CN111341645A - Method for manufacturing aluminum nitride semiconductor film and structure thereof - Google Patents

Method for manufacturing aluminum nitride semiconductor film and structure thereof Download PDF

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Publication number
CN111341645A
CN111341645A CN202010241854.4A CN202010241854A CN111341645A CN 111341645 A CN111341645 A CN 111341645A CN 202010241854 A CN202010241854 A CN 202010241854A CN 111341645 A CN111341645 A CN 111341645A
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aluminum nitride
nitride film
sapphire substrate
aluminum
film
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CN111341645B (en
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林辉
刘锐森
蓝文新
刘召忠
杨小利
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Jiangxi Litkang Optical Co ltd
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Jiangxi Xinzhengyao Optical Research Institute Co ltd
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Abstract

The application discloses a manufacturing method and a structure of an aluminum nitride semiconductor film, which relate to the field of film forming of semiconductor equipment and comprise the following steps: providing a sapphire substrate; forming an aluminum metal layer on one side of the sapphire substrate; carrying out nitridation treatment on the aluminum metal layer to generate a first aluminum nitride film; generating a second aluminum nitride film on one side of the first aluminum nitride film, which is far away from the sapphire substrate; annealing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film; and generating a third aluminum nitride film on the side of the second aluminum nitride film far away from the sapphire substrate. Before the second aluminum nitride film is generated, the first aluminum nitride film is generated on the sapphire substrate, and the stacking stress caused by the subsequent aluminum nitride films is effectively reduced through the first aluminum nitride film and the second aluminum nitride film, so that the cracking density and the hole defect density can be reduced, and the high-quality aluminum nitride semiconductor film is generated.

Description

Method for manufacturing aluminum nitride semiconductor film and structure thereof
Technical Field
The application relates to the field of film formation of semiconductor equipment, in particular to a manufacturing method and a structure of an aluminum nitride semiconductor film.
Background
With the continuous progress of led technology, leds in the ultraviolet band have been attracting much attention in recent years. Generally, when manufacturing an ultraviolet light emitting diode, especially in a deep ultraviolet light range with an emission wavelength below 320nm, an aluminum nitride semiconductor thin film is epitaxially grown on a sapphire substrate, so that the aluminum nitride semiconductor thin film serves as a buffer layer between the sapphire substrate and a structure of the ultraviolet light emitting diode, and a crystalline quality of the aluminum nitride semiconductor thin film buffer layer is crucial to the light emitting efficiency of a light emitting diode structure which is subsequently epitaxially grown.
Because the lattice constants of the aluminum nitride semiconductor film and the sapphire substrate are not matched and the difference of the thermal expansion coefficients is large, if the aluminum nitride semiconductor film is directly epitaxially grown on the sapphire substrate at a high temperature, cracking and high-density hole defects are easily generated, and the yield and the internal quantum efficiency of the ultraviolet light emitting diode are further reduced.
Disclosure of Invention
In view of the above, the present application provides a method for fabricating an aluminum nitride semiconductor thin film and a structure thereof, wherein before a second aluminum nitride thin film is formed, a first aluminum nitride thin film is formed on a sapphire substrate, and a stacking stress caused by subsequent aluminum nitride thin films is effectively reduced by the first aluminum nitride thin film and the second aluminum nitride thin film, so that a crack density and a void defect density can be reduced, and a high-quality aluminum nitride semiconductor thin film is formed.
In order to solve the technical problem, the following technical scheme is adopted:
in one aspect, the present application provides a method for fabricating an aluminum nitride semiconductor thin film, including:
providing a sapphire substrate;
placing the sapphire substrate in an organic metal chemical vapor deposition reaction chamber;
introducing an aluminum-containing precursor into the organic metal chemical vapor deposition reaction chamber, and forming an aluminum metal layer on one side of the sapphire substrate;
introducing an ammonia precursor into the organic metal chemical vapor deposition reaction cavity, and performing nitridation treatment on the aluminum metal layer to generate a first aluminum nitride film;
placing the sapphire substrate with the first aluminum nitride thin film into a radio frequency sputtering deposition reaction chamber, and generating a second aluminum nitride thin film on one side of the first aluminum nitride thin film, which is far away from the sapphire substrate;
annealing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film;
placing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film after annealing treatment into the organic metal chemical vapor deposition reaction chamber;
introducing the aluminum-containing precursor and the ammonia precursor into the organic metal chemical vapor deposition reaction chamber; and generating a third aluminum nitride film on the side of the second aluminum nitride film far away from the sapphire substrate.
Optionally, wherein:
before introducing an aluminum-containing precursor into the organometallic chemical vapor deposition reaction chamber, the method further comprises: and introducing hydrogen into the reaction cavity, and cleaning the surface of the sapphire substrate.
Optionally, wherein:
the aluminum-containing precursor comprises at least one of trimethyl aluminum and triethyl aluminum.
Optionally, wherein:
the ammonia precursor comprises at least one of ammonia gas and dimethyl hydrazine.
Optionally, wherein:
generating a second aluminum nitride film on one side of the first aluminum nitride film far away from the sapphire substrate, which specifically comprises the following steps:
introducing argon and nitrogen in a preset proportion into the radio frequency sputtering deposition reaction cavity by taking polycrystalline aluminum nitride powder as a target material, and forming a second aluminum nitride film on one side of the first aluminum nitride film, which is far away from the sapphire substrate; the value range of the preset ratio is 1:2-1: 4.
Optionally, wherein:
the annealing treatment is carried out on the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film, and the annealing treatment specifically comprises the following steps:
and placing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film in an annealing furnace, setting the temperature of the annealing furnace to be more than or equal to 1500 ℃ and less than or equal to 1800 ℃, introducing nitrogen into the annealing furnace, and annealing for 1-3 hours.
Optionally, wherein:
before the annealing process is performed on the sapphire substrate with the first aluminum nitride thin film and the second aluminum nitride thin film, the method further comprises the following steps:
and placing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film on a bearing base, and enabling the second aluminum nitride film to be located between the sapphire substrate and the bearing base.
In another aspect, the present application further provides a structure of an aluminum nitride semiconductor thin film, including:
a sapphire substrate;
a first aluminum nitride film located on one side of the sapphire substrate;
a second aluminum nitride film, wherein the second aluminum nitride film is positioned on one side of the first aluminum nitride film far away from the sapphire substrate;
and the third aluminum nitride film is positioned on one side of the second aluminum nitride film, which is far away from the sapphire substrate.
Compared with the prior art, the manufacturing method and the structure of the aluminum nitride semiconductor film have the following effects:
according to the manufacturing method and the structure of the aluminum nitride semiconductor film, before the second aluminum nitride film is deposited by radio frequency sputtering and annealed, an organic metal chemical vapor deposition method is firstly used for generating the aluminum metal layer on the sapphire substrate, the aluminum metal layer is subjected to nitridation treatment to generate the first aluminum nitride film, and the annealed first aluminum nitride film and the annealed second aluminum nitride film effectively reduce the stacking stress caused by the subsequent aluminum nitride films, so that the cracking density and the hole defect density can be reduced, and the high-quality aluminum nitride semiconductor film is generated. The aluminum nitride semiconductor film with low hole defect density and high quality is beneficial to improving the internal quantum efficiency of the aluminum nitride deep ultraviolet light-emitting diode; the aluminum nitride semiconductor film with low cracking density and high quality is beneficial to improving the uniformity of the photoelectric characteristics of the aluminum nitride deep ultraviolet light emitting diode epitaxial wafer, and can reduce the fragment rate of the thinning process in the chip manufacturing flow, thereby improving the manufacturing yield.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
FIG. 1 is a schematic diagram of a prior art aluminum nitride film;
FIG. 2 is a schematic view of another prior art structure of an aluminum nitride semiconductor film;
FIG. 3 is a schematic view of another conventional structure of an aluminum nitride semiconductor film;
FIG. 4 is a flow chart illustrating a method for fabricating an aluminum nitride semiconductor film according to an embodiment of the present disclosure;
FIG. 5 is a flow chart illustrating a method for fabricating an aluminum nitride semiconductor film according to an embodiment of the present disclosure;
FIG. 6 is a flow chart illustrating the formation of a second aluminum nitride film according to an embodiment of the present disclosure;
FIG. 7 is a flow chart illustrating a method for fabricating an aluminum nitride semiconductor film according to an embodiment of the present disclosure;
FIG. 8 is a schematic view of a structure of an aluminum nitride semiconductor film according to an embodiment of the present disclosure;
FIG. 9 is a graph showing a comparison of diffraction intensities between the aluminum nitride semiconductor thin films of the present application and the prior art.
Detailed Description
As used in the specification and in the claims, certain terms are used to refer to particular components. As one skilled in the art will appreciate, manufacturers may refer to a component by different names. This specification and claims do not intend to distinguish between components that differ in name but not function. In the following description and in the claims, the terms "include" and "comprise" are used in an open-ended fashion, and thus should be interpreted to mean "include, but not limited to. "substantially" means within an acceptable error range, and a person skilled in the art can solve the technical problem within a certain error range to substantially achieve the technical effect. Furthermore, the term "coupled" is intended to encompass any direct or indirect electrical coupling. Thus, if a first device couples to a second device, that connection may be through a direct electrical coupling or through an indirect electrical coupling via other devices and couplings. The description which follows is a preferred embodiment of the present application, but is made for the purpose of illustrating the general principles of the application and not for the purpose of limiting the scope of the application. The protection scope of the present application shall be subject to the definitions of the appended claims.
Fig. 1 is a schematic view showing a structure of an aluminum nitride film in the prior art, fig. 2 is a schematic view showing another structure of an aluminum nitride semiconductor film in the prior art, and fig. 3 is a schematic view showing another structure of an aluminum nitride semiconductor film in the prior art, please refer to fig. 1-3. At present, the methods for growing an aluminum nitride semiconductor film on a sapphire substrate mainly include the following methods:
1. firstly, a low-temperature aluminum nitride nucleation layer 02 is used as a stress buffer layer between the sapphire substrate 01, and then a high-temperature aluminum nitride semiconductor film 03 is epitaxially grown, as shown in fig. 1, the structure cannot simultaneously solve the problems of cracking and hole defects of the aluminum nitride semiconductor film.
2. Firstly, a layer of low-temperature aluminum nitride nucleation layer 05 is used as a stress buffer layer between the sapphire substrate 04, then a trimethyl aluminum precursor is introduced in a continuous mode, ammonia gas is introduced in a pulse mode, a first high-temperature aluminum nitride thin film layer 06 is epitaxially grown, and then a second high-temperature aluminum nitride thin film layer 07 and a third high-temperature aluminum nitride thin film layer 08 are respectively grown by using the same method, as shown in fig. 2. Although this structure can effectively solve the cracking problem of the aluminum nitride film and reduce the density of the void defects, it is difficult to obtain the optimum window of epitaxial conditions for the aluminum nitride film with higher quality because the growth rate of the pulse method is about one tenth of that of the continuous method and the time ratio of the ammonia gas on/off is not easy to control.
3. Firstly, a layer of polycrystalline aluminum nitride thin film 002 is formed on a sapphire substrate 001 by a sputtering method, then the polycrystalline aluminum nitride thin film 002 is re-nucleated by an annealing procedure of 1600-1700 ℃ for 1-3 hours to be transformed into a high-quality monocrystalline aluminum nitride thin film 003, and then the monocrystalline aluminum nitride thin film 003 is subjected to an MOCVD method to be followed by epitaxial growth of an aluminum nitride thin film 004, as shown in FIG. 3. Although the structure can effectively reduce the density of hole defects, the high-temperature re-nucleation method cannot effectively solve the cracking phenomenon caused by the mismatch of lattice constants and the overlarge difference of thermal expansion coefficients of the subsequent aluminum nitride films.
In view of the above, the present application provides a method for fabricating an aluminum nitride semiconductor thin film and a structure thereof, wherein before a second aluminum nitride thin film is formed, a first aluminum nitride thin film is formed on a sapphire substrate, and a stacking stress caused by subsequent aluminum nitride thin films is effectively reduced by the first aluminum nitride thin film and the second aluminum nitride thin film, so that a crack density and a void defect density can be reduced, and a high-quality aluminum nitride semiconductor thin film is formed.
The following detailed description is to be read in connection with the drawings and the detailed description.
Fig. 4 is a flowchart illustrating a method for fabricating an aluminum nitride semiconductor film according to an embodiment of the present disclosure, and referring to fig. 4, the method for fabricating an aluminum nitride semiconductor film according to an embodiment of the present disclosure includes:
step 10: providing a sapphire substrate;
step 20: placing the sapphire substrate in an organic metal chemical vapor deposition reaction chamber;
step 30: introducing an aluminum-containing precursor into the organic metal chemical vapor deposition reaction chamber, and forming an aluminum metal layer on one side of the sapphire substrate;
step 40: introducing an ammonia precursor into the organic metal chemical vapor deposition reaction cavity, and performing nitridation treatment on the aluminum metal layer to generate a first aluminum nitride film;
step 50: placing the sapphire substrate with the first aluminum nitride film into a radio frequency sputtering deposition reaction chamber, and generating a second aluminum nitride film on one side of the first aluminum nitride film, which is far away from the sapphire substrate;
step 60: annealing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film;
step 70: placing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film after annealing treatment into an organic metal chemical vapor deposition reaction chamber;
step 80: simultaneously introducing an aluminum-containing precursor and an ammonia precursor into the organic metal chemical vapor deposition reaction chamber; and generating a third aluminum nitride film on the side of the second aluminum nitride film far away from the sapphire substrate.
Specifically, referring to fig. 4, in the method for fabricating an aluminum nitride semiconductor thin film provided in the present embodiment, a sapphire substrate is provided in step 10, and the sapphire substrate is placed in a Metal-Organic Chemical Vapor Deposition (MOCVD) reaction chamber through step 20; setting the temperature of the MOCVD reaction cavity to be 1000-1300 ℃ in step 30, wherein the temperature range comprises 1000 ℃ and 1300 ℃, introducing an aluminum-containing precursor into the reaction cavity, and controlling the flow range of aluminum to be 20-200 sccm, so that the aluminum-containing precursor is decomposed at high temperature to form a pre-paved aluminum metal layer on the sapphire substrate, wherein the thickness range of the aluminum metal layer is 1-5 atomic layers, and 1-5 of the aluminum metal layer comprises 1 and 5; because an aluminum metal layer needs to be formed, a substance which can be decomposed to form the aluminum metal layer needs to be introduced, and the aluminum-containing precursor is referred to as an aluminum-containing precursor in the application and can be at least one of trimethyl aluminum and triethyl aluminum. The aluminum-containing precursor can generate aluminum atoms after pyrolysis and form an aluminum metal layer on the sapphire substrate. Then, through step 40, an ammonia precursor is introduced into the MOCVD reaction chamber, and the flow range of ammonia is controlled to be 300sccm-2000sccm, so that the aluminum metal layer can be subjected to nitridation treatment to form a first aluminum nitride thin film with the thickness of h1, wherein 0um < h1 is less than or equal to 2 um. Similar to the aluminum-containing precursor, the aluminum metal layer needs to be nitrided in step 40, and the nitridation is usually performed by using ammonia gas, so that a substance capable of generating nitrogen atoms after pyrolysis, which is referred to as an ammonia precursor in the present application, needs to be introduced into the reaction chamber, and includes at least one of ammonia gas and dimethylhydrazine. The ammonia precursor is decomposed to nitride the aluminum metal layer, thereby forming a first aluminum nitride film.
Referring to fig. 4, after the first aluminum nitride film is formed, the temperature of the reaction chamber is reduced to below 100 ℃, the sapphire substrate containing the first aluminum nitride film is taken out, and then in step 50, the sapphire substrate is placed in a radio frequency sputtering deposition (RFsputtering) reaction chamber, and a mixed gas of argon and nitrogen is introduced into the radio frequency sputtering deposition reaction chamber, so that a second aluminum nitride film with a thickness of h2 is formed on the surface of the first aluminum nitride film by using polycrystalline aluminum nitride powder as a target, wherein h2 is greater than or equal to 50nm and less than or equal to 400 nm. The thickness of the first aluminum nitride thin film and the second aluminum nitride thin film herein refers to the thickness in the vertical direction of the plane in which the sapphire substrate is located.
After the second aluminum nitride thin film is formed, the sapphire substrate having the first aluminum nitride thin film and the second aluminum nitride thin film is placed in an annealing furnace in step 60, the temperature of the annealing furnace is set to be between 1500 ℃ and 1800 ℃, and nitrogen gas is introduced into the annealing furnace to anneal the second aluminum nitride thin film. When annealing treatment is carried out, the second aluminum nitride film needs to be protected to a certain extent so as to avoid that nitrogen atoms on the surface of the second aluminum nitride film are volatilized by heating in the annealing process, and good crystallization quality cannot be obtained subsequently. The annealed sapphire substrate having the first aluminum nitride film and the second aluminum nitride film is placed in an MOCVD reaction chamber through step 70. Setting the temperature of the reaction cavity of the MOCVD to be more than 1200 ℃ in the step 80, introducing an aluminum-containing precursor and an ammonia precursor into the reaction cavity to generate a third aluminum nitride film, and setting the flow ranges of the aluminum precursor and the ammonia precursor to be 20sccm-200sccm and 300sccm-2000sccm respectively, so that the thickness h3 of the third aluminum nitride film ranges from 0um to h3 to 2 um.
According to the manufacturing method of the aluminum nitride semiconductor film, before the radio frequency sputtering deposition of the second aluminum nitride film is utilized, the vapor deposition method is firstly used for generating the aluminum metal layer on the sapphire substrate, the aluminum metal layer is subjected to nitridation treatment to generate the first aluminum nitride film, and the first aluminum nitride film and the second aluminum nitride film effectively reduce the stacking stress caused by the subsequent aluminum nitride films, so that the cracking density and the hole defect density can be reduced, and the high-quality aluminum nitride semiconductor film is generated. The aluminum nitride semiconductor film with low hole defect density and high quality is beneficial to improving the internal quantum efficiency of the aluminum nitride deep ultraviolet light-emitting diode; the aluminum nitride semiconductor film with low cracking density and high quality is beneficial to improving the uniformity of the photoelectric characteristics of the aluminum nitride deep ultraviolet light emitting diode epitaxial wafer, and can reduce the fragment rate of the thinning process in the chip manufacturing flow, thereby improving the manufacturing yield.
Optionally, referring to fig. 5, before introducing an aluminum-containing precursor into the organic metal chemical vapor deposition reaction chamber, a step 21 is further included: and introducing hydrogen into the reaction cavity to clean the surface of the sapphire substrate. Specifically, referring to fig. 5, in this embodiment, after the sapphire substrate is placed in the MOCVD, the surface of the sapphire substrate is cleaned in step 21, when the surface of the substrate is cleaned, the temperature of the reaction chamber is kept to be greater than 1050 ℃, then hydrogen with a purity level of 6N or more is introduced, the surface of the sapphire substrate is cleaned by heat treatment, organic matters or oxides and the like remaining on the surface of the sapphire substrate are volatilized at a high temperature and are taken away from the surface of the sapphire substrate and the outside of the MOCVD chamber along with the hydrogen, and therefore, the phenomenon that an incomplete aluminum metal film is formed on the surface of the substrate by subsequently introduced aluminum-containing precursors and a stable aluminum nitride film characteristic cannot be obtained in a subsequent process can be avoided.
Alternatively, referring to fig. 4, the aluminum-containing precursor includes at least one of trimethylaluminum and triethylaluminum. Specifically, referring to fig. 4, in step 30 and step 80, when the first aluminum nitride film and the third aluminum nitride film are manufactured, an aluminum-containing precursor is introduced into an MOCVD reaction chamber at a high temperature, and is easily decomposed by heat to form aluminum atoms, thereby forming an aluminum metal layer on the sapphire substrate, using trimethyl aluminum or triethyl aluminum as a raw material for the MOCVD process. It should be noted that, the use of trimethyl aluminum or triethyl aluminum as the aluminum precursor is only one embodiment in this embodiment, and in other embodiments, the aluminum precursor may also be other aluminum-containing compounds, which is not limited in this application.
Alternatively, referring to fig. 4, the ammonia precursor includes at least one of ammonia gas and dimethylhydrazine. Specifically, referring to fig. 4, in steps 40 and 80, when the ammonia precursor is introduced to form the first aluminum nitride film and the third aluminum nitride film, the ammonia precursor may be ammonia gas or dimethylhydrazine, and after the aluminum metal layer is formed in step 30, the aluminum metal layer needs to be nitrided, and the ammonia gas and the dimethylhydrazine are easily decomposed at a high temperature to generate nitrogen atoms, which can perform a nitridation reaction with the aluminum atoms of the aluminum metal layer to form the first aluminum nitride film. It should be noted that ammonia gas or dimethylhydrazine is used as the ammonia precursor, which is only an exemplary embodiment in this embodiment, and in other embodiments, the ammonia precursor may also be other compounds, which is not limited in this application.
Optionally, fig. 6 is a flowchart illustrating a process of forming a second aluminum nitride film according to an embodiment of the present application, please refer to fig. 6, wherein the forming of the second aluminum nitride film on a side of the first aluminum nitride film away from the sapphire substrate specifically includes: step 51: taking polycrystalline aluminum nitride powder as a target material; step 52: introducing argon and nitrogen in a preset proportion into the radio frequency sputtering deposition reaction cavity; step 53: forming a second aluminum nitride film on one side of the first aluminum nitride film, which is far away from the sapphire substrate; the predetermined ratio ranges from 1:2 to 1:4, where the ratio of argon to nitrogen ranges from 1:2 and 1: 4.
Optionally, referring to fig. 4, in step 60, the annealing process is performed on the sapphire substrate having the first aluminum nitride film and the second aluminum nitride film, specifically: and placing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film in an annealing furnace, setting the temperature of the annealing furnace to be more than or equal to 1500 ℃ and less than or equal to 1800 ℃, introducing nitrogen into the annealing furnace, and annealing for 1-3 hours. Specifically, referring to fig. 4, after the second aluminum nitride film is formed, the sapphire substrate having the first aluminum nitride film and the second aluminum nitride film is taken out from the rf sputtering deposition reaction chamber, and the sapphire substrate having the first aluminum nitride film and the second aluminum nitride film is annealed by step 60, which is first placed in an annealing furnace, the temperature of the annealing furnace is maintained between 1500 c and 1800 c, introducing nitrogen with the purity of 6N, annealing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film for 1-3 hours in the nitrogen atmosphere, rearranging the crystal lattices of the first aluminum nitride film and the second aluminum nitride film, thereby overcoming the defects of cracking and holes of the aluminum nitride film caused by the mismatch of the lattice constants of the aluminum nitride film and the sapphire substrate, thereby being beneficial to improving the structural quality of the ultraviolet light emitting diode which is grown by subsequent epitaxy and the yield of the chip.
Optionally, referring to fig. 7, which is another flowchart illustrating a method for manufacturing an aluminum nitride semiconductor film according to an embodiment of the present application, before performing an annealing process on a sapphire substrate having a first aluminum nitride film and a second aluminum nitride film, the method further includes step 61: and placing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film on a bearing base, and enabling the second aluminum nitride film to be located between the sapphire substrate and the bearing base. Specifically, referring to fig. 7, in order to avoid the volatilization of nitrogen atoms on the surface of the second aluminum nitride film due to heating during the annealing process, in the present embodiment, before the annealing process, in step 61, the sapphire substrate having the first aluminum nitride film and the second aluminum nitride film is placed on a supporting base, and the second aluminum nitride film is partially in contact with the supporting base, that is, one side of the second aluminum nitride film in the sapphire substrate having the first aluminum nitride film and the second aluminum nitride film is placed on the supporting base, since there is a gap smaller than 1 mm between the second aluminum nitride film and the supporting base, the saturated vapor pressure of nitrogen atoms can be maintained besides the effect of releasing the warp stress between the entire aluminum nitride film and the sapphire substrate, so that the problem of volatilization of nitrogen atoms in the second aluminum nitride film from the surface layer can be prevented, is favorable for generating the high-quality aluminum nitride semiconductor film.
Based on the same inventive concept, the present application further provides a structure 100 of an aluminum nitride semiconductor thin film, fig. 8 is a schematic view of the structure 100 of the aluminum nitride semiconductor thin film provided in the present application, and referring to fig. 8, the structure 100 of the aluminum nitride semiconductor thin film includes:
a sapphire substrate 110;
a first aluminum nitride film 120, the first aluminum nitride film 120 being located on one side of the sapphire substrate 110;
a second aluminum nitride film 130, wherein the second aluminum nitride film 130 is positioned on the side of the first aluminum nitride film 120 far away from the sapphire substrate 110;
and a third aluminum nitride film 140, wherein the third aluminum nitride film 140 is positioned on the side of the second aluminum nitride film 130 away from the sapphire substrate 110.
Specifically, referring to fig. 8, the aluminum nitride semiconductor thin film provided by the embodiment of the present application includes a sapphire substrate 110, a first aluminum nitride thin film 120, a second aluminum nitride thin film 130 and a third aluminum nitride thin film 140, wherein the second aluminum nitride thin film 130 is located on a side of the first aluminum nitride thin film 120 away from the sapphire substrate 110, and the third aluminum nitride thin film 140 is located on a side of the second aluminum nitride thin film 130 away from the sapphire substrate 110, wherein the first aluminum nitride thin film 120 has a thickness h1, 0um < h1 < 2um, the second aluminum nitride thin film 130 has a thickness h2, 50nm < h2 < 400nm, and the third aluminum nitride thin film 140 has a thickness h3, 0um < h3 < 2um, where the thicknesses of the first aluminum nitride thin film 120, the second aluminum nitride thin film 130 and the third aluminum nitride thin film 140 all refer to a thickness in a direction perpendicular to a plane of the sapphire substrate 110.
The structure 100 of the aluminum nitride semiconductor thin film provided by the application, before depositing the second aluminum nitride thin film by using radio frequency sputtering and annealing, firstly, an organic metal chemical vapor deposition method is used for generating an aluminum metal layer on the sapphire substrate, and the aluminum metal layer is subjected to nitridation treatment to generate a first aluminum nitride thin film, and the stacking stress caused by the subsequent aluminum nitride thin films is effectively reduced through the annealed first aluminum nitride thin film and the annealed second aluminum nitride thin film, so that the cracking density and the hole defect density can be reduced, and the high-quality aluminum nitride semiconductor thin film is generated. The aluminum nitride semiconductor film with low hole defect density and high quality is beneficial to improving the internal quantum efficiency of the aluminum nitride deep ultraviolet light-emitting diode; the aluminum nitride semiconductor film with low cracking density and high quality is beneficial to improving the uniformity of the photoelectric characteristics of the aluminum nitride deep ultraviolet light emitting diode epitaxial wafer, and can reduce the fragment rate of the thinning process in the chip manufacturing flow, thereby improving the manufacturing yield.
The following description will be made in conjunction with test data:
fig. 9 is a graph showing a comparison of diffraction intensities between the aluminum nitride semiconductor thin films of the present application and the prior art using a low-temperature aluminum nitride nucleation layer as a stress buffer layer and then epitaxially growing a high-temperature aluminum nitride semiconductor thin film, as shown in fig. 1, in which (a) shows a diffraction intensity graph of 002 plane, and (b) shows a diffraction intensity graph of 102 plane, where the abscissa shows diffraction angle, the ordinate shows diffraction intensity, the dotted line shows a variation tendency of diffraction intensity of the aluminum nitride semiconductor thin film grown in the prior art, and the solid line shows a variation tendency of diffraction intensity of the aluminum nitride semiconductor thin film grown in the present application. Referring to fig. 9, it can be seen that, compared to the prior art, the aluminum nitride semiconductor thin film provided by the present application has stronger diffraction intensity and narrower half-height bandwidth, indicating that the crystal quality is relatively improved. Therefore, the aluminum nitride semiconductor film generated in the application is utilized to manufacture the ultraviolet light-emitting diode, and the internal quantum efficiency of the ultraviolet light-emitting diode is favorably improved.
According to the embodiments, the application has the following beneficial effects:
according to the manufacturing method and the structure of the aluminum nitride semiconductor film, before the second aluminum nitride film is deposited by radio frequency sputtering and annealed, an organic metal chemical vapor deposition method is firstly used for generating the aluminum metal layer on the sapphire substrate, the aluminum metal layer is subjected to nitridation treatment to generate the first aluminum nitride film, and the annealed first aluminum nitride film and the annealed second aluminum nitride film effectively reduce the stacking stress caused by the subsequent aluminum nitride films, so that the cracking density and the hole defect density can be reduced, and the high-quality aluminum nitride semiconductor film is generated. The aluminum nitride semiconductor film with low hole defect density and high quality is beneficial to improving the internal quantum efficiency of the aluminum nitride deep ultraviolet light-emitting diode; the aluminum nitride semiconductor film with low cracking density and high quality is beneficial to improving the uniformity of the photoelectric characteristics of the aluminum nitride deep ultraviolet light emitting diode epitaxial wafer, and can reduce the fragment rate of the thinning process in the chip manufacturing flow, thereby improving the manufacturing yield.
As will be appreciated by one skilled in the art, embodiments of the present application may be provided as a method, apparatus, or computer program product. Accordingly, the present application may take the form of an entirely hardware embodiment, an entirely software embodiment or an embodiment combining software and hardware aspects. Furthermore, the present application may take the form of a computer program product embodied on one or more computer-usable storage media (including, but not limited to, disk storage, CD-ROM, optical storage, and the like) having computer-usable program code embodied therein.
The foregoing description shows and describes several preferred embodiments of the present application, but as aforementioned, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as excluding other embodiments and is capable of use in various other combinations, modifications, and environments and is capable of changes within the scope of the inventive concept as expressed herein, commensurate with the above teachings, or the skill or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the application, which is to be protected by the claims appended hereto.

Claims (8)

1. A method for manufacturing an aluminum nitride semiconductor film is characterized by comprising the following steps:
providing a sapphire substrate;
placing the sapphire substrate in an organic metal chemical vapor deposition reaction chamber;
introducing an aluminum-containing precursor into the organic metal chemical vapor deposition reaction chamber, and forming an aluminum metal layer on one side of the sapphire substrate;
introducing an ammonia precursor into the organic metal chemical vapor deposition reaction cavity, and performing nitridation treatment on the aluminum metal layer to generate a first aluminum nitride film;
placing the sapphire substrate with the first aluminum nitride thin film into a radio frequency sputtering deposition reaction chamber, and generating a second aluminum nitride thin film on one side of the first aluminum nitride thin film, which is far away from the sapphire substrate;
annealing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film;
placing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film after annealing treatment into the organic metal chemical vapor deposition reaction chamber;
introducing the aluminum-containing precursor and the ammonia precursor into the organic metal chemical vapor deposition reaction chamber; and generating a third aluminum nitride film on the side of the second aluminum nitride film far away from the sapphire substrate.
2. The method of claim 1, further comprising, prior to introducing an aluminum-containing precursor into the organometallic chemical vapor deposition reaction chamber: and introducing hydrogen into the reaction cavity, and cleaning the surface of the sapphire substrate.
3. The method for producing an aluminum nitride semiconductor film according to claim 1,
the aluminum-containing precursor comprises at least one of trimethyl aluminum and triethyl aluminum.
4. The method for producing an aluminum nitride semiconductor film according to claim 1,
the ammonia precursor comprises at least one of ammonia gas and dimethyl hydrazine.
5. The method for manufacturing an aluminum nitride semiconductor film according to claim 1, wherein a second aluminum nitride film is formed on a side of the first aluminum nitride film away from the sapphire substrate, specifically:
introducing argon and nitrogen in a preset proportion into the radio frequency sputtering deposition reaction cavity by taking polycrystalline aluminum nitride powder as a target material, and forming a second aluminum nitride film on one side of the first aluminum nitride film, which is far away from the sapphire substrate; the value range of the preset ratio is 1:2-1: 4.
6. The method for manufacturing an aluminum nitride semiconductor film according to claim 1, wherein the annealing of the sapphire substrate having the first aluminum nitride film and the second aluminum nitride film comprises:
and placing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film in an annealing furnace, setting the temperature of the annealing furnace to be more than or equal to 1500 ℃ and less than or equal to 1800 ℃, introducing nitrogen into the annealing furnace, and annealing for 1-3 hours.
7. The method of claim 1, wherein before the annealing the sapphire substrate having the first and second aluminum nitride films, the method further comprises:
and placing the sapphire substrate with the first aluminum nitride film and the second aluminum nitride film on a bearing base, and enabling the second aluminum nitride film to be located between the sapphire substrate and the bearing base.
8. A structure of an aluminum nitride semiconductor thin film, comprising:
a sapphire substrate;
a first aluminum nitride film located on one side of the sapphire substrate;
a second aluminum nitride film, wherein the second aluminum nitride film is positioned on one side of the first aluminum nitride film far away from the sapphire substrate;
and the third aluminum nitride film is positioned on one side of the second aluminum nitride film, which is far away from the sapphire substrate.
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