WO2017028555A1 - Gan base material based on si substrate and preparation method therefor - Google Patents

Gan base material based on si substrate and preparation method therefor Download PDF

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WO2017028555A1
WO2017028555A1 PCT/CN2016/080637 CN2016080637W WO2017028555A1 WO 2017028555 A1 WO2017028555 A1 WO 2017028555A1 CN 2016080637 W CN2016080637 W CN 2016080637W WO 2017028555 A1 WO2017028555 A1 WO 2017028555A1
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layer
substrate
type gan
reaction chamber
temperature
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PCT/CN2016/080637
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French (fr)
Chinese (zh)
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张进成
许晟瑞
陈智斌
宁静
任泽阳
郝跃
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西安电子科技大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
    • H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
    • H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
    • H01L33/325—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen characterised by the doping materials

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  • the present invention relates to a semiconductor material, and in particular to a GaN-based material that can be used to fabricate a yellow LED and a method of fabricating the same.
  • ⁇ -V nitride semiconductor materials have advantages such as direct band gap, high thermal conductivity, high electron saturation mobility, high luminous efficiency, high temperature resistance and radiation resistance, and have made great progress in applications in optoelectronics and microelectronics. . It has great application prospects in short-wavelength blue-ultraviolet light-emitting devices, microwave devices and high-power semiconductor devices. By adjusting the composition of In in the material of the device, theoretically, full coverage of visible light wavelength can be realized.
  • the object of the present invention is to provide a GaN-based material which can be used for fabricating a yellow LED and a manufacturing method thereof, in order to simplify the process complexity, improve the growth efficiency, reduce the cost, and improve the performance of the LED device.
  • An embodiment of the present invention provides a GaN-based material comprising: a p-type GaN layer, an active layer, a nucleation layer, and a substrate arranged from top to bottom; wherein the active layer is doped with C and Si A doped n-type GaN layer is introduced to introduce a deep level of C in the n-type GaN layer.
  • the substrate is a Si substrate, and a substrate of other materials may also be used.
  • the concentration of C doping in the active layer ranges from 1 ⁇ 10 17 cm ⁇ 3 to 1 ⁇ 10 19 cm ⁇ 3
  • the concentration of Si doping in the active layer ranges from 5 ⁇ 10 17 cm. -3 to 3 x 10 19 cm -3 .
  • the p-type GaN layer has a thickness of 0.01 to 10 ⁇ m, wherein the Mg doping concentration ranges from 1 ⁇ 10 17 cm -3 to 3 ⁇ 10 19 cm -3 .
  • the thickness of the active layer ranges from 0.2 to 100 ⁇ m.
  • Another embodiment of the present invention provides a method of fabricating a GaN-based material, the GaN-based material comprising: a p-type GaN layer, an active layer, a nucleation layer, and a substrate arranged from top to bottom; : growing a C-doped and Si-doped n-type GaN layer on the nucleation layer as the active layer to introduce a deep level of C into the n-type GaN layer.
  • the substrate is placed in a metal organic chemical vapor deposition MOCVD reaction chamber, and a mixed gas of hydrogen gas and ammonia gas is introduced into the reaction chamber, and the substrate is subjected to heat treatment.
  • a mixed gas of hydrogen gas and ammonia gas is introduced into the reaction chamber, and the substrate is subjected to heat treatment.
  • the vacuum of the reaction chamber is maintained during the heat treatment to be less than 2 x 10 -2 Torr, the heating temperature is 830-1150 ° C, the heat treatment time is 5-10 min, and the pressure of the reaction chamber is 30-700 Torr.
  • the nucleation layer grown on the substrate is a low temperature nucleation layer having a thickness of 10-200 nm and a temperature of 530-720 °C.
  • the n-type GaN layer grown on the nucleation layer is a high-temperature n-type GaN active layer having a thickness of 0.2 to 100 ⁇ m and a temperature of 850 to 1100 °C.
  • the p-type GaN layer grown on the active layer has a thickness of 0.01-10 ⁇ m, a Mg doping concentration of 1 ⁇ 10 17 cm ⁇ 3 to 3 ⁇ 10 19 cm ⁇ 3 , and a temperature of 850-1100° C. High temperature p-type GaN layer.
  • FIG. 1 is a schematic view showing the structure of a yellow LED material on a Si substrate according to an embodiment of the present invention
  • FIG. 2 is a flow chart of a method of fabricating a yellow LED material on a Si substrate in accordance with an embodiment of the present invention.
  • a GaN-based material that can be used to fabricate a yellow LED of this embodiment includes four layers, as shown in FIG. 1, which are a p-type GaN layer, an active layer, a nucleation layer, and a substrate, respectively, from top to bottom.
  • the first layer (ie, the lowest layer) is a substrate, and a Si material may be used; the second layer is a nucleation layer, and AlN is 10-200 nm in thickness; the third layer is an active layer, wherein the active layer is doped with C
  • the n-type GaN layer formed by doping with Si and Si introduces a deep level of C in GaN to provide a composite platform for yellow-emitting electrons and holes;
  • the fourth layer is a p-type GaN layer with a thickness of 0.01- 10 ⁇ m, Mg doped GaN having a doping concentration of 1 ⁇ 10 17 cm -3 to 3 ⁇ 10 19 cm -3 .
  • the active layer of the third layer may be a C-doped and Si-doped n-type GaN layer having a thickness of 0.2-100 ⁇ m, wherein the C-doping concentration is 1 ⁇ 10 17 cm -3 to 1 ⁇ 10 19 cm. -3 , the concentration of Si doping is 5 ⁇ 10 17 cm -3 to 3 ⁇ 10 19 cm -3 . Since C doping is introduced into GaN, a deep level is formed in GaN, which is yellowish Electrons and holes provide a composite platform.
  • the growth thickness is 0.2-100 ⁇ m on the low-temperature nucleation layer, the C doping concentration is 1 ⁇ 10 17 cm -3 to 1 ⁇ 10 19 cm -3 , and the concentration of Si doping is 5 ⁇ 10 17 cm - a high temperature n-type GaN active layer of 3 to 3 ⁇ 10 19 cm -3 and a temperature of 850-1100 ° C;
  • a high-temperature p-type having a thickness of 0.01 to 10 ⁇ m, a Mg doping concentration of 1 ⁇ 10 17 cm -3 to 3 ⁇ 10 19 cm -3 , and a temperature of 850-1100 ° C on the n-type GaN active layer GaN layer.
  • the C element is replaced with the N element to form a deep level, providing a composite level;
  • the C impurity can be introduced through the C source, or can be controlled by a process. This is achieved by the C impurity in MOCVD.
  • Si which is diffused to the active layer by the Si substrate is used as the Si source
  • C in the Ga source in the MOCVD is used as the C source, which reduces the production cost.
  • This embodiment is for producing an LED material of an n-type GaN active layer having a C doping concentration of 1 ⁇ 10 18 cm -3 and a Si doping concentration of 3 ⁇ 10 18 cm -3 . Specific steps are as follows:
  • the substrate substrate is subjected to heat treatment.
  • the wafer is placed, the Si substrate is placed in a metal organic chemical vapor deposition (MOCVD) reaction chamber, and a mixed gas of hydrogen and ammonia is introduced into the reaction chamber; the reaction chamber is evacuated to make the reaction chamber
  • the degree of vacuum was less than 2 ⁇ 10 -2 Torr; the Si substrate was heat-treated under the conditions of a reaction chamber pressure of 45 Torr, the substrate heating temperature was 1000 ° C, and the heating time was 7 min.
  • the temperature of the substrate substrate after the heat treatment was lowered to 600 ° C, an aluminum source having a flow rate of 5 ⁇ mol/min, a hydrogen gas having a flow rate of 1200 sccm, and an ammonia gas having a flow rate of 1200 sccm were introduced into the reaction chamber, and the thickness was grown under a holding pressure of 45 Torr. It is a 25 nm low temperature AlN nucleation layer.
  • a gallium source having a flow rate of 30 ⁇ mol/min, a flow rate of 1200 sccm of hydrogen, and a flow rate of 1500 sccm of ammonia gas were introduced into the reaction chamber, and the reaction chamber pressure was 45 Torr, the temperature was 985 ° C, and the C doping concentration was 1 ⁇ 10 18 cm - 3 , the Si doping concentration is 3 ⁇ 10 18 cm -3 , and an n-type GaN active layer having a thickness of 3 ⁇ m is grown on the low-temperature AlN nucleation layer.
  • the temperature of the C-doped and Si-doped n-type GaN layer substrate was maintained at 985 ° C, and a gallium source having a flow rate of 30 ⁇ mol/min, a flow rate of 1200 sccm of hydrogen, and a flow rate of 1500 sccm of ammonia gas were introduced into the reaction chamber. And a Mg source having a flow rate of 10 ⁇ mol/min, a pressure of 45 Torr in the reaction chamber, a temperature of 985 ° C, and a p-type GaN layer having a thickness of 200 nm were grown to form a c-plane GaN material.
  • This embodiment is for producing an LED material of an n-type GaN active layer having a C doping concentration of 1 ⁇ 10 17 cm -3 and a Si doping concentration of 5 ⁇ 10 17 cm -3 .
  • the specific implementation steps are as follows:
  • a gallium source having a flow rate of 5 ⁇ mol/min, a flow rate of 1000 sccm of hydrogen, and a flow rate of 1000 sccm of ammonia gas were introduced into the reaction chamber at a pressure of 30 Torr, a temperature of 850 ° C, and a C doping concentration of 1 ⁇ 10 17 cm. -3 , Si doping concentration is 5 ⁇ 10 17 cm -3 , and an n-type GaN active layer having a thickness of 200 nm is grown on the low-temperature AlN nucleation layer.
  • This embodiment is for producing an LED material of an n-type GaN active layer having a C doping concentration of 1 ⁇ 10 19 cm -3 and a Si doping concentration of 3 ⁇ 10 19 cm -3 .
  • the specific implementation steps are as follows:
  • the substrate substrate is subjected to heat treatment.
  • the Si substrate is placed in a metal organic chemical vapor deposition (MOCVD) reaction chamber, and a mixed gas of hydrogen and ammonia is introduced into the reaction chamber to perform heat treatment.
  • MOCVD metal organic chemical vapor deposition
  • the vacuum of the reaction chamber was less than 2 ⁇ 10 -2 Torr; the substrate heating temperature was 1150 ° C; the nitriding time was 10 min; and the reaction chamber pressure was 700 Torr.
  • a low temperature AlN nucleation layer having a thickness of 200 nm is grown on the heat-treated substrate substrate, and the process conditions are as follows:
  • the reaction chamber temperature was 720 ° C; the reaction chamber pressure was 700 Torr; the aluminum source flow rate was 100 ⁇ mol/min; the hydrogen flow rate was 10000 sccm; and the ammonia gas flow rate was 10000 sccm.
  • An n-type GaN active layer having a thickness of 100 ⁇ m is grown on the low temperature AlN nucleation layer, and the process conditions are as follows:
  • the reaction chamber temperature is 1100 ° C; the reaction chamber pressure is 700 Torr; the gallium source flow rate is 100 ⁇ mol/min; the hydrogen flow rate is 10000 sccm; the ammonia gas flow rate is 10000 sccm; the C doping concentration is 1 ⁇ 10 19 cm -3 ; It is 3 ⁇ 10 19 cm -3 .
  • a p-type GaN layer having a thickness of 10 ⁇ m is grown on the C-doped and Si-doped n-type GaN active layer to form a c-plane GaN material, and the process conditions are as follows:
  • the substrate temperature was 1100 ° C; the reaction chamber pressure was 700 Torr; the gallium source flow rate was 100 ⁇ mol/min; the hydrogen flow rate was 10000 sccm; the ammonia gas flow rate was 10000 sccm; and the Mg source flow rate was 100 ⁇ mol/min.

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Abstract

A GaN base material for manufacturing a yellow-light LED comprises a p-shaped GaN layer, an active layer, a nucleating layer, and a substrate arranged from top to bottom, the active layer using a C-doped and Si-doped n-shaped GaN layer, to introduce the deep energy level of C into the n-shaped GaN layer. By means of the GaN base material and the preparation method therefor, a production process can be simplified, growing efficiency can be improved, costs can be reduced, and the performance of an LED device can be improved.

Description

基于Si衬底的GaN基材料及其制作方法GaN-based material based on Si substrate and manufacturing method thereof 技术领域Technical field
本发明涉及一种半导体材料，具体涉及一种可用于制作黄光LED的GaN基材料及其制作方法。The present invention relates to a semiconductor material, and in particular to a GaN-based material that can be used to fabricate a yellow LED and a method of fabricating the same.
背景技术Background technique
Ш-V族氮化物半导体材料具有直接带隙、热导率高、电子饱和迁移率高、发光效率高、耐高温和抗辐射等优点，在光电子及微电子领域的应用都取得了巨大的进步。在短波长蓝光—紫外光发光器件、微波器件和大功率半导体器件等方面有巨大的应用前景，通过调节器件的材料中In的组分，理论上讲，可以实现对可见光波长的全覆盖。Ш-V nitride semiconductor materials have advantages such as direct band gap, high thermal conductivity, high electron saturation mobility, high luminous efficiency, high temperature resistance and radiation resistance, and have made great progress in applications in optoelectronics and microelectronics. . It has great application prospects in short-wavelength blue-ultraviolet light-emitting devices, microwave devices and high-power semiconductor devices. By adjusting the composition of In in the material of the device, theoretically, full coverage of visible light wavelength can be realized.
2014年Jianli Zhang等人提出了在Si衬底上生长InGaN基黄光LED全结构的方案，参见所发表的论文“High brightness InGaN-based yellow light-emitting diodes with strain modulation layers grown on Si substrate，Applied Physics A，(2014)114:1049–1053”。该方案采用InGaN/GaN量子阱作为有源区，由于黄光需要较高的铟(In)组分，高的In组分需要低的生长温度，同时高的In组分会在材料中产生较大的应力，这会退化GaN的结晶质量，退化器件性能。而且InGaN量子阱的生长工艺复杂，生长效率低，成本高。In 2014, Jianli Zhang et al. proposed a scheme for growing the full structure of InGaN-based yellow LEDs on Si substrates. See the published paper "High brightness InGaN-based yellow light-emitting diodes with strain modulation layers grown on Si substrate, Applied. Physics A, (2014) 114: 1049–1053”. The scheme uses InGaN/GaN quantum wells as the active region. Since yellow light requires a higher indium (In) composition, the high In composition requires a low growth temperature, while the high In composition causes a larger in the material. The stress, which degrades the crystalline quality of GaN, degrades device performance. Moreover, the growth process of the InGaN quantum well is complicated, the growth efficiency is low, and the cost is high.
发明内容Summary of the invention
本发明的目的在于针对上述已有技术的不足，提供一种可用于制作黄光LED的GaN基材料及其制作方法，以简化工艺复杂度，提高生长效率，降低成本，提高LED器件性能。 The object of the present invention is to provide a GaN-based material which can be used for fabricating a yellow LED and a manufacturing method thereof, in order to simplify the process complexity, improve the growth efficiency, reduce the cost, and improve the performance of the LED device.
本发明的一个实施例提供一种GaN基材料，包括：自上而下排列的p型GaN层、有源层、成核层和衬底；其中，所述有源层采用C掺杂和Si掺杂的n型GaN层，以在所述n型GaN层中引入C的深能级。An embodiment of the present invention provides a GaN-based material comprising: a p-type GaN layer, an active layer, a nucleation layer, and a substrate arranged from top to bottom; wherein the active layer is doped with C and Si A doped n-type GaN layer is introduced to introduce a deep level of C in the n-type GaN layer.
优选地，所述衬底采用Si衬底，也可采用其它材料的衬底。Preferably, the substrate is a Si substrate, and a substrate of other materials may also be used.
优选地，所述有源层中C掺杂的浓度范围是1×1017cm-3至1×1019cm-3，所述有源层中Si掺杂的浓度范围是5×1017cm-3至3×1019cm-3。Preferably, the concentration of C doping in the active layer ranges from 1×10 17 cm −3 to 1×10 19 cm −3 , and the concentration of Si doping in the active layer ranges from 5×10 17 cm. -3 to 3 x 10 19 cm -3 .
优选地，所述p型GaN层的厚度是0.01-10μm，其中的Mg掺杂浓度范围是1×1017cm-3至3×1019cm-3。Preferably, the p-type GaN layer has a thickness of 0.01 to 10 μm, wherein the Mg doping concentration ranges from 1 × 10 17 cm -3 to 3 × 10 19 cm -3 .
优选地，所述有源层的厚度范围是0.2-100μm。Preferably, the thickness of the active layer ranges from 0.2 to 100 μm.
本发明的另一实施例提供一种GaN基材料的制作方法，所述GaN基材料包括：自上而下排列的p型GaN层、有源层、成核层和衬底；所述方法包括：在所述成核层上生长C掺杂和Si掺杂的n型GaN层，作为所述有源层，以在所述n型GaN层中引入C的深能级。Another embodiment of the present invention provides a method of fabricating a GaN-based material, the GaN-based material comprising: a p-type GaN layer, an active layer, a nucleation layer, and a substrate arranged from top to bottom; : growing a C-doped and Si-doped n-type GaN layer on the nucleation layer as the active layer to introduce a deep level of C into the n-type GaN layer.
优选地，将所述衬底置于金属有机物化学气相淀积MOCVD反应室中，向所述反应室通入氢气与氨气的混合气体，对所述衬底进行热处理。Preferably, the substrate is placed in a metal organic chemical vapor deposition MOCVD reaction chamber, and a mixed gas of hydrogen gas and ammonia gas is introduced into the reaction chamber, and the substrate is subjected to heat treatment.
优选地，在所述热处理期间保持所述反应室的真空度小于2×10-2Torr，加热温度为830-1150℃，热处理时间为5-10min，所述反应室的压力为30-700Torr。Preferably, the vacuum of the reaction chamber is maintained during the heat treatment to be less than 2 x 10 -2 Torr, the heating temperature is 830-1150 ° C, the heat treatment time is 5-10 min, and the pressure of the reaction chamber is 30-700 Torr.
优选地，在所述衬底上生长的成核层是厚度为10-200nm、温度为530-720℃的低温成核层。Preferably, the nucleation layer grown on the substrate is a low temperature nucleation layer having a thickness of 10-200 nm and a temperature of 530-720 °C.
优选地，在所述成核层上生长的n型GaN层是厚度为0.2-100μm、温度为850-1100℃的高温n型GaN有源层。Preferably, the n-type GaN layer grown on the nucleation layer is a high-temperature n-type GaN active layer having a thickness of 0.2 to 100 μm and a temperature of 850 to 1100 °C.
优选地，在所述有源层上生长的p型GaN层是厚度为0.01-10μm、Mg掺杂浓度为1×1017cm-3至3×1019cm-3、温度为850-1100℃的高 温p型GaN层。Preferably, the p-type GaN layer grown on the active layer has a thickness of 0.01-10 μm, a Mg doping concentration of 1×10 17 cm −3 to 3×10 19 cm −3 , and a temperature of 850-1100° C. High temperature p-type GaN layer.
以下结合附图进一步描述本发明的实施例。Embodiments of the present invention are further described below in conjunction with the accompanying drawings.
附图说明DRAWINGS
图1是本发明的实施例的基于Si衬底上黄光LED材料的结构示意图；1 is a schematic view showing the structure of a yellow LED material on a Si substrate according to an embodiment of the present invention;
图2为本发明的实施例的制作基于Si衬底上黄光LED材料的方法流程图。2 is a flow chart of a method of fabricating a yellow LED material on a Si substrate in accordance with an embodiment of the present invention.
具体实施方式detailed description
第一实施例First embodiment
该实施例的一种可用于制作黄光LED的GaN基材料包括四层，如图1所示，自上而下分别为p型GaN层、有源层、成核层和衬底。其中第一层(即最底层)为衬底，可采用Si材料；第二层为成核层，采用厚度为10-200nm的AlN；第三层为有源层，其中有源层使用C掺杂和Si掺杂形成的n型GaN层，以在GaN中引入C的深能级，为发黄光的电子、空穴提供复合平台；第四层为p型GaN层，采用厚度为0.01-10μm，掺杂浓度为1×1017cm-3～3×1019cm-3的Mg掺杂GaN。A GaN-based material that can be used to fabricate a yellow LED of this embodiment includes four layers, as shown in FIG. 1, which are a p-type GaN layer, an active layer, a nucleation layer, and a substrate, respectively, from top to bottom. The first layer (ie, the lowest layer) is a substrate, and a Si material may be used; the second layer is a nucleation layer, and AlN is 10-200 nm in thickness; the third layer is an active layer, wherein the active layer is doped with C The n-type GaN layer formed by doping with Si and Si introduces a deep level of C in GaN to provide a composite platform for yellow-emitting electrons and holes; the fourth layer is a p-type GaN layer with a thickness of 0.01- 10 μm, Mg doped GaN having a doping concentration of 1 × 10 17 cm -3 to 3 × 10 19 cm -3 .
进一步，第三层的有源层可采用厚度为0.2-100μm的C掺杂和Si掺杂的n型GaN层，其中C掺杂的浓度为1×1017cm-3～1×1019cm-3，Si掺杂的浓度为5×1017cm-3～3×1019cm-3，由于在GaN中引入了C掺杂，因此在GaN中会形成深能级，为发黄光的电子、空穴提供了复合的平台。Further, the active layer of the third layer may be a C-doped and Si-doped n-type GaN layer having a thickness of 0.2-100 μm, wherein the C-doping concentration is 1×10 17 cm -3 to 1×10 19 cm. -3 , the concentration of Si doping is 5 × 10 17 cm -3 to 3 × 10 19 cm -3 . Since C doping is introduced into GaN, a deep level is formed in GaN, which is yellowish Electrons and holes provide a composite platform.
第二实施例Second embodiment
该实施例的基于Si衬底上黄光LED材料的制作方法包括如下步骤： The manufacturing method of the yellow LED material on the Si substrate of this embodiment comprises the following steps:
(1)将Si衬底置于金属有机物化学气相淀积(MOCVD)反应室中，并向反应室通入氢气与氨气的混合气体，对衬底进行热处理，反应室的真空度小于2×10-2Torr，衬底加热温度为830-1150℃，热处理时间为5-10min，反应室压力为30-700Torr；(1) placing the Si substrate in a metal organic chemical vapor deposition (MOCVD) reaction chamber, and introducing a mixed gas of hydrogen gas and ammonia gas into the reaction chamber, heat-treating the substrate, and the vacuum degree of the reaction chamber is less than 2×. 10 -2 Torr, substrate heating temperature is 830-1150 ° C, heat treatment time is 5-10 min, reaction chamber pressure is 30-700 Torr;
(2)在Si衬底上生长厚度为10-200nm、温度为530-720℃的低温成核层；(2) growing a low temperature nucleation layer having a thickness of 10-200 nm and a temperature of 530-720 ° C on the Si substrate;
(3)在低温成核层之上生长厚度为0.2-100μm、C掺杂浓度为1×1017cm-3～1×1019cm-3、Si掺杂的浓度为5×1017cm-3～3×1019cm-3、温度为850-1100℃的高温n型GaN有源层；(3) The growth thickness is 0.2-100 μm on the low-temperature nucleation layer, the C doping concentration is 1×10 17 cm -3 to 1×10 19 cm -3 , and the concentration of Si doping is 5×10 17 cm - a high temperature n-type GaN active layer of 3 to 3 × 10 19 cm -3 and a temperature of 850-1100 ° C;
(4)在n型GaN有源层之上生长厚度为0.01-10μm，Mg掺杂浓度为1×1017cm-3～3×1019cm-3，温度为850-1100℃的高温p型GaN层。(4) A high-temperature p-type having a thickness of 0.01 to 10 μm, a Mg doping concentration of 1 × 10 17 cm -3 to 3 × 10 19 cm -3 , and a temperature of 850-1100 ° C on the n-type GaN active layer GaN layer.
在该实施例中采用MOCVD的方法，通过在有源层中引入C掺杂，使C元素替换N元素形成深能级，提供复合能级；C杂质可以通过C源引入，也可以通过控制工艺利用MOCVD中的C杂质实现。In this embodiment, by the method of MOCVD, by introducing C-doping into the active layer, the C element is replaced with the N element to form a deep level, providing a composite level; the C impurity can be introduced through the C source, or can be controlled by a process. This is achieved by the C impurity in MOCVD.
该实施例由于采用Si衬底和C掺杂和Si掺杂的n型GaN作为有源层，与现有技术相比具有如下优点：This embodiment has the following advantages as compared with the prior art since the Si substrate and the C-doped and Si-doped n-type GaN are used as the active layer:
1.避免了传统LED结果中的InGaN量子阱生长，简化了工艺步骤，提高了生长效率。1. Avoid the growth of InGaN quantum wells in traditional LED results, simplify the process steps and improve the growth efficiency.
2.避免了InGaN的存在引起材料晶格失配大的问题，提高了材料的质量，从而提高LED器件的性能。2. Avoid the problem that the existence of InGaN causes a large lattice mismatch of the material, improve the quality of the material, and thereby improve the performance of the LED device.
3.利用Si衬底扩散到有源层的Si作为Si源，利用MOCVD中的Ga源中的C作为C源，降低了生产成本。3. Si which is diffused to the active layer by the Si substrate is used as the Si source, and C in the Ga source in the MOCVD is used as the C source, which reduces the production cost.
以下参照图2，进一步描述本发明的可用于制作黄光LED的GaN基材料的方法的三种实施例。Three embodiments of the method of the present invention that can be used to fabricate GaN-based materials for yellow LEDs are further described below with reference to FIG.
第三实施例Third embodiment
该实施例用于制作C掺杂浓度为1×1018cm-3、Si掺杂浓度为3 ×1018cm-3的n型GaN有源层的LED材料。具体步骤如下：This embodiment is for producing an LED material of an n-type GaN active layer having a C doping concentration of 1 × 10 18 cm -3 and a Si doping concentration of 3 × 10 18 cm -3 . Specific steps are as follows:
(1)对衬底基片进行热处理。(1) The substrate substrate is subjected to heat treatment.
首先是放片，将Si衬底基片放置于金属有机物化学气相淀积(MOCVD)反应室中，并向反应室通入氢气与氨气的混合气体；将反应室抽真空，使反应室的真空度小于2×10-2Torr；在反应室压力为45Torr的条件下，对Si衬底基片进行热处理，衬底加热温度为1000℃，加热时间为7min。First, the wafer is placed, the Si substrate is placed in a metal organic chemical vapor deposition (MOCVD) reaction chamber, and a mixed gas of hydrogen and ammonia is introduced into the reaction chamber; the reaction chamber is evacuated to make the reaction chamber The degree of vacuum was less than 2 × 10 -2 Torr; the Si substrate was heat-treated under the conditions of a reaction chamber pressure of 45 Torr, the substrate heating temperature was 1000 ° C, and the heating time was 7 min.
(2)生长AlN成核层。(2) Growing an AlN nucleation layer.
将热处理后的衬底基片温度降低为600℃，向反应室通入流量为5μmol/min的铝源、流量为1200sccm氢气和流量为1200sccm的氨气，在保持压力为45Torr的条件下生长厚度为25nm的低温AlN成核层。The temperature of the substrate substrate after the heat treatment was lowered to 600 ° C, an aluminum source having a flow rate of 5 μmol/min, a hydrogen gas having a flow rate of 1200 sccm, and an ammonia gas having a flow rate of 1200 sccm were introduced into the reaction chamber, and the thickness was grown under a holding pressure of 45 Torr. It is a 25 nm low temperature AlN nucleation layer.
(3)生长C掺杂和Si掺杂的n型GaN有源层。(3) Growing a C-doped and Si-doped n-type GaN active layer.
向反应室通入流量为30μmol/min的镓源、流量为1200sccm氢气和流量为1500sccm的氨气，保持反应室压力为45Torr，温度为985℃，取C掺杂浓度为1×1018cm-3，Si掺杂浓度为3×1018cm-3，在低温AlN成核层上生长厚度为3μm的n型GaN有源层。A gallium source having a flow rate of 30 μmol/min, a flow rate of 1200 sccm of hydrogen, and a flow rate of 1500 sccm of ammonia gas were introduced into the reaction chamber, and the reaction chamber pressure was 45 Torr, the temperature was 985 ° C, and the C doping concentration was 1 × 10 18 cm - 3 , the Si doping concentration is 3 × 10 18 cm -3 , and an n-type GaN active layer having a thickness of 3 μm is grown on the low-temperature AlN nucleation layer.
(4)生长p型GaN层。(4) Growing a p-type GaN layer.
将已经生长了C掺杂和Si掺杂的n型GaN层基片的温度保持在985℃，向反应室通入流量为30μmol/min的镓源、流量为1200sccm氢气、流量为1500sccm的氨气和流量为10μmol/min的Mg源，保持反应室的压力为45Torr，温度为985℃，生长厚度为200nm的p型GaN层，形成c面GaN材料。The temperature of the C-doped and Si-doped n-type GaN layer substrate was maintained at 985 ° C, and a gallium source having a flow rate of 30 μmol/min, a flow rate of 1200 sccm of hydrogen, and a flow rate of 1500 sccm of ammonia gas were introduced into the reaction chamber. And a Mg source having a flow rate of 10 μmol/min, a pressure of 45 Torr in the reaction chamber, a temperature of 985 ° C, and a p-type GaN layer having a thickness of 200 nm were grown to form a c-plane GaN material.
(5)从MOCVD反应室中取出所形成的片状GaN基材料。(5) The formed sheet-like GaN-based material was taken out from the MOCVD reaction chamber.
第四实施例Fourth embodiment
本实施例用于制作C掺杂浓度为1×1017cm-3、Si掺杂浓度为5×1017cm-3的n型GaN有源层的LED材料。具体的实现步骤如下： This embodiment is for producing an LED material of an n-type GaN active layer having a C doping concentration of 1 × 10 17 cm -3 and a Si doping concentration of 5 × 10 17 cm -3 . The specific implementation steps are as follows:
(1)将Si衬底基片置于金属有机物化学气相淀积(MOCVD)反应室中，并向反应室通入氢气与氨气的混合气体；在反应室的真空度小于2×10-2Torr、反应室压力为30Torr的条件下，对衬底基片进行热处理，衬底加热温度为830℃，加热时间为5min。(1) placing a Si substrate in a metal organic chemical vapor deposition (MOCVD) reaction chamber, and introducing a mixed gas of hydrogen and ammonia into the reaction chamber; the degree of vacuum in the reaction chamber is less than 2 × 10 -2 The substrate substrate was subjected to heat treatment under the conditions of Torr and a reaction chamber pressure of 30 Torr, and the substrate heating temperature was 830 ° C, and the heating time was 5 min.
(2)将热处理后的衬底基片温度降低为530℃，向反应室通入流量为5μmol/min的铝源、流量为1000sccm氢气和流量为1000sccm的氨气，在保持压力为20Torr的条件下生长厚度为10nm的低温AlN成核层。(2) The temperature of the substrate substrate after the heat treatment was lowered to 530 ° C, and an aluminum source having a flow rate of 5 μmol/min, a hydrogen gas having a flow rate of 1000 sccm, and an ammonia gas having a flow rate of 1000 sccm were introduced into the reaction chamber at a holding pressure of 20 Torr. A low temperature AlN nucleation layer having a thickness of 10 nm is grown underneath.
(3)向反应室通入流量为5μmol/min的镓源、流量为1000sccm氢气和流量为1000sccm的氨气，保持压力为30Torr，温度为850℃，取C掺杂浓度为1×1017cm-3、Si掺杂浓度为5×1017cm-3，在低温AlN成核层上生长厚度为200nm的n型GaN有源层。(3) A gallium source having a flow rate of 5 μmol/min, a flow rate of 1000 sccm of hydrogen, and a flow rate of 1000 sccm of ammonia gas were introduced into the reaction chamber at a pressure of 30 Torr, a temperature of 850 ° C, and a C doping concentration of 1 × 10 17 cm. -3 , Si doping concentration is 5 × 10 17 cm -3 , and an n-type GaN active layer having a thickness of 200 nm is grown on the low-temperature AlN nucleation layer.
(4)将已经生长了C掺杂和Si掺杂的n型GaN层基片的温度保持在850℃，向反应室通入流量为5μmol/min的镓源、流量为1000sccm氢气和流量为1000sccm的氨气、5μmol/min的Mg源，保持反应室的压力为30Torr，生长厚度为10nm的p型GaN层，形成c面GaN材料，并从MOCVD反应室中取出。(4) Maintaining the temperature of the C-doped and Si-doped n-type GaN layer substrate at 850 ° C, introducing a gallium source having a flow rate of 5 μmol/min into the reaction chamber, a flow rate of 1000 sccm of hydrogen, and a flow rate of 1000 sccm. The ammonia gas, a Mg source of 5 μmol/min, maintained a pressure of 30 Torr in the reaction chamber, and grown a p-type GaN layer having a thickness of 10 nm to form a c-plane GaN material, which was taken out from the MOCVD reaction chamber.
第五实施例Fifth embodiment
本实施例用于制作C掺杂浓度为1×1019cm-3、Si掺杂浓度为3×1019cm-3的n型GaN有源层的LED材料。具体的实现步骤如下：This embodiment is for producing an LED material of an n-type GaN active layer having a C doping concentration of 1 × 10 19 cm -3 and a Si doping concentration of 3 × 10 19 cm -3 . The specific implementation steps are as follows:
(1)对衬底基片进行热处理。(1) The substrate substrate is subjected to heat treatment.
将Si衬底基片置于金属有机物化学气相淀积(MOCVD)反应室中，并向反应室通入氢气与氨气的混合气体，进行热处理，其工艺条件如下：The Si substrate is placed in a metal organic chemical vapor deposition (MOCVD) reaction chamber, and a mixed gas of hydrogen and ammonia is introduced into the reaction chamber to perform heat treatment. The process conditions are as follows:
反应室的真空度小于2×10-2Torr；衬底加热温度为1150℃；氮化时间为10min；反应室压力为700Torr。 The vacuum of the reaction chamber was less than 2 × 10 -2 Torr; the substrate heating temperature was 1150 ° C; the nitriding time was 10 min; and the reaction chamber pressure was 700 Torr.
(2)生长AlN成核层。(2) Growing an AlN nucleation layer.
在热处理后的衬底基片上生长厚度为200nm的低温AlN成核层，其工艺条件如下：A low temperature AlN nucleation layer having a thickness of 200 nm is grown on the heat-treated substrate substrate, and the process conditions are as follows:
反应室温度为720℃；反应室压力为700Torr；铝源流量为100μmol/min；氢气流量为10000sccm；氨气流量为10000sccm。The reaction chamber temperature was 720 ° C; the reaction chamber pressure was 700 Torr; the aluminum source flow rate was 100 μmol/min; the hydrogen flow rate was 10000 sccm; and the ammonia gas flow rate was 10000 sccm.
(3)生长C掺杂和Si掺杂的n型GaN有源层。(3) Growing a C-doped and Si-doped n-type GaN active layer.
在低温AlN成核层上生长厚度为100μm的n型GaN有源层，其工艺条件如下：An n-type GaN active layer having a thickness of 100 μm is grown on the low temperature AlN nucleation layer, and the process conditions are as follows:
反应室温度为1100℃；反应室压力为700Torr；镓源流量为100μmol/min；氢气流量为10000sccm；氨气流量为10000sccm；C掺杂浓度为1×1019cm-3；Si掺杂的浓度为3×1019cm-3。The reaction chamber temperature is 1100 ° C; the reaction chamber pressure is 700 Torr; the gallium source flow rate is 100 μmol/min; the hydrogen flow rate is 10000 sccm; the ammonia gas flow rate is 10000 sccm; the C doping concentration is 1×10 19 cm -3 ; It is 3 × 10 19 cm -3 .
(4)生长p型GaN层。(4) Growing a p-type GaN layer.
在C掺杂和Si掺杂的n型GaN有源层上生长厚度为10μm的p型GaN层，形成c面GaN材料，其工艺条件为：A p-type GaN layer having a thickness of 10 μm is grown on the C-doped and Si-doped n-type GaN active layer to form a c-plane GaN material, and the process conditions are as follows:
基片温度为1100℃；反应室压力为700Torr；镓源流量为100μmol/min；氢气流量为10000sccm；氨气流量为10000sccm；Mg源流量为100μmol/min。The substrate temperature was 1100 ° C; the reaction chamber pressure was 700 Torr; the gallium source flow rate was 100 μmol/min; the hydrogen flow rate was 10000 sccm; the ammonia gas flow rate was 10000 sccm; and the Mg source flow rate was 100 μmol/min.
(5)将形成的c面GaN材料从MOCVD反应室中取出。(5) The formed c-plane GaN material was taken out from the MOCVD reaction chamber.
以上实施例仅用于对本发明的说明，不构成对本发明的限制。对于本领域的专业人员来说，在了解本发明内容和原理后，能够在不背离本发明的原理和范围的情况下，根据本发明的方法进行形式和细节上的各种修正和改变，但是这些基于本发明的修正和改变仍受本发明的权利要求保护。 The above embodiments are merely illustrative of the invention and are not to be construed as limiting. Various modifications and changes in form and detail may be made in accordance with the method of the present invention without departing from the principles and the scope of the invention. These modifications and variations based on the present invention are still protected by the claims of the present invention.

Claims (13)

  1. 一种GaN基材料，包括：自上而下排列的p型GaN层、有源层、成核层和衬底；其中，所述有源层采用C掺杂和Si掺杂的n型GaN层，以在所述n型GaN层中引入C的深能级。A GaN-based material comprising: a p-type GaN layer arranged from top to bottom, an active layer, a nucleation layer, and a substrate; wherein the active layer is a C-doped and Si-doped n-type GaN layer To introduce a deep level of C into the n-type GaN layer.
  2. 根据权利要求1的GaN基材料，其中，所述衬底为Si衬底。The GaN-based material according to claim 1, wherein said substrate is a Si substrate.
  3. 根据权利要求1的GaN基材料，其中，所述C掺杂的浓度为1×1017cm-3至1×1019cm-3，所述Si掺杂的浓度为5×1017cm-3至3×1019cm-3。The GaN-based material according to claim 1, wherein said C doping concentration is 1 × 10 17 cm -3 to 1 × 10 19 cm -3 , and said Si doping concentration is 5 × 10 17 cm -3 Up to 3 × 10 19 cm -3 .
  4. 根据权利要求1的GaN基材料，其中，所述p型GaN层的厚度为0.01-10μm，其中的Mg掺杂浓度为1×1017cm-3至3×1019cm-3。The GaN-based material according to claim 1, wherein said p-type GaN layer has a thickness of 0.01 to 10 μm, and a Mg doping concentration thereof is 1 × 10 17 cm -3 to 3 × 10 19 cm -3 .
  5. 根据权利要求1的GaN基材料，其中，所述有源层的厚度为0.2-100μm。The GaN-based material according to claim 1, wherein said active layer has a thickness of from 0.2 to 100 μm.
  6. 一种GaN基材料的制作方法，所述GaN基材料包括：自上而下排列的p型GaN层、有源层、成核层和衬底；所述方法包括：A method for fabricating a GaN-based material, comprising: a p-type GaN layer, an active layer, a nucleation layer, and a substrate arranged from top to bottom; the method comprising:
    在所述成核层上生长C掺杂和Si掺杂的n型GaN层，作为所述有源层，以在所述n型GaN层中引入C的深能级。A C-doped and Si-doped n-type GaN layer is grown on the nucleation layer as the active layer to introduce a deep level of C into the n-type GaN layer.
  7. 根据权利要求6的方法，其中，所述衬底为Si衬底。The method of claim 6 wherein said substrate is a Si substrate.
  8. 根据权利要求6或7的方法，还包括：A method according to claim 6 or 7, further comprising:
    将所述衬底置于金属有机物化学气相淀积MOCVD反应室中， 向所述反应室通入氢气与氨气的混合气体，对所述衬底进行热处理。The substrate is placed in a metal organic chemical vapor deposition MOCVD reaction chamber, A mixed gas of hydrogen gas and ammonia gas is introduced into the reaction chamber, and the substrate is subjected to heat treatment.
  9. 根据权利要求8的方法，其中，在所述热处理期间保持所述反应室的真空度小于2×10-2Torr，加热温度为830-1150℃，热处理时间为5-10min，所述反应室的压力为30-700Torr。The method according to claim 8, wherein said reaction chamber is maintained at a degree of vacuum of less than 2 × 10 -2 Torr during said heat treatment, a heating temperature of from 830 to 1150 ° C, and a heat treatment time of from 5 to 10 minutes, said reaction chamber The pressure is 30-700 Torr.
  10. 根据权利要求6的方法，其中，所述C掺杂的浓度为1×1017cm-3至1×1019cm-3，所述Si掺杂的浓度为5×1017cm-3至3×1019cm-3。The method according to claim 6, wherein said C doping has a concentration of from 1 × 10 17 cm -3 to 1 × 10 19 cm -3 , and said Si doping has a concentration of from 5 × 10 17 cm -3 to 3 ×10 19 cm -3 .
  11. 根据权利要求6的方法，其中，在所述衬底上生长的成核层是厚度为10-200nm、温度为530-720℃的低温成核层。The method of claim 6 wherein the nucleation layer grown on said substrate is a low temperature nucleation layer having a thickness of 10-200 nm and a temperature of 530-720 °C.
  12. 根据权利要求6、10或11的方法，其中，在所述成核层上生长的n型GaN层是厚度为0.2-100μm、温度为850-1100℃的高温n型GaN有源层。The method according to claim 6, 10 or 11, wherein the n-type GaN layer grown on the nucleation layer is a high-temperature n-type GaN active layer having a thickness of 0.2 to 100 μm and a temperature of 850 to 1100 °C.
  13. 根据权利要求6的方法，其中，在所述有源层上生长的p型GaN层是厚度为0.01-10μm、Mg掺杂浓度为1×1017cm-3至3×1019cm-3、温度为850-1100℃的高温p型GaN层。 The method according to claim 6, wherein the p-type GaN layer grown on said active layer has a thickness of 0.01 to 10 μm and a Mg doping concentration of 1 × 10 17 cm -3 to 3 × 10 19 cm -3 , A high temperature p-type GaN layer having a temperature of 850-1100 °C.
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