CN112086543A - AlGaN composite film with self-assembled template and preparation method thereof - Google Patents

AlGaN composite film with self-assembled template and preparation method thereof Download PDF

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CN112086543A
CN112086543A CN202010830369.0A CN202010830369A CN112086543A CN 112086543 A CN112086543 A CN 112086543A CN 202010830369 A CN202010830369 A CN 202010830369A CN 112086543 A CN112086543 A CN 112086543A
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algan
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CN112086543B (en
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张骏
岳金顺
梁仁瓅
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Suzhou Zican Technology Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02Semiconductor devices with at least one potential-jump barrier or surface barrier 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
    • H01L33/12Semiconductor devices with at least one potential-jump barrier or surface barrier 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 with a stress relaxation structure, e.g. buffer layer
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005Processes
    • H01L33/0062Processes for devices with an active region comprising only III-V compounds
    • H01L33/0066Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound
    • H01L33/007Processes for devices with an active region comprising only III-V compounds with a substrate not being a III-V compound comprising nitride compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02Semiconductor devices with at least one potential-jump barrier or surface barrier 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
    • H01L33/26Materials of the light emitting region
    • H01L33/30Materials of the light emitting region containing only elements of group III and group V of the periodic system
    • H01L33/32Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen

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Abstract

The invention discloses an AlGaN composite film with a self-assembly template and a preparation method thereof, wherein the AlGaN composite film with the self-assembly template is sequentially provided with a sapphire substrate, an AlN low-temperature buffer layer, a high-temperature AlN layer, an AlGaN self-assembly template layer and a high-temperature AlGaN film layer from bottom to top; the AlGaN self-assembly template layer is prepared by heating and annealing an AlInGaN thin layer and an AlGaN low-temperature layer which are arranged In a close manner until In sublimes, wherein the AlInGaN thin layer is positioned at one side close to the high-temperature AlN layer before heating and annealing, and the AlGaN low-temperature layer is positioned at one side close to the high-temperature AlGaN thin layer. According to the invention, the patterned AlGaN self-assembly template layer is formed by heating and annealing the AlInGaN thin film layer and the AlGaN low-temperature layer until In is sublimated, and the AlGaN self-assembly template layer can effectively filter threading dislocation from the high-temperature AlN layer and release thermal stress accumulated In the growth process, so that the quality of the AlGaN composite film is obviously improved and the film is prevented from cracking.

Description

AlGaN composite film with self-assembled template and preparation method thereof
Technical Field
The invention relates to the field of semiconductor photoelectricity, in particular to an AlGaN composite film with a self-assembled template and a preparation method thereof.
Background
Group III nitrides have been used as an outstanding representative of wide bandgap semiconductor materials, and have achieved high-efficiency solid-state light source devices such as blue-green Light Emitting Diodes (LEDs) and lasers, which have achieved great success in applications such as flat panel displays and white light illumination. In the last decade, it has been desired to apply such efficient luminescent materials in the ultraviolet band to meet the increasing demand of ultraviolet light sources. The ultraviolet band can be generally classified into: long wave ultraviolet (UVA, 320nm-400nm), medium wave ultraviolet (UVB, 280nm-320nm), short wave ultraviolet (UVC, 200nm-280nm), and vacuum ultraviolet (VUV, 10nm-200 nm). Ultraviolet light, while not perceived by the human eye, is used in a wide variety of applications. The long-wave ultraviolet light source has great application prospect in the fields of medical treatment, ultraviolet curing, ultraviolet photoetching, information storage, plant illumination and the like; medium-wave ultraviolet and short-wave ultraviolet (collectively called deep ultraviolet) have irreplaceable effects in the aspects of sterilization, disinfection, water purification, biochemical detection, non-line-of-sight communication and the like. At present, the traditional ultraviolet light source is mainly a mercury lamp, has the defects of large volume, high power consumption, high voltage, environmental pollution and the like, and is not beneficial to the application of the traditional ultraviolet light source in daily life and special environments. Therefore, it is highly desirable to develop a highly efficient semiconductor ultraviolet light source device to replace the conventional mercury lamp. The existing research shows that AlGaN in III group nitride is the best candidate material for preparing semiconductor ultraviolet light source devices. The AlGaN matrix ultraviolet LED has the advantages of no toxicity, environmental protection, small size, portability, low power consumption, low voltage, easy integration, long service life, adjustable wavelength and the like, is expected to make breakthrough progress and wide application in the coming years, and gradually replaces the traditional ultraviolet mercury lamp.
At present, the luminous efficiency of the deep ultraviolet LED is generally not more than 5%, which is caused by the low internal quantum efficiency and the low light extraction efficiency. The low light extraction efficiency is caused by the intrinsic characteristic that the high Al component AlGaN material mainly emits light from the side surface, and the low internal quantum efficiency is caused by the fact that the crystal quality of the high Al component AlGaN material does not reach the ideal level at present, and the dislocation density is mostly 109cm-2Magnitude. Group III nitride materials are typically heteroepitaxial due to the scarcity of homogeneous substratesOn a sapphire substrate, in order to reduce the dislocation density of an AlGaN material and improve the crystal quality of the AlGaN material, a layer of binary AlN material needs to be grown on the sapphire firstly before the AlGaN material is grown. On one hand, the binary AlN material does not have the problem of component segregation in the ternary AlGaN material, and the AlN material crystal growing at high temperature has better quality; on the other hand, the lattice constant of the AlGaN material is larger than that of the AlN material, and the AlGaN material is subjected to compressive stress from the AlN material, so that the AlGaN material can be prevented from being cracked due to over-thick epitaxy. At present, the dislocation density of the AlGaN material is still large due to the limitation of larger compressive stress and larger threading dislocation density from the AlN bottom layer, and the problem of AlGaN film cracking still exists. Therefore, it is necessary to provide a new scheme for preparing AlGaN thin films to solve the above problems.
Disclosure of Invention
The invention aims to provide an AlGaN composite film with a self-assembly template and a preparation method thereof, which are used for solving the problem of cracking caused by high dislocation density of an AlGaN material in the prior art.
To solve the above technical problem, the present invention provides a first solution: providing an AlGaN composite film with a self-assembled template, wherein the AlGaN film with the self-assembled template is sequentially provided with a sapphire substrate, an AlN low-temperature buffer layer, a high-temperature AlN layer, an AlGaN self-assembled template layer and a high-temperature AlGaN film layer from bottom to top; the AlGaN self-assembly template layer is prepared by heating and annealing an AlInGaN thin layer and an AlGaN low-temperature layer which are arranged In a close manner until In sublimes, wherein the AlInGaN thin layer is positioned on one side close to the high-temperature AlN layer before heating and annealing, and the AlGaN low-temperature layer is positioned on one side close to the high-temperature AlGaN thin layer.
Before temperature-rising annealing, the thickness of the AlInGaN thin film layer is 1-500 nm, wherein the mass ratio of In is 1-30%, and the mass ratio of Al is 30-90%.
Before heating and annealing, the thickness of the AlGaN low-temperature layer is 1-500 nm, wherein the mass ratio of Al is 30-90%.
Wherein, the specific steps of the temperature-rising annealing are any one of the following steps: (1) heating to 800-1300 ℃ in a hydrogen atmosphere, and keeping the temperature for 1-30 min; (2) and heating to 800-1400 ℃ in a nitrogen atmosphere, and keeping the temperature for 1-30 min.
To solve the above technical problem, the present invention provides a second solution: there is provided a method for preparing an AlGaN composite film having a self-assembled template, for preparing the AlGaN composite film having a self-assembled template in the first solution, the method including the steps of:
s1, preparing a film by adopting a metal organic chemical vapor deposition method, and carrying out nitridation pretreatment on the sapphire substrate to obtain the pretreated sapphire substrate.
S2, cooling to 400-800 ℃, and growing an AlN low-temperature buffer layer on the pretreated sapphire substrate, wherein the growth thickness of the AlN low-temperature buffer layer is 10-50 nm.
And S3, heating to 1100-1400 ℃, and growing a high-temperature AlN layer on the AlN low-temperature buffer layer.
S4, cooling to 400-1100 ℃, adjusting the V/III ratio to be 50-10000, and growing an AlInGaN thin film layer on the high-temperature AlN layer, wherein the mass ratio of In is 1-30%.
And S5, adjusting the temperature to 200-1200 ℃, adjusting the V/III ratio to 50-10000, and growing an AlGaN low-temperature layer on the AlInGaN thin film layer.
And S6, carrying out heating annealing treatment until In is sublimated to obtain the AlGaN self-assembled template layer.
And S7, adjusting the temperature to 900-1200 ℃, and growing a high-temperature AlGaN film layer on the AlGaN self-assembly template layer.
The step S1, in which the nitridation pretreatment is performed on the sapphire substrate, includes the following steps: heating to 900-1100 ℃ in a hydrogen atmosphere, and baking the sapphire substrate for 5 min; and keeping 900-1100 ℃, and introducing ammonia gas to treat the sapphire substrate for 5 min.
Preferably, in the step S4, the growth thickness of the AlInGaN thin film layer is 1-500 nm, and the mass ratio of Al is 30-90%.
Preferably, in the step S5, the growth thickness of the AlGaN low temperature layer is 1 to 500nm, and the mass ratio of Al in the AlGaN low temperature layer is 30 to 90%.
In the step S6, the specific step of the temperature-raising annealing is any one of the following: (1) heating to 800-1300 ℃ in a hydrogen atmosphere, and keeping the temperature for 1-30 min; (2) and heating to 800-1400 ℃ in a nitrogen atmosphere, and keeping the temperature for 1-30 min.
Preferably, the growth thickness of the high-temperature AlN layer is 100-10000 nm.
The invention has the beneficial effects that: different from the situation of the prior art, the invention provides the AlGaN composite film with the self-assembly template and the preparation method thereof, the AlInGaN film layer and the AlGaN low-temperature layer which are arranged In a close contact manner are heated and annealed until In is sublimated to form the graphical AlGaN self-assembly template layer, and the AlGaN self-assembly template layer can effectively filter threading dislocation from the high-temperature AlN layer and release thermal stress accumulated In the growth process, thereby obviously improving the quality of the AlGaN composite film and preventing the film from cracking.
Drawings
FIG. 1 is a schematic structural view of an embodiment of an AlGaN composite film with a self-assembled template according to the present invention;
fig. 2 is a process flow diagram of an embodiment of a method for preparing an AlGaN composite thin film having a self-assembled template according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Referring to fig. 1, fig. 1 is a schematic structural diagram of an embodiment of an AlGaN composite thin film with a self-assembled template according to the present invention. The AlGaN composite film with the self-assembly template is sequentially provided with a sapphire substrate, an AlN low-temperature buffer layer, a high-temperature AlN layer, an AlGaN self-assembly template layer and a high-temperature AlGaN film layer from bottom to top.
Specifically, the AlGaN self-assembly template layer is prepared by heating and annealing an AlInGaN thin film layer and an AlGaN low-temperature layer which are arranged In a close manner until In sublimes, wherein the AlInGaN thin film layer is positioned on one side close to the high-temperature AlN layer before heating and annealing, the AlGaN low-temperature layer is positioned on one side close to the high-temperature AlGaN thin film layer, and the AlGaN self-assembly template layer is positioned between the high-temperature AlN layer and the high-temperature AlGaN thin film layer.
In the embodiment, before the temperature-raising annealing, the thickness of the AlInGaN thin film layer is 1-500 nm, wherein the mass ratio of In is 1-30%, and the mass ratio of Al is 30-90%. Before temperature rise annealing, the thickness of the AlGaN low-temperature layer is 1-500 nm, wherein the mass ratio of Al is 30-90%. In addition, the specific steps of the temperature-raising annealing are any one of the following: (1) heating to 800-1300 ℃ in a hydrogen atmosphere, and keeping the temperature for 1-30 min; (2) and heating to 800-1400 ℃ in a nitrogen atmosphere, and keeping the temperature for 1-30 min. The process conditions of the temperature-rising annealing are closely related to the component proportion of the AlInGaN thin film layer, In other words, the temperature and time control of the annealing are closely related to the mass proportion of In the AlInGaN thin film layer, namely, the proper sublimation of In the AlInGaN thin film layer can be realized only by proper process conditions of the temperature-rising annealing, so that the effect of filtering the threading dislocation from the high-temperature AlN layer is achieved.
Referring to fig. 2 for a second solution of the present invention, fig. 2 is a process flow diagram of an embodiment of a method for preparing an AlGaN composite thin film having a self-assembled template according to the present invention. The preparation method of the AlGaN composite film with the self-assembly template in the present invention is used for preparing the AlGaN composite film with the self-assembly template in the first solution, and preferably, the film preparation is performed by a metal organic chemical vapor deposition method, and the preparation method includes the steps of:
s1, preparing a film by adopting a metal organic chemical vapor deposition method, and carrying out nitridation pretreatment on the sapphire substrate to obtain the pretreated sapphire substrate. In this step, the nitriding pretreatment of the sapphire substrate comprises the following specific steps: heating to 900-1100 ℃ in a hydrogen atmosphere, and baking the sapphire substrate for 5 min; and keeping 900-1100 ℃, and introducing ammonia gas to treat the sapphire substrate for 5 min. The sapphire substrate is subjected to nitridation pretreatment, so that the growth of a subsequent AlN low-temperature buffer layer is facilitated.
S2, cooling to 400-800 ℃, and growing an AlN low-temperature buffer layer on the pretreated sapphire substrate, wherein the growth thickness of the AlN low-temperature buffer layer is 10-50 nm.
And S3, heating to 1100-1400 ℃, and growing a high-temperature AlN layer on the AlN low-temperature buffer layer. In the step, the growth thickness of the high-temperature AlN layer is preferably 100-10000 nm.
S4, cooling to 400-1100 ℃, adjusting the V/III ratio to be 50-10000, and growing an AlInGaN thin film layer on the high-temperature AlN layer, wherein the mass ratio of In is 1-30%. In the embodiment, the growth thickness of the AlInGaN thin film layer is preferably 1-500 nm, and the mass ratio of Al is 30-90%; and preferably, the AlInGaN thin film layer is grown on the high-temperature AlN layer under a pressure of 50 Torr.
And S5, adjusting the temperature to 200-1200 ℃, adjusting the V/III ratio to 50-10000, and growing an AlGaN low-temperature layer on the AlInGaN thin film layer. In the embodiment, the growth thickness of the AlGaN low-temperature layer is preferably 1 to 500nm, and the mass ratio of Al in the AlGaN low-temperature layer is preferably 30 to 90%; and growing an AlGaN low-temperature layer on the AlInGaN thin film layer preferably under a gas pressure of 50 Torr.
And S6, carrying out heating annealing treatment until In is sublimated to obtain the AlGaN self-assembled template layer. In this embodiment, the specific step of the temperature-raising annealing is any one of the following: (1) heating to 800-1300 ℃ in a hydrogen atmosphere, keeping the pressure at 50Torr, and keeping the temperature for 1-30 min; (2) heating to 800-1400 ℃ in a nitrogen atmosphere, keeping the pressure at 50Torr, and keeping the temperature for 1-30 min.
And S7, adjusting the temperature to 900-1200 ℃, and growing a high-temperature AlGaN film layer on the AlGaN self-assembly template layer.
Further, based on the above description about the AlGaN composite thin film having a self-assembled template and the method for preparing the same, the mechanism and advantages of the AlGaN composite thin film having a self-assembled template are explained in detail. Heating and annealing the AlInGaN thin film layer and the AlGaN low-temperature layer according to the process steps, wherein the annealing temperature range only precipitates In but does not reach the lowest temperature for transferring Al and Ga atoms, and vacancies are generated due to precipitation of In and form the patterned AlGaN self-assembled template layer; the AlGaN self-assembly template layer with the vacancies can present a change trend of vacancy healing when a high-temperature AlGaN thin film layer grows in the subsequent process; in the process of regrowing and healing the AlGaN self-assembly template layer with vacancies, threading dislocation from the high-temperature AlN layer is bent into a ring along with the folding of materials and then annihilated, namely, the threading dislocation from the high-temperature AlN layer is bent and annihilated by introducing the AlGaN self-assembly template layer, thereby realizing the effect of filtering the threading dislocation. In the prior art, the dislocation density of the AlGaN material is still high due to the fact that the AlN bottom layer has high compressive stress and high threading dislocation density, and the AlGaN thin film is cracked; however, after the AlGaN self-assembly template layer is introduced, threading dislocation from a high-temperature AlN layer can be effectively filtered, so that the dislocation density of the AlGaN material is remarkably reduced, and thermal stress accumulated in the growth process is greatly released, thereby effectively solving the problem of cracking of the AlGaN film.
Different from the situation of the prior art, the invention provides the AlGaN composite film with the self-assembly template and the preparation method thereof, the AlInGaN film layer and the AlGaN low-temperature layer which are arranged In a close contact manner are heated and annealed until In is sublimated to form the graphical AlGaN self-assembly template layer, and the AlGaN self-assembly template layer can effectively filter threading dislocation from the high-temperature AlN layer and release thermal stress accumulated In the growth process, thereby obviously improving the quality of the AlGaN composite film and preventing the film from cracking.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The AlGaN composite film with the self-assembly template is characterized in that the AlGaN composite film with the self-assembly template is sequentially provided with a sapphire substrate, an AlN low-temperature buffer layer, a high-temperature AlN layer, an AlGaN self-assembly template layer and a high-temperature AlGaN film layer from bottom to top;
the AlGaN self-assembly template layer is prepared by heating and annealing an AlInGaN thin layer and an AlGaN low-temperature layer which are arranged In a close manner until In sublimes, wherein the AlInGaN thin layer is positioned at one side close to the high-temperature AlN layer before heating and annealing, and the AlGaN low-temperature layer is positioned at one side close to the high-temperature AlGaN thin layer.
2. The AlGaN composite film with the self-assembled template according to claim 1, wherein the thickness of the AlInGaN thin film layer is 1-500 nm before the temperature-raising annealing, and the mass ratio of In is 1-30%, and the mass ratio of Al is 30-90%.
3. The AlGaN composite thin film with a self-assembled template according to claim 1, wherein the thickness of the AlGaN low-temperature layer is 1 to 500nm before the temperature-raising annealing, and the mass ratio of Al is 30 to 90%.
4. The AlGaN composite film according to claim 1, wherein the annealing at elevated temperature specifically comprises any one of the following steps:
(1) heating to 800-1300 ℃ in a hydrogen atmosphere, keeping the pressure at 50Torr, and keeping the temperature for 1-30 min;
(2) heating to 800-1400 ℃ in a nitrogen atmosphere, keeping the pressure at 50Torr, and keeping the temperature for 1-30 min.
5. A method for preparing the AlGaN composite film with the self-assembled template as recited in any one of claims 1 to 4, comprising the steps of:
s1, preparing a film by adopting a metal organic chemical vapor deposition method, and performing nitridation pretreatment on the sapphire substrate to obtain a pretreated sapphire substrate;
s2, cooling to 400-800 ℃, and growing an AlN low-temperature buffer layer on the pretreated sapphire substrate, wherein the growth thickness of the AlN low-temperature buffer layer is 10-50 nm;
s3, heating to 1100-1400 ℃, and growing a high-temperature AlN layer on the AlN low-temperature buffer layer;
s4, cooling to 400-1100 ℃, adjusting the V/III ratio to be 50-10000, and growing an AlInGaN thin film layer on the high-temperature AlN layer, wherein the mass ratio of In is 1-30%;
s5, adjusting the temperature to 200-1200 ℃, adjusting the V/III ratio to 50-10000, and growing an AlGaN low-temperature layer on the AlInGaN thin film layer;
s6, heating and annealing until In sublimes to obtain an AlGaN self-assembly template layer;
and S7, adjusting the temperature to 900-1200 ℃, and growing a high-temperature AlGaN film layer on the AlGaN self-assembly template layer.
6. The method for preparing an AlGaN composite film having a self-assembled template according to claim 5, wherein the step of S1, in which the step of performing nitridation pretreatment on the sapphire substrate, comprises the specific steps of:
heating to 900-1100 ℃ in a hydrogen atmosphere, and baking the sapphire substrate for 5 min;
and keeping the temperature of 900-1100 ℃, and introducing ammonia gas to treat the sapphire substrate for 5 min.
7. The method of claim 5, wherein in the step S4, the AlInGaN thin film layer is grown to a thickness of 1-500 nm, and the mass ratio of Al is 30-90%.
8. The method of preparing an AlGaN composite film according to claim 5, wherein the growth thickness of the AlGaN low-temperature layer in the step of S5 is 1 to 500nm, and the mass ratio of Al in the AlGaN low-temperature layer is 30 to 90%.
9. The method of manufacturing an AlGaN composite thin film having a self-assembled template according to claim 5, wherein in the step of S6, the specific step of the temperature increase annealing is any one of the following:
(1) heating to 800-1300 ℃ in a hydrogen atmosphere, keeping the pressure at 50Torr, and keeping the temperature for 1-30 min;
(2) heating to 800-1400 ℃ in a nitrogen atmosphere, keeping the pressure at 50Torr, and keeping the temperature for 1-30 min.
10. The method of preparing an AlGaN composite thin film with a self-assembled template according to claim 5, wherein the high-temperature AlN layer is grown to a thickness of 100 to 10000 nm.
CN202010830369.0A 2020-08-18 2020-08-18 AlGaN composite film with self-assembled template and preparation method thereof Active CN112086543B (en)

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