度965℃，生长压力200torr，电子阻挡层6既可以有效地限制电子溢流，也可以减少对空穴的阻挡，提升空穴向量子阱的注入效率，减少载流子俄歇复合，提高LED的发光效率。Specifically, the electron blocking layer 6 has a thickness of 15 nm, in which the concentration of the Al component gradually changes from 0.01 to 0.05 along the growth direction of the epitaxial layer, the concentration of the In component is 0.01, the growth temperature is 965° C., and the growth pressure is 200 torr. The electron blocking layer 6 can not only effectively limit the overflow of electrons, but also reduce the blocking of holes, improve the injection efficiency of holes into the quantum well, reduce the Auger recombination of carriers, and improve the luminous efficiency of the LED.
最后，在所述电子阻挡层6上沉积P型GaN层7；Finally, depositing a P-type GaN layer 7 on the electron blocking layer 6;
其中，P型GaN层7生长温度900℃~1050℃，厚度10nm~50nm，生长压力100torr~600torr，Mg掺杂浓度1E19atoms/cm3~1E21atoms/cm3；Among them, the growth temperature of the P-type GaN layer 7 is 900°C~1050°C, the thickness is 10nm~50nm, the growth pressure is 100torr~600torr, and the Mg doping concentration is 1E19atoms/cm3 ~1E21atoms/cm3 ;
具体的，P型GaN层7生长温度985℃，厚度15nm，生长压力200torr，Mg掺杂浓度2E20atoms/cm3，Mg掺杂浓度过高会破坏晶体质量，而掺杂浓度较低则会影响空穴浓度。同时，对于含V 形坑的LED结构来说，P型GaN层7较高的生长温度也有利于合并V形坑，得到表面光滑的LED外延片。Specifically, the growth temperature of the P-type GaN layer 7 is 985° C., the thickness is 15 nm, the growth pressure is 200 torr, and the Mg doping concentration is 2E20 atoms/cm3 . If the Mg doping concentration is too high, the crystal quality will be damaged, and if the Mg doping concentration is too high, the hole concentration will be affected. At the same time, for the LED structure with V-shaped pits, the higher growth temperature of the P-type GaN layer 7 is also conducive to merging the V-shaped pits to obtain an LED epitaxial wafer with a smooth surface.
综上，在本发明中，首先，通过设置第一势垒子层521可以减少势阱层51、第三势垒子层523与第二势垒子层522之间的晶格失配，以提高复合势垒层52的晶体质量，减少电子与空穴发生非辐射复合，其次，本发明中的第二势垒子层522的势垒高度高于现有技术中AlGaN层的势垒高度，可以减少电子溢流，提高电子与空穴的辐射复合效率，降低发光二极管的droop效率，同时在第二势垒子层522中掺杂的Si可以屏蔽由极化电场引起的内部电场，降低量子限制斯塔克效应，提高电子和空穴的空间重叠度，因此本发明提高复合势垒层52的势垒高度，减少电子溢流，降低有源层5极化效应，提高有源层5的发光效率。To sum up, in the present invention, firstly, the lattice mismatch between the potential well layer 51, the third barrier sublayer 523 and the second barrier sublayer 522 can be reduced by setting the first barrier sublayer 521, so as to improve the crystal quality of the composite barrier layer 52 and reduce the non-radiative recombination of electrons and holes. Secondly, the barrier height of the second barrier sublayer 522 in the present invention is higher than that of the AlGaN layer in the prior art, which can reduce electron overflow and improve the radiative recombination efficiency of electrons and holes. Reduce the droop efficiency of the light-emitting diode, and at the same time, the Si doped in the second barrier sublayer 522 can shield the internal electric field caused by the polarization electric field, reduce the quantum confinement Stark effect, and increase the spatial overlap of electrons and holes. Therefore, the present invention increases the barrier height of the composite barrier layer 52, reduces electron overflow, reduces the polarization effect of the active layer 5, and improves the luminous efficiency of the active layer 5.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
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