CN112233970A - Method for manufacturing gallium arsenide-based semiconductor device - Google Patents
Method for manufacturing gallium arsenide-based semiconductor device Download PDFInfo
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- CN112233970A CN112233970A CN202011468551.2A CN202011468551A CN112233970A CN 112233970 A CN112233970 A CN 112233970A CN 202011468551 A CN202011468551 A CN 202011468551A CN 112233970 A CN112233970 A CN 112233970A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/0217—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
Abstract
The invention provides a manufacturing method of a gallium arsenide-based semiconductor device, and relates to the technical field of semiconductor device preparation. The manufacturing method of the gallium arsenide-based semiconductor device provided by the invention comprises the following steps: putting the gallium arsenide substrate into an acid solution for cleaning; flowing ammonia gas is introduced to the surface of the cleaned gallium arsenide substrate, and the ammonia gas is subjected to plasma reaction to remove oxides on the surface of the gallium arsenide substrate; and preparing a silicon nitride protective film on the gallium arsenide substrate. Before preparing the silicon nitride protective film on the gallium arsenide substrate, the method removes the oxide on the surface of the gallium arsenide substrate by utilizing the plasma reaction of ammonia gas and forms a complete nitrogen-hydrogen chemical bond on the gallium arsenide substrate, thereby obtaining the steady-state gallium arsenide substrate with a rough surface, ensuring that the silicon nitride protective film prepared on the gallium arsenide substrate is not easy to fall off, and improving the yield of products.
Description
Technical Field
The invention relates to the technical field of semiconductor device preparation, in particular to a manufacturing method of a gallium arsenide-based semiconductor device.
Background
In the process of manufacturing a gallium arsenide-based semiconductor device, a gallium arsenide substrate needs to be put into a hydrochloric acid solution for cleaning, then the gallium arsenide substrate is dried, and then a silicon nitride protective film is prepared on the dried gallium arsenide substrate by utilizing Plasma Enhanced Chemical Vapor Deposition (PECVD) equipment.
However, since arsenic and gallium are easily and rapidly oxidized in a natural state, and the gallium arsenide substrate is exposed to air for 5-10 minutes after being treated with hydrochloric acid and between the drying and the growth of the silicon nitride protective film, oxides are easily formed on the gallium arsenide substrate before the silicon nitride protective film is prepared on the gallium arsenide substrate, and in the process, the gallium arsenide substrate is very unstable, crack defects are easily generated, dangling bonds are formed, and the silicon nitride protective film prepared on the gallium arsenide substrate subsequently is easy to fall off, so that the product yield is reduced.
Disclosure of Invention
The invention aims to provide a manufacturing method of a gallium arsenide-based semiconductor device, which is used for solving the technical problems that in the prior art, before a silicon nitride protective film is prepared on a gallium arsenide substrate, an oxide is easily formed on the gallium arsenide substrate, and in the process, the gallium arsenide substrate is very unstable, is easy to generate crack defects and form dangling bonds, so that the silicon nitride protective film prepared on the gallium arsenide substrate subsequently is easy to fall off, and the product yield is reduced.
The invention provides a manufacturing method of a gallium arsenide-based semiconductor device, which comprises the following steps:
s1: putting the gallium arsenide substrate into an acid solution for cleaning;
s2: flowing ammonia gas is introduced to the surface of the cleaned gallium arsenide substrate, and the ammonia gas is subjected to plasma reaction to remove oxides on the surface of the gallium arsenide substrate;
s3: and preparing a silicon nitride protective film on the gallium arsenide substrate.
Further, step S2 includes flowing a mixture gas including ammonia gas and other non-oxygen-containing gas onto the cleaned surface of the gaas substrate, and subjecting the mixture gas to a plasma reaction to remove oxides on the surface of the gaas substrate.
Further, the mixed gas in step S2 includes ammonia and nitrogen.
Furthermore, the flow of ammonia in the mixed gas is 30-60SCCM, and the flow of nitrogen is 50-100 SCCM.
Furthermore, the environment temperature of the mixed gas for plasma reaction is 250-320 ℃, and the pressure is 900-1500 mTorr.
Further, the time of plasma reaction of the mixed gas is 2-5 min.
Further, the mixed gas in step S2 includes ammonia gas and inert gas.
Further, the inert gas is helium.
Further, the mixed gas in step S2 includes ammonia, nitrogen, and helium.
Further, step S2 and step S3 are both performed in a PECVD apparatus.
The manufacturing method of the gallium arsenide-based semiconductor device provided by the invention can produce the following beneficial effects:
the method for manufacturing a gallium arsenide-based semiconductor device provided by the present invention comprises the following steps, S1: putting the gallium arsenide substrate into an acid solution for cleaning; s2: flowing ammonia gas is introduced to the surface of the cleaned gallium arsenide substrate, and the ammonia gas is subjected to plasma reaction to remove oxides on the surface of the gallium arsenide substrate; s3: and preparing a silicon nitride protective film on the gallium arsenide substrate. Before preparing the silicon nitride protective film on the gallium arsenide substrate cleaned by the acid solution, flowing ammonia gas is introduced to the surface of the gallium arsenide substrate and is subjected to plasma reaction, then the plasma reaction of the ammonia gas can be utilized to remove oxides on the surface of the gallium arsenide substrate, and complete nitrogen-hydrogen chemical bonds are formed on the gallium arsenide substrate, so that the stable gallium arsenide substrate with a rough surface can be obtained, the adhesion and the stability of the gallium arsenide substrate are improved, the silicon nitride protective film prepared on the gallium arsenide substrate is not easy to fall off, and the yield of products is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a flowchart of a method for manufacturing a gallium arsenide based semiconductor device according to an embodiment of the present invention;
FIG. 2 is a schematic view of the surface of the GaAs substrate processed in step S2;
FIG. 3 is a schematic view of the surface of the GaAs substrate processed in step S2, when the ammonia gas in step S2 is replaced by argon gas;
FIG. 4 is a schematic view of the surface of the GaAs substrate processed in step S2, when the ammonia gas is replaced with oxygen gas in step S2;
FIG. 5 is a schematic view of the surface of the GaAs substrate processed in step S2, when the ammonia gas in step S2 is replaced with nitrogen gas;
FIG. 6 is a partial schematic view of a silicon nitride protective film formed on a GaAs substrate without being processed in step S2;
FIG. 7 is a partial schematic view of a silicon nitride protective film formed on a GaAs substrate after being processed in step S2;
fig. 8 is another flowchart of a method for manufacturing a gallium arsenide based semiconductor device according to an embodiment of the present invention;
fig. 9 is a flowchart of a method for manufacturing a gaas based semiconductor device according to an embodiment of the present invention.
Icon: a 1-gallium arsenide substrate.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example (b):
as shown in fig. 1, the method for manufacturing a gallium arsenide based semiconductor device provided in this embodiment includes:
step S1: putting the gallium arsenide substrate 1 into an acid solution for cleaning;
step S2: flowing ammonia gas is introduced to the surface of the cleaned gallium arsenide substrate 1, and the ammonia gas is subjected to plasma reaction to remove oxides on the surface of the gallium arsenide substrate 1;
step S3: a silicon nitride protective film is prepared on the gallium arsenide substrate 1.
Before the silicon nitride protective film is prepared on the gallium arsenide substrate 1 cleaned by the acid solution, flowing ammonia gas is introduced to the surface of the gallium arsenide substrate 1 and is subjected to plasma reaction, then the oxide on the surface of the gallium arsenide substrate 1 can be removed by utilizing the plasma reaction of the ammonia gas, and a complete nitrogen-hydrogen chemical bond is formed on the gallium arsenide substrate 1, so that the stable gallium arsenide substrate 1 with a rough surface can be obtained, the adhesion and the stability of the gallium arsenide substrate 1 are improved, the silicon nitride protective film prepared on the gallium arsenide substrate 1 is not easy to fall off, and the yield of products is improved.
Even if oxide is already formed on the surface of the gallium arsenide substrate 1 and a crack defect is generated due to exposure to air before the silicon nitride protective film is prepared on the gallium arsenide substrate 1, the method for manufacturing the gallium arsenide based semiconductor device according to the present embodiment can remove the oxide formed on the gallium arsenide substrate 1 by using the plasma reaction of ammonia gas and form a complete nitrogen-hydrogen chemical bond on the gallium arsenide substrate 1. Moreover, because the ammonia gas introduced to the surface of the gallium arsenide substrate 1 flows, after the oxide is removed, the flowing gas can also take away the removed oxygen molecules, so that the oxide can be completely separated from the gallium arsenide substrate 1.
Therefore, the manufacturing method of the gallium arsenide-based semiconductor device provided by the embodiment alleviates the technical problems that in the prior art, before the silicon nitride protective film is prepared on the gallium arsenide substrate, an oxide is easily formed on the gallium arsenide substrate, and in the process, the gallium arsenide substrate is very unstable, a crack defect is easily generated, a dangling bond is formed, and further the silicon nitride protective film prepared on the gallium arsenide substrate subsequently is easy to fall off, and the product yield is reduced.
The technical effects achieved by the method for manufacturing a gallium arsenide-based semiconductor device provided in the present embodiment can be further clearly shown in fig. 2 to 7. Fig. 2 is a schematic view of the surface of the gallium arsenide substrate 1 processed in step S2, fig. 3 is a schematic view of the surface of the gallium arsenide substrate 1 processed in step S2 when the ammonia gas in step S2 is replaced by argon gas, fig. 4 is a schematic view of the surface of the gallium arsenide substrate 1 processed in step S2 when the ammonia gas in step S2 is replaced by oxygen gas, fig. 5 is a schematic view of the surface of the gallium arsenide substrate 1 processed in step S2 when the ammonia gas in step S2 is replaced by nitrogen gas, as can be seen by comparing fig. 3, fig. 4 and fig. 5 with fig. 2, respectively, in step S2, compared with the case where the surface of the gallium arsenide substrate 1 is processed by argon gas, oxygen gas or nitrogen gas, the surface of the gallium arsenide substrate 1 is more uneven, has higher roughness and better adhesion, so that the method for manufacturing, ammonia gas is used to remove the oxide on the surface of the gallium arsenide substrate in step S2.
Fig. 6 is a partial schematic view of the silicon nitride protective film formed on the gallium arsenide substrate 1 without being processed in step S2, and it can be seen from fig. 6 that a large number of white spots are distributed on the surface of the silicon nitride protective film on the gallium arsenide substrate 1 in fig. 6, and the white spots are located at positions where the silicon nitride protective film is in the point-like falling positions, so that it can be seen that the silicon nitride protective film is easily in the point-like falling position and has a large falling area when the silicon nitride protective film is formed on the surface of the gallium arsenide substrate 1 by using the conventional method for manufacturing a gallium arsenide-based semiconductor device. Fig. 7 is a partial schematic view of the silicon nitride protective film prepared on the gallium arsenide substrate 1 after the processing of step S2, and it can be seen from comparing fig. 6 and fig. 7 that after the processing of step S2, the silicon nitride protective film prepared on the gallium arsenide substrate 1 is relatively coherent and complete, and basically does not drop in a dot shape, so that the silicon nitride protective film prepared on the gallium arsenide substrate 1 by the method for manufacturing a gallium arsenide semiconductor device according to this embodiment is not prone to drop, and can play a good role in protection.
As can be seen from the comparison between the above drawings, the gallium arsenide based semiconductor device manufactured by the method for manufacturing a gallium arsenide based semiconductor device according to the present embodiment has the silicon nitride protective film that is not easily peeled off from the gallium arsenide substrate 1, and the yield of the product can be greatly improved.
As shown in fig. 8, step S2 includes: and introducing flowing mixed gas comprising ammonia gas and other non-oxygen-containing gas to the surface of the cleaned gallium arsenide substrate 1, and carrying out plasma reaction on the mixed gas to remove oxides on the surface of the gallium arsenide substrate 1.
The process of introducing flowing ammonia gas to the surface of the cleaned gallium arsenide substrate 1 needs to be performed in a closed space. In order to realize the flowing process of the ammonia gas, the closed space can comprise a gas inlet and a gas outlet, the gas inlet and the gas outlet are opened simultaneously, and the ammonia gas entering the closed space can keep flowing on the surface of the gallium arsenide substrate 1. Wherein, other oxygen-free gas are the oxygen-free gas of non-ammonia, and it is used for enlarging the volume of gas mixture for the gas that enters into in above-mentioned airtight space can fill out above-mentioned airtight space rapidly, and then makes the ammonia can carry out plasma reaction fast and play the effect of getting rid of the oxide fast, promotes work efficiency.
It should be noted that the amount of ammonia gas required for removing the oxide on the surface of the gallium arsenide substrate 1 is not so large, and the effect of removing the oxide can be achieved even with the mixed gas containing ammonia gas. In this embodiment, the proportion of ammonia gas in the mixture gas may be less than half of the total amount of the mixture gas.
Further, the mixed gas in step S2 includes ammonia and nitrogen.
Nitrogen gas in the mixed gas not only helps filling up above-mentioned confined space fast, and can carry out plasma reaction simultaneously with the ammonia, helps forming nitrogen hydrogen chemical bond on gallium arsenide substrate 1 surface fast, further promotion work efficiency.
In the embodiment, the flow of ammonia in the mixed gas is preferably 30-60SCCM, and the flow of nitrogen is preferably 50-100 SCCM.
The flow of the ammonia gas is 30-60SCCM, the flow of the nitrogen gas is 50-100SCCM, and the working efficiency of the surface adhesion of the gallium arsenide substrate 1 can be improved to the maximum extent while the oxide on the surface of the gallium arsenide substrate 1 can be fully removed.
Wherein, the flow of the ammonia gas can be 40SCCM, and the flow of the nitrogen gas can be 60 SCCM.
Furthermore, the ambient temperature of the mixed gas during the plasma reaction is 250 ℃ to 320 ℃, and the pressure is 900 ℃ to 1500mTorr (millitorr).
The environment temperature of the mixed gas during the plasma reaction is 250 ℃ to 320 ℃, and the pressure is 900 ℃ to 1500mTorr, so that the environment requirement of the mixed gas during the plasma reaction can be met, and the plasma reaction can be smoothly carried out.
In this embodiment, the environment temperature of the mixed gas during the plasma reaction is preferably 290 ℃ to 310 ℃, and the pressure is 1400 mTorr.
Wherein the plasma reaction time of the mixed gas is 2-5 min.
The plasma reaction time of the mixed gas is 2-5min, so that a large amount of oxides on the surface of the gallium arsenide substrate 1 can be removed, and the adhesion of the surface of the gallium arsenide substrate 1 is effectively improved.
Further, in this embodiment, it is preferable that the plasma reaction time of the mixed gas is 3 min.
In the present embodiment, the mixed gas in step S2 may include ammonia gas and inert gas.
When the mixed gas comprises ammonia gas and inert gas, other non-oxygen-containing gas is the inert gas, wherein the inert gas does not react with the gallium arsenide substrate 1 and does not influence the process of removing oxide and forming nitrogen-hydrogen chemical bond by the ammonia gas.
Further, the inert gas may be helium.
It should be noted that argon is not used as the inert gas because argon is not used effectively.
In practical applications, the mixed gas in step S2 may include two or more gases, such as ammonia, nitrogen and helium.
In this embodiment, step S2 and step S3 are preferably performed in a PECVD apparatus.
The PECVD apparatus is an existing apparatus for preparing a protective film on a substrate, and the step S3 is generally performed in the PECVD apparatus.
In this embodiment, step S2 and step S3 are both performed in a PECVD apparatus, so that step S2 and step S3 can be performed in the same apparatus in sequence, thereby improving the process smoothness of the method for manufacturing the gallium arsenide based semiconductor device, preventing the gallium arsenide substrate 1 from being exposed to air again between step S2 and step S3, and improving the working efficiency of manufacturing the gallium arsenide based semiconductor device.
As shown in fig. 9, in step S3, a silicon nitride protective film is prepared on the gallium arsenide substrate 1 using a mixed gas of silane, nitrogen, and ammonia.
There are various options for the gas used for producing the silicon nitride protective film on the gallium arsenide substrate 1, and this embodiment preferably has a mixed gas including silane, nitrogen, and ammonia.
As shown in fig. 9, the method for manufacturing a gallium arsenide based semiconductor device provided by the present embodiment further includes step S10 between step S1 and step S2: the gallium arsenide substrate 1 is baked.
After step S1, a liquid acid solution is further attached to the gallium arsenide substrate 1, and in order to prevent the acid solution from contaminating the PECVD apparatus, it is preferable in this embodiment to dry the gallium arsenide substrate 1 after cleaning the gallium arsenide substrate 1.
There are many options for the acid solution used to clean the gallium arsenide substrate 1, and it is preferable that the acid solution in step S1 is hydrochloric acid in this embodiment.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (7)
1. A method of fabricating a gallium arsenide based semiconductor device, comprising:
s1: putting the gallium arsenide substrate (1) into an acid solution for cleaning;
s2: introducing flowing mixed gas containing ammonia gas and nitrogen gas to the surface of the cleaned gallium arsenide substrate (1), and carrying out plasma reaction on the mixed gas to remove oxides on the surface of the gallium arsenide substrate (1);
s3: preparing a silicon nitride protective film on the gallium arsenide substrate (1).
2. The method for manufacturing a gallium arsenide based semiconductor device as claimed in claim 1, wherein the flow of ammonia gas in said mixture gas is 30-60SCCM and the flow of nitrogen gas is 50-100 SCCM.
3. The method as claimed in claim 2, wherein the ambient temperature of the mixture gas during the plasma reaction is 250-320 ℃ and the pressure is 900-1500 mTorr.
4. The method for manufacturing a gallium arsenide based semiconductor device as claimed in claim 3, wherein the time for plasma reaction of said mixture is 2-5 min.
5. The method for manufacturing a gallium arsenide based semiconductor device as claimed in claim 1, wherein the mixed gas in step S2 comprises ammonia gas and inert gas.
6. The method for manufacturing a gallium arsenide based semiconductor device as claimed in claim 5, wherein said inert gas is helium.
7. The method for manufacturing a gallium arsenide based semiconductor device according to any of claims 1-6, wherein step S2 and step S3 are both performed in a PECVD apparatus.
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